Mineral Components in Food
Mineral Components in Food
Mineral Components in Food
Mineral
Components
in Foods
2234_C000.fm Page ii Thursday, October 26, 2006 9:01 AM
Toxins in Food
Edited by Waldemar M. Dąbrowski and Zdzisław E. Sikorski
Mineral
Components
in Foods
EDITED BY
Piotr Szefer
Medical University of Gdańsk
Gdańsk, Poland
Jerome O. Nriagu
University of Michigan
Ann Arbor, Michigan
CRC Press
Taylor & Francis Group
6000 Broken Sound Parkway NW, Suite 300
Boca Raton, FL 33487-2742
© 2007 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
This book contains information obtained from authentic and highly regarded sources. Reprinted
material is quoted with permission, and sources are indicated. A wide variety of references are
listed. Reasonable efforts have been made to publish reliable data and information, but the author
and the publisher cannot assume responsibility for the validity of all materials or for the conse-
quences of their use.
No part of this book may be reprinted, reproduced, transmitted, or utilized in any form by any
electronic, mechanical, or other means, now known or hereafter invented, including photocopying,
microfilming, and recording, or in any information storage or retrieval system, without written
permission from the publishers.
For permission to photocopy or use material electronically from this work, please access www.
copyright.com (http://www.copyright.com/) or contact the Copyright Clearance Center, Inc. (CCC)
222 Rosewood Drive, Danvers, MA 01923, 978-750-8400. CCC is a not-for-profit organization that
provides licenses and registration for a variety of users. For organizations that have been granted a
photocopy license by the CCC, a separate system of payment has been arranged.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and
are used only for identification and explanation without intent to infringe.
Mineral components in foods / [edited by] Piotr Szefer and Jerome O. Nriagu.
p. ; cm. -- (Chemical and functional properties of food components series)
Includes bibliographical references and index.
ISBN-13: 978-0-8493-2234-1 (hardcover : alk. paper)
ISBN-10: 0-8493-2234-0 (hardcover : alk. paper)
1. Nutrition. 2. Food--Analysis. 3. Food--Consumption. 4. Food--Toxicology.
I. Szefer, Piotr. II. Nriagu, Jerome O. III. Series.
[DNLM: 1. Food Analysis--methods. 2. Minerals--adverse effects. 3. Food
Contamination. 4. Metals--adverse effects. 5. Trace Elements--adverse effects.
QU 130 M664 2006]
RA1258.M56 2006
363.19’2--dc22 2006015225
Preface
Understanding of the mineral composition of foodstuff is important from nutritional
and toxicological points of view. According to the Paracelsian maxim, dose makes
poison and every element can become a human health hazard if its concentration in
food is high enough. On the other scale, lack of inadequate quantities of essential
trace elements can cause health problems for consumers. Therefore, the concern of
food manufacturers and processors is to make sure that food products do not breach
the essentiality/toxicity duality embodied in the various legal requirements or codes
of practice for metals in food.
Nutritional or essential elements required for normal bodily function are classi-
fied according to their relative amounts and requirement. Magnesium (Mg), calcium
(Ca), potassium (K), and sodium (Na) are classified as macronutrients while chro-
mium (Cr), cobalt (Co), copper (Cu), molybdenum (Mo), nickel (Ni), and selenium
(Se) are grouped as micronutrients. Chemical elements regarded as possibly essential
micronutrients include arsenic (As), boron (B), and vanadium (V), whereas the toxic
metals include beryllium (Be), cadmium (Cd), lead (Pb), and mercury (Hg). Among
the nontoxic, nonessential metals are aluminium (Al) and tin (Sn); these two elements
are sometimes called “packaging metals,” in recognition of their unique application
in industry and commerce. In the past, the term trace element was used for elements
that were present in biological systems in minute quantities (from nanogram [10–9 g]
to picogram [10–12 g]), near or below the detection limits of the analytical methods
of the time. In recent years, this term is commonly applied to an element that typically
occurs at a level of < 10 mg/100 g in biological systems. All the elements detectable
at this concentration are sometimes referred to as minor elements. The less common
term ultratrace element pertains to elements found at concentrations less than 0.001
mg/100 g.1
The essential micro- and macroelements in food are important for the develop-
ment and maintenance of life functions. They affect all aspects of growth, health,
and reproduction, from the formation of cells, tissues, and organs to the initiation
and development of host defense by the immune system in response to foreign
microbes and viruses. To deal with the essentiality/toxicity mirage, biological sys-
tems have developed sophisticated genomic recognition and transport mechanisms
to ensure delivery of the right metal ion to its target. Quite often, a toxic metal is
able to use an established metabolic pathway for an essential element to reach a
critical target to induce undesirable effects. A number of factors may influence the
absorption, recognition, and transport of essential elements including their bioavail-
ability, interelement interactions, dose-response effects, oxidation state (of the ele-
ment and cellular environment), and associations with biomolecules. These factors
also affect the ability of toxic metals to mimic the essential elements in their cellular
and genomic functions.
2234_C000.fm Page vi Thursday, October 26, 2006 9:01 AM
Recent studies on the biological mechanisms of life and the likely influence of
trace elements in the increasing incidence of chronic diseases, cancers, and degen-
erative diseases have given rise to growing concerns about the health effects of
dietary exposure to trace elements. It is estimated that poor diet is responsible for
trace element deficiencies (mainly related to iron, iodine, zinc, selenium, and copper)
in about 40% of the world’s population, especially in the developing countries. In
poor countries, food supply is usually limited and monotonous; for instance, ugali,
a porridge from white maize (corn), or gari (made of cassava) is eaten in many
African countries three times a day. Besides the geo-environmental factors,2 the
mineral composition of diet is dependent frequently on the sociocultural and reli-
gious habits which can reduce the bioavailabilty of several trace elements; for
instance, if one were to rely exclusively on vegetables for iron and calcium. Blood
losses, parasitic infections, sweating (especially under tropical condition), menstru-
ation, frequent pregnancies, and prolonged lactation tend to increase the mineral
requirements and losses, hence exacerbating the deficiency syndrome.
Not only deficiency but also excess in the intake of mineral components may
result in endocrine, cardiovascular, skeletal, gastrointestinal, kidney, genetic, and
opthalmologic disorders in various individuals. A comprehensive evaluation of the
linkage between diet and cancer in 1997 by the World Cancer Research Fund and
the American Institute for Cancer Regulation concluded that diets with very low or
elevated levels of iodine may lead to increased risk for thyroid cancer whereas
selenium may decrease the risk of lung cancer. The development of oxidative stress
due to increased cellular levels of reactive oxygen species in human immunodefi-
ciency virus (HIV) infection has been linked to depletion of essential mineral
components, especially zinc and selenium, and to altered iron metabolism as well
as to loss of magnesium and calcium. Such changes in body stores of minerals in
the HIV host may affect the course of HIV disease and progression to acquired
immune-deficiency syndrome (AIDS). The balance of essential elements is particu-
larly important for immune defense, and the moderating influence of mineral
components in pathogenesis of HIV would seem like a fertile field for further
investigation.2
Any advancement in the science of metallomics begins with improvements in
our ability to measure a given elements and its forms in the exposure matrices
(mainly foods and drinks) with high sensitivity, selectivity, and precision. Analytical
methods used in quantification of mineral components in foods are described in
Chapter 1. Knowledge of the total concentration of an element in food is not
necessarily sufficient for evaluating how well this element will be absorbed or how
it will be metabolized when consumed.1 Concerted effort has therefore been made
to establish the chemical forms of trace elements in foodstuffs as helpful adjuncts
in establishing dietary requirements and related legislation. Chapter 2 provides an
overview of analytical methods for the speciation of mineral components in food
products. In spite of important recent advancements in analytical techniques for
metal speciation in foods, there is obligation to validate the quality of the data
obtained using various quality assurance programs. Chapter 3 discusses the analytical
quality controls in analyses of foods for trace elements.
2234_C000.fm Page vii Thursday, October 26, 2006 9:01 AM
1 Reilly, C., Metal Contamination of Food: Its Significance for Food Quality and Human
Health, Blackwell Science, Oxford, 2002.
2 Bogden, J. D, and Klevay, L. M., Eds., Clinical Nutrition of the Essential Trace Elements
Editors
Piotr Szefer received his M.S., Ph.D., and D.Sc. degrees from the Medical Univer-
sity of Gdansk (MUG), Poland. He was granted a full professorship at MUG in
2000. Between 1990 and 2002, he was vice dean and the dean of the Faculty of
Pharmacy, MUG. Since 2000 he has been the head of the Department of Food
Sciences, MUG. Prof. Szefer’s research includes instrumental analysis of certain
groups of foodstuffs for mineral components and metaloorganic compounds such
as butyltins. He is involved in the development of novel multivariate statistical
techniques that can be used to estimate the quality, geographical origin, or authen-
ticity of food products. His research also covers the fate of environmental contam-
inants in the marine environments, speciation of chemical elements, and their bio-
availability and biomagnification in the aquatic food chain. Prof. Szefer has
published 160 scientific papers including 12 book issues. He has served on editorial
boards for seven scientific journals, including Science of the Total Environment
(Elsevier) and Oceanologia. Professor Szefer has been a visiting professor or visiting
researcher at several universities and research institutions including Miyazaki Uni-
versity, Japan; University of Aden, Yemen; the Geological Survey of Finland;
Karlsruhe University, Germany; Unidad Académica Mazatlán (UNAM), Mexico;
Andhra University, Visakhapatnam, India; Instituto de Radioproteçao e Dosimetria
(IRD), Rio de Janeiro, Brazil; French Research Institute for Exploitation of the Sea
(IFREMER), Nantes, France; Environmental Science and Technology Department,
Roskilde, Denmark; University of Plymouth, England; Fundación AZTI Technalia,
San Sebastian, Spain; Seoul National University and School of Earth and Environ-
mental Sciences, Seoul National University and Korea Research and Development
Information (KORDI), South Korea. He has supervised seven Ph.D. students and
more than 100 M.Sc. students.
List of Contributors
Marek Biziuk Smaragdi M. Galani-Nikolakaki
Department of Analytical Chemistry Analytical and Environmental
Gdansk University of Technology Chemistry Laboratory
Gdansk, Poland Technical University of Crete
Crete
Marcelo Enrique Conti Chania, Greece
Dipartimento di Controllo e Gestione
delle Merci e del loro Impatto Jerome O. Nriagu
sull’Ambiente Department of Environmental Health
Università La Sapienza Sciences
Rome, Italy School of Public Health
University of Michigan
Ann Arbor, Michigan
Malgorzata
⁄ Grembecka
Department of Food Sciences Zitouni Ould-Dada
Medical University of Gdansk Food Standards Agency
Gdansk, Poland Radiological Safety Unit
Contaminants Division
Nikolaos G. Kallithrakas-Kontos London, England
Technical University of Crete
Analytical and Environmental Peter J. Peterson
Chemistry Laboratory Division of Life Sciences
Crete King’s College
Chania, Greece University of London
London, England
·
Joanna Kuczynska Aleksandra Polatajko
Department of Analytical Chemistry Group of Bioinorganic Analytical
Gdansk University of Technology Chemistry
Gdansk, Poland Pau, France
Table of Contents
Chapter 1 Mineral Components in Food — Analytical Implications..................1
·
Marek Biziuk and Joanna Kuczynska
Index ......................................................................................................................447
2234_C001.fm Page 1 Tuesday, October 17, 2006 10:17 AM
1 Mineral Components in
Food — Analytical
Implications
·
Marek Biziuk and Joanna Kuczynska
CONTENTS
1.1 INTRODUCTION
The problem of the presence of mineral components in food is complicated. Some
metals are necessary for human life and play very important roles in bodily functions.
Macronutrients such as carbon, hydrogen, oxygen, nitrogen, potassium, sulfur, mag-
nesium, calcium, sodium, phosphorus, and chlorine are the main components of
organic matter but also have important metabolic functions. So-called macroelements
are the main cellular and structural building materials but also take part in osmotic
pressure and acid/base regulation. Micronutrients such as B, Co, Cr, Cu, F, Fe, I, Li,
Mo, Mn, Ni, Rb, Se, Si, V, and Zn participate in the metabolic functions and are the
constituents of enzymes, hormones, vitamins, etc.1 The contents of the main compo-
nents in an adult man are estimated to be 1200 g Ca, 800 g P, 200 g K, 160 g S, 95
g Na, 95 g Cl, 30 g Mg, 4 g Fe, 3.5 g F, 2 g Zn, 0.007 g Cu, and 0.003 g I.2 A deficiency
of these elements can cause adverse effects not only in humans but in other animal
species and plants. The main sources of mineral components, recommended daily
requirements, and diseases caused by the deficiency of selected elements are listed in
1
2234_C001.fm Page 2 Tuesday, October 17, 2006 10:17 AM
TABLE 1.1
Recommended Daily Intake, Main Exposure Routes, and Diseases Caused
by the Deficiency of Selected Macro- and Micronutrients2
Recommended
Daily Intake Main Exposure Routes for
Element (mg) Humans Effects of Deficiency
Table 1.1. Some of these elements (Cu, Cr, F, Mo, Ni, Se, or Zn) are toxic at higher
concentrations, so their levels in a human body and in food must be kept below the
toxic threshold, which should be higher than the level necessary for organisms. Very
often the difference between an indispensable and toxic dose is very small. Some of
these elements are antagonistic to organisms, and their presence can cause very harmful
effects.3–7 Most notorious among these are the so-called Big Four elements, namely,
Cd, Hg, As, and Pb.8,9 Intensive industrialization of the world has resulted in an
increased input of metals in the environment, drastically altering the quality of surface-
and groundwater as well as agricultural land and food.
Metals can be transported by water and air over long distances. Anthropogenic
pollution of drinking water supplies and resources indispensable for food production
has become a fact of life. The main route of introduction of metals to the human
organism is through ingestion of food and drinking water, but the inhalation route
can sometimes be significant. Metals are persistent in the environment and tend to
2234_C001.fm Page 3 Tuesday, October 17, 2006 10:17 AM
TABLE 1.2
Selected Metals Input, Their Levels in Main Food Sources, Organs and Tissues
in which Metals Are Accumulated, and Daily Dietary Intake (Adults in
U.S.)12–16
Total Input to
Freshwater, Main Food Sources Estimated Tissue and Organs
(103 metric Concentration Daily Dietary Accumulating
Metal tons/year) (mg/kg) Intake (µg) Metals
TABLE 1.3
Main Sources of Selected Metals in the Environment and Main Health Effects
Associated with Each Metal12,17,18
Metal Sources Health Effects
As Pesticides, feed additive for poultry Skin, liver, prostate and lung cancer,14,19
and swine production, domestic central nervous system effects leading to coma
wastewater, sewage sludge, and death, diseases of respiratory and
phosphate fertilizers, fossil-fuel gastrointestinal tract, neurological disorders,
combustion, pulp, and paper muscular weakness, nausea, peripheral vascular
industry, metallurgic (mining and diseases, hyperpigmentation, keratosis, etc.
smelting), and steam electrical
production
Cd Domestic wastewater, sewage Acute: nausea, vomiting, salivation, muscular
sludge, smelting and refining, cramps, liver injury, renal failure, convulsion,
manufacturing processes, steam shock; chronic: lung cancer, renal toxicity
electrical production, smoking (proteinuria)
cigarettes20
Cr Domestic wastewater, sewage Cr(VI) is extremely toxic and genotoxic; induces
sludge, manufacturing processes DNA crosslinks and breaks; causes nausea,
(metals, chemicals, pulp and paper, diarrhea, liver and kidney damage, dermatitis,
petroleum products), smelting and respiratory problems, tissue damage, and cancer
refining, and base metal mining and risk increases in the presence of arsenic and
dressing nickel21
Pb Production of cement, metals, Anemia, insomnia, hypertension, renal
chemicals, pulp and paper, dysfunction, sperm count suppression and
petroleum, fertilizers, combustion damage to the peripheral nervous system,
of leaded petrol cognitive and behavioral disorders in children,
carcinogenity
Ni Coal combustion, domestic Dermatoses, allergic sensitization; nickel is
wastewater, sewage sludge, carcinogenic in humans; among nickel refinery
petroleum products, smelting and workers statistically significant elevation in the
refining, and base metal mining and incidence of respiratory cancers was found22
dressing
Hg Coal burning power plants, Acute: nausea, vomiting, pharyngitis, bloody
atmospheric fallout, manufacturing diarrhea, nephritis, annuria, hepatitis, followed
processes, chlorine and caustic soda by death from gastrointestinal and kidney
production lesions; chronic: carcinogenic for animals and
humans, attacks nervous system (Minamata
disease) and brain
Se Natural, phosphate fertilizers, Hair and nails brittleness and loss, skin lesions,
sewage sludge, coal burning, liver enlargement; Deficiencies can cause:
smelting and refining cancer, heart diseases, reduced resistance to
microbiological and viral infection, reduced
antibody production, endemic cardiomyopathy,
and osteoarthropathy
2234_C001.fm Page 5 Tuesday, October 17, 2006 10:17 AM
1.2.2 SAMPLING
Sampling design depends strongly on the matrix of an analyzed object and its size.
Taking primary samples from large-sized objects (daily production, such as a load
of van, vehicle tracks, car, tank, etc.) and preparing representative samples are
described in various standard methods. Heterogeneous samples have to be homog-
enized by cutting, mixing, chopping, milling, grinding, mincing, and blending, using
hand or mechanical equipment.23 This is necessary not only for taking a represen-
tative sample, but also for better dissolution and digestion. After mixing, dividing,
and making the sample smaller, the aliquot for analysis is taken. It should be divided
in three parts: one for analysis, one for the client, and the third for archiving. Any
reagents, vessels, or equipment used during operations must not introduce or
absorb/adsorb the elements or compounds to be analyzed. This is why agate grinders,
porcelain or glass mortars, and equipment with titanium blades instead of stainless
steel are recommended.24 For some food samples, cryogenic grinding is necessary.25
Any analysis of biological samples should be carried out as soon as possible,
especially in the case of samples that can deteriorate, rot, or decompose (meat,
2234_C001.fm Page 6 Tuesday, October 17, 2006 10:17 AM
can be heated in the appropriate vessel (test tube, beaker, digestion flask, etc.) using
a burner, heating plate, or an aluminum block with a programmed temperature.
Nitric acid alone or as a mixture with perchloric or sulfuric acids is the most popular
reagent used for sample decomposition, as it is a strong oxidizing agent and forms
soluble nitrates with metals. Environmental chemists strongly recommend that all
acid digestion should be done in Teflon or similar plastic containers to minimize
sample contamination. To completely destroy the organic matrices, the addition of
stronger oxidizing agents, such as hydrogen peroxide is sometimes necessary.
Perchloric acid combined with metals can form spontaneously explosive com-
pounds and can react explosively with undigested fats and oils after evaporation
of HNO3. Extreme caution must be exercised when using this acid. Hydrochloric
acid and hydrofluoric acid are rarely used alone for the digestion of organic
matrices. Some volatile chlorides and fluorides (with As, Sb, Sn, Se, Ge, Hg, and
B) formed during digestion can cause the loss of analytes. Sulfuric acid, tradition-
ally used in combination with nitric acid, cannot be used during determination of
elements (particularly Ba, Ca, Pb, and Sr) which form sulfates with low water
solubility or when volatilization of trace elements (Ag, As, Ge, Hg, Re, and Se)
may occur during digestion.26 The use of phosphoric acid results in the formation
of phosphate ions, and difficulties in mass spectrometric determination (such as
the production of polyatomic species) should be avoided. To sum up, the choice
of acid or mixture of acids for sample digestion strongly depends on the type of
matrix and the elements to be determined.
Closed vessel digestion was introduced into elemental analysis by Carius in
1860; he described the digestion of samples with concentrated nitric acid in sealed,
strong-walled glass vials (Carius tube), but this method of mineralization was time-
consuming and dangerous. Modern devices for closed acid digestion with conductive
heating, called digestion bombs or Parr bombs, consist of nickel or a PTFE baker
(inside) and a stainless steel jacket (outside). After the introduction of weighed
samples and acids (mainly nitric acid) to the PTFE baker and sealing of the bomb,
it is placed in an oven and then heated to 110–250°C for periods of one to several
hours. The analyst should take necessary precautions during this step because sample
digestion under supercritical conditions can generate high pressure, leading to explo-
sive rupturing of the vessel. Organic samples should not be mixed with strong
oxidizing agents, and the PTFE baker should not be filled to more than a 10–20%
of its volume. After digestion, it is recommended that the bombs be cooled to room
temperature before they are opened — and then with great caution. The digestates
are next transferred to a volumetric flask (filtered, if necessary) and diluted to volume
with deionized water.
Closed vessel digestion has many advantages. The high temperature and pressure
enable a better and quicker decomposition of the sample to be achieved. Volatile
elements (As, B, Cr, Hg, Sn, Se, and Sb) do not escape from the vessel and are
retained in solution. The release of toxic fumes into laboratory air is avoided. Smaller
volumes of acids can be used, and the mixture is isolated from air, thereby reducing
contamination of the sample.
The advantages of closed-vessel acid digestion are equally applicable to pro-
cesses based on microwave heating. During irradiation, an aqueous phase is heated
2234_C001.fm Page 9 Tuesday, October 17, 2006 10:17 AM
6
3
5
7
8
FIGURE 1.1 Basic set for microwave digestion: (1) vessel underpart, (2) screw cap, (3)
closing cap, (4) rupture disc, (5) clumping cup, (6) connection tubing, (7) collecting vessel,
and (8) forming tool.
rapidly because polar molecules and ions are energized through the mechanism of
dipole rotation and ionic conductance.27 The energy is also absorbed by sample
molecules causing an increase in kinetic energy, internal heating, and differential
polarization that expand, agitate, and rupture surface layers of the solid materials,
exposing fresh surfaces to an acid attack.26 The efficiency of sample digestion is
much higher compared with conductive heating, and the time of digestion is much
shorter. A schematic drawing of vessels used in this method is shown in Figure
1.1. The vessels are made from PTFE; fluorocarbon resins cannot be used because
they cannot be heated convectively with their low heat-conducting capacity. PTFE
is a totally inert material thermally stable up to 250°C and has high tensile strength.
The vessels are generally thick-walled (Figure 1.1 [1]), and are suitable for use
under higher pressure and temperature with aggressive reagents. An aluminum
rupture disc (Figure 1.1 [4]) in the closing cap (Figure 1.1 [3]), form on a tranducer
(Figure 1.1 [8]), which provides a safe relief from excessive pressure load within
the digestion vessel (Figure 1.1 [1]) to the collecting vessel (Figure 1.1 [7]). Nitric
acid alone or its combination with hydrogen peroxide, hydrofluoric acid, or hydro-
chloric acid are most often used, but sulfuric acid must be avoided because its high
boiling point (338°C) is above PTFE’s melting point. Due to high microwave
transparency of the digestion vessel material, the vessel contents are heated directly
and the vessel itself can be heated only by energy radiation from vessel contents.
The thermal stress of the vessel within the first minutes is low but increases with
time, so that a maximum digestion time should not exceed 5–10 min. Opening of
the vessel after digestion is possible only after allowing enough time for cooling
(5–15 min). Microwave acid digestion is widely used in food analysis and standard
2234_C001.fm Page 10 Tuesday, October 17, 2006 10:17 AM
TABLE 1.4
Advantages and Disadvantages of Wet Digestion Methods30
Digestion Possible Way Source Sample Digestion Degree of Economical
Technique of Losses of Blank Size (g) Time Digestion Aspects
Open Systems
Conventional Volatilization Acids, <5 Several Incomplete Inexpensive,
heating vessels, hours needs
air supervision
Microwave Volatilization Acids, <5 <1h Incomplete Inexpensive,
heating vessels, needs
air supervision
UV digestion None Liquid Several High Inexpensive,
hours needs
supervision
Closed System
Conventional Retention Acids < 0.5 Several High Needs no
heating (low) hours supervision
Microwave Retention Acids < 0.5 <1h High Expensive,
heating (low) needs no
supervision
Source: Matusiewicz, H., Wet Digestion Methods, in New Horizons and Challenges in Environmental
· ·
Analysis and Monitoring, Namiesnik, J., Chrzanowski, W., Zmijewska, P., Eds., Centre of Excellence in
Environmental Analysis and Monitoring, Gdansk, 2003, p. 224, chap. 13. With permission.
few minutes. More than 70 elements including alkali, alkaline earth, transition, and
heavy metals can be determined in various samples with sensitivities from µg/g to
ng/g range using spectrophotometric methods.
In flame atomic emission spectrophotometry (FAES) or flame photometry (FP)
the sample is converted to atomic vapor by applying thermal energy (a flame). The
samples have to be transformed into dissolved forms, nebulized using a pneumatic
nebulizer, and in the form of aerosol, transported to the flame, where the solvent
and the sample are vaporized and atomized. As energy continues to be applied, a
number of atoms are changed to an excited state, in which they remain for a short
time (10–7 to 10–4 sec). After the outer electron occupies more highly excited energy
levels (orbitals), the excited atoms return to the ground state. In this process, the
energy difference between the excited level and electron ground state is released.
The atomic line radiation emitted is characteristic for each element. The character-
istic wavelength is selected using a filter or monochromator (for example, grating
or prism with entrance and exit slits) and detected using a suitable method. The
detector converts electromagnetic radiation into an electric signal that can be mea-
sured after amplification if needed. There are single-element detectors, such as
photovoltaic cells, solid-state photodiodes, photoemissive tubes, and photomultiplier
tubes, or multiple-element detectors such as solid-state array detectors. Detectors
can be characterized by precision, spectral sensitivity, limit of detection, and response
time. If the flame burns evenly and the substance is fed into the flame at a constant
rate over the period of the measurement, the intensity of the spectral lines observed
provides a measure of the concentration of substances. This method is now mainly
used for the determination of alkali metals and alkaline earth metals.
Atomic emission spectrometry with inductively coupled plasma excitation (ICP-
AES) has much wider applications and can be used, because of high temperature
of atomization, for the determination of most elements. At temperatures above
6000°C, a state that can be described as plasma occurs. Plasma is characterized by
the fact that electrically charged particles are created by the breaking up of gas
molecules — a process referred to as ionization. Plasma is thus a gas whose atoms
or molecules have, to greater or lesser extent, broken up into positively or negatively
charged carriers. For atoms to ionize, a specific energy, the so-called ionization
potential, must first be applied. This energy, furthermore, must be fed to the atom
itself. The ionization potential is expressed in electron volts (eV). The eV values
for the majority of elements lie between 4 and 25 eV. In emission spectrometry,
plasma is used to excite the atoms to be measured. In principle, plasma is an
electrically conductive, fluid system in predominantly gaseous matter. The properties
of plasma are determined by the charge carriers and by its quasi-neutrality, as the
plasma has an overall electrically neutral effect. Plasma is produced by transferring
electrical energy to a gas flow. In the case of inductively coupled plasma, a high
frequency generator with an induction coil is used to supply energy for the ionization
potential required. The energy is directly proportional to the density and temperature
of the plasma. It is particularly important for practical analytical application of
plasma that high temperature speeds up thermal ionization. This effect is used in
ICP. A gas is fed through a system of quartz tubes whose shape facilitates flow, and
to the end of these tubes a strong current of high frequency is applied. After ionization
2234_C001.fm Page 12 Tuesday, October 17, 2006 10:17 AM
Analyzer
Sample Ionizer Detector
m/z
Readout
TABLE 1.5
Analyses of Food Samples Using ICP-AES and ICP-MS
Elements Kind of Food References/Methods
Al, Ba, B, Ca, Co, Cu, Fe, Li, Lu, Mg, Mn, Orange juices, peel 33
Mo, Ni, P, K, Rb, Si, Na, Sr, Sn, Ti, V, Zn extracts, deacidifed juices ICP-AES and ICP-MS
Na, K, Ca, Mg, P, Fe, Cu, Mn, Zn, Cr, Al, Meat, fish, chicken, cereal, 35
B, Se, Mo sweet dishes ICP-AES
Ca, Co, Cu, Cr, Fe, Mg, Mn, Mo, Na, Zn, Milk 37
Ag, Al, As, Ba, Be, Cd, Hg, Ni, Pb, Sb, Sn, ICP-OES
Sr, Ti, Tl, U, V
Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr, Zn Tea beverages 38
ICP-AES
Pb Wine 39
ICP-MS
As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V, Zn Honey 40
ICP-MS
B Hazelnut 41
ICP-OES
LIGHT ATOMIZED
MONOCHROMATOR DETECTOR
SOURCE SAMPLE
READOUT AMPLIFIER
ejection of metal atoms from the cathode. As a consequence, some atoms are excited
and subsequently emit a radiation characteristic of the metal.
In order to perform a measurement the analyte must be vaporized and atomized.
There are two types of methods, that can be used to atomize the sample: flame
atomic absorption spectrometry (FAAS) and graphite furnace atomic absorption
spectrometry (GF-AAS or ET-AAS). In the first case, the sample is brought into a
flame using a nebulizer, whereas in the second method the samples are located in
the graphite tube with electrical heating, which provides the thermal energy to dry
the specimen, the ash organic component, and produces free ground–state atoms.
This technique is preferred for measuring concentrations of most elements in dif-
ferent samples for the reason that the graphite tube is a much more efficient atomizer
than the flame. The thermal energy, obtained by using one of the two methods above,
causes the transition of the atom from the ground state to the first excited state; the
absorption of some of the light (in the ultraviolet or visible wavelength) is generated
by a lamp that is specific for a target metal. The selection of the specific light, which
is absorbed by the sample, is done using a monochromator. This allows for the
determination of one element in the presence of others. The light selected is directed
to a detector, where an electrical signal proportional to light intensity is produced.
The amount of absorbed radiation is proportional to the concentration of the element
of the interest in solution. This dependence is described by the Beer–Lambert law,
which is expressed as:
A = ε ⋅c ⋅l
where:
A, is the measured absorbance,
ε, is a wavelength-dependent molar absorptivity coefficient,
c, is the analyte concentration and
l, is the path length.
TABLE 1.6
Analyses of Food Samples Using AAS
Elements Kind of Food References
Ca Cereal 43
Cr Seafood, cereals, vegetables, olive oils 44
Se Foodstuffs 45
Cd Wine 46
Ca, Cl, K, Mg, N, P, Al, As, Au, Br, Cd, Total diet 47
Co, Cr, Cs, Cu, Fe, Hg, I, Mn, Mo, Ni,
Pb, Rb, Sb, Sc, Se, Sn, Sr, V, Zn, W
Cd Flour 48
As, Se Foods 49
Zn, Mg Maize 50
Ca, Cu, Fe, Mg, Mn, K, Na, Zn Fruits 51
Hg, Se Seafood 52
Pb, Cd, Fe, Cu, Mn, Zn Fish 53
Fe, Cu Peanuts 54
Pb, Cu, Zn, Mg, Ca, Fe Eggs 55
Cd, Co, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Zn Fish 56
Ag, Ba, Cd, Cr, Cu, Fe, Mn, Pb, Zn Fish, shrimp 57
BH 4− + 3 H 2 O + H + → H 3 BO3 + 8 H
E + m + 8 H → EH n + H 2 excess( )
2234_C001.fm Page 16 Tuesday, October 17, 2006 10:17 AM
TABLE 1.7
Analyses of Food Samples Using Hydride
Generation Method
Elements Kind of Food References
TABLE 1.8
Selected Examples of Metals and Anions Determinations Using Molecular
Absorption Spectrophotometry70,71
Wave- Wave-
Length Length
Analyte Reagent (nm) Analyte Reagent (nm)
TABLE 1.9
Analyses of Food Samples Using NAA
Elements Kind of Food References
Br, Ca, Cl, Co, Cu, I, K, Mg, Mn, Na, Rb, S, Cereals, oils, sweeteners, 72
Ti, V vegetables
Ag, Br, Ca, Cl, Co, Cr, Cs, Fe, Hg, K, Mg, Mn, Diets of children and adolescents 73
Na, Rb, Sb, Se, Sr, Zn
Cs Daily diet 74
Co, Cr, Fe, Rb, Se, Zn Cheese 75
Ca, Mg, Mn, Cu, Cr, Zn, Se, I Daily diet 76
Se, Cr, Rb, Zn, Fe, Co, Sb, Ba, Ni, Ag, Hg, Sn Flour and bran 77
Ca, Cl, K, Mg, Al, As, Au, Br, Cd, Co, Cr, Cs, Total diet 47
Cu, Fe, Hg, I, Mn, Mo, Na, Rb, Sb, Sc, Se, Sn,
Sr, Zn
Al, As, Br, Cl, I, K, Mg, Mn, Na, Sb, Sm, Cr, Health food 78
Fe, Rb, Sc, Zn
Al, Ca, Cl, Cu, K, Mg, Mn, Na Tea leaf 79
SAMPLING
Sample processing
Irradiation
Unpacking
Measurement
Results interpreting
Results evaluation
β–
PROMPT
GAMMA RAY
TARGET RADIOACTIVE
NUCLEUS NUCLEUS
A
Z X
n
NEUTRON
COMPOUND STABLE
NUCLEUS NUCLEUS
A+1 * DECAY
Z X GAMMA RAY
FIGURE 1.5 Schematic diagram illustrating the successions of events for a typical (n,y)
reaction.
The physical effects on which NAA is based are the interaction of radiation with
matter, the properties of the nucleus, and radioactivity. The sequences of events are
illustrated in Figure 1.5.
When a particle (neutron, proton, and α-particle) or photon interacts with the
atomic nucleus in collision, radioactive nuclides are produced in a highly excited
state. The compound nucleus very quickly decays into a more stable configuration
through emission of one or more characteristic prompt gamma rays. The distinct
energy that is created during the process is unique to each element and provides
positive identification of the targeted element in the sample, when the quantification
of the element can be determined by relative standardization.80 In this method, an
unknown sample is irradiated with a calibration sample with known amounts of the
elements. Both the real and the calibration samples are treated under the same
conditions. The quantity of the element is determined by a comparison of the peak
areas of the measured spectra for the sample with reference material. In order to
evaluate the concentration of an individual element, the activities of one or more
specific isotopes have to be determined. This may be done in two different ways.
The first method depends on chemical separation and is generally referred to as
radiochemical neutron activation analysis (RNAA), whereas the second technique
is known as instrumental neutron activation analysis (INAA), refers to selective
counting of radiation emitted by the appropriate radionuclide in the mixture of
radionuclides.81 In this case, some information about the activity of an individual
radionuclide is obtained by using suitable measurement and calculation techniques.
The main advantage of NAA is that it is nondestructive and thus can be used in
unique and very precious samples such as moon rocks and archaeological artifacts.
The main component of the sample matrices, such as H, C, O, N, P, and Si, hardly
2234_C001.fm Page 21 Tuesday, October 17, 2006 10:17 AM
TABLE 1.10
Detection Limit of Activation Analysis Using a Thermal Neutron Flux
of 1013 n/cm2*s82
Sensitivity
10–12 g Elements
1 Dy, Eu
1–10 Mn, In, Lu
10–102 Co, Rh, Ir, Br, Sm, Ho, Re, Au
102–103 Na, Ge, Sr, Nb, Cs, La, Yb, U, Ar, V, Cu, Ga, As, Pd, Ag, I, Pr, W
103–104 Al, Cl, K, Sc, Se, Kr, Y, Ru, Gd, Tm, Hg, Si, Ni, Rb, Cd, Te, Ba, Tb, Hf, Ta, Os
104–105 Pt
105–106 P, Ti, Zn, Mo, Sn, Xe, Ce, Nd, Mg, Ca, Tl, Bi
107 F, Cr, Zr, Ne, S, Pb, Fe
form any radioactive isotopes, so they seem to be invisible. This makes the method
highly sensitive for measuring trace elements, because the main constituents do not
cause any interference.
Activation analysis, under the appropriate experimental parameters, simulta-
neously can determine concentrations for nearly 70 elements with a high degree of
sensitivity and accuracy (see Table 1.10).
The facility for sample treatment before analysis is another significant advantage
of NAA compared with other techniques. Depending on the type of samples to be
analyzed, sample preparation procedures may be very different. In most cases,
neither chemical treatment nor addition of reagent is required to prepare the sample
for analysis. Therefore, activation analysis is relatively free of sources of contami-
nation. In fact, the only steps where contamination may occur and have an impact
on the final result are sampling, sample handling and storage, and sample preparation.
Most often, before the sample analysis, there is a need to wash, peel, separate seeds
and stones, dry (oven drying or lyophilization),83 and to homogenize (with or without
cryogenic techniques). The aim of sample preparation is to reduce the sample size
suitable for encapsulation prior to conducting the irradiation procedure. Generally,
a suitable sample mass may vary between a few milligrams and several grams; its
size depends on the sensitivities required and on the specific nature of the analyzed
elements.
Despite all its advantages, NAA also has some limitations. The biggest disad-
vantage is the requirement for access to a nuclear research reactor. Also there is a
huge problem with turnaround time, which may be somewhat longer than in other
techniques, varying from a few days to one or more weeks. The cause of this
drawback is the different half-lives for radioactive isotopes, which can be divided
into three categories: short-lived, moderately-lived, and long-lived nuclides. Further-
more, some elements (Pb, Be, N, O, P, and Bi) cannot be determined by this method,
which also is not suitable for analysis of liquid (water) samples without extensive
pretreatment.
2234_C001.fm Page 22 Tuesday, October 17, 2006 10:17 AM
External
reference ISE
electrode
Internal
reference
electrode
Internal
electrolyte
solution
Analyte
solution
LaF3
membrane
FIGURE 1.6 An example of a measuring device with an ion-selective electrode used for
fluoride determination.
some interferences can occur. These interferences can result from the presence in
the sample solution of some components, which can prevent the probe from sensing
the ion of interest (for example, complexion) or other ions from being measured
together with the analyte.
analysis, when the mobile phase is often NaOH or NaHCO3, the eluent suppressor
supplies H+ to neutralize anions and retain or remove the Na+. During cation analysis
(HCl or HNO3 are often in the mobile phase), an eluent suppressor supplies OH–
anions for neutralizing an eluent. The suppressor improves the detection limits,
increasing the analyte conductivity signal while decreasing eluent background noise
and sample counter-ion interferences, but single column (only a separator column)
IC is also in wide use. Sometimes the third column, between the suppressor and the
detector (which replaces the analyte ions with other ions in order to improve the
detection sensitivity) can be used. Electric conductivity detectors are most often
used, but specific electrometric detectors such as solute-specific amperometric detec-
tors or colorimetric, fluorescence, ICP-AES, and UV-VIS spectrometric detectors
are also in use.88,89 In Table 1.11 some selected examples of inorganic ions deter-
mination in food using ion chromatography are listed.89
TABLE 1.11
Selected Examples of Inorganic Ions Determination in Food Using Ion
Chromatography
Analyte Types of Food Eluent Detector Reference
ABBREVIATIONS
AAS Atomic absorption spectrometry
AES Atomic emission spectrometry
ASE Accelerated solvent extraction
ASV Anodic stripping voltammetry
CV-AAS Cold vapor atomic absorption spectrometry
ET-AAS Electrothermal atomic absorption spectrometry
FAAS Flame atomic absorption spectrometry
FAES Flame atomic emission spectrometry
FP Flame photometry
GC-ECD Gas chromatography with electron capture detector
GF-AAS Graphite furnace atomic absorption spectrometry
GLP Good Laboratory Practice
HG Hydride generation
HG-AAS Atomic absorption spectrometry with hydride generation
DNA Deoxyribonucleic acid
IC Ion chromatography
ICP Inductively coupled plasma
ICP-AES Atomic emission spectrometry with inductively coupled plasma
excitation
ICP-MS Mass spectrometry with inductively coupled plasma excitation
ICP-OES Optical emission spectrometry with inductively coupled plasma
excitation
INAA Instrumental neutron activation analysis
ISE Ion-selective electrode
LE Liquid extraction
MeHg Methylmercury
MS Mass spectrometry
2234_C001.fm Page 26 Tuesday, October 17, 2006 10:17 AM
REFERENCES
·
/
1. Synowiecki, J., Skladniki mineralne, in Chemia Zywnosci´ (Food Chemistry), Sikor-
ski, Z., Ed., WN-T, Warszawa, 2000.
·
2. Gawecki,
¸ J. and Mossor-Pietraszewska, T., Red, Kompendium Wiedzy o Zywnosci, ´
·
Zywieniu i Zdrowiu, PWN, Warszawa, 2004.
3. Eichler, W., Gift in unserer Nahrung, Kilda, Greven, 1982.
4. Bull, R.J., Carcinogenic and mutagenic properties of chemicals in drinking water,
Sci. Total Environ., 47, 385, 1985.
5. Hartwig, A., Carcinogenicity of metal compounds: possible role of DNA repair
inhibition, Toxicol. Lett., 102, 235, 1998.
6. Kasprzak, K.S., Oxidative DNA and protein damage in metal-induced toxicity and
carcinogenesis, Free Radic. Biol. Med., 32, 958, 2002.
7. Pourahmad, J. et al., Carcinogenic metal induced sites of reactive oxygen species
formation in hepatocytes, Toxicol. Vitro, 17, 803, 2003.
8. Schwerdtle, T., Walter, I., and Hartwig, A., Arsenite and its biomethylated metabolites
interfere with the formation and repair of stable BPDE-induced DNA adducts in
human cells and impair XPAzf and Fpg, DNA Repair, 2, 1449, 2003.
9. Tully, D.B. et al., Effects of arsenic, cadmium, chromium, and lead on gene expression
regulated by a battery of 13 different promoters in recombinant HepG2 cells, Toxicol.
Appl. Pharmacol., 168, 79, 2000.
10. Connell, D.W., Bioaccumulation of Xenobiotic Compounds, CRC Press, Boca Raton.
FL, 1990.
11. Ferguson, L.R., Natural, man-made mutagens and carcinogens in the human diet,
Mutat. Res., 443, 1, 1999.
12. Moore, J.W., Inorganic Contaminants of Surface Water: Research and Monitoring
Priorities, Springer-Verlag, New York, 1991.
13. Nriagu, J.O. and Pacyna, J., Quantitative assessment of worldwide contamination of
air, water and soils by trace metals, Nature, 333, 134, 1988.
14. Rojas, E., Herrera, L.A., Poirier, L.A., and Ostrosky-Wegman, P., Are metals dietary
carcinogens?, Mutat. Res., 443, 157, 1999.
15. Kabata-Pendias, A., Trace Elements in Soil and Plants, CRC Press, Boca Raton, FL,
·
2001; Kabata-Pendias, A., Biogeochemia Pierwiastków Sladowych, PWN, Warszawa
1999.
16. Waalkes, M.P. and Misra, R.R., Cadmium carcinogenicity and genotoxicity, in Tox-
icology of Metals, Chang, L.W., Ed., CRC Press, Boca Raton, FL, 1996, p. 231.
2234_C001.fm Page 27 Tuesday, October 17, 2006 10:17 AM
17. Cohen, M.D. et al., Mechanisms of chromium carcinogenicity and toxicity, Crit. Rev.
Toxicol., 23, 255, 1993.
18. McLaughlin, M.J., Parker, D.R., and Clarke, J.M., Metals and micronutrients — food
safety issues, Field Crops Res., 60, 143, 1999.
19. Pershagen, G., The carcinogenity of arsenic, Environ. Health Perspect., 40, 93, 1981.
20. Pocock, S.J. et al., Blood cadmium concentration in the general population of British
middle-aged men, Hum. Toxicol., 7, 95, 1988.
21. Verougstraete, V., Lison, D., and Hotz, P., Cadmium, lung a prostate cancer: a
systematic review of recent epidemiological data, J. Toxicol. Environ. Heallth, Part
B, 6, 227, 2003.
22. Coogan, T.P. et al., Toxicity and carcinogenicity of nickel compounds, CRC Crit.
Rev. Toxicol., 19, 341, 1989.
23. Rains, T.C., Application of atomic absorption spectrometry to the analysis of foods,
in Atomic Absorption Spectrometry; Theory, Design and Applications, Haswell, S.J.,
Ed., Elsevier, Amsterdam, 1991.
24. Capar, S.G. and Szefer, P., Determination and speciation of trace elements in foods,
in Methods of Analysis of Food Components and Additives, Otles, S., Ed., CRC Press,
Boca Raton, FL, 2005, p. 111.
25. Santos, D. et al., Determination of Cd and Pb in food slurries by GFAAS using
cryogenic grinding for sample preparation, Anal. Bioanal. Chem., 373, 183, 2002.
26. Jarris, I., Sample preparation for ICP-MS, in Handbook of Inductively Coupled
Plasma Mass Spectrometry, Jarris, K.E., Gray, A.L., and Houk, R.S., Eds., Glasgow,
1993, p. 172.
27. Gilman, L.B., and Engelhart, W.G., Recent advances in microwave sample prepara-
tion, Spectroscopy, 4, 14, 1989.
28. Environmental Protection Agency, SW-846 EPA Method 3052, Microwave assisted
acid digestion of siliceous and organically based matrices, in Test Methods for Eval-
uating Solid Waste, U.S. E.P.A., Washington, D.C., 1996.
29. Official Methods of Analysis of AOAC International, Official Method 999.10, Lead,
Cadmium, Zinc, Copper, and Iron in Foods — Atomic Absorption Spectrophotometry
after Microwave Digestion, AOAC, Gaithersburg, 2002.
30. Matusiewicz, H., Wet Digestion Methods, in New Horizons and Challenges in Envi-
· ·
ronmental Analysis and Monitoring, Namiesnik, J., Chrzanowski, W., Zmijewska, P.,
´ 2003,
Eds., Centre of Excellence in Environmental Analysis and Monitoring, Gdansk,
p. 224, chap. 13.
31. Taylor, L.R., Pap, R.P., and Pollard, B.D., Instrumental Methods for Determining
Elements, VCH, New York, 1994.
32. Willard, H.H. et al., Instrumental Methods of Analysis, Wadsworth, Belmont, CA,
1981.
33. Simpkins, W.A. et al., Trace elements in Australian orange juice and other products,
Food Chem., 71, 423, 2000.
34. Munilla, M.A. et al., Determination of metals in seaweeds used as a food by induc-
tively coupled plasma atomic-emission spectrometry, Analusis, 23, 463, 1995.
35. Sawaya, W.N. et al., Nutritional profile of Kuwaiti composite dishes: minerals and
vitamins, J. Food Compos. Anal., 11, 70, 1998.
36. Eckhoff, K.M. and Maage, A., Iodine content in fish and other food products from
East Africa analyzed by ICP-MS, J. Food Compos. Anal., 10, 270, 1997.
37. Ikem, A. et al., Levels of 26 elements in infant formula from USA, UK, and Nigeria
by microwave digestion and ICP–OES, Food Chem., 77, 439, 2002.
2234_C001.fm Page 28 Tuesday, October 17, 2006 10:17 AM
38. Fernández, P.L. et al., Multi-element analysis of tea beverages by inductively coupled
plasma atomic emission spectrometry, Food Chem., 76, 483, 2002.
39. Marisa, C. et al., Determination of lead isotope ratios in port wine by inductively
coupled plasma mass spectrometry after pre-treatment by UV-irradiation, Anal. Chim.
Acta, 396, 45, 1999.
40. Caroli, S. et al., A pilot study for the production of a certified reference material for
trace elements in honey, Microchem. J., 67, 227, 2000.
41. Simsek,
¸ ¸ A. et al., Determination of boron in hazelnut (Corylus avellana L.) varieties
by inductively coupled plasma optical emission spectrometry and spectrophotometry,
Food Chem., 83, 293, 2003.
42. Bulska, E., Analytical advantages of using electrochemistry for atomic spectrometry,
Pure Appl. Chem., 73, 1, 2001.
43. Bazzi, A., Kreuz, B., and Fischer, J., Determination of calcium in cereal with Flame
Atomic Absorption Spectroscopy: an experiment for a quantitative methods of ana-
lysis course, J. Chem. Educ., 81, 1042, 2004.
44. Lendinez, E. et al., Chromium in basic foods of the Spanish diet: seafood, cereals,
vegetables, olive oils and dairy products, Sci. Total Environ., 278, 183, 2001.
45. Smrkolj, P. et al., Selenium content in selected Slovenian foodstuffs and estimated
daily intakes of selenium, Food Chem., 90, 691, 2005.
46. Jaganathan, J., Reisig, A.L., and Dugar, S.M., Determination of cadmium in wines
using Graphite Furnace Atomic Absorption Spectrometry with Zeeman background
correction, Microchem. J., 56, 221, 1997.
47. Iyengar, G.V. et al., Content of minor and trace elements, and organic nutrients in
representative mixed total diet composites from the U.S., Sci. Total Environ., 256,
215, 2000.
48. De-qiang, Z. et al., Determination of cadmium in flour by atom trapping flame atomic
absorption spectrometry using derivative signal processing, Anal. Chim. Acta, 405,
185, 2000.
49. Mindak, W.R. and Dolan, S.P., Determination of arsenic and selenium in food using
a microwave digestion-dry ash preparation and flow injection hydride generation
atomic absorption spectrometry, J. Food Compos. Anal., 12, 111, 1999.
50. Anzano, J.M. et al., Zinc and Manganese Analysis in Maize by Microwave Oven
Digestion and Flame Atomic Absorption Spectrometry, J. Food Compos. Anal., 13,
837, 2000.
51. Miller-Ihli, N.J., Atomic Absorption and Atomic Emission Spectrometry for the
determination of the trace element content of selected fruits consumed in the U.S.,
J. Food Compos. Anal., 9, 301, 1996.
52. Plessi, M., Bertelli, D., and Monzani, A., Mercury and selenium content in selected
seafood, J. Food Compos. Anal., 14, 461, 2001.
53. Tüzen, M., Determination of heavy metals in fish samples of the middle Black Sea
(Turkey) by graphite furnace atomic absorption spectrometry, Food Chem., 80, 119,
2003.
54. Anzano, J.M. and Gónzalez, P., Determination of iron and copper in peanuts by flame
atomic absorption spectrometry using acid digestion, Microchem. J., 64, 141, 2000.
55. Kiliç, Z. et al., Determination of lead, copper, zinc, magnesium, calcium and iron in
fresh eggs by atomic absorption spectrometry, Food Chem., 76, 107, 2002.
56. Karadede, H. and Unlu, E., Concentration of some heavy metals in water, sediment
and fish species from the Ataturk Dam Lake (Euphrates), Turkey, Chemosphere, 41,
1371, 2000.
2234_C001.fm Page 29 Tuesday, October 17, 2006 10:17 AM
57. Vazquez, F.G. et al., Metals in fish and shrimp of the Campeche Sound, Gulf of
Mexico, Bull. Environ. Contam. Toxicol., 67, 756, 2001.
58. Pohl, P., Hydride generation — recent advances in atomic emission spectrometry,
Trends Anal. Chem., 23, 87, 2004.
59. Yang, J. et al., Evaluation of continuous hydride generation combined with helium
and argon microwave induced plasmas using a surfatron for atomic emission spec-
trometric determination of arsenic, antimony and selenium, Spectrochim. Acta Part
B, 50, 1351, 1363, 1995.
60. Sun, H., Suo, R., and Lu, Y., Determination of zinc in food using atomic fluorescence
spectrometry by hydride generation from organized media, Anal. Chim. Acta, 457,
305, 2002.
61. Boutakhrit, K. et al., Open digestion under reflux for the determination of total arsenic
in seafood by inductively coupled plasma atomic emission spectrometry with hydride
generation, Talanta, 66, 1042, 2005.
62. Murphy, J. and Cashman, K. D., Selenium content of a range of Irish foods, Food
Chem., 74, 493, 2001.
63. Ródenas-Torralba, E., Morales-Rubio, A., and de la Guardia, M., Multicommutation
hydride generation atomic fluorescence determination of inorganic tellurium species
in milk, Food Chem., 91, 181, 2005.
64. Cava-Montesinos, P. et al., Determination of arsenic and antimony in milk by hydride
generation atomic fluorescence spectrometry, Food Chem., 60, 787, 2003.
65. Klapec, T. et al., Selenium in selected foods grown or purchased in eastern Croatia,
Food Chem., 85, 445, 2004.
·
66. Biziuk, M., Namiesnik, J., and Zaslawska, L., Heavy metals in food products and
biological samples from the Gdansk district, in Radionuclides and Heavy Metals in
Environment, Frontasyeva, M.V., Perelygin, V.P., Vater, P., Eds., NATO Science Series,
IV. Earth and Environmental Sciences, Vol. 5, Kluwer Academic Publ., Dordrecht,
Holland, 2001, p. 209.
67. Dabeka, R., Bradley, P., and McKenzie, A.D., Routine, high-sensitivity, cold vapor
atomic absorption spectrometric determination of total mercury in foods after low-
temperature digestion, J. AOAC Int., 85, 1136, 2002.
68. Palmieri, H.E.L., and Leonel, L.V., Determination of methylmercury in fish tissue by
gas chromatography with microwave-induced plasma atomic emission spectrometry
after derivatization with sodium tetraphenylborate, Fresenius J. Anal. Chem., 363,
466, 2000.
69. Grinberg, P. et al., Solid phase microextraction capillary gas chromatography com-
bined with furnace plasma emission spectrometry for speciation of mercury in fish
tissue, Spectrochim. Acta Part B, 58, 427, 2003.
70. Marczenko, Z., Separation and Spectrophotometric Determination of Elements, Ellis
Harwood, London, 1986.
71. Cresser, M.S. and Marr, I.L., Optical spectrometry in the analysis of pollutants, in
Instrumental Analysis of Pollutants, Hewitt, C.N., Ed., Elsevier, London 1991, p. 99,
chap. 3.
72. Soliman, K. and Zikovsky, L., Determination of Br, Ca, Cl, Co, Cu, I, K, Mg, Mn,
Na, Rb, S, Ti, and V in cereals, oils, sweeteners and vegetables sold in Canada by
neutron activation analysis, J. Food Compos. Anal., 12, 85–89, 1999.
73. Zaichick, V. et al., Instrumental neutron activation analysis of essential and toxic
elements in child and adolescent diets in the Chernobyl disaster territories of the
Kaluga Region, Sci. Total Environ., 192, 269, 1996.
2234_C001.fm Page 30 Tuesday, October 17, 2006 10:17 AM
74. Akhter, P., Orfi, S.D., and Ahmad, N., Cesium concentration in the Pakistani diet, J.
Environ. Radioact., 67, 109, 2003.
75. Gambelli, L. et al., Minerals and trace elements in some Italian dairy products, J.
Food Compos. Anal., 12, 27, 1999.
76. Pokorn, D. et al., Elemental composition (Ca, Mg, Mn, Cu, Cr, Zn, Se, and I) of
daily diet samples from some old people’s homes in Slovenia, J. Food Compos. Anal.,
11, 47–53, 1998.
77. Bonafaccia, G. et al., Trace elements in flour and bran from common and tartary
buckwheat, Food Chem., 83, 1, 2003.
78. Chien-Yi, C., Trace elements in Taiwanese health food, Angelica keiskei, and other
products, Food Chem., 84, 545, 2004.
79. Jonah, S.A. and Williams, I.S., Nutrient elements of commercial tea from Nigeria by
an instrumental neutron activation analysis technique, Sci. Total Environ., 258, 205,
2000.
80. Bode, P. and De Goeij, J.J.M., Activation analysis, in Encyclopedia of Environmental
Analysis and Remediation, Meyers, R.A., Ed., John Wiley & Sons, New York, 1998,
p. 68.
81. Bode, P., Nuclear analytical techniques for environmental research, in New Horizons
and Challenges in Environmental Analysis and Monitoring, Namienik, J., Chrza-
nowski, W., and Mijewska, P., Eds., Centre of Excellence in Environmental Analysis
and Monitoring, Gdansk,´ 2003, chap. 1, p. 1.
82. IAEA-TECDOC-564, Practical Aspects of Operating a Neutron Activation Analysis
Laboratory, IAEA, Vienna 1990.
83. Howe, A. et al., Elemental composition of Jamaican foods 1: a survey of five food
crop categories, Environ. Geochem. Health, 27, 19, 2005.
84. Achterberg, E.P. and Braungardt, Ch., Stripping voltammetry for the determination
of trace metal speciation and in-situ measurement of trace metal distribution in marine
waters, Anal. Chim. Acta, 400, 381, 1999.
85. Bersier, P.M., Howell, J., and Bruntlett, C., Advanced electroanalytical techniques
versus Atomic Absorption Spectrometry, Inductively Coupled Plasma Mass Spec-
trometry in environmental analysis, Analyst, 119, 219, 1994.
86. Locatelli, C. and Torsi, G., Cathodic and anodic stripping voltammetry: simultaneous
determination of As-Se and Cu-Pb-Cd-Zn in the case of very high concentration
ratios, Talanta, 50, 1079, 1999.
87. Wang, J., Stripping Analysis: Principles, Instrumentation and Applications, VCH,
Deerfield Beach, 1985.
88. Nollet, L.M.L., Ed., Handbook of Water Analysis, Marcel Dekker, Basel, New York,
2000.
89. Buldini, P.L., Cavalli, S., and Trifiro, A., State-of-art ion chromatographic determi-
nation of inorganic ions in food, J. Chromatogr. A, 789, 529, 1997.
90. Kaine, L.A., Crowe, J.B., and Wolnik, K.A., Forensic application of coupling non-
suppressed ion-exchange chromatography with ion-exclusive chromatography, J.
Chromatogr. A, 673, 141, 1992.
91. Bosch-Bosch, N. et al., Determination of nitrite levels in refrigerated and frozen
spinach by ion chromatography, J. Chromatogr. A, 706, 221, 1995.
92. Saccani, G. et al., Use of ion chromatography for the measurement of organic acids
in fruit juices, J. Chromatogr. A, 706, 395, 1995.
93. Nieto, M.T. et al., Nitrite and nitrate contents in cereal-based baby foods, Alimentria,
265, 71, 1995.
2234_C001.fm Page 31 Tuesday, October 17, 2006 10:17 AM
94. Ding, M.Y., Chen, P.R., and Luo, G.A., Simultaneous determination of organic acids
and inorganic anions in tea by ion chromatography, J. Chromatogr. A, 764, 341, 1997.
95. Mongay, C., Pastor, A., and Olmmos, C., Determination of carboxylic acids and
inorganic anions in wines by ion-exchange chromatography, J. Chromatogr. A, 736,
351, 1996.
96. Villasenor, S.K., Matrix elimination in liquid chromatography using heart-cut column
switching techniques, Anal. Chem., 63, 1362, 1991.
97. Kim, H.J., Determination of sulfite in food and beverages with ion-exclusive chro-
matography with electrochemical detection: collaborative study, J. Assoc. Off. Anal.
Chem., 73, 216, 1990.
98. Kim, H.J. and Conca, K.R., Determination of sulfur dioxide in grapes, comparison
of Monier-Williams method and two ion exclusion chromatographic methods, J.
Assoc. Off. Anal. Chem., 73, 983, 1990.
99. Buldini, P.L., Cavalli, S., and Mevoli, A., Sample pretreatment by UV photolysis for
the ion chromatographic analysis of plant material, J. Chromatogr. A, 739, 167, 1996.
100. Novic, M. et al., Determination of chlorine, sulphur and phosphorus in organic
materials by ion chromatography using electrodialysis sample pretreatment, J. Chro-
matogr. A, 704, 530, 1995.
101. Smolders, E., van Dael, M., and Merckx, R.J., Simultaneous determination of extract-
able sulfate and malate in plant extracts using ion-chromatography, J. Chromatogr.
A, 514, 371, 1990.
102. Schnetger, B. and Muramatsu, Y., Determination of halogens, with special reference
to iodine, in geological and biological samples using pyrohydrolysis for preparation
and inductively coupled plasma mass spectrometry and ion chromatography for
measurement, Analyst, 121, 1627, 1996.
103. Heitkemper, D.T. et al., Practical application of element-specific detection by induc-
tively coupled plasma atomic emission spectroscopy and inductively coupled plasma
mass spectrometry to ion chromatography of food, J. Chromatogr. A, 671, 101, 1994.
104. Mehra, M.C. and Kandil, M., Ion chromatographic determinations of ionic analytes
with benzendisulfonic acid eluent using indirect ultraviolet detection, Analusis, 24,
17, 1996.
105. Chadha, K. and Lawrence, J. F., Ion chromatographic determination of cyanide
contamination in fruit and evaluation of a colorimetric test kid, Int. J. Environ. Anal.
Chem., 44, 197, 1991.
106. Yan, D. and Schwedt, G., Trace determination of aluminum and iron by ion chroma-
tography and post chromatographic derivatization, Fresenius Z. Anal. Chem., 320,
252, 1985.
107. Trifiro, E. et al., Determination of cations in fruit juices and purées by ion chroma-
tography, J. Chromatogr. A, 739, 175, 1996.
108. Jones, R., Foulkes, M., and Paull, B., Determination of barium and strontium in
calcium containing matrices using high-performance chelation ion chromatography,
J. Chromatogr. A, 673, 173, 1994.
109. Morawski, J., Alden, P., and Sims, A., Analysis of cation nutrients from food by ion
chromatography, J. Chromatogr. A, 640, 359, 1993.
110. Saari-Nordhaus, R. and Anderson, J.M., Jr., Simultaneous analysis of anions and
cations by single-column ion chromatography, J. Chromatogr. A, 549, 1991.
2234_C001.fm Page 32 Tuesday, October 17, 2006 10:17 AM
2234_C002.fm Page 33 Tuesday, October 17, 2006 10:30 AM
2 Speciation of Mineral
Components in Food —
Analytical Implications
Aleksandra Polatajko and Joanna Szpunar
CONTENTS
2.1 INTRODUCTION
The safety and nutritional quality of food are determined by both the total level and
the speciation (distribution among different chemical forms) of trace elements.
Because bioavailability and metabolism are often highly variable between different
chemical forms of the same element, information on trace element speciation is
essential. It provides an understanding of how the absorption and bioavailability of
elements can be reduced for toxic elements or improved for essential nutrients. As
a result, accurate, reproducible, and precise methodologies are needed for food
sampling, sample pretreatment, and analysis to maintain the initial species intact
and to determine them at the levels required.
According to the International Union of Pure and Applied Chemistry (IUPAC)
definition, metal speciation in foods comprises analytical activities of identifying
33
2234_C002.fm Page 34 Tuesday, October 17, 2006 10:30 AM
1. Those which contain a covalent bond between a carbon atom and a metal
or metalloid atoms such as
• tetraalkylated lead compounds used an antiknock additives to gasoline,
which are degraded to trialkyl or dialkyl species
• ingredients of antifouling paints, such as butyl, octyl, and phenyl tin
species, released into the aquatic environment and found in seafood
products
• methylmercury, a product of biomethylation of mercury by marine
organisms
• products of the metabolism of arsenic by marine biota leading to the
formation of the carbon–arsenic bond, e.g., as in arsenobetaine or
arsenosugars
• selenoaminoacids, selenopeptides, and proteins, biosynthesized by
plants and animals
2. Coordination complexes in which a metal is coordinated by a bio-ligand
present in a biological matrix (e.g., metal-binding peptides, which are
enzymatically synthesized in living organisms exposed to heavy-metal
stress)
Arsenic and selenium species of interest for food analysis are listed in Table 2.1
and Table 2.2, respectively.
TABLE 2.1
Arsenic Species of Interest for Food Analysis
Species Formula
Arsenous acid (arsenite) OH-As(OH)2
Arsenic acid (arsenate) O=As(OH)3
Monomethylarsonic acid CH3AsO(OH)2
Dimethylarsinic acid (CH3)2AsO(OH)
Tetramethylarsonium (CH3)4As+
Arsenobetaine (CH3)3As-CH2-COOH
Arsenobetaine-CH2 (CH3)3-CH2As-CH2-COOH
Arsenocholine (CH3)3As-CH2-CH2-OH
DMAsEt (CH3)2AsO(C2H5)
DMAsAc (CH3)2AsO(CH3CO)
Arsenosugar 392
O
O SO3H
H3C As O
OH
CH3
HO OH
Arsenosugar 328
O
O OH
H3C As O
OH
CH3
HO OH
Arsenosugar 482 HO O
O P
O O O OH
H3C As O
OH OH
CH3
HO OH
Arsenosugar 408
O
O O SO3H
H3C As O
OH
CH3
HO OH
2234_C002.fm Page 36 Tuesday, October 17, 2006 10:30 AM
TABLE 2.2
Selenium Species of Interest for Food Analysis
Species Formula
Selenite SeO32-
Selenate SeO42-
Trimethylselenonium (CH3)3Se+
Selenocysteine H3N+-CH(COO-)-CH2-SeH
Selenocystine H3N+-CH(COO-)-CH2-Se-Se-CH2-CH(COO-)-NH3+
Selenomethionine H3N+-CH(COO-)-CH2-CH2-SeH
Se-methylselenocysteine H3N+-CH(COO-)-CH2-Se-CH3
y-glutamylmethylselenocysteine H3N+-CH2-CH2-CO-NH-CH(COO-)-CH2-Se-CH3
Selenocystathionine H3N+-CH(COO-)-CH2-CH2-Se-CH2-CH(COO-)-NH3+
Selenohomocysteine H3N+-CH(COO-)-CH2-CH2-SeH
Selenocystamine H3N+-CH2-CH2-Se-Se-CH2-CH2-NH2
R Se N
O N
HO OH
2234_C002.fm Page 37 Tuesday, October 17, 2006 10:30 AM
Isotope intensity
Size-exclusion measurement
Mass Isotope
Spectrometry dilution
Ion-exchange (ICP-MS) Isotope ratio analysis
HPLC measurement
Reversed-phase
Tracer
Affinity studies
Element-specific
Separation detection
Packed
column
Capillary Gas Atomic Absorption Spectrometry
column chromatography
analyte species to arrive at the detector well separated from potential matrix inter-
ferents and from other species of the same element, (2) sensitivity of the element
selective detection technique as the already low concentrations of trace elements are
usually distributed among several species, (3) capability of species identification;
for this purpose retention-time matching with standards is usually employed. When
standards are not available, the use of a molecule-specific detection technique
(molecular mass spectrometry) is necessary.
The hyphenated techniques available for speciation analysis in foods are sche-
matically shown in Figure 2.1. In the most frequent cases, a separation technique,
notably chromatography (gas or liquid) is combined with inductively coupled
plasma-mass spectrometric (ICP-MS) detection.
The separation technique used becomes of particular concern when the target
species have similar physicochemical properties. Gas chromatography offers high
separation efficiency, and very low detection limits can be achieved in the absence
of the condensed mobile phase. For nonvolatile species, liquid phase column sepa-
ration techniques, such as high performance liquid chromatography (HPLC) and
cation exchange (CE), are the usual choice. They can be easily coupled online with
ICP-MS. A variety of separation mechanisms and mobile phases can be used to
allow the preservation of the species identity.
For element-specific detection in gas chromatography, a number of dedicated
spectrometric detection techniques can be used, e.g., quartz furnace atomic absorption
or atomic fluorescence for mercury, or microwave-induced plasma atomic emission
for lead or tin. However, ICP-MS is virtually the only technique capable of coping,
in the online mode, with the trace element concentrations (the femtogram level absolute
detection limits) in liquid chromatography (LC) and capillary electrophoresis (CE)
effluents. The isotope specificity of ICP-MS offers a still underexploited potential for
tracer studies and for improved accuracy via isotope dilution analysis.
2234_C002.fm Page 38 Tuesday, October 17, 2006 10:30 AM
TABLE 2.3
Most Popular Sample Preparation Procedures Used for Speciation Analysis
in Food Samples
Sample Preparation Procedure Species Recovered
Leaching with water, water–methanol mixtures, Low molecular species of arsenic and selenium
or neutral buffers and metal complexes from solid foodstuffs
Organic solvents (methanol) Arsenolipids
Proteolysis Alkylmetals, amino acids resulting from protein
hydrolysis (including selenoamino acids)
Pectinolysis Metals complexed with polysaccharides
Leaching with SDS, CHAPS Denaturated proteins (including proteins
containing selenium)
Digestion with artificial gastric and/or intestinal Bioavailable species
juice
Alkaline digestion (e.g., with TMAH) Alkylmetals
9
60
Signal intensity, emission units
50
6
40 7
1 4
30
2 5
20
10
3
8
0
2 4 6 8 10
Retention time, min
shown in Figure 2.2. Speciation analysis for mercury in seafood has recently been
reviewed by Carro et al.25
Leaching with water, water–methanol mixtures, and neutral buffers is an estab-
lished technique for the recovery of metal complexes and low molecular species
of arsenic and selenium from solid foodstuffs. Sonication with a water–methanol
2234_C002.fm Page 42 Tuesday, October 17, 2006 10:30 AM
AsC
unknown 1 TMAs+
AsSug D
unknown 2 AsSug B
DMA
2.0 x104
AsB-CH2
AsB
Intensity, cps
1.5
AsB
1.0
AsSug B
AsC+
0.5 TMAs+ AsSug D
U1
DMA U2 As(V)
AsBCH2
0
0 5 10 15 20 25
Time, mins
FIGURE 2.3 Determination of arsenic species in oyster tissue by anion-exchange HPLC-
ICP-MS.
solution is the most popular method used for extraction of arsenic species from rice
powder,26,27 algae,28,29 chicken meat,30 oyster tissue,31,32 and baby foods.33 A typical
HPLC-ICP-MS chromatogram of arsenic species in a seafood sample is presented
in Figure 2.3.
Because selenoaminoacids are water-soluble, leaching with hot water has been
judged sufficient to recover selenium species not incorporated into larger molecules.
The typical recoveries of selenium extracted in this way from selenized yeast samples
are usually ca. 10 to 20%.34–37 A total of 27 different procedures employing buffering
systems between pH 1 and 9 were compared for extraction of selenium compounds
from high-selenium broccoli.38 In extractions using nonbuffered solvents, more than
40% of the spiked Se-methylselenocysteine was not recovered. When buffer solu-
tions were used for extraction, losses for Se-methylselenocysteine ranged from 10
to 20%. It was found that ca. 30% of the selenium naturally occurring in broccoli
samples was volatilized and lost to the atmosphere in the course of extractions with
buffer solutions.38
Figure 2.4 shows two examples dealing with the recovery of high molecular
species from food samples. Speciation of zinc in infant formula (Figure 2.4a) after
the centrifugation of the sample homogenized with a Tris buffer led to a chro-
matogram with one major signal corresponding to ca. 20 to 30% of the total zinc
initially present. After the addition of sodium dodecylsulfate (SDS), a quantitative
recovery of zinc into the 0.2 µm filtrable fraction was achieved. In addition to the
increase in the concentration of the compounds excluded from the column, an
additional compound could be released from the sample. The proteolytic hydrolysis
of the proteins excluded from the column resulted in the formation of a mixture
of oligopeptides that still contained firmly bound zinc. The recovery of zinc from
the sample did not increase in comparison with the extraction with SDS. In Figure
2.4b, speciation of lead in an apple homogenate sample was investigated. The
supernatant obtained after ultracentrifugation of the sample contained ca. 40% of
the lead initially present, which was eluted as a 60-kDa polysaccharide compound
(as confirmed by the refractometric method). The rest of the lead was retained in
the solid residue that consisted of cellulose and complex water-insoluble pectic
polysaccharides. An extraction using a mixture of pectinolytic enzymes that are
known to degrade efficiently large pectic polysaccharides51 allowed the partial
destruction of the residue to release a dimer of Rhamnogalacturonan II. The lead
fraction in the residue was insignificant (ca. 5%).
Some attention has been paid to the analysis of enzymatic digests of foodstuffs in
the quest for molecular information to contribute to the knowledge of the bioavail-
ability of some elements. Sequential enzymolyses in simulated gastric and gas-
trointestinal juice were proposed for an estimation of bioavailability of heavy metal
species from meat52 and cocoa samples.53,54 The soluble fractions of the stomach
and upper intestinal contents of guinea pigs on different diets were investigated for
estimating the bioavailable forms of Al, Cu, Zn, Mn, Sr, and Rb.55
An in vitro model simulating enzymatic activity in the gastrointestinal tract was
developed for the assessment of the potential bioavailability of Cd and Pb in cocoa
powder and cocoa liquor of different geographical origins. The model was based on
the sequential extraction with simulated gastric and intestinal juices. The residue
after the latter extraction was further investigated by using, in parallel, solutions of
phytase and cellulose.53
The chemical stability of four arsenosugars isolated from seaweed extracts was
investigated. Four arsenosugars were subjected to simulated gastric juice and acidic
artificial stomach degradation, which resulted in a single common product tentatively
identified by electrospray ionization tandem mass spectrometry (ESI-MS/MS), and
an acid hydrolysis mechanism was proposed for its formation from each of the native
arsenosugars.56
The in vitro gastric and intestinal digests of selenized yeast food supplements
were investigated by successive HPLC–ICP-MS and HPLC–ESI-MS/MS. The main
compound extracted by both gastric and intestinal juice was Se-methionine, which
2234_C002.fm Page 45 Tuesday, October 17, 2006 10:30 AM
(a)
1.50×105
1.25
1.00
Intensity, cps
0.75
0.50
0.25
0
0 5 10 15 20 25 30 35 40 45
Elution time, min
(b)
1.25×105
0.18 kDa
48.0 kDa
23.7 kDa
12.2 kDa
5.8 kDa
1.00
Intensity, cps
0.75
0.50
0.25
0
0 5 10 15 20 25 30
Elution time, min
TABLE 2.4
Standard Reference Materials for Species-Selective Analysis in Food
Matrices
Standard
Reference Species
Element Material Name Matrix Certified Concentration
was also the main Se-compound extracted by proteolytic digestion from the yeast
supplements. Two other minor compounds were identified as Se-cystine and Se(O)-
methionine, a degradation product of Se-methionine.57
REFERENCES
1. Templeton, D. et al., Guidelines to speciation analysis, Pure Appl. Chem., 72, 1453,
2000.
2. Szpunar, J. and Lobinski, R., Hyphenated Techniques for Speciation Analysis, Royal
Society of Chemistry, Cambridge, MA, 2003.
3. Szpunar, J., Bioinorganic speciation analysis by hyphenated techniques, Analyst, 125,
963, 2000.
4. Cornelis, R. et al., Handbook of Speciation Analysis, John Wiley & Sons, New York,
2002.
5. Lobinski, R., Elemental speciation and coupled techniques, Appl. Spectrom., 51,
260A, 1997.
2234_C002.fm Page 48 Tuesday, October 17, 2006 10:30 AM
6. Bouyssiere, B., Szpunar, J., and Lobinski, R., Gas chromatography with inductively
coupled plasma mass spectrometric detection in speciation analysis, Spectrochim.
Acta, B 57, 805, 2002.
7. Lobinski, R. and Adams, F.C., Speciation analysis by gas chromatography with
plasma source spectrometric detection, Spectrochim. Acta, 52B, 1865, 1997.
8. García Fernandez, R.G. et al., Comparison of different derivatization approaches for
mercury speciation in biological tissues by gas chromatography/inductively coupled
plasma mass spectrometry, J. Mass Spectrom., 35, 639, 2000.
9. Mester, Z. et al., Determination of methylmercury by solid-phase microextraction
inductively coupled plasma mass spectrometry: a new sample introduction method
for volatile metal species, J. Anal. At. Spectrom., 15, 837, 2000.
10. Slaets, S. et al., Optimization of the coupling of multicapillary GC with ICP-MS for
mercury speciation analysis in biological materials, J. Anal. At. Spectrom., 14, 851,
1999.
11. Tseng, C.M. et al., Field cryofocussing hydride generation applied to the simultaneous
multi-elemental determination of alkyl-metal(loid) species in natural waters using
ICP-MS detection, J. Environ. Monit., 2, 603, 2000.
12. Casiot, C. et al., Sample preparation and HPLC separation approaches to speciation
analysis of selenium in yeast by ICP MS, J. Anal. At. Spectrom., 14, 645, 1999.
13. Casiot, C. et al., An approach to the identification of selenium species in yeast extracts
using pneumatically-assisted electrospray tandem mass spectrometry, Anal. Com-
mun., 36, 77, 1999.
14. Morita, M. and Shibata, Y., Speciation of arsenic compounds in marine life by high-
performance liquid chromatography combined with inductively coupled argon-
plasma atomic-emission spectrometry, Anal. Sci., 3, 575, 1987.
15. Shibata, Y. and Morita, M., Exchange of comments on identification and quantification
of arsenic species in a dogfish muscle reference material for trace elements, Anal.
Chem., 61, 2116, 1989.
16. Shibata, Y. and Morita, M., Speciation of arsenic by reversed-phase high-performance
liquid chromatography inductively coupled plasma mass spectrometry, Anal. Sci., 5,
107, 1989.
17. Yoshinaga, J. et al., NIES certified reference materials for arsenic speciation, Accred.
Qual. Assur., 2, 154, 1997.
18. Makarov, A. and Szpunar, J., The coupling of size-exclusion HPLC with ICP MS in
bio-inorganic analysis, Analusis, 26, M44, 1998.
19. Francesconi, K.A. and Kuehnelt, D., Determination of arsenic species: a critical
review of methods and applications, 2000–2003, Analyst, 129, 373, 2004.
20. Uden, P.C. et al., Selective detection and identification of Se containing compounds-
review and recent developments, J. Chromatogr. A, 1050, 85, 2004.
21. Caruso, J.A., Sutton, K.L., and Ackley, K.L., Elemental speciation: new approaches
for trace element analysis, in Comprehenisve Analytical Chemistry, Barcelo, D., Ed.,
Elsevier, Amsterdam, 2000.
22. Michalke, B., The coupling of LC to ICP-MS in element speciation — Part II: recent
trends in application, Trends Anal. Chem., 21, 154, 2002.
23. Michalke, B., The coupling of LC to ICP-MS in element speciation: I. General
aspects, Trends Anal. Chem., 21, 142, 2002.
24. Szpunar, J. et al., Rapid speciation of butyltin compounds in sediments and bioma-
terials by capillary gas chromatography-microwave induced plasma atomic-emission
spectrometry after microwave-assisted leaching-digestion, J. Anal. At. Spectrom., 11,
193, 1996.
2234_C002.fm Page 49 Tuesday, October 17, 2006 10:30 AM
25. Carro, A.M. et al., Different extraction techniques in the preparation of methylmercury
biological samples: classic extraction, supercritical-fluid and microwave extraction,
Int. Lab. 28, 23, 1998.
26. Pizarro, I. et al., Evaluation of stability of arsenic species in rice, Anal. Bioanal.
Chem., 376, 102, 2003.
27. D’Amato, M., Forte, G., and Caroli, S., Identification and quantification of major
species of arsenic in rice, J. AOAC. Int., 87, 238, 2004.
28. McSheehy, S. et al., Identification of dimethylarsinyl-riboside derivatives in seaweeds
by pneumatically assisted electrospray tandem mass spectrometry (ESI MS/MS),
Anal. Chim. Acta, 410, 71, 2000.
29. McSheehy, S. and Szpunar, J., Speciation of arsenic in edible algae by bi-dimensional
size-exclusion anion exchange HPLC with dual ICP MS and electrospray MS/MS
detection, J. Anal. At. Spectrom., 15, 79, 2000.
30. Polatajko, A. and Szpunar, J., Speciation of arsenic in chicken meat by anion-
exchange liquid chromatography with inductively coupled plasma-mass spectrometry,
J. AOAC Int., 233, 2004.
31. McSheehy, S. et al., Investigation of arsenic speciation in oyster test reference material
by multidimensional HPLC-ICP MS and electrospray tandem mass spectrometry (ES
MS/MS), Analyst, 126, 1055, 2001.
32. Velez, D., Ybanez, N., and Montoro, R., Determination of arsenobetaine in manufac-
tured seafood products by liquid chromatography, microwave-assisted oxidation and
hydride-generation atomic-absorption spectrometry, J. Anal. At. Spectrom., 12, 91,
1997.
33. Vela, N.P. and Heitkemper, D.T., Total arsenic determination and speciation in infant
food products by ion chromatography-inductively coupled plasma-mass spectrometry,
J. AOAC Int., 244, 2004.
34. McSheehy, S. et al., Identification of selenocompounds in yeast by electrospray
quadrupole-time of flight mass spectrometry, J. Anal. At. Spectrom., 17, 507, 2002.
35. McSheehy, S. et al., Speciation of selenocompounds in yeast aqueous extracts by
three dimensional liquid chromatography with ICP MS and electrospray MS detec-
tion, Analyst, 127, 223, 2002.
36. McSheehy, S. et al., Analysis for selenium speciation in selenized yeast extracts by
two-dimensional liquid chromatography with ICP MS and electrospray MS/MS detec-
tion, J. Anal. At. Spectrom., 16, 68, 2001.
37. Ruiz Encinar, J. et al., Methodological advances for selenium speciation analysis in
yeast, Anal. Chim. Acta, 500, 171, 2003.
38. Roberge, M.T., Borgerding, A.J., and Finley, J.W., Speciation of selenium compounds
from high selenium broccoli is affected by the extracting solution, J. Agric. Food
Chem., 51, 4191, 2003.
39. Polatajko, A. et al., A systematic approach to selenium speciation in selenized yeast,
J. Anal. At. Spectrom., 19, 114, 2004.
40. Kannamkumarath, S.S. et al., HPLC-ICP MS determination of selenium distribution
and speciation in different types of nut, Anal. Bioanal. Chem., 373, 454, 2002.
41. B’Hymer, C. and Caruso, J.A., Evaluation of yeast-based selenium food supplements
using HPLC-ICP MS, J. Anal. At. Spectrom., 15, 1531, 2000.
42. Montes-Bayon, M. et al., Selenium in plants by mass spectrometric techniques:
developments in bio-analytical methods, J. Anal. At. Spectrom., 17, 1015, 2002.
43. Capelo, J.L. et al., Enzymatic probe sonication: enhancement of protease-catalyzed
hydrolysis of selenium bound to proteins in yeast, Anal. Chem., 76, 233, 2004.
2234_C002.fm Page 50 Tuesday, October 17, 2006 10:30 AM
44. Dernovics, M., Stefanka, Z., and Fodor, P., Improving selenium extraction by sequen-
tial enzymatic processes for Se-speciation of selenium-enriched Agaricus bisporus,
Anal. Bioanal. Chem., 372, 473, 2002.
45. Stefánka, Z. et al., Comparison of sample preparation methods based on proteolytic
enzymatic processes for Se-speciation of edible mushroom (Agaricus bisporus) sam-
ples, Talanta, 55, 437, 2002.
46. Wrobel, K. et al., Hydrolysis of proteins with methanesulfonic acid for improved
HPLC-ICP MS determination of seleno-methionine in yeast and nuts, Anal. Bioanal.
Chem., 375, 133, 2003.
47. Bird, S.M. et al., Speciation of selenoamino-acids and organoselenium compounds
in selenium-enriched yeast using high-performance liquid chromatography induc-
tively coupled plasma mass spectrometry, J. Anal. At. Spectrom., 12, 785, 1997.
48. Kotrebai, M. et al., Selenium speciation in enriched and natural samples by HPLC-
ICP-MS and HPLC-ESI-MS with perfluorinated carboxylic acid ion-pairing agents,
Analyst, 125, 71, 2000.
49. Diaz Huerta, V., Fernandez Sanchez, M.L., and Sanz-Medel, A., Quantitative selenium
speciation in cod muscle by isotope dilution ICP MS with a reaction cell: comparison
of different reported extraction procedures, J. Anal. At. Spectrom., 19, 644, 2004.
50. Caruso, J.A., Heitkemper, D.T., and B’Hymer, C., An evaluation of extraction tech-
niques for arsenic species from freeze-dried apple samples, Analyst, 126, 136, 2001.
51. Szpunar, J. et al., Speciation of metal-carbohydrate complexes in fruit and vegetable
samples by size-exclusion HPLC-ICP MS, J. Anal. At. Spectrom., 14, 639, 1999.
52. Crews, H.M. et al., Application of HPLC-ICP MS to the investigation of cadmium
speciation in pig kidney following cooking and in vitro gastro-intestinal digestion,
Analyst, 114, 895, 1989.
53. Mounicou, S. et al., Development of a sequential enzymolysis approach for the
evaluation of the bioaccessibility of Cd and Pb from cocoa, Analyst, 127, 1638, 2002.
54. Mounicou, S. et al., Bioavailability of cadmium and lead in cocoa: comparison of
extraction procedures prior to size-exclusion fast-flow liquid chromatography with
inductively coupled plasma mass spectrometric detection (SEC-ICP-MS), J. Anal. At.
Spectrom., 17, 880, 2002.
55. Owen, L.M.W. et al., Determination of copper, zinc and aluminum from dietary
sources in the femur, brain and kidney of guinea pigs and a study of some elements
in vivo intestinal digestion by size-exclusion chromatography inductively coupled
plasma mass spectrometry, Analyst, 120, 705, 1995.
56. Gamble, B.M. et al., An investigation of the chemical stability of arsenosugars in
simulated gastric juice and acidic environments using IC-ICP-MS and IC-ESI-
MS/MS, Analyst, 127, 781, 2002.
57. Dumont, E., Vanhaecke, F., and Cornelis, R., Hyphenated techniques for speciation
of Se in in vitro gastrointestinal digests of Saccharomyces cerevisiae, Anal. Bioanal.
Chem., 379, 504, 2004.
58. Quevauviller, P., Method Performance Studies for Speciation Analysis, Royal Society
of Chemistry, Cambridge, MA, 1998.
59. Bodo, E.T. et al., Preparation, homogeneity and stability studies of a candidate LRM
for Se speciation, Anal. Bioanal. Chem., 377, 32, 2003.
60. Moreno, P. et al., Stability of total selenium and selenium species in lyophilized
oysters and in their enzymatic extracts, Anal. Bioanal. Chem., 374, 466, 2002.
61. Vinas, P. et al., Stability of arsenobetaine levels in manufactured baby foods, J. Food
Prot., 66, 2321, 2003.
2234_C003.fm Page 51 Wednesday, October 25, 2006 2:07 PM
3 Criteria of Evaluation of
Food Elements Analysis
Data
Barbara Szteke
CONTENTS
3.1 INTRODUCTION
Food quality is one of the most important factors determining the consumer’s
perception and acceptance, attraction to, and purchase of the product. As food is the
main source of major and trace elements for humans, their levels are among the
factors that characterize the quality and safety of foodstuffs. Consumer pressure for
safer, cleaner, and better quality foods cannot be overemphasized. For that reason,
regulation in many countries define recommended levels of nutritive and essential
elements, and permissible levels of toxic or potentially toxic elements in food
products, raw materials, and food additives.
The determination of levels of both major and trace constituent elements in food
and food products is becoming increasingly important in nutritional and food safety
considerations. What might be a major (%) constituent in one food product can often
be at a trace (milligram or microgram) concentration in another. For example,
calcium is a major constituent in dairy product but found in relatively low concen-
trations in cereal grains.1
Food analysis, especially to satisfy the requirements of the labeling laws, is far
more complicated than traditional chemical analysis. Determinations of elements
present in food can be very complex as a task and complicated in execution. They
can range from measuring simple elements in simple matrices (drinks) to complex
51
2234_C003.fm Page 52 Wednesday, October 25, 2006 2:07 PM
TABLE 3.1
Some Examples of Results of Interlaboratory Comparisons
Concentration “True” Content
Year Material na Element Range (mg/kg) (mg/kg) References
we can only speculate as to the cause of the poor performance of analytical chemists
as exhibited by the large number of outliers apparent in collaborative studies. Within
a single generation of scientists, analytical chemistry has changed precipitously from
being a science of macroanalysis to one of trace analysis. In macrochemistry, gross
errors are relatively easy to identify by the principle of consistency. A misplaced
decimal point in concentration usually means that the physical, chemical, biological
or sensory properties of substances were changed sufficiently to arouse suspicions as
to accuracy of the analysis. For example, a moisture content of 8% is typical of rather
2234_C003.fm Page 54 Wednesday, October 25, 2006 2:07 PM
dry solid, but a moisture content of 80% is more typical of a fruit. A misplaced decimal
point at the parts-per-million level can be discovered only by a completely independent
analysis.
There are a number of analytical techniques from which the analyst of today
can choose when conducting an elemental assay. The choice of analytical procedure
depends on a number of factors, but it is necessary to consider the potential sources
of error and all that may affect the final result, e.g., improper sampling and storage
of the sample, sample preparation, calibration, instrumentation, analysis, and inter-
pretation.
In sampling, a fraction or portion of a greater quantity of some bulk material is
taken in order to facilitate its handling for the analysis. This procedure of reduction
of bulk by selection must not change the ratio of matrix to element constituents.
The relationship must be the same in the sample drawn and in the original bulk. All
samples of fresh foods (vegetables, fish, fruits, meat, etc.) are liable to change in
matrix and element concentrations. Almost always, the sampling will include some
enrichment step. Obviously, the homogeneity of the bulk material is the most critical
parameter of the entire sampling procedure. The food matrices met in elemental
analysis are often inhomogeneous.
Sample preparation is still a difficult problem for the analyst as he or she must
convert the substance into a suitable form for analysis without contaminating it or
causing a loss of dry weight or a loss of any elements of interest. Drying, grinding,
and solubilization techniques are frequently difficult and uncertain in their final
result. Progress made analytically in recent years has far exceeded progress made
towards improving sample preparation procedure. Usually, in the first stage, the solid
sample has to be transferred to a homogenous liquid phase. With organic matrices
of food, this always includes a sample destruction. Sample preparation often includes
separation or preconcentration of the analytes, and at these stages one can make
fatal errors. The analyte may be lost by adsorption (surfaces of tools and vessels)
or volatilization (elements — Hg, As, Se; compounds — oxides, halogenides,
hydrides), and it can also be added to the sample from the air, laboratory glassware,
acids, reagents, etc.
In such multistage procedures, the actual step of determination for which many
methods are available today can easily be calibrated and is, in general, least subject
to systematic errors. Hence, the causes of systematic errors inherent to multistage
procedures lie, in the first instance, in all the steps of sample preparation that have
to precede the actual determination. The main concern is to avoid contamination
from vessels and containers, reagents, and the laboratory air. It is also important to
keep the blank as low and constant as possible. So, sample preparation is probably
still the weakest link in the determination of the elemental content of biological
substances.
Among others potential sources of error are chemical reactions: change of valency
of ions, precipitation reaction, ion exchange, complex formation of volatile and
nonvolatile compounds, and interference of the signal, such as matrix effects, target,
overlapping of signals, signal background, and incorrect calibration and evaluation.
2234_C003.fm Page 55 Wednesday, October 25, 2006 2:07 PM
Other risks include incorrect standards, instable standard solutions, blanks, errors
during measurements, false calibration functions, inadmissible extrapolation, etc.
Sherlock and others stated:4
Users of analytical data should be made aware by those who provide it, that customer
gets what he pays for. If a customer wants accurate and reliable data, then they will
not come cheaply. Since inaccurate and unreliable data will rarely meet the customer’s
needs, their continued generation will be both a waste of consumers’ money and of
analysts’ time.
Quality assurance describes the overall measures that a laboratory uses to ensure
the quality of its operations. Examples of typical items are: quality control, suitable
and reference materials, traceability, proficiency testing, nonconformance manage-
ment, and internal audits, statistical analysis. The quality assurance activities should
be embedded in a managerial quality system.
1. The analyst is denied freedom of choice, and thus may be required to use
an inappropriate method in some situations.
2. The procedure inhibits the use of advanced methodology, especially if the
“official” method is dated.
3. The procedure inhibits the use of automation.
4. It is administratively difficult to change a method found to be unsatisfac-
tory or inferior to another currently available.
Laboratories may use any method of analysis provided it has been validated as
performing to the adequate standards. Before the decision on use any analytical
method, the following should also be taken into consideration:
Unfortunately, the terms “quality control” and “quality assurance” are frequently
not correctly interpreted, and sometimes even abused. As an example, it sometimes
occurs that the analysis of a sample of a reference material is considered to be the
laboratory’s quality assurance. It is not.
Organizations that provide standard methods of analysis, such as AOAC, the
American Society for Testing and Materials (ASTM), ISO, and the International
Union of Pure and Applied Chemistry (IUPAC) have developed their own interlab-
oratory procedures to predict how a given method of analysis will perform in actual
practice. Such a study requires analyses of identical test samples by a number of
laboratories over the concentration and commodity ranges of interest.
Analytical research laboratories are often involved in other activities such as
routine analyses and teaching. In this situation, making such duties compatible
introduces an additional difficulty in implementing a quality system. There is a
pressing need for analytical laboratories involved in research and development activ-
ities to implement gradually quality systems with a view to improving performance.12
For elemental analysis in food, appropriate methods should be assessed by the
laboratory from the following main criteria defined by international standards:10,11
The term accuracy, when applied to a set of test results, involves a combination
of random components and a common systematic error or bias component.
Bias is the total systematic error as contrasted to random error. There may be
one or more systematic error components contributing to bias. A larger systematic
difference from the accepted reference value is reflected by a larger bias value.
Estimation of bias (the difference between the measured value and the true value)
is one of the most difficult elements of method validation, but appropriate reference
materials (RMs) can provide valuable information within the limits of uncertainty
of the RM’s certified value(s) and the uncertainty of the method being validated.
Precision depends only on the distribution of random errors and does not relate
to the true value or the specified value. The measure of precision is usually expressed
in terms of imprecision and computed as a standard deviation of the test results.
Less precision is reflected by a larger standard deviation. “Independent test results”
means results obtained in a manner not influenced by any previous result on the
same or similar test object. Quantitative measures of precision depend critically on
the stipulated conditions. Repeatability and reproducibility conditions are particular
sets of extreme conditions:
When different methods give test results that do not differ significantly, or when
different methods are permitted by the design of the experiment, as in a proficiency
study or a material-certification study for the establishment of a consensus value of
a reference material, the term “reproducibility” may be applied to the resulting
parameters. The conditions must be explicitly stated.
provide widely accepted reference standards, and at the individual laboratory level
to demonstrate the necessary links to the standards.14
The parameter may be, for example, a standard deviation (or a given multiple
of it), or the half-width of an interval having a stated level of confidence. Uncertainty
of measurement comprises, in general, many components. Some of these components
may be evaluated from the statistical distribution of results of a series of measure-
ments and can be characterized by experimental standard deviations. The other
components, which can also be characterized by standard deviations, are evaluated
from assumed probability distributions based on experience or other information.
Important to and required by standard ISO 170259 is that analysts be aware of
the uncertainty associated with each analytical result and that the uncertainty be
estimated. The measurement uncertainty may be derived by a number of procedures.
Food analysis laboratories are required to be in control, use collaboratively tested
methods when available, and verify their application before taking them into routine
use. Such laboratories, therefore, have available to them a range of analytical data
that can be used to estimate their measurement uncertainty.
Most quantitative analytical results take the form of a ± 2u or a ± U, where “a”
is the best estimate of the true value of the measurand’s concentration (the analytical
2234_C003.fm Page 60 Wednesday, October 25, 2006 2:07 PM
result) and “u” is the standard uncertainty, and “U” (equal to 2u) is the expanded
uncertainty. The range a ± 2u represents a 95% level of confidence where the true
value would be found. The value of “U” or 2u is the value that is normally used
and reported by analysts and is hereafter referred to as measurement uncertainty,
and may be estimated in a number of different ways.
The parameter may be, for example, a standard deviation (or a given multiple
of it), or the half-width of an interval having a stated level of confidence. The
measurement uncertainty of an analytical result may be estimated by a number of
procedures, notably those described by ISO15 and EURACHEM.16
The measurement uncertainty and its level of confidence must, on request, be
made available to the user (customer) of the results.
Summarizing, according to Hu and Liu,17 suitable analytical methods for trace
elements in food should have the following features:
• Simulates or artifacts
• Spiked and unspiked real life samples
• Analytes
• Matrices
• Applications18
Certified reference materials (CRMs) and reference materials (RMs) are widely
used in food analysis. The basic purpose of all CRMs is to improve the comparability
of measurements, but CRMs can be used at two different stages of the measurement
process:
2234_C003.fm Page 61 Wednesday, October 25, 2006 2:07 PM
CRMs are being used for the validation of new analytical methods and also for
checking the performance of new laboratory, new analyst, etc. They are also
employed as control samples for routine monitoring of laboratory performance with
the use of control charts.
A targeted use of certified reference materials is one approach to the quality
control of food analysis. CRMs are used to evaluate the accuracy of analytical
procedures and compare different preparation procedures and techniques of deter-
minations. They are also used for internal quality control of routine food analysis.
In order to demonstrate the credibility of analytical results in all these areas, several
CRMs are used, chosen with respect to the analyte, levels of certified values, and
matrix composition.
CRMs serve in elemental analysis as a means of transferring measuring quality.
When the determination of an element in CRM gives the correct result (i.e., the one
that is in agreement with the certificate), it may be assumed that the results for the
same element in an unknown sample is also correct, provided the overall composition
of both materials and the concentrations levels of the analyte are not too different.
So, the use of CRMs assures the transfer of accuracy and achievement of meas-
urement compatibility on a global scale.20
The need that drives the production of certified reference materials is where
regulation exists in terms of tolerance, and there is scope for disagreement between
parties as to the true values. Reference materials provide an unequivocal benchmark
against which the abilities of laboratories or contrasting methodologies can be com-
pared. Moreover, where there are unusual analytical difficulties (and this is particularly
the case with trace elements), reference materials offer the way to demonstrate inter-
nally that all is well. Required limits of determination are frequently very low, which
may be a source of difficulty.
Reference materials provide a means of assessing whether this is a potential
problem. Frequently the tried-and-tested methods, such as the official AOAC method,
2234_C003.fm Page 62 Wednesday, October 25, 2006 2:07 PM
may not employ the latest technology; reference materials enable one to demonstrate
that the new technologies can give the same results as the established procedure.
For elemental food analysis, many specific CRMs are available, among them
are NIST SRMs: nonfat milk powder, oyster tissue, wheat flour, rice flour, spinach
leaves, bovine liver, baking chocolate, slurried spinach or BCR CRMs: skim milk
powder, bovine muscle, pig kidney, cod muscle, wholemeal flour, single cell protein,
white cabbage, rye flour, wheat flour, haricots verts (French Beans), and pork muscle.
There is frequently the misconception that reference materials should be used
for quality assurance purposes for routine use in laboratories. CRMs are in fact too
expensive for this routine purposes and participation in proficiency testing (PT) or
interlaboratory comparisons (ILC), and the purchase and use of surplus material
from these exercises is a better and cheaper alternative.
The determination of the bulk content of elements in food and other materials
is often not sufficient for the estimation of, for example, health hazards, and therefore
the determination of individual species of various elements, for instance, methyl-
mercury, organotins, As species, Cr(III), and Cr(VI), is requested. Very few CRMs
certified for individual species of elements is available so far. The problems with
their production and certification are more complex than the problems of production
of CRMs for total element content analysis.20
Z = (x X̂)/σ
where x is the reported value of analyte concentration in the test material; X̂ is the
assigned value, the best estimation of the true concentration of the analyte; and σ
is the target value for standard deviation of value of x.
As the Z score is standardized, it is comparable for all analytes and methods.
The Z scores for all participants can then be plotted on a graph or performance limit
can be interpreted as follows:
| Z score | ≤ 2 Satisfactory
2 < | Z score | < 3 Questionable
| Z score | ≥ 3 Unsatisfactory
• From the technical point of view, posses the necessary means, expertise
and methods
• Be able to provide assurance of the quality of its services, i.e., has a well-
developed quality assurance system
quality system, are technically competent, and are able to generate technically valid
results. The Standard9 specifies the general requirements for the competence to carry
out tests and calibrations, including sampling. It covers testing and calibration
performed using standard method, nonstandard methods, and laboratory-developed
methods. The standard is for use by laboratories in developing their quality, and
administrative and technical systems that govern their operations. The acceptance
of testing results between countries should be facilitated if laboratories comply with
this standard and if they obtain accreditation from bodies that have entered into
mutual recognition agreements with equivalent bodies in other countries using this
international standard.
Many countries around the world have one or more organizations responsible
for the accreditation of their laboratories. Most of these accreditation bodies have
now adopted an international standard, ISO 17025,9 as the basis for the accreditation
of their country’s testing and calibration laboratories. Adoption of this international
standard has helped countries formulate a uniform approach to determining labora-
tory competence. Such a uniform approach allows countries with similar accredita-
tion systems to establish agreements between themselves, based on mutual evalua-
tion and acceptance of each other’s accreditation systems.
Such international agreements, usually called mutual recognition arrangements,
are crucial in enabling test data to be accepted between countries. In effect, each
partner in such an arrangement recognizes the other partner’s accredited laboratories
as if they themselves had undertaken the accreditation.
The provision for accreditation is thus globally the same for all accrediting
organizations respecting these requirements. They may, however, differ in certain
practical details from one country to another.
However, even if the task of obtaining and maintaining accreditation remains
difficult over the first years, it clearly constitutes a minimum level of organization
and an intermediate step. The laboratory must continue to improve its quality system
and not consider ISO 170259 as simply a series of requirements and constraints but
consider it as a true management model.
Laboratory accreditation provides a means of determining the competence of
laboratories to perform specific types of testing, measurement, and calibration. As
laboratory accreditation involves an independent assessment by technical experts, it
also allows a laboratory to determine whether it is performing its work correctly
and to appropriate standards. Importantly, laboratory accreditation provides formal
recognition to competent laboratories, thus providing a ready means for customers
to access reliable testing and calibration services.
This developing system of mutual recognition between accreditation bodies has
enabled accredited laboratories to achieve a form of international recognition and
allowed test data accompanying exported goods to be more readily accepted in
overseas markets. This effectively reduces costs for both the manufacturer and the
importers, as it reduces or eliminates the need for products to be retested in another
country.
Countries without viable accreditation systems can also seek to have their lab-
oratories certified by those with established accreditation systems, so that their test
data and associated goods can be accepted in foreign markets. These countries can
2234_C003.fm Page 66 Wednesday, October 25, 2006 2:07 PM
also endeavor to develop their own accreditation system based on the structure and
experience of those in other countries.
GEMS/Food maintains links with the FAO, UNEP, and other international organ-
izations, such as the International Atomic Energy Agency, as well as with relevant
international nongovernmental organizations such as the Association of Official
Analytical Chemists International on specific food contamination monitoring and
surveillance matters. In particular, GEMS/Food remains most active in the work of
the Codex Alimentarius Commission and its scientific advisory bodies such as the
Joint FAO/WHO Meeting on Pesticide Residues (JMPR) and the Joint FAO/WHO
Expert Committee on Food Additives (JECFA).
In the past, contaminant data have been submitted to WHO by the participating
institution or collaborating center via written forms transcribed from laboratory
reports. In 1996, WHO started the development of a new data structure for food
contaminant data and protocols for the electronic submission of such data. Electronic
submission of data on dietary intakes is the subject of a separate manual. In addition
to protocols for electronic data submission, WHO has also developed a computer
system to allow the direct entry of data into — as well as the retrieval of data and
creation of reports from — the GEMS/Food program database.
The laboratory (or the majority of the contributing laboratories) which success-
fully participates in relevant proficiency tests during the sampling and analysis period
should be officially accredited.
For the analytical method used in the program, it is necessary to document the
following: identification of method, validation, limit of detection/ limit of quantifi-
cation, recoveries, measurement uncertainty, calibrants, laboratory accreditation, and
interlaboratory comparison studies. GEMS/Food-EURO has sponsored two work-
shops on this topic. Details of recommendations of the second GEMS/Food-EURO
workshop may be found in the report of the workshop titled “Reliable Evaluation
of Low-level Contamination of Food.”25
REFERENCES
1. Benton Jones, J. Jr., Developments in the measurement of trace metal constituents in
foods, in Analysis of Food Contaminants, J. Gilbert, Ed., Elsevier, London and New
York, 1984, p. 157.
2. Tölg, G., Assets and deficiencies in elemental analysis of food-stuffs, in Recent
Development in Food Analysis, I Euro Food Chem., Verlag Chemie, Weinheim,
Deerfield Batch, Florida-Basel 1982, p. 335.
3. Canet, C., Importance of international cooperation in food safety, Food Addit. Con-
tam., 10, 97, 1993.
4. Sherlock, J.C. et al., Analysis — accuracy and precision?, Chemistry in Britain, 1019,
November 1985.
´
5. Dybczynski, R., Reference materials and their role in quality assurance in inorganic
´ Analizy Śladowej w Badaniach Środowiska Przy-
trace analysis, in Problemy Jakosci
·
rodniczego, Kabata-Pendias A. and Szteke, B., Eds., Zak, Warsaw, 41, 1998 (in
Polish).
6. GEMS/Food-Euro, Report to participants in Proficiency Testing Exercise 93/01, Min-
istry of Agriculture, Fisheries and Food, Food Science Laboratory, U.K., 1994.
2234_C003.fm Page 68 Wednesday, October 25, 2006 2:07 PM
4 Chemometric
Techniques in Analytical
Evaluation of Food
Quality
Piotr Szefer
CONTENTS
69
2234_C004.fm Page 70 Wednesday, October 25, 2006 2:54 PM
Summary ................................................................................................................112
References..............................................................................................................114
4.1 INTRODUCTION
The aim of multivariate data analysis is to break down mixed data structure into its
components. In order to reduce relatively large number of variables to a smaller
number of orthogonal factors, the data are treated by multivariate statistical methods,
i.e., principal components analysis (PCA), factor analysis (FA), linear discrimination
analysis (LDA), canonical discriminant analysis (DA), end-member analysis, cluster
analysis (CA), neural network (NN), etc.1 Defernez and Kemsley2 have reported the
use and misuse of chemometrics for treating classification problems. Multivariate
data analysis has been presented extensively by several authors.3–8
Because of PCA, it is possible to create “new” dimensions of the data9 and evaluate
a reduced number of independent factors or principal components describing the
information included in a system of characteristic but partly dependent variables. PCA
and FA are techniques for finding a few components or factors that explain the major
variations within the data matrix. Each component or factor in PCA or FA is a weighted
linear combination of the original variables. Components or factors only with eigen-
values higher than unity should be preferably considered.10,11 The factor loading char-
acterizes quantitatively the contribution of individual variables to the corresponding
factors. The ranking of the factors is characterized by the amount of variances they
explain.12 However, the difficulties in interpreting the components may sometimes be
observed because of the lack of information about their meaning in either a physical
or chemical sense. Moreover, in the process of reducing numerous original variables
to a few orthogonal factors or components (mostly 3), some information is omitted.11
However, this unexplained variance can be taken into account, resulting in an improve-
ment in the reliability of this approach.13
Cluster analysis consists of various techniques.14 The objects are grouped so that
“similar” objects fall into the same class. Objects in one cluster should be homog-
enously distributed relative to some characteristics explaining within cluster prop-
erties, and they should also be clearly separated from other object score groupings.11
Cluster analysis assigns particular variables with similar courses to clusters of
variables.12 Clustering techniques are divided into two basic groups, namely hierar-
chic and nonhierarchic methods. It is important to decide which clustering procedure
is the most suitable. According to Sharma,14 Wards’s minimum variance technique
was superior because it gives a larger amount of correctly classified observations as
compared to most other methods, although it is not always better than average linkage
clustering. This finding was supported by Massart and Kaufman.15 One of the major
difficulties and criticisms of the technique is defining objectivity.11,16 Clustering
always produces some clusters even if the results are completely random. Most
methods are biased towards finding spherically and elliptically shaped clusters. When
clusters with another shape are obtained, these are not always found to result in a
loss of information and sometimes even misleading data.5,16,17
Discriminant analysis makes possible the determination of variations between
groups of nominal elements characterized by numerical variables. Discriminant
2234_C004.fm Page 71 Wednesday, October 25, 2006 2:54 PM
functions (DFs) that depend linearly on the element concentration studied are
formed. The numerical values are the coordinates of the locations in a plane described
by the two discriminant functions.12 The particular endmember analysis (EA) is
described by Renner et al.18 An objective definition of external endmembers in the
analysis of mixtures was presented by Full et al.19 In general, there are indefinitely
many sets of extreme points for a particular set of exact mixtures. However, since
associations between elements of a geochemical dataset are not arbitrary, a conser-
vative strategy is to seek extreme compositions (datapoints) that are geometrically
close to the data and therefore close to observed reality.19–21 A detailed examination
of the multivariate analysis was performed by Renner21–24 and Renner et al.25
Multivariate analysis has been applied to estimate food quality in view of its
quantitative characteristic of mineral composition. They have been useful in processing
elemental data of abiotic components, e.g., atmospheric deposits and marine aero-
sols,26–28 marine suspended matter,29 bottom sediments,18,30–36 and iron–manganese
concretions.37 To biotic compartments, categorized chemometrically in relation to their
elemental composition, belong seaweeds,12,38 plankton,26 mussels,12,39–41 fish,41–43 and
sea mammals.44–47
2.9
Co Mn
Cu
1.9 Ni
0.9
Component 2
Cr
Weight
-0.1
-1.1 Factory
Zn
-2.1
Fe Country
-3.1
-4 -2 0 2 4
Component 1
FIGURE 4.1 Biplot defined by PC1 and PC2 (black squares Type I, open squares Type II,
grey squares Type III). (Adapted from Brito, G. et al., Differentiation of heat-treated pork
liver pastes according to their metal content using multivariate data analysis, Eur. Food Res.
Technol., 218, 584, 2004. With permission.)
11
Ireland
Nitrogen isotope composition (δ13N ‰)
10 Other European
Brazil
USA
9
4
-28 -24 -20 -16 -12 -8
Carbon isotope composition (δ13C ‰)
FIGURE 4.2 C and N stable isotope ratios in defatted bovine muscle tissue (International
study). (Adapted from Schmidt, O. et al., Inferring the origin and dietary history of beef from
C, N, and S stable isotope ratio analysis, Elsevier, Food Chem., 91, 545, 2005. With permission.)
4.2.2 FISH
The application of PCA and FA to the data matrix (Ca, Cu, Fe, K, Mg, Na, and Zn
determined in the muscle samples of the fish Chromis limbatus by Flame (F)-AAS
and Graphite Furnace (GF)-AAS was able to differentiate between two groups of
elements and between object samples belonging to different seasons. This distribution
2234_C004.fm Page 73 Wednesday, October 25, 2006 2:54 PM
pattern was confirmed by CA (k- nearest neighbors method, KNN).50 Szefer et al.42
have reported multivariate distribution of loadings such as Hg, Cd, Pb, Cu, and Zn in
muscle and hepatic samples of perch from the Pomeranian Bay, southern Baltic.
Concentrations of the metals were analyzed by F-AAS and the data obtained processed
by means of FA. A biplot of the object scores shows a grouping of the muscle samples
(Figure 4.3A). Seasonal differences, similarly to hepatic objects (Figure 4.4A), are
also clearly visualized. Muscle samples corresponding to the summer season are
separated from those attributable to winter; however age-related differences (Figure
4.3B) show no such regular distribution pattern as in the case of hepatic samples
(Figure 4.4B). As can be seen in the distribution pattern of loadings (Figure 4.3C), the
winter muscle samples are generally loaded with Cd and Pb, whereas both muscle Zn
and Cu are mainly determinants of summer objects.
PCA has been a useful method for processing data concerning concentration of
chemical elements (Al, As, B, Ca, Cd, Cu, Fe, Li, Mg, Mn, Pb, Rb, Se, Si, V, Zn)
determined by ICP-MS in the yellowtail flounder.43 As can be seen in Figure 4.5A,
muscle scores (Numbers 1–8) described by the lower values of PC1 are distinctly
isolated from hepatic scores (Numbers 15–20) identified by higher PC1 values. To
elements responsible for such clustering belong Ca and Fe, Mn, Cd, Cu, and Se,
respectively (Figure 4.5B). PC2 (Figure 4.5A) differentiates muscle scores of off-
shore fish (Numbers 1–6 with higher PC2 values) from those corresponding to
inshore flounder (Numbers. 7 and 8 with lower PC2 values). On the other hand,
hepatic scores (with higher PC2 values) attributable to males are distinguished from
the remaining, e.g., females (with lower PC2 values). The distribution of the loadings
(Figure 4.5B) indicates that muscle Ca is the main identifier of inshore flounder
(low Ev2), whereas hepatic Cu is attributable to males. According to Hellou et al.,43
an increase in the concentration of Al, Ca, Li, and Pb is registered between the
muscle of inshore and offshore fish (two times greater than mean concentration and
above the offshore concentration range).
4.2.3 SEAFOOD
PCA has been successfully applied in the analytical evaluation of the degree of
seafood pollution by toxic trace elements. Popham and D’Auria39 have used PCA
for deciding if blue mussels have been collected from the coastal waters of British
Columbia, polluted with trace metals such as Pb, Zn, Cu, Mn, and Fe. These metals
were determined by X-ray energy spectroscopy (XES). The authors identified areas
in which mussels contained very high levels of tissue heavy metals reflecting indus-
trial pollution of the ambient water. An interesting aspect of their study is that it
was possible to identify regions characterized by less Zn and Pb pollution or a much
higher extent in relation to the reference area. These areas have been identified in
spite of the fact that specimens of the mussels analyzed were different in size (age)
and were collected in different times of the year.
In order to characterize and differentiate polluted and unpolluted edible mussels
taken from the waters of the Adriatic Sea, two multivariate techniques, i.e., LDA
and LPCA (linear principal component analysis), have been successfully applied by
Favretto et al.51 after the determination of Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg, and Pb
2234_C004.fm Page 74 Wednesday, October 25, 2006 2:54 PM
4.5
autumn
spring A
3.5 winter
summer
2.5
1.5
F2
0.5
-0.5
-1.5
-2.5
-3 -2 -1 0 1 2 3 4 5
F1
4.5
age class 1
age class 2
B
3.5
age class 3
2.5
1.5
F2
0.5
-0.5
-1.5
-2.5
-3 -2 -1 0 1 2 3 4 5
F1
1.2
1.0
Cd C
0.8
0.6 Pb
0.4
F2
Zn
0.2
Hg
0.0
Cu
-0.2
-0.4
-0.6 -0.4 -0.2 -0.0 0.2 0.4 0.6 0.8 1.0
F1
FIGURE 4.3 Biplot of scores showing seasonal (A) and age (B) variations of concentrations
of trace metals (C) in the muscle of Perca fluviatilis from the Pomeranian Bay and Szczecin
Lagoon, Baltic Sea. (Adapted from Szefer, P. et al., Distribution and relationships of mercury,
lead, cadmium, copper and zinc in perch (Perca fluviatilis) from the Pomeranian Bay and
Szczecin Lagoon, southern Baltic, Elsevier, Food Chem., 81, 73, 2003. With permission.)
4
autumn A
3 spring
winter
2 summer
F2
0
-1
-2
-2.5 -1.5 -0.5 0.5 1.5 2.5 3.5
F1
4
age class 1 B
3 age class 2
age class 3
2
1
F2
0
-1
-2
-2.5 -1.5 -0.5 0.5 1.5 2.5 3.5
F1
0.9
Cd C
0.8
0.7 Cu
0.6
0.5
F2
0.4 Pb
0.3 Zn
0.2
0.1
-1.0 -0.6 -0.2 0.2 0.6 1.0
F1
FIGURE 4.4 Biplot of scores showing seasonal (A) and age (B) variations of concentrations
of trace metals (C) in the liver of Perca fluviatilis from the Pomeranian Bay and Szczecin
Lagoon, Baltic Sea. (Adapted from Szefer, P. et al., Distribution and relationships of mercury,
lead, cadmium, copper and zinc in perch (Perca fluviatilis) from the Pomeranian Bay and
Szczecin Lagoon, southern Baltic, Elsevier, Food Chem., 81, 73, 2003. With permission.)
noncontrolled factors during the period of harvest, packing, transport, etc., affect-
ing the quality of the seafood studied. The simplified algorithm for potential
curves permitted classifying of mussel groups and a simple understanding of
quality control in commercial fresh and frozen products.52
Bechmann et al.53 have reported spatial-related trends of metal concentrations
in edible mussels from Limfjord, Denmark. High-resolution inductively coupled
plasma–mass spectrometry (HR-ICP-MS) was used for the determination of metals
such as Ba, Cd, Co, Cr, Cu, Ga, Ni, Pb, Rb, and V in the soft tissue of blue mussel
(Mytilus edulis). PCA appeared to be a useful technique in cases when a decision
had to be made regarding which regions were appropriate for mussel fishery. Figure
4.7A differentiates mussel scores with respect to their size and location of sampling
2234_C004.fm Page 76 Wednesday, October 25, 2006 2:54 PM
4
14 A
12
3
13
1
2
PC2
1816
1 17
0
24 11 19
5 18
-1 3 9
20
-2 7 10
6
8
-3
-3 -2 1 0 1 2 3 4 5 6 7
PC1
0.2 Pb B
Zn
Bi Cu
Se
0
SiV Fe
MnCd
Ev2
-0.2
U As
Al
-0.4 Ca
Mg
Pb
-0.2 0.0 0.2 0.4
Ev1
FIGURE 4.5 Biplot of distribution of scores (A) and the concentration of 16 elements (B) in
the tissues of yellowtail flounder (Pleuronectes ferruginea). Numbers 1–6 represent the muscle
of offshore fish, 7 and 8 represent the muscle of inshore flounder, 9–14 represent the gonads, and
15–20 the livers. The first three numbers of each subset are due to males (pc, principal component).
(Adapted from Hellou, J. et al., Distribution of elements in tissues of yellowtail flounder Pleu-
ronectes ferruginea, Elsevier, Sci. Total Environ., 181, 137, 1996. With permission.)
EIGENVECTOR 2
Mn
2 Fe
Co
Cu Ni
Hg
Pb
1 Cd
Zn
EIGENVECTOR 1
-3 -2 -1 1 2 3
-1
-2
-3
FIGURE 4.6 Eigenvector projection of component scores of mussels: circles, polluted mus-
sels; triangles, unpolluted mussels. Scores were calculated from the unrotated matrix of
correlations between variable and principal components. (Adapted from Favretto, L. and
Favretto, L.G., Principal component analysis and pollution by trace elements in a mussel
survey, John Wiley & Sons, J. Chemometrics, 3, 301, 1988. With permission.)
statistically the metal data (Cd, Cu, Fe, Mn, Ni, Zn) for the soft tissue of Cerasto-
derma glaucum from four geographical regions, i.e., the Gulf of Gdansk ´ (Baltic
Sea), Marennes–Oleron Bay, Arcachon Bay (French Atlantic coast), and Embiez
Islands (Mediterranean Sea). It was shown from comparison between the distribution
of the object scores and the loading vector direction (Figure 4.8) that mainly Mn
2234_C004.fm Page 78 Wednesday, October 25, 2006 2:54 PM
A
3 PC2 Scores
•F•G
••FF• F
2 •C
••F
•F• F •FF
•••FFF • CC
•F
•F•F
•F
•F •C •C
•F•G •C
•B•G
•B
•B
•B •G •C
1 •B
•B •G •C C•
•B
•B •G
•C
•B
•B•G •C
•G•G •G •C
•G
•G •G •C • C• C • C
0 •G •G • C• C• C
•G
•G •A
•A•A
•G•A •A
•A
•A
•G •A
•A
•A •D
•D
•D
-1 • D •D
•D •D • D • D
•D•D
•D •E • E
• D• E E •••E
••DD••DE• •E
•E
••D
E E • C• C
• C• C • C
• D• D •D •E D
•E
•E
•E • E •E
•E
-2 •E•E • E PC1
-4 -2 0 2 4 6 8
B
0.8 PC2 X-loadings
• Cd
0.6
• Cu
0.4
• Rb
0.2
• Ni
0.0
• Co
• Ba• Cr•Pb
-0.2
• V•Ga
-0.4
-0.6 PC1
-0.2 -0.1 0 0.1 0.2 0.3 0.4
FIGURE 4.7 Scatterplot of scores (A) and loadings (B), i.e., 10 elements (V, Cr, Co, Ni, Cu,
Ga, Rb, Cd, Ba, Pb) for all mussel samples analyzed. The letters A–G correspond to the seven
sampling sites. (Adapted from Bechmann, I.E., Stürup, S., and Kristensen, L.V., High reso-
lution inductively coupled plasma mass spectrometry (HR-ICPMS) determination and mul-
tivariate evaluation of 10 trace elements in mussels from 7 sites in Limfjorden, Denmark,
Springer, Fresenius J. Anal. Chem., 368, 708, 2000. With permission.)
4.7
A
2.7 Fe
PC2
0.7
Cd
Zn
-1.3
Ni
Cu
-3.3 Mn
-2.9 -0.9 1.1 3.1 5.1
PC1
4.7
B
2.7 Fe
PC2
0.7
Cd
Zn
-1.3
Ni
-3.3 Mn Cu
-2.9 -0.9 1.1 3.1 5.1
PC1
FIGURE 4.8 Biplot for object scores of the first two principal vectors of 50 mollusc samples:
A — regional differences are illustrated by clusters of points corresponding to samples from
´ (), Marennes–Oleron Bay (●), Arcachon Bay (), and Embiez Islands
the Gulf of Gdansk
(). Association between principal components (PCI × PC2) and variable (metal) vectors are
also indicated; B — season-dependent variations are illustrated by clusters of points corre-
sponding to samples collected during January — May. These groupings are indicated by
shaded areas. (Adapted from Szefer, P. and Wolowicz,
⁄ M., Occurrence of metals in the cockle
Cerastoderma glaucum from different geographical regions in view of principal component
analysis, SIMO-Mar. Pollut., 64, 253, 1993. With permission.)
7 3 A
2
B 28
6
1 26 27
Factor 1
5 0
-1
4
Factor 1
-2
3 -3
53 -2 -1 0 1
Factor 2
2 3
2 54
1
Yemen Mexico Japan
0 Russia France Spain
Sweden Brazil Holland
Poland S. Korea
-1
-6 -5 -4 -3 -2 -1 0 1 2 3
Factor 2
1.1 0.8 C
0.6 Pb Co Zn
D Pb Cu
• • • Fe Cd • •
0.9 0.4 Cr
• • Cd
•
Factor 1
0.2 • Mn
•
0.7 0.0
Zn
-0.2 •
Factor 1
-0.4 Ni Cu
0.5 • •
-0.6
-0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Factor 2
0.3 Co
• Fe
• Cr Mn
0.1 • Ni •
•
-1.1
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4
Factor 2
composition of Mytilus edulis from the Baltic Sea and North Sea, which are inde-
pendent of the presence of trace elements, DA was performed for macroelement
concentrations in the mussel as variables.12 This distribution pattern made it possible
to distinguish Baltic and North Sea locations such as in the case of F. vesiculosus
in spite of different food habits between these two zoobental organisms. Location
groups based on the trace element concentration patterns showed a less distinctive
geographical arrangement in comparison to the location clusters based on macro-
element concentration patterns. This picture suggests modified conditions for the
accumulation of trace elements in M. edulis as in F. vesiculosus compared to the
uptake of macroelements.12 The concentration of 15 elements in the seafood was
determined by F-AAS (Ca, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Zn), GF-AAS (Cd,
Pb), CV-AAS (Hg) and HG-AAS (Se).66 FA made it possible to distinguish different
2234_C004.fm Page 81 Wednesday, October 25, 2006 2:54 PM
4
A
shrimp
3 crab
octopus
2 mussels
squid
lobster
F2
1 surimi
-1
-2
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
F1
1.0
Mn B
0.8
0.6 Fe
•
0.4 • K
• Zn
Cd
•
F2
0.2
0.0
• Se
•Mg•
-0.2 Na
-0.4
• Cu Hg
•• •
Ca
-0.6
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0
F1
FIGURE 4.10 Biplot of the distribution of object scores (A) and loadings (B) in commercially
distributed seafood from different countries such as India, Thailand, Canada, Philippines, New
Zealand, Spain, Norway, and Great Britain. (Adapted from Kwoczek, M. et al., Essential and
toxic elements in seafood available in Poland from different geographical regions, ACS,
J. Agric. Food Chem., 54, 3015, 2006. With permission.)
species of seafood as well as being useful for the identification of elements respon-
sible for the separation of raw seafoods from technologically processed sea products.
For instance, there is discrimination between mussels and octopus with higher values
of F2 and the squids described by intermediate values of F2 (Figure 4.10A). It
appeared that factor F2 is associated with taxonomic groups of the raw seafood
distinguishing mussels, octopuses, squids, and crustaceans (shrimp, lobster, and
crab). In the case of the loadings distribution, F1 achieves the lowest values for Na
corresponding to seafood processed technologically, i.e., Kamaboko crab, Torpedo
shrimp, surimi crab, and coated squid rings, which are clearly distinct from the group
connected with Cd, Fe, Mn, Ca, K, Se, Cu, Mg, Hg, and Zn (Figure 4.10B). The
latter group of elements is ascribed to the scores mostly associated with unprocessed,
raw seafoods (Figure 4.10A), i.e., with higher values of F1. Presumably, a consid-
erable pool of these essential elements reflects a natural elemental composition of
the invertebrates studied. Hence, F1 is connected with the diverse ways in which
some of the studied samples were processed, and some unprocessed. Factor F2
allows us to distinguish metals responsible for grouping object samples (Figure
2234_C004.fm Page 82 Wednesday, October 25, 2006 2:54 PM
4.2.4.2 Cheeses
The results obtained by Brescia et al.69 were evaluated using several chemometric
techniques (PCA, HCA [hierarchical cluster analysis], DA) for the geographical
3
Caserta 11
Foggia
2 6 8
5
10
1
12
2
PC2
0 7
3
14
-1 1 13
-2 4
9
-3
-3.5 -2.5 -1.5 -0.5 0.5 1.5 2.5 3.5
PC1
FIGURE 4.11 Scatterplot of the scores of milk samples from the first two principal components
PC1 and PC2 obtained using analytical data. (Adapted from Brescia, M.A. et al., Characterisation
of the geographical origin of Buffalo milk and mozzarella cheese by means of analytical and
spectroscopic determinations, Elsevier, Food Chem., 89, 139, 2005. With permission.)
2234_C004.fm Page 83 Wednesday, October 25, 2006 2:54 PM
2.5
87
1.5 Sr
PC3 (14%)
13 REGION
0.5 2C
H Allgau (D)
-0.5 Bretagne (F)
Finland
15
N Savoie (F)
-1.5
Switzerland
-2.5 Vorarlberg (A)
-2.5 -1.5 -0.5 0.5 1.5 2.5
PC1 (53%)
FIGURE 4.12 PCA of parameters δ13C, δ2H, δ15N, and δ87Sr. Separation of the groups
“Finland,” “Savoie,” and “Bretagne.” (Adapted from Pillonel, L. et al., Stable isotope ratios,
major, trace and radioactive elements in emmental cheeses of different origins, Elsevier,
Lebensm.-Wiss. u.-Technol., 36, 615, 2003. With permission.)
classification of buffalo milk mozzarella cheeses produced in the Foggia and Caserta
provinces, southern Italy. It is pointed out that the coupling of the isotopic ratios
data with NMR data gave satisfactory results concerning geographical origin distin-
guishing. A variety of 20 emmenthal cheeses from six regions of four European
countries (Germany, France, Austria, Switzerland) have been analyzed for concen-
trations of radioactive elements (90Sr, 234U, 238U), stable isotope ratios (13C/12C,
15N/14N, 18O/16O, 2H/1H, 87Sr/86Sr), major elements (Ca, K, Mg, Na) and trace ele-
ments (Cu, I, Mn, Mo). Based on the stable isotope ratios and major or trace
elements, it was possible to distinguish geographically distinct areas.70 PCA of the
data such as δ13C, δ15N, δ2H and δ87Sr, as well as Ca, Cu, Mo, I, Mn, Na and Zn,
played the most important role in the separation of clusters attributable to the
geographically different regions (Figure 4.12). However, most of these parameters
are affected by seasonal conditions because of variations in forage composition.70
Chemometric studies of goat’s cheeses based on their mineral composition and
concentration of fat, protein, pH, dry matter, and percentage of fat have been
reported.71 Ca, Cu, Fe, K, Mg, Na, Se, and Zn were determined by AAS. FA and
DA appeared to be useful in the classification of samples with respect to their type
(Figure 4.13A), season of production (Figure 4.13, B and C), and the type of goat’s
diet, although unsatisfactory separation was obtained in the case of criterion such
as the region of production.
4.2.5 RICE
Isotopic (δ18O, δ13C) and elemental (B, Se, Rb, W, Gd, Ho, Mg) analyses using
Isotope Ratio Mass Spectrometry (IRMS) and inductively coupled plasma mass
spectrometry (ICP-MS), respectively, have been applied to determine the geograph-
ical origin of premium long-grain rice.72 The maximum discrimination between rice
samples from regions such as America, Europe, and India/Pakistan was clearly
identified by canonical discriminant analysis (CDA) (Figure 4.14).
2234_C004.fm Page 84 Wednesday, October 25, 2006 2:54 PM
3 A
Factor 1
0
-1
-2 Type of cheese
Semi-hard
Fresh
-3
-3 -2 -1 0 1 2 3 4 5
Factor 2
Spring 01 B
Autumn 00
4 Winter 00
Summer 99
2
Function 2
-2
-4 -2 0 2 4 6
Function 1
C
2
Function 2
-2
Spring 01
Autumn 00
Winter 00
Summer 99
-4 -2 0 2 4 6
Function 1
FIGURE 4.13 Scatter diagram of sample scores representing the first two factors differentiating
the type of cheese (A); the first two-function discriminants are differentiated by the season of
production of the fresh cheese samples (B) and the semi-hard cheese samples (C). (Adapted
from Puerto, P. et al., Chemometric studies of fresh and semi-hard goats’ cheeses produced in
Tenerife (Canary Islands), Elsevier, Food Chem., 88, 361, 2004. With permission.)
2234_C004.fm Page 85 Wednesday, October 25, 2006 2:54 PM
2
Function 2
0 Country of Origin
Group 3
2 USA
Group 2
-4 Europe
Group 1
-6
-4 -2 0 2 4 6 8 PAKISTAN
Function 1
4.2.6 VEGETABLES
Chemomertic techniques appeared to be very useful in assessing the quality of
different vegetables. For instance, 210 samples of onion and 190 samples of pea
have been analyzed by HR–ICP-MS for 63 chemical elements (Ag, Al, Au, B, Ba,
Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, In, Ir,
K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, P, Pb, Pr, Pt, Rb, Re, Ru, S, Sb, Sc, Si,
Sm, Sn, Sr, Tb, Te, Th, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr) and 55 chemical elements
(Ag, Al, Au, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge,
Hf, Ho, Ir, La, Lu, Mn, Mo, Nb, Nd, P, Pb, Pd, Pr, Pt, Re, Rh, Sb, Sc, Se, Si, Sm,
Sr, Ta, Tb, Te, Th, Ti, Tl, Tm, U, V, Y, Yb, Zn, Zr), respectively.73 PCA split up the
sites into two groups with respect to the cultivation methods for onions and peas,
which affected the concentrations of some elements in the crops. Comparative
statistical tests of element concentrations identified crop areas with organically and
conventionally cultivated vegetables based on statistically different (p < 0.05) dis-
tribution pattern between Ca, B, Ba, Be, Bi, Co, Cu, Dy, Fe, Gd, Ge, La, Lu, Mo,
Nd, Rb, Sc, Sr, Ti, U, and Y in onions and P, Gd, and Ti in peas (see, for instance,
Figure 4.15). PCA has been also successfully applied for identification of tomato
fruits cultivated in three different substrate systems.74 Based on the different ele-
mental composition of fruits (namely Ca, Cd, Fe, Mn, Mo, Na, Ni, Sr, Zn; and Ca,
Cd, Fe, Mn, Na, Ni, Sr, Zn, Cu, K, Mg, P, Sn, and V), it was possible to identify
crops from the different substrates and collected at three harvest times, respectively
(Figure 4.16). According to Gundersen et al.,74 the concentrations of Ca, Cd, Fe,
Mn, Mo, Na, Ni, Sr, and Zn were significantly different (p < 0.05) for tomato fruits
cultivated on different substrates. The use of PCA made it possible to distinguish
the two groups attributable to soil-grown fruits and rockwool-grown fruits with the
2234_C004.fm Page 86 Wednesday, October 25, 2006 2:54 PM
PC3 Scores A
5 HE
HE
FE HE
IE
IE
KE GE HE IE
HE AEE
KE KE GE IE FEIE ME XC
LE JE HE FE AEE XC
KEKE HE LE IE HE XC
LE LE JEIEJE AEE AEE IE YC RC XC XC
LE GE FE FEJE IE XC RC
GEFE ME AEE YC RC
GE
GE FE MEIE ME PC XC
LE LE AEEXC RC
ME AEE PC RC
GE ME FE AEE
0 GE YC
YC OCPC XCRC VC
ME YCOCVC PC
SCZE PCXCRC
YC OC PC SC VC PC
OC OC SCZE
YC
SCSCQC QC YC VC
SC ZEVC UC PC VC
ZE
SC
OC SC QCUC UC UC VC
OCOC SC
OC ZE OC QC VC QC
UC VC
OC SC TC QC
OC QC QC
OC UC QC UC
OC OC OC UC QC
UC
OC TC
-5 PC1
-6 -4 -2 0 2 4 6 8 10 12
0.3
Rb
Bi Cu
Dy
0.2
Gd Fe
W
Be Mg MnSnNb
V
Zn Sm Ba
0.1 Lu Ag Ho Pb Cr La
Zr S Ga Co Ge
Mo Tl Cs K Th Pr
Nd
0 Pt Re Tm Er Ir Cd
Yb
Hf InSe Ru Al
Tb Y
Te P Sb U
B Ca
-0.1 Eu Sc
Si Au Ti
Ce
Na
-0.2 Sr
-0.3
Li PC1
-0.10 -0.05 0 0.05 0.10 0.15 0.20 0.25 0.30
FIGURE 4.15 Biplot of scores (A) and loadings (B) for the first and third principal compo-
nent of the PCA model for individual onion samples. Sites with second letter E are organic
and sites with second letter C are conventional. (Adapted from Gundersen, V. et al., Com-
parative investigation of concentrations of major and trace elements in organic and conven-
tional Danish agricultural crops. 1. Onions (Allium cepa Hysam) and Peas (Pisum sativum
Ping Pong), ACS, J. Agric. Food Chem., 48, 6094, 2000. With permission.)
2234_C004.fm Page 87 Wednesday, October 25, 2006 2:54 PM
PC2 Scores A
H
N
S N H
NNH N H
H
S N HN N H
S
N HH H
SSS SS S H H
S S H
HH
SS N N H
S SSS H NN H
SS
SS N
N N
H H
H
N N
N
N N
N
N
PC1
-5 -4 -3 -2 -1 0 1 2 3 4
PC2 X-loadings B
0.5
K
S P Mg
Zn Mn
Ca Na
Ni
Fe
Ca Cd V Pb
Cr Mo
Sr Sn
0
PC1
-0.5 -0.4 -0.3 -0.2 -0.1 0 0.1 0.2 0.3 0.4
FIGURE 4.16 Biplot of scores (A) and loadings (B) for the first and second principal
component of the PCA model for individual tomatoes samples. The letters in the plot refer
to the treatment, (i.e., S, soil; N, rockwool with normal electrical conductivity (EC); H,
rockwool with high EC treatment). (Adapted from Gundersen, V., McCall, D., and Bechmann,
I.E., Comparison of major and trace element concentrations in Danish greenhouse tomatoes
(Lycopersicon esculentum Cv. Aromata F1) cultivated in different substrates, J. Agric. Food
Chem., 49, 3808, 2001. With permission.)
two different nutrient solutions. Data for Ca, Cu, Fe, K, Mg, Mn, Na, Rb, and Zn
(determined by AAS) in eight potato cultivars harvested in Tenerife (Spain) have
been processed with FA and CA.75 Traditionally and recently imported potatoes
(Solanum tuberosum) were clearly separated by the application of CA. FA is the
appropriate technique to identify potato samples according to the location of the
farm (Figure 4.17A) and irrigation procedure (Figure 4.17B). It was also possible
2234_C004.fm Page 88 Wednesday, October 25, 2006 2:54 PM
3
A
2
Factor 1
0
-1
Location of farm
-2 South
-3 North
-2 -1 0 1 2 3 4
Factor 3
3
B
2
1
Factor 1
-1
Irrigation procedure
-2 Irrigation
-3 Non-irrigation
-2 -1 0 1 2 3 4
Factor 3
3 C
2
Factor 1
0
S.tuberosum
-1
Recently imported
-2 Traditional
-2 -1 -1 0 1 1 2 2
Factor 2
FIGURE 4.17 Scores of the potato samples on axes representing the two factors, differenti-
ated by location of farms (A), irrigation procedure used (B), and recently imported and
traditional vegetables (C). (Adapted from Rivero, R.C. et al., Mineral concentrations in
cultivars of potatoes, Elsevier, Food Chem., 83, 247, 2003. With permission.)
25
15
10 1 2 3 4
NNNSNNNNNNNSNNNNNNNNNNNNNNNNNNNNNNNNSNNNNNNNNNNNNNNSNNNNSNSSNSNNSSSSSSSSSS
FIGURE 4.18 Dendrogram of the cluster analysis. (Adapted from Rivero, R.C. et al., Mineral
concentrations in cultivars of potatoes, Elsevier, Food Chem., 83, 247, 2003. With permission.)
0.0
0.1
0.2
Similarity 0.3
0.4
0.5
A B C D
0.6
0.7
0.8
0.9
1.0 DDDDDDDDDDDDDDDDDDDDDDDDDXXXXXXXXXXXXXXDDDWWWWWWWWWWWWWWWWDDDDWWWWWWWWWWWDDDD
FIGURE 4.19 Dendrogram of cluster analysis. Sample codes: D, Galician CBOQ; W, Gali-
cian non-CBOQ; X, non-Galician non-CBOQ. (Adapted from Padín, P.M. et al., Character-
ization of Galician (N.W. Spain) quality brand potatoes: a comparison study of several pattern
recognition techniques, Analyst, 126, 97, 2001. With permission.)
grocery chains in four geographical regions/cities in Sweden during four seasons of
one year. Data on the following descriptors were obtained from the samples: Ca,
Fe, K, N, Na, and P, as well as moisture, ash, and fat. A combination of PCA and
analysis of variance (ANOVA) were used to explain the influence of some factors,
i.e., geographic region, season, and store chain. For most vegetables, the seasonal
variations were dominant, especially for tomato. In the case of animal products, the
spatial differences appeared to have a greater contribution, and for hot dog it was
the dominant factor. Pork, egg, and chicken exhibited somewhat pronounced influ-
ence of the different store chains. Torelm et al.80 have also interpreted variations in
the chemical elements in dishes prepared in ordinary households. PCA appeared to
be useful for finding patterns in the manner of preparing dishes; the dominant
variation pattern was associated with fat content, although enhanced by the closure
effect (Figure 4.20).
4.2.8 HONEY
Correspondence factor analysis (CFA), CA, and hierarchical cluster analysis (HCA)
have been applied to the interpretation of data for trace elements in 86 honey samples
sold in France. Concentrations of Ag, Al, Ca, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Mn,
Mo, Ni, P, Pb, S, and Zn were determined by ICP-AES.82 Crude relationships were
obtained between the distribution pattern of chemical elements in the honey samples
and their botanical provenance. Based on PC data, it was possible to record the
influence of metallic and nonmetallic elements on the factorial distribution of par-
ticular object samples in biplot PC1–PC2 (Figure 4.21). For instance, scores num-
bered 63 and 73, and 19 and 56, reflected the highest levels of Al and Fe respectively,
implying that these elements are responsible for contamination of the honey samples
located in the bottom and upper right part of the two-dimensional scatterplot. Accord-
ing to Devillers et al.,82 honeys originating from caducous trees appear to be less
2234_C004.fm Page 91 Wednesday, October 25, 2006 2:54 PM
A
4
•
2
• •9 • 7 •
8 3
PC2
10 • •
5 6
• 1
•
•
Scores PC1
B
• Na
Ash
•
PC2
Fat Fe
• • N
•
Ca • •K• P
Loadings PC1
PC2
56
5
69 7
17
11
23
27 5930
28 2
29
5424
47
45
44
82 19
52
558 18
46 1
76 253
1877 16
12 8 48 50 PC1
75 86 35 76
72 9 10 4 45 25
81 14 37
22
13
26
61
66
3
32 3964
38 55
40
49 44
43
69 62 71
24
71 65 7036
68
33 67
73
44
5
-6 5
63
-6
B
PC2
Fe
AgCr
P Cd Zn C
Ca PC1
Mg
Mo Cu
Mn S
Ni
2.6 Co
-2 2.6
-2 Al A
FIGURE 4.21 PC1-PC2 factorial maps for the 15 elements (A) and 86 honey samples (B).
Graph of the eigenvalues (C). (Adapted from Devillers J. et al., Chemometrical analysis of
18 metallic and nonmetallic elements found in honeys sold in France, ACS, J. Agric. Food
Chem., 50, 5998, 2002. With permission.)
(Figure 4.23). According to the authors, the mineral content was too low to achieve
much differentiation of the five unifloral honey classes considered, except the above
mentioned Eucalyptus and honeydew. In order to improve the ability for distinguish-
ing these object categories, it is recommended that other parameters be used,
2234_C004.fm Page 93 Wednesday, October 25, 2006 2:54 PM
2
4.4
2
3.4 2
22 2
EIGENVECTOR 3
2.4 2 222
2 1 11
2 22 1 1 1 1
1.4 2
222 1121 1
1 1 1 1
0.4
1 11
1 2.8
1
-0.6 1 0.8
2
R
O
-1.2
CT
-1.6
VE
-2.5 -3.2
-0.5
EN
1.5 3.5 -5.2
G
5.5
EI
7.5
EIGENVECTOR 1
FIGURE 4.22 Eigenvector projection of honey samples. 1: natural Galician honey, 2: pro-
cessed non-Galician honey. (Adapted from Latorre, M.J. et al., Chemometric classification
of honeys according to their type: II. Metal content data, Elsevier, Food Chem., 66, 263, 1999.
With permission.)
4.2.9 TEA
Based on measurements of different physical and chemical parameters, and after
applying PCA and especially LDA, Fernández et al.87 have concluded that the profiles
of metals studied (Al, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr, Zn determined by ICP-
AES) are a good descriptor for distinguishing the common types of tea beverages
such as infusions, instant teas, and soft drinks (Figure 4.24). Statistical comparison
shows that infusions prepared with black teas are enriched in Mn, Mg, Al, Ca, and
K, and that there are significant differences between the mineral composition of
infusions prepared with different extraction times. Moreda-Piñeiro et al.88 have
applied PCA, CA, LDA, and SIMCA for the classification of teas according to their
region of origin based on data for 17 chemical elements determined by ICP-AES
and ICP-MS. Descriptors such as Al, Ba, Ca, Cd, Co, Cr, Cu, Cs, Mg, Mn, Ni, Pb,
Rb, Sr, Ti, V, and Zn have been determined in 85 tea samples from various Asian
2234_C004.fm Page 94 Wednesday, October 25, 2006 2:54 PM
4 A
2
DF 2
-2
-4
-6
-4 -2 0 2 4 6 8 10 12
DF 1
2 B
1
0
Factor 2
-1
-2
-3
-4
-1.5 -0.5 0.5 1.5 2.5 3.5 4.5
Factor 1
FIGURE 4.23 Linear discriminant analysis (A) and principal component analysis (B) of some
Moroccan unifloral honeys, as shown by a scatter diagram representing the projection of the point
of each sample on the plane formed by the first two discriminant functions (A) and the first two
factors (B): open circles, Eucalyptus; diamonds, Citrus; squares, Lythrum; full circles, Apiacae;
triangles, honeydew. (Adapted from Terrab, A. et al., Mineral content and electrical conductivity
of the honeys produced in Northwest Marocco and their contribution to the characterization of
unifloral honeys, J. Sci. Food Agric., 83, 637, 2003. With permission.)
and African countries, as well as commercial blends and samples of unknown origin.
The results obtained indicate that the differentiation and classification of tea samples
from Africa and Asia (Figure 4.25) as well as identification of teas from China and
India and Sri Lanka, in contrast to samples from Malaysia, Bangladesh, Japan, and
Papua New Guinea, is possible (Figure 4.26). The authors concluded that it is also
possible to assign unknown samples and tea blends with respect to their geographic
origin. Marcos et al.89 used the concentrations of Al, Ba, Ca, Cu, Fe, La, Mg, Mn,
Sr, Ti, Zn (ICP-AES), and Cd, Co, Cr, Cs, Hg, La, Li, Nd, Ni, Pb, Pr, Rb, Se, Sn,
Ti, V and Zr (ICP-MS) to achieve a distinction between African and Asian as well
as between Chinese and other Asian teas using PCA (Figure 4.27A) and LDA (Figure
4.27B) methods. According to Herrador and González,90 eight metals such as Al,
Ca, Cu, Ba, Mg, Mn, K, and Zn determined by ICP-AES in 48 samples of commercial
tea are good descriptors for the differentiation of green, black, and Oolong teas
(Figure 4.28). Four statistical techniques, namely, PCA, CA, LDA, and ANN, have
2234_C004.fm Page 95 Wednesday, October 25, 2006 2:54 PM
0
DF2
-2
-4
-6
-8
-10
-6 -4 -2 0 2 4 6 8 10 12
DF1
INFUSIONS TEA SOFT DRINKS
INSTANT TEAS (100%) INSTANT TEAS (<2%)
FIGURE 4.24 Scatterplot of tea beverages in the space of the two first discriminant functions.
(Adapted from Fernández, P.L. et al., Multi-element analysis of tea beverages by inductively
coupled plasma atomic emission spectrometry, Elsevier, Food Chem., 76, 483, 2002. With per-
mission.)
1200
1000
800
Distance
600
400
200
0
BBBBBBBBBBBBBBBBBBBBBBABABBAABAAAAAAAABBABBBAAAABBBB
FIGURE 4.25 Dendrogram of cluster analysis. (A) African tea samples; (B) Asian tea sam-
ples. (Adapted from Moreda-Piñeiro, A., Fisher, A., and Hill, S.J., The classification of tea
according to region of origin using pattern recognition techniques and trace metal data,
Elsevier, J. Food Compos. Anal., 16, 195, 2003. With permission.)
2234_C004.fm Page 96 Wednesday, October 25, 2006 2:54 PM
6.4
China
India
Discriminant Function 2
4.4 Sri Lanka
Centroids
2.4
0.4
-1.6
-3.6
-6 -3 0 3 6 9
Discriminant Function 1
FIGURE 4.26 Projections of tea samples from China, India, and Sri Lanka in the space formed
by the two discriminant functions after LDA. (Adapted from Moreda-Piñeiro, A., Fisher, A., and
Hill, S.J., The classification of tea according to region of origin using pattern recognition tech-
niques and trace metal data, Elsevier, J. Food Compos. Anal., 16, 195, 2003. With permission.)
been applied successfully, with ANN being able to achieve a prediction ability of
~95% (Figure 4.29).
4.2.10 COFFEE
Recently, there has been an increasing practice of selling coffees based on their
varietal and geographic origin.91–94 In order to characterize coffee varieties (Arabica
and Robusta, roasted and green coffees from Brazil, Salvador, Costa Rica, Colombia,
Honduras, Nicaragua, Guatemala, Cameroon, Uganda, Thailand, Indonesia, Viet-
nam, Ivory Coast) and resolve coffee mixtures, several authors have applied PCA,
CA, and LDA, using as chemical descriptors concentrations of Ba, Ca, Cu, Fe, K,
Mg, Mn, Na, P, Sr, and Zn (determined by ICP-AES) (Figure 4.30). The concentra-
tions of P, Mn, and Cu appeared to be the most discriminating variables. These
statistical techniques are useful in assessing the quality of the coffee product in case
of fraudulent or accidental mislabeling.94 The determination of mineral nutrients and
nonessential metals including Al, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S,
Sb, Sn, and Zn was performed in 21 samples of Brazilian soluble coffee by ICP-
AES.95 The PCA and AHC (agglomerative hierarchical clustering) data indicated
differences in the process of industrial production and factors influencing the culti-
vation of the coffee plant, i.e., the geochemical type of soil, the use of different
fertilizers, and the surrounding conditions. The ICP-AES method has also been used
to determine 18 elements (Al, Ca, Cd, Co, Cu, Cr, Fe, K, Mg, Mn, Mo, Na, Ni, P,
Pb, S, V, Zn) in 160 samples of coffee beans from Indonesia, East Africa, and
Central/South America.96 Applying the PCA, DFA, and NN models revealed signif-
icantly different groupings into the three major geographical regions that the coffee
was grown in (Figure 4.31). The use of NN models and DFA successfully differen-
tiated the coffees with respect to their subregional growing areas (70–86% successful
classification).
Hasswell and Walmsley97 have applied the PCA and CA models to data from
multielemental (Br, Ca, Cr, Cu, Fe, K, Mn, Ni, Rb, Sr, Zn) analysis of coffees using
total reflection X-ray fluorescence analysis (TXRF). Although the coffee samples
2234_C004.fm Page 97 Wednesday, October 25, 2006 2:54 PM
Scores on PC3
+2 +4 Kenyan
0 Indian Teas +13
China Teas
+1 +15
-0.2 +3 +6 +5
+14
-0.4
+8
-0.6 Japanese
-0.8
-1 -0.5 0 0.5 1 1.5
Scores on PC2
8 Assam
Oolong
Jasmine
6
Gunpowder
Zindi
4
Ceylon
Eng. Brekfast
2
Mponda
0
0 500 1000 1500
Distance to K-nearest neighbor
FIGURE 4.27 PCA plot of the ICP-AES data minus La results (A) and dendrogram using
the untreated data (B). (Adapted from Marcos, A. et al., Preliminary study using trace element
concentrations and a chemometrics approach to determine the geographical origin of tea, J.
Anal. At. Spectrom., 13, 521, 1998. With permission.)
were not adequately separated by the above techniques, most of the samples were
grouped with respect to manufacturer rather than country of origin. The use of star
plots has been a valuable means for identifying different coffee samples, and these
plots, showing the importance of each variable in the sample, offer considerable
potential in quality control applications.
According to Grembecka et al.,98 loadings such as Co, Mn, Fe, Cr, Ni, Zn, Cu
Ca, Mg, K, Na, and P (determined by F-AAS) are good descriptors for different
kinds of coffees. Based on the mineral composition of coffee, it was possible to
differentiate chemometrically particular types of coffee by distinguishing Arabica
from Robusta, ground from soluble coffees, and their infusions.
As can be seen in Figure 4.32, F1 distinguishes Arabica group (lower values)
from Arabica group (higher values). The elements responsible for identification of
the latter include Mn and Mg, whereas the former cluster is attributable to Zn, Cu,
Ca, Na, K, P, Fe, and Ni. Figure 4.32 shows that the ground coffee group, described
2234_C004.fm Page 98 Wednesday, October 25, 2006 2:54 PM
CV2 2
-2
Black tea
-4 Green tea
Oolong tea
-4 -2 0 3 4 6
CV1
FIGURE 4.28 Scatterplot of tea samples using CV1 and CV2 as axes. (Adapted from Her-
rador, A.M. and González, A.G., Pattern recognition procedures for differentiation of Green,
Black and Oolong teas according to their metal content from inductively coupled plasma
atomic emission spectrometry, Elsevier, Talanta, 53, 1249, 2001. With permission.)
Input Zn Mn Mg Cu Al Ca Ba K
layer Bias
Hidden
layer Bias
Output
B G O
layer
FIGURE 4.29 Architecture scheme of the multivariate neural network used. (Adapted from
Herrador, A.M. and González, A.G., Pattern recognition procedures for differentiation of
Green, Black and Oolong teas according to their metal content from inductively coupled
plasma atomic emission spectrometry, Elsevier, Talanta, 53, 1249, 2001. With permission.)
by higher values of F2, is well distinguished from the soluble coffee group, described
by lower values of F2, whereas the ground coffee infusion cluster is located in the
middle part of the F2/F1 biplot. Ground coffee and soluble coffee scores are iden-
tified by Fe, Mn, and Zn, and Cd, Na, and Ni, respectively, whereas the other samples
are identified by P, Mg, and K.
Multivariate estimation of the geographical origin of coffees has been performed
successfully by Costa Freitas and Mosca.99
4.2.11 MUSHROOMS
Chemometrical techniques such as CA and DA have been used to analyze the data for
fruiting bodies of mushroom Xerocomus badius (caps and stalks) and the underlying
2234_C004.fm Page 99 Wednesday, October 25, 2006 2:54 PM
Ba K P
Mg Sr
Ca
PC2
Mn Fe
0
Na
Cu
-1 Zn
Arabica
Robusta
-2 -1 0 1 2 3
PC1
FIGURE 4.30 PCA biplot of the first two PCs illustrating distribution of scores and loadings
for coffee samples Arabica and Robusta. (Adapted from Martin, M.J., Pablos, F., Gonzales,
A.G., Characterization of green coffee varieties according to their metal content, Elsevier,
Anal. Chim. Acta, Vol. 358, 177, 1998. With permission.)
soil substratum collected from northeastern Poland.100 In the caps, three first func-
tions explained 75.8% of the total variance. The lowest values of F1 identified caps
samples coming from Trójmiejski Landscape Park, adjacent to the Tricity agglom-
eration (Figure 4.33). The CA data (hierarchical clustering, Ward’s method) for the
sampling sites as objects are shown in Figure 4.34. The dendrogram is built up of
two main clusters. The first one contains two subclusters with the objects from
Ilawskie
⁄ Lake district (C59–C68) and the adjacent area of Morag (C43–C58), the
most similar regions by environmental conditions. A second cluster contains five
subclusters with the objects from Augustowska Forest (C1–C16), Bialowieska
⁄ Forest
(C17–C27), Borecka Forest (C28–C42), Wdzydzki Landscape Park (C69–C83), and
the adjacent area of Kolobrzeg
⁄ (C139–C145). The most similar areas were distin-
guished, e.g., Augustowska and Bialowieska
⁄ Forests are protected areas, deprived of
industrial or urban influences (observed also for Trójmiejski Landscape Park). The
principal factor governing the accumulation of trace elements in mushrooms is
pollution via atmospheric deposition. Apart from the anthropogenic factor, natural
effects such as geochemical composition of bed rock, pH, and granulometric struc-
ture of soil, genetic makeup of fungi, ectomycorrhizal occurrence, and the kind of
undergrowth (mosses, lichens, ferns) have a real influence on some metal concen-
trations in mushrooms.100 The dendrogram from the CA model made it possible to
separate the most similar forest areas with respect to the chemical composition of
both the underlying soil substratum and biomass overgrown with X. badius in the
studied areas.100
2234_C004.fm Page 100 Wednesday, October 25, 2006 2:54 PM
PRIN2
6
u s
u
2 u c c
u u c
u uu u cc
u u cc c k
u u c c cc c
u s r c cc c k k k
u u ucr rrr r r k k k
0 u u c r r rr s s k k k
s s rs reer gg p kk p k
s rs e eggeee ppp k kk
s e eee ee p p k
gs e ee e p
e
-2 s
-4 -2 0 2 4
PRIN1
FIGURE 4.31 PC1 vs. PC2 for chemical profile of elements in roasted coffee beans from
eight different growing regions: r, Costa Rica; c, Colombia; p, Panama; s, Sulawesi; u,
Sumatra; k, Kenya; e, Ethiopia. There are 41 observations that are hidden. (Adapted from
Anderson, K.A. and Smith, B.W., Chemical profiling to differentiate geographic growing
origins of coffee, ACS, J. Agric. Food Chem., 50, 2068, 2002.)
4.2.13 SWEETS
Different cane sugar products (cane sugar plants, crude and syrup juices, molasses,
the end products of consumer sugar) have been analyzed by instrumental neutron
activation analysis (INAA), AAS, and ICP-AES for Al, Ca, Cl, Co, Cr, Fe, Mg, Mn,
Na, Sc (INAA), Cu, Li, P, Sn, V and Zn (ICP-AES), and Pb and As (AAS).103 The
data obtained have been processed by CA applying Euclidean distance as a similarity
coefficient and the group average. It is concluded that particular groups of multielement
2234_C004.fm Page 101 Wednesday, October 25, 2006 2:54 PM
A 3 B
M6 0.8 Zn
2 Cu Mn
M5 M12
M4 D21 M3
0.4 Ca
1 R
M1M11AV K Na
M7 AC
A AB
F2
M20M8 M14
F2
0 D21 M15 M13 M19 0.0
M20 AL M17 P
-1 Ni Mg
M16 M18
-0.4 Fe
D23
-2 Arabica Cr
Robusta -0.8
Mix
-3
-2 -1 0 1 2 -0.9 -0.6 -0.3 0.0 0.3 0.6
F1 F1
2
0.8 Cu
1 Zn
Na
0.4 Fe Mn
0 Cr Ni
F2
F2
0.0 Ca
-1
-0.4 PMg
Ground coffee
-2 Soluble coffee K
Ground coffee infusions -0.8
Soluble coffee infusions
-3
-2 -1 0 1 2 -1.0 -0.9 -0.8 -0.7 -0.6 -0.5
F1 F1
FIGURE 4.32 A biplot of the first two factors visualizing distribution of scores (A) and loadings
(B) for coffee samples available in the Polish market. (Adapted from Grembecka, M. et al.,
Assessment of mineral composition of market coffee and its infusions, 2nd International IUPAC
Symposium on Trace Elements in Food, Brussels, Belgium, 2004, p. 94. With permission.)
A 1.0
B
6 Pb
4 0.5
Cr
2 Ag
Fe Cd
F2
F2
Zn
0 0.0 Co Cu
-2 K NiNa Mn
-4 -0.5
Mg
-6
-1.0
-10 -5 0 5 10 -1.0 -0.5 0.0 0.5 1.0
F1 F1
FIGURE 4.33 A) Scatterplot of object scores of the two first discriminant functions of 166
caps samples; (B) location of loadings for 14 metals in the cap. (Adapted from Malinowska,
E., Szefer, P., and Falandysz, J., Metals bioaccumulation by bay bolete, Xerocomus badius,
from selected sites in Poland, Elsevier, Food Chem., 84, 405, 2004. With permission.)
2234_C004.fm Page 102 Wednesday, October 25, 2006 2:54 PM
80
A
70
60
50
40
30
20
10
0
C-62
C-61
C-67
C-65
C-68
C-66
C-64
C-63
C-60
C-59
C-53
C-57
C-54
C-56
C-52
C-55
C-58
C-51
C-50
C-49
C-47
C-46
C-44
C-48
C-45
C-43
C-142
C-141
C-143
C-145
C-140
C-144
C-139
C-82
C-81
C-80
C-73
C-78
C-77
C-76
C-83
C-74
C-79
C-70
C-75
C-72
C-71
C-69
C-32
C-31
C-30
C-29
C-36
C-35
C-34
C-42
C-38
C-37
C-33
C-40
C-41
C-39
C-28
C-24
C-23
C-21
C-25
C-20
C-19
C-18
C-22
C-27
C-26
C-17
C-12
C-11
C-10
C-13
C-15
C-16
C-9
C-7
C-14
C-6
C-8
C-5
C-4
C-3
C-2
C-1
30
B
25
20
15
10
Na Mg K Zn Cu Ag Cd Co Ca Cr Fe Ni Mn Hg Pb
FIGURE 4.34 Hierarchical dendrogram for 90 objects samples (A) and chemical elements
(B); sampling sites as (1–16) Augustowska Forest, 17–27 Bialowieska
⁄ Forest, 28–42 Borecka
Forest, 43–58 Adjacent area of Morag, 59–68 Ilawskie Lake district, 69–83 Wdzydzki Land-
scape Park, 139–145 Adjacent area of Kolobrzeg.
⁄ (Adapted from Malinowska, E., Szefer, P.,
and Falandysz, J., Metals bioaccumulation by bay bolete, Xerocomus badius, from selected
sites in Poland, Elsevier, Food Chem., 84, 405, 2004. With permission.)
clusters are attributable to specific sample composition, i.e., to their different texture,
structure, and different soil types, reflecting differences or similarities in the processing
steps in five Egyptian sugar-industry factories.103 The dendrogram illustrates such clear
differentiation between the above-mentioned groups (Figure 4.36).
2234_C004.fm Page 103 Wednesday, October 25, 2006 2:54 PM
Principal component 3
2 2
2 2 22 2
22
2 2 2222222222 3 3
222222 33 3
2 1 1 3 3
0 1 1 111 1111111111111111111 11 3 3 3 33 3 3 3 3 3 3 3
1 11
11111 11 1 1
111111 111 31 3 3 3 33 3 3 3333 3 3 3 3 3
3
11111 3 3 3 33
1 31
-2 1
1 1
-4 1
-6
-3.0 -1.0 1.0 3.0 5.0 7.0
Principal component 1
0.5 •Rb
Principal component 3
0.3 • Zn
• Ba•
Mn
• Mo • Al
0.1 •K •P • Mg • Fe • Ca
• Na • Sr
-0.1 • Cu
•B
-0.3
• Co• Ni
-0.5
-0.3 -0.1 0.1 0.3 0.5
Principal component 1
FIGURE 4.35 Scores (A) and loadings (B) of principal components analysis of trace elements
in (1) Australian and (2) Brazilian reconstituted juices, and (3) Australian peel extract.
(Adapted from Simpkins, W.A. et al., Trace elements in Australian orange juice and other
products, Elsevier, Food Chem., 71, 423, 2000. With permission.)
A
b1
b2
b12
b11
b13
b22
b21
b22b
b22a
y
FIGURE 4.36 Cluster analysis of all sugar samples. (Adapted from Awadallah, R.M., Ismail,
S.S., and Mohamed, A.E., Application of multi-element clustering techniques of five Egyptian
industrial sugar products, J. Radioanal. Nucl. Chem., 196, 377, 1995. With permission.)
70
60
50
Mo 40
30
20
600
500
400
300
Ti 200 120
100 110
100 80 90
70 Mg
FIGURE 4.37 Scatter diagram with the three most discriminant variables. () Nebbiolo
d’Alba, (❏) Langhe Nebbiolo, (◆) Barolo, () Barbaresco, (●) Roero. (Adapted from
Marengo, E. and Aceto, M., Statistical investigation of the differences in the distribution of
metals in Nebbiolo-based wines, Food Chem., 81, 621, 2003. With permission.)
in the identification of Spanish wines relative to their geographical origin and the
ripening state of the grapes.
A total of 34 chemical components including metals (Co, Fe, Li, Mn, Na, Ni,
K, Rb, Zn), and volatile and phenolic compounds determined in 39 red wines from
Galicia (northwest Spain) have been categorized into two different geographic
groups based on CA, PCA, LDA, KNN, and SIMCA.113 A satisfactory discriminant
2234_C004.fm Page 105 Wednesday, October 25, 2006 2:54 PM
11
PC2
5
-1
-4
-5 -3 -1 1 3 5 7
PC1
FIGURE 4.38 Scores of the wine samples on the first two principal components (57.5% of
total variance). Codification: (❏) dry wines from El Hierro; (x) dry wines from Lanzarote;
() dry wines from La Palma; (+) sweet wines from Lanzarote; (*) sweet wines from La
Palma. (Adapted from Frías, S. et al., Classification of commercial wines from the Canary
Islands (Spain) by chemometric techniques using metallic contents, Elsevier, Talanta, 59,
335, 2003. With permission.)
500
400
Distance
300
200
100
0
DH
DH
DH
DH
DH
DH
DH
DP
DP
DP
DP
DP
DP
DP
DP
DP
DP
DP
SP
SP
SP
SP
SP
SP
SP
SP
SP
DL
DL
DL
DL
DL
DL
DL
DL
DL
SL
SL
SL
SL
SL
SL
SL
SL
FIGURE 4.39 Dendrogram built with all the variables using Ward’s method and Euclidean
squared distance. Codification: SL = sweet wines from Lanzarote; DL = dry wines from
Lanzarote; DH = dry wines from El Hierro; DP = dry wines from La Palma; SP = sweet
wines from La Palma. (Adapted from Frías, S. et al., Classification of commercial wines from
the Canary Islands (Spain) by chemometric techniques using metallic contents, Elsevier,
Talanta, 59, 335, 2003. With permission.)
model has been presented to differentiate Spanish rosé PDO wines.114 Ethanol and
Ca content appeared to be the most important descriptors. The results reported by
Marengo and Aceto108 have indicated that the elemental composition of Italian wines
could be a fast way to characterize and classify their samples and discriminate
between two high-quality wines and three poor-quality wines.108 PCA applied to the
analytical data (Al, B, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, Sr, Zn, Br, Cl, NH4, NO3,
PO4, SO4, organic acids, alcohol content, acidity, etc.) showed that Italian wines
2234_C004.fm Page 106 Wednesday, October 25, 2006 2:54 PM
could be divided into three groups according to their geographical origin.115 The
analysis of 48 elements, including the rare earths (REE), in 112 samples of Spanish
and English wines by ICP-MS has been performed to identify the region of origin
of wines using CA.116 It was possible to identify the Spanish wines originated from
three regions as well as differentiate between English and Spanish white wines.
Application of PCA to elemental data (Ca, Cu, Fe, K, Mg, Mn, Na, P, Zn) and other
descriptors (organic and sensor) resulted in satisfactory classification of Greek red
wines in terms of their geographical provenance.117 According to Frías et al.,107 a
high degree of sensitivity and specificity has been obtained for classification of
commercial Spanish wines using SIMCA as a modeling multivariate technique. The
metal content (Ca, Cu, Fe, K Mg, Na, Zn, determined by AAS) of Spanish red wines
from the certified denomination of origin (DOC) has been processed with CA and
LDA.118 Sodium was identified as descriptor that best may differentiate wines accord-
ing to the DOCs. González and Peña-Méndez105 have used PCA, CA, BA (biplot
analysis), and FA in the classification and differentiation of must and Canarian wine
samples. It has been pointed out106 that application of DA and especially ANNs are
very useful in differentiating between dry and sweet wines from the Canary Islands
according to their location on the island and the ripening state of grapes. ANNs
appeared to be more useful techniques than LDA and showed 100% recognition and
prediction abilities using only Rb, Sr, and Mn.106 Back propagation artificial neural
network (BP-ANN) has been successfully applied to classify wine samples in six
different regions of Germany based on the concentrations of Al, B, Ba, Ca, Cu, Fe,
K, Mg, Mn, Na, P, Rb, Sr, V, and Zn measured with ICP-OES.119 The ANN data
were compared to those obtained by CA, PCA, the Bayes discrimination method,
and the Fisher discrimination method. Concentrations of different trace and ultratrace
elements (As, Au, Ba, Be, Cd, Co, Cs, Cu, Ni, Re, Pb, Pt, Rb, Sb, Sn, Sr, Te, Ti,
Tl, V, W, Zn, Zr, and 16 REEs) have been determined by ICP-MS in 153 samples
of white, rosé, and red wines from the Canary Islands.120,121 From the FA data, the
23 chemical elements, in contrast to the 16 REEs, presented significant discrimina-
tion according to type of wine and area of origin.121 LDA and BP-ANN are recom-
mended techniques to classify wines with respect to island of origin using the eight
descriptors, i.e., Sr, Rb, Pb, Be, Ba, Tl, Ti, and Au. Similarly promising data have
been obtained for 125 samples of bottled wines from the Tenerife Island (Spain)
based on data of 11 chemical elements (Ca, Cu, Fe, K, Li, Mg, Mn, Na, Rb, Sr, Zn)
using PCA and LDA.122 Benítez et al.123 have conducted a study on the influence of
the Cu, Fe, and Mn content of fine sherry wine on its susceptibility to browning.
Based on CA data, it was concluded that Fe and Mn appeared to influence the
tendency of wine to undergo browning.
The SIMCA technique was used to assess eight denominations of origin (DOs)
of wines bottled in the Canary Islands, based on their contents of trace elements
grouped in three blocks (rare earths, lead isotopes ratios, and other metals such as
As, Ba, Be, Au, Cd, Co, Cs, Cu, Ni, Pb, Pt, Rb, Re, Sb, Sn, Sr, Te, Ti, Tl, V, W, Zn,
Zr determined by ICP-MS).124 The model constructed with all the above element
blocks was taken as the reference model and found to be adequately sensitive and
specific. CA, using the Ward hierarchical clustering method, showed similar results
with respect to the different DOs, and the models were similar with respect to their
2234_C004.fm Page 107 Wednesday, October 25, 2006 2:54 PM
4.2.14.2 Brandies
Concentrations of eight elements, i.e., Ca, Cu, Fe, Mg, Na, Ni, Pb, and Zn, deter-
mined in 35 Scotch Whiskies by GF-AAS, have been processed with CA.132 It was
shown that the fingerprinting of the data cannot be used as criteria to identify regions
of whisky production. However, a simple analysis for Cu concentration could be
used for distinguishing a malt whisky from a blended or grain whisky.
2234_C004.fm Page 108 Wednesday, October 25, 2006 2:54 PM
2.0
PCA
12 months
24 months
A
O60-1 60 months
O60-3 132 months
A24-1
1.0 A24-3
O12-1 O12-3 A24-2
A60-1
Factor 2
O12-2 O132-1
A60-3
O132-3
0.0
O60-2
A60-2
-1.0
O132-3
A12-1
A12-3
A12-2
-2.0
LDA
6
B
2
Root 2
-2
12 months
24 months
-4 60 months
132 months
-15 -10 -5 0 5 10 15 20 25
Root 1
FIGURE 4.40 Principal component analysis (A) and linear discriminant analysis (B) biplots
from the inorganic composition of 18 Marsala samples grouped according to their age (B)
and their age and color (A). The used variables were Cd2+, Cl–, Cu2+, NO3–, Pb2+, SO42–, and
Zn2+ levels. (Adapted from Dugo, G. et al., Determination of some inorganic anions and heavy
metals in D.O.C. Golden and Amber Marsala wines: statistical study of the influence of ageing
period, colour and sugar content, Elsevier, Food Chem., 91, 355, 2005. With permission.)
Elements such as Cu, Fe, and Zn have been determined by F-AAS in Cocuy de
Penca firewater, a spirituous beverage very popular in Northwestern Venezuela, and
the chemometric approach was followed to assess the geographic location of the
manufacturers and the presence or absence of sugar in the end product.133 Three
chemometric approaches were applied, i.e., LDA, quadratic discriminant analysis
(QDA), and various ANNs. The use of the classification procedure based on ANNs
led to overall 97% hits of prediction ability.
2234_C004.fm Page 109 Wednesday, October 25, 2006 2:54 PM
INPUT LAYER
Bias
HIDDEN Bias
LAYER
OUTPUT LAYER
FIGURE 4.41 Architecture of the BPNN: 4 × 2 × 2 plus bias. Four metal descriptors for the
input layer (Ca, Fe, Cu, and Mg), a hidden layer of two nodes (empirically established), and
an output layer with two nodes (the two categories J and C). (Adapted from Cameán, A.M. et
al., Differentiation of Spanish brandies according to their metal content, Elsevier, Talanta, 54,
53, 2001. With permission.)
4.2.14.5 Beers
Using a chemometric approach, the resulting mineral composition of beer has pro-
vided valuable information on how to distinguish the samples characterized as low
alcoholic content beers, lagers, and dark beers (Figure 4.42).134 Zinc, Mn, B, Fe, Al,
Ba, P, Sr, Ca, Mg, Na, and K were considered as chemical descriptors and determined
by ICP-AES in the 32 beer samples. The use of supervised learning PR methods,
such as LDA, based on artificial neural networks-multilayer perceptions trained by
back-propagation [BP-MLP]; Figure 4.43) was also found to be useful.
Differentiation and classification of beer samples have been achieved by Bellido-
Milla et al.135 with data obtained by flame AAS (Fe, Mn, Zn, Cu, Mg, Ca, Al) and
flame AES (Na, K). The combination of the data obtained by flame AAS and the
spectrum obtained by UV-VIS molecular absorption spectrometry provided infor-
mation on the inorganic and organic components of the samples analyzed. The
application of LDA appeared to be extremely useful for beer quality control and
grouping the beers analyzed in spite of the new beer styles that had been introduced
lately by the brewing industry. Based on the distribution of the grouping variables
on the plot of the first discriminant functions (Df2/Df1), four types of beer were
identified, namely, stout, ale, lager, and wheat beer (Figure 4.44). Three raw materials
were also distinguished, i.e., barley, and other cereals as adjuncts of malt, as well
2234_C004.fm Page 110 Wednesday, October 25, 2006 2:54 PM
4
DF2
-2
DF1
FIGURE 4.42 Plot of the two discriminant functions. (Adapted from Alcázar, A. et al.,
Multivariate characterisation of beers according to their mineral content, Elsevier, Talanta,
57, 45, 2002. With permission.)
Input layer
(Metal concentrations)
12 + bias Zn P B Mn Fe Mg Al Sr Ca Ba Na K
Output layer
3 Lo La Da
(Beer classes)
FIGURE 4.43 Architecture of the network. (Adapted from Alcázar, A. et al., Multivariate char-
acterisation of beers according to their mineral content, Elsevier, Talanta, 57, 45, 2002. With
permission.)
as wheat (Figure 4.45). Without the molecular absorption spectrum variable, the
discrimination was poorer because of misclassification of stout with the lager.135 The
ANOVA model made possible the classification of beers based on the two types of
2234_C004.fm Page 111 Wednesday, October 25, 2006 2:54 PM
Discriminant function 2 4
-2
-4
L
-6
S
W
-8
-6 -4 -2 0 2 4 0 8 A
Discriminant function 1
FIGURE 4.44 Biplot of the first DF vs. the second DF for types of beer: L, larger; S, stout;
W, wheat beer; A, ale. (Adapted from Bellido-Milla, D., Moreno-Perez, J.M., and Hernandez-
Artiga, M.P., Differentiation and classification of beers with flame atomic spectrometry and
molecular absorption spectrometry and sample preparation assisted by microwaves, Elsevier,
Spectrochim. Acta B. 55, 855, 2000. With permission.)
containers, namely bottle and can. A total of 23 elements (Ag, As, Bi, Cd, Co, Cr,
Cs, Cu, Fe, Ga, Hg, In, Mn, Ni, Pb, Rb, Sb, Sn, Th, Tl, U, V, Zn) were determined
in 35 bottled and canned Polish beers by ICP-MS.136 Assessment of the data with
PCA showed that the trace elements may originate from natural sources (soil, water,
cereal, hops, yeast) and environmental pollution (fertilizers, pesticides, industrial
processing, containers).
According to Guerrero et al.,137 the mineral composition (As, Ca, Cu, Fe, K, Mg,
Mn, Na, and Zn determined by F-AAS, FES, HG-AAS) of 40 wine vinegars from
Spain may be used for distinguishing quick and slow processed vinegars by applying
the PCA (Figure 4.46), CA, SIMCA, and especially, the nonparametric KNN, LDA,
and artificial neural networks trained by back propagation (BPANN). According to
Benito et al.,138 it is possible to characterize the vinegars obtained from wines with
DOC Rioja (66 vinegars) and Jerez (18 vinegars) according to their chemical com-
position (e.g., Ca, Cl, Cu, Fe, K, Na).
4.2.15.2 Must
Multivariate data analyses (PCA, FA) have been successfully applied for differen-
tiating between must and wines based on descriptors such as B, Ca, Cu, Fe, K, Mg,
K, Na, Pb, S, and Zn, and other basic parameters such as ashes, density, reducing
2234_C004.fm Page 112 Wednesday, October 25, 2006 2:54 PM
3.5
Discriminant function 2
0.0
B
BC
-2.5
-6 0 10 W
Discriminant function 1
FIGURE 4.45 Biplot of the first DF vs. the second DF for raw materials: B, barley; BC,
barley plus cereals; W, wheat. (Adapted from Bellido-Milla, D., Moreno-Perez, J.M., and
Hernandez-Artiga, M.P., Differentiation and classification of beers with flame atomic spec-
trometry and molecular absorption spectrometry and sample preparation assisted by micro-
waves, Elsevier, Spectrochim. Acta B. 55, 855, 2000. With permission.)
3 Q
Q
2
Q Q S
1 Q QQQ Q S
PC2
S SQ S
Q S S
0 Q S SS S Q
Q S S S S
QSQ S S S S
-1 Q
Q
-2 S
-3
-2 -1 0 1 2 3 4
PC1
FIGURE 4.46 Scores plot of the vinegar samples using the two first PCs (Q and S stand for
samples belonging to the “quick” and “slow” classes). (Adapted from Guerrero, M.I. et al.,
Multivariate characterization of vine vinegars from the south of Spain according to their
metallic content, Elsevier, Talanta, 45, 379, 1997. With permission.)
sugars, alcohol strength, tartaric acid, and total acidity.105 For instance, the successful
use of PCA in differentiating between musts and wines is illustrated in Figure 4.47.
SUMMARY
The applicability of advanced statistical chemometric techniques such as principal
component analysis (PCA), factor analysis (FA), linear discrimination analysis
2234_C004.fm Page 113 Wednesday, October 25, 2006 2:54 PM
5 Mg
Ca
K
3 Ashes K
Component 2
Na Total acidity
1 Reducing sugars
Density Zn Pb Total SO2
Tartaric acid Fe
Cu Volatil acidity
-1 Free SO2 Alcoholic strength
pH
-3
-5
-5.3 -3.3 -1.3 0.7 2.7 4.7
Component 1
7 B
Musts Wines
5
Component 2
-1
-3
-5
-5 -3 -1 1 3 5
Component 1
FIGURE 4.47 Biplot of loadings (A) and scores (B) for PCA. The first two scores, from the
must and wine samples, on PCA. Outlier must samples. (Adapted from González, G. and
Peña-Méndez, E.M., Multivariate data analysis in classification of must and wine from
chemical measurements, Eur. Food Res. Technol., 212, 100, 2000. With permission.)
can be recommended in monitoring the quality of foods and can help reduce the
cost of such surveys. The chemometric approach is also a good tool in the analytical
evaluation of foodstuff quality. The techniques may be useful, especially as combined
techniques (e.g., SOAN and MLF), in detecting fraud to preserve the brand name
of the original product and for protecting the consumer from being deceived and
cheated financially.
REFERENCES
1. Szefer, P., Application of chemometric techniques in analytical evaluation of biolog-
ical and environmental samples, in New Horizons and Challenges in Environmental
´ ·
Analysis and Monitoring, Namiesnik, J., Chrzanowski, W., and Zmijewska P., Eds.,
CEEAM, Gdansk, ´ chap. 18, p. 355.
2. Defernez, M. and Kemsley, E.K., The use and misuse of chemometrics for treating
classification problems, Trends Anal. Chem., 16, 216, 1997.
3. Cooley, W.W. and Lohnes, P.R., Multivariate Data Analysis, John Wiley & Sons,
New York, 1971.
4. Morrison, D.F., Multivariate Statistical Methods, McGraw-Hill International, Auck-
land, 1978.
5. Mardia, K.V., Kent, J.T., and Bibby, J.M., Multivariate Analysis, Academic Press,
London, 1989.
6. Deming, S.N. and Morgan, S.L., Experimental Design: A Chemometric Approach,
Elsevier, Amsterdam, 1993.
7. Malinowski, E.R., Factor Analysis in Chemistry, A Wiley-Interscience Publication,
John Wiley & Sons, New York, 1991.
8. Wackernagel, H., Multivariate Geostatistic: An Introduction with Application, 3rd
ed., Springer-Verlag, Berlin, 2003.
9. Flury, B. and Riedwyl, H. Multivariate Statistics — A Practical Approach, Chapman
& Hall, London, 1988.
10. Beebe, K.R., Pell, R.J., and Seasholtz, M.B., Chemometrics: A Practical Guide, John
Wiley & Sons, New York 1998.
11. Danielsson, Å. et al., Spatial clustering of metals in the sediments of the Skager-
rak/Kattegat, Appl. Geochem., 14, 689, 1999.
12. Struck, B.D. et al., Statistical evaluation of ecosystem properties influencing the
uptake of As, Cd, Co, Cu, Hg, Mn, Ni, Pb, Zn in seaweed (Fucus vesiculosus) and
common mussel (Mytilus edulis), Sci. Total Environ., 207, 29, 1997.
13. Kuik, P. et al., The use of Monte Carlo methods in factor analysis, Atmos. Environ.,
27A, 1967, 1993.
14. Sharma, S., Applied Multivariate Techniques, John Wiley & Sons, New York, 1996.
15. Massart, D.L. and Kaufman, L., The Interpretation of Chemical Data by the Use of
Cluster Analysis, John Wiley & Sons, New York, 1983.
16. Danielsson, Å., Spatial Modelling in Sediments, Linköping Studies in Arts and Sci-
ence, Sweden, 1998.
17. Everitt, B.S. and Dunn, G., Applied Multivariate Data Analysis, Edward Arnold,
London, 1991.
18. Renner, R.M., Glasby, G.P., and Szefer, P., Endmember analysis of heavy-metal
´ and Southern Baltic
pollution in surficial marine sediments from the Gulf of Gdansk
Sea, Appl. Geochem., 13, 293, 1998.
2234_C004.fm Page 115 Wednesday, October 25, 2006 2:54 PM
19. Full, W.E., Ehrlich, R., and Klovan, J.E., EXTENDED QMODEL — Objective
definition of external endmembers in the analysis of mixtures, Math. Geol., 13, 331,
1981.
20. Ehrlich, R. and Full, W.E., Sorting out geology — unmixing mixtures, in Use and
Abuse of Statistical Methods in the Earth Sciences, Size, W.B., Ed., International
Association for Mathematical Geology Studies in Mathematical Geology, Oxford
University Press, Oxford, 1, 1987, p. 33.
21. Renner, R.M., The construction of extreme compositions, Math. Geol., 27, 485, 1995.
22. Renner, R.M., An examination of the use of the log ratio transformation for the testing
of endmember hypotheses, Math. Geol., 23, 549, 1991.
23. Renner, R.M., The resolution of a compositional data set into mixtures of fixed source
compositions, Appl. Stat., J. R. Stat. Soc., Ser. C 42, 615, 1993a.
24. Renner, R.M., A constrained least-squares subroutine for adjusting negative estimated
element concentrations to zero, Comp. Geosci., 19, 1351, 1993b.
25. Renner, R.M. et al., A partitioning process for geochemical datsets, in Statistical
Applications in the Earth Sciences, Agterberg, F.P. and Bonham-Carter, G.F., Eds.,
Geological Survey of Canada Paper, 89-9, 1989, p. 319.
26. Li, Y.H., Geochemical cycles of elements and human perturbation, Geochim. Cos-
mochim. Acta, 45, 2073, 1981.
27. Hopke, P.K. et al., The use of multivariate analysis to identify sources of selected
elements in the Boston urban aerosol, Atmos. Environ., 10, 1015, 1976.
28. Heidam, N.Z., On the origin of the Arctic aerosol: a statistical approach, Atmos.
Environ., 15, 1421, 1981.
29. Bernard P.C., van Grieken, R.E., and Brügmann, L., Geochemistry of suspended
matter from the Baltic Sea. 1. Results of individual particle characterization by
automated electron microprobe, Mar. Chem., 26, 155, 1989.
30. Szefer, P. et al., Distribution of selected heavy metals and rare earth elements in
surficial sediments from the Polish sector of the Vistula Lagoon, Chemosphere, 39,
2785, 1999.
31. Selvaraj, K., Ram Mohan, V., and Szefer, P., Evaluation of metal contamination in
coastal sediments of the Bay of Bengal, India: geochemical and statistical approaches,
Mar. Pollut. Bull., 49, 174, 2004.
32. Szefer, P., Distribution and behaviour of selected heavy metals and other elements
in various components of the southern Baltic ecosystem, Appl. Geochem., 13, 287,
1998.
33. Szefer, P. et al., Extraction studies of heavy-metal pollutants in surficial sediments
from the southern Baltic Sea off Poland, Chem. Geol., 120, 111, 1995.
34. Glasby G.P. et al., Heavy-metal pollution of sediments from Szczecin Lagoon and
the Gdansk Basin, Poland, Sci. Total Environ., 330, 249, 2004.
35. Hallberg, R.O., Environmental implications of metal distribution in Baltic Sea sedi-
ments, Ambio, 20, 309, 1991.
36. Virkanen, J., Effect of urbanization on metal deposition in the Bay of Töölönlahti,
southern Finland, Mar. Pollut. Bull., 36, 729, 1998.
37. Li, Y.H., Interelement relationship in abyssal Pacific ferromanganese nodules and
associated pelagic sediments, Geochim. Cosmochim. Acta, 46, 1053, 1982.
·
38. Zbikowski, R., Szefer, P., and Latala, A., Distribution and relationships between
selected chemical elements in green alga Enteromorpha sp. from the southern Baltic,
Environ. Pollut., 143, 435, 2006.
2234_C004.fm Page 116 Wednesday, October 25, 2006 2:54 PM
39. Popham, J.D. and D’Auria, J.M., Statistical approach for deciding if mussels (Mytilus
edulis) have been collected from a water body polluted with trace metals, Environ.
Sci. Technol., 17, 576, 1983.
40. Szefer, P. et al., Distribution and relationships of trace metals in soft tissue, byssus
and shells of Mytilus edulis trossulus from the southern Baltic, Environ. Pollut., 120,
423, 2002.
41. Julshamn, K. and Grahl-Nielsen, O., Distribution of trace elements from industrial
discharges in the Hardangerfjord, Norway: a multivariate data analysis of saithe,
flounder and blue mussel as sentinel organisms, Mar. Pollut. Bull., 32, 564, 1996.
42. Szefer, P. et al., Distribution and relationships of mercury, lead, cadmium, copper
and zinc in perch (Perca fluviatilis) from the Pomeranian Bay and Szczecin Lagoon,
southern Baltic, Food Chem., 81, 73, 2003.
43. Hellou, J. et al., Distribution of elements in tissues of yellowtail flounder Pleuronectes
ferruginea, Sci. Total Environ., 181, 137, 1996.
44. Szefer, P. et al., Intercomparison studies on distribution and coassociations of heavy
metals in liver, kidney and muscle of harbour porpoise, Phocoena phocoena, from
southern Baltic Sea and coastal waters of Denmark and Greenland, Arch. Environ.
Contam. Toxicol., 42, 508, 2002.
45. Ciesielski, T. et al., Relationships and bioaccumulation of chemical elements in the
Baikal seal (Phoca sibirica), Environ. Pollut., 139, 372, 2006.
46. Julshamn, K. and Grahl-Nielsen, O., Trace element levels in harp seal (Pagophilus
groenlandicus) and hooded seal (Cystophora cristata) from the Greenland Sea: a
multivariate approach, Sci. Total Environ., 250, 123, 2000.
47. Nyman, M. et al., Current levels of DDT, PCB and trace elements in the Baltic ringed
seals (Phoca hispida baltica) and grey seals (Halichoerus grypus), Environ. Pollut.,
119, 399, 2002.
48. Brito, G. et al., Differentiation of heat-treated pork liver pastes according to their
metal content using multivariate data analysis, Eur. Food Res. Technol., 218, 584,
2004.
49. Schmidt, O. et al., Inferring the origin and dietary history of beef from C, N, and S
stable isotope ratio analysis, Food Chem., 91, 545, 2005.
50. Astorga-Espana, M.S., Pena-Mendez, E.M., and Garcia-Montelongo, F.J., Application
of principal component analysis to the study of major cations and trace metals in fish
from Tenerife (Canary Islands), Chemometrics Intell. Lab. Syst., 49, 173, 1999.
51. Favretto, L. and Favretto, L.G., Principal component analysis and pollution by trace
elements in a mussel survey, J. Chemometrics, 3, 301, 1988.
52. Machado Mesa, L. et al., Interpretation of heavy metal data from mussel by use of
multivariate classification techniques, Chemosphere, 38, 1103, 1999.
53. Bechmann, I.E., Stürup, S., and Kristensen, L.V., High resolution inductively coupled
plasma mass spectrometry (HR-ICPMS) determination and multivariate evaluation
of 10 trace elements in mussels from 7 sites in Limfjorden, Denmark, Fresenius J.
Anal. Chem., 368, 708, 2000.
54. Favretto, L. and Favretto, L.G., Multivariate data analysis of some xenobiotic trace
metals in mussels from the Gulf of Trieste, Z. Lebensm. Unters. Forsch., 179, 201,
1984a.
55. Favretto, L. and Favretto, L.G., Principal component analysis as a tool for studying
interedependences among trace metals in edible mussels from the Gulf of Trieste, Z.
Lebensm. Unters. Forsch., 179, 377, 1984b.
2234_C004.fm Page 117 Wednesday, October 25, 2006 2:54 PM
56. Favretto, L. et al., Terrigenous debris and mussel pollution — a differentiation based
on trace element concentration by means of multivariate analysis, Anal. Chim. Acta,
344, 251, 1997.
57. Roméo, M. et al., Mussel transplantation and biomarkers as useful tools for assessing
water quality in the NW Mediterranean, Environ. Pollut., 122, 369, 2003.
58. Bermejo-Barrera, P., Moreda-Piñeiro, A., and Bermejo-Barrera, A., Sample pretreat-
ment for trace elements determination in seafood products by atomic absorption
spectrometry, Talanta, 57, 969, 2001.
59. Szefer, P. and Wolowicz,
⁄ M., Occurrence of metals in the cockle Cerastoderma
glaucum from different geographical regions in view of principal component analysis,
SIMO-Mar. Pollut., 64, 253, 1993.
60. Szefer, P. et al., Distribution and relationships of selected trace metals in molluscs and
associated sediments from the Gulf of Aden, Yemen, Environ. Pollut., 106, 299, 1999.
61. Szefer, P. et al., Toxic metals in soft tissue and byssus of mollusc Mytilidae from
different marine ecosystems, III Conference on Trace Metals “Effects on Organisms
and Environment,” Polish Academy of Sciences, Sopot, Poland, 2000, 186/P2-14.
62. Szefer, P. et al., Distribution and coassociations of trace elements in soft tissue and
byssus of Mytillus edulis galloprovincialis relative to the surrounding seawater and
suspended matter of the southern part of Korean Peninsula, Environ. Pollut., 129,
209, 2004.
63. Szefer, P., Monitors of pollution in the Baltic Sea, International Symposium Analytical
Forum 2004, Book of Abstracts, Warsaw, Poland, 2004, p. 41.
64. Szefer, P. et al., Distribution of metallic pollutants in molluscs Mytilidae from the
temperate, tropical and subtropical marine environments, First International Sympo-
sium, IEP ’98 Issues in Environmental Pollution, The State and Use of Science and
Predictive Models, Elsevier Science Ltd., Denver, CO, 1998, Section of Abstract
Book 4.04.
65. Szefer, P. et al., A comparative assessment of heavy metal accumulation in soft parts
and byssus of mussels from subarctic, temperate, subtropical and tropical marine
environments, Environ. Pollut., 139, 70, 2006.
66. Kwoczek, M. et al., Essential and toxic elements in seafood available in Poland from
different geographical regions, J. Agric. Food Chem., 54, 3015, 2006.
67. Szefer, P. and Grembecka, M., Applications of chemometry in analytical evaluation
of foods quality based on their mineral composition, 2nd International IUPAC Sym-
posium on Trace Elements in Food, Brussels, Belgium, 2004, p. 48.
68. Bermejo-Barrera, P. et al., The multivariate optimisation of ultrasonic bath-induced
acid leaching for the determination of trace elements in seafood products by atomic
absorption spectrometry, Anal. Chim. Acta, 439, 211, 2001.
69. Brescia, M.A. et al., Characterisation of the geographical origin of Buffalo milk and
mozzarella cheese by means of analytical and spectroscopic determinations, Food
Chem., 89, 139, 2005.
70. Pillonel, L. et al., Stable isotope ratios, major, trace and radioactive elements in
emmental cheeses of different origins, Lebensm.-Wiss. u.-Technol., 36, 615, 2003.
71. Puerto, P. et al., Chemometric studies of fresh and semi-hard goat’s cheeses produced
in Tenerife (Canary Islands), Food Chem., 88, 361, 2004.
72. Kelly, S. et al., The application of isotopic and elemental analysis to determine the
geographical origin of premium long rice, Eur. Food Res. Technol., 214, 72, 2002.
2234_C004.fm Page 118 Wednesday, October 25, 2006 2:54 PM
93. Martin, M.J., Pablos, F., and González, A.G., Discrimination between arabica and
robusta green coffee varieties according to their chemical composition, Talanta, 46,
1259, 1998b.
94. Martin, M.J., Pablos, F., and González, A.G. Characterization of arabica and robusta
roasted coffee varieties and mixture resolution according to their metal content, Food
Chem., 66, 365, 1999.
95. dos Santos, E.J. and de Oliveira, E., Determination of mineral nutrients and toxic
elements in Brazilian soluble coffee by ICP-AES, J. Food Compos. Anal., 14, 523,
2001.
96. Anderson, K.A. and Smith, B.W., Chemical profiling to differentiate geographic
growing origins of coffee, J. Agric. Food Chem., 50, 2068, 2002.
97. Haswell, S.J. and Walmsley, A.D., Multivariate data visualisation methods based on
multi-elemental analysis of wines and coffees using total reflection X-ray fluorescence
analysis, J. Anal. At. Spectrom., 13, 131, 1998.
98. Grembecka, M. et al., Assessment of mineral composition of market coffee and its
infusions, 2nd International IUPAC Symposium on Trace Elements in Food, Brussels,
Belgium, 2004, p. 94.
99. Costa Freitas, A.M. and Mosca, A.I., Coffee geographic origin — an aid to coffee
differentiation, Food Res. Int., 32, 565, 1999.
100. Malinowska, E., Szefer, P., and Falandysz, J., Metals bioaccumulation by bay bolete,
Xerocomus badius, from selected sites in Poland, Food Chem., 84, 405, 2004.
101. Simpkins, W.A. et al., Trace elements in Australian orange juice and other products,
Food Chem., 71, 423, 2000.
102. Camara, M., Diez, C., and Torija, E., Chemical characterization of pineapple juices
and nectars: principal component analysis, Food Chem., 54, 93, 1995.
103. Awadallah, R.M., Ismail, S.S., and Mohamed, A.E., Application of multi-element
clustering techniques of five Egyptian industrial sugar products, J. Radioanal. Nucl.
Chem., 196, 377, 1995.
104. Moret I. et al., Multiple discriminant analysis in the analytical differentiation of
Venetian white wines: 4. Application to several vintage years and comparison with
the k nearest-neighbor classification, J. Agric. Food Chem., 32, 329, 1984.
105. González, G. and Peña-Méndez, E.M., Multivariate data analysis in classification of
must and wine from chemical measurements, Eur. Food Res. Technol., 212, 100, 2000.
106. Frías, S. et al., Classification and differentiation of bottled sweet wines of Canary
Islands (Spain) by their metallic content, Eur. Food Res. Technol., 213, 145, 2001.
107. Frías, S. et al., Classification of commercial wines from the Canary Islands (Spain)
by chemometric techniques using metallic contents, Talanta, 59, 335, 2003.
108. Marengo, E. and Aceto, M., Statistical investigation of the differences in the distri-
bution of metals in Nebbiolo-based wines, Food Chem., 81, 621, 2003.
109. Li, X.S., Danzer, K., and Thiel, G., Classification of wine samples by means of
artificial neural networks and discrimination analytical methods, Fresenius J. Anal.
Chem., 359, 143, 1997.
110. Frías, S. et al., Metallic content of wines from the Canary Islands (Spain). Application
of artificial neural networks to the data analysis, Nahrung/Food, 46, 370, 2002.
˘
111. Sperkova, J. and Suchánek, M., Multivariate classification of wines from different
Bohemian regions (Czech Republic), Food Chem., 93, 659, 2005.
112. Nogueira, J.M.F. and Nascimento, A.M.D., Analytical characterization of Madeira
wine, J. Agric. Food Chem., 47, 566, 1999.
113. Rebolo, S. et al., Characterisation of Galician (NW Spain) Ribeira Sacra wines using
pattern recognition analysis, Anal. Chim. Acta, 417, 211, 2000.
2234_C004.fm Page 120 Wednesday, October 25, 2006 2:54 PM
CONTENTS
5.1 INTRODUCTION
Minerals are inorganic elements that occur in nature. They originate from the earth’s
crust, and in animal or plant cellules constitute only a small proportion of the body
tissue. During dry or wet ash-destruction process, the organic matrix of the biological
sample is completely decomposed and removed in the form of volatile carboneous
material, and the remaining material, which is the nondestructive residue, contains
only mineral compounds.
Many mineral elements are essential constituents of enzymes, regulate a variety
of physiologic processes (e.g., maintenance of osmotic pressure, oxygen transport,
muscle contraction, and central nervous system integrity), and are required for the
growth and maintenance of tissues and bones. They are so potent and so important
that without them the organism would not be able to use the other remaining
constituents of foods.
123
2234_C005.fm Page 124 Wednesday, October 25, 2006 3:04 PM
The total daily diet contains minerals within the range of 0.2–0.3% of all
nutrients. The main mass of these minerals is made up of six minerals (mentioned
in the following paragraph), whereas dozens of others, present in trace quantities,
constitute only a hundredth of a percent of the total mass of daily eaten nutrients.
Because of their broad biochemical activity, many inorganic compounds are also
intentionally used as functional agents in processing a variety of foods. On the other
hand, cations in foods, such as Fe2+ and Cu2+, may induce a diversity of undesirable
effects that influence the nutritional quality of foods. Iron, for example, can actively
catalyze lipid oxidation, and its presence even in trace amounts has long been
recognized as potentially detrimental to the shelf-life of fats, oils, and fatty acids.
Iron compounds can activate molecular oxygen by producing superoxide, which
through dismutation and other steps of biochemical changes results in the formation
of hydroxyl free radicals.
Minerals play an important role in plant life. They function as catalysts for many
biochemical reactions, are responsible for changes in the state of cellular colloids,
directly affect the cell metabolism, and are involved in changes in protoplasm turgor
and permeability. They often become centers of electrical and radioactive processes
in living organisms. Minerals are usually classified into two main groups on the
basis of their relative amounts in the body. Those occurring in relatively large
amounts and needed in quantities of 100 mg or more per day are called macroele-
ments or macrominerals. This group includes calcium, magnesium, sodium, potas-
sium, chloride, and phosphorus. Minerals occurring in small amounts and needed
in quantities of a few milligrams or less per day are called microelements or
microminerals or trace elements. The group known as essential microelements
includes iron, iodide, zinc, copper, manganese, fluorine, selenium, cobalt, nickel,
chromium, boron, and silicon. Recently, a few other elements have sometimes been
considered as potentially essential, such as lithium and strontium.1–5
In body tissues, other trace minerals also occur, such as arsenic, aluminum,
cadmium, lead, and mercury, which until now have been recognized as potentially
harmful, although recently, Al, As, Cd, and Pb in very small quantities have been
suggested to have some characteristics of essentiality but lacking a defined biochem-
ical function.4,6 Elevated levels of this group of elements are present in the organism
mainly as a result of environmental contamination, with very small quantities often
derived from natural sources. According to the WHO Experts7 the trace elements
are divided into three groups from the point of view of their nutritional significance
in humans: (1) essential elements, (2) elements that are probably essential, and (3)
potentially toxic elements, some of which as mentioned above, may nevertheless
have some essential function.
The heavy metals have been studied intensively, and recent data suggest that
insufficient intake of aluminum, lead, and cadmium in experimental animal diets
may exhibit apparent deficiency signs, such as depressed growth, anemia, disturbed
iron metabolism, and some other effects very specific for each animal and each trace
element.4,6,7 More experimental data is necessary to prove that trace amounts of lead,
aluminum, and cadmium may have a defined positive biological function in the
organism and thus be recognized as nutritionally necessary.
2234_C005.fm Page 125 Wednesday, October 25, 2006 3:04 PM
TABLE 5.1
Data of Mean Daily Intake, Percentage of Absorption from the Gastrointestinal Tract, and RDAb or SAIc14–16,20 in Milligrams
per Adult Person
Macroelements
Element Calcium Phosphorus Chloride Sodium Potassium Magnesium
Element Iron Zinc Manganese Copper Fluorine Iodine Molybdenum Chromium Nickel
DI 15 12, 18 5.6, 8 2.4 < 1.4 < 1.0 > 0.15 < 0.15 0.16–0.20
PA 10–40 30–70 40 25–60 Higha 100 70–90 < 1.0 or 10–25 in 30–50
form of GTFf
RDAb or SAIc 10–15b 12–15b 2–3c 1.5–3.0c 1.5–4.0c 0.15b 0.075–0.250c 0.05–020c 0.05, 0.3c
role in adaptation to low trace element status or high demands by modifying the
activity as well as the concentration of receptors and the level of their saturation,
which can influence the uptake of minerals from the gastrointestinal tract during
normal life, pregnancy, or disease states.
The extrinsic (dietary) factors include the solubility and molecular dimensions
of trace element species within food, the mixture of digestive secretion, and the gut
lumen conditions that can influence mucosal uptake (e.g., the nonavailable iron
oxalates, copper sulfides, trace-element silicates, zinc, iron, and lead, and phytates
associated with calcium). Synergists promoting, among other things, zinc absorption
include citrate, histidine, ascorbate-modifying iron/copper antagonism, and those
metabolic processes that maintain the transport and mobility of some elements
(transferrins, albumins, and other plasma ligands). On the other hand, there are also
antagonists that restrict gastrointestinal lumen solubility of components such as
phytates of calcium and zinc, or minerals such as cadmium, zinc, and copper, which
compete for receptor sites involved in absorption, transport, storage, and other less
known mechanisms.
Element Cr Mn Fe Co Ni Cu Zn
Elemental state 3d5 4s1 3d5 4s2 3d6 4s2 3d7 4s2 3d8 4s2 3d10 4s1 3d10 4s2
Divalent cationic state 3d4 3d5 3d6 3d7 3d8 3d9 3d10
As can be seen from the above arrangement, copper may exist in either the
monovalent or divalent ion state, and the sum of its biological importance is related
to its ability to oscillate between the cuprous (I) or cupric (II) states, i.e., the ability
to accept and donate electrons. The divalent zinc (3d10) is not strictly a transition
element because its orbital d is filled but its atomic structure is similar and thus
ready to form complexes analogous to those formed by the transition metal ions.
Some of the other divalent cations such as cadmium Cd2+ (4d10) and lead Pb2+ (6d10
6s2), which are not transition metals, also have a pronounced tendency to form
coordinate covalent bounds with ligands that contain electron donor atoms such as
N, O, and S, found frequently in proteins. Some examples of similar tendencies to
form coordination complexes by cations such as Zn2+, Cd2+, and Cu+ are discussed
in the following text.
There is a degree of selectivity of metal ions for electron donor atoms; copper
tends to prefer nitrogen, whereas zinc prefers sulfur, but several different donor
atoms will complex with each metal ion. The amino-acid residues in proteins serve
as rich sources of electron donor atoms. For example, the imidazole group of
histidine supplies nitrogen, the carboxyl groups of aspartic and glutamic acids supply
oxygen, and the sulfhydryl group of cysteine supplies sulfur for complexation.
The interactions between a metal atom and ligands can be thought of as a Lewis
acid-base reaction. Ligands as Lewis base are capable of donating one or more electron
pairs, and a transition metal atom acts as Lewis acids accepting or sharing a pair of
electrons from the Lewis bases. Thus, metal–ligand interactions that share pairs of
electrons are coordinate covalent bound. Interesting data on competitive interaction in
biological systems exist between the divalent cations such as zinc and cadmium, or
zinc, copper, and iron. Zinc and cadmium, together with mercury, belong to the group
12 of the recent form of the Periodic Table and have very similar tendencies to form
complexes with a coordination number of 4 and a tetrahedral disposition of ligands
around the metal. They have, as divalent cations, very similar electronic structure to
the monovalent cation of copper (3d10), and a consequence of this is the possibility of
isomorphous replacement between these elements in biological systems.17
The essential microelements prefer the coordination number of 4 or 6. Copper
and zinc in the cationic form have filled their orbitals (they are d10 ions), and both
Cu+ and Zn2+ form tetrahedral complexes. Cu+ ion may lose one of its d orbital
electrons and become a d9 ion (Cu2+), and thus form square planar complexes. On
the other hand, the ferrous d6 ion (Fe2+) forms octahedral configuration. According
to the brief review above, it is possible to predict that Cu+, having the same d orbital
configuration as that of Zn2+ and Cd2+, may interact with both of cations, and that
Zn2+ may be antagonistic to Cu+ rather than Cu2+.
In systematic studies of the complex interactions between Cd, Zn, Cu, and Fe
in chicks, rats, and mice, it has been demonstrated that increased dietary intake of
2234_C005.fm Page 129 Wednesday, October 25, 2006 3:04 PM
cadmium can cause increased mortality, poor growth, and hypochromic microcytic
anemia.17 The growth rate could be restored by zinc supplementation, and the
mortality and severity of anemia signs may be reduced by copper supplementation
of the diet. Zinc also restored the activity of heart cytochrome oxidase and additional
Cu prevented the degeneration of aortic elastin. According to Bremner,17 it is evident
that Cd can have antagonistic effects on zinc and copper metabolism.
Diets low in calcium promote significant increases in the absorption and retention
of lead and cadmium in rats and promote the manifestation of pathologic changes
associated with Cd toxicity. It is important to note that low intake of phosphorus
had effect on Pb retention similar to Ca, and that the effects of Ca and P deficiencies
are additive.7,17 Many nutritional and nonnutritional components of dietary supple-
ments and some medications can interact with minerals in the gastrointestinal tract
and affect their absorption. Amino acids act as intraluminar binders for some trace
minerals. Large complexes, and weakly digestible proteins, on the other hand, may
bind minerals strongly and reduce their absorption.
Triacyloglicerols and long-chain fatty acid derived from triacyloglicerols may
form soaps with calcium and magnesium and decrease the bioavailability of these
two nutrients. Also pectins, cellulose, hemicellulose, and polymers produced by
Maillard reaction during cooking, processing, and storage bind minerals in the lumen
and thus reduce their biological availability. Lactose, on the other hand, increases
calcium absorption from milk.
Interactions between and among minerals, or minerals with some anionic species
such as ascorbic acid, have important effect on mineral absorption. Absorption of
iron is hindered by fiber and phosphates and promoted by ascorbic acid, copper, and
meat protein. Ascorbic acid also enhances absorption of selenium but reduces the
absorption of copper. A high protein intake appears to increase the excretion of
calcium, whereas vitamin D increases ingestion and retention of calcium.
Intestinal parasites, dietary fiber phylates, and excessive sweating interfere with
zinc absorption. Phytates, oxalates, and tannates can interfere with the absorption
of a number of minerals. Certain medications such as tetracycline can also inhibit
absorption of minerals, whereas others such as jodoquinol function as antibacterial
agent by chelating trace metals at bacterial surface, thereby inhibiting their growth.
It may be concluded that chemically similar minerals share certain “channels” for
absorption, and the simultaneous ingestion of two or more such minerals may result
in competition for absorption. The possible competition mechanisms of some min-
erals have already been discussed. When nonphysiological imbalances among com-
petitive nutrients exist as the result of excessive ingestion (occasioned by leaching
from water pipes, storage in unlacquered tin cans, or improper formulation of
vitamin–mineral supplements), nutritionally important consequences of the min-
eral–mineral interaction can be observed. Finally, to participate in a nutritionally
relevant process for the organism as a whole, a mineral must be transported away
from the intestine. The concentration of circulating binding proteins and the degree
of saturation of their metallic binding sites may influence the rate and magnitude of
transport of the absorbed minerals.
Minerals require a suitable mucosal surface across which they enter the body.
Reaction in or diversion of a large portion of the small bowel obviously affects
2234_C005.fm Page 130 Wednesday, October 25, 2006 3:04 PM
Calcium Bone and tooth formation, blood clotting, cell permeability, nerve Stunted growth, rickets, Milk, hard cheese, salmon, and small fish
stimulation, muscle contraction, enzyme activation osteomalacia, osteoporosis, tetany eaten with bones, some dark green
vegetables, legumes
Magnesium Component of bones and teeth, activation of many enzymes, Seen in alcoholism or renal disease, Green leafy vegetables, nuts, whole
nerve stimulation, muscle contraction tremors leading to conclusive grains, meat, milk, seafood
seizures
Phosphorus Bone and tooth formation, energy metabolism component of ATP Stunted growth, rickets Milk, meats, poultry, fish, eggs, cheese,
and ADP, protein synthesis, component of DNA and RNA, fat nuts, legumes, whole grains
2234_C005.fm Page 131 Wednesday, October 25, 2006 3:04 PM
Potassium Osmotic pressure, water balance, acid-based balance, nerve Nausea, vomiting, muscular Meats, fish, poultry, whole grains, fruits,
stimulation, muscle contraction, synthesis of protein, glycogen weakness, rapid heartbeat, heart vegetables, legumes
formation failure
Sodium Osmotic pressure, water balance, acid-based balance, nerve Rare: nausea, vomiting, giddiness, Table salt, salted foods, MSG and other
stimulation, muscle contraction, cell permeability exhaustion, cramps sodium additives, milk, meat, fish,
poultry, eggs, bread
Microelements
Chromium Trivalent chromium increases glucose tolerance and plays role Impaired growth, glucose Whole-grain cereals, condiments, meat
in lipid metabolism, useful in prevention and treatment of intolerance, elevated blood products, cheeses, and brewer’s yeast
diabetes; hexavalent chromium is toxic cholesterol
131
132
Cobalt Cofactor of vitamin B12, plays role in immunity Rarely observed, but if exists: Organ meats (liver, kidney), fish, dairy
pernicious anemia with products, eggs
hematological and neurologic
manifestations may be observed due
to vitamin B12 deficiency
Copper Necessary for iron utilization and hemoglobin formation; Anemia, neutropenia, leucopenia, Liver, kidney, oysters, nuts, fruits, dried
constituent of cytochrome oxidase; involved in bone and elastic skeletal demineralization legumes
tissue development
2234_C005.fm Page 132 Wednesday, October 25, 2006 3:04 PM
Iron Hemoglobin and myoglobin formation, essential component of Anemia, decrease in oxygen transport Liver, lean meats, legumes, dried fruits,
many enzymes and cellular immunity, muscle green leafy vegetables, whole grain, and
weakness, etc. fortified cereals
Manganese Cofactor of large number of enzymes; in aging process has a role In animals: chondrodystrophy, Tea, whole grain, nuts; moderate levels:
as an antioxidant (Mn-superoxide dismutase); important for abnormal bone development, fruits, green vegetables, organ meat, and
normal brain function, reproduction, and bone structure reproductive difficulties; in humans: shellfish contain well absorbable
shortage of evidence manganese
Molybdenum Component of three enzymes: sulfite oxidase, xanthine Intolerance of sulfur-containing Organ meats, grain, legumes, leafy
dehydrogenase, aldehyde oxidase. These enzymes catalyse amino acids in patients fed vegetables, milk, beans
oxidative hydroxylations of substrate molecules at the intravenously reduces conversion of
molybdenum center and subsequently transfer electrons to other hypoxanthine and xanthine to uric
redox-active cofactors and ultimately to the electron acceptors acid, resulting in development of
cytochrome c, molecular oxygen, or NAD+. Sulfite oxidase xanthine renal calculi; deficiency
detoxifies in the body sulfiting agents used for food preservation, state may be potentiated by high
activates nitrate reductase (found in nitrogen-fixing bacteria), and copper intake
promotes formation of assimilatory nitrite crucial to the global
nitrogen cycle in biological systems, copper antagonist
Mineral Components in Foods
Zinc Constituent of many enzyme systems, carbon dioxide transport, Delayed wound healing, impaired Oysters, fish, meat, liver, milk, whole
vitamin A utilization taste sensitivity; severe deficiency: grains, nuts, legumes
retarded growth and sexual
development, dwarfism
Fluoride Resistance to dental decay Tooth decay in young children Drinking water rich in fluoride, seafood,
teas
Iodine Synthesis of thyroid hormones that regulate basal metabolic rate Goiter, cretinism, if deficiency is Iodized salt, seafood, food grown near the
severe sea
Selenium Protects against number of cancers Cataract, muscular dystrophy, growth Broccoli, mushrooms, radishes, cabbage,
depression, liver cirrhosis, celery, onions, fish, organ meats
infertility, cancer, aging due to
deficiency of selenoglutathione
peroxidase, insufficiency of cellular
immunity
Boron Prevents osteoporosis in postmenopausal women, beneficial in Probably impairs growth and Foods of plant origin
2234_C005.fm Page 133 Wednesday, October 25, 2006 3:04 PM
(recently treatment of arthritis, builds muscle; its essentiality still has to development
considered as be proven
Functional Role of Some Minerals in Foods
essential)
133
2234_C005.fm Page 134 Wednesday, October 25, 2006 3:04 PM
TABLE 5.3
Contents of Selected Minerals in Some Foods
Mineral Food Amount (mg/100g) References
TABLE 5.4
List of Selected Mineral Compounds Used as Food Additives According to FAO/WHO Expert Committee on Food Additives
Chemical Name of ADI, TADI, PMTDI
Compound and (INS)* Synonyms or Other Chemical Name Functional Class and Comments (mg/kg body weight)
Aluminum sodium sulphate (521) Soda alum, Sodium alum Buffering, neutralizing, and firming agent No ADI allocated
Aluminum potassium sulphate (522) Aluminum potassium sulphate dodecahydrate Acidity regulator, stabilizer No ADI allocated
Aluminum ammonium sulphate (523) Aluminum ammonium sulphate Stabilizer, firming agent, temporary 0–0.6
acceptance, group ADI for aluminum
Calcium alginate (404) Calcium alginate Thickening agent, stabilizer ADI “not specified”
Calcium ascorbate (302) Calcium ascorbate dihydrate Antioxidant ADI “not specified”
Calcium benzoate (213) Monocalcium benzoate Antimicrobial agent, preservative ADI 0–5.0
Calcium chloride (509) Calcium chloride Firming agent ADI “not specified”
2234_C005.fm Page 138 Wednesday, October 25, 2006 3:04 PM
Calcium citrate (333) Tricalcium citrate, tricalcium salt of beta Acidity regulator, firming agent, sequestrant ADI “not specified”
hydroxytricarballylic acid
Calcium dihydrogen phosphate (341i) Calcium dihydrogen tetraoxophosphate, Buffer, firming, raising, leavening, and MTDI 70.0
monobasic calcium phosphate, monocalcium texturing agents, used in fermentation
phosphate processes
Calcium disodium ethylene Calcium disodium EDTA Antioxidant, preservative sequestrant (no ADI 0–2.5
diaminetetraacetace (385) excess of disodium EDTA should remain in
food)
Calcium glutamate (623) Monocalcium DI-L-glutamate Flavor enhancer, salt substitute ADI “not specified”
Calcium hydroxide (526) Slaked lime Neutralizing agent, buffer, firming agent ADI “not limited”
Calcium hydrogen carbonate (170ii) Calcium hydrogen carbonate Surface colorant, anticaking agent, stabilizer ADI “not specified”
Calcium lactate (327) Calcium dilactate hydrate Buffer, dough conditioner
Calcium sorbate (203) Calcium sorbate Antimicrobial, fungistatic, preservative agent ADI 0–25.0 (as sum of calcium,
potassium, and sodium salt)
Magnesium chloride (511) Magnesium chloride hexahydrate Firming, color retention agent ADI “not specified”
Magnesium carbonate (504i) Magnesium carbonate Anticaking and antibleaching agent ADI 0–50.0
Mineral Components in Foods
Magnesium gluconate (580) Magnesium gluconate dihydrate Buffering, firming agents in yeast food. ADI “not specified”
Magnesium glutamate DI-L (625) Magnesium glutamate Flavor enhancer, salt substitute ADI “not specified” (group ADI
for α glutamic acid and its
monosodium, potassium,
calcium, magnesium, and
ammonium salts)
Magnesium hydrogen Phosphate Magnesium hydrogen ortophosphate Dietary supplement MTDI 70 (expressed as
(343ii) trihydrate, dimagnesium phosphate phosphorus from all sources)
Magnesium hydroxide (528) Magnesium hydroxide Alkali, color adjunct ADI “not limited”
Magnesium hydroxide carbonate Magnesium carbonate hydroxide hydrated Alkali, anticaking, color retention, carrier, ADI “not specified”
(504ii) drying agent
Magnesium lactate D,L- (also Magnesium DI-D,L-lactate Buffering agent, dough conditioner, dietary ADI “not limited”
magnesium lactate L) (329) supplement
Magnesium oxide (530) Magnesium oxide Anticaking, neutralizing agent ADI “not limited”
Magnesium sulfate (518) Magnesium sulfate Firming agent ADI “not specified”
2234_C005.fm Page 139 Wednesday, October 25, 2006 3:04 PM
Potassium acetate (261) Potassium acetate Antimicrobial agent, preservative, buffer ADI “not specified” (also includes
Functional Role of Some Minerals in Foods
Sodium aluminum phosphate acidic Salp. Sodium trialuminium tetradecahydrogen, Raising agent ADI 0–0.6
(541i) octaphosphate tetrahydrate (A), trisodium
dialuminum pentadecahydrogen
octaphosphate (B)
Sodium aluminum phosphate basic Kasal. Autogenous mixture of an alkaline Emulsifier ADI 0–0.6
(541ii) sodium aluminium phosphate
Sodium ascorbate (301) Sodium L-ascorbate Antioxidant ADI “not specified”
Sodium benzoate (211) Sodium salt of benzenecarboxylic acid Antimicrobial, preservative ADI 0–5.0
2234_C005.fm Page 140 Wednesday, October 25, 2006 3:04 PM
Sodium dihydrogen phosphate (339i) Monosodium dihydrogen monophosphate Buffer, neutralizing agent, sequestrant in MTDI 70.0
(ortophosphate) cheese, milk, fish, and meat products
Disodium ethylenedia- Disodium EDTA Disodium edeteate Antioxidant, sequestrant, preservative, ADI 0–2.5 (as calcium disodium
minetetraacetate (386) synergist EDTA)
Potassium ascorbate (303) Potassium ascorbate Antioxidant ADI “not specified” (group ADI
for ascorbic acid and its sodium,
potassium, and calcium salts)
Potassium benzoate (212) Potassium benzoate Antimicrobial agent, preservative ADI 0–5.0 (expressed as benzoic
acid)
Potassium bromate (924a) Potassium bromate Oxidizing agent (previous acceptable level of ADI withdrawn
treatment of flours for breadmaking
withdrawn)
Potassium carbonate (501i) Potassium carbonate Alkali, flavor ADI “not specified”
Potassium chloride (508) Potassium chloride, sylvine, sylvite Seasoning and gelling agent, salt substitute ADI “not specified” (group ADI
for hydrochloric acid and its
magnesium, potassium, and
ammonium salts)
Mineral Components in Foods
Potassium or sodium copper Potassium or sodium chlorophyllin Color of porphyrin ADI 0–15
chlorophyllin (141ii)
Potassium hydrogen carbonate Potassium bicarbonate Alkali, leavening agent, buffer ADI “not specified”
(501ii)
Sodium glutamate (621) Monosodium L-glutamate, (MSG), glutamic Flavour enhancer ADI 0–0.7 (group ADI for sulfur
acid monosodium salt monohydrate dioxide and sulfites expressed as
SO2, covering sodium and
potassium salt)
Sodium phosphate (339iii) Trisodium phosphate, trisodium mono- Sequestrant, emulsion stabilizer, buffer agent MTDI 70.0
phosphate, ortophosphate, sodium phosphate
Sodium or potassium sorbate (201, Sodium or potassium sorbate Antimicrobial, fungistatic agent ADI 0–25.0
202)
Notes:
TADI — Temporary ADI, a term established by the JECFA for a substance for which toxicological data are sufficient to conclude that use of the substance is safe over
the relative short period of time required to evaluate further safety data but are insufficient to conclude that use of the substance is safe over a lifetime. A higher-than-
2234_C005.fm Page 141 Wednesday, October 25, 2006 3:04 PM
normal safety factor is used when establishing a TADI, and an expiration date is established by which time appropriate data to resolve the safety issue should be submitted
to JECFA.
Functional Role of Some Minerals in Foods
MTDI — Maximum Tolerable Daily Intake or Provisional Maximum Tolerable Daily Intake (PMTDI), terms used for description of the end point of contaminants with
no cumulative properties. Its value represents permissible human exposure as a result of the natural occurrence of the substance in food or drinking water. In the case
of trace elements that are both essential nutrients and unavoidable constituents of food, a range is expressed, the lower value representing the level of essentiality and
the upper value the PMTDI.
∗ INS — International numbering system, prepared by the Codex Committee for Food Additives for the purpose of providing an agreed international numerical system
for identifying food additives in ingredient list as an alternative to the declaration of the specific name (Codex Alimentarius, Vol. 1, Second Edition, Section 5.1, 1992).
ADI — Acceptable Daily Intake is an estimate of the amount of a substance in food or drinking water, expressed on a body weight basis, for a standard human of 60
kg weight, that can be ingested daily over a lifetime without appreciable risk for health.
a -ADI “not specified” or ADI “ not limited” — Terms applicable to a food substance of very low toxicity that, on the basis of the available data — chemical,
biochemical, toxicological, and others, as well as of the total dietary intake of the substance arising from its use at the levels to achieve the desired effect and from its
acceptable background in food — does not, in the opinion of the Joint FAO/WHO Expert Committee on Food Additives (JECFA), represent a hazard to health. For that
reason, and for reasons stated in individual evaluations, the establishment of ADI in numerical form is not deemed necessary. An additive meeting this criterion must
be used within the bound of good manufacturing practice, i.e., it should be technologically efficacious and should be used at the lowest level.
Source: From FAO/WHO Ed., Summary of Evaluations Performed by the Joint FAO/WHO Expert Committee on Food Additives 1956–1993, International Life Science
Inst. Press, Geneva, 1994.
141
2234_C005.fm Page 142 Wednesday, October 25, 2006 3:04 PM
EDTA is reported to be an effective chelating agent for metal ions and is approved
for use in the food industry as a preservative and antioxidant. It acts as an inhibitor
of Staphylococcus aureus by forming stable chelates in the media with multivalent
cations that are essential for cell growth. The effect is largely bacteriostatic and
easily reversed by releasing the complexed cations with other cations for which
EDTA has higher affinity.46
The addition of phosphates (pyro-, tripoly-, and hexametaphosphate) also pro-
tects cooked meat from autooxidation. Orthophosphate gives no protection. The
mechanism by which phosphates prevent autooxidation appears to be related to their
ability to sequester metal ions, particularly ferrous iron, which is the major pro-
oxidant.40 The addition of NaCl increases retention of moisture in meat and meat
products.
well as in food processing. The highest losses of minerals are encountered in the
milling and polishing process of cereals and groats. All milled cereals undergo a
significant reduction of nutrients. The extent of the loss is governed by the efficiency
with which the endosperm of the seed is separated from the outer seed coat (bran)
and the germ. The loss of certain minerals and vitamins is deemed so relevant to
health that in many countries a supplementation procedure has been introduced for
food products so derived to enrich them with the lost nutrients, e.g., iron and calcium.
In some countries, regulations have been issued for standards of identity for enriched
bread. If bread is labeled “enriched,” it must meet these standards. In white flours,
the losses of magnesium and manganese may reach 90%. These minerals remain
mainly in the bran — the outer part of cereals. For this reason, it seems reasonable
to recommend consumption of bread baked from meals of whole grains instead of
white breads. Sometimes, recommendation of steady consumption of bran alone,
for dietary purpose, needs great care because it may contain many contaminants
such as toxic metals and residue of organic pesticides.
During preparation for cooking or canning, vegetables should be thoroughly
washed before cutting to remove dirt and traces of insecticide spray. Root vegetables
should be scrubbed. The dark outer leaves of greens are rich in iron, calcium, and
vitamins, so they should be trimmed sparingly. Peeling of vegetables and fruit should
be avoided, whenever possible, because minerals and vitamins are frequently con-
centrated just beneath the skin. Potatoes should be baked or cooked in their skins
even for hashed browns or potato salad. However, True et al.53 showed that cooking
potatoes by boiling whole or peeled tubers, as well as microwave cooking and oven
baking, may have a negligible effect on the losses of Al, B, Ca, Na, K, Mg, P, Fe,
Zn, Cu, Mn, Mo, I, and Se. Microwaved potatoes retain nutrients well, and contrary
to popular belief, peeling potatoes does not strip away their vitamin C and minerals.
Whenever practical, any remaining cooking liquid should be served with the vege-
table or used in a sauce or gravy soup. To retain minerals in canned vegetables, one
should pour the liquid from the can into a saucepan and heat at low temperature to
reduce the liquid; then add vegetables to the remaining liquid and heat before serving.
Low temperatures reduce shrinkage and loss of many other nutrients. Cooking and
blanching lead to the most important nutrient losses. The liquid of cooked vegetables
contain about 30–65% of potassium, 15–70% of magnesium and copper, and 20 to
more than 40% of zinc in the fresh samples. Thus, it is reasonable to use these
liquids for soup preparation and diminish the losses this way.54,55 Mineral losses
depend on both the kind of vegetables cooked and the course of the applied process.
Steam blanching generally results in smaller losses of nutrients because leaching is
minimized in this process. Frozen meat and vegetables thawed at ambient temper-
atures lose many nutrients, including minerals in the thaw drip. To avoid these losses,
the drip should be added to the pot where the meal is prepared for consumption.
Frozen fruits should be eaten without delay, fresh just after thawing, together with
the secreted juice. Foods blanched, cooked, or reheated in a microwave oven gen-
erally retain about the same or even higher amounts of nutrients as those cooked by
conventional methods.
2234_C005.fm Page 144 Wednesday, October 25, 2006 3:04 PM
The acid ionization constant (pKa) of the aqua complex ion determines whether
or not the ion would form complexes with a protein. This depends greatly on the
pH of the medium. Because the ionization constant of low charge is 12.6, a metal
ion would form a stable complex only with negatively charged protein in alkaline
media. It cannot bind to cationic proteins because it does not share electrons to form
a covalent bond. This consideration explains why the activity of Ca2+-activated
protease is optimum in the alkaline pH range. Thus a decrease in its activity at acidic
pH values may partly be due to a change in the electronic state of Ca2+.51,52 Generally,
sodium and potassium react only to a limited extent with proteins, whereas calcium
and magnesium are somewhat more reactive. Transition metals, e.g., ions of Cu, Fe,
Hg, and Ag, react readily with proteins, many forming stable complexes with thiol
groups. Calcium ions and ferrous, cupric, and magnesium cations may be integral
parts of certain protein molecules or molecular associations. Their removal by
dialysis or sequestration appreciably lowers the stability of the protein structure
toward heat and proteases.
of many toxic substances but has only limited ability to cope with large quantities
of any single one. Almost any chemical can have a harmful effect if taken in a large
quantity. This is especially true for trace minerals and, to some degree, also for
macroelements, as well as vitamins. For this reason, it is important to understand
the difference between toxicity and hazard. Varieties of food contain toxic chemicals,
but these chemicals do not present a hazard if consumed in allowable amounts.
A number of minerals can produce chronic toxicity when absorbed and retained
in excess of the body’s demands. The quantity of elements accumulated by the
organism is different from the amount in the environment, and this results in bio-
concentration of metals within the organism. Some of the elements are necessary to
the organism for metabolic processes; others, however, that are accumulated in high
proportions — sometimes specifically in some organs — do not have any metabolic
significance for the organism (e.g., arsenic, cadmium, mercury, lead) and are rec-
ognized as toxic. Compounds of metals such as aluminum, arsenic, cadmium, lead,
and mercury contaminate the environment and enter the food supply. However,
among these elements, aluminum compounds are less toxic, and some of the alu-
minum compounds are even used as food additives, e.g., bread leavening, firming,
and emulsifying agents. They may be also applied as drugs, e.g., antiacids, and as
such they enter the gastrointestinal tract, along with aluminum compounds naturally
present in foods.
The toxicity of these metals is a function of the physical and chemical properties
as well as the dose that enters the body. Toxicity is also a function of the ability of
metals to bioaccumulate in body tissues. For this reason, it is very important to have
adequate information about the chemical forms of metals. Currently, this may be
done by applying speciation analysis, which makes it possible to differentiate the
chemical form of the element and assess the safety level of its residue in foods or
drinking water.
5.7.2 ALUMINUM
Aluminum was previously considered to be a completely indifferent element in terms
of metabolic function. Recent studies, however, have shown that the health risk of
aluminum exposure is greatly increased in persons with impaired kidney function.
Alfrey et al.56,57 have found that dialysis encephalopathy in a large number of patients
with renal failure, undergoing chronic dialysis, is attributable to the high aluminum
content of water used for the preparation of dialysates. Patients on dialysis who died
of a neurologic syndrome of unknown cause (dialysis encephalopathy syndrome)
had brain matter concentration of 25 mg aluminum per kg dry weight, while in
controls 2.2 mg/kg was measured. But whether the metal has a causative role in the
pathogenesis of these diseases still remains unconfirmed.
Aluminum is a ubiquitous metal that constitutes about 8% of the Earth’s crust
— the third most abundant crustal element. No wonder that this element continuously
enters the animal organism, both with the feed and drinking water, and also via the
lung and skin. Aluminum is abundantly present in planets of the solar system and
is generally found in biological organisms in trace levels. The concentrations of
aluminum in human tissues from different geographic regions were found to vary
2234_C005.fm Page 146 Wednesday, October 25, 2006 3:04 PM
Nabrzyski and Gajewska29 examined the normal hospital diets and discovered
that the mean daily intake of aluminum was about 21.3±12.4 mg/person. According
to Pennington’s Report,60 the aluminum levels in some special hospital diets were
markedly lower and ranged from 1.8 to 7.33 mg/day. The major food sources of
aluminum in daily diets are grain products, which contain 36.5–69.4%, the next are
milk, yoghurt, and cheese contributing 11.0–36.5%, and the contribution of all other
products was small, in most cases less than 1%.60
Certain plants are able to absorb high levels of aluminum; an example are black
tea leaves, which can contain 445–1552 mg Al/kg, whereas herbal or fruit teas
contain about 45 mg/kg, and herbal teas that were partially supplemented with black
teas can have up to 538 mg Al/kg.29,61 Aluminum in wild mushrooms and cultivated
Agaricus bisporus was determined by Müller et al.62 They found that cultivated
Agaricus bisporus had the lowest level of 14 ± 7 mg/kg of dry matter. Also, the
most popular species such as Boletus and Xerocomus were low in aluminum (30–50
mg/kg dry matter). However, several other species of the genus Suillus, Macrolepiota
rhacodes, Hyoholoma capnoides, as well as individual samples of Russula ochro-
leuca and Amanita rubescens contained high aluminum levels of up to 100 mg/kg
dry matter. The conclusion is that none of the investigated species of mushrooms
contributes significantly to the daily intake of aluminum by humans.
Edible parts of different seafood species such as fish, crustacean, and molluscan
shellfish caught in the North Sea, the Barents Sea, the Baltic Sea, the Northeast
Atlantic, the Greenland waters, as well as in the coastal waters of Norway near an
aluminum smelting plant were analyzed for aluminum. Fillets of lean and fatty fish
contained very low amounts of Al, below 0.2 mg/kg wet weight. Fillets of fish caught
near the smelting plant were characterized by significantly higher levels of alumi-
num, especially in the case of haddock of up to 1 mg/kg wet weight. Presumably
the contamination of the coastal waters by aluminum originating from smelting
plants was responsible for the elevated tissue concentrations. Edible part of crusta-
cean and molluscan shellfish were found to contain up to 5 mg Al/kg wet weight.
A comparison between fillets and different organs of cod showed higher aluminum
concentration in organs, especially in gills (above 0.6 mg/kg wet weight), which are
in continuous contact with the ambient water, and in the brain and heart (above 0.4
mg/kg wet weight). Generally, comparison of the provisional daily intake of 1 mg
aluminum/kg body weight/day, established by the Experts Committee of WHO, and
its content in the edible parts of seafood indicated that the contribution of aluminum
from the edible part of aquatic food does not pose a significant risk in daily diets.9,63
It is worth mentioning that some quantities of the metal can migrate from aluminum
packaging materials, storage containers, and cooking utensils into foods and bever-
ages, especially when the food was in direct and prolonged contact during storage
or boiling process.
It is suggested that the additional daily intake of aluminum resulting from
preparing all foods in uncoated aluminum pans is approximately 3.5 mg. In recent
times, however, most pans are made of stainless steel or Teflon-coated aluminum,
which diminish the migration of aluminum into foods. In Switzerland, for example,
where most pans are of stainless steel or Teflon-treated aluminum, the average
contribution from the use of aluminum utensils to the daily intake of 2–5 mg in the
2234_C005.fm Page 149 Wednesday, October 25, 2006 3:04 PM
diet is estimated to be less than 0.1 mg.64 However, it is worth mentioning that the
migrated quantities of the metal into foods depends to a certain extent on the acidity
of the food and can markedly increase, especially where acidic beverages are stored
or heated in aluminum cans. Generally, it may be said that the quantities of aluminum
contributed to the daily diet from such adventitious sources are rather inconsistent
and insignificant.
Some of the intentional aluminum-containing additives, such as aluminum
ammonium sulphate (officially numbered E 523), aluminum potassium sulphate (E
522), aluminum sodium sulphate (E 521) and sodium aluminum phosphate, acidic
and basic (E 541i and 541ii), are used as stabilizers, buffers, and neutralizing agents.
Other compounds are used as anticaking agents, dough strengtheners, leavening
agents, acid-reacting ingredients in self-rising flour or cornmeal, emulsifying agents
for processed cheese, firming agents, processing aids, stabilizers, thickeners, curing
agents, components in bleaching agents, and texturizers’ agents. The acidic form of
sodium aluminum phosphate reacts with sodium bicarbonate to cause a leavening
action. It is used in biscuit, pancake, waffle, cake, doughnut, and muffin mixes,
frozen rolls and yeast doughs, and canned biscuits and self-rising flours. The basic
form of sodium aluminum phosphate is used in processed cheese and cheese foods
as an emulsifying agent to give cheese products a soft texture and to allow easy
melting. It is commonly used in individually wrapped, sliced, processed cheeses,
and may result in about 50 mg of aluminum per slice. Sodium aluminum phosphate
is also used as a meat binding agent. Sodium aluminum sulphate is an acidifying
agent found in many household baking powders. It contains about 70 mg of alumi-
num per teaspoon. A slice of cake or bread made with an aluminum-containing
baking powder may contain 5–15 mg of aluminum. Most commercial baking pow-
ders and some that are sold for household use contain monocalcium phosphate rather
than aluminum salts. Recently, the use of aluminum salts as firming agents in pickled
vegetables and some pickled fruits has largely been replaced by calcium oxide in
both industrial and home pickling, although several brands of commercially packed
pickles still may contain ammonium or potassium sulphates of aluminum. Aluminum
silicates (sodium aluminum silicate, aluminum calcium silicate, and hydrated sodium
calcium aluminosilicate) are found in anticaking agents in salt, nondairy creamers,
and other dry, powdered products.60 The most commonly used foods that may contain
substantial amounts of aluminum from food additives are processed cheeses, baking
powders, cake mixes, frozen dough, pancake mixes, self-rising flours, and pickled
vegetables.
A Committee of the Life Sciences Research Office of the Federation of American
Societies for Experimental Biology reviewed the safety of GRAS substances
including aluminum compounds under contract with the FDA and estimated that the
average daily intake of aluminum from aluminum compounds added to foods was
about 20 mg, and that about 75% of this was in the form of sodium aluminum
phosphate.60
Current estimates of aluminum intake range from about 2–6 mg/day for children,
and 6–14 mg/day for teenagers and adults. Low total body burden of aluminum
coupled with urinary excretion suggests that even at high levels of consumption,
only small amounts, ca. 1% of the normally consumed doses, are absorbed by a
2234_C005.fm Page 150 Wednesday, October 25, 2006 3:04 PM
healthy person from the gastrointestinal tract. These small amounts absorbed from
diets are then excreted by healthy kidneys, so no bodily accumulation occurs. On
the other hand, patients with renal failure are at greater risk of high doses of
aluminum because administered aluminum may be retained consequent on the func-
tional impairment of the kidneys. Aluminum is primarily localized in bone, liver,
brain, heart, and spleen.9
In conclusion, there is unknown risk to healthy people from typical dietary
intakes of aluminum. Risk may arise only from habitual consumption of gram-
quantities of aluminum antacids over long period of time, and may increase sub-
stantially in persons with impaired kidney function. Long-term intravenous appli-
cation also results in serious toxicity.
Factors influencing exposure to aluminum and its tolerance by human subjects
have been extensively reviewed by the Joint FAO/WHO Expert Committee on Food
Additives, and the provisional tolerable weekly intake of 7 mg/kg body weight has
been established.9
5.7.3 ARSENIC
Pentavalent and trivalent arsenicals react with biological ligands in different ways.
The trivalent form reacts with the thiol protein groups, resulting in enzyme inacti-
vation, structural damage, and a number of functional alterations. The pentavalent
arsenicals, however, do not react with –SH groups. Arsenates can competitively
inhibit phosphate insertion into the nucleotide chains of the DNA of cultured human
lymphocytes, causing false formation of DNA because of instability of the arsenate
esters. Dark repair mechanisms are also inhibited, leading to persistence of these
errors in the DNA molecules. Binding differences of the trivalent and pentavalent
forms arsenic to differences in the accumulation of this element. Trivalent inorganic
arsenic is accumulated at a higher level than its pentavalent form. Organic arsenic
compounds are considered less toxic or nontoxic in comparison to inorganic arsenic,
of which trivalent arsenicals are the most toxic forms.
Dietary arsenic represents the major source of arsenic exposure for most of the
general population. Consumers eating large quantities of fish usually ingest signif-
icant amounts of arsenic, primarily as organic compounds, especially those with
structures similar to arsenobetaine and arsenocholine as well as various other arsenic
derivatives. Fish of many species contain arsenic between 1 and 10 mg/kg. Arsenic
levels at or above 100 mg/kg have been found in bottom feeders and shellfish. Both
lipid and water-soluble organoarsenic compounds have been found, but the water-
soluble forms, mainly the quaternary arsonium derivates, constitute the larger portion
of the total arsenic in marine animals.9,65 Studies in mice have demonstrated that
after the administration of organoarsenic compounds, over 90% of the arsenobetaine
and arsenocholine doses were absorbed, and about 98% of the administered dose of
arsenobetaine was excreted unchanged in the urine, whereas 66 and 9% of the single
oral dose of arsenocholine was excreted in the urine and feces, respectively, within
3 days. Most of the arsenocholine was oxidized in animal organism to arsenobetaine,
and in this form was excreted in the urine. The retention of arsenocholine in the
2234_C005.fm Page 151 Wednesday, October 25, 2006 3:04 PM
animal body, following administration, was greater than the retention of arsenobe-
taine. The fate of organic arsenicals in humans still has not been fully clarified.
The little information available on organoarsenicals present in fish and other
seafood may indicate that these compounds appear to be readily excreted in the
urine in an unchanged chemical form, with most of the excretion occurring within
2 d of ingestion. Volunteers who consumed flounder excreted 75% of the ingested
arsenic in urine within 8 d after eating the fish. The excreted arsenic was in the same
chemical form as it was in the fish. Less than 0.35% was excreted in the feces. There
are no data on tissue distribution of arsenic in humans after ingestion of arsenic
present in fish and seafood. Also, there have been no reports of ill effects among
ethnic populations consuming large quantities of fish that result in organoarsenic
intakes of about 0.05 mg/kg of body weight per day.9 Inorganic tri- and pentavalent
arsenicals are metabolized in humans, dogs, and cows to less toxic methylated forms
such as monomethylarsonic and dimethylarsinic acids.66
5.7.4 MERCURY
Contrary to organic arsenicals, organic mercury compounds, especially methyl-
mercury, are recognized as the more dangerous for humans than the inorganic
compounds. Most foods with the exception of fish contain very low amounts of total
mercury (< 0.01 mg/kg), almost entirely in the form of inorganic compounds. Over
90% of mercury in fish and shellfish is in the form of methylmercury. This is so
because the fish feed on aquatic organisms that contain this compound derived from
the biomethylation of inorganic mercury by microorganisms. Marlin is the only
pelagic fish known to have more than 80% of the total muscle mercury present as
inorganic mercury.67 The amount of methylmercury is especially high in large, old
fish of predatory species such as the shark and swordfish. In freshwater fish, the
mercury content depends on its concentration in water and sediment and on the pH
of water. The concentration of methylmercury in most fish is generally less than 0.4
mg/kg, although predators such as swordfish, shark, and pike may contain up to
several milligrams of methylmercury per kilogram in the muscles. The intake of
methylmercury depends on fish consumption and the concentration of methyl-
mercury in the fish consumed. Many people eat about 20–30 g of fish per day, but
certain groups eat 400–500 g per day. Apparently, the daily dietary intake of methyl-
mercury can range from about 0.2 to 3–4 µg/kg body weight.
Studies of the biokinetics of methylmercury after ingestion show that its distri-
bution in the tissues is more homogenous than that of other mercury compounds,
with the exception of elemental mercury. The most important features of the distri-
bution pattern of methylmercury are a high blood concentration, a high ratio of
erythrocyte/plasma concentrations (about 20), and a high deposition in the brain.
Another important characteristic is slow demethylation, which is a critical detoxifi-
cation step. Methylmercury and other mercury compounds have a strong affinity for
sulphur and selenium. Although selenium has been suggested to provide protection
against the toxic effect of methylmercury, no such antagonistic effect has been
demonstrated in humans.
2234_C005.fm Page 152 Wednesday, October 25, 2006 3:04 PM
A variety of effects have been observed in animal experiments with toxic doses,
but some of the adverse health effects, such as renal damage and anorexia, have not
been observed in humans exposed to high doses. The primary tissues of concern in
humans are the nervous system and particularly the developing brain, and these have
stimulated a wide range of epidemiologial studies. Methylmercury passes about 10
times more readily through the placenta than other mercury compounds. The dermal
absorption of methylmercury is similar to that of inorganic mercury salts.
The LD50 values after oral administration are 25 mg/kg of body weight in old
rats (450 g of body weight) and 40 mg/kg in young rats (200 g). The clearance half-
time of methylmercury for the human whole body is about 74 d, and for blood
compartment it is about 52 d.10
5.7.5 CADMIUM
Cadmium shares a number of chemical properties with zinc and mercury, but in
contrast to mercury, it is incapable of environmental methylation due to the instability
of the monoalkyl derivative. Similarities and differences also exist in the metabolism
of zinc, cadmium, and mercury. Metallothioneins (MTs) and other Cd-binding pro-
teins hold and transport Cd, Zn, and Hg within the body. MTs are metal-binding
proteins of relatively low molecular mass with a high content of cysteine residues
that have a particular affinity for cadmium, as well as for zinc and copper, and can
affect their toxicity. The MT synthesis in organisms is induced by these metals, and
MT is involved in their storage in the organs. Zinc metallothionein can detoxify free
radicals. Cadmium-induced metallothionein is able to bind cadmium intracellularly
and, in this way, protects the organism against the toxicity of this metal. Cadmium
is transported in the plasma as a complex with metallothionein and may be toxic to
the kidney when excreted in the glomerular filtrate.
Most cadmium in urine is bound to metallothionein. This protein occurs in the
organism as at least four genetic variants. The two major forms, I and II, are
ubiquitous in most organs, particularly in the liver and kidney, and also in brain.
Metallothionein isolated from adult or fetal human livers contained mainly zinc and
copper, whereas that from human kidney contained zinc, copper, and cadmium. 9,11
Cadmium, along with the other two metals, is bound to the peptide by mercaptide
bonds and are arranged in two distinct clusters, namely, a four-metal cluster called
the α domain and a three metal-cluster called cluster β, at the C terminal of the
protein. The α cluster is an obligate zinc cluster, whereas the zinc in cluster β may
be replaced by copper or by cadmium.
Reaction with metallothionein is the basis for metabolic interactions between
these metals. Metallothionein III is found in the human brain and differs from I and
II by having six glutamic acid residues near the terminal part of the protein. Met-
allothionein III is thought to be a growth inhibitory factor, and its expression is not
regulated by metals; however, it does bind zinc. Another proposed role for metal-
lothionein III is participation in the use of zinc as a neuromodulator, as metallothio-
nein III is present in the neurons that store zinc in their terminal vesicles. Metal-
lothionein IV occurs during differentiation of stratified squamous epithelium, but it
is known to have a role in the absorption or toxicity of cadmium. Metallothionein
2234_C005.fm Page 153 Wednesday, October 25, 2006 3:04 PM
5.7.6 LEAD
The JECFA and other WHO committees have recognized that infants and children
are the groups at highest risk of lead exposure from food and drinking water. Lead
as an anthropogenic contaminant finds its way into the air, water, and surface soil.
Lead-containing manufactured products also contribute to the lead body burden. The
domestic environment in which infants and children spend the greater part of their
2234_C005.fm Page 154 Wednesday, October 25, 2006 3:04 PM
TABLE 5.5
Metals Toxicity for Human7–11,29,60,63,65–70
Daily Intake Absorption
Metal Toxic Effects (mg/adult person) Source of Exposure (%)
Aluminum Encephalopathy (dialysis dementia), 9–36 Grain, some bakery and dairy products made < 1–7%
osteodystrophy in patients exposed to with aluminum additives acting as buffers,
high doses, elevated content in brain, dough strengtheners, and leavening agents,
cerebrospinal fluids, serum, and hair in acid-reacting ingredients in self-rising flour or
patients with dialysis dementia. It is cornmeal, emulsifying agents for processed
proposed that signs of neurotoxicity are cheeses, stabilizers, texturizes, and anticaking
manifested when the brain concentration agents, thickeners and curing agents, and a
exceeds 10–20 times the normal level few other intentional used additives. High
2234_C005.fm Page 156 Wednesday, October 25, 2006 3:04 PM
(> 2 mg/kg dry weight of the grey levels are observed in seafood, black and
matter). Aluminum concentration in herbal teas, as well as spices. Level of
human tissues probably reflects the aluminum naturally present in water is
geochemical environment of individuals generally low (0.001–1 mg/l), but when water
and locally grown food products. There is treated with aluminum sulphate salts (as
is no risk of toxicity to healthy people coagulating agent), its content may rise
from typical dietary intakes threefold (to 0.6 mg/l) of the normal accepted
level (0.2 mg/l)
Arsenic Inorganic compounds cause abnormal 0.0–0.29 Contaminated water, food containing residue > 90% organoarsenic
skin hyperpigmentation, hyperkeratosis, of arsenic pesticides, and veterinary drugs, compounds and high
skin, and lung cancer. Organoarsenic fish, and shellfish are the richest source of inorganic trivalent
compounds present in fish are less or organic compounds, e.g., arsenobetaine and compounds
nontoxic arsenocholine
Mineral Components in Foods
Cadmium Accumulates mainly in liver and renal < 0.01–0.1 Oysters, cephalopods, crops growing on land 3–10%, cadmium
cortex, nephrotoxicity, tubular damage fertilized with high contaminated phosphate bound to
impairing the reabsorption of calcium and sewage sludge, cadmium leaching from metallothionein is
and phosphate resulting in enamel and pottery glazes, contaminated well absorbed
decalcification, osteoporosis, and water
osteomalacia. Disturbs vitamin D
hydroxylation to its active form, Itai Itai
disease, embryotoxic in early gestation.
Impairs immune system, and calcium
and iron absorption. Causes
hypertension and cardiovascular disease;
kidney is the critical organ
Lead At blood levels greater than 40 µg/100 ml, < 0.1–0.2 Food contaminated from leaching of glazes of 5–10% in adult person,
exerts a significant effect on hemopoietic ceramic foodware, as well as from motor 40–50% in children
2234_C005.fm Page 157 Wednesday, October 25, 2006 3:04 PM
TABLE 5.6
Provisional Tolerable Weekly Intake (PTWI) of Toxic Elements According
to the Joint FAO/WHO Expert Committee on Food Additives for Man8,9
Element PTWI Comments
REFERENCES
1. Anke, M. et al., Lithium, in Handbook of Nutritionally Essential Mineral Elements,
O’Del, B.L. and Sunde, R.A., Eds., Marcel Dekker, New York, Basel, Hong Kong,
1997, p. 465.
2. Morohashi, T., Sano, T., and Yamada, S., Effects of strontium on calcium metabolism
in rats: I. A distinction between the pharmacological and toxic doses, Jpn. J. Phar-
macol., 64, 155, 1994.
3. Morohashi, T. et al., Effects of strontium on calcium metabolism in rats. II. Strontium
prevents the increased rate of bone turnover in ovariectomized rats, Jpn. J. Pharma-
col., 68, 153, 1995.
4. O’Dell, B.L. and Sunde, R.A., Eds., Handbook of Nutritionally Essential Mineral
Elements, Marcel Dekker, New York, 1997.
5. Nabrzyski, M. and Gajewska, R., Content of strontium, lithium and calcium in
selected milk products and in some marine smoked fish, Nahrung/Food, 46, 204, 2002.
6. Nielsen, F.H., Ultratrace elements in nutrition: Current knowledge and speculation,
J. Trace Elements Exp. Med., 11, 251, 1998.
7. WHO, Trace Elements in Human Nutrition and Health, WHO, Geneva, 1996, p. 222.
8. WHO, Food Additives Series, 21, Toxicological Evaluation of Certain Food Additives
and Contaminants, 30th Meeting of the Joint FAO/WHO Expert Committee on Food
Additives, Cambridge, U.K., 1986.
9. WHO, Food Additives Series, 24, Toxicological Evaluation of Certain Food Additives
and Contaminants, 33rd Meeting of the Joint FAO/WHO Expert Committee on Food
Additives, Cambridge, U.K., 1989.
2234_C005.fm Page 159 Wednesday, October 25, 2006 3:04 PM
10. WHO, Food Additives Series, 44, Safety Evaluation of Certain Food Additives and
Contaminants, 53 Meeting of the Joint FAO/WHO Expert Committee on Food Addi-
tives, Geneva, 2000.
11. WHO, Food Additives Series, 46, Safety Evaluation of certain Food Additives and
Contaminants, 55th Meeting of the Joint FAO/WHO Expert Committee on Food
Additives. Geneva, 2001.
12. WHO, Food Additives Series, 17, Toxicological Evaluation of Certain Food Additives,
26 Report of Joint FAO/WHO Expert Committee on Food Additives, Geneva, WHO,
Technical Report, Ser. 683, Rome, 1982.
13. WHO, Food Additives Series, 18, IPCS, Toxicological Evaluation of Certain Food
Additives and Contaminants, 27 Report of Joint FAO/WHO Expert Committee on
Food Additives, Technical Report, Ser. 696, Geneva, 1983.
14. Recommended Dietary Allowances, 10th ed., National Research Council, Food and
Nutrition Board, National Academy Press, Washington, D.C., 1989.
15. Feltman, J., Ed., Prevention’s Giant Book of Health Facts, Rodale Press, Emmaus,
PA, 1990.
16. Johnson, J.L., Molybdenum, in Handbook of Nutritionally Essential Mineral Ele-
ments, O’Dell, B.L. and Sunde, R.A., Eds., Marcel Dekker, New York, 1997.
17. Bremner, I., Heavy metal toxicities, Q. Rev. Biophys., 7, 75, 1974.
18. Rosenberg, J.H. and Solomons, N.W., Physiological and pathophysiological mecha-
nism in mineral absorption, in Absorption and Malabsorption of Minerals, Vol. 12,
Solomons, N.W. and Rosenberg, J.H., Eds., Alan R. Liss, Inc., New York, 1984.
19. Eschleman, M., Ed., Introductory Nutrition and Diet Therapy, Lippincot J.B. Co.,
London, 1984.
20. Gajewska, R. and Nabrzyski, M., Molybdenum content in children and adults full
day’s food and in some foodstuffs, Bromat. Chem. Toksykol., 24, 185, 1991.
21. Hendler, S.S., Ed., The Doctor’s Vitamin and Mineral Encyclopaedia, Simon and
Schuster, New York, 1990.
22. Causeret, J., Fish as a source of mineral nutrition, in Fish as Food, Vol. 2, Borgstrom,
G., Ed., New York, London, Academic Press, 1962, p. 205.
23. Çelik, U. and Oehlenschläger, J., Zinc and copper in marine fish samples collected
from the Eastern Mediterranean Sea, Eur. Food Res. Technol., 220, 37, 2005.
24. Gajewska, R. et al., Trace levels of metals in bee honey, Bromat. Chem. Toksykol.,
17, 259, 1984 (in Polish).
25. Gajek, O., Nabrzyski, M., and Gajewska, R., Metallic impurities in imported canned
fruit and vegetables and bee honey. Roczniki PZH, 38, 14, 1987 (in Polish).
26. Lopez, A., Ward, D.R., and Williams, H.L., Essential elements in oysters (Crassostrea
virginica) as affected by processing method, J. Food Sci., 48, 1680, 1961, 1983.
27. Marzec, Z., Kunachowicz, H., Iwanow, K., and Rutkowska, U., Eds., Tables of Trace
Elements in Food Products, National Food and Nutrition Institute, Warsaw, 1992 (in
Polish).
28. Mateos, C.J. et al., Chromium content in breakfast cereals depending on cereal grains
used in their manufacture, Eur. Food Res. Technol., 220, 42, 2005.
29. Nabrzyski, M. and Gajewska, R., Aluminum and fluoride in hospital daily diets and
teas, Z. Lebensm. Unters. Forsch., 201, 307, 1995.
30. Paslawska,
⁄ S. and Nabrzyski, M., Assay of iodine in powdered milk, Bromat. Chem.
Toxicol., 8, 73, 1975 (in Polish).
31. WHO, Environmental Health Criteria, in Fluorine and Fluorides, WHO, Geneva, 36,
1984.
2234_C005.fm Page 160 Wednesday, October 25, 2006 3:04 PM
32. Williams, D.M., Clinical significance of copper deficiency and toxicity in the world
Population, in Clinical Biochemical and Nutritional Aspects of Trace Elements, Vol.
6, Prasad, A.S., Ed., Alan R. Liss, Inc., New York, 1982, p. 277.
33. Wilpinger, M., Schönsleben, I., and Pfanhauser, W., Chrom in Oesterreichischen
Lebensmitteln, Z. Lebensm. Unters. Forsch. 201, 521, 1995 (in German).
34. Wojnowski, W., Skladniki
⁄ ⁄ ´
mineralne, in Chemiczne i Funkcjonalne Wlasciwosci ´ Sklad-
⁄
· ´ Sikorski, Z. E., Ed., Wydawnictwa Naukowo-Techniczne, Warszawa,
ników Zywnosci,
1994, p. 76 (in Polish).
35. FAO/WHO Ed., Summary of Evaluations Performed by the Joint FAO/WHO Expert
Committee on Food Additives 1956–1993, International Life Science Inst. Press,
Geneva, 1994.
36. Du, Z. and Bramlage, W.J., Superoxide dismutase activities in Senescin Aplle Fruit
(Malus domestica borkh), J. Food Sci., 59, 581, 1994.
37. Ramanathan, L., and Das, N. P., Effect of natural copper chelating compounds on
the prooxidant activity of ascorbic acid in steam-cooked ground fish, Int. J. Food Sci.
Technol., 28, 279, 1993.
38. Hultin, H.O., Oxidation of Lipids in seafoods, in Seafoods: Chermistry, Processing
Technology and Quality, Shahidi, F. and Botta, J.R., Eds., Chapman and Hall, London,
1994, p.49.
39. Wu, S.Y. and Brewer, M.S., Soy protein isolate antioxidant effect on lipid peroxidation
of ground beef and microsomal lipids, J. Food Sci., 59, 702, 1994.
40. Pearson, A.M., Love, J.D., and Shorland, F.B., “Warmed over” flavor in meat, poultry,
and fish, Adv. Food Chem., 23, 2, 1977.
41. Oelingrath, I.M. and Slinde, E., Sensory evaluation of rancidity and off-flavor in
frozen stored meat loaves fortified with blood, J. Food Sci. 53, 967,1988.
42. Miller, D.K. et al., Lipid oxidation and warmed-over aroma in cooked ground pork
from swine fed increasing levels of iron, J. Food Sci., 59, 751, 1994.
43. Miller, D.K. et al., Dietary iron in swine affects nonheme iron and TBAR’s in pork
skeletal muscles, J. Food Sci., 59, 747, 1994.
44. Castell, C.H., MacLeam, J., and Moore, B., Rancidity in lean fish muscle. IV Effect
of sodium chloride and other salts, J. Fish. Res. Board Can., 22, 929, 1965.
45. Castell, C.H. and Spears, D. M., Heavy metal ions and the development of rancidity
in blended fish muscle, J. Fish. Res. Board Can., 25, 639, 1968.
46. Kraniak, J.M. and Shelef, L. A., Effect of ethylenediaminetetraacetic acid (EDTA)
and metal ions on growth of Staphylococcus aureus 196 E in culture media, J. Food
Sci., 53, 910, 1988.
47. Ha, Y.W. et al., Calcium binding of two microalgal polysaccharides and selected
industrial hydrocolloids, J. Food Sci., 54, 1336, 1989.
48. WHO, Food Additives Series, 30, Toxicological Evaluation of Certain Food Additives
and Naturally Occurring Toxicants, 39 Meeting of the Joint FAO/WHO Expert Com-
mittee on Food Additives, Geneva, 1993.
49. WHO, Food Additives Series, 32, Toxicological Evaluation of Certain Food Additives
and Contaminants, 41 Meeting of the Joint FAO/WHO Expert Committee on Food
Additives, Geneva, 1993.
50. Samant, S.K. et al., Protein-polysaccharide interactions: a new approach in food
formulation, Int. J. Food Sci. Technol., 28, 547, 1993.
51. Barbut, S. and Mittal, G.S., Rheological and gelation properties of meat batters
prepared with three chloride salts, J. Food Sci., 53, 1296, 1985.
2234_C005.fm Page 161 Wednesday, October 25, 2006 3:04 PM
52. Asghar, A. and. Bhatti A. R., Endogenous proteolytic enzymes in skeletal muscle:
their significance in muscle physiology and during postmortem aging events in
carcasses, Adv. Food Res., 31, 343, 1987.
53. True, R.H. et al., Changes in the nutrient composition of potatoes during home
preparation, III, Miner. Am. Potato J., 56, 339, 1979.
54. Trzebska-Jeske, I. et al., The effect of mechanical processing on nutritional value of
groats produced in Poland, Roczniki PZH., 24, 717, 1973 (in Polish).
55. Rutkowska, U., The effect of the grinding process on contents of copper, zinc, and
manganese in rye and wheat flour, Roczniki PZH., 26, 339, 1975 (in Polish).
56. Alfrey, A.C., Le Gendre, G.R., and Kaehney, W.D., The dialysis encephalopathy
syndrome, N. Engl. J. Med., 294, 184, 1976.
57. Alfrey, A.C., Hegg, A., and Craswell, P., Metabolism and toxicity of aluminum in
renal failure, Am. J. Clin. Nutr., 33, 1509, 1980.
58. Kraus, A.S. and Forbes, W.F., Aluminum, fluoride and the prevention of Alzheimer’s
disease, Can. J. Publ. Health, 83, 97, 1992.
59. Schenkel, H. and Klüber, J., Mögliche Auswirkungen einer erhöhten Aluminiu-
maufnahme auf Landwirtschaftliche Nutziere, Obers. Tierernährung., 15, 273, 1987.
60. Pennington, J.A.T., Aluminum content of foods and diets, Food Addit. Contam., 5,
161, 1987.
61. Fairweather-Tait, S.J. et al., Aluminum in the diet Human Nutrition, Food Sci. Nutr.,
41F, 183, 1987.
62. Müller, M., Anke M., and Illing-Günther, H., Aluminum in wild mushrooms and
cultivated Agaricus bisporus, Z. Lebensm. Unters. Forsch., 205, 242, 1997.
63. Ranau, R., Oelhlenschläger, J., and Steinhart, H., Aluminum content in edible parts
of seafood, Eur. Food Res. Technol., 212, 431, 2001.
64. Müller, J.P., Steinegger, A., and Schlatter, C., Contribution of aluminum from pack-
aging materials and cooking utensils to the daily aluminum intake, Z. Lebensm.
Unters. Forsch., 197, 332, 1993.
65. Vaessen, H.A.M.G. and van Ooik, A., Speciation of arsenic in Dutch total diets:
methodology and results, Z. Lebensm. Unters. Forsch., 189, 232, 1989.
66. Peoples, S.A., The metabolism of arsenic in man and animals, in Arsenic-Industrial,
Biomedical, Environmental Perspectives, Proceedings of the Arsenic Symposium,
Lederer, W.H. and Fensterheim, R.J., Eds., Van Nostrand Reinhold Co., New York,
1983, p. 125.
67. Cappon, C.J. and Smith, J.C., Chemical form and distribution of mercury and sele-
nium in edible sea food, J. Anal. Toxicol., 6, 10, 1982.
68. Nabrzyski, M. and Gajewska, R., Determinations of mercury, cadmium and lead in
food, Roczniki PZH, 35, 1, 1984 (in Polish).
69. Nabrzyski, M., Gajewska, R., and Lebiedzinska, A., Arsenic in daily food rations of
adults and children, Roczniki PZH, 36, 113, 1985 (in Polish).
70. WHO, Environmental health criteria, in Arsenic, WHO, Geneva, 18, 1981.
71. Beyersmann, D., The significance of interactions in metal essentiality and toxicity,
in Metals and Their Compounds in the Environment, Merian, E., Ed., VCH Verlags-
gesellschaft Weinheim, NewYork., Basel, 1991, p. 491.
2234_C005.fm Page 162 Wednesday, October 25, 2006 3:04 PM
2234_C006.fm Page 163 Thursday, October 26, 2006 8:00 AM
6 Mineral Components in
Foods of Animal Origin
and in Honey
Piotr Szefer and Malgorzata
/ Grembecka
CONTENTS
163
2234_C006.fm Page 164 Thursday, October 26, 2006 8:00 AM
6.1 INTRODUCTION
In general, variations in levels of mineral components in nonplant food are not as
broad as those recorded for food of plant origin. Transfer of nutritional elements
goes primarily from soil to humans by means of plants, although it can also go,
except for vegetarians, via a secondary step from the bodies of farm animals.1,2 This
disparity can have serious implications for human health. For instance, iron has a
great ability to concentrate in animals, especially in their livers, kidneys, and mus-
cles, whereas this metal usually occurs in plant tissues at lower levels and in chemical
form, not readily absorbed by the human gut. Zinc, like iron, occurs in animal tissues
in greater amounts than in cereals. Moreover, meat does not contain phytic acid and
other plant compounds responsible for inhibition of metal absorption in the digestive
canal of humans. In general, meat is a poor source of trace elements, except for liver
and kidney, which are enriched in some metals such as cadmium, copper, and zinc.
Therefore, offal is generally a rich source of these metals. An example of accumu-
lative abilities is the liver of sea mammals, which contains metalothionein (MT) as
low-molecular-weight protein, which plays an important role in metal homeostasis
and detoxification. MT exhibits a strong, competitive affinity for some trace elements
(e.g., copper and zinc) and can constitute a reservoir for these metals.
Some common seafood, especially soft tissue of oysters and the whole body of
squids, can contain extremely high levels of copper, zinc, and cadmium, respectively.
Trace elements such as selenium, mercury, and arsenic can be biomagnified along
the trophic chain in the marine ecosystems, thereby reaching higher concentrations
at the top of the chain. For instance, significant bioaccumulation of methylmercury
in seafood has resulted in a serious food safety problem. This organomercury com-
pound is characterized by significantly higher toxicity as compared to inorganic
species of mercury.3 Seafood may be also contaminated by organotins, especially
2234_C006.fm Page 165 Thursday, October 26, 2006 8:00 AM
tributyltin (TBT). In the case of inorganic tin, few serious problems have been
reported in food except when elevated levels are occasionally found in some canned
products, usually acidic foods. As regards arsenic, its total concentration in fish
products is relatively high, with a great percentage consisting of the nontoxic orga-
noarsenic compound arsenobetaine. Therefore, consumers do not expose themselves
to high risk by consuming significant amounts of arsenic in seafood.
Knowledge of the total level of trace elements in foodstuffs is very important
for establishing dietary requirements; however, the levels of the forms of elements
in foods are also needed to estimate their safety and nutritional quality. Although
most regulations on metals and metalloids in food are based on their total concen-
trations, only a few regulations consider the specific forms of chemical elements.
Some organizations, e.g., the World Health Organization (WHO) or the U.S. Food
and Drug Administration (FDA), appear to pay great attention to the speciation of
the elements, and it has been reported that they are just starting to recommend
speciation analysis and regulate food, based on the species of mercury, arsenic, or
tin.4,5 With this requirement in mind, consideration has been given to individual
species of mercury, arsenic, selenium, and tin in different groups of foods in Chapter
6 and Chapter 7 of this book. It should be stressed that there are various factors
responsible for modifying metal toxicity, including interactions which occur among
the metals themselves or between metals and other dietary components. Such pro-
cesses can either decrease or enhance the metal toxicity.6 For instance, selenium
protects against acute toxicity of mercury, whereas zinc deficiency enhances lead
toxicity, and iron deficiency favors gastrointestinal cadmium absorption. Metals such
as arsenic, cadmium, chromium, nickel, and lead have been classified as posing a
potential cancer risk to human beings.6
6.2.2 MAGNESIUM
Magnesium (Mg) is commonly found in foods. Meat products contain this mineral
from 13.0 to 42.6 mg Mg/100 g (see Table 6.1). As can be seen in Table 6.2, a
similar range of concentrations is reported for dairy products (7.9 to 56.0 mg/100
g). Cow milk contains lower levels of Mg (10.9 mg/100 g) than raw goat milk (75.7
mg/100 g) and sheep milk (62.6 mg/100 g). The concentrations of magnesium in
166
TABLE 6.1
Macronutrients in Meat and Seafood (in mg/100 g w/wa)
Name Origin n Ca K Mg Na P Ref.
Meat
Pork loin Spain 42 38.7 ± 6.55 3684 ± 300 — 405 ± 37.6 — 10
Carcass meatb U.K. 9 — — — — 7
Poultryb U.K. 7.8 — — — — 7
Poultryb U.S. 22.4 ± 18.4 295 ± 42.8 26.9 ± 2.78 308 ± 283 221 ± 21.7 8
8.0 – 54.6 246 – 350 25.2 – 30.7 59.5 – 663 197 – 254
Meat productsb U.K. 35 — — — — 7
Meat productsb U.S. 22.1 ± 19.5 318 ± 94.7 22.7 ± 5.96 620 ± 625 225 ± 57.2 8
5.1 – 69.3 121 – 420 13.0 – 34.0 61.5 – 1950 133 – 354
2234_C006.fm Page 166 Thursday, October 26, 2006 8:00 AM
Fish
Fishb U.K. 131 — — — — 7
Fishb U.S. 44.7 ± 51.8 235 ± 112 33.6 ± 6.27 286 ± 126.3 190 ± 18.2 8
12.2 – 122 95.5 – 369 28.9 – 42.6 136 – 445 179 – 217
Seafood
Shrimp Polish market 29.9 ± 14.6 40.1 ± 45.3 21.7 ± 13.7 536 ± 226 — 14
Shrimp Polish market 12.3 30.3 14.5 667 — 14
Crab claws meat Turkey 149 256 — 266 — 12
Crab claws meat Turkey 151 308 — 354 — 12
Crab body meat Turkey 64.9 244 — 327 — 12
Crab body meat Turkey 87.6 303 — 319 — 12
Crab claws meat boiled Polish market 379 221 72.1 255 — 14
Mineral Components in Foods
Lobster claws meat Polish market 162 73.7 38.3 369 — 14
boiled
Mussel Greenland — — — 272 – 802 — 13
Mussel boiled Polish market 7.13 ± 6.83 117 ± 159 19.7 ± 3.36 184 ± 197 — 14
Mussel raw Polish market 14.0 97.5 53.2 194 — 14
Octopus raw tentacles Polish market 6.12 ± 2.85 155 ± 117 36.3 ± 12.8 411 ± 404 — 14
Octopus raw small Polish market 9.3 62.8 13.3 534 — 14
a w/w = wet weight.
b Total diet studies, mean of all the products from the group.
c Recalculated from dry to wet weight.
2234_C006.fm Page 167 Thursday, October 26, 2006 8:00 AM
TABLE 6.2
Macronutrients in Milk and Dairy Products (in mg/100 g w/w)
Name Origin n Ca K Mg Na P Ref.
Milk
Dairy milk Sweden 114 ± 3 160 ±4 12 ± 0 40 ± 2 90 ± 2 15
110 – 121 160 – 170 12.0 – 12.0 37 – 45 88 – 93
Low-fat (2%) milk, fluid U.S. 106 153 11.1 40.4 89.2 8
Milkb U.S. 104 ± 6.92 149 ± 8.14 10.8 ± 0.74 39.5 ± 2.29 86.6 ± 5.30 8
95.8 – 109 140 – 155 10.0 – 11.4 36.9 – 41.2 80.5 – 90.1
Milkb U.K. 83.5 — — — — 7
Raw cow milkc Canary Islands 151 161 ± 20.1 11.1 ± 1.81 11.1 ± 1.81 51.8 ± 10.6 — 16
2234_C006.fm Page 168 Thursday, October 26, 2006 8:00 AM
Milk-based powder formulasc Nigeria 6 37.4 ± 3.38 — 2.54 ± 0.16 16.4 ± 1.66 — 24
Milk-based powder formulasc U.K. 12 33.4 ± 5.15 — 4.10 ± 0.37 17.9 ± 4.33 — 24
Milk-based powder formulasc U.S. 9 38.6 ± 6.90 — 3.53 ± 0.96 18.6 ± 4.46 — 24
Soy-based infant formula, oil-filled 5 377 ± 7.91 530 ± 16.2 39.5 ± 1.01 172 ± 13.5 220 ± 5.95 22
374 – 391 512 – 564 31.5 – 40.2 158 – 197 214 – 231
Soy-based powder formulac U.S. 6 50 ± 5.01 — 3.81 ± 1.07 22.5 ± 4.53 — 24
Whey-based formula, partially oil-filled 5 599 ± 8.97 722 ± 30.5 54.4 ± 1.52 220 ± 6.18 387 ± 16.4 22
584 – 608 674 – 764 52.6 – 56.5 212 – 231 357 – 407
Whey-based infant formula, oil-filled 5 389 ± 20.0 544 ± 36.2 38.6 ± 22.6 203 ± 11.1 275 ± 14.8 22
Mineral Components in Foods of Animal Origin and in Honey
370 – 427 499 – 596 36.6 – 42.9 187 – 211 249 – 295
Whey-based formula, partially oil-filled 5 599 ± 8.97 722 ± 30.3 54.4 ± 1.52 220 ± 6.18 387 ± 16.4 22
584 – 608 674 – 764 52.6 – 56.5 212 – 231 357 – 407
Cow milk wheyc 5 0.07 ± 0.001 — 8.15 ± 0.29 41.7 ± 0.87 — 23
Milk whey coming from cow milkc 5 46.1 ± 3.40 — 7.09 ± 0.582 46.31 ± 3.5 — 18
Milk whey coming from UHT cow milkc 5 31.7 ± 2.82 — 5.05 ± 0.49 44.7 ± 3.20 — 18
UHT cow milk wheyc 5 0.04 ± 0.001 — 5.82 ± 0.19 42.8 ± 0.87 — 23
169
170
Dairy Products
Commercial yoghurtsc 16 140 ± 24.8 193 ± 30.0 12.5 ± 1.63 65.1 ± 8.44 — 25
106 – 199 150 – 255 9.80 – 17.2 46.2 – 75.4
Dairy productsb U.K. 232 — — — — 7
Milk productsb U.S. 305 ± 289 153 ± 74.1 19.2 ± 10.2 349 ± 453 254 ± 207 8
2234_C006.fm Page 170 Thursday, October 26, 2006 8:00 AM
71.9 – 792 74.7 – 303 7.9 – 37.8 51.7 – 1460 84.3 – 567
Plain yoghurt, low-fat U.S. 155 214 15.7 59.7 123 8
Fruit-added yoghurts 7 98.5 ± 7.1 118 ± 15.2 9.4 ± 0.8 36.6 ± 3.5 — 26
Yoghurt, low-fat, fruit U.S. 112 174 13 51.7 96.5 8
Mayonnaise U.S. 7.8 10.2 < 1.4 504 24.8 8
Butter (regular, salted) U.S. 23.4 23.7 1.7 576 22.9 8
Swiss cheese U.S. 792 77.2 37.8 192 567 8
American cheese U.S. 551 171 27 1460 548 8
Cheddar cheese U.S. 688 74.7 28.4 589 458 8
Emmental cheese 6 0.96 ± 0.05 89.4 ± 6.39 36.4 ± 1.91 181 ± 51.9 — 27
0.93 – 1.05 80 – 97.7 33.6 – 39 132 – 256
Hard cheeses 969 48 35 876 — 28
766 – 1120 20 – 60 30 – 45 180 – 2270
Semi-hard cheese Canary Islands 1020 ± 310 200 ± 80 56 ± 18 1090 ± 450 — 29
Cream cheese U.S. 72 110 7.9 297 93.4 8
Cottage cheese, 4% U.S. 71.9 97 8.1 341 142 8
Mineral Components in Foods
Commercial goat cheese 2 — — 36.5 ± 8.05 — — 19
Soft cheeses 294 86 18 234 — 28
93 – 510 50 – 115 10 – 44 25 – 645
Commercial sheep cheese 4 — — 32.2 ± 9.38 — — 19
21.3 – 44.3
Quark cheeses 90 127 12 163 — 28
73 – 109 107 – 156 9 – 14 27 – 397
Fresh cheese Canary Islands 980 ± 170 170 ± 20 47 ± 8 600 ± 280 — 29
Market white brine cheese Turkey 10 309 ± 18 90 ± 10 18 ± 4 999 ± 225 — 30
Soft white cheese Turkey 20 300 ± 58 79 ± 20 23 ± 6 1583 ± 650 — 30
Stirred curd cheeses 646 45 23 557 — 28
337 – 800 8 – 80 10 – 40 140 – 966
Soft white cheese melted Turkey 20 347 ± 13 53 ± 14 17 ± 4 1431 ± 190 — 30
2234_C006.fm Page 171 Thursday, October 26, 2006 8:00 AM
Eggs
Eggsb U.K. 52.8 — — — — 7
Egg productsb U.S. 59.3 ± 4.19 130 ± 6.81 12.1 ± 0.2 163 ± 60.8 190 ± 16.0 8
54.5 – 61.8 122 – 135 11.9 – 12.3 123 – 233 172 – 201
Mineral Components in Foods of Animal Origin and in Honey
171
172
TABLE 6.3
Macronutrients in Honey (in mg/100 g w/w)
Name Origin n Ca K Mg Na P Ref.
honey show a wide range in values, from 0.14 to 30.0 mg/100 g; the highest level
observed in syrup-feed honey was 133 mg Mg/100 g (see Table 6.3).
6.2.3 POTASSIUM
Potassium (K), like sodium, plays an important role in animal physiology and is
distributed abundantly in human diets with relatively uniform concentrations in most
animal foods. Pork loin is characterized by higher levels of potassium, i.e., 3680
mg/100 g and seafood contained an order of magnitude lower its concentration (244
to 308 mg/100 g) (see Table 6.1). The potassium concentrations in cow milk ranged
from 6.94 to 15.4 mg/100 g (see Table 6.2) and were smaller than those in dairy
products, e.g., cheeses (20 to 200 mg/100 g). Honey contained variable levels of
potassium, ranging from 1.5 to 239 mg/100 g in honeydew and 150 mg/100 g in
sesame honey. However, the highest levels of this macroelement occurred in syrup-
feed honey, i.e., 1555 mg/100 g (see Table 6.3).
6.2.4 SODIUM
Sodium chloride is widely used as a preservative and hence is found in most
animal foods. Its levels are generally in the range of 25.0 and 277 mg/100 g,
although higher levels have been reported in some meat products (405 mg/100 g
in pork loin) and hard cheeses (2270 mg/100 g) (see Table 6.1 and Table 6.2).
Honey from the U.S. contains from 2.01 to 2.53 mg Na/100 g; however, the highest
levels of the macroelement were noted for thyme honey (38.9 mg/100 g) and
sesame honey (37.8 mg/100 g). Syrup-feed honey was characterized by an order
of magnitude greater sodium concentration of about 255 mg/100 g (see Table 6.3).
6.2.5 PHOSPHORUS
As can be seen in Table 6.2, foods such as milk and dairy products, especially many
types of cheeses such as Swiss cheese, are good sources of phosphorus (P) (up to
567 mg/100 g). Offal and eggs are also rich in this element containing 452 and up
to 201 mg P/100 g, respectively (see Table 6.1 and Table 6.2). Phosphorus in
foodstuff is not exclusively natural in origin as polyphosphates are common additives
in many meat products, e.g., ready-sliced ham, luncheon meat, and prepared frozen
poultry.9 Concentrations of this macroelement in honey range from 1.28 to 39.8
mg/100 g (see Table 6.3).
low and found at or below the detection limits of most analytical methods, generally
< 0.0001 mg/100 g. Somewhat higher concentrations of this element (up to 0.010
and 0.020 mg/100 g) are detected in some meat products and dairy products,
especially cheeses (see Table 6.5). Concentrations of Cr in honey range from 0.0001
to 0.070 mg/100 g with the highest values noted for pine tree honey (see Table 6.6).
6.3.2 COBALT
Whether cobalt (Co) is an essential trace element remains equivocal. Adequate
information on the distribution of cobalt in food is not available. As can be deduced
from Table 6.4, the concentrations of this element in meat are very low (< 0.013
mg/100 g) with its somewhat higher levels reported for offal. Cobalt is a constituent
of vitamin B12 or cobalamin, and is a good source for yeast extract.1 Human milk
contains very small amount of cobalt of < 0.00001 to 0.002 mg/100 g whereas the
levels in raw goat and sheep milk range from 0.001 to 0.003 mg/100 g (see Table
6.5). Significantly higher mean level is reported for soft white cheese, i.e., 0.15 mg
Co/100 g (see Table 6.5). The metal occurs in honey in wide range of levels, from
< 0.005 to 0.18 mg/100 g with the lowest concentration found in acacia and Galician
honey and the highest in orange and sesame honey (see Table 6.6).
6.3.3 COPPER
As an essential element, copper (Cu) is widely distributed in different kinds of animal
foods, occurring at levels of between 0.00001 mg/100 g (veal) and 5.37 mg/100 g
fresh weight (crab meat). Among the foodstuffs, mammalian liver is exceptionally
rich in copper, with concentrations of up to 8.0 mg/100 g.1 Offal, like bovine muscle,
can contain considerable amounts of this element (up to 4 mg/100 g, see Chapter
10 of this book) but somewhat less than in mammalian liver. The kidney and liver
of hens contain 0.28 and 0.58 mg Cu/100 g, respectively, whereas copper levels in
geese muscle meat (5.4 mg/100 g) are among the highest values reported (see Table
6.4). Crab meat also has high levels of copper, up to 5.37 mg/100 g (see Table 6.4).
The lowest values are observed in human and cow milk (0.01 to 0.14 mg/100 g).
Goat and sheep milk contain from 0.05 to 0.08 mg Cu/100 g. The richest dietary
sources of the metal are infant milk formula and emmenthal cheese which can contain
up to 0.64 and 1.31 mg Cu/100 g, respectively. Concentrations of copper in honey
range from 0.003 to 0.29 mg/100 g, depending on geographical origin of the product
and species of tree or plant from which it is obtained (see Table 6.6). For instance,
pine tree honey contains one order of magnitude higher levels of copper (0.15 mg/100
g) than Lythrum honey (0.03 mg/100 g).
6.3.4 IRON
Iron (Fe) is an essential element that is present in all food products, and its concen-
tration can vary significantly depending on the kind of food and its technological
processing.1 It should be emphasized that iron in animal food is considerably more
bioavailable to man than that found in plant food. In meat and fish skeletal muscles
15 to 25% of iron is bound as heme iron, which is easily adsorbed and hence
176
TABLE 6.4
Micronutrients in Meat and Its Products (in mg/100 g w/w)
Name Origin n Co Cr Cu Fe Mn Mo Ni Se Zn Ref.
Meat
Carcass meatb U.K. 0.0004 0.02 0.14 2.1 0.01 0.001 0.004 0.01 5.1 7
Pork meat Poland 10 — — 0.07 ± 0.01 1.28 ± 0.10 0.02 ± 0.001 — — — 2.57 ± 0.13 51
0.06 – 0.08 1.20 – 1.35 0.02 – 0.02 2.48 – 2.66
Pork loin Spain 42 — — — 13.3 ± 4.67 — — — — 22.0 ± 5.56 10
Pork shoulderc Switzerland 25 — — — 1.89 ± 0.49 — — — — 7.84 ± 1.44 52
Porkc Switzerland 25 — — — 0.63 ± 0.07 — — — — 2.15 ± 0.30 52
Swine muscle Poland 334 — — n = 658 n = 658 n = 658 — — — n = 658 53
meat 0.11 ± 0.06 1.28 ± 0.46 0.01 ± 0.003 2.55 ± 0.07
2234_C006.fm Page 176 Thursday, October 26, 2006 8:00 AM
Pork liver Spain 80 0.01 ± 0.001 0.01 ± 0.003 0.05 ± 0.03 0.16 ± 0.01 0.03 ± 0.02 — 0.02 ± 0.002 — 0.05 ± 0.005 59
pastes 0.01 – 0.01 0.01 – 0.01 0.01 – 0.08 0.14 – 0.17 0.01 – 0.05 0.02 – 0.02 0.04 – 0.06
Polish Poland 140 — — 0.04 – 0.13 0.61 – 16.2 0.01 – 0.07 — — — 0.83 – 4.5 51
sausages
Morcilla de Spain — — — 9.18 ± 2.89 — — — — — 11
Burgos blood 3.78 – 17.8
sausagec
Meat U.K. 0.001 0.02 0.15 2.3 0.14 0.01 0.01 0.01 2.5 7
productsb
Meat U.S. — — 0.11 ± 0.02 1.52 ± 0.73 < 0.2 — < 0.02 0.03 ± 0.01 3.57 ± 1.92 8
Mineral Components in Foods of Animal Origin and in Honey
productsb < 0.09 – 0.14 0.7 – 2.77 0.01 – 0.05 1.42 – 7.96
Poultry
Poultryb U.K. 0.0003 0.02 0.07 0.71 0.02 0.004 0.004 0.015 1.6 7
Poultryb U.S. — — < 0.09 0.79 ± 0.32 0.12 ± 0.03 — < 0.01 – 0.12 0.03 ± 0.01 1.26 ± 0.41 8
0.47 – 1.22 < 0.1 – 0.14 0.02 – 0.04 0.86 – 1.87
Chicken Switzerland 25 — — — 0.44 ± 0.06 — — — — 0.80 ± 0.06 52
breastc
177
178
Smoked Poland 5 — — 0.05 ± 0.01 0.70 ± 0.16 0.04 ± 0.01 — — — 0.95 ± 0.21 51
chicken 0.04 – 0.05 0.55 – 0.96 0.04 – 0.05 0.68 – 1.20
Smoked Poland 4 — — 0.03 ± 0.01 1.0 ± 0.5 0.02 ± 0.01 — — — 1.0 ± 0.4 60
chicken
muscles
Geese muscle Poland 32 — — 0.73 3.5 0.03 — — — 1.4 58
meat 0.15 – 5.4 1.5 – 5.6 0.02 – 0.04 0.6 – 2.5
Turkey’s Poland 10 — — 0.05 ± 0.02 0.50 ± 0.09 0.04 ± 0.01 — — — 1.02 ± 0.22 51
breasts 0.03 – 0.09 0.41 – 0.60 0.03 – 0.05 0.76 – 1.29
Turkey’s Poland 10 — — 0.09 ± 0.01 1.24 ± 0.37 0.04 ± 0.01 — — — 2.76 ± 0.23 51
thighs 0.07 – 0.10 0.03 – 0.05 0.53 – 3.1
Ducks muscle Poland 57 — — 0.6 3.0 0.02 — — — 1.3 58
meat 0.22 – 1.7 1.6 – 8.1 0.01 – 0.04 0.56 – 5.2
Duck meat Polska 10 — — 0.31 ± 0.03 2.81 ± 0.27 0.03 ± 0.003 — — — 1.82 ± 0.22 51
0.28 – 0.35 0.46 – 3.10 0.03 – 0.04 0.61 – 2.13
Hen kidney Poland 1 — — 0.28 18 0.19 — — — 2.1 58
Hen liver Poland 13 — — 0.38 7.1 0.16 — — — 2.9 58
0.17 – 0.58 1.8 – 33.0 0.10 – 0.23 1.8 – 5.9
Mineral Components in Foods
Poultry Polish Poland 25 — — 0.03 – 0.10 0.37 – 1.46 0.04 – 0.08 — — — 0.48 – 2.54 51
sausages
Poultry Poland 11 — — 0.1 ± 0.09 1.6 ± 0.1 0.02 ± 0.001 — — — 1.7 ± 0.2 60
sausage
Fish
Fishb U.K. 0.001 0.02 0.11 1.6 0.11 0.003 0.008 0.039 0.91 7
Fishb U.S. — — < 0.1 – 0.23 1.09 ± 0.30 < 0.1 – 0.21 — < 0.01 – 0.01 0.04 ± 0.02 0.79 ± 0.56 8
< 0.3 – 1.43 0.02 – 0.07 0.43 – 1.62
Atlantic Southern 2 0.001 — 0.01 – 0.06 0.3 – 0.49 0.01 – 0.03 — 0.01 — 1.12 – 1.9 96
salmon Baltic
Cod Southern 70 < 0.0005 – 0.001 — 0.02 ± 0.005 0.4 ± 0.06 0.02 ± 0.005 — 0.03 ± 0.01 — 0.3 ± 0.05 96
Baltic 0.001 – 0.11 0.11 – 1.29 0.005 – 0.08 0.002 – 0.10 0.09 – 0.88
Eel Southern 2 0.001 — 0.20 – 0.29 0.45 0.03 — 0.02 — 1.36 – 1.7 96
Baltic
2234_C006.fm Page 179 Thursday, October 26, 2006 8:00 AM
Sprat Southern 5 0.001 ± 0.0001 — 0.04 ± 0.01 1.35 0.04 ± 0.005 — 0.03 ± 0.01 — 1.26 ± 0.06 96
Baltic < 0.001 – 0.001 0.015 – 0.05 0.95 – 1.9 0.02 – 0.05 0.01 – 0.07 1.14 – 1.38
Whiting Southern 2 < 0.0005 — 0.01 – 0.02 0.32 – 0.38 0.03 — 0.04 — 0.13 – 0.21 96
Baltic
Seafood
Shrimp Taiwan — — 0.24 – 0.30 — — — — — 1.02 – 1.25 61
Shrimp Spain — — — — — — — 0.03 — 62
179
Mussel boiled Polish market — — 0.12 ± 0.07 3.54± 3.10 2.49 ± 2.13 — — 0.04 ± 0.01 2.99 ± 1.93 14
Mussel raw Polish market — — 0.08 9.47 0.23 — — 0.06 1.80 14
Octopus Polish market — — 0.24 ± 0.00 0.091 ± 0.001 0.02 ± 0.01 — — 0.015 ± 0.0 1.44 ± 0.36 14
Octopus Polish market — — 0.17 0.40 0.06 — — 0.026 1.19 14
Mineral Components in Foods of Animal Origin and in Honey
181
182
TABLE 6.5
Micronutrients in Milk, Dairy Products, and Eggs (in mg/100 g w/w)
Name Origin n Co Cr Cu Fe Mn Mo Ni Se Zn Ref.
Milk
Bottled cow 3 — ND — — 0.004 ± 0.0002 0.003 ± 0.001 — — — 73
milkc
Cow milk fat — — 0.004 ± 0.0001 — — — — — 0.31 ± 0.0001 74
content 3.8%c
Cow milk 22 — — — — — — — 0.002 ± 0.0005 — 75
0.001 – 0.003
Dairy milk Sweden — < 0.0004 0.01 ± 0.01 0.04 ± 0.01 <0.01 0.003 ± 0.0002 — 0.002 ± 0.0003 0.44 ± 0.06 15
< 0.01 – 0.3 0.01 – 0.06 0.003 – 0.003 0.001 – 0.002 0.38 – 0.54
Low-fat (2%) U.S. — — — — — — — < 0.004 0.4 8
milk, fluid
2234_C006.fm Page 182 Thursday, October 26, 2006 8:00 AM
Skimmed UHT 5 — 0.0001 ± 0.00002 0.002 ± 0.0002 0.02 ± 0.001 0.002 ± 0.0001 — — 0.001 ± 0.0001 0.22 ± 0.02 18
cow milkc
Nonfat milk 3 — ND — — 0.03 ± 0.01 0.03 ± 0.003 — — — 73
powder
183
184
formula, oil-
filled
Milk-infant 3 — — 0.34 ± 0.06 6.9 ± 1.23 — — — — 3.24 ± 0.33 83
formula 0.27 – 0.41 5.28 – 8.26 2.8 – 3.58
adapted
Milk-infant 3 — 0.24 ± 0.08 7.91 ± 0.19 — — — — 3.71 ± 0.28 83
formula 0.13 – 0.3 7.67 ± 8.13 3.42 – 4.09
follow-up
Milk-infant 3 — — 0.50 ± 0.09 8.19 ± 1.63 — — — — 3.29 ± 0.34 83
formula 0.38 – 0.59 6.35 – 10.3 2.93 – 3.75
preterm
Ready-to-drink 0.0001 – 0.0001 < 0.0001 – 0.002 0.09 – 0.26 0.14 – 1.25 0.003 – 0.01 — 0.001 – 0.002 — — 80
infant
formulas
Mineral Components in Foods of Animal Origin and in Honey
185
186
Milk-based London, 12 — 0.0005 ± 0.0005 0.04 ± 0.01 0.61 ± 0.23 0.01 ± 0.002 0.002 ± 0.001 — — 0.31 ± 0.09 24
powder U.K.
formulasc
Milk-based U.S. 9 — 0.001 ± 0.001 0.05 ± 0.01 0.90 ± 0.05 0.01 ± 0.004 0.001 ± 0.0003 0.000002 ± 0.00001 — 0.36 ± 0.08 24
powder
formulasc
Milk-infant 3 — — 0.62 ± 0.022 8.65 ± 2.28 — — — — 4.18 ± 0.25 83
formula soya- 0.59 – 0.64 5.93 – 11.5 3.94 – 4.53
based
Soy-based 5 — — 0.21 ± 0.02 2.53 ± 0.14 0.40 ± 0.01 — — — 1.46 ± 0.08 22
infant 0.18 – 0.25 2.40 – 2.79 0.38 – 0.41 1.37 – 1.56
formula, oil-
filled
Soy-based U.S. 6 — 0.001 ± 0.001 0.07 ± 0.011 0.89 ± 0.03 0.02 ± 0.004 0.003 ± 0.001 0.0002 ± 0.0004 — 0.50 ± 0.11 24
powder
formulac
Powdered 5 — — — — — — — 0.01 ± 0.003 — 81
infant 0.002 – 0.01
formula
Mineral Components in Foods
Whey-based 5 — — 0.47 ± 0.02 7.83 ± 0.22 0.11 ± 0.06 — — — 4.3 ± 0.12 22
formula, 0.45 – 0.49 7.57 – 8.09 0.10 – 0.11 4.14 – 4.49
partially oil-
filled
Whey-based 5 — — 0.39 ± 0.01 6.81 ± 0.13 0.08 ± 0.003 — — — 3.92 ± 0.13 22
infant 0.38 – 0.41 6.62 – 7.02 0.08 – 0.09 3.76 – 4.15
formula, oil-
filled
Whey-based 5 — — 0.47 ± 0.02 7.83 ± 0.22 0.11 ± 0.06 — — — 4.3 ± 0.12 22
formula, 0.45 – 0.49 7.57 – 8.09 0.10 – 0.11 4.14 – 4.49
partially oil-
filled
Cow milk 5 — — 0.001 ± 0.0001 0.01 ± 0.0003 0.002 ± 0.0001 — — 0.0004 ± 0.00002 0.13 ± 0.01 23
wheyc
Milk whey 5 — — 0.001 ± 0.0002 0.01 ± 0.001 0.002 ± 0.0003 — — — 0.10 ± 0.01 18
coming from
cow milkc
Milk whey 5 — — 0.001 ± 0.0001 0.01 ± 0.001 0.001 ± 0.0001 — — — 0.09 ± 0.01 18
coming from
UHT cow
2234_C006.fm Page 187 Thursday, October 26, 2006 8:00 AM
milkc
UHT cow milk 5 — — 0.001 ± 0.00005 0.004 ± 0.0002 0.0005 ± 0.00004 — — 0.0004 ± 0.00002 0.08 ± 0.01 23
wheyc
Human milk 5 — — 0.01 ± 0.001 0.02 ± 0.001 0.001 ± 0.00004 — — 0.001 ± 0.0005 0.12 ± 0.01 23
wheyc
Milk whey 5 — — 0.02 ± 0.001 0.019 ± 0.0016 0.001 ± 0.0001 — — — 0.17 ± 0.02 18
coming from
human milkc
Whey milkc 10 — — — 0.01 ± 0.004 — — — — 0.04 ± 0.01 78
0.001 – 0.01 0.03 – 0.08
Milk whey 5 — 0.0001 ± 0.00003 0.01 ± 0.0004 0.03 ± 0.002 0.005 ± 0.0004 — — — 0.16 ± 0.02 18
coming from
formula milkc
Mineral Components in Foods of Animal Origin and in Honey
187
188
Dairy Products
Commercial 16 — — — — — — — — 0.5 ± 0.08 25
yoghurtsc 0.39 – 0.71
Dairy U.K. 0.0004 0.09 0.05 1.2 0.03 0.01 0.002 0.005 1.4 7
productsb
Milk productsb U.S. — — < 0.09 – < 0.12 < 0.3 < 0.1 – < 0.2 — < 0.01 0.02 ± 0.01 1.53 ± 1.59 8
< 0.004 – 0.02 0.38 – 4.36
Plain yoghurt, U.S. — — < 0.09 < 0.3 — — — < 0.004 0.56 8
lowfat
Fruit-added 7 — — 0.02 ± 0.01 0.14 ± 0.14 0.07 ± 0.06 — — — 0.31 ± 0.03 26
2234_C006.fm Page 188 Thursday, October 26, 2006 8:00 AM
yoghurts
Yoghurt, U.S. — — — < 0.3 < 0.1 — < 0.01 < 0.004 0.44 8
lowfat, fruit
Mayonnaise U.S. — — — < 0.3 — — — < 0.005 < 0.2 8
Butter Poland 3 — — 0.01 ± 0.003 0.11 ± 0.07 0.01 ± 0.002 — — — 0.09 ± 0.02 77
0.004 – 0.01 0.04 – 0.17 0.004 – 0.01 0.06 – 0.11
Butter (regular, U.S. — — — < 0.3 — — — — < 0.1 8
salted)
Swiss cheese U.S. — — < 0.12 < 0.3 < 0.2 — — 0.02 4.36 8
American U.S. — — < 0.12 < 0.3 < 0.2 — — 0.02 2.8 8
cheese
Cheddar U.S. — — < 0.12 < 0.3 < 0.2 — — 0.02 3.55 8
cheese
Emmenthal 6 — — 0.73 ± 0.39 — 0.03 ± 0.01 0.01 ± 0.003 — — 4.44 ± 0.24 27
cheese < 0.1 – 1.31 0.02 – 0.04 0.001 – 0.02 4.13 – 4.78
Hard cheeses 0.0003 0.005 — 0.17 — — — 0.01 3.88 46
0.0003 – 0.0005 0.001 – 0.01 0.13 – 0.21 0.005 – 0.01 3.37 – 4.50
Mineral Components in Foods
Swiss Cheese Poland 13 — — 0.03 ± 0.01 0.55 ± 0.51 0.07 ± 0.02 — — — 1.6 ± 1.3 77
0.01 – 0.04 0.16 – 2.1 0.04 – 0.12 0.44 – 5.3
Cream cheese U.S. — — — < 0.3 — — — < 0.005 0.51 8
Cream cheese Poland 4 — — 0.02 ± 0.005 0.43 ± 0.12 0.07 ± 0.04 — — — 2.0 ± 0.2 77
0.02 – 0.03 0.25 – 0.51 0.03 – 0.12 1.7 – 2.2
Cottage U.S. — — — < 0.3 — — < 0.01 0.01 0.38 8
cheese, 4%
Commercial 2 0.001 ± 0.00005 0.01 ± 0.0005 0.11 ± 0.03 0.24 ± 0.04 0.02 ± 0.0001 — 0.001 ± 0.0004 — 1.81 ± 0.11 19
goat cheese
Soft cheeses 0.0002 0.01 — 0.15 — — — 0.004 1.06 46
0.0002 – 0.0003 0.004 – 0.03 0.04 – 0.24 0.001 – 0.01 0.36 – 2.81
Commercial 4 0.002 ± 0.0003 0.004 ± 0.001 0.10 ± 0.04 0.33 ± 0.13 0.04 ± 0.01 — 0.002 ± 0.0004 — 1.94 ± 0.33 19
sheep cheese 0.002 – 0.002 0.003 – 0.005 0.05 – 0.16 0.23 – 0.56 0.03 – 0.05 0.001 – 0.002 1.55 – 2.29
Quark cheeses 0.0005 0.003 — 0.13 — — — 0.003 4.41 46
0.0003 – 0.001 0.001 – 0.01 0.08 – 0.21 0.002 – 0.005 3.37 – 5.18
Semihard Canary — — 0.09 ± 0.03 0.21 ± 0.05 — — — 0.02 ± 0.005 0.47 ± 0.18 29
cheese Islands
Cream partially Spain 6 — — — — — — — 0.002 ± 0.0005 — 84
skimmed 0.001 – 0.003
2234_C006.fm Page 189 Thursday, October 26, 2006 8:00 AM
Market white Turkey 10 0.02 ± 0.005 0.01 ± 0.0003 0.04 ± 0.01 0.20 ± 0.03 0.005 ± 0.003 0.03 ± 0.01 0.11 ± 0.01 — 1.26 ± 0.08 30
brine cheese
189
190
Soft white Turkey 20 0.15 ± 0.16 0.02 ± 0.02 0.05 ± 0.04 0.54 ± 0.85 0.01 ± 0.004 0.03 ± 0.03 0.12 ± 0.16 — 1.77 ± 0.42 30
cheese
Stirred curd 0.0001 0.01 — 0.17 — — — 0.01 3.47 46
cheeses 0.0002 – 0.001 0.01 – 0.01 0.10 – 0.21 0.01 – 0.01
Soft cheeses 0.0002 0.01 — 0.15 — — — 0.004 1.06 46
0.0002 – 0.0003 0.004 – 0.03 0.04 – 0.24 0.001 – 0.01 0.36 – 2.81
Commercial 4 0.002 ± 0.0003 0.004 ± 0.001 0.10 ± 0.04 0.33 ± 0.13 0.04 ± 0.01 — 0.002 ± 0.0004 — 1.94 ± 0.33 19
sheep cheese 0.002 – 0.002 0.003 – 0.005 0.05 – 0.16 0.23 – 0.56 0.03 – 0.05 0.001 – 0.002 1.55 – 2.29
Quark cheeses 0.0005 0.003 — 0.13 — — — 0.003 4.41 46
0.0003 – 0.001 0.001 – 0.01 0.08 – 0.21 0.002 – 0.005 3.37 – 5.18
Semi-hard Canary — — 0.09 ± 0.03 0.21 ± 0.05 — — — 0.02 ± 0.005 0.47 ± 0.18 29
2234_C006.fm Page 190 Thursday, October 26, 2006 8:00 AM
cheese Islands
Cream partially Spain 6 — — — — — — — 0.002 ± 0.0005 — 84
skimmed 0.001 – 0.003
Cream partially Spain 6 — — — — — — — 0.002 ± 0.0005 — 82
skimmed 0.001 – 0.003
Cream Spain 8 — — — — — — — 0.002 ± 0.0005 — 84
skimmed 0.001 – 0.002
Cream Spain 6 — — — — — — — 0.002 ± 0.0005 — 82
skimmed 0.001 – 0.002
Full cream Spain 4 — — — — — — — 0.001 ± 0.0002 — 84
0.001 – 0.002
Full cream Spain 4 — — — — — — — 0.001 ± 0.0002 — 82
0.001 – 0.002
Fresh cheese Canary — — 0.08 ± 0.03 0.22 ± 0.05 — — — 0.01 ± 0.0002 0.65 ± 0.25 29
Islands
Market white Turkey 10 0.02 ± 0.005 0.01 ± 0.0003 0.04 ± 0.01 0.20 ± 0.03 0.005 ± 0.003 0.03 ± 0.01 0.11 ± 0.01 — 1.26 ± 0.08 30
brine cheese
Soft white Turkey 20 0.15 ± 0.16 0.02 ± 0.02 0.05 ± 0.04 0.54 ± 0.85 0.01 ± 0.004 0.03 ± 0.03 0.12 ± 0.16 — 1.77 ± 0.42 30
cheese
Stirred curd 0.0001 0.01 — 0.17 — — — 0.01 3.47 46
cheeses 0.0002 – 0.001 0.01 – 0.01 0.10 – 0.21 0.01 – 0.01
Mineral Components in Foods
Soft white Turkey 20 0.08 ± 0.03 0.02 ± 0.004 0.05 ± 0.01 0.70 ± 0.03 0.01 ± 0.01 0.02 ± 0.002 0.09 ± 0.04 — 2.99 30
cheese
melted
Fat 5 — — 0.03 ± 0.01 0.28 ± 0.22 0.03 ± 0.005 — — — 0.77 ± 0.35 77
White 0.01 – 0.04 0.12 – 0.62 0.02 – 0.04 0.53 – 1.4
cheese
Eggs Nigeria 151 0.001 ± 0.0 — 0.08 ± 0.002 2.32 ± 0.08 — — 0.003 ± 0.001 — 1.38 ± 0.02 85
0.001 – 0.001 0.07 – 0.08 2.18 – 2.41 0.002 – 0.003 1.29 – 1.45
Eggsb U.K. 0.0002 0.02 0.06 2 0.031 0.01 0.003 0.02 1.1 7
Egg productsb U.S. — — < 0.09 1.70 ± 0.21 < 0.1 — < 0.01 0.03 ± 0.004 1.23 ± 0.125 8
1.46 – 1.85 0.02 – 0.03 1.09 – 1.32
Eggs Poland 20 — — 0.06 ± 0.003 1.8 ± 0.14 0.03 ± 0.003 — — — 1.2 ± 0.14 86
0.06 – 0.06 1.7 – 1.9 0.02 – 0.03 1.1 – 1.3
Eggs 20 — — 0.06 ± 0.01 1.8 ± 0.3 0.02 ± 0.01 — — — 1.2 ± 0.2 77
0.05 – 0.07 1.4 – 2.3 0.02 – 0.05 0.86 – 1.6
2234_C006.fm Page 191 Thursday, October 26, 2006 8:00 AM
bioavailable.9 Therefore, the richest source of this element are animal liver, offal,
and meat products, which can contain up to 6.9 mg Fe/100 g. Concentrations of iron
range from 0.14 to 33.0 mg/100 g in meat (see Table 6.4) with the highest values
for chicken kidney (18.0 mg/100 g) and chicken liver (up to 33.0 mg/100 g). Elevated
levels of iron have been reported in crab meat (up to 42.1 mg/100 g). On the other
hand, low levels of iron are observed in cow milk (0.018 to 0.097 mg/100 g)
containing the nonheme iron protein. This protein, named lactoferrin, transports iron
in the bloodstream.1 Honey contains iron in a wide range of values, from 0.01 to
20.2 mg/100 g (see Table 6.6); sesame honey contains two orders of magnitude
higher levels of iron (20.2 mg/100 g) compared to acacia honey (0.12 mg/100 g).
Some attention should be paid to controlling the concentration of iron in canned
food. According to Reilly,1 the age of the can as well as the duration of storage are
important factors which can affect the iron release from the container. An example
of extreme contamination with iron is a can of anchovies stored for 4 years that
contained 580 mg Fe/100 g.
6.3.5 MANGANESE
As can be seen in Table 6.4, animal foods contain small amounts of manganese
(Mn), in the range of 0.003 to 0.14 mg/100 g in meat with higher levels in bovine
and elk muscles. Crab meat has elevated levels of manganese, up to 8.19 mg/100
g. Human and cow milk and their products contain very low levels, from 0.0002 to
0.02 mg Mn/100 g. The concentration of manganese in infant formula can become
elevated (reaching 0.12 mg/100 g), whereas soy-based infant milk formula contains
up to 11.5 mg Mn/100 g (see Table 6.5). As for geographic variations in Mn
concentrations, it seems that there are insignificant differences in reported food levels
for several countries.1 Honey contain from 0.003 to 4.28 mg Mn/100 g; higher levels
are noted for eucalyptus and acacia tree honey whereas lower values are associated
with citrus and Apiaceae honey (see Table 6.6).
6.3.6 MOLYBDENUM
Molybdenum (Mo) concentrations in animal foods range from 0.001 to 0.12 mg/100
g. The lowest values are reported for carcass meat, and the highest for offal. Milk
and dairy products contain from 0.003 to 0.005 mg Mo/100 g and from 0.001 to
0.03 mg Mo/100 g, respectively (see Table 6.5).
6.3.7 NICKEL
Nickel (Ni) is probably an essential trace element. A number of reports1,43 suggest that
Ni can migrate from stainless steel containers to dairy products and other foods. Nickel
occurs in animal foods in small concentrations, ranging between < 0.00001 and 0.12
mg/100 g in milk and dairy products. Meat and its products contain on the average
0.020 mg Ni/100 g (see Table 6.5). Concentrations of nickel in honey vary over a broad
range, from 0.0002–0.41 mg/100 g. The highest levels are observed for clover honey
(see Table 6.6). According to Ysart et al.,7 canned foods contain higher levels of Ni, the
result of contamination from cooking equipment and containers.1
TABLE 6.6
Micronutrients in Honey (in mg/100 g w/w)
Name Origin n Co Cr Cu Fe Mn Ni Se Zn Ref.
honey
Eucalyptus Northwest 12 — — 0.10 ± 0.03 0.98 ± 0.13 0.60 ± 0.07 — — 0.27 ± 0.11 32
honey Morocco 0.04 – 0.05 0.38 – 2.01 0.09 – 1.15 0.04 – 1.25
Heuchalipt Italy 10 — — 0.16 ± 0.20 — — — — 0.42 ± 0.56 87
honey
Honey Turkey 30 0.1 ± 0.06 — 0.18 ± 0.17 0.66 ± 0.32 0.1 ± 0.07 — — 0.27 ± 0.25 34
Honey — — — 0.42 <0.1 < 0.01 — 0.11 8
Honeydew Northwest 3 — — 0.23 ± 0.01 3.13 ± 0.27 0.28 ± 0.05 — — 0.30 ± 0.06 32
Morocco 0.17 – 0.27 2.60 – 3.50 0.20 – 0.37 0.18 – 0.39
Honey Italy — 0.0003 ± 0.00003 0.01 ± 0.001 0.23 ± 0.02 — 0.001 ± 0.00005 — — 88
Mineral Components in Foods of Animal Origin and in Honey
< 0.005 – 0.02 0.004 – 0.01 <0.4 – 1.59 0.04 – 0.08 < 0.002 – 0.002 0.34 – 0.46
194
Honey Italy 10 < 0.03 – 0.03 — 0.09 ± 0.002 0.12 ± 0.06 — 0.04 ± 0.001 — 0.29 89
< 0.005 – 0.09 0.07 – 0.18 < 0.005 – 0.04 0.26 – 0.32
Indian India 30 — — 0.21 ± 0.04 1.08 ± 0.15 — — — 0.82 ± 0.55 37
honey 0.17 – 0.29 0.89 – 1.33 0.26 – 1.68
Industrial Spain 20 < 0.005 — 0.01 ± 0.01 0.38 ± 0.3 0.11 ± 0.11 < 0.002 — 0.15 ± 0.07 38
Galician
honey
Lazio honey Italy 84 — — 0.03 ± 0.005 0.45 ± 0.04 0.3 ± 0.04 — — 0.31 ± 0.03 39
Lythrum Northwest 7 — — 0.03 ± 0.01 0.83 ± 0.24 0.03 ± 0.005 — — 0.26 ± 0.11 32
2234_C006.fm Page 194 Thursday, October 26, 2006 8:00 AM
honey Morocco 0.002 – 0.06 0.19 – 1.87 0.008 – 0.04 0.04 – 0.83
Orange Egypt 0.15 ± 0.03 — 0.08 ± 0.0 6.51 ± 1.38 0.04 ± 0.08 0.14 ± 0.02 — 0.41 ± 0.08 33
honey
Natural Spain 22 < 0.005 — 0.09 ± 0.07 0.37 ± 0.17 0.52 ± 0.31 < 0.002 — 0.2 ± 0.13 38
Galician
honey
Pine tree Slovenia 25 — 0.07 ± 0.01 0.15 ± 0.01 0.7 ± 0.04 0.5 ± 0.1 0.08 ± 0.02 — 0.54 ± 0.03 40
honey
Saudi Saudi — — 0.05 ± 0.01 0.13 ± 0.03 0.01 ± 0.005 — — 0.21 ± 0.07 41
Arabia Arabia 0.04 – 0.06 0.10 – 0.19 0.003 – 0.02 0.15 – 0.30
honey
Sesame Egypt 0.15 ± 0.03 — 0.14 ± 0.03 16.4 ± 1.79 0.14 ± 0.02 0.11 ± 0.03 — 0.59 ± 0.03 33
honey
Syrup-feed Egypt 0.26 ± 0.03 — 0.08 ± 0.0 300 ± 6.43 0.46 ± 0.03 0.24 ± 0.0 — 0.57 ± 0.08 33
honey
Mineral Components in Foods
2234_C006.fm Page 195 Thursday, October 26, 2006 8:00 AM
6.3.8 SELENIUM
The range between toxic and safe doses of selenium (Se) (an essential element) is
very narrow. Selenium is present in foods in levels ranging from 0.0007 to 0.020 mg/kg
in milk and dairy products and 0.04 to 0.15 mg/100 g in seafood and offal (see Table
6.5). The protective role of selenium against certain toxic metals has been reported
and discussed extensively by Reilly1,2. For instance, no sign of mercury intoxication
was observed in the study of an Inuit fishing community with elevated blood mercury
levels that often exceeded 200 µg/l. The reduced risk of mercury poisoning was
attributed to the protective presence of high amounts of selenium in fish and seal meat,
which constituted the major component of the diet of the local people.1,44,45 Concen-
tration of selenium in foods of animal origin is determined by its levels in plant foods
eaten by the animals. Because toxic properties of this metalloid are strongly dependent
on its chemical speciation, it is important to assess the chemical forms of Se in certain
foods. Van Deal46 has quantified the species of selenium in foodstuffs, including cooked
cod and cow, goat, and sheep milk. Speciation analysis of selenium in food is discussed
elsewhere (see Chapter 2 of this book).
6.3.9 ZINC
Zinc (Zn) is an essential element found at elevated levels in foods of animal origin.
In many African and Asian regions, zinc intakes are low, especially where the
customary diets of children contain insufficient amounts of animal products.1,47 For
instance, poor communities in developing countries of the Middle East, e.g., Iran
and Egypt, as well as in Bangladesh, suffer from marginal zinc deficiency as their
diet consists mainly of cereals rich in phytate and fiber in which the zinc is unavail-
able for absorption.1,47 – 49 In order to improve zinc nutrition especially in the devel-
oping countries, some effort is underway to provide zinc supplements to local
populations or fortify staple foods with this element.1,50
Concentrations of zinc in meat and its products range from 0.004 to 22.0 mg/100
g with lower values for beef and the highest for pork loin (see Table 6.4). Mammalian
liver as well as carcass meat and offal may be important sources of zinc with some
seafoods also being highly enriched in this element.1 Milk and milk products are
characterized by lower levels of zinc. Concentrations of this element in human and
cow milk range between 0.17 and 0.88 mg/100 g. Higher levels are reported for
infant formula (4.53 mg/100 g) and some cheeses (5.30 mg/100 g) (see Table 6.5).
Concentrations of zinc in honey range from 0.004 mg/100 g (acacia tree honey) to
2.9 mg/100 g (Indian honey). High levels are also reported for clover honey, up to
0.93 mg/100 g (see Table 6.6).
and meat products (0.0003-0.005 mg/100 g), but much higher levels have been
reported in fish meat (up to 0.53 mg/100 g, see Table 6.7). As can be deduced from
Table 6.8, very low levels of As are reported for milk (< 0.0001 to 0.004 mg/100 g)
with 2 to 3 times higher values in dairy products (0.0003 to 0.004 mg/100 g). Honey
contain from 0.00005 to 0.003 mg As/100 g (see Table 6.9).
It should be kept in mind that arsenic in seafoods (edible mollusks, shrimp,
lobster, and algae) occurs mainly in nontoxic compounds such as arsenobetaine and
arsenocholine. Therefore, food safety assessment requires data not only on total
arsenic concentration but also on its speciation in foods. In consequence, the con-
sumers may not be exposing themselves to much risk by eating food of marine origin
that is rich in arsenobetaine. On the other hand, it is still impossible to assess the
health risk for arseno-sugars because of the lack of toxicity data for this orga-
noarsenic compound.3 Environmental contamination of foods with arsenic is dis-
cussed in detail in Chapter 10 of this book.
6.4.2 BORON
Dietary boron (B) is characterized by a low degree of toxicity, because it is rapidly
excreted. Levels of this element in animal foods are lower than those in plant foods,
with reported values ranging between < 0.04 and 0.05 mg/100 g (see Table 6.7 and
Table 6.8).
6.4.3 VANADIUM
Vanadium (V) is probably an essential trace element. There is limited information
on levels of vanadium in animal foods. Data listed in Table 6.7 to Table 6.9 show
that levels of vanadium are generally within the values of < 0.00001 and 0.02 mg/100
g. According to data in Table 6.8, milk contains significantly lower levels (< 0.00001
to 0.0004 mg/100 g) of vanadium compared to dairy products (0.012 to 0.020 mg/100
g). Seafood represent the richest source of vanadium.1 Concentration of the element
in honey is small and range between 0.0001 and 0.0002 mg/100 g (see Table 6.9).
TABLE 6.7
“Possibly Essential” Micronutrients and Nontoxic, Nonessential Metals
in Meat, Fish, and Poultry (in mg/100 g w/w)
Name Origin n Al As B Sn Ref.
Meat
Carcass meatb U.K. 0.05 0.0004 < 0.04 0.002 7
Beef Galicia 56 — n = 12 — — 54
0.0005 ± 0.00005
0.001 – 0.002
Veal Galicia 438 — n = 48 — — 54
0.0004 ± 0.00001
0.001 – 0.002
Cattle liver Galicia 437 — n = 134 — — 54
0.004 ± 0.0004
0.001 – 0.04
Offalb U.K. 0.035 0.0004 < 0.04 0.002 7
Offalsb U.S. — < 0.004 — — 8
Meat productsb U.K. 0.32 0.0004 0.04 0.03 7
Meat productsb U.S. — < 0.004 – < 0.005 — — 8
Poultry
Poultryb U.K. 0.03 0.0003 < 0.04 < 0.002 7
Poultryb U.S. — < 0.004 — — 8
Fish
Fishb U.K. 0.55 0.43 0.05 0.04 7
Fishb U.S. — 0.20 ± 0.22 — — 8
0.08 – 0.53
6.5.2 TIN
Tin (Sn) does not constitute any serious problems in most foods except when there
is incidental contamination in canned food products that are acidic.1 The levels of
tin range from < 0.002 mg/100 g in poultry and eggs to 0.044 mg/100 g in fish (see
Chapter 10 of this book). Milk-based powder formulas contain from 0.002 to 0.01
mg Sn/100 g (see Table 6.8). Lower levels are reported for honey with values in the
range of < 0.0004 to 0.002 mg Sn/100 g (see Table 6.9). Meat and offal contain, on
the average, 0.002 mg Sn/100 g (see Chapter 10 of this book). Uptake of tin by
foodstuffs is dependent on the kind of the food, the age of the cans or whether cans
are lacquered or not.1 It has been reported that tin in canned food occurs in the
inorganic form; however, certain food, especially fish, may also contain organic tin
species that are more toxic than the inorganic compounds. Among the organotin
compounds such as tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT),
the TBT is known to be the most highly bioaccumulated in fish and other edible
marine organisms such as mollusks and crustaceans.1,3 A major source of butyltins
in fish and seafood is TBT-based antifouling paint agents used extensively on ships.3
198
TABLE 6.8
“Possibly Essential” Micronutrients and Nontoxic, Nonessential Metals in Milk, Dairy Products, and Eggs
(in mg/100 g w/w)
Name Origin n Al As B Sn V Ref.
Milk
Bottled cow milkc 3 0.08 ± 0.005 — — — 73
Milkb U.S. — < 0.004 — — — 8
Milkb U.K. <0.03 0.0002 < 0.04 < 0.002 — 7
Skimmed bottled cow milkc 3 0.04 ± 0.002 — — — — 73
Whole raw bovine milk Calabria, Italy 40 — 0.004 — — — 79
< 0.00002 – 0.07
2234_C006.fm Page 198 Thursday, October 26, 2006 8:00 AM
Dairy Products
Dairy productsb U.K. 0.06 0.3d 0.04 0.03 — 7
Milk productsb U.S. — < 4 – < 5d — — — 8
Yoghurt, low-fat, fruit U.S. — < 4d — — — 8
Butter (regular, salted) U.S. — < 4d — — — 8
Swiss cheese U.S. — < 5d — — — 8
Commercial goat cheese 2 0.14 ± 0.04 — — — — 19
2234_C006.fm Page 200 Thursday, October 26, 2006 8:00 AM
0.11 – 0.18
Commercial sheep cheese 4 0.47 ± 0.24 — — — — 19
0.26 – 0.88
Cream cheese U.S. — < 0.005 — — — 8
Skimmed cream 4 — 0.0005 ± 0.0001 — — — 82
0.0003 – 0.001
Cream partially skimmed Spain 6 — 0.001 ± 0.0002 — — — 84
0.001 – 0.001
Cream partially skimmed Spain 6 — 0.001 ± 0.0002 — — — 82
0.001 – 0.001
Cream partially skimmed 3 — 0.001 ± 0.0002 — — — 82
0.001 – 0.001
Cream skimmed Spain 8 — 0.0005 ± 0.0001 — — — 84
0.0003 – 0.001
Cream skimmed Spain 6 — 0.0005 ± 0.0001 — — — 82
0.0003 – 0.001
Full cream Spain 4 — 0.001 ± 0.0003 — — — 84
0.0004 – 0.001
Mineral Components in Foods
Full cream Spain 4 — 0.001 ± 0.0003 — — — 82
0.0004 – 0.001
Full cream 2 — 0.003 ± 0.002 — — — 82
0.001 – 0.004
Market white brine cheese Turkey 10 0.24 ± 0.01 — — — 0.01 ± 0.0002 30
Soft white cheese Turkey 20 0.53 ± 0.21 — — — 0.02 ± 0.02 30
Soft white cheese melted Turkey 20 1.12 ± 0.04 — — — 0.02 ± 0.01 30
Eggs
Eggsb U.K. 0.03 0.0002 < 0.04 < 0.002 — 7
Egg productsb U.S. — < 0.004 — — — 8
d = µg/100 g w/w
2234_C006.fm Page 201 Thursday, October 26, 2006 8:00 AM
TABLE 6.9
“Possibly Essential” Micronutrients and Nontoxic, Nonessential Metals in
Honey (in mg/100 g w/w)
Name Origin n Al As Sn V Ref.
6.6.2 CADMIUM
The concentration of cadmium (Cd) in foodstuffs is usually very low. Shellfish may
be rich in this element. Australian beef and sheep offal have been reported to contain
high levels of cadmium.1 Animal foods contain, on the average, from < 0.00001 to
0.02 mg Cd/100 g in milk and dairy products (see Table 6.11) and from 0.0001 to
0.03 mg Cd/100 g in meat and its products (see Table 6.10). Cattle liver and chicken
kidneys contain up to 0.80 and 0.51 mg Cd/100 g, respectively. Concentrations in
honey range from < 0.00005 to 0.06 mg Cd/100 g. Further discussion of food
contamination with cadmium is provided in Chapter 10 of this book.
6.6.3 LEAD
Organic species of lead (Pb) are generally characterized by higher toxicity than
inorganic lead compounds. The concentrations of lead in animal foods range from
0.00001 to 0.02 mg/100 g (see Table 6.11). Meat and offal can contain high levels
of lead. Milk and milk products contain, on the average, 0.0002 and 0.001 mg Pb/100
g, respectively (see Table 6.11). High levels of lead have been reported in chicken
TABLE 6.10
Toxic Metals in Meat and Its Products (in mg/100 g w/w)
Name Origin n Cd Hg Pb Ref.
Meat
Carcass meatb U.K. 0.0001 0.0003 0.001 7
Swine muscle meat Poland 334 n = 658 n = 1181 0.002 ± 0.004 53
0.001 ± 0.0001 0.0002 ± 0.0001 <0.001 – 0.01
0.0005 – 0.001 0.0001 – 0.0003
Beef Galicia 56 n = 27 — n = 40 54
0.0001 ± 0.00002 0.002 ± 0.0002
0.0001 – 0.001 0.001 – 0.005
Bovine muscle Egypt 54 0.002 ± 0.001 — 0.01 ± 0.002 55
2234_C006.fm Page 203 Thursday, October 26, 2006 8:00 AM
Meat Products
Meat productsb U.K. 0.001 0.0003 0.001 7
Meat productsb U.S. < 0.001 – < 0.001 NA < 0.005 8
Poultry
Poultryb U.K. 0.0002 0.0004 < 0.001 7
Poultryb U.S. < 0.0005 – 0.001 ND < 0.004 8
Hen muscle meat Poland 1 0.003 < 0.003 < 0.003 58
Mineral Components in Foods
Smoked chicken Poland 4 0.001 ± 0.001 0.0002 0.01 ± 0.01 60
Geese muscle meat Poland 32 0.0005 < 0.001 < 0.001 58
< 0.0005 – 0.001 < 0.001 – 0.003 < 0.001 – 0.003
Turkey muscle meat Poland 30 — 0.001 — 58
0.0003 – 0.001
Duck muscle meat Poland 57 0.0005 0.002 0.002 58
< 0.0005 – 0.001 < 0.001 – 0.01 < 0.001 – 0.01
Chicken liver Kuwait 33 0.01 — 0.01 100
0.004 – 0.02 0.002 – 0.04
Hens kidney Poland 1 0.51 0.001 0.13 58
Hens liver Poland 13 0.01 0.0005 0.02 58
0.002 – 0.04 0.0002 – 0.001 0.001 – 0.01
Poultry sausage Poland 11 < 0.0005 0.0002 ± 0.0001 0.005 ± 0.002 60
Fish
2234_C006.fm Page 205 Thursday, October 26, 2006 8:00 AM
Seafood
Shrimp Taiwan 0.0005 – 0.001 0.004 – 0.02 < 0.001 61
Shrimp Spain 0.00 – 0.001 — 0.005 – 0.01 63
Shrimp 0.002 – 0.005 — 0.002 – 0.01 63
2234_C006.fm Page 206 Thursday, October 26, 2006 8:00 AM
TABLE 6.11
Toxic Metals in Milk, Dairy Products, and Eggs (in mg/100 g w/w)
Name Origin n Be Cd Hg Pb Ref.
Milk
Cow milk fat content 3.8%c — 0.00001 ± 0.0002 — 0.0002 ± 0.0001 74
Lowfat (2%) milk, fluid U.S. — — — <0.003 8
Milkb U.S. — <0.0004 ND <0.002 – <0.003 8
Milkb U.K. — 0.0001 0.00007 <0.001 7
Milk 6 — — 0.0004 — 103
fat content 2% 0.0001 – 0.001
Milk 4 — — 0.0001 — 103
2234_C006.fm Page 208 Thursday, October 26, 2006 8:00 AM
Dairy Products
Bioyoghurt natural 10 — — 0.0004 — 103
0.0001 – 0.001
Dairy productsb U.K. — 0.0002 0.0002 0.001 7
Milk productsb U.S. — <0.0005 – <0.001 NA <0.003 – <0.005 8
Plain yoghurt, lowfat U.S. — <0.0005 — <0.003 8
209
210
TABLE 6.12
Toxic Metals in Honey (in mg/100 g w/w)
Name Origin n Cd Hg Pb Ref.
kidney (0.13 mg/100 g) and in offal (up to 0.011 mg/100 g) (see Table 6.10).
Concentrations of lead in honey range from 0.0003 mg/100 g (Saudi Arabia honey)
to 0.63 mg/100 g (sesame honey). Syrup-feed honey contains 0.93 mg Pb/100 g (see
Table 6.12). More detailed information on occurrence of lead as a contaminant in
animal foods is presented in Chapter 10 of this book.
6.6.4 MERCURY
The levels of mercury (Hg) in animal foods are generally low, ranging from 0.00005
to 0.0020 mg/100 g in milk and dairy products (see Table 6.11) and 0.00004 to
0.0002 mg/100 g in meat and its products (see Table 6.10). Seafoods may bioaccu-
mulate higher levels of mercury, up to 0.07 mg/100 g (see Table 6.10). Organ meat
also tends to contain higher levels of the element, derived mostly from industrial
sources (see Chapter 10 of this book). Manifestations of such contamination include
the elevated renal levels of 0.0001 to 0.014 mg Hg/100 g in cattle from the Neth-
erlands and the concentrations of up to 0.16 mg/100 g Hg in fish from the Alexandria
coast.94,95 Concentration of the metal in honey can be up to 0.0001 mg/100 g (see
Table 6.12).
Analysis of foodstuffs for particular species of mercury is very important from
both the hygienic and toxicological points of view. Organic compounds of mercury
are characterized by high toxicity, greater than for its inorganic species. A spectacular
example of marine contamination by mercury is the Minamata Bay in Japan where
2234_C006.fm Page 213 Thursday, October 26, 2006 8:00 AM
6.7.2 BARIUM
It is questionable whether barium (Ba) is an essential trace element for human beings.
Barium is detected in animal foods in levels from 0.002 mg/100 g in poultry to ca.
0.03 mg/100 g in meat and dairy products (see Table 6.13 and Table 6.14). Cow,
goat, and sheep milk contain from 0.11 to 0.39 mg Ba/100 g; lower levels are
observed in milk-based powder formulas. The concentrations of this metal in cheese
range widely, from 0.03 to 0.50 mg/100 g (see Table 6.14). Toxicity, as well as
absorption of this element from food, depends on its chemical speciation. Most of
the barium present in foods seems to be relatively insoluble, and hence a large
proportion of the barium ingested is promptly excreted.1 Other chemical forms of
barium are effectively dissolved in digestive fluids. Chronic barium poisoning due
to consumption of contaminated table salt in a Chinese community was connected
with increased cardiovascular disease.1,106
6.7.3 BISMUTH
Levels of bismuth (Bi) in meat and meat products are usually very low, typically in
the range of 0.00001 to 0.00009 mg/100 g (see Table 6.13). Milk and eggs contain
low amount of the element (0.00001 mg/100 g). Among dairy products, cream
skimmed contain from 0.001 to 0.003 mg Bi/100 g (see Table 6.14).
TABLE 6.13
Other Metals in Meat, Fish, and Poultry (in µg/100 g w/w)
Name Origin Au Ba Bi Ge Ir Li Pd Pt Rh Ru Sb Sr Th Tl U Ref.
Carcass meatb U.K. 0.1 5 0.02 0.2 0.1 2 0.04 0.01 < 0.01 < 0.2 0.2 10 — 0.3 — 7
Emu meat — ND — — — — — — — — — 10 — — — 112
Meat productsb U.K. 0.1 30 0.04 0.2 < 0.1 1 0.1 < 0.01 < 0.01 < 0.2 0.4 60 — 0.1 — 7
Poultryb U.K. 0.1 2 0.01 < 0.2 < 0.1 1 < 0.03 0.01 < 0.01 < 0.2 0.1 10 — 0.2 — 7
Offalb U.K. 0.1 10 0.03 0.2 0.1 3 0.2 < 0.01 0.05 < 0.2 0.1 10 — 0.3 — 7
Fishb U.K. 0.1 20 0.1 0.2 < 0.1 10 0.2 < 0.01 0.02 < 0.2 0.3 360 — 0.1 — 7
Fish Poland — — — — — — — — — — — — < 0.03 – 0.2 < 0.02 – 0.1 113
2234_C006.fm Page 214 Thursday, October 26, 2006 8:00 AM
Milk
Milkb U.K. — 0.00004 0.01 0.00001 <0.0002 7
Raw goat milk 2 — — 0.19 ± 0.02 — — 19
0.17 – 0.21
Raw sheep milk 4 — — 0.31 ± 0.05 — — 19
0.26 – 0.39
Human milk < 0.00001 – 0.004 0.00001 – 0.0002 — — — 80
Raw milk 7 — — 0.21 ± 0.08 — — 17
0.11 – 0.37
Milk based liquid London, 18 — — 0.005 ± 0.004 — — 24
2234_C006.fm Page 215 Thursday, October 26, 2006 8:00 AM
melted
Dairy productsb U.K. — 0.00004 0.031 0.0001 0.0002 7
Eggsb U.K. 0.00004 0.05 0.00001 < 0.0002 7
Milkb U.K. < 0.0002 0.0003 < 0.00003 < 0.00001 — 0.00003 0.0002 7
Raw goat milk 2 — — — 0.05 ± 0.00005 — — — 19
Raw sheep milk 4 — — — 0.04 ± 0.002 — — — 19
0.04 – 0.05
Human milk — — — < 0.000001 – 0.000004 — — — 80
Raw milk 7 — — — < 0.00001 — — — 17
Ready to drink — — — < 0.000001 — — — 80
infant formulas
Dairy Products
Commercial goat 2 — — — 0.03 ± 0.002 — — — 19
cheese
Mineral Components in Foods
Soft cheeses — — — — 0.15 — — 28
0.07 – 0.35
Commercial sheep 4 — — — 0.03 ± 0.004 — — — 19
cheese 0.02 – 0.03
Hard cheeses — — — — 0.08 — — 28
0.07 – 0.11
Quark cheeses — — — — 0.11 — — 28
0.1 – 0.16
Stirred curd cheeses — — — — 0.06 — — 28
0.01 – 0.11
Dairy productsb U.K. 0.0002 0.0005 0.00004 0.00001 — 0.00001 0.0002 7
Eggsb U.K. < 0.0002 0.001 0.00004 < 0.00001 — < 0.00001 < 0.0002 7
Milk
2234_C006.fm Page 217 Thursday, October 26, 2006 8:00 AM
2
Spain 0.0002 – 0.0003
Formula milkc 5 — — 0.07 ± 0.003 — — — 18
Formula milk wheyc 5 — — 0.03 ± 0.001 — — — 23
Milk-based liquid London, 18 0.0004 ± 0.001 — 0.02 ± 0.005 — 0.01 ± 0.005 0.001 ± 0.002 24
first and follow-on U.K.
formulasc
Ready-to-drink — < 0.00001 — — < 0.0003 – 0.0005 — 80
infant formulas
Skimmed formula 5 — — 0.06 ± 0.003 — — — 18
milkc
Milk-based powder Lagos, 6 0.0003 ± 0.0003 — 0.01 ± 0.001 — 0.001 ± 0.0003 0.003 ± 0.001 24
formulasc Nigeria
Milk-based powder London, 12 0.001 ± 0.001 — 0.01 ± 0.003 — 0.001 ± 0.0004 0.001 ± 0.001 24
formulasc U.K.
Milk-based powder U.S. 9 0.001 ± 0.002 — 0.02 ± 0.01 — 0.002 ± 0.001 0.004 ± 0.002 24
formulasc
Soy-based powder U.S. 6 0.001 ± 0.001 — 0.02 ± 0.01 — 0.003 ± 0.001 0.002 ± 0.001 24
formulac
Mineral Components in Foods
Cow milk wheyc 5 — — 0.03 ± 0.001 — — — 23
Milk whey coming 5 — — 0.03 ± 0.001 — — — 18
from cow milkc
Milk whey coming 5 — — 0.02 ± 0.001 — — — 18
from UHT cow
milkc
UHT cow milk 5 — — 0.03 ± 0.002 — — — 23
wheyc
Human milk wheyc 5 — — 0.01 ± 0.0005 — — — 23
Milk whey coming 5 — — 0.01 ± 0.0005 — — — 18
from human milkc
Milk whey coming 5 — — 0.02 ± 0.001 — — — 18
from formula
milkc
Dairy products
Commercial goat — — 0.38 ± 0.09 — — — 19
2234_C006.fm Page 219 Thursday, October 26, 2006 8:00 AM
2
cheese
Commercial sheep 4 — — 0.35 ± 0.07 — — — 19
cheese 0.27 – 0.45
Goat full creamc 3 — — — 0.001 ± 0.00002 — — 111
Skimmed cream 4 0.001 ± 0.0002 — — — — — 82
0.0003 – 0.001
Cream partially Spain 6 0.001 ± 0.0003 — — 0.001 ± 0.0001 — — 84
skimmed 0.0005 – 0.001 0.001 – 0.001
Cream partially Spain 6 0.001 ± 0.0003 — — — — — 82
skimmed 0.0005 – 0.001
Mineral Components in Foods of Animal Origin and in Honey
6.7.6 GOLD
Concentrations of gold (Au) in animal foods range from 0.00004 to 0.00010 mg/100
g. Milk, dairy products, and eggs contain 0.00001 to 0.00004 mg Au/100 g, but the
levels in offal, fish, and meat products are somewhat higher, being up to 0.0001
mg/100 g (see Table 6.14). Lower levels are noted for ready-to-drink instant formulas
(< 0.000005 to 0.000020 mg/100 g).
6.7.7 LITHIUM
Different groups of animal food contain low levels of lithium (Li), ranging from 0.0003
to 0.006 mg/kg. The lowest values are registered for milk and dairy products, whereas
the highest levels are found in fish (see Table 6.13 and Table 6.14). Concentrations of
this element in honey broadly range from 0.0003 to 0.005 mg/100 g (see Table 6.15).
6.7.9 RUBIDIUM
The concentrations of rubidium (Rb) in dairy products range from 0.01 to 0.35 mg
/100 g (see Table 6.14). Honey contains similar levels of the metal, in the range of
0.01 to 0.15 mg /100 g (see Table 6.15).
2234_C006.fm Page 222 Thursday, October 26, 2006 8:00 AM
6.7.10 SCANDIUM
Concentrations of scandium (Sc) in animal foods are low and range from < 0.00001
to 0.0001 mg/100 g in human milk and infant formulas (see Table 6.14) and < 000003
to 0.02 mg/100 g in honey (see Table 6.15).
6.7.11 SILVER
Silver (Ag) occurs naturally at low levels in animal foods, mostly at or below
detection limits of many analytical instruments. The intake of silver may be increased
where silver or silver-plated utensils are used in preparation and storage of food.1
Concentration of this metal in milk and ready to drink formula range from < 0.00001
to 0.004 mg/100 g (see Table 6.14). Honey contains from 0.01 to 0.02 mg Ag/100
g (see Table 6.15).
6.7.12 STRONTIUM
Meat products typically contain 0.06 mg Sr/100 g, whereas lower levels of this metal
have been reported in carcass meat and offal (0.01 mg/100 g), and higher in fish
meat (0.36 mg/100 g) (see Table 6.13). The concentrations of strontium (Sr) in cow
milk range from 0.03 to 0.06 mg/100 g. Sheep and goat milk shows higher its levels,
from 0.47 to 0.62 mg/100 g (see Table 6.14). Similar values for strontium are reported
in dairy products, e.g., cheese (0.27-0.45 mg/100 g). Honey contains from 0.05 to
0.32 mg Sr/100 g (see Table 6.15). Most of studies on occurrence of radiostrontium
TABLE 6.15
Other Metals in Honey (in mg/100 g w/w)
Name Origin n Ag Li Rb Sc Sr Ref.
(90Sr) in food, especially fish and other seafood, were undertaken after the Chernobyl
disaster96 (see Chapter 11 of this book).
6.7.13 TELLURIUM
Levels of tellurium (Te) in animal products are very low, generally below 0.0005
mg/100 g.1 Among dairy products, skimmed cow milk contains from 0.00001 to
0.001 mg Te/100 g whereas cheese (parmesan) and cream may contain up to 0.001
mg Te/100 g (see Table 6.14). Concentration of this element in vegetal-based milk
range from 0.0002 to 0.0003 mg/100 g.
6.7.14 THALLIUM
Thallium (Tl) is totally absorbed from food and highly toxic. Its levels in animal
food are somewhat lower than in plant products and are almost near or below the
analytical detection, i.e., 0.0001 mg/100 g. The concentrations of this element in
milk-based formulas and soy-based powder formula range from < 0.0001 to 0.004
mg/100 g (see Table 6.14). Meats, meat products, offal, and poultry contain from
0.0001 to 0.0003 mg Tl/100 g (see Table 6.13).
6.7.15 TITANIUM
There is little or no information on levels of titanium (Ti) in animal foods. It is
believed that most of the reported concentrations (low) can be attributed to external
contamination.1 Among the animal foods, somewhat higher levels are noted for dairy
products; these data need to be validated using reliable certified materials (CRMs),
however.1,110 Recent studies report concentration of titanium in milk and milk-based
infant formula to be in the range of < 0.0003 to 0.01 mg/100 g (see Table 6.14).
REFERENCES
1. Reilly, C., Metal Contamination of Food: Its Significance for Food Quality and Human
Health, Blackwell Science, Oxford, 2002.
2. Reilly, C., The Nutritional Trace Metals, Blackwell Publishing, Oxford, 2004.
3. Capar, S.G. and Szefer P., Determination and speciation of trace elements in foods,
in Methods of Analysis of Food Components and Additives, Otles, S., Ed., CRC Press,
Boca Raton, FL, 2005, chap. 6.
2234_C006.fm Page 224 Thursday, October 26, 2006 8:00 AM
4. Sutton, K.L. and Heitkemper, D.T., Speciation analysis of biological, clinical and
nutritional samples using plasma spectrometry, in Elemental Speciation. New
Approaches for Trace Element Analysis, Caruso, J.A., Sutton, K.L., and Ackley, K.L.,
Eds., Elsevier Science, Amsterdam, 2000, p. 501.
5. González, E.B. and Sanz-Medel, A., Liquid chromatographic techniques for trace
element speciation analysis, in Elemental Speciation: New Approaches for Trace
Element Analysis, Caruso, J.A., Sutton, K.L., and Ackley, K.L., Eds., Elsevier Science,
Amsterdam, 2000, p. 81.
6. Rojas, E. et al., Are metals dietary carcinogens?, Mutation Res., 443, 157, 1999.
7. Ysart, G. et al., Dietary exposure estimates of 30 elements from the U.K. Total Diet
Study, Food Addit. Contam., 16, 391, 1999.
8. Capar, G.S. and Cunningham, W.C., Element and radionuclide concentrations in food:
FDA total diet study 1991–1996, J. AOAC Int., 83, 157, 2000.
9. Coultate, T.P., Food: The Chemistry of Its Components, Royal Society of Chemistry,
Cambridge, MA, 2002.
10. González-Martín, I. et al., Mineral analysis (Fe, Zn, Ca, Na, K) of fresh Iberian pork
loin by near infrared reflectance spectrometry: determination of Fe, Na, and K with
remote fiber-optic reflectance probe, Anal. Chim. Acta, 468, 293, 2002.
11. Santos, E.M. et al., Physicochemical and sensory characterisation of Morcilla de
Burgos, a traditional Spanish blood sausage, Meat Sci., 65, 893, 2003.
′ N. and Yerlikaya, P., Determination of proximate composition and mineral
12. Göko∂lu,
contents of blue crab (Callincetes sapidus) and swim crab (Portunus pelagicus) caught
off the Gulf of Antalya, Food Chem., 80, 495, 2003.
13. Riget, F., Johansen, P., and Asmund, G., Influence of length of elements concentra-
tions in Blue Mussels (Mytilus edulis), Mar. Pollut. Bull., 32, 745, 1996.
14. Kwoczek, M. et al., Essential and toxic elements in seafood available in Poland from
different geographical regions, J. Agric. Food Chem., 54, 3015, 2006.
15. Lindmark-Månsson, H., Fondén, R., and Pettersson, H.-E., Composition of Swedish
dairy milk, Int. Dairy J., 13, 409, 2003.
16. Rodríguez Rodríguez, E.M., Sanz Alaejos, M., and Romero, C.D., Mineral concen-
trations in cow’s milk from the Canary Island, J. Food Compos. Anal., 14, 419, 2001.
17. Coni, E. et al., Preliminary evaluation of the factors influencing the trace element
content of milk and dairy products, Food Chem., 52, 123, 1995.
18. Rivero Martino, F.A., Fernández Sánchez, M.L., and Sanz-Medel, A., The potential
of double focusing-ICP-MS for studying elemental distribution patterns in whole
milk, skimmed milk and milk whey of different milks, Anal. Chim. Acta, 442, 191,
2001.
19. Coni, E. et al., Minor and trace element content in sheep and goat milk and dairy
products, Food Chem., 57, 253, 1996.
20. Bocca, B. et al., Determination of the total content and binding pattern of elements
in human milk by high performance liquid chromatography-inductively coupled
plasma atomic emission spectrometry, Talanta, 53, 295, 2000.
21. Booth, C.K., Reilly, C., and Farmakalidis, E., Mineral composition of Australian
ready-to-eat breakfast cereals, J. Food Compos. Anal., 9, 135, 1996.
22. Hua, K.M., Kay, M., and Indyk, H.E., Nutritional element analysis in infant formulas
by direct dispersion and inductively coupled plasma-optical emission spectrometry,
Food Chem., 68, 463, 2000.
23. Rivero Martino, F.A., Fernández, M.L., and Sanz Medel, A., Total determination of
essential and toxic elements in milk whey by double focusing ICP-MS, J. Anal. At.
Spectrom., 15, 163, 2000.
2234_C006.fm Page 225 Thursday, October 26, 2006 8:00 AM
24. Ikem, A. et al., Levels of 26 elements in infant formula from USA, U.K., and Nigeria
by microwave digestion and ICP–OES, Food Chem., 77, 439, 2002.
25. De La Fuente, M.A. et al., Total and soluble contents of calcium, magnesium,
phosphorus and zinc in yoghurts, Food Chem., 80, 573, 2003.
26. Sánchez-Segarra, P.J. et al., Influence of the addition of fruit on the mineral content
of yoghurts: nutritional assessment, Food Chem., 70, 85, 2000.
27. Pillonel, L. et al., Stable isotope ratios, major, trace and radioactive elements in
emmental cheeses of different origins, Lebensm.-Wiss. u-Technol., 36, 615, 2003.
28. Gambelli, L. et al., Minerals and trace elements in some Italian dairy products, J.
Food Compos. Anal., 12, 27, 1999.
29. Peláez Puerto, P. et al., Chemometric studies of fresh and semi-hard goats’ cheeses
produced in Tenerife (Canary Islands), Food Chem., 88, 361, 2004.
30. Merdivan, M. et al., Basic nutrients and element contents of white cheese of diyarbakir
in Turkey, Food Chem., 87, 163, 2004.
31. Devillers, J. et al., Chemometrical analysis of 18 metallic and nonmetallic elements
found in honeys sold in France, J. Agric. Food Chem., 50, 5998, 2002.
32. Terrab, A. et al., Mineral content and electrical conductivity of the honeys produced
in Northwest Morocco and their contribution to the characterization of unifloral
honeys, J. Sci. Food Agric., 83, 637, 2003.
33. Rashed, M.N. and Soltan, M.E., Major and trace elements in different types of
Egyptian mono-floral and non-floral bee honeys, J. Food Compos. Anal., 17, 725,
2004.
34. Yilmaz, H. and Yavuz, O., Content of some trace metals in honey from south-eastern
Anatolia, Food Chem., 65, 475, 1999.
35. López-García, I. et al., Fast determination of calcium, magnesium and zinc in honey
using continuous flow flame atomic absorption spectrometry, Talanta, 49, 597, 1999.
36. Iskander, F.Y., Trace and minor elements in four commercial honey brands, J. Radio-
anal. Nucl. Chem. Lett., 201, 401, 1995.
37. Nanda, V. et al., Physico-chemical properties and estimation of mineral content in
honey produced from different plants in Northern India, J. Food Compos. Anal., 16,
613, 2003.
38. Latorre, M.J. et al., Chemometric classification of honeys according to their type. II.
Metal content data, Food Chem., 66, 263, 1999.
39. Conti, M.E., Lazio region (central Italy) honeys: a survey of mineral content and
typical quality parameters, Food Contr., 11, 459, 2000.
˘
40. Kump, P., Necemer, M., and S̆najder, J., Determination of trace elements in bee
honey, pollen and tissue by total reflection and radioisotope x-ray fluorescence
spectrometry, Spectrochim. Acta Part B, 51, 499, 1996.
41. Al-Khalifa, A.S. and Al-Arify, I.A., Physicochemical characteristics and pollen spec-
trum of some Saudi honeys, Food Chem., 67, 21, 1999.
42. Darrie, G., The importance of chromium in occupational health, in Trace Element
Speciation for Environment, Food and Health, Ebdon, L. et al., Eds., Royal Society
of Chemistry, Cambridge, MA, 2001, p. 315.
43. Koops, J., Klomp, H., and Westerbeek, D., Spectroscopic determination of nickel and
furildioxime with special reference to milk and milk products and to the release of
nickel from stainless steel by acidic dairy products and by acid cleaning, Neth. Milk
Dairy J., 36, 333, 1982.
44. Margolin, S., Mercury in marine seafood: the scientific medical margin of safety as
a guide to the potential risk to public health, World Rev. Nutr. Diet, 34, 182, 1980.
2234_C006.fm Page 226 Thursday, October 26, 2006 8:00 AM
45. Hansen, J.C., Kromann, N., and Wulf H.C., Selenium and its interrelation with
mercury in wholeblood and hair in an East Greenland population, Sci. Total Environ.,
38, 33, 1984.
46. Van Deal, P., Trace element speciation in food: a tool to assure food safety and
nutritional quality, in Trace Element Speciation for Environment, Food and Health,
Ebdon, L. et al., Eds., Royal Society of Chemistry, Cambridge, MA, 2001, p. 232.
47. Osendarp, S.J.M. et al., Zinc supplementation during pregnancy and effects on growth
and morbidity in low birthweight infants: a randomized placebo controlled trial,
Lancet, 357, 1080, 2001.
48. Prasad, A.S. et al., Zinc metabolism in patients with the syndrome of iron deficiency
anemia, hepatosplenomegaly, dwarfism and hypogonadism, J. Lab. Clin. Med., 61,
537, 1963.
49. Walsh, C.T. et al., Zinc health effects and research priorities for the 1990s, Environ
Health Perspect., 102, 5, 1994.
50. Gibson, R.S. and Ferguson, E.L., Nutrition interventions to combat zinc deficiencies
in developing countries, Nutr. Res. Rev., 11, 115, 1998.
51. Kot, A., Zareba,
¸ S., and Wyszogrodzka-Koma, L., Copper, zinc, manganese and iron
in Polish poultry, pork, bovine meat and meat products, Bromat. Chem. Toksykol.,
35, 39, 2002.
52. Leonhardt, M. and Wenk, C., Variability of selected vitamins and trace elements of
different meat cuts, J. Food Compos. Anal., 10, 218, 1997.
53. Falandysz, J., Some toxic and essential trace metals in swine from Northern Poland,
Sci. Total Environ., 136, 193, 1993.
54. López Alonso, M. et al., Contribution of cattle products to dietary intake of trace and
toxic elements in Galicia, Spain, Food Addit. Contam., 19, 533, 2002.
55. Abou-Arab, A.A.K., Heavy metal contents in Egyptian meat and the role of detergent
washing on their levels, Food Chem. Toxicol., 39, 593, 2001.
56. Sedki, A. et al., Toxic and essential trace metals in muscle, liver and kidney of bovines
from a polluted area of Morocco, Sci. Total Environ., 317, 201, 2003.
57. Falandysz, J., Some toxic and essential trace metals in cattle from the northern part
of Poland, Sci. Total Environ., 136, 177, 1993.
58. Falandysz, J., Manganese, copper, zinc, iron, cadmium, mercury and lead in muscle
meat, liver and kidneys of poultry, rabbit and sheep slaughtered in the northern part
of Poland, 1987, Food Addit. Contam., 8, 71, 1991.
59. Brito, G. et al., Differentiation of heat- treated pork liver pastes according to their
metal content using multivariate data analysis, Eur. Food Res. Technol., 218, 584,
2004.
¸·
60. Falandysz, J. and Kotecka, W., Stezenia metali w wybranych produktach spozywc-·
zych Trójmiasta, Bromat. Chem. Toksykol, 26, 143, 1993.
61. Jeng, M.-S. et al., Mussel Watch: a review of Cu and other metals in various marine
organisms in Taiwan, 1991–1998, Environ. Pollut., 110, 207, 2000.
62. Mendez, H. et al., Ultrasonic extraction combined with fast furnace analysis as an
improved methodology for total selenium determination in seafood by electrothermal-
atomic absorption spectrometry, Anal. Chim. Acta., 452, 217, 2002.
63. Blasco, J., Arias, A.M., and Saenz, V., Heavy metals in organisms of the River
Guadalquivir estuary: possible incidence of the Aznalcollar disaster, Sci. Total Envi-
ron., 242, 249, 1999.
64. Páez-Osuna, F. and Ruiz-Fernández, C., Trace metals in the Mexican shrimp Penaeus
vannamei from estuarine and marine environments, Environ. Pollut., 87, 243, 1995.
2234_C006.fm Page 227 Thursday, October 26, 2006 8:00 AM
65. Páez-Osuna, F. and Tron-Mayen, L., Concentration and distribution of heavy metals
in tissues of wild and farmed shrimp Panaeus vannamei from the north-west coast
of Mexico, Environ. Int., 22, 442, 1996.
66. Johansen, P., Pars T., and Bjerregaard, P., Lead, cadmium, mercury and selenium
intake by Greenlanders from local marine food, Sci. Total Environ., 245, 187, 2000.
67. Turoczy, N.J. et al., Cadmium, copper, mercury, and zinc concentrations in tissues
of the King Crab (Pseudocarcinus gigas) from Southeast Australian waters, Environ.
Int., 27, 327, 2001.
68. Páez-Osuna, F. et al., Trace metal concentrations and their distribution in the lobster
Panulirus inflatus (Bouvuer, 1895) from the Mexican Pacific coast, Environ. Pollut.,
90, 163, 1995.
69. Yerba, M.C. and Moreno-Cid, A., On-line determination of manganese in solid
seafood samples by flame atomic absorption spectrometry, Anal. Chim. Acta, 477,
149, 2003.
70. Yap, C.K., Ismail, A., and Tan, S.G., Heavy metal (Cd, Cu, Pb and Zn) concentrations
in the green-lipped mussel Perna viridis (Linnaeus) collected from some wild and
aquacultural sites in the west coast of Peninsular Malaysia, Food Chem., 84, 569,
2004.
71. Wong, C.K.C., Cheung, R.Y.H., and Wong, M.H., Heavy metal concentrations in
green-lipped mussels collected from Tolo Harbor and markets in Hong Kong and
Shenzhen, Environ. Pollut., 109, 165, 2000.
72. Park, J. and Presley, B.J., Trace metal contamination of sediments and organisms
from the Swan Lake area of Galveston Bay, Environ. Pollut., 98, 209,1997.
73. Viñas, P. et al., Electrothermal atomic absorption spectrometric determination of
molybdenum, aluminum, chromium and manganese in milk, Anal. Chim. Acta, 356,
267, 1997.
74. Tripathi, R.M. et al., Daily intake of heavy metals by infants through milk and milk
products, Sci. Total Environ., 227, 229, 1999.
75. Rodríguez Rodríguez, E.M., Alaejos, M.S., and Romero, C.D., Comparison of min-
eralization methods for fluorimetric determination of selenium in milks, Z. Lebensm.
Unters. Forsch. A, 204, 425, 1997.
76. Aleixo, P.C. and Nóbrega, J.A., Direct determination of iron and selenium in bovine
milk by graphite furnace atomic absorption spectrometry, Food Chem., 83, 457, 2003.
77. Falandysz, J. and Kotecka, W., Zawartosć ·
´ manganu, miedzi, cynku i zelaza w produk-
tach nabialowych,
⁄ ·
odzywkach dla dzieci i slodyczach,
⁄ Bromat. Chem. Toksykol.,
XXVII, 77, 1994.
78. Bermejo, P., Dominguez, R., and Bermejo, A., Direct determination of Fe and Zn in
different components of cow milk by FAAS with a high performance nebulizer,
Talanta, 45, 325, 1997.
79. Licata, P. et al., Levels of “toxic” and “essential” metals in samples of bovine milk
from various dairy farms in Calabria, Italy, Environ. Int., 30, 1, 2004.
80. Prohaska, T. et al., Determination of trace elements in human milk by inductively
coupled plasma sector field mass spectrometry (ICP-SFMS), J. Anal. At. Spectrom.,
15, 335, 2000.
81. Rodríguez Rodríguez, E.M., Alaejos, M.S., and Romero, C.D., Concentrations of
selenium in human milk, Z. Lebensm. Unters. Forsch. A, 207, 174, 1998.
82. Cava-Montesinos, P. et al., Determination of arsenic and antimony in milk by hydride
generation atomic fluorescence spectrometry, Talanta, 60, 787, 2003.
83. López, J.C. et al., Mathematic predictive models for calculating copper, iron and zinc
dialysability in infant formulas, Eur. Food. Res. Technol., 212, 608, 2001.
2234_C006.fm Page 228 Thursday, October 26, 2006 8:00 AM
84. Cava-Montesinos, P. et al., Determination of As, Sb, Se, Te, and Bi in milk by slurry
sampling hydride generation atomic fluorescence spectrometry, Talanta, 62, 175,
2004.
85. Fakayode, S.O. and Olu-Owolabi, I.B., Trace metal content and estimated daily
human intake from chicken eggs in Ibadan, Nigeria, Arch. Environ. Health, 58, 245,
2003.
¸·
86. Falandysz, J. and Kotecka, W., Stezenia metali w wybranych produktach spozywc-·
zych Trójmiasta, Bromat. Chem. Toksykol., 26, 143, 1993.
87. Sanna, G. et al., Determination of heavy metals in honey by anodic stripping vol-
tammetry at microelectrodes, Anal. Chim. Acta, 415, 165, 2000.
88. Caroli, S. et al., Determination of essential and potentially toxic trace elements in
honey by inductively coupled plasma-based techniques, Talanta, 50, 327, 1999.
89. Buldini, P.L. et al., Ion chromatographic and voltammetric determination of heavy
and transition metals in honey, Food Chem., 73, 487, 2001.
90. Koo, W.W.K., Kaplan, L.A., and Krug-Wispe, S.K., Aluminum contamination of
infant formulas, J. Parenter. Enteral. Nutr., 12, 170, 1988.
91. Bouglé, D. et al., Concentrations en aluminum des formules pour prématurés, Arch.
Pédiatr., 46, 768, 1989.
92. Baxter, M.J., Burrell, J.A., and Massey, R.C., The aluminum content of infant formula
and tea, Food Addit. Contam., 7, 101, 1990.
93. Coni, E., Bellomonte, G., and Caroli, S., Aluminum content in of infant formulas, J.
Trace Elem. Electrol. Health Dis., 7, 83, 1993.
94. Vos, G., Hovens, J.P.C., and Delft, W.V., Arsenic, cadmium, lead and mercury in
meat, livers and kidneys of cattle slaughtered in the Netherlands during 1980–1985,
Food Addit. Contam., 4, 73, 1987.
95. Moharram, Y.G. et al., Mercury content of some marine fish from the Alexandria
coast, Nahrung, 31, 899, 1987.
96. Szefer, P., Metals, Metalloids and Radionuclides in the Baltic Sea Ecosystem, Elsevier
Science, Amsterdam, 764 pp, 2002.
97. Capon, C.J. and Smith, J.C., Chemical form and distribution of mercury and selenium
in edible seafood, J. Anal. Toxicol., 6, 10, 1982.
98. Miranda, M. et al., Cadmium levels in liver, kidney and meat in calves from Asturias
(North Spain), Eur. Food Res. Technol., 212, 426, 2001.
99. López Alonso, M. et al., Mercury concentration in cattle from NW Spain, Sci. Total
Environ., 302, 93, 2003.
100. Husain, A. et al., Toxic metals in food products originating from locally reared animals
in Kuwait, Bull. Environ. Contam. Toxicol., 57, 549, 1996.
101. Haraguchi, K. et al., Detection of localized methylmercury contamination by use of
the mussel adductor muscle in Minamata Bay and Kagoshima Bay, Japan, Sci. Total
Environ., 261, 75, 2000.
102. Vaz-Pires, P. and Barbosa, A., Sensory, microbiological, physical and nutritional
properties of iced whole common octopus (Octopus vulgaris), Lebensm.-Wiss. u-
Technol., 37, 105, 2004.
103. Gajewska, R., Nabrzyski, M., and Kania, P., Zawartosć ´ rteci
¸ w mleku i jego przet-
worach, Bromat. Chem. Toksykol., XXVII, 29, 1994.
104. Schaum, J. et al., A national survey of persistent, bioaccumulative and toxic (PBT)
pollutants in the U.S. milk supply, J. Expo. Anal. Environ. Epidemiol., 13, 177, 2003.
105. Mendil, D., Mineral and trace metal levels in some cheese collected from Turkey,
Food Chem., 96, 532, 2006.
2234_C006.fm Page 229 Thursday, October 26, 2006 8:00 AM
106. Rossa, O. and Berman, L.B., Barium poisoning due to consumption of contaminated
salt, J. Pharmacol. Exp. Ther., 177, 433, 1971.
107. Hodge, V.F. and Stallard, M.O., Platinum and palladium in roadside dust, Environ.
Sci. Technol., 20, 1058, 1986.
108. Helmers, E. and Kummerer, K., Platinum group elements in the environment —
anthropogenic impact: platinum fluxes: quantification of sources and sinks, and out-
look, Environ. Sci. Pollut. Res., 6, 29, 1999.
109. Sures, B. et al., First report on the uptake of automobile catalyst emitted palladium
by European eels (Anguilla anguilla) following experimental exposure to road dust,
Environ. Pollut., 113, 341, 2001.
110. Iyengar, V. and Wottiez, J., Trace elements in human clinical specimens evaluation
of literature data to identify reference values, Clin. Chem., 34, 474, 1988.
111. Ródenas-Torralba, E., Morales-Rubio, A., and de la Guardia, M., Multicommutation
hydride generation atomic fluorescence determination of inorganic tellurium species
in milk, Food Chem., 91, 181, 2005.
112. Pegg, R.B., Amarowicz, R., and Code W.E., Nutritional characteristics of emu (Dro-
maius novaehollandiae) meat and its value-added products, Food Chem., 97, 193,
2006.
113. Szefer, P., Szefer, K., and Falandysz J., Uranium and thorium in muscle tissue of fish
taken from the southern Baltic, Helgol. Meeresunters., 44, 31, 1990.
2234_C006.fm Page 230 Thursday, October 26, 2006 8:00 AM
2234_C007.fm Page 231 Thursday, October 26, 2006 8:28 AM
7 Mineral Components in
Food Crops, Beverages,
Luxury Food, Spices, and
Dietary Food
Piotr Szefer and Malgorzata
⁄ Grembecka
CONTENTS
231
2234_C007.fm Page 232 Thursday, October 26, 2006 8:28 AM
7.1 INTRODUCTION
The levels of essential and nonessential elements in food crops are dependent on
many factors, including genetic properties of the plants, nature of soil on which the
plants grow, climatic conditions, and the degree of maturity of the plants during
harvesting. There are marked regional variations in metal concentrations even for
the same group of plants and vegetables. The spatial variability can be explained by
different geochemical structures of soils constituting the substratum for cultivated
plants. For instance, the concentration of selenium in rice grown in a selenium-rich
region of China is much higher than that in rice produced from New Zealand.1
Although soils can be a rich source of essential trace elements for plants requiring
mineral nutrients to grow, nonessential and toxic elements, e.g., mercury, cadmium,
and lead, can also be taken up by plants. An example of such accumulation is the
contamination of potatoes and cereals by cadmium in some areas of Australia as a
result of the use of cadmium-containing phosphate fertilizers.1,2 The concentration
of a given element in plants is dependent not only on the geochemical composition
of the soil material but also on the availability of the element in the soil. Some plants
themselves can assist in the uptake by modifying the geochemical composition of
the associated soil solution by releasing hydrogen ions and organic chelating agents.
The distribution of mineral components within the plant depends on whether or not
the absorbed metal can be translocated upwards to the leaves and fruits, seeds, and
2234_C007.fm Page 233 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 233
other storage organs. Many metals can be retained in the roots. Some plants are
characterized by the unusual ability to take up several metals from the soil substratum
and accumulate them in specific tissues to abnormally high levels. Among plants
known to accumulate metals are the tea plant, Camellia sinensis.
Environmental contamination may sometimes be a serious source of toxic ele-
ments such as lead and cadmium in food. The use of cast iron cooking pots may
result in the significant increase of iron concentration in the diet. Stainless steel used
in food processing and as storage equipment can be an important source of chromium
and nickel, whereas brass and copper utensils are responsible for copper release into
foods.1,3,4
Fortification of food by the addition of several nutrients, including mineral
components, is commonly practiced and can have a serious effect on the nutritional
status of the food supply. For instance, most of the cereals are poor dietary sources
of trace elements and hence are often fortified with iron, copper, manganese, and
zinc.1 On the other hand, spinach and cauliflower appear to be good sources of
cadmium, whereas Brussels sprout and Chinese beets are rich in lead content.5
Besides interactions occurring among metals and with other major food components,
any risk assessment must also consider metal pharmacokinetics and differences in
the dietary habits of local populations and in the geographical distribution of metals.5
7.2.2 MAGNESIUM
As can be seen in Table 7.1 and Table 7.2, grain products contain somewhat more
magnesium (Mg, 7.57–156 mg/100 g) than vegetables and fruits (5.5–67.5 mg/100
g). Higher levels of this element are reported for tea leaves (56.3–266 mg/100 g),
nuts (118–191 mg/100 g), and especially for instant coffee (212–415 mg/100 g)
234
TABLE 7.1
Macroelements in Miscellaneous Cerealsa
Name Origin n Ca K Mg Na P Ref.
Bread
Breadb U.K. 146 — — — — 7
Breadb U.S. 91.5 ± 14.4 163 ± 39.1 39.8 ± 22.3 519 ± 65.3 140 ± 37.8 9
71.8 – 108 121 – 223 18.6 – 73.7 441 – 622 91 – 193
Bread 23 — 27 — — 8
Bagel plain U.S. 76.9 102 25.5 467 94.1 9
White bread U.S. 103 121 22.3 518 91 9
Whole white bread U.S. 89.1 223 73.7 508 193 9
2234_C007.fm Page 234 Thursday, October 26, 2006 8:28 AM
Cereals
Corn flakes U.S. 2.8 90 8.5 1010 39 9
Oat flakes 50 ± 4 397 ± 1 154 ± 1 — — 11
Rolled oats 6 47.1 ± 1.9 — 174 ± 12 — — 1
44 – 61 151 – 262
Raisin bran cereal U.S. 46.1 599 143 489 372 9
Fruit- flavored cereal U.S. 27.9 112 28.3 489 100 9
Rice
Rice India, Pakistan 28 — — 2.58 — — 12
7.57 – 46.9
Mineral Components in Foods
Rice Europe 25 — — 81.1 — — 12
21.4 – 138
Rice Different 7.65 141 24.4 — — 13
Ricec 20.0 – 60.8 130–313 130 – 136 5.21 – 52.1 269 – 282 14
White rice 6 4.94 ± 0.06 — 32.5 ± 0.6 — — 1
4.66–5.36 28.6 – 36.7
Brown rice 7 10.6 ± 0.2 — 124 ± 1.3 — — 1
9.8–11.7 118 – 134
Grits — — —
Grits 10 0.82 ± 0.06 — 16.7 ± 1.6 — — 1
0.54 – 1.05 8.4 – 31.3
— — —
Flour
Flour 23 — 27 — — 8
2234_C007.fm Page 235 Thursday, October 26, 2006 8:28 AM
Miscellaneous Cereals
Miscellaneous cerealsb U.K. 73.1 — — — — 7
Miscellaneous cerealsb U.S. 62.0 ± 54.4 158 ± 140 36.6 ± 39.8 507 ± 366 169 ± 130 9
< 1.0 – 191 22.7 ± 599 60 – 143 < 3.0 – 1090 17.5 – 447
Oat bran 81 ± 0.8 630 ± 12.0 231 ± 8.3 — — 11
235
236
Vegetables
Butterhead lettuce 47 ± 14 318 ± 92 18 ± 5 5±2 — 16
Cabbage 44 ± 6 266 ± 87 14 ± 2 3±1 — 16
Cabbages Saudi Arabia 5 93.8 25.9 19.1 29.6 — 17
Canned vegetablesb U.K. 27.8 — — — — 7
Canned vegetablesb U.S. 28.0 ± 25.0 117 ± 53.9 10.6 ± 6.08 340 ± 36.1 39.2 ± 22.6 9
3.2 – 63.8 21.5 – 245 4.3 – 31.3 224 – 577 13.9 – 91
Carrots Saudi Arabia 5 66.5 23.4 20.48 77.2 — 17
Celery U.S. 32.4 260 9.2 73.1 23 9
2234_C007.fm Page 237 Thursday, October 26, 2006 8:28 AM
Green vegetablesb U.S. 32.2 ± 23.2 218 ± 117 23.5 ± 16.3 22.3 ± 17.3 62.9 ± 51.0 9
8.1 – 97.7 104 – 437 7.8 – 49.6 < 3.0 – 53.7 17.9 – 147
Iceberg lettuce U.S. 17 161 7.8 11.6 22.7 9
Kale 286 ± 43 712 ± 517 51 ± 4 12 ± 4 — 16
Leek Saudi Arabia 5 283 29.3 25.6 67.0 — 17
237
238
2234_C007.fm Page 238 Thursday, October 26, 2006 8:28 AM
Other vegetablesb U.S. 28.0 ± 34.0 191 ± 83.2 15.3 ± 9.10 261 ± 352 41.9 ± 32.5 9
2.9 – 138 61.1 – 356 3.2 – 35.9 < 3 – 1330 11.3 – 145
Parsley Saudi Arabia 5 396 41.5 34.1 84.7 — 17
Peas conventional Denmark 23.1 ± 9.6 — — — 129 ± 24.5 20
1.52 – 64.5 80.1 – 179
Peas organic Denmark 21.9 ± 5.79 — — — 182 ± 63.9 20
14 – 53.5 110 – 329
Potatoes Spain 8.5 ± 1.13 427 ± 68.6 24.4 ± 3.75 9.8 ± 7.35 — 21
7.7 – 9.3 378 – 475 21.7 – 27 4.6 – 15.0
Potatoes Saudi Arabia 5 8.52 37.7 37.0 60.4 — 17
Potatoesc Idaho 342 11.8 ± 3.64 464 ± 74.8 26.7 ± 4.22 — 55.6 ± 15.3 22
4.38 – 26.0 228 – 728 17.0 – 44.7 26.0 – 114
Potatoesc non-Idaho 266 7.94 ± 4.09 472 ± 63.6 25.9 ± 4.26 — 57.4 ± 15.1 22
2.22 – 25.8 302 – 694 16.3 – 41.3 27.8 – 98.2
Potatoesb U.K. 10.9 — — — — 7
Potatoesb U.S. 21.5 ± 16.1 393 ± 127 22.0 ± 6.69 109 ± 101 71.1 ± 31.0 9
5.6 – 50.8 225 – 596 14.6 – 34.4 < 2.0 – 261 43 – 129
Mineral Components in Foods
Radish U.S. 19.4 207 8.2 28.6 16.5 9
Red pepper Tenerife 60 18.6 ± 3.86 195 ± 31.7 16.0 ± 2.19 6.61 ± 11.8 30.5 ± 3.91 18
Island 13.0 – 33.2 120 – 250 12.3 – 23.1 4.13 – 8.60 24.4 – 40
Rucola 98 ± 12 363 ± 92 30 ± 9 4±2 — 16
Salq Saudi Arabia 5 284 23.1 24.4 534 — 17
Spinach Saudi Arabia 5 146 26.4 20.1 46.6 — 17
Spinach substitute 64 ± 21 537 ± 130 55 ± 16 94 ± 49 — 16
Tomato Saudi Arabia 5 19.6 1.01 11.2 14.2 — 17
Tomato fruits, rockwool high EC Denmark 5.1 153 8.7 0.78 31 23
Tomato fruits, rockwool norm EC Denmark 7.1 151 8.5 0.73 32 23
Tomato fruits, soil norm EC Denmark 11 164 9 0.55 33 23
Tomato red U.S. 8.3 221 10.3 <3 24.9 9
Marrow (zucchini) Saudi Arabia 5 44.7 12.6 14.41 10.5 — 17
Watercress 127 ± 24 271 ± 54 30 ± 5 14 ± 4 — 16
Watercress Saudi Arabia 5 199 12.6 14.1 29.9 — 17
2234_C007.fm Page 239 Thursday, October 26, 2006 8:28 AM
Mushrooms
Bay boletec Poland 166 1.26 ± 0.67 279 ± 39.0 3.88 ± 2.02 8.69 ± 6.16 — 24
0.14 – 4.43 129 – 518 0.58 – 7.56 1.23 – 44.8
Mushrooms U.S. 2.1 270 7.7 3.6 68.6 9
Mushrooms, canned 19 ± 7 — 6.2 ± 0.4 — 43 ± 6 19
Fruits
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Banana pulp Tenerife 18.9 ± 1.41 509 ± 36.1 37.4 ± 5.37 11.7 ± 0.42 59.1 ± 6.15 25
10.1 – 30.8 59 – 733 21.2 – 67.5 9.08 – 23.9 42.4 – 94.3
Cantaloupe U.S. 9.1 261 11.1 17.4 13.8 9
Currants 6 90.8 ± 4.6 — 52.9 ± 1.1 — — 1
64.5 – 115 48.3 – 58.2
Fresh fruitb U.K. 11.3 — — — — 7
Fresh fruitb U.S. 11.8 ± 7.55 208 ± 109 12.1 ± 7.73 11.2 ± 8.84 20.1 ± 9.97 9
4.6 – 32.2 104 – 498 < 5.0 – 29.7 < 2.0 – 17.4 9.9 – 50.1
Fruit productsb U.K. 12.7 — — — — 7
2234_C007.fm Page 240 Thursday, October 26, 2006 8:28 AM
Fruit productsb U.S. 14.1 ± 14.5 211 ± 238 12.7 ± 11.7 3.95 ± 2.74 21.9 ± 29.3 9
2.9 – 49 34.2 – 744 2.9 – 41.9 < 2.0 – 10.5 5.6 – 101
Grapefruit U.S. 20.6 138 8.9 <2 16.4 9
Grapes, seedless U.S. 9.8 182 7 < 2.0 19.3 9
Tea
Tea Africa 18 358 ± 84.7 — 157 ± 23.4 — — 27
Tea Asia 36 351 ± 57.2 — 56.3 ± 31.6 — — 27
Tea China 13 323 ± 85.6 — 165 ± 26.6 — — 27
Tea India, Sri Lanka 13 366 ± 58.2 — 157 ± 14.1 — — 27
Tea U.S. < 0.4 17.6 1.1 1 <2 9
(from tea bag)
US tea brands U.S. 7 — 1810 ± 350 — 33.8 ± 28.6 — 28
2234_C007.fm Page 241 Thursday, October 26, 2006 8:28 AM
Green tea beveragesd 20 0.74 ± 0.05 18 ± 1.41 0.5 – 1.4 0.04 – 0.33 — 33
0.57 – 0.99 9.4 – 25.9
Tea soft drinksd 8 1.7 7.8 1.4 14.6 — 33
0.1 – 5.7 1.0 – 17.6 0.5 – 5.0 2.6 – 33
Coffee
Decaffeinated instant coffee U.S. 2.5 46.2 4.8 1.5 4.2 9
Ground coffee U.S. 1.5 36.7 2.6 <2 <3 9
2234_C007.fm Page 242 Thursday, October 26, 2006 8:28 AM
Soluble coffee Brazil 21 139 ± 20 3810 ± 530 340 ± 50 111 ± 148 350 ± 50 34
106 – 189 3250 – 5170 212 – 415 27.4 – 667 223 – 410
Roasted coffee beans Costa Rica 20 104 ± 14.5 1793 ± 115 213 ± 9.7 4 ± 0.67 185 ± 13.5 35
Roasted coffee beans Colombia 20 109 ± 14.5 1851 ± 133 219 ± 13.5 3.87 ± 1.06 191 ± 19.3 35
Roasted coffee beans Guatemala 20 119 ± 28 1836 ± 854 233 ± 13.5 2.79 ± 0.57 189 ± 17.4 35
Roasted coffee beans Panama 20 96.3 ± 16.4 1804 ± 122 210 ± 10.6 0.93 ± 0.22 168 ± 8.7 35
Roasted coffee beans Ethiopia 20 97.8 ± 13.5 1862 ± 133 199 ± 12.5 1.94 ± 0.45 180 ± 14.5 35
Roasted coffee beans Kenya 20 94.2 ± 16.4 1690 ± 99.5 208 ± 15.4 3.6 ± 0.97 165 ± 13.5 35
Roasted coffee beans Sulawesi 20 90.2 ± 11.6 1850 ± 105 227 ± 15.4 142 ± 0.51 204 ± 15.4 35
Roasted coffee beans Sumatra 20 110 ± 18.3 1893 ± 135 203 ± 10.6 1.02 ± 0.94 187 ± 20.3 35
Roasted coffeec Mixture 18 101 ± 9.7 1371 ± 57.9 168 ± 9.66 1.8 ± 0.75 150 ± 19.3 36
84 – 119 1229 – 1488 141 – 187 0.64 – 3.3 120 – 189
Green coffeec Mixture 41 110 ± 19.3 1540 ± 160 178 ± 9.3 5.16 ± 2.03 160 ± 19.3 36
89.8 – 156 1170 – 1831 155 – 199 1.76 – 11.4 136 – 212
Mineral Components in Foods
Confectionary Products
Sugar and preservesb U.K. 61.2 — — — — 7
Sugar and preservesb U.S. 47.1 ± 46.6 140.2 ± 88.4 17.1 ± 15.0 232 ± 136 89.5 ± 61.2 9
1.1 – 188 < 3.0 – 403 < 1.0 – 65.8 9.8 – 410 < 4.0 – 232
Sugar Egypt 2 145 ± 7.07 3.45 ± 0.21 0.10 ± 0.01 0.16 ± 0.01 — 37
Sugar Egypt 1000 ± 500 100 ± 100 0.0 ± 0.0 8 ± 13 0.001 ± 0.004 38
White sugar, granulated U.S. < 2.0 <3 — <3 — 9
Sugar cane plant Egypt 3 490 ± 271 118 ± 19.7 2.14 ± 0.05 0.38 ± 0.77 — 37
Cocoa powder 4 191 ± 4.4 — 727 ± 11 — — 1
182 – 202 691 – 774
Molasses Egypt 7100 ± 4500 2200 ± 700 100 ± 100 130 ± 60 2.6 ± 1.9 38
Sugar cane juice Egypt 3 393 ± 344 66.0 ± 13.6 1.24 ± 0.30 1.92 ± 0.99 — 37
Sugar juice Egypt 2200 ± 1300 1900 ± 500 200 ± 100 80 ± 30 7.2 ± 6.3 38
2234_C007.fm Page 243 Thursday, October 26, 2006 8:28 AM
243
244
TABLE 7.4
Macronutrients in Nuts, Seeds and Oils (in mg/100 g w/w)
Name Origin n Ca K Mg Na P Ref.
Hazelnutc Turkey 173 ± 44.4 439 ± 35.6 191 ± 21.8 2.24 ± 0.71 — 42
Mixed nuts (no peanuts) U.S. 105 578 238 283 448 9
Nutsb U.K. 86.1 — — — — 7
Nutsb U.S. 64.6 ± 35.0 633 ± 56.0 199 ± 34.4 386 ± 95.7 392 ± 49.5 9
43.2 – 105 578 – 690 174 – 238 283 – 472 354 – 448
Peanut 65 ± 10 — 160 ± 50 — — 39
Peanut butter U.S. 43.2 632 174 404 354 9
Peanut greensc U.S. 2 1172 ± 225 1703 ± 722 641 ± 435 139 ± 57.1 — 43
986 – 1422 882 – 2237 322 – 1138 85.3 – 199
Walnut 76 ± 5 — 160 ± 30 — — 39
Oils
Oils and fatsb U.K. 8.7 — — — — 7
Oils and fatsb U.S. 14.4 ± 12.7 22.9 ± 1.13 1.55 ± 0.21 657 ± 115 16.3 ± 9.40 9
< 2.0 – 23.4 < 3 – 23.7 < 1.2 – 1.7 < 3.0 – 738 < 4.0 – 22.9
Olive or sunflower oil U.S. <2 <3 < 1.2 <3 <4 9
Juices
Cactus pear juice 59 — 98.4 — — 44
Grapefruit juice 5.72 137 8.66 1.18 18.2 45
Lemon juice 11.6 145 11.4 1.82 19.1 45
2234_C007.fm Page 245 Thursday, October 26, 2006 8:28 AM
Pineapple juiced 14.6 ± 3.48 96.7 ± 35.2 13.4 ± 3.69 5.11 ± 3.35 3.14 ± 0.83 48
9.64 – 18.5 40.2 – 132 6.96 – 17.3 1.52 – 9.66 1.87 – 4.01
Pineapple nectard 9.75 ± 3.23 33.1 ± 7.49 6.39 ± 2.59 9.34 ± 10.2 1.14 ± 0.52 48
5.40 – 14.8 21.3 – 40.9 4.25 – 10.8 1.72 – 32.0 0.54 – 1.86
Pummelo juice 10.4 156 7.5 0.42 18.5 45
Seville orange juice 10.8 147 8.71 1.04 13.3 45
Tangello juice 12.9 167 10.4 1.84 17.3 45
245
246
Alcoholic Beverages
Beer U.S. 4.2 24.5 5.8 3.1 14.4 9
Beerd 32 5.71 ± 2.34 40.6 ± 12.7 8.74 ± 5.09 3.90 ± 2.60 21.6 ± 7.22 49
1.99 – 10.8 20.0 – 83.3 4.31 – 26.7 0.84 – 10.3 10.9 – 38.1
Martini U.S. < 0.4 2.8 < 0.4 <1 <2 9
Whiskey U.S. < 0.5 <2 < 0.5 <1 <2 9
2234_C007.fm Page 246 Thursday, October 26, 2006 8:28 AM
2234_C007.fm Page 247 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 247
(Table 7.3 and Table 7.4). Data in Table 7.3 suggests that cocoa powder is the richest
source of magnesium (691–774 mg/100 g). Fruit juices contain from 4.11 to 20.8
mg Mg/100 g except cactus pear juice concentrate, which has 98.4 mg Mg/100 g.
The concentration of magnesium in alcoholic beverages such as beer and wine range
from 4.31 to 26.7 mg/100 g (Table 7.5).
7.2.3 POTASSIUM
Grain products, fruits, and vegetables show levels of potassium (K) in the range of
20 to 730 mg/100 g (Table 7.1). Concentrations of this macroelement in some plant
products are relatively high, with values >700 mg/100 g in Idaho potatoes, banana
pulp, and avocado (Table 7.2). Seeds and nuts are rich in potassium, with values of
up to 2240 mg/100 g (Table 7.4). Tea leaves (2840 mg K/100 g) and instant coffee
(5170 mg K/100 g) are very important sources of potassium (Table 7.3). Fruit juices
contain from 21.3 to 257 mg K/100 g (Table 7.5), similar to typical values for beer
and wine (20.0–160 mg/100 g).
7.2.4 SODIUM
Concentrations of sodium (Na) in cereals range from 5.21 to 1010 mg/100 g (Table
7.1). Raw vegetables and fruit juices contain relatively low levels of sodium in the
range of 2.28 to 94.0 mg/100 g and from 0.04 to 277 mg/100 g (Table 7.2). Tea
leaves (2.14–79.6 mg/100 g) and grain coffee (0.64–11.39 mg/100 g) are also poor
sources of sodium (Table 7.3), as are fruit juices and alcoholic beverages (Table 7.5).
7.2.5 PHOSPHORUS
Concentrations of phosphorus (P) in miscellaneous cereals and vegetables are similar
and range from 16.2 to 437 mg/100 g (Table 7.1 and Table 7.2). Table 7.3 and Table
7.4 show that tea leaves (247–665 mg/100 g) and nuts (309–448 mg/100 g) have
somewhat higher levels of this macroelement. Fruits contain smaller amounts of
phosphorus, typically in the range of 9.9 to 94.3 mg/100 g (Table 7.2).
TABLE 7.6
Micronutrients in Miscellaneous Cereals (in mg/100 g w/w)
Name Origin n Co Cr Cu Fe Mn Mo Ni Se Zn Ref.
Bread
Breadb U.K. 0.002 0.01 0.16 2.1 0.8 0.02 0.01 0.004 0.9 7
Breadb U.S. — — 0.19 ± 0.04 2.66 ± 0.65 0.85 ± 0.64 — 0.02 ± 0.003 0.02 ± 0.01 1.0 ± 0.43 9
< 0.09 – 0.23 1.55 – 3.18 0.2 – 1.82 < 0.01 – 0.02 0.01 – 0.03 0.6 – 1.63
Bread — — — 1 — — — — 1 8
Bagel plain U.S. — — 0.13 3.03 0.44 — < 0.012 0.03 0.77 9
Bread Poland 26 — — 0.10 – 0.21 1.4 – 3.0 0.82 – 2.3 — — — 0.88 – 1.7 65
White bread U.S. — — < 0.12 3.03 0.42 — 0.02 0.02 0.62 9
2234_C007.fm Page 248 Thursday, October 26, 2006 8:28 AM
Cereals
Cereals 27 — — — — — — — 0.003 — 66
0.0002 – 0.01
Corn flakes — — < 0.09 19.6 0.12 — < 0.01 0.005 0.81 9
Oat flakes — — — 5.5 ± 0.2 5.3 ± 0.4 — — — 3.9 ± 0.1 11
Rolled oats 6 — — 0.53 ± 0.06 5.39 ± 0.29 7.14 ± 0.95 — — — 3.66 ± 0.48 56
0.43 – 0.61 4.51 – 7.49 5.0 – 13.9 2.74 – 7.26
Mineral Components in Foods
Raisin bran U.S. — — 0.45 34 2.88 — 0.04 <0.004 10.3 9
cereal
Breakfast Spain 36 — 0.02 ± 0.01 — — — — — — — 67
cereals 0.01–0.05
Fruit- flavored U.S. — — 0.1 18 0.73 — 0.04 0.01 14 9
cereal
Rice
Rice India, 28 — — — — — — — 0.01 — 12
Pakistan 0.0005 – 0.02
Rice Europe 25 — — — — — — — 0.005 — 12
0.001 – 0.02
Rice Different 0.002 0.06 0.37 — 0.64 — 0.10 0.03 1.05 13
Ricec 0.004 — 0.22 – 0.26 2.26 – 4.95 0.96 – 1.74 — — 0.02 1.04 – 1.48 14
White rice 6 — — 0.14 ± 0.00 0.38 ± 0.01 2.14 ± 0.06 — — — 1.21 ± 0.02 56
2234_C007.fm Page 249 Thursday, October 26, 2006 8:28 AM
Grits
Grits 10 — — 0.06 ± 0.02 0.39 ± 0.03 0.14 ± 0.01 — — — 0.46 ± 0.11 56
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Flour
Chickpea 1 — 0.01 ± 0.001 — — — — 0.05 ± 0.003 — — 70
flour
Flour — — — 1.63 — — — — 0.95 8
249
250
Common Slovenia 0.01 ± 0.0002 0.01 ± 0.001 — 7.10 ± 0.07 — — 0.09 ± 0.01 0.003 ± 0.0005 1.73 ± 0.02 71
buckwheat
flourc
Tartary Slovenia 0.002 ± 0.0001 0.01 ± 0.001 — 3.20 ± 0.03 — — 0.1 ± 0.02 <0.001 1.23 ± 0.01 71
buckwheat
fine flourc
Tartary Slovenia 0.01 ± 0.0001 0.03 ± 0.001 — 12.8 ± 0.04 — — 0.16 ± 0.02 0.001 ± 0.001 2.26 ± 0.02 71
buckwheat
flourc
2234_C007.fm Page 250 Thursday, October 26, 2006 8:28 AM
Miscellaneous Cereals
Common Slovenia 0.01 ± 0.0002 0.01 ± 0.0002 — 8.02 ± 0.08 — — 0.17 ± 0.03 0.004 ± 0.001 2.67 ± 0.03 71
buckwheat
branc
Miscellaneous U.K. 0.001 0.01 0.18 3.2 0.68 0.02 0.02 0.003 0.86 7
cerealsb
Miscellaneous U.S. — — 0.20 ± 0.12 7.39 ± 9.83 0.90 ± 0.93 — 0.05 ± 0.06 0.014 ± 0.01 2.62 ± 4.28 9
cerealsb < 0.09 – 0.45 0.81 – 34 < 0.1 – 3.38 < 0.01 – 0.23 < 0.004 – 0.031 0.12 – 14
2234_C007.fm Page 251 Thursday, October 26, 2006 8:28 AM
Tartary Slovenia 0.05 ± 0.0005 0.02 ± 0.001 — 13.0 ± 0.13 — — 0.35 ± 0.01 0.005 ± 0.0005 6.97 ± 0.07 71
buckwheat
branc
Oat bran — — — 7.5 ± 1.0 5.5 ± 1.9 — — — 4.6 ± 0.2 11
Wheat branc Sweden n = 13 n = 19 n = 30 n = 30 n = 30 — n = 22 — n = 30 72
< 0.001 – 0.003 < 0.0035 – 0.003 1.24 ± 0.20 13.4 ± 2.12 11.1 ± 1.68 0.06 ± 0.05 8.23 ± 1.42
0.72 – 1.50 9.11 – 17.8 8.32—15.0 0.02 – 0.19 6.11 – 11.5
Stabilized 3 — — 1.47 ± 0.08 10.5 ± 0.4 19.4 ± 1.1 — — — 9.2 ± 0.05 56
wheatgerm 1.23 – 1.55 6.8 – 12.3 13.3 – 25.2 6.65 – 11.8
Quinoac 0.003 — 0.48 5.06 – 16.6 0.86 — — 0.01 2.36 14
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Corn grainsc 0.003 – 0.004 — 0.29 – 0.35 1.66 – 2.62 0.42 – 0.44 — — 0.003 – 0.01 1.31 – 2.19 14
Soft whole 4 — — 0.33 ± 0.003 3.54 ± 0.07 6.72 ± 0.12 — — — 2.1 ± 0.04 56
wheat 0.33 – 0.34 3–4 6.1 – 7.7 1.9 – 2.2
Spelt wheat 9 — — 0.4 ± 0.1 4.4 ± 0.6 4.2 ± 0.7 — — — 3.7 ± 0.4 15
Rye grainsc Northeast — — 0.30 ± 0.003 — 2.52 ± 0.03 — — 0.02 ± 0.001 2.09 ± 0.03 73
Poland
251
252
Common Slovenia 0.01 ± 0.0002 0.01 ± 0.001 — 5.28 ± 0.053 — — 0.1 ± 0.01 0.002 ± 0.0002 2.27 ± 0.02 71
buckwheat
grainc
Tartary Slovenia 0.05 ± 0.0004 0.10 ± 0.01 — 40.3 ± 0.40 — — 0.27 ± 0.05 0.003 ± 0.002 3.05 ± 0.03 71
buckwheat
grainc
Barley grainsc Northeast — — 0.22 ± 0.002 — 1.19 ± 0.01 — — 0.02 ± 0.001 2.19 ± 0.03 73
Poland
Raw maize 6 — — 0.26 ± 0.08 2.54 ± 0.07 0.78 ± 0.02 — — — 2.45 ± 0.07 56
2234_C007.fm Page 252 Thursday, October 26, 2006 8:28 AM
Macaroni, Polish 0.01 ± 0.003 0.02 ± 0.002 0.51 ± 0.02 6.76 ± 0.83 9.92 ± 0.21 — 0.01 ± 0.01 — 4.84 ± 0.10 75
graham market
Mineral Components in Foods
Macaroni, Polish 0.03 ± 0.001 0.22 ± 0.002 0.08 ± 0.01 2.50 ± 0.14 0.28 ± 0.08 — 0.08 ± 0.03 — 7.75 ± 0.92 75
soya market
Wheat germ Polish 0.01 ± 0.003 0.01 ± 0.001 0.79 ± 0.03 10.4 ± 0.51 38.1 ± 1.75 — 0.12 ± 0.04 — 18.3 ± 1.2 75
market
White roll U.S. — — 0.13 3.19 0.46 — < 0.01 0.03 0.81 9
Gluten 4 — — 0.55 ± 0.03 5.19 ± 0.1 1.73 ± 0.1 — — — 2.96 ± 0.22 56
0.41 – 0.68 4.82 – 5.6 1.32 – 2.3 3.95 – 1.81
Dough — — — 1.18 — — — — 1 8
2234_C007.fm Page 253 Thursday, October 26, 2006 8:28 AM
TABLE 7.7
Micronutrients in Vegetables, Mushrooms, and Fruits (in mg/100 g w/w and in µg/100 g w/wa)
Name Origin n Co Cr Cu Fe Mn Mo Ni Se Zn Ref.
Vegetables
Artichoke Spain — — — — — — — — — 76
Butterhead — — 0.04 ± 0.02 0.5 ± 0.2 0.4 ± 0.3 — — — 0.33 ± 0.04 16
lettuce
Cabbage — — 0.05 ± 0.05 0.14 ± 0.03 0.2 ± 0.1 — — — 0.2 ± 0.1 16
Cabbages Saudi 5 0.01 — 0.004 0.78 0.22 — 0.003 — 0.15 17
Arabia
Canned U.K. 0.001 0.01 0.15 1.2 0.18 0.03 0.03 0.002 0.39 7
vegetablesb
Canned U.S. — — 0.15 ± 0.04 0.57 ± 0.35 0.24 ± 0.02 — 0.02 ± 0.01 < 0.003 0.28 ± 0.13 9
2234_C007.fm Page 254 Thursday, October 26, 2006 8:28 AM
vegetablesb < 0.08 – 0.18 < 0.3 – 1.47 < 0.1 – 0.34 < 0.01 – 0.04 0.1 – 0.76
Carrot Greece 0.001 0.01 0.07 0.46 0.08 — 0.01 0.0005 0.14 77
Carrots Saudi 5 0.02 — 0.01 0.35 0.07 — 0.21 — 0.11 17
Arabia
Celery U.S. — — < 0.09 < 0.3 < 0.1 — <0.01 < 0.004 < 0.1 9
Celery leaf Greece 0.001 0.03 0.18 1.7 0.43 — 0.04 < 0.0001 0.44 77
Celery root Greece 0.003 0.09 0.22 1.67 0.49 — 0.03 < 0.0001 0.49 77
Chicory — — 0.06 ± 0.03 0.5 ± 0.2 0.3 ± 0.1 — — — 0.24 ± 0.03 16
Chinese — — 0.04 ± 0.02 0.20 ± 0.03 0.05 ± 0.14 — — — 0.23 ± 0.04 16
cabbage
Cucumber U.S. — — < 0.09 < 0.3 < 0.1 — < 0.01 — 0.11 9
Cucumber Saudi 5 0.00 — 0.01 0.33 0.03 — 0.04 — 0.13 17
Arabia
Eggplant Saudi 5 0.01 — 0.02 3.19 0.16 — 0.09 — 0.37 17
Arabia
Green pepper Tenerife 60 — — 0.05 ± 0.02 0.27 ± 0.07 0.05 ± 0.01 — — — 0.13 ± 0.04 18
Island 0.02 – 0.08 0.14 – 0.41 0.03 – 0.07 0.08 – 0.23
Green pepper U.S. — — < 0.09 < 0.3 0.11 — 0.0103 — 0.12 9
Mineral Components in Foods
Green pepper Saudi 5 0.01 — 0.04 0.44 0.05 — 0.12 — 0.08 17
Arabia
Green U.K. 0.001 0.02 0.08 1.1 0.2 0.02 0.01 0.001 0.34 7
vegetablesb
Green U.S. — 0.18 ± 0.08 1.21 ± 0.76 0.28 ± 0.17 — 0.04 ± 0.03 <0.003 – 0.01 0.49 ± 0.38 9
vegetablesb < 0.07 – 0.26 < 0.2 – 2.19 0.11 – 0.55 < 0.01 – 0.07 < 0.1 – 1.04
Iceberg lettuce U.S. — — < 0.07 0.32 0.12 — 0.01 < 0.003 0.13 9
Kale — — 0.04 ± 0.02 0.4 ± 0.2 0.3 ± 0.1 — — — 0.29 ± 0.05 16
Leek Saudi 5 0.02 — 0.02 1.43 0.17 — 0.001 — 0.21 17
Arabia
Leek leaf Greece — — — — 0.21 — 0.04 < 0.0001 0.24 77
Leek root Greece < 0.001 0.003 0.17 0.35 0.08 — 0.02 < 0.0001 0.24 77
Legumes 7 — — — — — — — 0.01 — 66
0.002 – 0.03
Legumes 40 — 0.005 – 0.06 0.15 – 0.5 — — — 0.002 – 0.03 — 3.26 – 7.02 78
Lentils canned — — — 1.24 ± 0.15 — — — — — 19
2234_C007.fm Page 255 Thursday, October 26, 2006 8:28 AM
Lettuce Greece < 0.001 0.004 0.02 0.40 0.09 — 0.005 < 0.0001 0.10 77
Lettuce Saudi 5 0.003 — 0.005 1.68 0.11 — 0.004 — 0.22 17
Arabia
Maize — — — — 0.27 — — — 1.71 79
0.25 – 0.28 1.63 – 1.78
Onion Saudi 5 0.01 — 0.03 1.07 0.04 — 0.21 — 0.20 17
Arabia
Onion U.S. — — < 0.09 < 0.3 0.12 — < 0.01 < 0.004 0.15 9
Onion Denmark 0.2 ± 0.1a 0.001 ± 0.001 0.05 ± 0.01 0.27 ± 0.08 0.16 ± 0.06 0.001 ± 0.001 — 0.01 ± 0.002 0.34 ± 0.14 20
conventional 0.01 – 0.5 0.0002 – 0.005 0.02 – 0.10 0.13 – 0.52 0.05 – 0.36 0.0 – 0.003 0.003 – 0.01 0.14 – 1.0
Onion leaf Greece 0.001 0.03 0.09 0.72 0.11 — 0.01 <0.0001 0.28 77
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Onion organic Denmark 0.1 ± 0.1a 0.001 ± 0.0004 0.06 ± 0.02 0.32 ± 0.07 0.15 ± 0.05 0.002 ± 0.004 — 0.005 ± 0.002 0.35 ± 0.12 20
0.01 – 0.5 0.0003 – 0.003 0.025 – 0.11 0.19 – 0.53 0.07 – 0.38 0.0 – 0.02 0.002 – 0.01 0.17 – 0.83
Onion root Greece 0.002 0.01 0.19 0.73 0.22 — 0.03 0.0005 0.68 77
Other U.K. 0.001 0.01 0.09 0.75 0.16 0.01 0.01 0.002 0.26 7
vegetablesb
Other U.S. — — 0.15 ± 0.05 0.66 ± 0.40 0.23 ± 0.17 — 0.02 ± 0.02 0.01 ± 0.004 0.29 ± 0.15 9
vegetablesb < 0.07 – 0.22 < 0.3 – 1.56 < 0.1 – 0.59 < 0.01 – 0.05 < 0.003 – 0.01 < 0.1 – 0.62
Parsley Greece 0.002 0.01 0.03 0.72 0.15 — 0.03 < 0.0001 0.09 77
255
256
Potatoesc Idaho 342 0.01 ± 0.02 0.01 ± 0.01 0.1 ± 0.03 0.78 ± 0.30 0.15 ± 0.04 0.01 ± 0.02 0.02 ± 0.02 — 0.28 ± 0.07 22
0 – 0.07 0 – 0.06 0 – 0.19 0.29 – 2.02 0.04 – 0.41 0 – 0.08 0 – 0.10 0.09 – 0.52
Potatoesc Non-Idaho 266 0.01 ± 0.02 0.02 ± 0.01 0.12 ± 0.06 0.90 ± 0.39 0.23 ± 0.11 0.01 ± 0.02 0.02 ± 0.03 — 0.39 ± 0.11 22
0 – 0.07 0 – 0.05 0 – 0.40 0.26 – 2.91 0.03 – 0.78 0 – 0.11 0 – 0.11 0.14 – 1.29
Potatoesb U.K. 0.002 0.01 0.13 0.81 0.19 0.01 0.01 0.001 0.45 7
Potatoesb U.S. — — 0.13 ± 0.02 0.58 ± 0.28 0.21 ± 0.11 — 0.01 ± 0.01 < 0.003 0.31 ± 0.09 9
< 0.08 – 0.14 0.29 – 0.91 0.11 – 0.4 < 0.01 – 0.02 0.21 – 0.46
Radish U.S. — — < 0.09 < 0.3 < 0.1 — — — 0.11 9
Red pepper Tenerife 60 — — 0.07 ± 0.03 0.31 ± 0.07 0.07 ± 0.04 — — — 0.17 ± 0.03 18
Island 0.03 – 0.13 0.22 – 0.46 0.03 – 0.08 0.10 – 0.23
Rucola — — 0.1 ± 0.2 1.1 ± 0.6 0.3 ± 0.3 — — — 0.4 ± 0.1 16
Salq Saudi 5 0.03 — 0.02 1.49 0.31 — 0.21 — 0.29 17
Arabia
Spinach Greece 0.003 0.01 0.24 2.15 0.44 — 0.05 < 0.0001 0.30 77
Spinach Saudi 5 0.01 — 0.02 1.41 0.08 — 0.15 — 0.08 17
Arabia
Spinach — — 0.05 ± 0.03 1 ± 0.8 1 ± 0.8 — — — 0.3 ± 0.1 16
substitute
Tomato Saudi 5 0.01 — 0.03 0.35 0.04 — 0.09 — 0.08 17
Arabia
Mineral Components in Foods
Tomato fruits Denmark — 0.0001 0.04 0.28 0.09 0.01 0.0005 — 0.11 23
rockwool
high EC
Tomato fruits Denmark — 0.0001 0.03 0.24 0.09 0.01 0.0005 — 0.10 23
rockwool
norm EC
Tomato fruits Denmark — 0.0001 0.03 0.26 0.07 0.003 0.001 — 0.12 23
soil norm EC
Tomato red U.S. — — < 0.09 < 0.3 0.1 — < 0.01 — 0.13 9
Marrow Saudi 5 0.01 — 0.04 0.91 0.09 — 0.06 — 0.23 17
(zucchini) Arabia
Watercress — 0.2 ± 0.1 0.9 ± 0.2 0.2 ± 0.1 — — — 0.8 ± 0.4 16
Watercress Saudi 5 0.02 — 0.01 1.62 0.12 — 0.28 — 0.68 17
Arabia
White — — — 0.44 ± 0.01 — — — — — 19
asparagus
Whole peeled — — — 0.38 ± 0.09 — — — — — 19
2234_C007.fm Page 257 Thursday, October 26, 2006 8:28 AM
tomatoes,
canned
Mushrooms
Bay boletec Poland 166 0.004 ± 0.001 0.005 ± 0.002 0.33 ± 0.14 0.98 ± 0.52 0.19 ± 0.1 — 0.01 ± 0.004 — 1.61 ± 0.42 24
0.0003 – 0.02 0.0002 – 0.08 0.01 – 0.84 0.09 – 6.10 0.02 – 1.91 0.0002 – 0.03 0.66 – 4.80
Lactarius Turkey 0.005 ± 0.0002a 0.01 ± 0.0005a 0.31 ± 0.03 2.88 ± 0.21 0.4 ± 0.02a — 0.02 ± 0.001a — 0.82 ± 0.07 80
deliceusc
Morchella Turkey 0.01 ± 0.001a 0.43 ± 0.03 1.46 ± 0.12 0.3 ± 0.02a — 0.01 ± 0.001a — 0.45 ± 0.04 80
esculentac
Mushrooms U.S. — — 0.22 < 0.3 < 0.1 — — 0.01 0.36 9
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Fruits
Apple red U.S. — — < 0.09 < 0.3 < 0.1 — < 0.009 < 0.004 < 0.1 9
Apricot U.S. — — < 0.09 0.41 < 0.1 — 0.01 — 0.18 9
Avocado U.S. — 0.22 0.48 < 0.2 — 0.02 < 0.005 0.61 9
257
258
Banana U.S. — — 0.11 0.28 0.27 — < 0.01 < 0.003 0.16 9
Banana pulp Tenerife — — 0.12 ± 0.01 0.32 ± 0.057 0.07 ± 0.0 — — — 0.17 ± 0.014 25
Island 0.09 – 0.20 0.16 – 0.54 0.06 – 0.12 0.10 – 0.24
Cantaloupe U.S. — — < 0.07 < 0.2 < 0.1 — 0.01 < 0.003 0.14 9
Currants 6 — — 1.98 ± 0.13 1.98 ± 0.09 0.49 ± 0.03 — — — 1.1 ± 0.5 56
1.49 – 2.7 1.62 – 2.54 0.33 – 0.66 0.23 – 12.7
Dried apple 6 — — 0.20 ± 0.01 1.17 ± 0.04 0.19 ± 0.01 — — — 0.19 ± 0.01 56
0.16 – 0.24 0.95 – 1.34 0.13 – 0.27 0.13 – 0.27
Dry fruits 9 — — — — — — — 0.03 — 66
0.01 – 0.06
2234_C007.fm Page 258 Thursday, October 26, 2006 8:28 AM
Fresh fruitb U.K. 0.0004 < 0.01 0.09 0.27 0.2 0.001 0.003 0.0004 0.08 7
Fresh fruitb U.S. — — 0.13 ± 0.06 0.34 ± 0.10 0.32 ± 0.06 — 0.01 ± 0.01 < 0.003 0.23 ± 0.19 9
< 0.07 – 0.22 < 0.2 – 0.48 < 0.1 – 0.36 < 0.01 – 0.03 < 0.1 – 0.61
Fruit productsb U.K. 0.0005 < 0.01 0.07 0.32 0.22 0.001 0.01 0.0005 0.07 7
Fruit productsb U.S. — — 0.32 ± 0.04 0.85 ± 0.59 0.42 ± 0.39 — 0.03 ± 0.02 < 0.003 0.28 ± 0.13 9
< 0.07 – 0.34 < 0.2 – 1.85 < 0.1 – 1.0 0.005 – 0.07 < 0.1 – 0.43
Grapefruit U.S. — — < 0.07 < 0.2 < 0.1 — < 0.01 < 0.003 < 0.1 9
Grapes, U.S. — — 0.11 0.31 < 0.1 — < 0.01 — < 0.1 9
seedless
Orange U.S. — — < 0.07 < 0.2 < 0.1 — < 0.01 — < 0.1 9
Peach U.S. — — < 0.07 0.22 < 0.1 — 0.01 — 0.17 9
Pear U.S. — — 0.08 < 0.2 < 0.1 — 0.01 — < 0.1 9
Plums U.S. — — < 0.07 < 0.2 < 0.1 — < 0.01 — < 0.1 9
Strawberries U.S. — — < 0.07 0.41 0.36 — 0.01 < 0.003 0.1 9
Strawberry Finland 12 — — 0.06 0.32 0.32 — — — 0.12 26
0.04 – 0.1 0.21 – 0.45 0.23 – 0.44 0.08 – 0.15
Sultanas 6 — — 0.51 ± 0.02 2.05 ± 0.13 0.42 ± 0.02 — — — 0.42 ± 0.04 56
0.40 – 0.64 1.72 – 3.01 0.29 – 0.60 0.30 – 0.67
Mineral Components in Foods
Sweet cherries U.S. — — < 0.09 < 0.3 < 0.1 — — — < 0.1 9
Watermelon U.S. — — < 0.07 0.25 < 0.1 — 0.01 < 0.003 < 0.1 9
Frozen Fruits
Gooseberry Polish 5 — 0.01 ± 0.004 0.06 ± 0.01 — — — 0.01 ± 0.004 — 0.15 ± 0.03 81
market 0.01 – 0.02 0.05 – 0.07 0.004 – 0.01 0.12 – 0.2
Black Polish 5 0.03 ± 0.01 0.10 ± 0.01 — — — 0.03 ± 0.01 — 0.19 ± 0.02 81
chokeberry market 0.02 – 0.05 0.08 – 0.11 0.03 – 0.05 0.16 – 0.22
Blackberry Polish 5 — 0.02 ± 0.01 0.14 ± 0.03 — — — 0.01 ± 0.004 — 0.22 ± 0.03 81
market 0.01 – 0.03 0.11 – 0.18 0.01 – 0.02 0.19 – 0.26
Raspberry Polish 5 — 0.01 ± 0.003 0.10 ± 0.01 — — — 0.03 ± 0.01 — 0.31 ± 0.02 81
market 0.01 – 0.02 0.08 – 0.12 0.02 – 0.05 0.28 – 0.33
Fruits Polish 71 — 0.02 0.09 — — — 0.02 — 0.17 81
market 0.005 – 0.06 0.03 – 0.18 0.004 – 0.05 0.06 – 0.33
Black currant Polish 5 0.02 ± 0.01 0.08 ± 0.01 — — — 0.01 ± 0.005 — 0.21 ± 0.04 81
market 0.01 – 0.03 0.08 – 0.09 0.005 – 0.02 0.16 – 0.26
2234_C007.fm Page 259 Thursday, October 26, 2006 8:28 AM
Red currant Polish 5 0.01 ± 0.003 0.08 ± 0.02 — — — 0.01 ± 0.01 — 0.15 ± 0.03 81
market 0.01 – 0.02 0.06 – 0.11 0.01 – 0.02 0.12 – 0.19
Plum Polish 5 — 0.01 ± 0.004 0.05 ± 0.02 — — — 0.01 ± 0.003 — 0.12 ± 0.05 81
market 0.01 – 0.02 0.03 – 0.07 0.005 – 0.01 0.08 – 0.20
Strawberry Polish 6 — 0.01 ± 0.004 0.06 ± 0.01 — — — 0.01 ± 0.005 — 0.15 ± 0.02 81
market 0.005 – 0.02 0.05 – 0.08 0.01 – 0.02 0.12 – 0.18
Cherry Polish 7 — 0.01 ± 0.005 0.09 ± 0.01 — — — 0.01 ± 0.01 — 0.10 ± 0.03 81
market 0.01 – 0.02 0.07 – 0.1 0.01 – 0.03 0.06 – 0.14
a µg/100 g w/w
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
259
260
TABLE 7.8
Micronutrients in Tea, Coffee, and Confectionary Products (in mg/100 g w/w)
Name Origin n Co Cr Cu Fe Mn Mo Ni Se Zn Ref.
Tea
Tea Africa 18 0.02 ± 0.02 0.2 ± 0.12 1.91 ± 0.88 17.9 ± 14.8 56.3 ± 31.6 — 0.48 ± 0.26 — 2.51 ± 0.98 27
Tea Asia 36 0.02 ± 0.02 0.22 ± 0.1 1.23 ± 0.41 15.3 ± 4.89 84.4 ± 41.5 — 0.42 ± 0.16 — 2.63 ± 1.13 27
Tea China 13 0.03 ± 0.01 0.12 ± 0.07 1.91 ± 0.96 28.1 ± 20.3 72.0 ± 31.4 — 0.49 ± 0.19 — 2.78 ± 1.24 27
Tea India, Sri 13 0.02 ± 0.01 0.11 ± 0.08 2.12 ± 0.88 10.2 ± 1.63 36.7 ± 13.8 — 0.41 ± 0.13 — 2.44 ± 0.74 27
Lanka
Tea (from tea — — — — 0.29 — < 0.005 < 0.001 < 0.04 9
bag)
2234_C007.fm Page 260 Thursday, October 26, 2006 8:28 AM
Coffee
Decaffeinated U.S. — — — < 0.1 < 0.04 — < 0.005 < 0.001 < 0.04 9
instant coffee
2234_C007.fm Page 261 Thursday, October 26, 2006 8:28 AM
beans
Roasted coffee Colombia 20 — — 1.66 ± 0.16 1.64 ± 0.29 3.67 ± 0.97 — — — 0.77 ± 0.17 35
beans
261
262
Roasted coffee Guatemala 20 — — 1.35 ± 0.22 1.25 ± 0.19 2.41 ± 0.48 — — — 0.77 ± 0.13 35
beans
Roasted coffee Panama 20 — — 1.62 ± 0.17 1.93 ± 0.48 2.51 ± 0.39 — — — 0.68 ± 0.17 35
beans
Roasted coffee Ethiopia 20 — — 1.33 ± 0.09 1.16 ± 0.29 2.03 ± 0.39 — — — 0.75 ± 0.18 35
beans
Roasted coffee Kenya 20 — — 1.72 ± 0.21 1.45 ± 0.48 3.77 ± 1.06 — — — 0.69 ± 0.18 35
beans
Roasted coffee Sulawesi 20 — — 1.21 ± 0.33 2.03 ± 0.58 2.8 ± 0.67 — — — 0.76 ± 0.16 35
beans
2234_C007.fm Page 262 Thursday, October 26, 2006 8:28 AM
Roasted coffee Sumatra 20 — — 1.27 ± 0.19 2.99 ± 0.68 1.83 ± 0.48 — — — 0.63 ± 0.11 35
beans
Roasted Mixture 18 — — 1.39 ± 0.21 5.23 ± 0.82 1.96 ± 0.94 — — — 1.41 ± 1.03 36
coffeec 1.08 – 1.72 3.89 – 7.09 1.18 – 4.31 0.48 – 3.56
Green coffeec Mixture 41 — — 1.90 ± 0.94 3.78 ± 1.40 2.64 ± 0.97 — — — 1.01 ± 0.95 84
1.38 – 7.43 2.39 – 9.01 1.4 – 4.83 0.35 – 5.92
Confectionary Products
Sugar and U.K. 0.003 0.02 0.15 0.94 0.15 0.003 0.03 0.001 0.38 7
preservesb
Sugar and U.S. — — 0.24 ± 0.09 1.45 ± 1.05 0.31 ± 0.10 — 0.04 ± 0.03 0.008 ± 0.004 0.43 ± 0.25 9
preservesb < 0.08 – 0.41 < 0.3 – 3.85 < 0.1 – 0.49 < 0.01 – 0.09 < 0.003 – 0.01 < 0.1 – 1.34
Sugar Egypt 2 0.001 ± 0.0001 0.001 ± 0.001 0.002 ± 0.001 0.02 ± 0.01 0.001 ± 0.0004 — 0.001 ± 0.0004 — 0.0004 ± 0.0 37
Sugar Egypt 0.0001 ± 0.0 0.0001 ± 0.0 0.001 ± 0.0004 2.1 ± 0.4 0.04 ± 0.02 — — — 0.002 ± 0.001 38
Mineral Components in Foods
White sugar, U.S. — — — < 0.3 — — — — < 0.1 9
granulated
Sugarcane Egypt 3 0.003 ± 0.0002 0.02 ± 0.005 0.01 ± 0.003 0.44 ± 0.15 0.05 ± 0.02 — 0.01 ± 0.002 — 0.04 ± 0.05 37
plant
Cocoa powder 4 — — 5.55 ± 0.04 21.9 ± 1.8 6.34 ± 0.12 — — — 8.96 ± 0.14 56
5.48 – 5.62 16 – 25.8 6.38 – 6.52 8.5 – 9.43
Molasses Egypt 0.002 ± 0.001 0.03 ± 0.02 0.005 ± 0.0025 17.4 ± 16.3 1.02 ± 0.62 — — — 0.01 ± 0.003 38
Sugarcane Egypt 3 0.003 ± 0.0005 0.021 ± 0.001 0.01 ± 0.004 0.31 ± 0.18 0.01 ± 0.001 — 0.005 ± 0.001 — 0.005 ± 0.002 37
juice
Sugar juice Egypt 0.002 ± 0.001 0.02 ± 0.02 0.01 ± 0.01 42.4 ± 7.4 1.79 ± 1.17 — — — 0.01 ± 0.01 38
2234_C007.fm Page 263 Thursday, October 26, 2006 8:28 AM
TABLE 7.9
Micronutrients in Nuts, Seeds, and Oils (in mg/100 g w/w)
Name Origin n Co Cr Cu Fe Mn Mo Ni Se Zn Ref.
Nuts, Seeds
Almond Spain 6 — 0.04 1.11 4.5 — — 0.03 — 3.88 78
0.04 – 0.05 1.05 – 1.26 4.03 – 4.87 0.02 – 0.05 2.79 – 5.0
Almond — — 2 ± 0.0 14 ± 1 — — — — 6 ± 0.3 39
Sliced almonds 6 — — 1.04 ± 0.04 2.74 ± 0.09 1.48 ± 0.05 — — — 2.75 ± 0.08 56
0.91 – 1.23 2.06 – 3.09 1.25 – 1.56 2.08 – 2.95
Cashew Spain 3 — 0.03 0.78 1.42 — — 0.02 — 4.0 78
2234_C007.fm Page 264 Thursday, October 26, 2006 8:28 AM
0.03 – 0.03 0.66 – 0.85 1.03 – 1.56 0.02 – 0.02 3.75 – 4.96
Chestnut Spain 6 — 0.03 0.48 0.9 — — 0.02 — 3.39 78
0.03 – 0.03 0.4 – 0.56 0.73 – 1.02 0.01 – 0.02 3.06 – 3.77
Different types Brazil 3 — — — — — — — 0.74 ± 1.39 — 85
of nuts 0.01 – 3.51
Poppy seeds Polish 0.02 ± 0.01 0.05 ± 0.01 1.39 ± 0.12 12.11 ± 1.17 7.18 ± 1.43 — 0.07 ± 0.06 — 7.02 ± 1.66 86
market 0.01 – 0.02 0.05 – 0.06 1.28 – 1.60 10.6 – 13.3 5.72 – 8.49 0.01 – 0.12 5.43 – 8.60
Sesame Polish 0.03 ± 0.01 0.02 ± 0.01 1.32 ± 0.10 5.58 ± 0.29 1.55 ± 0.04 — 0.06 ± 0.01 — 5.24 ± 0.23 86
market 0.01 – 0.04 0.02 – 0.03 1.21 – 1.50 5.23 – 5.93 1.51 – 1.62 0.05 – 0.07 4.95 – 5.55
Hazelnut Spain 5 — 0.03 1.66 1.73 — — 0.04 — 4.25 78
0.04 – 0.04 1.4 – 1.72 1.33 – 1.99 0.03 – 0.05 3.8 – 4.56
Hazelnut Turkey 11 — — 0.65 ± 0.29 2.32 ± 0.21 6.09 ± 4.17 — — — 1.95 ± 0.25 40
0.10 – 0.90 2.05 – 2.56 1.77 – 15.8 1.71 – 2.44
Hazelnut Turkey — — 3.16 ± 0.28 3.63 ± 0.92 8.37 ± 3.22 — — — 4.11 ± 0.95 41
Hazelnut Spain 24 — — 1.60 ± 0.42 3.49 ± 0.61 2.35 ± 1.46 — — — — 87
1.0 – 2.52 2.5 – 4.5 0.73 – 5.8
Mineral Components in Foods
Hazelnut — — 2 ± 0.0 8±2 — — — — 3±1 39
Hazelnutc Turkey — — 1.72 ± 0.36 3.79 ± 0.44 1.95 ± 0.50 — — — 2.48 ± 0.2 42
Mixed nuts (no U.S. — — 1.55 4.16 2.32 — 0.30 0.06 4.1 9
peanuts)
Nutsb U.K. 0.01 0.07 0.85 3.4 1.5 0.10 0.25 0.03 3.1 7
Nutsb U.S. — — 0.88 ± 0.58 2.55 ± 1.40 1.99 ± 0.34 — 0.16 ± 0.13 0.03 ± 0.04 3.25 ± 0.74 9
0.52 – 1.55 1.71 – 4.16 1.65 – 2.32 0.07 – 0.304 < 0.005 – 0.06 2.71 – 4.1
Peanut Spain 5 — 0.04 0.69 2.28 — — 0.03 — 3.19 78
0.04 – 0.04 0.56 – 1.03 2.0 – 2.66 0.02 – 0.04 2.99 – 3.78
Peanut Spain — — 1.01 ± 0.01 3.94 ± 0.02 — — — — — 88
0.99 – 1.02 3.91 – 3.96
Peanut — — 1 ± 0.1 6 ± 0.1 — — — — 4 ± 0.2 39
Peanut butter — — 0.52 1.78 1.65 — 0.07 0.01 2.71 9
Peanut greensc U.S. 2 — — — 15.2 ± 1.64 — — — — 5.05 ± 2.89 43
2234_C007.fm Page 265 Thursday, October 26, 2006 8:28 AM
0.04 – 0.1 1.0 – 1.57 3.88 – 4.33 0.02 – 0.03 5.06 – 6.9
Walnut — — 2 ± 0.2 7 ± 0.3 — — — — 4 ± 0.4 39
Walnuts Spain 5 — 0.04 2.2 2.25 — — 0.02 — 2.85 78
0.03 – 0.04 2.01 – 2.56 2.0 – 2.44 0.02 – 0.02 2.56 – 3.97
265
266
Oils
Grape seeds oil 3 — — 0.01 ± 0.001 — — — — — 0.03 ± 0.01 90
Maize oil 5 — — 0.005 ± 0.002 — — — — — 0.005 ± 0.002 90
Nuts oil 3 — — 0.02 ± 0.004 — — — — — 0.06 ± 0.01 90
Oils and fatsb U.K. 0.0003 0.04 0.005 0.05 0.002 0.002 0.003 0.001 0.06 7
Oils and fatsb U.S. — — ND < 0.3 ND — < 0.04 ND < 0.1 9
Olive or U.S. — — — < 0.3 — — — — < 0.1 9
sunflower oil
2234_C007.fm Page 266 Thursday, October 26, 2006 8:28 AM
Beveragesb U.K. 0.0002 < 0.01 0.01 0.04 0.27 0.0003 0.003 0.0003 0.03 7
Beveragesb U.S. — — < 0.05 <0.1 – 0.28 0.2 ± 0.13 — <0.005 < 0.003 < 0.1 9
< 0.04 – 0.29
Juices
Grapefruit 0.0001 — 0.04 0.07 0.02 0.001 0.002 — 0.05 45
juice
Lemon juice < 0.0001 — 0.02 0.10 0.02 < 0.0001 0.001 — 0.05 45
Lime juice < 0.0001 — 0.03 0.05 0.03 0.001 0.003 — 0.06 45
2234_C007.fm Page 267 Thursday, October 26, 2006 8:28 AM
Mandarin < 0.0001 — 0.14 0.1 0.03 < 0.0001 0.01 — 0.05 45
juice
Orange juice Australia 290 0.0003 ± 0.0 — 0.03 ± 0.001 0.07 ± 0.01 0.020 ± 0.002 0.0003 ± 0.0 0.003 ± 0.0 — 0.03 ± 0.001 45
< 0.0001 – 0.002 0.004 – 0.1 0.002 – 0.18 0.01 – 0.05 < 0.0001 – 0.003 < 0.0001 – 0.02 0.01 – 0.07
Orange 8 — — 0.01 – 0.02 0.09 – 0.36 0.04 – 0.06 — — — 0.03 – 0.03 47
juiceb
Orange juice Australia 83 0.0002 ± 0.0001 — 0.03 ± 0.005 0.07 ± 0.02 0.02 ± 0.003 0.0003 ± 0.0003 0.004 ± 0.002 — 0.02 ± 0.01 45
concentrate < 0.0001 – 0.0004 0.01 – 0.05 0.03 – 0.15 0.01 – 0.03 < 0.0001 – 0.001 0.001 – 0.003 0.01 – 0.04
Orange juice Brazil 42 0.0001 ± 0.0001 — 0.02 ± 0.004 0.06 ± 0.01 0.03 ± 0.01 0.0001 ± 0.0002 0.001 ± 0.001 — 0.03 ± 0.01 45
concentrate < 0.0001 – 0.001 0.02 – 0.03 0.03 – 0.09 0.01 – 0.05 <0.0001 – 0.001 0.0003 – 0.003 0.01 – 0.04
Pineapple — — 0.05 ± 0.01 0.23 ± 0.07 0.84 ± 0.36 — — — 0.07 ± 0.03 48
juiceb
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Tangello < 0.0001 — 0.02 0.06 0.02 < 0.0001 0.003 — 0.04 45
juice
Tomato juice — — < 0.09 0.36 < 0.1 — 0.02 < 0.004 0.11 9
Alcoholic Beverages
Beer — — — — < 0.1 — — < 0.003 < 0.1 9
Beerd 32 — — — 0.02 ± 0.02 0.01 ± 0.01 — — — 0.01 ± 0.02 49
0.01 – 0.11 0.003 – 0.03 0.0001 – 0.1
Beerd Poland 35 0.00002 0.001 0.01 0.02 0.02 — 0.001 — 0.002 91
0.00001 – 0.0001 0.0004 – 0.004 0.003 – 0.01 0.004 – 0.05 0.005 – 0.05 0.0004 – 0.02 0.0004 – 0.01
2234_C007.fm Page 268 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 269
7.3.2 COBALT
Published levels of cobalt (Co) in food crops and animal food products are very
scarce in the scientific literature. The reported levels are generally low (often ≤ 0.001
mg/100 g), with the lowest levels observed in vegetables, i.e., 0.00001–0.02 mg/100
g (Table 7.7) and the highest values in some cereal products such as common
buckwheat bran, grain, and flour (0.05 mg/kg), tartary buckwheat grain (0.05 mg/100
g), and tartary buckwheat leaf flour (0.356 mg/100 g; see Table 7.6). A good source
of cobalt is Marmite or Vegemite yeast extracts sold in the U.K. and Australia.1 The
concentrations of cobalt in tea leaves range from 0.015 to 0.08 mg/100 g (Table
7.8). Fruit juices and alcoholic beverages contain very low levels of the metal,
generally below 0.0001 mg/100 g (Table 7.10). The use of cobalt salts as food
additives, for example in beer to improve its foaming efficiency, has been well
known.1
7.3.3 COPPER
Grain products contain from < 0.04 to 1.71 mg Cu/100 g, with the lowest values
noted for grits and maize flour (0.04–0.09 mg/100 g) and the highest for soya flour
and stabilized wheatgerm (Table 7.6). Cereals, especially in wholegrain, contain up
to 10 mg Cu/kg in ready-to-eat Australian breakfast cereals that are based on wheat
bran.1,56 Among other miscellaneous cereals, stabilized wheatgerm (1.55 mg/100 g),
wheat bran (1.50 mg/100 g), and wild rice (1.31 mg/100 g) have high levels of this
metal (Table 7.6). Low levels of copper occur in vegetables (Table 7.7), ranging
from 0.004 to 0.24 mg/100 g, except legumes (which can be up to 0.5 mg/100 g).
Fruits contain small amounts of Cu (0.01–0.24 mg/100 g), whereas currants biocon-
centrate copper to 2.7 mg/100 g (Table 7.7). Tea leaves and coffee beans contain
generally from 0.16 to 3.69 mg Cu/100 g and from 1.08 to 7.43 mg/100 g, respec-
tively (Table 7.8). Copper contents of nuts range widely (0.10–3.16 mg/100 g), with
the highest level in Turkish hazelnut — up to 3.16 mg/100 g (Table 7.9).
7.3.4 IRON
Vegetables and fruits contain low levels of iron (Fe), from 0.13 to 3.01 mg/100 g
(Table 7.7). The iron in food crop is mostly present in the form of insoluble
complexes of Fe3+ with phytic acid, phosphates, oxalates, and carbonates. Less than
8% of Fe in food crops is found to be present in bioavailable form. Food crops,
therefore, tend to be a poor source of iron. Eggplant from Saudi Arabia, however,
2234_C007.fm Page 270 Thursday, October 26, 2006 8:28 AM
is an exception in having relatively high levels of iron (3.2 mg/100 g). Among cereal
products, rye flour contains from 0.002 to 0.04 mg Fe/100 g, whereas other miscel-
laneous products can be a significant source of iron (0.22–19.6 mg/100 g). Wild rice
and especially tartary buckwheat leaf flour contain as much as 43.7 and 138 mg
Fe/100 g (Table 7.6). Breakfast cereals fortified voluntarily, and flour with the
addition of iron, show relatively high levels of this metal.1 As seen in Table 7.8, the
concentration of iron in tea leaves (up to 97.2 mg/100 g) is significantly higher than
that of grain coffee (up to 9.01 mg/100 g). Nuts and cocoa powder may be good
sources of iron, containing up to 16.1 and 25.8 mg Fe/100 g (Table 7.8 and Table
7.9). Among the spices, curry powder can have as much as 58 mg Fe/100 g.1 Fruit
juices and alcoholic beverages are poor sources of iron (Table 7.10).
It has been reported1,57 that canned foods can have particularly high levels of
iron — up to 130 mg/100 g in canned blackcurrants.
7.3.5 MANGANESE
In general, cereals and cereal products are relatively rich in manganese (Mn),
whereas vegetables and fruits are characterized by low Mn contents. For instance,
the concentrations of the element in wheat bran and stabilized wheatgerm range
from 8.32 to 15.0 and 13.3 to 25.2 mg/100 g, respectively (Table 7.6). Hazelnuts
contain high levels of manganese, up to 15.8 mg/100 g (Table 7.9). Vegetables
(0.01–0.0.78 mg/100) and fruits (0.01–0.66 mg/100) are a minor source of the
element (Table 7.7).
Although foods of plant origin are estimated to be relatively low sources of
manganese, it is interesting to note that tea can be the richest source with concen-
trations of up to 139 mg per 100 g in tea leaves (Table 7.8). According to Reilly1
and Wenlock et al.,58 British dry tea leaves may contain up to 90 mg Mn/100 g, and
the tea beverage from 0.71 to 3.8 mg/100 g. By comparison, concentrations of Mn
in ground coffee and instant coffee are 1.18–4.83 and 0.36–3.88 mg/100 g, respec-
tively (Table 7.8). Nuts may be rich in manganese, with high levels (up to 15.9
mg/100 g) found in hazelnut (Table 7.9). Fruit juices and alcoholic beverages are
poor source of the metal (Table 7.10).
7.3.6 MOLYBDENUM
In spite of large-scale variations in levels of individual food samples, molybdenum
(Mo) occurs in food crops generally at low levels. Some food crops may bioconcentrate
extremely high levels of the metal. In certain parts of India and Armenia, inhabitants
have been exposed to abnormally high levels of molybdenum as a result of consuming
locally produced foods cultivated on molybdenum-rich soil.1,59,60 Anthropogenic activ-
ity such as treatment of soils with sewage sludge and fertilizers may be also responsible
for Mo contamination of plants grown in some areas.
Concentrations of molybdenum in foods range widely, from values of 0.000001
(wine) to 0.15 mg/100 g (peas) (Table 7.7 and Table 7.10). Ranges in concentrations
of molybdenum in U.S. peas cultivated conventionally and organically were found
2234_C007.fm Page 271 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 271
7.3.7 NICKEL
Concentrations of nickel (Ni) in most foodstuffs are generally low, often being
≤ 0.001 mg/100 g. Reported levels in vegetables vary from 0.0005 to 0.28 mg/100
g, and in fruits between < 0.004 and 0.05 mg/100 g (Table 7.7). Low concentrations
are likewise found in the sugarcane plant (0.01 mg/100 g) and sugar (0.001 mg/100
g) (Table 7.8). As can be seen in Table 7.7, grain products contain from 0.002 to
0.35 mg Ni/100 g. The values (up to 2.12 mg/100 g) are significantly higher for
leaves of tea (Table 7.8). According to Reilly,1 and Smart and Sherlock,61 British
instant tea can contain up to 1.7 mg Ni/100 g. The cacao bean, used to produce
cocoa and chocolate, is also rich in nickel, with concentrations that can reach 1.0
mg/100 g. Some herbs and spices are also characterized by high levels of the
element.1 Table 7.9 shows that good sources of nickel also include nuts (up to 0.30
mg/100 g).
Concentration of nickel in processed foods can be increased because of leaching
of Ni from cooking equipment and containers. Canned vegetables show higher nickel
levels than other vegetables.1
7.3.8 SELENIUM
Concentrations of this metalloid (Se) range from < 0.0001 to 0.06 mg/100 g in grain
products, vegetables, and fruit products (Table 7.6 and Table 7.7). The highest levels
reported include 0.69 mg/100 g in tea leaves to 0.74 mg/100 g in nuts with one
extraordinarily high value of 3.51 mg/100 g found in an individual nut (Table 7.8
and Table 7.9). Selenium deficiency has significant negative health effects manifested
as diseases such as Keshan disease, which is common in Jilin Province of China.62
This endemic cardiovascular syndrome occurs especially in children and young
women and is common in parts of China where levels of selenium in soils are very
low.1 It has been reported by Capar and Szefer63 that intestinal absorption of selenium
is higher for its organic compounds. In view of this, food crops such as soybean,
wheat-enriched, garlic, onion, broccoli, and selenium-rich yeast have been analyzed
for selected chemical species of selenium. The following species have been quanti-
fied: Se4+, Se6+, selenomethionine, selenocysteine, and methylselenocysteine.
According to Reilly,1 the dominant chemical form of selenium in cereals is the amino
acid selenomethionine, although in some plants significant amounts of the selenate
occur. It has also been reported that in leaves of cabbage, beets, and garlic, up to
50% of the total selenium can be present as inorganic species.1 Selenocystathionine
has been identified as a toxic compound in South American nut.64 It is important to
note that selenate, selenite, and selenomethionine are the main components of nutri-
tional supplements and enriched yeast preparations.1,60
2234_C007.fm Page 272 Thursday, October 26, 2006 8:28 AM
7.3.9 ZINC
Concentrations of zinc (Zn) in foods of plant origin are generally small and vary
from 0.05 to 11.8 mg/100 g fresh weight. Important sources of this element are
cereals such as wheat bran and stabilized wheatgerm, which may contain up to 11.5
and 11.8 mg Zn/100 g, respectively (Table 7.6). Significant sources of zinc include
nuts shown to contain from 1.71 to 6.03 mg Zn/100 g (Table 7.9). Seeds with elevated
levels of zinc include poppy and sunflower seeds, which contain up to 8.6 mg Zn/100
g (Table 7.9). The lowest levels are generally found in fresh fruits and their products
(0.02–0.61 mg/100 g), with the exception of dried apple, sultanas and, especially,
currants, which contain up to 0.27, 0.67 and 12.7 mg Zn/100 mg (Table 7.7). Cocoa
powder contain from 8.5 to 9.43 mg Zn/100 g (Table 7.8). Fruit juices and alcoholic
beverages are characterized by lower levels of zinc (Table 7.10).
7.4.2 BORON
Concentrations of boron (B) in food crops are generally higher than those in animal
food products.1 Grain products contain boron in range of 0.01 to 0.15 mg/100 g,
whereas values in vegetables are from 0.01 to 2.64 mg/100 g (Table 7.11 and Table
7.12). Among the vegetables, pea is characterized by the highest levels of boron.
High levels of boron are reported in raisins (2.2 mg/100 g), peanuts (1.7 mg/100 g),
peanut butter (1.45 mg/100 g), nuts (1.4 mg/100 g)1,94 and in Beiqishen tea (1.29
mg/100 g) (Table 7.13). Banana pulp and fruit juices contained from 0.08 to 0.32
mg B/100 g and from 0.03 to 0.29 mg B/100 g, respectively (Table 7.15).
Among alcoholic beverages, wine and beer contain from 0.21 to 1.21 mg
B/100g and 0.01 to 0.05 mg B/100 g (Table 7.15). According to Murray95 and
Reilly,1 concentrations of boron in dry table wine and brewed leaf tea vary from
0.09 to 6.1 mg/100 g.
2234_C007.fm Page 273 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 273
7.4.3 VANADIUM
Vanadium (V) is present in vegetables in a wide range of concentrations, from
0.000005 to 0.16 mg/100 g (Table 7.12), with the highest values in potatoes. The
concentration in cereals and cereal products average about 2.3 mg V/100 g.1 Accord-
ing to Schroeder and Nason96 and Badmaev et al.,97 vegetable oils, some cereals,
and vegetables generally contain elevated levels of vanadium. The richest food
sources of this element include skimmed milk, seafoods, especially lobster, and
mushrooms. Some dietary supplements can contain up to 1.3 mg V/100 g.1,98 Con-
centrations of vanadium in alcoholic beverages vary significantly (Table 7.15), with
the levels in beer (0.001–0.005 mg/100 g) being higher than those in wine
(0.000001–0.0001 mg/100 g). Beer is a good source of vanadium, especially in
Germany where beer drinking it is the principal exposure route for men.1,99 Processed
foods always contain less vanadium than unprocessed ones.1,100
7.5.2 TIN
The concentrations of tin (Sn) in food crops are usually very low, typically in the
range of < 0.00016 to 0.001 mg/100 in vegetables (Table 7.12), and < 0.001 to 0.38
mg in grain products (Table 7.11). Tartary buckwheat leaf flour can be a rich source
of tin. Canned vegetables can contain as much as 4.4 mg Sn/100 g. Some fruit
products seem to have elevated levels of this element, up to 1.7 mg/100 g. Normal
levels of tin in foods are low, except for canned products (see Chapter 10) such as
canned vegetables where the Sn content can be as high as 4.4 mg/100 g. According
to Biégo et al.,104 fresh tomatoes contain, on average, 0.005 ± 0.001 mg Sn/100 g,
whereas the average levels of tin in tomatoes preserved in unlacquered and lacquered
cans may increase significantly — up to 0.60 ± 0.39 and 8.43 ± 6.21 mg/100 g,
respectively. Concentration of this element in tins of Italian peaches reach levels of
2234_C007.fm Page 274 Thursday, October 26, 2006 8:28 AM
TABLE 7.11
Possibly Essential Micronutrients and Nontoxic, Nonessential Metals in
Miscellaneous Cereals (in mg/100 g w/w)
Name Origin n Al As B Sn Ref.
Bread
Breadb U.K. 0.37 0.001 0.05 0.003 7
Breadb U.S. — < 0.004 — — 9
Whole white bread U.S. — < 0.004 — — 9
Cornbread U.S. — < 0.004 — — 9
Rye bread U.S. — < 0.004 — — 9
Cereals
Rolled oats 6 0.2 ± 0.04 — — — 56
0.09 – 0.51
Raisin bran cereal U.S. — < 0.004 — — 9
Fruit-flavored U.S. — < 0.004 — — 9
cereal
Rice
Rice India, 28 — — 0.05 — 12
Pakistan 0.04 – 0.09
Rice Europe 25 — — 0.06 — 12
0.01 – 0.15
Rice Different — 0.02 — — 13
White rice 6 < 0.002 — — — 56
Brown rice 7 0.20 ± 0.02 — — — 56
0.14 – 0.3
Wild rice 26 — 0.01 — — 68
0.001 – 0.01
Grits
Grits 10 < 0.002 — — — 56
Flour
Common Slovenia — — — < 0.001 71
buckwheat flourc
Tartary buckwheat Slovenia — — — < 0.001 71
fine flourc
Tartary buckwheat Slovenia — — — 0.09 ± 0.05 71
flourc
Maize flour 4 0.03 ± 0.01 — — — 56
0.03 – 0.04
Refined oat flour 1 0.04 ± 0.02 — — — 56
< 0.002 – 0.1
Wholemeal oat 2 0.33 ± 0.014 — — — 56
flour < 0.002 – 0.37
Wheat flour Spain — 0.002 ± 0.0002 — — 107
Wheat flour U.S. — 0.002 ± 0.0001 — — 106
Wheat flour Hungary — 0.002 ± 0.0002 — — 106
Wheat flour France — 0.002 ± 0.0001 — — 106
2234_C007.fm Page 275 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 275
Miscellaneous Cereals
Common Slovenia — — — < 0.001 71
buckwheat branc
Miscellaneous U.K. 7.8 0.001 0.09 0.002 7
cerealsb
Miscellaneous U.S. — 0.01 ± 0.004 — — 9
cerealsb < 0.004 – 0.01
Tartary buckwheat Slovenia — — — 0.12 ± 0.06 71
branc
Stabilized 3 0.41 ± 0.05 — — — 56
wheatgerm 0.4 – 0.71
Soft whole wheat 4 0.03 ± 0.01 — — — 56
0.01 – 0.1
Common Slovenia — — — < 0.001 71
buckwheat grainc
Tartary buckwheat Slovenia — — — 0.20 ± 0.1 71
grainc
Raw maize 6 0.16 ± 0.03 — — — 56
0.03 – 0.4
Kibbled wheat 6 0.14 ± 0.01 — — — 56
0.06 – 0.17
Decorticated Rye 4 < 0.002 — — — 56
Gluten 4 0.75 ± 0.13 — — — 56
0.49 – 1.29
276
TABLE 7.12
Possibly Essential Micronutrients and Nontoxic, Nonessential Metals in Vegetables (in mg/100 g w/w)
Name Origin n Al As B Sn V Ref
Vegetables
Bottle ground leaf — 0.03 — — — 107
Canned vegetablesb U.K. 0.11 0.0003 0.12 4.4 — 7
Canned vegetablesb U.S. — < 0.004 – 0.01 — — — 9
Carrot Greece — < 0.0001 — — 0.01 77
Celery leaf Greece — 0.001 — — 0.02 77
Celery root Greece — < 0.0001 — — 0.02 77
Cucumber U.S. — < 0.004 — — — 9
2234_C007.fm Page 276 Thursday, October 26, 2006 8:28 AM
0 – 0.16
Potatoesb U.K. 0.22 0.0005 0.14 < 0.002 — 7
Potatoesb U.S — < 0.004 — — — 9
Radish U.S. — < 0.004 — — — 9
Red pepper Tenerife Island 60 — — 0.07 ± 0.04 — — 18
0.01 – 0.21
Snake gourd India — 0.05 — — — 108
Spinach Greece — 0.001 — — 0.01 77
Taro India — 0.04 — — — 108
Tomato fruits, Denmark — — — 0.0001 0.00001 23
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
rockwool high EC
Tomato fruits, Denmark — — — 0.0001 0.00001 23
rockwool norm
EC
Tomato fruits, soil Denmark — — — 0.0001 0.00001 23
norm EC
277
278
Fruits
Apple red U.S — < 0.004 — — — 9
Avocado U.S. — < 0.005 — — — 9
Banana pulp Tenerife — — 0.20 ± 0.02 — — 25
Islandd 0.08 – 0.32
Cantaloupe U.S — < 0.003 — — — 9
2234_C007.fm Page 278 Thursday, October 26, 2006 8:28 AM
Tea
Tea Africa 18 79.0 ± 40.6 — — — 0.03 ± 0.02 27
Tea Asia 36 75.4 ± 26.1 — — — 0.02 ± 0.01 27
Tea China 13 87.1 ± 49.8 — — — 0.04 ± 0.03 27
Tea India, Sri Lanka 13 58.2 ± 13.9 — — — 0.01 ± 0.01 27
Beiqishen tea China 171 ± 19.9 1.02 ± 0.28 1.29 ± 0.07 — < 0.03 30
Chinese tea China 5 76.8 ± 1.12 — — — — 31
2234_C007.fm Page 279 Thursday, October 26, 2006 8:28 AM
Coffee
Ground coffeec Mixture 48 1.83 ± 0.97 — — — — 108
Soluble coffee 21 8.75 ± 8.10 — — 0.86 ± 0.12 — 34
< 0.5 – 23.3 0.64 – 1.16
Roasted coffee beans Costa Rica 20 1.25 ± 0.19 — — — — 35
2234_C007.fm Page 280 Thursday, October 26, 2006 8:28 AM
Confectionary Products
Sugar and preservesb U.K. 0.36 0.001 0.08 0.002 — 7
Sugar and preservesb U.S. — < 0.004 – 0.01 — — — 9
Sugar Egypt 0.0005 ± 0.0002 0.00001 ± 0.00001 — 0.0001 ± 0.0002 0.001 ± 0.001 38
Cocoa powder 4 7.42 ± 0.34 — — — — 56
6.1 – 9.03
Molasses Egypt 0.004 ± 0.01 0.0001 ± 0.00001 — 0.0003 ± 0.0003 0.005 ± 0.002 38
Sugar juice Egypt 0.004 ± 0.002 0.00001 ± 0.0 — 0.0002 ± 0.0002 0.003 ± 0.001 38
Mineral Components in Foods
2234_C007.fm Page 281 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 281
TABLE 7.14
Possibly Essential Micronutrients and Nontoxic, Nonessential Metals in Nuts,
Seeds, and Oils (in mg/100 g w/w)
Name Origin n Al As B Sn Ref.
Oils
Olive or sunflower oil U.S. — < 0.004 — — 9
Oils and fatsb U.K. 0.12 0.001 0.04 0.002 7
Oils and fatsb U.S. — < 0.004 — — 9
up to 40.0 mg/100 g.1 It should be noted that a high level of corrosion of the tin
plate may result in high levels of nitrate in the water used to process fruits.1,105
Contamination of foods by tin is discussed further in Chapter 10.
7.6.2 CADMIUM
The levels of cadmium (Cd) in food crops range from ca. < 0.00003 to 0.004 mg/100
g in fruits, and from < 0.0004 to 0.03 mg/100 g in vegetables (Table 7.17). The high
levels of this element in some vegetables can be attributable, in many instances, to the
application of fertilizers and contaminated sewage sludge to agricultural soils.1 Con-
tamination of rice paddies with cadmium was the cause of the outbreak of itai-itai
syndrome in the Jintsu River basin in Japan, which killed about 200 people. In Zhejiang
province in China, levels of cadmium in rice have been reported to be about 50 times
higher than those in the control area.62 Green leaf vegetables, some of which are
“cadmium accumulators” grown on soil in brownfield urban sites of England, contain
Cd from 0.31 to 1.00 mg/100 g (dry weight).1,110 Further discussion on the contamination
foods and alcoholic beverages with cadmium can be found in Chapter 10.
282
TABLE 7.15
Possibly Essential Micronutrients and Nontoxic, Nonessential Metals in Beverages (in mg/100 g w/w)
Name Origin n Al As B Sn V Ref.
0.0001 – 0.1 0.06 – 0.29 < 0.0001 – 0.01 < 0.0001 – 0.001
Orange juiced 8 0.02 – 0.06 — — — — 47
Orange juice concentrate Australia 83 0.01 ± 0.01 — 0.11 ± 0.02 0.0002 ± 0.0001 < 0.0001 45
0.001 – 0.05 0.03 – 0.17 < 0.0001 < 0.0001
Orange juice concentrate Brazil 42 0.01 ± 0.01 — 0.06 ± 0.02 0.0004 ± 0.0003 < 0.0001 45
0.003 – 0.04 0.03 – 0.1 < 0.0001 – 0.004 < 0.0001
Pummelo juice 0.01 — 0.07 < 0.0001 < 0.0001 45
Seville orange juice 0.03 — 0.11 < 0.0001 < 0.0001 45
Tangello juice 0.003 — 0.13 < 0.0001 < 0.0001 45
Alcoholic Beverages
Beerd 32 0.02 ± 0.01 — 0.02 ± 0.01 — — 49
0.004 – 0.06 0.01 – 0.04
Beerd Poland 35 — 0.001 — 0.0001 0.002 91
0.0002 – 0.001 0.00004 – 0.0003 0.001 – 0.005
Dry table wine U.S. — < 0.002 — — — 9
Wined Italy 0.02 – 0.18 0.000004 – 0.0001 0.21 – 1.21 0.002 – 0.1 0.000001 – 0.0001 53
Mineral Components in Foods
2234_C007.fm Page 283 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 283
7.6.3 LEAD
Lead (Pb) is present in all foods and beverages, primarily as a natural component
as well as an accidental additive picked up during food processing. The levels of
this metal in food crops, except those affected by environmental contamination, can
range between 0.00004 and 0.08 mg/100 g. Lead concentrations in cereals and
vegetables typically are 0.0004–0.06 and 0.00004–0.08 mg/100 g, respectively
(Table 7.16 and Table 7.17). Low levels of lead have also been reported for fruits
and oils (0.001–0.023 mg/100 g), whereas elevated concentrations (up to 0.77
mg/100 g) have been observed in tea (Table 7.17, Table 7.18, and Table 7.19). Foods
in lead-soldered cans generally contain higher levels of lead as compared to fresh
and frozen foods.1 For instance, extremely high levels of lead, up to 2.0 mg/100 g,
have been reported in Italian canned vegetables.1,111 Contamination of alcoholic
beverages and vegetables by lead, with special attention paid to contamination of
wines, is discussed in Chapter 9 and Chapter 10. Wines preserved in bottles with
lead seals represent a potential health hazard. According to Reilly2 and Shaper et
al.,112 concentrations of lead in the blood of middle-aged British men were positively
correlated with alcohol consumption. Serious exposure to lead can also occur among
children and pregnant and lactating women who consume calcium supplements made
from dolomite and bonemeal; these dietary supplements can have unexpectedly high
levels of contaminant lead.1,113
7.6.4 MERCURY
The levels of mercury (Hg) in food crops range from 0.00006 mg/100 g in fruit
products to 0.0004 mg/100 g in canned vegetables. Beer contain very small amounts
of this element, in the range of 0.00001 to 0.0001 mg/100 g (Table 7.20). Very high
levels of mercury have been reported in vegetables grown on mercury-contaminated
soil — for example, up to 0.004 mg Hg/100 g in lettuce cultivated on sludge-amended
soil.1,114 Although fish and seafoods are well known to be a major source of methyl-
mercury in the diet (see Chapter 10), contamination may also occur from adventitious
sources. The best-known incidence occurred in northern Iraq where a large number
of the local population was poisoned from eating homemade bread prepared from
grains that had been dressed with alkylmercury compounds as antifungal agents.115
It is estimated that 100,000-500,000 inhabitants had suffered permanent disabilities
from this inadvertent exposure.62,116,117
TABLE 7.16
Toxic Metals in Miscellaneous Cereals (in mg/100 g w/w)
Name Origin n Cd Hg Pb Ref.
Bread
Breadb U.K. 0.003 0.0004 0.002 7
Breadb U.S. 0.002 ± 0.001 — < 0.004 9
0.001 – 0.002
Breade 10 0.002 — — 118
Bagel plain U.S. 0.002 — < 0.004 9
Bread Poland 26 0.001 – 0.004 — 0.005 – 0.01 65
White bread U.S. 0.002 — < 0.004 9
Whole white bread U.S. 0.002 — < 0.004 9
Cornbread U.S. 0.001 — < 0.004 9
Rye bread U.S. 0.002 — < 0.004 9
—
Cereals
Corn flakes U.S. < 0.001 — < 0.004 9
Raisin bran cereal U.S. 0.005 — < 0.004 9
Fruit-flavored cereal U.S. 0.001 — < 0.004 9
Rice
Raw ricee 10 0.005 — — 118
Rice Different — — 0.01 13
Rice nonglutinous NE China 17 0.001 ± 0.001 — 0.002 ± 0.002 74
0.0004 – 0.003 0.0004 – 0.01
Wild rice 26 0.005 — 0.004 68
0.001 – 0.01 0.0005 – 0.01
Rice glutinous NE China 6 0.004 ± 0.004 — 0.01 ± 0.02 74
0.0005 – 0.01 0.001 – 0.04
Grits
Foxtail millet NE China 8 0.001 ± 0.0003 — 0.01 ± 0.004 74
0.001 – 0.002 0.003 – 0.01
Noodlee 10 0.0004 — — 118
Flour
Floure 10 0.002 — — 118
Common buckwheat Slovenia — < 0.001 — 71
flourc
Tartary buckwheat Slovenia — < 0.001 — 71
fine flourc
Tartary buckwheat Slovenia — < 0.001 — 71
flourc
Maize flour NE China 7 0.001 ± 0.0003 — 0.004 ± 0.002 74
0.0002 – 0.001 0.001 – 0.01
Wheat flour NE China 9 0.002 ± 0.001 — 0.004 ± 0.003 74
0.001 – 0.003 0.0015 – 0.01
2234_C007.fm Page 285 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 285
Miscellaneous Cereals
Common buckwheat Slovenia — 0.001 ± 0.0004 — 71
branc
Miscellaneous U.K. 0.002 0.0004 0.002 7
cerealsb
Miscellaneous U.S. 0.002 ± 0.001 < 0.004 < 0.005 9
cerealsb < 0.0005 – 0.01
Tartary buckwheat Slovenia — < 0.001 — 71
branc
Wheat branc Sweden n = 30 — n = 26 72
0.01 ± 0.005 < 0.002 – 0.01
0.005 – 0.02
Adzuki bean NE China 3 0.01 ± 0.01 — 0.003 ± 0.001 74
0.002 – 0.03 0.002 – 0.004
Fava bean (broad NE China 1 0.01 — 0.002 74
bean)
Kidney bean NE China 11 0.003 ± 0.003 — 0.003 ± 0.001 74
0.001 – 0.01 0.001 – 0.01
Green gram (mung NE China 5 0.01 ± 0.002 — 0.003 ± 0.002 74
bean) 0.005 – 0.01 0.001 – 0.01
Cowpea (blackeyed NE China 1 0.04 — 0.01 74
pea)
Soybean NE China 11 0.01 ± 0.01 — 0.004 ± 0.004 74
0.002 – 0.02 0.001 – 0.01
Sorghum NE China 3 0.001 ± 0.001 — 0.01 ± 0.005 74
0.001 – 0.002 0.002 – 0.01
Common buckwheat Slovenia — < 0.001 — 71
grainc
Tartary buckwheat Slovenia — < 0.001 — 71
grainc
Maize grain NE China 9 0.0004 ± 0.0001 — 0.01 ± 0.02 74
0.0002 – 0.001 0.001 – 0.06
White roll U.S. 0.002 — < 0.004 9
e geometrical mean
286
TABLE 7.17
Toxic Metals in Vegetables, Mushrooms, and Fruits (in mg/100 g w/w)
Name Origin n Be Cd Hg Pb Ref.
Vegetables
Artichoke Spain — — — 0.01 ± 0.01 76
Cabbage Spain — — — 0.004 ± 0.004 76
Cabbage leaves 5 — — — 0.08 ± 0.001 119
Cabbages Saudi Arabia 5 — 0.01 — — 17
Canned vegetablesb U.K. 0.001 0.0004 0.002 7
Canned vegetablesb U.S. 0.001 ± 0.0003 NA < 0.003 9
< 0.0005 – 0.002
2234_C007.fm Page 286 Thursday, October 26, 2006 8:28 AM
Fruits
Apple, red U.S. — < 0.001 — < 0.003 9
Apricot U.S. — < 0.001 — < 0.003 9
Avocado U.S. — 0.003 — < 0.01 9
Cantaloupe U.S. — 0.001 — < 0.002 9
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Frozen Fruits
Gooseberry 5 — 0.001 ± 0.0004 — 0.01 ± 0.01 81
0.001 – 0.002 0.01 – 0.02
Black chokeberry 5 — 0.003 ± 0.001 — 0.02 ± 0.005 81
0.002 – 0.004 0.01 – 0.02
Blackberry 5 — 0.002 ± 0.0003 — 0.02 ± 0.003 81
0.001 – 0.002 0.012 – 0.02
Raspberry 5 — 0.002 ± 0.0003 — 0.01 ± 0.005 81
0.001 – 0.002 0.005 – 0.02
Fruits 71 — 0.002 — 0.01 81
0.0004 – 0.004 0.004 – 0.03
Mineral Components in Foods
Blackcurrant 5 — 0.001 ± 0.001 — 0.01 ± 0.004 81
0.0004 – 0.002 0.01 – 0.02
Red currant 5 — 0.001 ± 0.0004 — 0.01 ± 0.01 81
0.001 – 0.002 0.004 – 0.02
Plum 5 — 0.001 ± 0.0003 — 0.01 ± 0.01 81
0.001 – 0.001 0.01 – 0.02
Strawberry 6 — 0.002 ± 0.001 — 0.01 ± 0.004 81
0.0004 – 0.004 0.005 – 0.02
Cherry 7 — 0.001 – 0.0003 — 0.01 ± 0.003 81
0.0005 – 0.001 0.005 – 0.01
2234_C007.fm Page 291 Thursday, October 26, 2006 8:28 AM
TABLE 7.18
Toxic Metals in Tea, Coffee, and Confectionary Products (in mg/100 g w/w)
Name Origin n Cd Hg Pb Ref.
Tea
Tea Africa 18 — — 0.11 ± 0.01 27
Tea Asia 36 — — 0.02 ± 0.01 27
Tea China 13 — — 0.21 ± 0.10 27
Tea India, Sri Lanka 13 — — 0.05 ± 0.02 27
Teac China 39 — — 0.14 ± 0.12 29
0.03 ± 0.77
Beiqishen tea China < 0.01 < 0.05 < 0.13 30
Chinese tea China 5 0.003 ± 0.001 — 0.02 ± 0.02 82
0.005 – 0.05
Indian tea India 3 0.001 ± 0.0001 — 0.01 ± 0.004 82
0.001 – 0.001 0.005 – 0.01
Beiqishen tea China < 0.0003 < 0.00013 < 0.002 30
extractd
Coffee
Decaffeinated U.S. — — < 0.002 9
instant coffee
Ground coffee U.S. < 0.0003 — < 0.002 9
7
Confectionary Products
Sugar and U.K. 0.001 0.0004 0.001
preservesb
Sugar and U.S. 0.002 ± 0.001 NA < 0.005 9
preservesb < 0.0004 – 0.003
Sugar Egypt 2 — — 0.001 ± 0.001 37
Sugar Egypt — — 0.0001 ± 0.0001 38
White sugar, U.S. < 0.001 — < 0.01 9
granulated
Sugar cane Egypt 3 — — 0.002 ± 0.002 37
plant
Sugar cane rootc Brazil 0.02 ± 0.01 0.003 ± 0.002 0.80 ± 0.42 123
0.01 – 0.04 0.001 – 0.01 0.29 – 2.23
Sugar cane Brazil 0.02 ± 0.01 0.002 ± 0.001 0.67 ± 0.24 123
stemc 0.01 – 0.03 0.001 – 0.01 0.35 – 1.38
Sugar cane leafc Brazil 0.01 ± 0.06 0.002 ± 0.001 0.21 ± 0.12 123
0.004 – 0.03 0.001 – 0.01 0.05 – 0.55
Cocoa powder Malaysia 7 0.06 ± 0.01 — 0.02 ± 0.01 125
Cocoa powder Venezuela 3 0.18 ± 0.002 — 0.02 ± 0.001 125
Cocoa powder Ecuador 1 0.07 ± 0.005 — 0.02 ± 0 125
Cocoa powder El Oro, 1 0.05 ± 0.002 — 0.001 ± 0.0003 125
Ecuador
Cocoa powder Bahia, Brazil 1 0.01 ± 0.001 — 0.02 ± 0.001 125
Cocoa powder Habuna, Brazil 1 0.02 ± 0.002 — 0.08 ± 0.015 125
2234_C007.fm Page 293 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 293
7.7.2 BARIUM
Concentration of barium (Ba) in plant foods is generally greater than that in animal
products and ranged between 0.002 and 0.17 mg/100 g in vegetables, and from 0.001
to 0.08 mg/100 g in fruit juices (Table 7.22 and Table 7.25). Miscellaneous cereals
contained from 0.03 to 0.08 mg Ba/100 g (Table 7.21). Higher levels of this element
were observed in nuts containing up to 5.6 mg Ba/100 g (Table 7.24). It is interesting
to note that the Brazil nut seems to be the richest source of barium because some
kernels contained extremely high levels of this metal, i.e., up to 300 mg/100 g.124
Tea leaves contained up to 3.88 mg Ba/100 g, whereas roasted coffee contained
from 0.09 to 0.97 mg/100 g (Table 7.23). Low levels of barium are reported for fruit
juices and alcoholic beverages (Table 7.25) such as beer (0.001–0.008 mg/100 g)
and wine (0.003–0.01 mg/100 g).
7.7.3 GALLIUM
Concentration of gallium (Ga) in rice (0.0016 mg/100 g) is several orders of mag-
nitude higher than that in vegetables (0.0000006–0.00017 mg/100 g). Beer and wine
contain this element in the range of 0.000001 to 0.00004 mg/100 g (Table 7.25).
TABLE 7.19
Toxic Metals in Nuts, Seeds, and Oils (in mg/100 g w/w)
Name Origin n Cd Hg Pb Ref.
Oils
Grape seeds oil 3 0.0004 ± 0.0001 — 0.001 ± 0.0004 91
Maize oil 5 0.001 ± 0.0002 — 0.001 ± 0.0002 91
Nuts oil 3 0.0002 ± 0.0001 — 0.005 ± 0.001 91
Oils and fatsb U.K. 0.002 0.0003 0.002 7
Oils and fatsb U.S. < 0.002 NA < 0.01 9
Peanut oil 6 0.0003 ± 0.0001 — 0.001 ± 0.0004 90
Rice oil 5 0.0001 ± 0.00004 — 0.001 ± 0.0002 90
Soy oil 5 0.0004 ± 0.0001 0.003 ± 0.001 90
Soy oil Poland 1 — < 0.0001 — 65
Sunflower oil 5 0.0002 ± 0.0002 0.002 ± 0.003 90
TABLE 7.20
Toxic Metals in Beverages (in mg/100 g w/w)
Name Origin n Be Cd Hg Pb Ref.
Alcoholic Beverages
Beerd Poland 35 — 0.00001 0.00003 0.0003 91
0.000002 – 0.00005 0.00001 – 0.0001 0.0001 – 0.001
2234_C007.fm Page 295 Thursday, October 26, 2006 8:28 AM
TABLE 7.21
Other Metals in Miscellaneous Cereals (in mg/100 g w/w)
Name Origin n Ag Au Ba Bi Cs Ga Ge Ir Li Ref.
Bread
Breadb U.K. — 0.0001 0.1 0.00003 — — 0.0003 0.0001 0.001 7
Rice
Rice Different — — 0.03 — 0.001 0.002 — — — 13
Miscellaneous Cereals
Miscellaneous U.K. — 0.0002 0.08 0.00003 — — 0.0004 0.0002 0.002 7
cerealsb
Common Slovenia 0.002 ± 0.0002 — — — — — — — — 77
2234_C007.fm Page 296 Thursday, October 26, 2006 8:28 AM
buckwheat
flourc
Tartary Slovenia 0.0003 ± 0.0001 — — — — — — — — 77
buckwheat
fine flourc
Tartary Slovenia 0.001 ± 0.0003 — — — — — — — — 77
buckwheat
flourc
Tartary Slovenia 0.003 ± 0.001 — — — — — — — — 77
buckwheat
leaf flourc
Soya flour — — — — — — 0.36 — — 131
Common Slovenia 0.003 ± 0.0004 — — — — — — — — 77
buckwheat
branc
Mineral Components in Foods
Tartary Slovenia 0.001 ± 0.0002 — — — — — — — — 77
buckwheat
branc
Common Slovenia 0.002 ± 0.0003 — — — — — — — — 77
buckwheat
grainc
Tartary Slovenia 0.001 ± 0.0002 — — — — — — — — 77
buckwheat
grainc
Pearl barley — — — — — — 0.16 — — 129
Bread
Breadb U.K. — 0.0002 0.00001 — 0.00002 < 0.0002 0.0001 0.37 0.0001 — — 7
Rice
2234_C007.fm Page 297 Thursday, October 26, 2006 8:28 AM
buckwheat
branc
Quinoac — — — — — 0.001 ± 0.0001 — — — — 77
Common Slovenia — — 1.12 ± 0.011 — — — — — — — 77
buckwheat
grainc
Tartary Slovenia — — 1.64 ± 0.001 — — — — — — — 77
buckwheat
grainc
Wheat grainsc — — — — — < 0.0004 — — — — 77
Mineral Components in Foods
2234_C007.fm Page 299 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 299
(Table 7.25). Among grain products, rice can contain up to 0.001 mg Cs/100 g,
whereas concentrations of germanium in bread and miscellaneous cereals are often
in the range of < 0.0003 to 0.0004 mg/100 g. Somewhat higher levels of germanium
have been reported in soya flour (0.36 mg/100 g) and pearl barley (0.16 mg/100 g)
(Table 7.21).
7.7.5 GOLD
Gold (Au) is found in food crops in very low amounts, typically from 0.00001 to
0.001 mg/100 g in vegetables (Table 7.22), and 0.00004 to 0.001 mg/100 g in
sugarcane plant and sugar (Table 7.23). Concentrations of gold in bread and mis-
cellaneous cereals are in the range of 0.0001 to 0.0002 mg/100 g (Table 7.21).
7.7.6 INDIUM
Compilation of published data (Table 7.22 and Table 7.25) suggests that indium (In)
contents in vegetables range from < 0.00001 to 0.0003 mg/100 g, whereas beer is
characterized by extremely low levels of this element (< 0.000001 mg/100 g).
7.7.7 LITHIUM
Average concentrations of lithium (Li) in bread and miscellaneous cereals are esti-
mated to be 0.001 and 0.002 mg/100 g, respectively, and < 0.0001 to 0.003 mg/100
g has been reported for vegetables (Table 7.21 and Table 7.22). Higher lithium levels
are reported for Spanish potatoes, up to 0.30 mg/100 g. Fresh fruits and alcoholic
beverages (wine) generally contain from < 0.0002 to 0.005 mg Li/100 g (Table 7.22
and Table 7.25).
7.7.8 NIOBIUM
Concentrations of niobium (Nb) in vegetables are in the extremely low range of
0.000000004 to 0.0003 mg/100 g. Wines contain from 0.000001 to 0.00001 mg
Nb/100 g (Table 7.22 and Table 7.25).
TABLE 7.22
Other Metals in Vegetables, Mushrooms, and Fruits (in mg/100 g w/w)
Name Origin n Ag Au Ba Bi Cs Ga Ref.
Vegetables
Canned U.K. — 0.00004 0.03 0.00005 — — 7
vegetablesb
Green U.K. — < 0.00004 0.04 0.0001 — — 7
vegetablesb
Onion Denmark 0.0001 ± 0.00003 0.0001 ± 0.0002 0.01 ± 0.01 0.00001 ± 0.000005 0.00002 ± 0.00003 0.00002 ± 0.00003 20
conventional 0.00001 – 0.0002 0.00002 – 0.001 0.002 – 0.05 0.000001 – 0.00003 0.0 – 0.0001 0.000001 – 0.0002
Onion organic Denmark 0.0001 ± 0.00003 0.0001 ± 0.00004 0.01 ± 0.01 0.00002 ± 0.00001 0.00005 ± 0.0001 0.00002 ± 0.00002 20
0.00002 – 0.0002 0.000015 – 0.0002 0.002 – 0.04 0.000002 – 0.00004 0.0 – 0.0003 0.0 – 0.0001
Other vegetablesb U.K. — 0.00005 0.05 0.00003 — — 7
2234_C007.fm Page 300 Thursday, October 26, 2006 8:28 AM
Peas Denmark 0.0001 ± 0.00005 0.0001 ± 0.00004 0.02 ± 0.01 0.00001 ± 0.00001 — 0.00004 ± 0.00002 20
conventional 0.000012 – 0.0003 0.00001 – 0.0003 0.003 – 0.07 0.000001 – 0.00004 0.00001 – 0.0001
Peas organic Denmark 0.0001 ± 0.00004 0.0001 ± 0.0001 0.02 ± 0.02 0.00001 ± 0.00001 — 0.00003 ± 0.00002 20
0.00002 – 0.0003 0.00003 – 0.0004 0.005 – 0.07 0.000001 – 0.0001 0.00001 – 0.0001
Potatoesc Idaho 342 — 0.03 ± 0.01 — — — 22
0 – 0.08
Potatoes c Non-Idaho 266 — — 0.04 ± 0.04 — — — 22
0 – 0.17
Potatoesc U.K. — 0.00004 0.02 0.00001 — — 7
Mushrooms
Bay boletec Poland 166 0.01 ± 0.004 — — — — — 24
0.0003 – 0.04
Fruits
Fresh fruitb U.K. — 0.00004 0.04 0.00003 — — 7
Fruit productsb U.K. — 0.00004 0.03 0.00002 — — 7
Mineral Components in Foods
Name Origin n Ge Hf In Ir Li Nb Ref.
Vegetables
Carrot 0.06 — — — — — 129
Canned vegetablesb U.K. < 0.0002 — — < 0.0001 0.001 — 7
Garlic 0.28 — — — — — 129
Green pepper 0.02 — — — — — 129
Green vegetablesb U.K. < 0.0002 — — < 0.0001 0.001 — 7
Onion 0.03 — — — — — 129
Onion Denmark 0.001 ± 0.001 0.0001 ± 0.0002 0.00004 ± 0.00003 0.000003 ± 0.00001 0.0001 ± 0.0002 0.0001 ± 0.0001 20
conventional 0.00005 – 0.003 0.0 – 0.001 0.0 – 0.0003 0.0 – 0.00003 0.0 – 0.0005 0.0 – 0.001
Onion organic Denmark 0.0001 ± 0.00004 0.00004 ± 0.00005 0.00003 ± 0.00005 0.000001 ± 0.000003 0.0 – 0.0002 0.0001 ± 0.0001 20
0.0001 – 0.002 0.0 – 0.0002 0.0 – 0.0003 0.0 – 0.00001 0.000000004 – 0.001
Other vegetablesb U.K. 0.0002 — — < 0.0001 0.003 — 7
Peas conventional Denmark 0.01 ± 0.002 0.00003 ± 0.00004 — 0.0 – 0.00001 — 0.0001 ± 0.0001 20
0.004 – 0.01 0.0 – 0.0002 0.00002 – 0.0003
Peas organic Denmark 0.01 ± 0.002 0.00004 ± 0.00005 — 0.000001 ± 0.000005 — 0.0002 ± 0.0001 20
2234_C007.fm Page 301 Thursday, October 26, 2006 8:28 AM
Vegetables
Canned vegetablesb U.K. 0.00004 < 0.00001 — — < 0.00001 < 0.0002 7
Green vegetablesb U.K. 0.0001 0.00001 — — < 0.00001 < 0.0002 7
Onion Denmark — 0.00002 ± 0.00003 0.04 ± 0.02 0.000001 ± 0.000003 — 0.00002 ± 0.00002 20
conventional 0.0 – 0.0002 0.01 – 0.09 0.0 – 0.00001 0.0 – 0.0001
Onion organic Denmark — 0.00002 ± 0.00002 0.07 ± 0.02 0.000001 ± 0.000002 — 0.00001 ± 0.00002 20
0.0 – 0.0001 0.03 – 0.11 0.0 – 0.00001 0.0 – 0.00005
Other vegetablesb U.K. 0.00005 0.00001 — — < 0.00001 < 0.0002 7
301
302
Fruits
Fresh fruitb U.K. 0.00004 < 0.00001 — — < 0.00001 < 0.0002 7
2234_C007.fm Page 302 Thursday, October 26, 2006 8:28 AM
Vegetables
Green vegetablesb U.K. < 0.0001 — 0.16 — — 7
Canned vegetablesb U.K. 0.0002 — 0.09 — — 7
Onion Denmark 0.0002 ± 0.0001 0.0002 ± 0.0001 0.09 ± 0.05 — 0.0002 ± 0.0001 20
conventional 0.00002 – 0.0005 0.00002 – 0.0005 0.02 – 0.31 0.00005 – 0.0005
Onion organic Denmark 0.0001 ± 0.0001 0.0001 ± 0.0001 0.06 ± 0.03 — 0.0002 ± 0.0001 20
0.00003 – 0.0004 0.00003 – 0.0004 0.02 – 0.16 0.00002 – 0.001
Other vegetables b U.K. 0.0001 — 0.13 — — 7
Peas conventional Denmark 0.0001 ± 0.0001 0.0002 ± 0.0001 0.05 ± 0.02 0.0001 ± 0.0001 0.0002 ± 0.0001 20
0.00002 – 0.0003 0.0001 – 0.001 0.02 – 0.11 0.000002 – 0.0004 0.00001 – 0.0005
Peas organic Denmark 0.0001 ± 0.0001 0.0002 ± 0.0001 0.05 ± 0.01 0.0001 ± 0.0001 0.0002 ± 0.0002 20
0.00002 – 0.0004 0.0001 – 0.0005 0.02 – 0.09 0.00001 – 0.001 0.00004 – 0.001
Potatoesc Idaho 342 — — 0.05 ± 0.03 — — 22
0 – 0.14
Potatoesc non-Idaho 266 — — 0.03 ± 0.04 — — 22
0 – 0.16
Potatoesb U.K. 0.0001 — 0.08 — — 7
Mineral Components in Foods
Tomato fruits, Denmark — — 0.01 — — 23
rockwool high
EC
Tomato fruits, Denmark — — 0.01 — — 23
rockwool norm
EC
Tomato fruits, soil Denmark — — 0.02 — — 23
norm EC
Fresh fruitb U.K. 0.0001 — 0.08 — — 7
Fruit productsb U.K. 0.0001 — 0.10 — — 7
Vegetables
Green vegetablesb U.K. — 0.0003 — — — 7
Canned vegetablesb U.K. — 0.0001 — — — 7
Onion, Denmark 0.09 ± 0.06 0.0001 ± 0.0001 0.002 ± 0.001 0.00002 ± 0.00002 0.0003 ± 0.0003 20
2234_C007.fm Page 303 Thursday, October 26, 2006 8:28 AM
conventional 0.01 – 0.25 0.00001 – 0.0003 0.001 – 0.004 0.000003 – 0.0001 0.00003 – 0.001
Onion, organic Denmark 0.04 ± 0.03 0.0001 ± 0.00004 0.002 ± 0.001 0.00001 ± 0.00001 0.0003 ± 0.0003 20
0.01 – 0.14 0.00002 – 0.0002 0.0005 – 0.005 0.000003 – 0.00003 0.0001 – 0.002
Other vegetables b U.K. — 0.0001 — — — 7
Peas, conventional Denmark 0.10 ± 0.04 0.00003 ± 0.00003 — 0.00002 ± 0.00001 0.0002 ± 0.0001 20
0.04 – 0.19 0.0 – 0.0002 0.00001 – 0.0001 0.00004 – 0.0005
Peas, organic Denmark 0.06 ± 0.02 0.00004 ± 0.00004 — 0.00002 ± 0.000005 0.0003 ± 0.0004 20
0.03 – 0.11 0.00000001 – 0.0002 0.00001 – 0.00004 0.00005 – 0.003
Potatoesb U.K. — 0.0002 — — — 7
Fruits
Fresh fruitb U.K. — 0.0001 — — — 7
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
7.7.10 RUBIDIUM
Ranges in the rubidium (Rb) content of grain products and vegetables typically are
0.02 to 1.36 mg/100 g and 0.01 to 0.25 mg/100 g, respectively (Table 7.21 and Table
7.22). Fruit juices contain from 0.01 to 1.1 mg Rb/100 g. Concentration of the
element in wine (0.06–0.42 mg/100 g) is an order of magnitude higher than that in
beer (0.01–0.04 mg/100 g) (Table 7.25). Tea leaves contain elevated levels of rubid-
ium — from 2.31 to 13.8 mg/100 g (Table 7.23).
7.7.11 SILVER
Levels of silver (Ag) in miscellaneous cereals and vegetables vary from 0.0003 to
0.003 mg/100 g and from 0.00001 to 0.0003 mg/100 g, respectively (Table 7.21 and
Table 7.22). Mushrooms often show elevated levels of silver — up to 0.04 mg Ag/100
g. Extremely small amounts of this metal (0.000001–0.00002 mg/100 g) are present
in beer (Table 7.25), whereas the richest dietary source are nuts with concentrations
of 0.27 to 2.01 mg Ag/100 g (Table 7.24). Some vegetables, e.g., the Brassica species,
have the ability to selectively accumulate silver to very high levels.1
7.7.12 STRONTIUM
Concentrations of strontium (Sr) vary from 0.01 to 0.37 mg/100 g in vegetables and
grain products, with the highest levels registered for rice (Table 7.21 and Table 7.22).
Wines and fruit juices contain this element in the range of 0.004 to 0.26 mg/100 g,
whereas the values for beers can vary from 0.01 to 0.07 mg/100 g (Table 7.25).
Higher levels are reported for nuts (0.86 mg Sr/100 g) and especially tea leaves
(2.22 mg Sr/100 g) (Table 7.23 and Table 7.24).
7.7.13 TELLURIUM
The few reported levels of tellurium (Te) in plant products are mostly below the
detection limit of analytical measurements, i.e., < 0.0005 mg/100 g1 (Table 7.22 and
Table 7.25). Higher levels of up to 0.001 mg/100 g have been reported for onion.
It should be noted that contamination of metal containers with tellurium may be its
main source in foods.1
7.7.14 THALLIUM
Little is known about the levels of thallium (Tl) in food crops. Concentration of this
element in vegetables is usually extremely small, ranging from < 0.000001 to 0.0002
mg/100 g (Table 7.22). Grain products, sugar, nuts, and oils show slightly higher
levels, from 0.0001 to 0.0002 mg/100 g (Table 7.21, Table 7.23, and Table 7.24).
Wine and beer have lower levels, in the range of 0.000001 to 0.00002 mg/100 g
(Table 7.25). Thallium is readily accumulated from contaminated soil by various
vegetables; concentrations of up to 4.2 mg/100 g have been reported in cabbage
grown on heavily contaminated soil of Ghizhou Province in China.126 Vegetables
TABLE 7.23
Other Metals in Tea, Coffee, and Confectionary Products (in mg/100 g w/w and in µg/100 g w/wa)
Name Origin n Ag Au Ba Bi Cs Ge Ir Li Pd Ref.
Tea
Tea Africa 18 — — 1.97 ± 1.07 — 0.05 ± 0.04 — — — — 27
Tea Asia 36 — — 2.62 ± 0.89 — 0.03 ± 0.02 — — — — 27
Tea China 13 — — 1.77 ± 1.1 — 0.05 ± 0.03 — — — — 27
Tea India, Sri 13 — — 2.03 ± 0.81 — 0.02 ± 0.01 — — — — 27
Lanka
Teac China 39 — — 1.82 ± 0.81 — — — — — — 29
0.28 – 3.88
Beiqishen tea China — — 2.84 ± 0.07 — — — — < 0.02 — 30
2234_C007.fm Page 305 Thursday, October 26, 2006 8:28 AM
Coffee
Roasted coffeec Mixture 18 — — 0.45 ± 0.23 — — — — — — 36
0.09 – 0.97
Green coffeec Mixture 41 — — 0.43 ± 0.15 — — — — — — 84
0.17 – 0.76
305
306
Confectionary Products
Sugar Egypt 2 0.0002 ± 0.0 0.5 ± 0.1a — — — — — — — 37
Sugar Egypt — — — — — — — 0.0003 ± 0.001 — 38
Sugar cane plant Egypt 3 0.4 ± 0.005a 0.001 ± 0.001 — — — — — — — 37
Molasses Egypt — — — — — — — 0.001 ± 0.001 — 38
Sugar cane juice Egypt 3 0.0002 ± 0.0 0.001 ± 0.0002 — — — — — — — 37
Sugar juice Egypt — — — — — — — 0.001 ± 0.001 — 38
Sugar and preservesb U.K. — 0.00004 0.08 0.00003 — 0.0002 < 0.0001 0.001 0.00005 7
2234_C007.fm Page 306 Thursday, October 26, 2006 8:28 AM
Tea
Tea Africa 18 — 6.15 ± 3.17 — — — — 1.0 ± 0.58 2.58 ± 1.0 — 27
Tea Asia 36 — 8.25 ± 3.29 — — — — 2.09 ± 0.72 2.78 ± 0.7 — 27
Tea China 13 — 8.17 ± 3.12 — — — — 0.88 ± 0.4 2.63 ± 1.38 — 27
Tea India, Sri 13 — 4.59 ± 1.74 — — — — 1.1 ± 0.39 2.46 ± 0.53 — 27
Lanka
Teac China 39 — 7.62 ± 2.92 — — — — 1.13 ± 0.44 2.12 ± 1.2 — 29
2.31 – 13.8 0.32 – 2.22 0.37 – 6.46
Instant tead (<2% tea 3 — — — — — — 0.001 — — 33
extract) 0.001 – 0.001
Instant tead (100% 2 — — — — — — 0.002 — — 33
extract) 0.001 – 0.002
Black tea beveragesd 23 — — — — — — 0.004 – 0.02 — — 33
Green tea beveragesd 20 — — — — — — 0.004 – 0.01 — — 33
Tea soft drinksd 8 — — — — — — 0.02 0 – 0.07 — — 33
Mineral Components in Foods
Coffee
Roasted coffeec Mixture 18 — — — — — — 0.62 ± 0.18 — — 36
0.40 – 1.15
Green coffeec Mixture 41 — — — — — — 0.55 ± 0.21 — — 84
0.12 – 1.12
Confectionary Products
Sugar Egypt 2 — — — — — — 0.003 ± 0.001 — — 37
Sugar Egypt — — — — — — 0.3 ± 0.2a — — — 38
Sugarcane plant Egypt 3 — — — — — — 0.004 ± 0.002 — — 37
Molasses Egypt — — — — — 0.002 ± 0.002 — — — 38
Sugarcane juice Egypt 3 — — — — — — 0.003 ± 0.0008 — — 37
Sugar juice Egypt — — — — — 0.001 ± 0.001 — — — 38
2234_C007.fm Page 307 Thursday, October 26, 2006 8:28 AM
Sugar and preservesb U.K. 0.01a — < 0.01a 0.0002 0.0002 — 0.11 — 0.0001 7
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
307
308
TABLE 7.24
Other Metals in Nuts, Seeds, and Oils (in mg/100 g w/w)
Name Origin n Ag Au Ba Bi Ge Ir Li Pd Pt Rh Ru Sb Sr Tl Ref.
Oils
Oils and fatsb U.K. — 0.0001 0.003 0.00002 0.0002 <0.0001 0.0003 0.00004 0.00002 <0.00001 0.0002 0.0002 0.01 0.0001 7
Mineral Components in Foods
TABLE 7.25
Other Metals in Beverages (in mg/100 g w/w)
Name Origin n Ag Au Ba Bi Cs Ga Ref.
Juices
Grapefruit juice — — 0.001 — — — 45
Lemon juice — — 0.02 — — — 45
Lime juice — — 0.02 — — — 45
Mandarin juice — — 0.002 — — — 45
Orange juice Australia 290 — — 0.02 ± 0.001 — — — 45
0.001 – 0.04
Orange juice Australia 83 — — 0.01 ± 0.003 — — — 45
concentrate 0.01 – 0.03
Orange juice Brazil 42 — — 0.03 ± 0.02 — — — 45
2234_C007.fm Page 309 Thursday, October 26, 2006 8:28 AM
Alcoholic Beverages
Beerd 32 — — 0.003 ± 0.001 — — — 49
0.001 – 0.01
Beerd Poland 35 0.000004 — — 0.000005 0 0.00003 0.00001 91
0.000001 – 0.00002 0.0000005 – 0.00005 0.00001 – 0.0001 0.000001 – 0.00002
Wined Italy — — 0.003 – 0.01 — 0.000001 – 0.0001 0.000004 – 0.00004 53
Beveragesd U.K. — 0.00004 0.01 0.00001 — — 7
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Juices
Grapefruit juice — — — — < 0.0002 45
Lemon juice — — — — < 0.0002 45
Lime juice — — — — < 0.0002 45
Mandarin juice — — — — < 0.0002 45
309
310
Alcoholic Beverages
Beerd Poland 35 — — 0.000001 — — 91
0.0000001 – 0.000002
Wine d Spain 125 — — — — 0.001 ± 0.0003 52
0.0002 – 0.002
Wined Italy 0.000001 – 0.0001 0.000001 – 0.00001 — — 0.001 – 0.005 53
Beveragesd U.K. 0.0002 — — < 0.0001 0.0004 7
Juices
Grapefruit juice — — — 0.02 — — — 0.004 45
Lemon juice — — — 0.07 — — — 0.04 45
Lime juice — — — 0.17 — — — 0.02 45
Mandarin juice — — — 0.07 — — — 0.01 45
Orange juice Australia 290 — — — 0.09 ± 0.04 — — — 0.07 ± 0.01 45
0.02 – 1.1 0.01 – 0.26
Orange juice Australia 83 — — — 0.06 ± 0.02 — — — 0.07 ± 0.02 45
concentrate 0.02 – 0.10 0.04 – 0.15
Orange juice Brazil 42 — — — 0.21 ± 0.05 — — — 0.04 ± 0.02 45
concentrate 0.09 – 0.31 0.02 – 0.1
Mineral Components in Foods
Pummelo juice — — — 0.24 — — — 0.01 45
Seville orange juice — — — 0.03 — — — 0.10 45
Tangello juice — — — 0.04 — — — 0.16 45
Alcoholic Beverages
Beerd 32 — — — — — — — 0.03 ± 0.02 49
0.01 – 0.07
Beerd Poland 35 — — — 0.02 — — 0.00004 — 91
0.01 – 0.04 0.00002 – 0.0001
Red winesd Brazil — — — — 0.18–0.46 — — — 0.04–0.1 51
Red winesd Portugal — — — 0.08 – 0.4 — — — 0.07 – 0.15 51
Red winesd Chile — — — 0.25 — — — 0.08 51
White winesd Brazil — — — 0.13 – 0.3 — — — 0.03 – 0.03 51
White winesd Chili — — — 0.33 — — — 0.04 51
Wined Spain 125 — — — 0.19 ± 0.08 — — — 0.05 ± 0.02 52
0.07 – 0.42 0.02 – 0.13
Wined Italy 0.000001 – 0.00001 0.000001 – 0.0001 — 0.06 – 0.23 0.000001 – 0.00001 — 0.000001 – 0.0001 0.03 – 0.24 53
2234_C007.fm Page 311 Thursday, October 26, 2006 8:28 AM
Beveragesd UK — 0.00004 < 0.00001 — 0.00001 < 0.0002 < 0.0001 0.01 7
Juices
Grapefruit juice — 0.0001 — — — 45
Lemon juice — 0.0001 — — — 45
Lime juice — 0.0001 — — — 45
Mandarin juice — 0.0001 — — — 45
Orange juice Australia 290 — 0.001 ± 0.0004 — — — 45
< 0.0001 – 0.002
Orange juice Australia 83 — 0.0001 ± 0.0001 — — — 45
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food
Alcoholic Beverages
Beerd Poland 35 — — 0.000005 — — 92
0.000002 – 0.00002
Red winesd Brazil — 0.02 — — — 51
Red winesd Portugal — 0.01 – 0.01 — — — 51
White winesd Brazil — 0.01 — — — 51
Wined Italy 0.000001 – 0.0001 0.00001 – 0.0001 0.000001 – 0.00001 0.000001 – 0.0001 0.000001 – 0.0001 53
Beveragesb UK — — < 0.000 — — 7
2234_C007.fm Page 312 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 313
such as lettuce, kohlrabi, and broccoli cultivated in contaminated areas have been
associated with levels of thallium that can exceed 0.01 mg/100 g.1,127,128
7.7.15 TITANIUM
Little information is available on levels of titanium (Ti) in food crops. Concentrations
of ca. 0.2 mg Ti/100 g were detected in cereals and vegetables but these values may
be questionable.1 Recent studies20 have reported more reliable data, with average
concentrations in onions and peas given as 0.05 and 0.08 mg Ti/100 g, respectively
(Table 7.22). The concentrations of titanium in fruit juices range from < 0.0001 to
0.002 mg/100 g, whereas the range for wines is 0.00001 to 0.02 mg/100 g (Table
7.25). According to Moreda-Piñeiro et al.,27 tea leaves are characterized by high
concentration of titanium, up to 2.63 ± 1.38 mg/100 g. Chinese tea may contain up
to 6.46 mg Ti/100 g (Table 7.23).
7.7.16 TUNGSTEN
There is little information on tungsten (W) in foods. Its concentration is low and
range from 0.0005 to 0.005 mg/100 g in vegetables, and from < 0.00003 to 0.0004
mg/100 g in rice (Table 7.21 and Table 7.22). Wines contained from 0.000001 to
0.0001 mg W/100 g (Table 7.25).
TABLE 7.26
Ce i REE in Food Crops and Beverages in µg/100 g w.w.
Name Origin n Ce Dy Er Eu Gd Ho La Lu Ref.
Peas organic Denmark 0.1 ± 0.2 0.001 ± 0.001 0.002 ± 0.002 0.1 ± 0.1 0.01 ± 0.005 — — — 20
0.0 – 1 0.0 – 0.004 0.0 – 0.01 0.01 – 0.4 0.003 – 0.02
Beerd Poland 35 — — — — — — — — 91
Wined Italy 0.001 – 0.1 0.001 – 0.01 0.001 – 0.01 0.001 – 0.01 0.001 – 0.01 0.001 – 0.01 0.001 – 0.01 — 53
REFERENCES
1. Reilly, C., Metal Contamination of Food: Its Significance for Food Quality and Human
Health, Blackwell Science, Oxford, 2002.
2. Bennet-Chambers, M., Davies, P., and Knott, B., Cadmium in aquatic ecosystems in
Western Australia; a legacy of nutrient-deficient soils, J. Environ. Manage., 57, 283,
1999.
3. Smart, G.A. and Sherlock, J.C., Chromium in foods and diets, Food Addit. Contam.,
2, 139, 1985.
4. Borigiato, E.V.M. and Martinez, F.E., Iron nutritional status is improved in Brazilian
preterm infants fed food cooked in iron pots, J. Nutr., 128, 855, 1998.
5. Rojas, E. et al., Are metals dietary carcinogens?, Mutation Res., 443, 157, 1999.
6. Coultate, T.P., Food — The Chemistry of Its Components, Royal Society of Chemistry,
Cambridge, MA, 2002.
7. Ysart, G. et al., Dietary exposure estimates of 30 elements from the U.K. total diet
study, Food Addit. Contam., 16, 391, 1999.
8. Isserliyska, D., Karadjov, G., and Agelov, A., Mineral composition of Bulgarian wheat
bread, Eur. Food Res. Technol., 213, 244, 2001.
9. Capar, G.S. and Cunningham, W.C., Element and radionuclide concentrations in food:
FDA total diet study 1991–1996, J. AOAC Int., 83, 157, 2000.
10. Skibniewska, K.A. et al., Influence of starter culture and complex dough improver
on in vitro digestibility of some minerals from bread, Current Trends in Commodity
Science, II, Poznań 2002.
11. Ekholm, P. et al., Effects of natural chelating agents on the solubility of some
physiologically important mineral elements in oat bran and oat flakes, Cereal Chem.,
77, 562, 2000.
12. Kelly, S. et al., The application of isotopic and elemental analysis to determine the
geographical origin of premium long grain rice, Eur. Food Res. Technol., 214, 72,
2002.
13. Al-Dayel Omar, A.F., Al-Kahtani Saad, A., and Hefne Jameel, A., Quantification of
trace elements in rice by ICP-MS, Asian J. Spectr., 6, 23, 2002.
14. Debski,
¸ ·
B. and Gralak, M.A., Komosa ryzowa-charakterystyka i wartosć
´ dietetyc-
·
zna, Zyw. Czlow.
⁄ Metab., XXVIII, 360, 2001.
15. Ranhotra, G.S. et al., Nutrient composition of spelt wheat, J. Food Compos. Anal.,
9, 81, 1996.
16. Kawashima, L.M. and Valente Soares, L.M. Mineral profile of raw and cooked leafy
vegetables consumed in Southern Brazil, J. Food Compos. Anal., 16, 605, 2003.
17. Mohamed, A.E., Rashed, M.N., and Mofty, A., Assessment of essential and toxic
elements in some kinds of vegetables, Ecotoxicol. Environ. Saf., 55, 251, 2003.
18. Rubio, C. et al., Mineral composition of the red and green pepper (Capsicum annuum)
from Tenerife Island, Eur. Food Res. Technol., 214, 501, 2002.
2234_C007.fm Page 317 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 317
39. Plessi, M. et al., Dietary fiber and some elements in nuts and wheat brans, J. Food
Compos. Anal., 12, 91, 1999.
40. Açkurt, F. et al., Effects of geographical origin and variety on vitamin and mineral
composition of hazelnut (Corylus avellana L.) varieties cultivated in Turkey, Food
Chem., 65, 309, 1999.
41. Ozdemir, F. and Akinci, I., Physical and nutritional properties of four major com-
mercial Turkish hazelnut varieties, J. Food Eng., 63, 341, 2004.
42. Özdemir, M. et al., Evaluation of new Turkish hybrid hazelnut (Corylus avellana L.)
varieties: fatty acid composition, α-tocopherol content, mineral composition and
stability, Food Chem., 73, 411, 2001.
43. Almazan, A.M. and Begum F., Nutrients and antinutrients in peanut greens, J. Food
Compos. Anal., 9, 375, 1996.
44. Stintzing, F.C., Schieber, A., and Carle, R., Phytochemical and nutritional significance
of cactus pear, Eur. Food Res. Technol., 212, 396, 2001.
45. Simpkins, W.A. et al., Trace elements in Australian orange juice and other products,
Food Chem., 71, 423, 2000.
46. Stuckel, J.G. and Low, N.H., The chemical composition of 80 pure maple syrup
samples produced in North America, Food Res. Int., 29, 373, 1996.
47. Fili, S.P., Oliveira, E., and Oliveira, P.V., On line digestion in a focused microwave-
assisted oven for elements determination in orange juice by inductively coupled
plasma optical emission spectrometry, J. Braz. Chem. Soc., 14, 435, 2003.
48. Cámara, M., Díez, C., and Torija, E., Chemical characterization of pineapple juices
and nectars: principal component analysis, Food Chem., 54, 93, 1995.
49. Alcázar, A. et al., Multivariate characterization of beers according to their mineral
content, Talanta, 57, 45, 2002.
50. Adam, T., Duthie, E., and Feldmann, J., Investigations into the use of copper and
other metals as indicators for the authenticity of Scotch whiskies, J. Inst. Brew., 108,
459, 2002.
51. Anjos, M.J. et al., Trace elements determination in red and white wines using total-
reflection x-ray fluorescence, Spectrochim. Acta Part B, 58, 2227, 2003.
52. Conde, J.E. et al., Characterization of bottled wines from the Tenerife island (Spain)
by their metal ion concentration, Ital. J. Food Sci., 14, 375, 2002.
53. Marengo, E. and Aceto, M., Statistical investigation of the differences in the distri-
bution of metals in Nebbiolo-based wines, Food Chem., 81, 621, 2003.
54. Offenbachr, E.G. and Pi-Sunyer, F.X., Temperature and pH effects on the release of
chromium from stainless steel into water and fruit juices, J. Adv. Food Chem., 31,
89, 1983.
55. Saner, G., The metabolic significance of dietary chromium, Nutr. Int., 2, 213, 1986.
56. Booth, C.K., Reilly, C., and Farmakalidis, E., Mineral composition of Australian
ready-to-eat breakfast cereals, J. Food Compos. Anal., 9, 135, 1996.
57. Crosby, N.T., Determination of heavy metals in food, Proc. Institute of Food Science
and Technology, 10, 65, 1977.
58. Wenlock, R.W., Buss, D.H., and Dixon, E.J., Trace nutrients. 2. Manganese in British
foods, Br. J. Nutr., 41, 253, 1979.
59. Coughlan, M.P., The role of molybdenum in human biology, J. Inherit. Metab. Dis.,
6, S7, 1983.
60. Reilly, C., The Nutritional Trace Metals, Blackwell Publishing, Oxford, 2004.
61. Smart, G.A. and Sherlock, J. C., Nickel in foods and diets, Food Addit. Contam., 4,
61, 1987.
2234_C007.fm Page 319 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 319
62. Szefer, P., Metals, Metalloids and Radionuclides in the Baltic Sea Ecosystem, Elsevier
Science B.V., Amsterdam, p. 764.
63. Capar, S.G. and Szefer, P., Determination and speciation of trace elements in foods,
in Methods of Analysis of Food Components and Additives, Otles, S., Ed., CRC Press,
Boca Raton, FL, 2005, chap. 6.
64. Kerdel-Vergas, F., The depilatory and cytotoxic action of ‘Coco de Mono’ (Lecythis
ollaria) and its relation to chronic selenosis, Econ. Bot., 20, 187, 1966.
65. Falandysz, J. and Kotecka W., Stezenia¸· metali w wybranych produktach spozywc- ·
zych Trójmiasta, Bromat. Chem. Toks., 26, 143, 1993.
66. Díaz-Alarcón, J.P., Navarro-Alarcón, M., and López-García de la Serrana H., Deter-
mination of selenium in cereals, legumes and dry fruits from southeastern Spain for
calculation of daily dietary intake, Sci. Total Environ., 184, 183, 1996.
67. Mateos, C.J., Aguilar, M.V., and Martínez-Para, M.C., Determination of the chromium
content in commercial breakfast cereals in Spain, J. Agric. Food Chem., 51, 401, 2002.
68. Nriagu, J.O. and Lin, T.-S., Trace metals in wild rice sold in the United States, Sci.
Total Environ., 172, 223, 1995.
69. Kennedy, G. and Burlingame, B., Analysis of food composition data on rice from a
plant genetic resources perspective, Food Chem., 80, 589, 2003.
70. González, M., Gallego, M., and Valcárcel, M., Determination of nickel, chromium
and cobalt in wheat flour using slurry sampling electrothermal atomic absorption
spectrometry, Talanta, 48, 1051, 1999.
71. Bonafaccia, G. et al., Trace elements in flour and bran from common and tartary
buckwheat, Food Chem., 83, 1, 2003.
72. Jorhem, L., Sundström, B., and Engman, J., Cadmium and other metals in Swedish
wheat and rye flours: longitudinal study, 1983–1997, J. AOAC Int., 84, 1984, 2001.
73. Zielinski,
´ H., Kozlowska,
⁄ H., and Lewczuk, B., Bioactive compounds in the cereal
grains before and after hydrothermal processing, Innov. Food Sci. Emerg. Technol.,
2, 159, 2001.
74. Zhang, Z.-W. et al., Lead and cadmium contents in cereals and pulses in north-eastern
China, Sci. Total Environ., 220, 137, 1998.
75. Malinowska, E. and Szefer, P., Distribution of some chemical elements in certain
grains, seeds and cereal products, in Proc. 2nd International IUPAC Symposium on
Trace Elements in Food, Kortsen, B., Bickel, M., and Grobecker, K.-H., Eds., Euro-
pean Commission, Directorate-General Joint Research Centre, Brussels, Belgium,
2004, p. 96.
76. Bellés, M. et al.., Reduction of lead concentrations in vegetables grown in Tarragona
province, Spain, as a consequence of reduction of lead in gasoline, Environ. Int., 21,
821, 1995.
77. Stalikas, C.D., Mantalovas, A.Ch., and Pilidis, G.A., Multielement concentrations in
vegetable species grown in two typical agricultural areas of Greece, Sci. Total Envi-
ron., 206, 17, 1997.
78. Cabrera, C. et al., Mineral content in legumes and nuts: contribution to the Spanish
dietary intake, Sci. Total Environ., 308, 1, 2003.
79. Anzano, J.M. et al., Zinc and manganese analysis in maize by microwave oven
digestion and flame atomic absorption spectrometry, J. Food Compos. Anal., 13, 837,
2000.
80. Tüzen, M., Determination of heavy metals in soil, mushroom and plant samples by
atomic absorption spectrometry, Microchem. J., 74, 289, 2003.
2234_C007.fm Page 320 Thursday, October 26, 2006 8:28 AM
81. Michalak, A. and Bulinski,´ R., Badania zawartosci´ niektórych pierwiastków śladow-
ych w produktach spozywczych · krajowego pochodzenia. Cz. XVII. Zawartosc ´´
wybranych pierwastków śladowych w niektórych mrozonkach · owocowych, Bromat.
Chem. Toks., 28, 29, 1995.
82. Górecka, D. et al., Ocena jakosci ´ wybranych gatunków herbat róznego· pochodzenia,
Bromat. Chem. Toks., XXXVII, 145, 2004.
83. Grembecka M. et al., Assessment of mineral composition of market coffee and its
infusions, in Proc. 2nd International IUPAC Symposium on Trace Elements in Food,
Kortsen, B., Bickel, M., and Grobecker, K.-H., Eds., European Commission, Direc-
torate-General Joint Research Centre, Brussels, Belgium, 2004, p. 94.
84. Martín, M.J., Pablos, F., and González, A.G. Characterization of green coffee varieties
according to their metal content, Anal. Chim. Acta, 358, 177, 1998.
85. Kannamkumarath, S.S. et al., HPLC–ICP–MS determination of selenium distribution
and speciation in different types of nut, Anal. Bioanal. Chem., 373, 454, 2002.
86. Grembecka, M., unpublished data, 2006.
87. Parcerisa, J. et al., Influence of variety and geographical origin on the lipid fraction
of hazelnuts (Corylus avellana L.) from Spain: (III) Oil stability, tocopherol content
and some mineral contents (Mn, Fe, Cu), Food Chem., 53, 71, 1995.
88. Anzano, J.M. and Gónzalez, P., Determination of iron and copper in peanuts by flame
atomic absorption spectrometry using acid digestion, Microchem. J., 64, 141, 2000.
89. Kreft, I., Stibilj, V., and Trkov, Z., Iodine and selenium contents in pumpkin (Cucubita
pepo L.) oil and oil-cake, Eur. Food Res. Technol., 215, 279, 2002.
90. Dugo, G. et al., Determination of Cd(II), Cu(II), Pb(II) and Zn(II) content in com-
mercial vegetable oils using derivative potentiometric stripping analysis, Food Chem.,
87, 639, 2004.
91. Wyrzykowska, B. et al., Application of ICP sector field MS and principal component
analysis for studying interdependences among 23 trace elements in Polish beers, J.
Agric. Food Chem., 49, 3425, 2001.
92. Stijve, T. and Bourqui, B., Arsenic in edible mushrooms, Deuts. Lebensm.-Runds.,
87, 307, 1991.
93. Woolson, E.A., Arsenic in cotton seed byproducts, J. Agric. Food Chem., 23, 677,
1975.
94. Rainey, C.J. et al., Daily boron intake from the American diet, J. Am. Diet. Assoc.,
99, 335, 1999.
95. Murray, F.J., A human health risk assessment of boron (boric acid and borax) in
drinking water, Regul. Toxicol. Pharmacol., 22, 221, 1995.
96. Schroeder, H.A. and Nason, A.P., Trace element analysis in clinical chemistry, Clin.
Chem., 17, 461, 1971.
97. Badmaev, V., Prakash, S., and Majeed, M., Vanadium: a review of its potential role
in the fight against diabetes, J. Altern. Compl. Med., 5, 273, 1999.
98. Hight, S.C. et al., Analysis of dietary supplements for nutritional, toxic and other
elements, J. Food Compos. Anal., 6, 121, 1993.
99. Anke, M. et al., Vanadium — an essential element for animals and humans?, in Trace
Elements in Man and Animals, Roussel, A.M., Anderson, R.A., and Favier, A.E.,
Eds., Kluwer, New York, 2000, p. 221.
100. Myron, D.R., Givand, S.H., and Nielsen, F.H., Vanadium content of selected foods
as determined by flameless atomic absorption spectroscopy, J. Agric. Food Chem.,
25, 297, 1977.
101. Koo, W.W.K., Kaplan, L.A., and Krug-Wispe, S.K., Aluminum contamination of
infant formulas, J. Parenter. Enteral. Nutr., 12, 170, 1988.
2234_C007.fm Page 321 Thursday, October 26, 2006 8:28 AM
Food Crops, Beverages, Luxury Food, Spices, and Dietary Food 321
102. Bouglé, D. et al., Concentrations en aluminum des formules pour prématurés, Arch.
Pédiatr., 46, 768, 1989.
103. Baxter, M.J., Burrell, J.A., and Massey, R. C., The aluminum content of infant formula
and tea, Food Addit. Contam., 7, 101, 1990.
104. Biégo, G.H. et al., Determination of dietary tin intake in an adult French citizen,
Arch. Environ. Contam. Toxicol., 36, 227, 1999.
105. Board, P.W., The chemistry of nitrate-induced corrosion of tinplate, Food Technol.
Aust., 25, 16, 1973.
106. González, M.M., Gallego, M., and Valcárcel, M., Determination of arsenic in wheat
flour by electrothermalatomic absorption spectrometry using a continuous precipita-
tion-dissolution flow system, Talanta, 55, 135, 2001.
107. Alam, M.G.M., Snow, E.T., and Tanaka, A., Arsenic and heavy metal contamination
of vegetables grown in Samta village, Bangladesh, Sci. Total Environ., 308, 83, 2003.
108. Müller, M., Anke, M., and Illing-Günther, H., Availability of aluminium from tea and
coffee, Z. Lebensm. Unters. Forsch. A, 205, 170, 1997.
109. Simsek,
¸ ¸ A. et al., Determination of boron in hazelnut (Corylus avellana L.) varieties
by inductively coupled plasma optical emission spectrometry and spectrophotometry,
Food Chem., 83, 293, 2003.
110. MacIntosh, D.L. et al., Dietary exposure to selected metals and pesticides, Environ.
Health Perspect., 104, 202, 1996.
111. Branca, P., Uptake of metal by canned food with length of storage, Bull. Chim. Lab.,
33, 495, 1982.
112. Shaper, A.G. et al., Effects of alcohol and smoking on blood lead in middle-age
British men, Br. Med. J., 284, 289, 1982.
113. Bourgoin, B.P. et al., Lead content in 70 brands of dietary supplements, Am. J. Public
Health, 83, 1155, 1993.
114. Capon, C.J., Mercury and selenium content and chemical form in vegetable crops
grown on sludge-amended soil, Arch. Environ. Contam. Toxicol., 10, 673, 1981.
115. Bakir, F., Methyl mercury poisoning in Iraq, Science, 181, 230, 1973.
116. Förstner, U. and Wittmann, G.T.W., Metal Pollution in the Aquatic Environment, 2nd
ed., Springer-Verlag, Berlin, 1983.
117. Phillips, D.J.H. and Rainbow, P.S., Biomonitoring of Trace Aquatic Contaminants,
Elsevier Science, London, 1993.
118. Shimbo, S. et al., Cadmium and lead contents in rice and other cereal products in
Japan in 1998–2000, Sci. Total Environ., 281, 165, 2001.
119. Fang, G. et al., Spectrophotometric determination of lead in vegetables with dibromo-
p-methyl-carboxysulfonazo, Talanta, 57, 1155, 2002.
120. Svoboda, L. et al., Leaching of cadmium, lead and mercury from fresh and differently
preserved edible mushroom, Xerocomus badius, during soaking and boiling, Food
Chem. 79, 41, 2002.
121. Svoboda, L., Zimmermannová, K., and Kalac, ˘ P., Concentrations of mercury, cad-
mium, lead and copper in fruiting bodies of edible mushrooms in an emission area
of a copper smelter and a mercury smelter, Sci. Total Environ., 246, 61, 2000.
122. Svoboda, L. and Kalac, ˘ P., Contamination of two edible Agaricus spp. mushrooms
growing in a town with cadmium, lead, and mercury, Bull. Environ. Contam. Toxicol.
71, 123, 2003.
123. Segura-Muñoz, S.I. et al., Metal levels in sugar cane (Saccharum spp.) samples from
an area under the influence of a municipal landfill and a medical waste treatment
system in Brazil, Environ. Int., 32, 52, 2006.
2234_C007.fm Page 322 Thursday, October 26, 2006 8:28 AM
124. Lisk, D.J. et al., Absorption and excretion of selenium and barium from consumption
of Brazil nuts, Nutr. Rep. Int., 38, 183, 1988.
125. Mounicou, S. et al., Concentrations and bioavailability of cadmium and lead in cocoa
powder and related products, Food Addit. Contam., 20, 343, 2003.
126. Zhoud, X. and Liu, D.-N., Chronic thallium poisoning in a rural area of Ghizhou
Province, China, J. Environ. Health, 48, 14, 1985.
127. Hislop, J.S. et al., An Assessment of Heavy Metal Pollution of Vegetables Grown
near a Secondary Lead Smelter, Rep. No. AERE 2383, Atomic Energy Research
Establishment, Harwell.
128. Richter, U., Thallium in food, Ernahrungs-Umschau, 46, 360, 1999.
129. McMahon, M., Regan, F., and Huges, H., The determination of total germanium in
real food samples including Chinese herbal remedies using graphite furnace atomic
absorption spectroscopy, Food Chem., 97, 411, 2006.
2234_C008.fm Page 323 Tuesday, October 17, 2006 1:16 PM
8 Elemental Content of
Wines
Smaragdi M. Galani-Nikolakaki and
Nikolaos G. Kallithrakas-Kontos
CONTENTS
8.1 INTRODUCTION
Wine is an ethanol-aqueous solution containing several organic and inorganic sub-
stances.1 Although its elemental content can be a source of essential minerals and
trace elements to human beings, there is also a universal concern for the heavy metals
and other trace elements present in musts and wines. The elemental content of wines
depends upon factors such as the type of ground and underground soil of the vineyard,
the climatic conditions of the geographical region (temperature, sun exposure, prox-
imity to sea, and amount of rainfall), the proximity of the vineyard to areas of high
323
2234_C008.fm Page 324 Tuesday, October 17, 2006 1:16 PM
traffic and to areas overburdened with industrial activities, the agrochemical treatment
of the vine plant, the vinification methods, the wine-processing equipment and, finally,
the type of storage container, including the type of the cork used for bottling.
Eschnauer and Neeb2 have referred to about 50 inorganic species that have been
identified in wine, including all nonmetals, the alkali metals, the alkaline earth metals,
the metalloids boron, silicon and arsenic, many heavy metals, rare earths, and natu-
rally-occurring radioactive elements. Trace and ultratrace elements are determined in
wine in an effort to investigate the sources of contamination and possible methods of
adulteration.
For decades, the adulteration of wines was easily accomplished due to its world-
wide availability and chemical consistency (high alcohol content and low pH). In
recent years, there has been an intense and systematic effort made to apply novel
techniques for accurate determination of wine authenticity and detection of possible
adulteration. For this purpose, certain elements in wine are being studied, together
with other physicochemical parameters.3–5 Several investigators have used specific
elements such as Si, Mg, Ti, Mn, Mo, U, V, Al, Sb, Co, Zn, Sr, Rb, and the rare
earth elements (REE) in order to discriminate between wine regions and wine
types.4,6–11 Although several countries have individually established maximum per-
missible levels for several elements, the International Office of Vine and Wine
(OIV)12 has established lower limits only for the following elements: As 0.2 mg/l,
Cd 0.01 mg/l, Cu 1 mg/l, Pb 0.2 mg/l, and Zn 5 mg/l.
This chapter describes briefly the sources of the most important trace elements
in wine. We also examine the role that each element plays in the wine-making
and aging processes. Table 8.1 gives the concentration range in mg/l of 20 elements
found in wine and lists those that are discussed in the text.
8.2 ALUMINUM
Aluminum toxicity and its effect on the stability of wines are two problems resulting
from excessive aluminum. The contamination of wine with aluminum may result in
spoilage due to haze formation and creation of an undesirable and unpleasant metallic
taste.13 The presence of aluminum can result in the formation of hydrogen sulfide
by the reduction of sulfur dioxide and reduction of the color of white wines to an
almost watery white condition.13,14 Average concentrations usually are from 0.50 to
0.90 mg/l,2 although in many countries the reported values have been higher. Stability
problems have risen with concentrations greater than 10 mg/l, whereas the recom-
mended upper limit is 3 mg/l.15
Grapes usually contain less than 1 mg/l,13,16 and 90% of aluminum in grape juice
is removed by yeast during fermentation.16 Musts and wines are contaminated by
contact with equipment made of aluminum or aluminum alloys and materials added
to them.2 The acidity of wine (low pH) results in the leaching of the inert aluminum
oxide film that is formed on the outer side of all aluminum surfaces. This process
is followed by the oxidation and corrosion of the aluminum, with the rate of
aluminum dissolution in wine increasing, as the pH decreases.15 Therefore, all
aluminum surfaces that come in contact with wines must be treated with a permanent
and durable inert coating.13 McKinnon et al.15 have reported that the addition of
TABLE 8.1
Range of Concentration in mg/l for the Analysis of 20 Elements in Wines
Element Range References Element Range References
bentonite in wines as a fining agent and the use of different filter aids can increase
the aluminum content by at least twofold. The fining of white wines is mainly done
with bentonite, so these wines may have higher aluminum values than red wines of
the same region and producer. Interesse et al.17 have also shown that an increase of
aluminum concentration may be due to the leaching of the metal from glass con-
tainers after a period of 9 months. The replacement of lead caps on wine bottles
with aluminum ones has resulted in the addition of aluminum in wine, due to the
aluminum migration from caps to the wine.18
The major problem of the aluminum haze appearance, which usually ranges
from faint opalescence to some type of precipitate, depends on the amount of the
metal present in the particular wine. Maximum haziness occurs at pH 3.8.13 Alumi-
num haze can be distinguished from iron and copper hazes because it dissolves on
addition of hydrochloric acid but does not react with H2O2 or H2S (ibid.).
8.3 ARSENIC
The use of arsenic compounds as pesticides and insecticides goes back to antiquity,
and there are ancient references to arsenic compounds used for vineyard spraying.19
Vines absorb arsenic from the soil in its most stable form of As(V) and about 60%
of this amount is reduced during fermentation to the highly toxic trivalent state –
As(III).20 In wines, methylarsenic acid (MAA) and dimethylarsinic acid (DMAA)
are usually in concentrations below detection limits of most analytical instruments.
The reduction of As(V) is followed by a 10 to 30% precipitation of As(III) as As2S3,
and the remaining amount stays dissolved in the wine.21
When vineyards are treated with arsenic pesticides, the corresponding wines
appear to have relatively high arsenic concentrations (up to 1 mg/l).20,22,23 Other
factors that may influence the arsenic content of wines include soil composition and
the possible corrosion of metallic caps.21 The use of arsenic pesticides has been
forbidden in all wine producing countries, but even after the prohibition of arsenic
pesticides, the uptake of large amounts of arsenic in grapes from the residue in the
soil remained a serious problem for a long time.
8.4 BORON
Boron can enter wines through two routes: (1) from the soil and (2) by application
of boron compounds to vineyards, musts, and wines.24 Boron fertilization delays
grape maturity.14 Although in some countries boron addition is illegal under wine
legislation, boron compounds are added to wines in order to prevent tartrate precip-
itation or are used as antiseptics. The compounds used for treatment of wines as
antiseptics include sodium borate, sodium borotartrate, or fluroborate.25
The OIV12-recommended upper level of boron is 80 mg/l. If the concentrations
found (expressed as boric acid) exceed 100 mg/l, the wine samples must be checked
further for possible illegal addition of boron or boron compounds.25 The estimated
intake of boron through drinks and food is around 40 mg/d, and for wine consumers,
wine can be one of the main sources of intake.25,26 It has been noted that the boron
2234_C008.fm Page 327 Tuesday, October 17, 2006 1:16 PM
content increases from musts to fresh wine and then to aged wine. This tendency
can be explained by the fact that high levels of boron can be found in grape skins,
pips, and stalks and are extracted during the maceration period.25
8.5 CALCIUM
Calcium is a natural constituent of musts and wines, necessary for the normal course
of alcoholic fermentation. The well-drained and therefore warm, calcaneous soils
produce the best wines because warmth helps vine growth and grape ripening. Also,
the grape vines cultivated in high calcium soils produce grapes with a higher
potassium and magnesium concentration than those produced in neutral or slightly
acidic soils.14
During fermentation, the Mg/Ca ratio increases as the calcium content
decreases.27 This decrease continues during the storage and the stabilization stages.28
Elevated calcium levels influence the performance of wine yeasts, resulting in fer-
mentation suppression. The problem can be solved by maintaining a high Mg/Ca
ratio.29
Calcium sources for musts and wines include the soil, the treatment of the musts
with calcium sulfate or calcium carbonate, filtering aids and pads, fining agents such
as calcium bentonite, concrete tanks for storage, and ion exchange treatment.30 When
concrete tanks are used, it seems that the high acid wines extract more calcium than
the low acid ones, especially when the tank is new.
When calcium reacts with the tartaric acid present in wine, calcium tartrate
precipitates through a process that usually lasts during the first and the second winter
of wine aging.28 The precipitation reaction occurs best at pH 3.7. It is a slow process
and occurs often after bottling.27 The presence of calcium tartrate may not affect the
real quality of wine, but its presence in bottled wines has a negative effect on
prospective consumers. Although the addition of calcium carbonate reduces the
excess acidity and stabilizes the wine, the calcium tartrate thus formed cannot be
effectively removed by chilling as potassium tartrate can be.14 McKinnon et al.31
have shown that high concentrations of polyuronic acids present in wines can inhibit
the calcium tartrate crystal formation.
8.6 CADMIUM
Although only traces of cadmium have been found in grapes, musts and wines can
be contaminated by agrochemical products such as pesticides and fungicides from
vineyards located near factory discharges, from atmospheric pollution, and from
winery processing equipment, if it is made from alloys containing cadmium. Painted
surfaces or metal joints of equipment are another source of contamination.32 The
natural cadmium content of musts is < 5 mg/l, and about two-thirds of this quantity
precipitates out during fermentation.33 During fermentation, extraction of cadmium
from the must takes place and chemical factors such as alcohol content and acidity
of the must help this type of extraction.32
2234_C008.fm Page 328 Tuesday, October 17, 2006 1:16 PM
8.8 COPPER
Trace amounts of copper in musts and wines play the role of catalyst for yeast
metabolism. Copper originates partially from enzymes, especially oxidases, which
are found in abundance on fresh grapes.38 In musts and fresh wines, copper concen-
tration is usually 0.1–0.3 mg/l.30 For concentrations greater than 0.5 mg/l there is
the possibility of haze formation.39 For concentrations equal to or greater than 1
mg/l the organoleptical properties of wine change, and when copper exceeds 9 mg/l
it becomes very toxic for the fermentation process and can either reduce its rate or
stop it at all.40
The main sources of copper in wines include the winery equipment made of
copper alloys,21 fungicides such as copper sulfate, bordeaux mixture, and zinc
thiocarbamate for spraying the vines,9,41 and the addition of copper sulfate salts
during the stage of vinification.40 Elevated copper concentrations in wines are mainly
due to the first or the second pathways.40,42
Although most dissolved copper can be converted to insoluble precipitates such
as copper sulfide during fermentation, the residual dissolved copper plays an impor-
tant role in the chemistry of wine. Copper complexes catalyze oxidation reactions
more than iron complexes.14 When the wine has suffered reduction there is mostly
Cu+ in wine leading to the appearance of copper turbidity or “browning.”39 Copper
casse appears in bottled white wines, when they contain small amounts of dissolved
copper together with sulfur dioxide, in the absence of oxygen and ferric ions.14 This
casse appears to have a bluish-white glistering hue and may add a bitter taste to the
wine.43 The exposure to light and the high temperatures accelerates the casse for-
mation.40 Copper can be removed from wines together with iron, but if a wine is
poor in iron, there is never a complete removal of copper. In this case, the wine is
treated with sodium sulfide, and copper sulfide is produced. The advantage of this
method is that if there are traces of arsenic in the wine, they are removed as well.
2234_C008.fm Page 329 Tuesday, October 17, 2006 1:16 PM
The disadvantage is that it cannot be applied with wood barrels, where oxygen
gradually converts cuprous atoms into Cu2+.39
Copper casse can be prevented with levels of copper < 0.3 mg/l, with the addition
of bentonite for protein removal from white wines and with limited SO2 addition.40
For many years, Cu (and sometimes Fe3+ and Mn3+) reduction in wines was accom-
plished with the addition of potassium hexacyanoferrate (II). Recently, ion exchange
techniques have been used for the removal of these metals from wines but, although
the metal reduction is successful, the organoleptic properties may also be affected.44
8.9 IRON
The presence of iron is required, among other elements, for the initiation of wine
fermentation.14 Its evaluation in wines is of major importance because of the effect
it may have on the stability of the wine, its oxidation, and its aging.45 The iron
content of wines is partly due to natural sources and partly to technological pro-
cesses.9 Natural sources include the soil, the percentage of iron in the dust covering
the berries prior to vintage, and the atmospheric pollution during the same period.
A natural source of iron in the berries is mitochondria, which are composed of
iron–porphyrin–protein complexes, and they degrade during wine fermentation,
releasing iron into the wine.38
A significant amount of the iron content of must is lost during fermentation
because it is used by the yeast growth.30 The percentage of iron lost through this
route varies from 25 to 80%, depending on the amount of yeast present during
fermentation, on the degree of aeration of the must, on the presence or absence of
polyphenolic compounds, and the presence of coloring material. Fresh wines with
no contact with equipment made from iron or iron alloys have iron content around
1 to 5 mg/l. For the cases where steel equipment has been used (pumps, tubes, or
iron containers), normal iron concentrations vary from 10 to 30 mg/l.30 An acceptable
concentration of iron in wine is considered to be around 4 to 5 mg/l. Concentrations
higher than 10 mg/l are more likely to cause cloudiness or color change.14,39
The yeast requires about 1 to 5 g/l of trace elements including iron. In such
concentrations, iron plays a very important role for metabolism as enzyme initiator,
stabilizer, and as necessary constituent of proteins. If the concentrations become a
little higher (7 to 10 mg/l), the role of iron changes. It catalyzes oxidation of the
wine, taking part in the creation of tannins and phosphoric salts that destroy certain
characteristics of the wine such as clarity, flavor, and color.40
The oxidation state of iron in wine depends on the redox conditions of the wine.
Under reducing conditions, as in the case of bottled wines, iron is mostly present
as Fe(II) (80 to 95%), whereas Fe(III) is usually present as complex molecules with
organic ligands and in much lower concentrations. On the other hand, the aerated
wines exhibit higher concentrations of Fe(III).39,45
The technological sources that introduce iron in wines include the corrosion of
vinification equipment and steel containers used for the transfer of berries or must.38
Excess iron in wine results in the formation of the white precipitate
(FePO4.2H2O) with phosphate ions. Ferric phosphate is a colloidal substance
that coagulates under the influence of calcium, potassium ions, and proteins and
2234_C008.fm Page 330 Tuesday, October 17, 2006 1:16 PM
8.10 LEAD
Wine is one of the main sources for the lead exposure of human beings. Lead
poisoning from homemade wine has been reported even during the twenty-first
century.48 It was found that the absorbance of lead from food by adults is around
10% whereas the absorption rate from beer is about 20%. Assuming that the absor-
bance of lead from wine is the same as from beer, around 20%, we can estimate the
amount of lead, that an adult absorbs weekly from consuming wine or beer. The
possible increase of lead concentration in the wine or the increase of wine consump-
tion becomes a significant source of lead intake.49
Lead should not be found in normal musts and wines, and its existence in either
medium indicates one or more of three possible sources of contamination: (1) the
soil, (2) the atmosphere, and (3) the technological sources due to the equipment
used for the handling of these products during the harvesting, the pressing, the
fermentation, and the bottling periods.50 Such sources include soil and air polluted
with lead from cars, lead sprays used in vineyards, unlined cement tanks, lead-based
paints, lead-containing metals in several kinds of vinification equipment, lead in
filter pads and in bentonite, several fining compounds, lead capsules in wine bottles,
and lead-containing crystal decanters and glasses.14,51
Vines should not be cultivated in regions rich in lead minerals because it has
been found that the corresponding wines contain lead in high concentrations.51 The
regions around industrial installations producing lead batteries or handling lead
compounds and alloys should not be used for grapevines.51 For many years, the use
of certain agrochemicals such as insecticide lead arsenate, the fungicide copper
sulphate (containing traces of lead), and the fertilizer superphosphate have been
2234_C008.fm Page 331 Tuesday, October 17, 2006 1:16 PM
major sources of contamination for vines and grapes.52 The following inferences
have been made by Stockley et al:52
1. About 40% of the lead available for plant absorption in the top 30 cm of
soil is accumulated in the 10 cm surface layer of the ground.
2. The concentration of lead in grape berries is about 400 times less than
that of the corresponding soil.
3. The lead content of the grape juice is about 10 times less than that of the
whole grape berries.
4. The concentration of lead in wine is approximately 20 times higher than
that of the corresponding grape juice.52
compounds can be produced by prolonged contact of the cap with the wine, espe-
cially when the bottles are stored on their side. The pH of a wine, as well as the
porosity of the cork, are two of the major parameters that influence the degree of
the metal cap deterioration.58 Such capsules were banned by the U.S. Food and Drug
Administration (FDA) in 1996, but bottles sealed in this manner may still be around.
8.12 MAGNESIUM
Magnesium is a natural constituent of musts. Magnesium plays a key role during
several stages of the glycolytic cycle, together with K, Zn, Co, I, Fe, Ca, Cu, P, and
S, over 20 enzymes, and 6 coenzymes. For growth alone, yeasts require Cu, Fe, Mg,
K, P, and S, which they find in satisfactory amounts in musts.14 The concentration
of magnesium in wine depends on the grape variety,60 the rate of pressing, the pH,
the time and temperature at which the maceration process takes place, the addition
of carbonates as disacidificants, the wine storage in concrete tanks, the relative
concentration of alcohols and other constituents, and the use of ion-exchange res-
ins.14,27,42 The taste and the tartrate stability of wine are also affected by the amount
of magnesium present.27
8.13 MANGANESE
Manganese is a natural wine constituent. The amount found in wines depends on
the corresponding soil composition, the subsequent absorption by the vine, the
atmospheric contamination, the use of herbicides, the process of wine making, and
the fining agents added.46 Manganese together with iron is responsible for the
browning of white wines. When manganese concentrations are 0.8 mg/l, there is a
strong possibility for browning formation to occur if there is also an increase in iron
concentration.46 Cacho et al.61 have shown that manganese in wine helps the forma-
tion of acetaldehyde, whereas the iron present catalyzes the reaction of acetaldehyde
with the polyphenolic compounds to form polymers that precipitate out. Benítez et
al.46 have found that in “fino” sherry wine, the two metals act synergistically. Iron
acts as catalyst for the browning process in the presence of manganese. Elimination
of browning can be achieved if there is a simultaneous elimination of the manganese
and iron content.
Manganese is also one of the metals often used to differentiate wines according
to their geographical origin.5,8-10,62
2234_C008.fm Page 333 Tuesday, October 17, 2006 1:16 PM
8.14 PLATINUM
The necessity for platinum analyses in wine became an issue with the widespread
introduction of vehicles equipped with catalytic converters. Other anthropogenic
pollution sources include fertilizers and therapeutics, active charcoal, and bento-
nite.63 Concentrations of platinum found in wines vary from 0.0005 to 0.0024 µg/l.63
8.15 POTASSIUM
Potassium is required for yeast growth and fermentation and constitutes about 75%
of the total cation content of wines.14 Its concentration in musts and wines is
influenced by soil, climate, grape variety, time of harvest, temperature of fermenta-
tion, storage conditions, percentage of alcohol, pH, ion-exchange resins, and fining
agents.30 Grapes grown on alkaline chalky soils contain more K and Mg than those
from neutral or slightly acidic soils14
The potassium content of wines is increased by pressing, by addition of potas-
sium caseinate used for wine fining,14 and by addition of potassium metabisulfite or
carbonate to the crushed grapes during vinification.9 Red wines have a higher
potassium content than white ones.14
Potassium reacts with tartaric acid to form potassium bitartrate, an unstable
compound that precipitates under certain conditions during vinification and preser-
vation.30 Excess potassium ions can be removed almost completely by using ion
exchange resins charged with sodium or hydrogen atoms.14 The potassium content
of wine can be used, together with other properties or characteristics, for the deter-
mination of the geographical origin and the variety of the wine.5
8.16 SODIUM
The interest of enologists in the sodium content of wines started when it was reported
that people suffering from hypertension should be on low sodium diets. The sources
of sodium in wine can be natural or industrial. Proximity to the sea constitutes a
major natural source whereas artificial sources include addition of several sodium
compounds in wine and use of ion exchangers.30 Sodium bisulfite in dilute sulfuric
acid is used for keeping the tanks or barrels in good condition, sodium caseinate as
fining agent for clarification of wine, sodium carbonate for reducing the natural
acidity of wines, and sodium metabisulfite for sterilizing and preserving wines,
whereas the sodium salt of ascorbic acid is a sterilizing and preserving agent, which
can also be used for inhibition of secondary fermentation and mold growth.14
Sodium ion-exchange resins are used for the removal of excess potassium,
magnesium, calcium, and tartrate without changing the pH of the wine. When the
wine is treated with the hydrogen form of the resin, sodium is also removed, and
the wine becomes more acidic. Sometimes, a combination of the two types of resins
are used to give the desired result.14
2234_C008.fm Page 334 Tuesday, October 17, 2006 1:16 PM
8.17 STRONTIUM
Strontium in wines is associated with the vineyard soil composition and used for
assessing wine authenticity.8,10,64 Almeida et al.64 have shown that the release of
strontium into the must from grape skins and seeds results in wines with higher
strontium concentrations than the corresponding grape juice. They also observed
that the 87Sr/86Sr isotope ratio was statistically identical in wines and soil and, hence,
can be used as tracer of wine origin.64
8.18 TIN
Tin is seldom found in wines, and its presence, when detected, is due to contact of
wine with tin utensils or tin-plated equipment or containers. The possibility of tin
contamination should be avoided, because its presence at concentrations greater than
1 mg/l results in the formation of tin–albumin haziness. The protein precipitation
appears also by heating the tin-containing wine. Tin can also react with sulfites
present in wine, resulting in the formation of hydrogen sulfide and free sulfur.14
8.19 ZINC
In vines and musts, zinc originates from soil, from fungicides, and insecticides
used, such as Bordeaux mixture and zinc thiocarbamates, and from vinification
equipment.9 Low zinc concentrations in wines play a vital role during fermentation,
whereas high concentrations influence badly its organoleptic properties.65 Zinc can
create cloudiness if its concentration exceeds the recommended limit of 5 mg/l,
established by OIV.10 The haziness due to excess of zinc can be treated effectively
with the careful addition of blue fining (potassium ferrocyanide).66 Karadjova et
al.47 have found that less than 15% of the zinc present in wines is complexed with
polyphenols, whereas more than 60% of the same metal is present as an active
labile ion.
REFERENCES
1. Cabrera-Vique, C. et al., Determination and levels of chromium in French wine and
grapes by graphite atomic absorption spectrometry, J. Agric. Food Chem., 45 1808,
1997.
2. Eschnauer, H., and Neeb, R., Micro-element analysis in wine and grapes, in Wine
Analysis, 6, Linskens, H.F. and Jackson, J.F., Eds., Springer-Verlag, Berlin, Heidel-
berg, New York, London, Paris, Tokyo, 1988, p. 67.
3. Moret, I., Scarpini, G., and Cescon P., Chemometric characterization and classifica-
tion of five Venetian white wines, J. Agric. Food Chem., 42, 1143, 1994.
4. Almeida, C.M.R. and Vasconcelos, M.T.S.D., Multielement composition of wines
and their precursors including provenance soil and their potentialities as fingerprints
of wine origin, J. Agric. Food Chem., 51, 4788, 2003.
2234_C008.fm Page 335 Tuesday, October 17, 2006 1:16 PM
5. Arvanitoyannis, I.S. et al., Application of quality control methods for assessing wine
authenticity: use of multivariate analysis (chemometrics), Trends Food Sci. Technol.,
10, 321, 1999.
6. Jakubowski, N., et. al., Analysis of wines by ICP-MS: is the pattern of the rare earth
elements a reliable fingerprint for the provenance?, Fresenius J. Anal. Chem., 364,
424, 1999.
7. Barbaste M. et al., Analysis and comparison of SIMCA models for denominations
of origin of wines from de Canary Islands (Spain) builds by means of their trace and
ultratrace metals content, Anal. Chim. Acta, 61, 472, 2002.
8. Taylor, V.F., Longerich, H.P., and Greenough, J.D., Multielement analysis of Canadian
wines by inductively coupled mass spectrometry (ICP-MS) and multivariate statistics,
J. Agric. Food Chem., 51, 856, 2003.
9. Marengo, E. and Aceto, M., Statistical investigation of the differences in the distri-
bution of metals in Nebbiolo-based wines, Food Chem., 81, 621, 2003.
10. Díaz, C., Application of multivariate analysis and artificial neural networks for the
differentiation of red wines from Canary Islands according to the island of origin, J.
Agric. Food Chem., 51, 4303, 2003.
11. Frías, S. et al., Classification of commercial wines from the Canary Islands (Spain)
by chemometric techniques using metallic contents, Talanta, 59, 335, 2003.
12. O.I.V. Office International de la Vigne et du Vin Recueils des Methodes Interntionals
d’Analyse des Vins et des Mouts, Paris, 1990.
13. Rankine, B., Aluminum haze in wine, The Australian Grapegrower and Winemaker,
18, 1983.
14. Amerine, M.A., Berg, H.W., and Cruess, W.V., The Technology of Wine Making, The
AVI Publishing Co, INC, Westport, CT, 1972, chaps. 3, 5, 6, 15.
15. McKinnon, A.J., Cattrall, R.W., and Scollary, G.R., Aluminum haze in wine-its
measurement and identification of major sources, Am. J. Enol. Vitic., 43, 166, 1992.
16. Rankine, B., Aluminum haze in wine, Aust. Wine, Brew. Spirit Rev., 15, 1962.
17. Interesse, F.S., Lamparelli F., and Allogio V., Mineral contents of some southern
Italian wines, Z. Lebensm. Unters. Forsch., 178, 272, 1994.
18. Larroque, M. and Cabanis, J.C., Determination of aluminum in wines by direct
graphite furnace atomic absorption spectrometry, J. AOAC Int., 77, 463, 1994.
19. Nriagu, J.O. and Azcue, J.M., Food contamination with arsenic in the environment,
in Food Contamination from Environmental Sources, Nriagu, J.O. and Simmons,
M.S., Eds., John Wiley & Sons, New York, 1990, chap. 5.
20. Crecelius, E.A., Arsenite and arsenate levels in wine, Bull. Environ. Contam. Toxicol.,
18, 227, 1977.
21. Eschnauer, H.R. and Stoeppler, M., Wine: an enological specimen bank, in Hazardous
Metals in the Environment, Stoppler, M., Ed., Elsevier, Amsterdam, London, New
York, Tokyo, 1992, chap. 4.
22. Noble, A.C. et al., Trace element analysis of wine by proton-induced x-Ray fluores-
cence spectrometry, J. Agric. Food Chem., 24, 532, 1976.
23. Handson, D.P., Lead and arsenic levels in wines produced from vineyards where lead
arsenate sprays are used for caterpillar control, J. Sci. Food Agric., 35, 215, 1984.
24. Sanz, J. et al., Use of methyl borate generation-flame emission spectrometry combined
technique for boron determination in wine, Analusis, 18, 279, 1990.
25. Hernández, G.G., de La Torre, and León, J.J.A., Boron sulphate, chloride and phos-
phate contents in musts and wine of the Tacoronte-Acentejo D.O.C. region (Canary
Islands), Food Chem., 60, 339, 1997.
2234_C008.fm Page 336 Tuesday, October 17, 2006 1:16 PM
26. Lutz, O., Ascertainment of boric acid esters in wine by 11B NMR, Naturwissen-
schaften, 78, 67, 1991.
27. Themelis, D.G. et al., Direct and selective flow injection method for the simultaneous
spectrophotometric determination of calcium and magnesium in red and white wines
using in line dissolution based on “zone sampling,” J .Agric. Food. Chem., 49, 5152,
2001.
28. Baluja-Santos, C., Gonzelez-Portal, A., and Bermejo-Martinez, F., Evolution of ana-
lytical methods for the determination of calcium and magnesium in wines, Analyst,
109, 797, 1984.
29. Birch, R.M., Ciani, M., and Walker, G.M., Magnesium, calcium and fermentative
metabolism in wine yeasts, J. Wine Res., 14, 3, 2003.
30. Amerine, M.A. and Ough, C.S., Methods for Analysis of Musts and Wines, John Wiley
& Sons, New York, Chichester, Brisbane, Toronto, 1980, chap. 9.
31. McKinnon, A.J., Williams, P.J., and Scollary, G.R., Influence of uronic acids on the
spontaneous precipitation of calcium L-(+)-tartrate in a model wine solution, J. Agric.
Food Chem., 44, 1382, 1996.
32. Mena, C. et al., Cadmium levels in wine, beer and other alcoholic beverages: possible
sources of contamination, Sci. Total Environ., 181, 201, 1996.
33. Danilatos, N. and Salaxa-Moutsopoulou, M., Amount of trace elements in Greek
wines. I Lead and cadmium, Hellenica Georgika Chronika, 3, 87, 1983 (in Greek).
34. Eschnauer, H., Trace elements in must and wine primary and secondary contents,
Am. J. Enol. Vitic., 33, 226, 1982.
35. Carvalho, M.L. et al., Study of heavy metals in Madeira wine by total reflection x-ray
fluorescence analysis, X-Ray Spectrom., 25, 29, 1996.
36. Lazos, E.S. and Alexakis, A., Metal ion content of some Greek wines, Int. J. Food
Sci. Technol., 24, 39, 1989.
37. Boulet, D. et al., The development of behaviour of wine consumption in France,
Ovinis infos, 26, 72, 1995.
38. Hsia, C.L., Plank R.W., and Nagel C.W., Influence of must processing on iron and
copper contents of experimental wines, Am. J. Enol. Vitic., 26, 57, 1975.
39. Tsakiris, A., Oenology: From Grape to Wine, Psihalou, Athens, 1994, p. 179 (in
Greek).
40. Zoeklein, B.W. et al., Production Wine Analysis, Chapman and Hall, New York,
London, 1990, chaps. 14–16.
41. Almeida, A. A., Cardoso, M. I., and Lima, J. L. F. C., Determination of copper in
Port wine and Madeira wine by electrothermal atomization AAS, At. Spectrosc., 73,
1994.
42. Pérez-Magariño, S., Ortega-Heras, M., and González-San José, M.L., Multivariate
classification of rosé wines from different Spanish protected designations of origin,
Anal. Chim. Acta, 458, 187, 2002.
43. Kontos, G., Technology of Wine Making, Lyhnos, Athens, 1980, p. 64 (in Greek).
44. Benítez, P. et al., Influence of metallic content of fino sherry wine on its susceptibility
to browning, Food Res. Int., 35, 785, 2002.
45. Costa, R.C.D.C. and Araújo, A.N., Determination of Fe(III) and total Fe in wines by
sequential injection analysis and flame atomic absorption spectrometry, Anal. Chim.
Acta, 438, 227, 2001.
46. Benítez, P., Castro, R., and Barroso, C.G., Removal of iron, copper and manganese
from white wines through ion exchange techniques: effects on their organoleptic
characteristics and susceptibility to browning, Anal. Chim. Acta, 458, 197, 2002.
2234_C008.fm Page 337 Tuesday, October 17, 2006 1:16 PM
47. Karadjova, I., Izgi, B., and Gucer, S., Fractionation and speciation of Cu, Zn, and Fe
in wine samples by atomic absorption spectrometry, Spectrochim. Acta Part B, 57,
581, 2002.
48. Mangas, S., Visvanathan, R., and Alphen, M., Lead poisoning from homemade wine:
a case study, Environ. Health Perspect., 109, 433, 2001.
49. Smart, G.A., Pickford, C.J., and Sherlock, J.C., Lead in alcoholic beverages: a second
survey, Food Addit. Contam., 7, 93, 1990.
50. Edwards, M.A. and Amerine M.A., Lead content of wines determined by atomic
absorption spectrophotometry using flameless atomization, Am. J. Enol. Vitic., 28,
239, 1977.
51. Kourakou-Dragona, S., Choices in Oenology, 1st ed., Troxalia, Athens, 1997, 57 (in
Greek).
52. Stockley, C.S. et al., The relationship between vineyard soil lead concentration of
lead in grape berries, Aust. J. Grape Wine Res., 3, 127, 1997.
53. Teissedre, P.L. et al., On the origin of organolead compounds in wine, Sci. Total
Environ., 153, 247, 1994.
54. Mena, C.M. et al., Determination of lead contamination in Spanish wines and other
alcoholic beverages by flow injection atomic absorption, J. Agric. Food Chem., 45,
1812, 1997.
55. Teissdre, P.L., Cabanis, M.T., and Cabanis J.C., Comparaison de deux méthodes de
minéralisation en vue du dosage du plomb par spectrométrie d’absorption atomique
électrothermique, Applicationà des échantillons de sols, feuilles de vignes, raisins,
moûts, marcs et lies, Analusis, 21, 249, 1993.
56. Vasconcelos, M.T., Azenha, M., and De Freitas V., Electrochemical studies of com-
plexation of Pb in red wines, Analyst, 125, 743, 2000.
57. McKinnon, A.J. and Scollary, G.R., Size fractionation of metals in wine using ultra-
filtration, Talanta, 44, 1649, 1997.
58. Wai, C.M., Knowles, C.R., and Keely J.F., Lead caps on wine bottles and their
potential problems, Bull. Environ. Contam. Toxicol., 21, 2, 1979.
59. Zerbinati, O., Balduzzi, F., and Dell’Oro, V., Determination of lithium in wines by
ion chromatography, J. Chromatogr. A, 881, 645, 2000.
60. Sauvage, L. et.al., Trace metal studies of selected white wines: an alternative
approach, Anal. Chim. Acta, 458, 223, 2002.
61. Cacho J. et al., Iron, copper, and manganese influence on wine oxidation, Am. J.
Enol. Vitic., 46, 380, 1995.
62. Frías, S. et al., Metallic content of wines from the Canary Islands (Spain): application
of artificial neural networks to the data analysis, Nahrung/Food, 46, 370, 2002.
63. Alt, F. et al., A contribution to the ecology and enology of platinum, Fresenius J.
Anal. Chem., 357, 1013, 1997.
64. Almeida, C.M.R. and Vasconcelos, M.T.S.D., Does the wine making process influence
the wine 87Sr/86Sr? A case study, Food Chem., 85, 7, 2004.
65. Salvo, F. et al., Influence of different mineral and organic pesticide treatments on
Cd(II), Cu(II), Pb(II) and Zn(II) contents determined by derivative potentiometric
stripping analysis in Italian white and red wines, J. Agric. Food Chem., 51, 1090, 2003.
66. Peynaud, E., Knowing and Making Wine, John Wiley & Sons, New York, Chichester,
Brisbane, Toronto, Singapore, 1984, chaps. 26, 29.
67. Baxter, M.J. et. al., The determination of the authenticity of wine from its trace
element composition, Food Chem., 60, 443, 1997.
2234_C008.fm Page 338 Tuesday, October 17, 2006 1:16 PM
68. Brescia, M.A. et. al., Chemomertic classificationof Apulian and Slovenian wines
using 1H NMR and ICP-OES together with HPICE data, J. Agric. Food Chem., 55,
21, 2003.
69. Buldini, P.L., Cavalli, S., and Sharma, J.L., Determination of transition metals in
wine by IC, DPASV-DPCSV and ZGFAAS coupled with UV photolysis, J. Agric.
Food Chem., 47, 1993, 1999.
70. Galani-Nikolakaki, S., Kallithrakas-Kontos, N., and Katsanos, A.A., Trace element
analysis of Cretan wines and wine products, Sci. Total Environ., 285, 155, 2002.
71. Peña, R.M. et. al., Pattern recognition analysis applied to classification of Galician
(NW Spain) wines with certified brand of origin Ribeira Sacra, J. Sci. Food Agric.,
79, 2052, 1999.
72. Rebolo, S. et al., Characterisation of Galician (NW Spain) Ribeira Sacra wines using
pattern recognition analysis, Anal. Chim. Acta, 417, 211, 2000.
73. Thiel, G. and Danzer, K., Direct analysis of mineral components in wine by induc-
tively coupled plasma optical emission spectrometry (ICP-OES), Fresenius J. Anal.
Chem., 357, 553, 1997.
74. Almeida, C.M.R. et. al., ICP-MS multi-element analysis of wine samples — a com-
parative study of the methodologies used in two laboratories, Anal. Bioanal. Chem.,
374, 314, 2002.
75. Almeida, C.M. and Vanconcelos, M.T.S.D., Advantages and limitations of the semi-
quantitative operation mode of an inductively coupled plasma-mass spectrometer for
multi-element analysis of wines, Anal. Chim. Acta, 463, 65, 2002.
2234_C009.fm Page 339 Thursday, October 26, 2006 8:34 AM
CONTENTS
…any substance not intentionally added to food, which is present in such food as a
result of the production (including operations carried out in crop husbandry, animal
husbandry and veterinary medicine), manufacture, processing, preparation, treatment,
packing, packaging, transport or holding of such food or as a result of environmental
contamination. The term does not include insect fragments, rodent hairs and other
extraneous matter.
339
2234_C009.fm Page 340 Thursday, October 26, 2006 8:34 AM
The directive also establishes that all articles intended for food use shall be
explicitly labeled “for food use” or bear the corresponding symbol (a glass and a
fork) as stated by Directive 80/590/EEC.10 There are specific directives for three
groups of materials and articles: plastics, regenerated cellulose films, and ceramics.
In addition, there are other prepromulgation rules issued by the Council of Europe
(CoE) or by European Committee for Standardization (CEN). The CoE promulgates
resolutions and guidelines that are not binding for member states but constitute a
common legal reference. The CEN issued EU standards of reference to be included
in the EU directives.
The Food and Drug Administration (FDA),11 in Title 21, Parts 170–190, regulates
substances intended to make contact with foodstuffs. They are classified as direct
and indirect food additives. In the area of the indirect food additives (Parts 174–178)
adhesives, coatings components, paper, paperboards and polymers are considered.
The section highlights the chemical characteristics of substances and the authorized
commodities with some use limitations (similar to EU positive lists) and the allowed
analytical methods. Migration tests with liquid simulants, at different temperatures
and time conditions, are expected for polymers and papers intended for food pack-
aging applications.
2234_C009.fm Page 341 Thursday, October 26, 2006 8:34 AM
The level of migration of the metals into foodstuffs should be determined under
conditions that represent the worst case scenario. It is recommended that the max-
imum potential release of metals into foodstuffs should be evaluated, according to
protocols described in the Appendix of the Directive 97/48/EC19 with the exception
of the acidic foodstuffs. At present, there are many ongoing research programs for
selecting the most appropriate test to replace the traditional (now outdated) acetic
acid 3% test. Any procedure for the determination of heavy metals concentration in
foodstuffs and food simulants has to be adequately validated to gain the status of
“reference method.”
containing printing inks, adhesives, or “stickies” that come from paper not used in
food contact applications.
Guidelines on test conditions and methods of analysis for paper and board
materials and articles intended to come into contact with foodstuffs, and paper and
board materials and articles made from recycled fibers are given. The document also
gives a guide for good manufacturing practice (GMP).
Paper and paper derivatives are used extensively in food packagings all over the
world. Paper packagings are more inexpensive and have high quality standards of
safety of use.54 Like plastic materials, toxicological effects of heavy metals generally
occur at higher concentrations than expected in most packaging materials (at µg/g
levels). Analytical methods used for trace elements analysis of paper and paper board
are similar to those of plastic materials (e.g., AAS and ICP) and have been the
subject of many exhaustive reviews.55–57 Several studies determine the total trace
elements concentrations in food packaging paper. This method involves acid diges-
tion to mineralize the matrix and then liberates the elements before their analysis.55–58
Castle et al.59 report a multielement screening by semiquantitative ICP-MS for 10
paper and board samples previously digested in a pressure bomb. Results show that
As and Hg were not detected in all samples (LODs were 1.8 and 0.4 µg/g, respec-
tively). Cadmium was detected in 2 samples only: teabag tissue and unbleached
Kraft paper at 0.3 µg/g (LOD = 0.1 µg/g). There were 7 out of 10 samples in the
range from 1.1 to 7.8 µg/g for total Cr (LOD = 1.0 µg/g). Lead was also detected
in 9 out of 10 samples in the range of 0.3–6.6 µg/g (LOD = 0.1 µg/g). Also, Cd
levels were too low in digested food packaging papers (candy wrappers, tea bags,
flour sacks, kitchen towels, etc.), and it can be concluded that the health risk from
exposure to this source of Cd is negligible.60
Other publications have described the heavy metals in paper and paperboard
packaging after a migration test in a contact liquid (usually acetic acid 3%). Methods
of preparation of paper and board samples were well described,61–62 i.e., the content
of heavy metals in food packaging paper boards should be determined only on the
internal (back) side in direct contact with food.
Conti and Botrè61 conducted heavy metals migration (3% acetic acid) tests in 7
samples of food packaging papers and reported the following results: n.d.–4.38;
n.d.–0.11; n.d.–0.52, and 0.13–0.22 µg/g of Pb, Cd, total Cr, and Cr(VI), respectively.
Conti62 also reports data on migration (3% acetic acid) tests for 15 food packaging
paper boards. The results were in the range: n.d.–2.37, n.d.–0.08, n.d.–0.51, and
0.024–0.033 µg/g of Pb, Cd, total Cr, and Cr(VI), respectively. Mercury was not
detected for any samples of paper and paper boards. The LODs in Conti’s62 study
were [Pb] < 4 µg/l, [Cd ] < 0.1 µg/l, [Cr] < 4 µg/l, and [Hg] < 1 µg/l in the contact
liquid. These studies show that substantial amounts of heavy metals are present in
some of the assayed samples. Metals that have been detected in higher concentrations
are primarily Pb and Cd whereas the levels of Cr are in most samples below the
detection limits. Cr(VI) can be present at very low levels. It should be noted that
where the product is made with 100% of virgin pulp, heavy metals are rarely detected
(e.g., pizza samples).
At present, EU countries are promoting the recycling of cellulose fibers. Accord-
ing to European Declaration on Paper Recovery,63 the amount of used paper that
2234_C009.fm Page 347 Thursday, October 26, 2006 8:34 AM
was recycled was 48.7% in 2000, and it is expected to reach 56% in 2005 in Europe.
Paper pulp has a remarkable capability to absorb high quantities of heavy metals
even during short time exposures. Recycled pulps usually contain higher heavy
metals concentrations than primary pulps.64 In a laboratory test,65 the percentage of
migrated cadmium into a virgin conifer’s pulp was found to be between 30% and
90% of initial reference solutions. There is a need of analytical methods and kinetics
of migration studies with the aim to identify and quantify residues of concern in
paper and paperboard.66,67 Odorous substances can be present in paperboard food
packaging and can cause tainting of the packaged food products.68 Also, microbio-
logical quality should be a very important purity test of recycled fiber materials.69
Sankey diagrams are useful tools to represent balances of heavy metal loads in paper
making process that uses waste paper as raw material.70
Conti et al.71 studied 14 samples of paper produced with “second use” fibers
from different types of waste paper and migration tests were conducted (3% acetic
acid). The Pb range was 0.8 to 37.2 µg/g in 7 samples out of 14. The Cd levels in
11 samples out of 14 were in the range of 0.01 to 0.37 µg/g. Total Cr concentration
(3 samples out of 14) was in the range of 0.67 to 2.61 µg/g; these 3 samples showed
remarkable Cr(VI) levels (0.25 to 0.34 µg/g). Mercury was not detected in any
samples (LOD = 1 µg/l in the contact liquid). The authors concluded that samples
did not come from good quality waste paper.
The de-inking process is often used in the recycling industry to enhance the
quality of the recycled paper. The ink dispersion has a negative impact on the overall
pulp brightness72 and, as mentioned above, inks can contain certain levels of heavy
metals. The increasing use of recycled fiber in a wide variety of paper applications
requires that de-inked pulp must meet always higher quality standards.73 However,
little information is available on heavy metals in recycled fiber base materials and,
to a greater extent, in food packaging papers. Several changes in EU laws and
regulations in the past decade have probably influenced the very complex data
interpretation obtained with many analytical methods. In view of this, it is also
important to consider the difficulties of establishing limits of toxicological concern.
Some metals such as Cr, Fe, Cu, and Zn are used in alloy form. Stainless steels
are iron-chromium alloys that contain high percentage of Cr (17 to 18 %) and are
widely used in food contact materials.78 Chromium has an important role in the
formation and stabilization of the passive film which acts as a very thin (few Å
thick) protective surface layer. This film confers the typical corrosion resistance of
stainless steels. Stainless steels containing Cr are used in many food-related fields:
for processing equipment (e.g., dairy, chocolate, and fruit industries), for containers
(e.g., wine tanks, brew kettles, and beer kegs), processing of dry foods (e.g., cereals,
flour, and sugar), utensils (e.g., blenders, and bread dough mixers), and kitchen
appliances (e.g., knives, spoons, forks, electric kettles, cookware, etc.).78
Kuligowski and Halperin80 have investigated the leaching of Cr(VI) of 6 sauce-
pans that were more than 1 year old. Results show that 5% acetic acid did not cause
Cr leaching from any of the saucepans. If the acid was boiled for 5 min in the
saucepans, the concentration of Cr observed was not distinguishable from the ana-
lytical background (0.035 mg/l) in 3 cases, whereas it was 2-fold higher in 2 other
cases and 8-fold higher (0.3 mg/l) in the 6th case. Offenbacher and Pi-Sunyer81 have
measured the release of Cr from stainless steel pots into acidified water. Cr-free
water was acidified with HCl to pH 2.5 and 3.0. This acidity represents pH encoun-
tered in some foods. The Cr levels in leachate were in the range of 31 to 50 ng/g
in the case of canned tomato juice, bottled pineapple juice, and lemon juice after 1-
h boiling in a stainless steel pot; no Cr leaching was observed in unacidified water.
It was concluded that Cr release from stainless steel was mainly dependent on pH
of the food or drink.
Kumar et al.82 have observed that there is no leaching of chromium into tea,
coffee, milk, or fruit juice from either old or new stainless steel bowls and tumblers
(with a Cr content 9.74 to 20.80%), whereas the leaching was 0.04 to 0.4 µg/g to
curd or lemon pickle from new utensils and 0.03 to 0.3 µg/g from old utensils.
Neither Cr nor Pb was released into water from twenty-six kettles sold on the Danish
market in a study simulating regular household use. However, 10 out of 26 kettles
released more than 50 µg/l of nickel into the water. Coffee machines similarly tested
did not show significant liberation of Pb, Cr, Ni, and Al.83
The cooking process can induce migration of trace elements. The chromium
content of crayfish hepatopancreas cooked in a stainless steel pan increased from
approximately 0.05 to 0.15 µg/g fresh weight (f.w.). The cooking process for crayfish
abdominal muscle did not reveal relevant changes in Cr concentrations compared
with the raw fish.84
New saucepans on first use have the highest rates of Cr and Ni release.85,86 After
the first two cooking operations, the highest chromium release for apricots and
rhubarb was 0.05 and 0.01 µg/g, respectively.86 Generally, the contribution of Cr
and Ni released from cooking utensils and glass pots to the average daily diet is
negligible.78,85–89 There does not appear to be significant differences in migration
observed between ferritic and austenitic stainless steels and glass pots.78,87
Chromium and its compounds are also used in electroplating and in surface
treatment of food cans. A “can” is defined as an hermetically sealed container in
which food is subjected to a “canning” process, that is, heat treatment to increase
shelf life.90 Most cans are made from tinplate, that is, a composite packaging material
2234_C009.fm Page 349 Thursday, October 26, 2006 8:34 AM
consisting of a low carbon mild steel base. To prevent oxidation, the tinplate is
“passivated” with a thin layer by the same process above described. Acidic foods
can corrode the metal, thus, cans are frequently coated internally with a lacquer that
is mostly a polymerized resin.90 At present, in Europe, about 25,000 million food
cans are produced every year; about 20% of these are unlacquered cans. The total
worldwide production for food packaging is approximately 80,000 million cans.91
The performance of the lacquered food cans is greatly affected by the coating
thickness. Low-aggressive foods such as apricots and beans require a thickness of
4 to 6 µm, whereas tomato concentrate needs a layer of 8 to 12 µm to prevent
interaction between the can and its content.
porcelain dishes can release Cd. Doemling105 reported levels of more than 0.5 µg/g
of Cd for 25% of the samples tested. At present, there are glazes that are free of Pb
and Cd in their formulation.106 An adherent glass coating for glass ceramic surfaces
for cooking food free of Cd and Pb has recently been reported.107
The FDA has recently improved methods of determination of Pb and Cd
extracted from ceramic foodware.108,109 The flame atomic absorption spectrometry
(FAAS) interlaboratory study reported excellent results in the quantification of the
metals, and the data obtained among different laboratories (0.005 to 0.019 µg/ml
for Pb and 0.0004 to 0.0019 µg/ml for Cd) were adopted as a First Action by AOAC
International.108 Since 1981, the International Organization for Standardization (ISO)
issued international regulations on ceramic foodware in contact with food.110
Instances of heavy metal poisoning from ceramic foodware surfaces remain rare,
however.
At high exposure times (nearly 5 months), it was found that 2 µg/g of Pb was
leached from a lead crystal wine glass (containing 24 wt.% lead oxide).111 Guadag-
nino et al.112 tested the Pb release from crystal glasses into some beverages (3 h of
continuous contact) and found that the release increased in the order: cola drink >
HOAc > whisky > white wine. If the number of contacts for both cola drink and
wine was increased, the Pb levels showed a steep decrease. The study concluded
that there were no significant health risks associated with ingestion of beverages in
contact with crystalware. Lead migration is strongly correlated with the hydrolytic
resistance of glass. There is a linear correlation of Pb migration after the first contact
and the Na migration from the glass.113 Many studies show that the Pb migration
from beverages decreases significantly after the first contact, similar to the results
of the 4% acetic acid tests.114–116 Lead release in acetic acid (pH = 2.39) was higher
than that for wine (pH= 3.14) because of higher pH and ethanol content of wine.117
Coca Cola has an extraction ability similar to that of 4% HOAc.118 Repeated-leaching
experiments with Pb crystal wine glasses show that total Pb released (in micrograms)
in 30 min decreased according to the following function:117,119
LR = a + b/L2
where:
LR = lead concentration in the extractant
L = contact number
a = constant depending on glass composition
b = constant depending on the characteristics of surface layer
The EC directive 94/62 regulates tolerable concentration levels of Pb, Cd, Hg,
and Cr(VI) in glass packaging.27 Recent (December 2003) guidelines on Pb leaching
from glass tableware into foodstuffs is derived from a draft resolution.119 This
document establishes fundamental principles for Pb leaching from glass hollowware
and flatware and recommends washing the food equipment before first use because
of the tendency for a high release of lead to occur at the very first contact. Lead
release decreased by nearly 20% after washing of unused crystal wine goblets.116
The weekly Pb intake attributable to lead extraction from tableware has been
2234_C009.fm Page 351 Thursday, October 26, 2006 8:34 AM
estimated as 35 µg/week, if one assumes a daily use of lead crystal stemware and
a daily consumption of 5 dL beverage.119 Glazes on the outside part of drinking
glasses can release up to 300 mg Pb/dm2 and up to 30 mg Cd/ dm2 on 24-h extraction
with 4% acetic acid.120
The data above, although still under evaluation, show that there is a need to
improve the quality control of glass analysis in the food industry. At present, the
CRM 664 is available at the Institute for Reference Materials and Measurements
(IRMM). Elements certified include As, Ba, Cd, Co, Cl, Cr, Pb, Sb, and Se.121,122 In
the absence of a standard procedure, a method was proposed to evaluate the presence
of hexavalent chromium in glasses. In this procedure, the glass sample is digested
with H2SO4 and NH4HF2, then diphenylcarbazide is added, and a pink colored
complex is obtained, which is measured with a spectrophotometer at 840 nm.123,124
Mercury in glass packaging can be determined by a CV-AAS.125
The primary source of tin is associated with the can; 78,91,100,126 in the U.K., most
dietary intake of Sn (94%) comes from canned fruit and vegetables.127 Unprocessed
foodstuffs contain generally less than 1 µg/g of Sn.78,128 The PTWI for Sn is 14
mg/kg body weight,129 and the recommended maximum permissible levels of Sn in
food are typically 150 µg/g for canned beverages and 250 µg/g (200 µg/g for the
U.K.130) in other canned foods. These levels of tin in foods can produce acute
manifestations of gastric irritation in some individuals.129 The typical organic acids
found naturally in fruits and juices such as citric acid, malic acid, and their mixture
with oxalic acid, can increase the rate of Sn liberation from tinplate cans.131 Corrosion
of tinplates is highly induced by the nitrate-containing acid foods.132 Tin is used in
alloys with Cu and Zn and to coat kitchen utensils.78 Ceramic industry uses inorganic
Sn compounds as pigments. The Cr-SnO2 pigment has long been used in the ceramic
industry.133 Plastic materials containing chlorine are stabilized by organotin com-
pounds.100
The MAAF134 has conducted a survey on the levels of Sn in canned fruits and
vegetables. All the 400 samples tested, with the exception of only 2 products, were
found to contain levels of Sn below the legal limit of the U.K. (200 µg/g). The 234
food samples packaged in unlacquered cans showed an average Sn concentration of
59 µg/g and, overall, the Sn concentrations were lower than those found in earlier
surveys.134,135 Other studies reported that tin levels in foodstuffs stored in lacquered
cans, in contrast to unlacquered cans (> 100 µg/g), were generally below 25 µg/g.128
WHO136 did not fix a threshold value in drinking water for inorganic Sn, possibly
because of its low toxicity level.
Aluminum is a ubiquitous element naturally present in foods. It constitutes
8.13% of the earth’s crust and appears in a large variety of minerals.137 Foodstuffs
and water are the main sources of Al intake in the diet. The JECFA has established
a PTWI of 7 mg Al/kg of body weight.138 The daily intake of Al from food and
beverages in adults ranges between 2.5 and 13 mg. This is nearly 90 to 95 percent
of total intake. Drinking-water may contribute roughly 0.4 mg/d according to present
international guideline values, but it is more likely to be generally around 0.2 mg/d.137
Foodstuffs that contain Al concentrations greater than 1 µg/g of food are said
to contain high values of Al;139 alkaline and salty foodstuffs can further increase the
Al intake. Usually, the levels of Al naturally present in food are very low,140,141 with
2234_C009.fm Page 352 Thursday, October 26, 2006 8:34 AM
the exception of specific plants and crops like tea leaves that naturally bioconcentrate
Al to levels of up to the 699 to 1943 µg/g found in dry leaves of some types of tea
grown on acidic soils.142–144 Mature tea leaves collected at Hong Kong accumulated
very high concentrations of Al and F (15300 and 2070 µg/g, respectively).143 A
number of studies have demonstrated that Al leaching from food plants in the
presence of fluoride is insignificant.144,145 Ingestion of Al per cup through tea (100
ml capacity) can expose one to Al doses of between 1.1 and 1.4 mg.144
Aluminum is mainly used in packaging materials such as saucepans, pressure
cookers, foils, wrappers, frozen dinner trays, cans, roasting pans, etc. Usually,
aluminum packaging materials are covered with an intermediate resin-based coating.
Thus, Al migration from coated food contact materials is negligible.78 Generally,
sauces and drinks packaged in Al coated cans at different storage times and
temperature conditions do not leach out significant amounts of Al and thus do not
represent a significant risk for human health.146,147 Sauce samples stored at 50˚C
showed slightly higher Al contents than those stored at room temperature.146 Acidic
foodstuffs such as tomatoes, cabbage, soft fruits, etc., take up more Al from the
containers than nonacidic foods. In particular, tomatoes and rhubarb in Al pans
showed a significant increase in Al levels (0.5 µg/g wet weight of raw tomatoes to
3.3 µg/g wet weight of the cooked), whereas the accumulation in prepared rice or
potatoes showed only a slight increase.148 Aluminum cans can be corroded over time
by canned beer. Beer has a pH of 4.15 and can extract Al despite the coating of the
can.149 Beer stored at room temperature (5 months at 23˚C) showed Al levels that
were significantly higher (546 and 414 µg/l in 2 brands) than those observed for
refrigerated beers (50 and 117 µg/l for 5 months at 5˚C). At the beginning of the
experiment, Al levels ranged between 50 and 118 µg/l for the 2 sampled brands.149
Cola and citrate–based drinks can also corrode Al coated cans. Ortophosphoric acid
found in some soft drinks is more corrosive than citric acid.150 Soft drinks from Al
cans are a negligible source of dietary Al intake, however. The longer the storage
period and higher the storage temperature, the more the leaching of Al from the
packaging.78,150,151
Other contributors of Al to human diet are Al containing food additives, tooth-
paste, which can contain significant amounts of Al, above all, when packed in Al
tubes, and some over-the-counter drugs such as antacids and buffered analgesics. In
this context, Lione152 has reported that the exposure to aluminum in antacids ranged
from 840 to 5000 mg/d for antacids and 130 to 730 mg/d in buffered analgesics.
This leads to an overall 2–3 fold increase with respect to the normal dietary intake.
Aluminum from cookware and uncoated articles in contact with foodstuff can
migrate into foodstuffs; e.g., uncoated Al camping bottles can release up to 7 mg/l
Al in tea acidified with lemon juice within 5 d storage.153 The leaching of Al from
aluminum cooking vessels in boiling test was 0.2 to 0.8 µg/g for boiling milk. Boiling
of tap water in an aluminum pan can result in the migration of 0.54 to 4.3 mg/l
Al.154 Muller et al.153 found levels of up to 2.6 mg/l after boiling tap water for 15
min in Al pans. In general, the rate of aluminum release depends on the water acidity
and chemical compositions of the Al utensils.155,156
Some disorders (or their correlated events) have been associated with an exces-
sive intake of Al in the human body such as dialysis, osteomalacia, fractures and
2234_C009.fm Page 353 Thursday, October 26, 2006 8:34 AM
9.6 CONCLUSIONS
Food packaging materials have changed more in the past 15 years than in the previous
150 years, with a general, marked improvement of the quality, safety and nutritional
content of packaged foods. The progress in understanding the toxicological relevance
of the presence of heavy metals in food packaging is dependent primarily on the
possibility of exactly determinating their content in selected matrices, and conse-
quently on the further development of sensitive, accurate, fast, and precise analytical
methods. The success of such analytical techniques is strictly correlated with both
the simplification of sample treatment and the reduction of the corresponding costs.
In general, electrothermal atomization has been allowed to establish sufficient
sensitivity limits for heavy metals determination in food simulants and food pack-
aging articles. GFAAS and FAAS are the more widespread techniques used in
analytical laboratories. More recently, advanced analyzers suitable for multielement
analysis, such as ICP-MS, became available. There is also the need to have more
suitable CRMs for the analytical quality control of packaging materials.
Further studies are also necessary to detail more precisely the toxicological
relevance of heavy metals in food packaging, with the aim of refining the existing
guidelines. In this view, it is mandatory to consider the rapidly growing area of metal
speciation research. The major advances of this area are coming from coupling of
the separation processes, carried out by universal techniques such as capillary elec-
trophoresis or high-performance liquid chromotography (HPLC), with dedicated
detectors for heavy metals analysis.
The improvement of analytical techniques should therefore correspond with a
constant advance in the study of the role of heavy metals in food packagings, with
special emphasis on health aspects. In this context, heavy metals limitations stated
in EU and U.S. regulations can constitute a good starting point for similar guidelines
in other countries, especially concerning those toxic heavy metals particularly rel-
evant to the risk of contamination by food packagings.
2234_C009.fm Page 354 Thursday, October 26, 2006 8:34 AM
REFERENCES
1. Codex Alimentarius Commission (1997), Procedural Manual, 10th ed., Joint
FAO/WHO Food Standards Programme, Rome.
2. Nriagu, J.O. and Pacyna, J.M., Quantitative assessment of worldwide contamination
of air, water and soils by trace metals, Nature, 333, 134, 1988.
3. Szefer, P., Metal pollutants and radionuclides in the Baltic Sea: an overview, Ocean-
ologia, 44, 129, 2002.
4. Conti, M.E. and Cecchetti, G., A biomonitoring study: trace metals in algae and
molluscs from Tyrrhenian coastal areas, Environ. Res., 93, 99, 2003.
5. Fergusson, J.E., The Heavy Elements: Chemistry, Environmental Impact and Health
Effects, Pergamon Press, Oxford, 1990.
6. Castle, L., Chemical migration from food packaging, in Food Chemical Safety —
Volume 1: Contaminants, Watson, D.H., Ed., CRC Press, Woodhead Publishing Ltd.,
2001, chap. 9.
7. Gilbert, J. and Rossi, L., European priorities for research to support legislation in the
area of food contact materials and articles, Food Addit. Contam., 17, 83, 2000.
8. EU Food Contact materials Resource Centre, http://cpf.jrc.it/webpack/, 2005.
9. Directive 89/109/EEC: European Community, Council Directive on the approxima-
tion of the laws of the Member States relating to materials and articles intended to
come into contact with foodstuffs, December 21, 1988.
10. Directive 80/590/EEC: European Community, Council directive determining the sym-
bol that may accompany materials and articles intended to come into contact with
foodstuffs, June 9, 1980.
11. Code of Federal Regulations. Title 21 Parts 170–190, http://www.access.gpo.gov/cgi-
bin/cfrassemble.cgi?title=200121.
12. Directive 2002/72/EC: European Community, Council directive relating to plastic
materials and articles intended to come into contact with foodstuffs, August 6, 2002.
13. Directive 90/128/EEC: European Community, Council directive relating to plastic
materials and articles intended to come into contact with foodstuffs, February 23,
1990.
14. O’Brien, A.P., Cooper, I., and Tice, P.A., Correlation of specific migration (Cf) of
plastics additives with their initial concentration in the polymer (Cp), Food Addit.
Contam., 14, 705, 1997.
15. Tice, P.A. and Cooper, I., Migration tests for food packaging, Food Sci. Rev., 2, 3,
1994.
16. Tice, P.A., Testing polymeric coatings on metal and paper substrates, Food Addit.
Contam., 11, 187, 1994.
17. Directive 82/711/EEC: European Community, Council directive laying down the basic
rules necessary for testing migration of the constituents of plastic materials and
articles intended to come into contact with foodstuffs, October 18, 1982.
18. Directive 93/8/EEC: European Community, Council directive amending Council
Directive 82/711/EEC laying down the basic rules necessary for testing migration of
constituents of plastic materials and articles intended to come into contact with
foodstuffs, March 15, 1993.
19. Directive 97/48/EC: European Community, Council directive amending for the sec-
ond time Council Directive 82/711/EEC laying down the basic rules necessary for
testing migration of the constituents of plastic materials and articles intended to come
into contact with foodstuffs, July 29, 1997.
2234_C009.fm Page 355 Thursday, October 26, 2006 8:34 AM
20. Mark, F.E., Metals in source separated plastics packaging waste: a European overview
— analytical methods and results, a report for the Association of Plastics Manufac-
tures in Europe (APME), November 1996.
21. Ministry of Agriculture, Fisheries and Food of U.K. (MAAF), Joint Food Safety and
Standards Group, Metallic Compounds in Plastics, Food Surveillance, Information
Sheet, No 1, July 1993.
22. Fordham, P.J. et al., Element residues in food contact plastics and their migration
into food simulants, measured by inductively-coupled plasma-mass spectrometry,
Food Addit. Contam., 12, 651,1995.
23. Zweifel, H., Ed., Plastics Additives Handbook, 5th ed., Hanser Gardner, Munich,
Germany, 2001.
24. Zweifel, H., Stabilization of Polymeric Materials State-Of-The-Art, Scope and Lim-
itations, www.sun.ac.za/unesco/PolymerED2000/Conf2000/ZweifelC(s).pdf.
25. Fordham, P.J. et al., Determination of trace elements in food contact polymers by
semi-quantitative inductively coupled plasma mass spectrometry: performance eval-
uation using alternative multi-element techniques and in house polymer reference
materials, J. Anal. At. Spectrom., 10, 303, 1995.
26. Perring, L. et al., An evaluation of analytical techniques for determination of lead,
cadmium, chromium, and mercury in food-packaging materials, Fresenius J. Anal.
Chem., 370, 76, 2001.
27. Directive 94/62/EC: European Community, Council directive on packaging and pack-
aging waste, December 20, 1994.
28. Van Borm, W., Lamberty, A., and Quevauviller, P., Collaborative study to improve
the quality control of trace element determinations in polymers, part 1: interlaboratory
study, Fresenius J. Anal. Chem., 365, 361, 1999.
29. Lamberty, A., Van Borm, W., and Quevauviller, P., Collaborative study to improve
the quality control of trace element determinations in polymers, part 2: certification
of polyethylene reference materials (CRMs 680 and 681) for As, Br, Cd, Cl, Cr, Hg,
Pb, and S content, Fresenius J. Anal. Chem., 370, 811, 2001.
30. Lamberty, A., Schimmel, H., and Pauwels, J., The study of the stability of reference
materials by isochronous measurements, Fresenius J. Anal. Chem., 360(3–4), 359,
1998.
31. Pauwels, J., Lamberty, A., and Schimmel, H., Homogeneity testing of reference
materials, Accred. Qual. Assur., 3, 51, 1998.
32. Linsinger, T.P.J. et al., Homogeneity and stability of reference materials, Accred.
Qual. Assur., 6(1), 20, 2001.
33. Thompson, D., Parry, S.J., and Benzing, R., The validation of a method for deter-
mining the migration of trace elements from food packaging materials into food, J.
Radioanal. Nucl. Chem., 217, 147, 1997.
34. Conti, M.E. et al., Biomonitoring of heavy metals and their species in the marine
environment: the contribution of atomic absorption spectroscopy and inductively
coupled plasma spectroscopy, Trends Appl. Spectrosc., 4, 295, 2002.
35. Vollrath, A. et al., Comparison of dissolution procedures for the determination of
cadmium and lead in plastics, Fresenius J. Anal. Chem., 344, 269, 1992.
36. Besecker, K.D. et al., A simple closed-vessel nitric acid digestion method for a
polyethylene/polypropylene polymer blend, At. Spectrom., 19, 193, 1998.
37. Bonn, A. and Knezevic, G., A rapid method for analysis of metals in plastic, Coating,
30, 141, 1997.
2234_C009.fm Page 356 Thursday, October 26, 2006 8:34 AM
38. Diemer, J. and Heumann, K.G., Development of an ICP-IDMS method for accurate
routine analysis of toxic heavy metals in polyolefins and comparison with results by
TI-IDMS, Fresenius J. Anal. Chem, 368, 103, 2000.
39. Kil-Yong, L. et al., An accurate and sensitive analysis of trace and ultratrace metallic
impurities in plastics by NAA, J. Radioanal. Nucl. Chem., 241(1), 129, 1999.
40. Resolution AP (89) 1: On the Use of Colorants in Plastic Materials Coming into
Contact with Food, Council of Europe, September 13, 1989, www.coe.int/soc-sp.
41. Resolution AP (96) 5: On Surface Coatings Intended to Come into Contact with Food,
Council of Europe, October 2, 1996. www.coe.int/soc-sp.
42. Partial Agreement in the Social and Public Health Field. Draft Resolution AP (2004).
RD 8/1-42, On Packaging Inks Applied to the Non Food Contact Surface of Food
Packaging Articles Intended to Come into Contact with Foodstuffs, 42nd session,
Strasbourg, December 2–5, 2003, www.coe.int/soc-sp.
43. Partial Agreement in the Social and Public Health Field, Council of Europe Draft
Technical Document No 1, RD 8/2-42, On requirements for the selection of packaging
ink raw materials applied to the non food contact surface of food packaging articles
intended to come into contact with foodstuffs, 42nd session, Strasbourg, December
2–5, 2003, www.coe.int/soc-sp.
44. Faigle, W., Lectures at the University of Printing and Media, Stuttgart/Germany,
Dittmer, C. and Mayer D.T., Eds., 1997, www.hdm-stuttgart.de/projekte/printing-
inks/inf_text.htm.
45. Davey, A.C., Printing inks for packaging applications, Adv. Col. Sci. Technol., 4, 76,
2001.
46. Brede, C., Skjevrak I., and Fjeldal, P., Colors Substances in Food Packaging Material,
SNT — Norwegian Food Control Authority, March 3, 2003, http://snt.mattilsy-
net.no/dokumentasjon/rapporter/2003/snt_arbeidsrapporter/200303.pdf.
47. Directive 91/338/EEC: European Community, Council Directive amending for the
10th time Directive 76/769/EEC on the approximation of the laws, regulations and
administrative provisions of the Member States relating to restrictions on the mar-
keting and use of certain dangerous substances and preparations, June 18, 1991.
48. Inthorn, D. et al., Factors affecting lead leaching from microwavable plastic ware
made with lead-containing pigments, J. Food Prot., 65, 1166, 2002.
49. European Council of Paint, Printing Ink and Artists’ Colors Industry (CEPE),
www.cepe.org/CEPE.htm, exclusion list for printing inks and related products, Sep-
tember 2001 (Brussels).
50. Directive 67/548/EEC: European Community, Council directive on the approximation
of laws, regulations and administrative provisions relating to the classification, pack-
aging and labeling of dangerous substances, June 27, 1967.
51. De Bruijn Boogaerd, F.H., Production of Inorganic Pigments Based on Non-Heavy
Metals, Spanish Patent WO 9700918, PCT Int. Appl., 1997.
52. DaRocha, M. et al., Analyzing for CONEG heavy metals in printing inks, Am. Ink
Maker (1923–2001), 73, 56, 58, 61–2, 64, 66, 68, 1995.
53. Resolution AP (2002) 1: On paper and board materials and articles intended to come
into contact with foodstuffs, Council of Europe, September 18, 2002,
www.coe.int/soc-sp.
54. Bureau, G. and Multon, J.L., Food Packaging Technology, Vol. 1–2, VCH, Weinheim,
1996.
55. Maeck, K., Determination of heavy metals in paper, PTS-Manuskript, (83), 7/1–7/17,
1999.
2234_C009.fm Page 357 Thursday, October 26, 2006 8:34 AM
56. Toeppel, O., Griebenow, W., and Werthmann, B., Application of atomic absorption
spectroscopy to the cellulose and paper fields. II. Developments and work towards
the production and introduction of standardized AAS methods for the study and
testing of cellulose and paper, Papier (Bingen, Germany), 31, 508, 1977.
57. Griebenow, W., Werthmann, B., and Toeppel, O., Application of atomic absorption
spectroscopy to the cellulose and paper fields. I. Principles of atomic absorption
spectroscopy and special application to the cellulose and paper fields, Papier (Bingen,
Germany), 31, 503, 1977.
58. Knezevic, G. and Kurfuerst, U., Determination of heavy metals in papers — a
comparison of methods (solid sampling and digestion analysis by graphite-tube AAS),
Fresenius Z. Anal. Chem., 322, 717, 1985.
59. Castle, L. et al., Migration studies from paper and board food packaging materials:
1. compositional analysis, Food Addit. Contam., 14, 35, 1997.
60. Griebenow, W., Werthmann, B., and Schwarz, B., Cadmium contents of food pack-
aging papers and paper in domestic use, Papier (Bingen, Germany), 39, 105, 1985.
61. Conti, M.E. and Botrè, F., The content of heavy metals in food packaging paper: an
atomic absorption spectroscopy investigation, Food Control, 8, 131, 1997.
62. Conti, M.E., The content of heavy metals in food packaging paper boards: an atomic
absorption spectroscopy investigation, Food Res. Int., 30, 343, 1997.
63. European declaration on Paper Recovery, Confederation of European Paper Industries
(CEPI), 2000, www.paperrecovery.org/files/English-164625A.pdf.
64. Jokinen, K. and Siren, K., Harmful residues in recycled fiber-metals and compounds,
Paperi ja Puu, 77, 106, 109, 1995.
65. Garcia-Gomez, C., Carbonell, G., and Tarazona, J.V., Binding of cadmium on raw
paper pulp: relationship between temperature and sorption kinetics, Chemosphere,
49, 533, 2002.
66. Triantafyllou, V.I., Akrida-Demertzi, K., and Demertzis, P.G., Migration studies from
recycled paper packaging materials: development of an analytical method for rapid
testing, Anal. Chim. Acta, 467, 253, 2002.
67. Song, Y.S., Park, H.J., and Komolprasert, V., Analytical procedure for quantifying
five compounds suspected as possible contaminants in recycled paper/paperboard for
food packaging, J. Agric. Food Chem., 48, 5856, 2000.
68. Tice, P.A. and Offen, C.P., Odors and taints from paperboard food packaging, Tappi
J., 77, 149, 1994.
69. Sipilainen-Malm, T. et al, Purity of recycled fiber-based materials, Food Addit. Con-
tam., 14, 695, 1997.
70. Hamm, U. and Goettsching, L., Heavy metals in paper making process using waste
paper as raw material: sources, depressions and valuation-criterions, Papier (Bingen,
Germany), 43, V39, 1989.
71. Conti, M.E. et al., Heavy metals and optical whitenings as quality parameters of
recycled paper for food packaging, J. Food Process. Preservation, 20, 1, 1996.
72. Seccombe, R., Brackenbury, K., and Vandenberg, D., Disperser bleaching with hydro-
gen peroxide — a tool for brightening recycled fibers, Appita Annual Conference
Proceedings, 2002, p. 229, Rotorua (New Zealand).
73. Nada, A.M.A. and Hussein, A.Y., High efficiency recycling of newsprint. Cellulose
and Paper Dep., National Research Centre, Cairo, Egypt., IPPTA, 13, 7, 2001.
74. Expert consultation WHO/FAO/IAEA: Trace Elements in Human Nutrition and
Health, World Health Organization, Geneva, 1996.
75. Anderson, R.A., Chromium, glucose intolerance and diabetes, J. Am. Coll. Nutr., 17,
548, 1998.
2234_C009.fm Page 358 Thursday, October 26, 2006 8:34 AM
76. Krejpcio, Z., Essentiality of chromium for human nutrition and health, Polish J.
Environ. Stud., 10, 399, 2001.
77. Gauglhofer, J. and Bianchi, V., Chromium, in Metals and Their Compounds in the
Environment, Merian, E., Ed., VCH, Weinheim, 1991, p. 853.
78. Partial Agreement in the Social and Public Health Field, Council of Europe, Policy
statement concerning metals and alloys, Technical Document: Guidelines on metals
and alloys used as food contact materials, February 13, 2002, www.coe.int/soc-sp.
79. Von Berg, R. and Liu, D., Chromium and hexavalent chromium, J. Appl. Toxicol.,
13, 225, 1993.
80. Kuligowski, J. and Halperin, K.M., Stainless steel cookware as a significant source
of nickel, chromium, and iron, Arch. Environ. Contam. Toxicol., 23, 211, 1992.
81. Offenbacher, E.G. and Pi-Sunyer, F.X., Temperature and pH effects on the release of
chromium from stainless steel into water and fruit juices, J. Agric. Food Chem., 31(1),
89, 1983.
82. Kumar, R., Srivastava, P.K., and Srivastava, S.P., Leaching of heavy metals (Cr, Fe,
and Ni) from stainless steel utensils in food simulants and food materials, Bull.
Environ. Contam. Toxicol., 53, 259, 1994.
83. Berg, T. et al., The release of nickel and other trace elements from electric kettles
and coffee machines, Food Addit. Contam., 17, 189, 2000.
84. Jorhem, L. et al., Trace elements in crayfish: regional differences and changes induced
by cooking, Arch. Environ. Contam. Toxicol., 26, 137, 1994.
85. Flint, G.N. and Packirisamy, S., Systemic nickel: the contribution made by stainless-
steel cooking utensils, Contact Dermatitis, 32, 218, 1995.
86. Flint, G.N. and Packirisamy, S., Purity of food cooked in stainless steel utensils, Food
Addit. Contam., 14, 115, 1997.
87. Haudrechy, P. et al., Innocuousness of stainless steels in contact with food or skin,
in Stainless Steels’96, Proceedings (2nd European Congress), Verein Deutscher
Eisenhuettenleute, Düsseldorf, June 3–5, 1996, p. 228.
88. Accominotti, M. et al., Contribution to chromium and nickel enrichment during
cooking of foods in stainless steel utensils, Contact Dermatitis, 38, 305, 1998.
89. Kawamura, Y. et al., Migration of metals from stainless steel kitchenware and table-
ware, Shokuhin Eiseigaku Zasshi, 38, 170, 1997.
90. Reilly, C., Metal Contamination of Food, 2nd ed., Elsevier Applied Science, Barking,
England, 1991.
91. Blunden, S. and Wallace, T., Tin in canned food: a review and understanding of
occurrence and effect, Food Chem. Toxicol., 41, 1651, 2003.
92. Nriagu, J. O., A silent epidemic of environmental metal poisoning?, Environ. Pollut.,
50, 139, 1988.
93. JECFA, Evaluation of Certain Food Additives and Contaminants, Fifty-third report
of the Joint FAO/WHO Expert Committee on Food Additives, World Health Organi-
zation, Technical Report Series 896, 53/81, 1999.
94. JECFA, Evaluation of Certain Food Additives and Contaminants. Fifty-fifth report
of the Joint FAO/WHO Expert Committee on Food Additives, World Health Organi-
zation, Technical Report Series 901, 55/61, 2000.
95. Kent County Council, Trading Standards Report, September 2002, http://www.trad-
ingstandards.gov.uk/kent/.
96. Jorhem, L. and Slorach, S., Lead, chromium, tin, iron and cadmium in foods in welded
cans, Food Addit. Contam., 4, 309, 1987.
2234_C009.fm Page 359 Thursday, October 26, 2006 8:34 AM
97. Branca, P. and Pelizzone, G., Lead release from tinplated cans: theoretical and legal
aspects and experimental results, Bollettino dei Chimici dell’Unione Italiana dei
Laboratori Provinciali, 34, 325, 1983.
98. Stilwell, D.E. and Mustane, C.L., Lead content in grapefruit juice and its uptake upon
storage in open containers, J. Sci. Food Agric., 66, 405, 1994.
99. Herrmann, H.J., Ceramics, glass, enamel: release of harmful substances from every-
day articles for foodstuffs, limit values, test, and analysis methods, Keramische Z.,
45, 267, 1993.
100. Beliles, R.P., The metals, in Patty’s Industrial Hygiene and Toxicology, 4th ed.,
Clayton, G.D. and Clayton, F.E., John Wiley & Sons, New York, 1994, 2(Pt. C), 1879.
101. Directive 84/500/EEC: European Community, Council Directive on the approxima-
tion of the laws of the Member States relating to ceramic articles intended to come
into contact with foodstuffs, October 15, 1984.
102. Sheets, R.W., Extraction of lead, cadmium and zinc from overglaze decorations on
ceramic dinnerware by acidic and basic food substances, Sci. Total Environ., 197,
167, 1997.
103. Gould, J. H. et al., Influence of automatic dishwashings and scrubbings on release
of lead from glazed ceramicware, J. Assoc. Off. Anal. Chem., 73, 401, 1990.
104. Ishiwata, H. et al., Determination of low levels of lead and cadmium released from
ceramic ware into 4% acetic acid and grapefruit juice, Shokuhin Eiseigaku Zasshi,
32, 168, 1991.
105. Doemling, H. J., The extraction of cadmium from dishes, Fresenius Z. Anal. Chem.,
267, 118, 1973.
106. Clifford, J.F., Glaze Compositions. U.K. Patent, EP 509792, Eur. Pat. Appl., 1992.
107. Mitra, Ina, S. et al., Abrasion-Resistant Adherent Glass Coating Compositions Free
of Cadmium and Lead for Glass Ceramic Surfaces for Cooking Food, U.S. Patent
6525300, 2003.
108. Hight, S.C., Graphite furnace atomic absorption spectrometric determination of lead
and cadmium extracted from ceramic foodware: collaborative study, J. AOAC Int.,
83, 1174, 2000.
109. Hight, S.C., Determination of lead and cadmium in ceramicware leach solutions by
graphite furnace atomic absorption spectroscopy: method development and interlab-
oratory trial, J. AOAC Int., 84, 861, 2001.
110. Lehman, R.L., International standards for lead and cadmium: release from ceramic
foodware surfaces, Ceramic Eng. Sci. Proc., 17, 129, 1996.
111. Seddon, A.B., and Whall, M.E., The extraction of lead from lead crystalware, Glass
Technol., 34, 71, 1993.
112. Guadagnino, E. et al., Estimation of lead intake from crystalware under conditions
of consumer use, Food Addit. Contam., 17, 205, 2000.
113. Guadagnino, E. et al., Parameters affecting lead migration from crystal glass in contact
with 4% acetic acid, wine and brandy, Rivista della Stazione Sperimentale del Vetro
(Murano, Italy), 29(1), 5, 1999.
114. Barbee, S.J. and Constantine, L.A., Release of lead from crystal decanters under
conditions of normal use, Food Chem. Toxicol., 32, 285, 1994.
115. Frederes, K.P. and Varshneya, A.K., The leaching of lead and other metal ions from
lead crystal glass, Ceramic Trans. (Advances in Fusion and Processing of Glass), 29,
419, 1993.
116. Guadagnino, E. et al., Surface analysis of 24% lead crystal glass articles: correlation
with lead release, Glass Technol., 43, 63, 2002.
2234_C009.fm Page 360 Thursday, October 26, 2006 8:34 AM
117. Hight, S.C., Lead migration from lead crystal wine glasses, Food Addit. Contam., 13,
747, 1996.
118. Carelli, G. et al., Determination of lead in Coca Cola after leaching from crystal
glasses by graphite furnace atomic absorption spectrometry (GFAAS), Rivista della
Stazione Sperimentale del Vetro (Murano, Italy), 29, 57, 1999.
119. 3Partial Agreement in the Social and Public Health Field. Council of Europe Draft
Technical Document No 1. RD 5/1-42, Guidelines on Lead Leaching from Glass
Tableware into Foodstuffs, 42nd session, Strasbourg, December 2–5, 2003,
www.coe.int/soc-sp.
120. Doemling, H.J., Leaching of cadmium and lead from enamel and enamel colors:
enamel utensils and glass drinking vessels, Deutsche Lebensmittel-Rundschau, 70,
439, 1974.
121. Guadagnino, E. and Quevauviller, Ph., Improvement of the quality control of glass
analysis, part 1: interlaboratory studies, Proc. Contr. Qual., 11, 147, 1998.
122. Quevauviller, Ph. and Guadagnino, E., Improvement of the quality control of glass
analysis, part 2: certification of a glass reference material, Proc. Contr. Qual., 11,
323, 1999.
123. Guadagnino, E. et al., Determination of hexavalent chromium as a requisite to comply
with the packaging directive, Rivista della Stazione Sperimentale del Vetro (Murano,
Italy), 28, 63, 1998.
124. Guadagnino, E., Sundberg, P., and Corumluoglu, O., A collaborative study on the
determination of hexavalent chromium in container glasses, Glass Technol., 42, 148,
2001.
125. Guadagnino, E., Sundberg, P., and Heinrich, H.J., A collaborative study for the
determination of mercury in glass packaging by cold vapor atomic absorption spectro-
metry, Glass Technol., 42, 24, 2001.
126. Sherlock, J.C. and Smart, G.A., Tin in foods and the diet, Food Addit. Contam., 1,
277, 1984.
127. Food Standards Agency (FSA), U.K., Tin in Canned Fruit and Vegetables, Report
No. 29, 2002.
128. Codex, 1998, Position Paper on Tin Codex Committee on Food Additives and Con-
taminants, Thirtieth Session, The Hague Netherlands, March 1998. Joint FAO/WHO
Food Standards Programme, CX/FAC/98/24.
129. JECFA, Evaluation of Certain Food Additives and Contaminants, Fifty-fifth Report
of the Joint FAO/WHO Expert Committee on Food Additives, World Health Organi-
zation, Technical Report Series, 901, 55/69, 2000.
130. Ministry of Agriculture, Fisheries and Food of U.K. (MAAF), The Tin in Food
Regulations, S.I. 496, HMSO, London, 1992.
131. Codex Alimentarius Commission, Doc. No. CX/FAC 96/17, Joint FAO/WHO Food
Standards Programme, Codex General Standard for Contaminants and Toxins in
Foods, 1995.
132. Albu-Yaron, A. and Semel, A., Nitrate-induced corrosion of tin plate as affected by
organic acid food components, J. Agric. Food Chem., 24, 344, 1976.
133. Juliàn, B. et al., A study of the method of synthesis and chromatic properties of the
Cr-SnO2 pigment, Eur. J. Inorg. Chem., 10, 2694, 2002.
134. Ministry of Agriculture, Fisheries and Food of U.K. (MAAF), Total Diet Study:
Metals and Other Elements, Food Surveillance Information Sheet 131, HMSO, Lon-
don, 1997.
2234_C009.fm Page 361 Thursday, October 26, 2006 8:34 AM
135. Ministry of Agriculture, Fisheries and Food of U.K. (MAAF), Survey of Lead and
Tin in Canned Fruits and Vegetables, Food Surveillance Information Sheet 122,
HMSO, London, 1999.
136. World Health Organization, Guidelines for Drinking-Water Quality: Recommenda-
tions, Vol. 1, Geneva, 1993.
137. WHO, World Health Organization, International Programme on Chemical Safety
(IPCS), Environmental Health Criteria, 194, Aluminum, 1997, www.inchem.org/doc-
uments/ehc/ehc/ehc194.htm.
138. JECFA, Evaluation of Certain Food Additives and Contaminants, Thirty-third Report
of the Joint FAO/WHO Expert Committee on Food Additives, World Health Organi-
zation, Technical Report Series, 776, 33/26, 1988.
139. Birchall, J.D. and Chappell, J.S., Aluminum, chemical physiology, and Alzheimer’s
disease, Lancet, 2, 1008, 1988.
140. Pennington, J.A.T., Aluminum content of foods and diets, Food Addit. Contam., 5,
161, 1988.
141. Pennington, J.A.T. and Jones, J.W., Dietary intake of aluminum, in Aluminum and
Health — A Critical Review, Gitelman, H.J., Ed., Marcel Dekker, New York, 1989,
p. 67.
142. Zhou, C.Y. et al., The behavior of leached aluminum in tea infusions, Sci. Total
Environ., 177, 9, 1996.
143. Fung, K.F. et al., Aluminum and fluoride concentrations of three tea varieties growing
at Lantau Island, Hong Kong, Environ. Geochem. Health, 25, 219, 2003.
144. Rajwanshi, P. et al., Studies on aluminum leaching from cookware in tea and coffee
and estimation of aluminum content in toothpaste, baking powder and paan masala,
Sci. Total Environ., 193, 243, 1997.
145. Savory, J., Nicholson, J.R., and Wills, M.R., Is aluminum leaching enhanced by
fluoride?, Nature, 327, 107, 1987.
146. Joshi, S.P. et al., Detection of aluminum residue in sauces packaged in aluminum
pouches, Food Chem., 83, 383, 2003.
147. Sugden, J.K. and Sweet, N.C., A study of the leaching of aluminum ions from drink
containers, Pharm. Acta Helv., 64(5–6), 130, 1989.
148. Greger, J.L., Goetz, W., and Sullivan, D., Aluminum levels in foods cooked and stored
in aluminum pans, trays and foil, J. Food Prot., 48, 772, 1985.
149. Vela, M.M. et al., Detection of aluminum residue in fresh and stored canned beer,
Food Chem., 63, 235, 1998.
150. Seruga, M. and Hasenay, D., Corrosion of aluminum in soft drinks, Z. Lebensm.-
Unters. Forsch., 202, 308, 1996.
151. Seruga, M., Grgic, J., and Mandic, M., Aluminum content of soft drinks from alu-
minum cans, Z. Lebensm.-Unters. Forsch., 198, 313, 1994.
152. Lione, A., The prophylactic reduction of aluminum intake, Food Chem. Toxicol., 21,
103, 1983.
153. Muller, J.P., Steinegger, A., and Schlatter, C., Contribution of aluminum from pack-
aging materials and cooking utensils to the daily aluminum intake, Z. Lebensm.-
Unters. Forsch., 197, 332, 1993.
154. Liukkonen-Lilja, H. and Piepponen, S., Leaching of aluminum from aluminum dishes
and packages, Food Addit. Contam., 9, 213, 1992.
155. Nagy, E. and Jobst, K., Aluminum dissolved from kitchen utensils, Bull. Environ.
Contam. Toxicol., 52, 396, 1994.
156. Mei, L. and Yao, T., Aluminum contamination of food from using aluminum ware,
Int. J. Environ. Anal. Chem., 50, 1, 1993.
2234_C009.fm Page 362 Thursday, October 26, 2006 8:34 AM
157. Von Burg, R. and Greenwood, M.R., Mercury, in Metals and Their Compounds in
the Environment, Merian, E., Ed., VCH, Weinheim, 1991, p. 1045.
158. JECFA, Evaluation of Certain Food Additives and Contaminants, Twenty-second
Report of the Joint FAO/WHO Expert Committee on Food Additives, World Health
Organization, Technical Report Series, 631, 22/26, 1978.
2234_C010.fm Page 363 Thursday, October 26, 2006 8:39 AM
10 Pollutants in Food —
Metals and Metalloids
Conor Reilly
CONTENTS
363
2234_C010.fm Page 364 Thursday, October 26, 2006 8:39 AM
ciency. However, if concentrations are high, they may show signs of toxicity. Other
elements also present may not harm the plants but could be a hazard to consumers.
normally prevent this. Some types of detergents used to clean equipment can result
in leaching from stainless steel of As, Pb, Hg, and Cd.13
Though it has been claimed that Pb is essential for certain species of mammals,26
there is little doubt that it has no nutritional benefits for humans and can cause both
chronic and acute poisoning. It affects many different functions, with bone marrow,
where hemoglobin synthesis is carried out, as its “critical organ” target.27 Symptoms
of acute inorganic Pb poisoning are relatively easily recognized. It usually manifests
itself in gastrointestinal effects, accompanied by general weakness and malaise.28
Encephalopathy is rare in adults but more common in children.
The effects of low-level chronic Pb poisoning are not so easily recognized.
Symptoms attributed to it, such as tiredness and mild anaemia, can also be due to
other causes. There is evidence that in children it interferes with neurophysiological
development.29
The organic compounds of Pb are, in general, more toxic than inorganic com-
pounds. They primarily affect the central nervous system. Tetraethyl Pb (TEL), for
example, is rapidly distributed to various tissues, particularly brain, where it decom-
poses to triethyl Pb and inorganic Pb, resulting in toxic psychosis.
TABLE 10.1
Lead Content of Foods in Different Countries (mg/kg)
Food Canada Japan U.K.
Source: Data adapted from Dabeka, R.W., McKenzie, A.D., and Lacroix, G.M.A., Dietary intake of
lead, cadmium, arsenic and fluoride by Canadian adults: a 24 h duplicate diet study, Food Addit.
Contam., 4, 89–102, 1987; Ministry of Agriculture, Fisheries and Food, Lead, Arsenic and Other
Metals in Food. Food Surveillance Paper No. 52, The Stationery Office, London, 1998; Teraoka, H.,
Morii, F. and Kobayashi, J., The concentration of 24 elements in foodstuffs and estimation of their
daily intake, Eiyo to Shokuryo, 32, 221, 1981.
Most natural waters contain about 5 µg Pb/l. Normally, municipal supplies contain
well below this level, but there can be exceptions, especially in old urban areas
where Pb plumbing is used. Surveys in the U.K. in the 1980s found that almost half
the water samples in certain cities were above the WHO limit of 50 µg/l.34
Lead in domestic water can be a significant source of the metal in the diet.
Infants in older houses in a U.K. city have been found to have an average intake of
3.4 mg/week, 0.4 mg higher than the WHO Provisional Tolerable Weekly Intake
(PTWI) for adults. Intakes were even higher when food was prepared using water
from the hot rather than the cold tap.35
Vegetables can be a source of high Pb intake when grown in urban areas. Soil in
some urban areas in the U.K. contains as much as 1676 mg/kg (dry weight). Lead
levels in vegetables grown on these soils have been found to exceed the statutory
limit of 1 mg/kg, with, for example, 1.5 mg/kg in cabbage and 1.7 mg/kg in spinach.31
2234_C010.fm Page 369 Thursday, October 26, 2006 8:39 AM
TABLE 10.2
Mercury in Foods in the U.K.
Food Group Mean Concentration (mg/kg Fresh Weight)
TABLE 10.3
Cadmium in Foods in the U.K.
Food Group Mean Concentration (mg/kg Fresh Weight)
Bread 0.03
Meat 0.001
Offal 0.07
Fish 0.02
Vegetables (green) 0.006
Potatoes 0.03
Beverages 0.001
Milk 0.001
Nuts 0.05
Levels of Cd in domestic water are generally less than 1 µg/l. Contamination can
occur when zinc-plated (galvanized) pipes and cisterns are used. Up to 21 µg/l in
drinking water in a Scottish hospital were traced to this source. In Australia, where
in rural areas rain is stored in galvanized tanks, levels of 3.6 µg/l have been detected
in the water.62 Soft drinks in vending machines with cadmium-plated parts have been
found to contain up to 16 mg/l.63
TABLE 10.4
Total Arsenic in Foods in the U.K.
Food Group Mean Concentration (mg/kg Fresh Weight)
Bread 0.008
Meat 0.004
Offal 0.004
Fish 4.3
Vegetables (green) 0.003
Potatoes 0.005
Beverages 0.002
Milk 0.002
Nuts 0.009
seaweed, where As is naturally present at levels above 1 ppm in that fish or sea-
weed.”72
Most potable waters contain some As, usually inorganic and usually in the lower
reaches of a range of 0 to 200 µg/l.73 Springs and spas can have higher levels than
domestic water. This is recognized in the standards of some countries, such as the
U.K., where higher levels are permitted in bottled mineral waters than in home
supplies.74
Very high levels of As occur in groundwater in some countries. Up to 4 mg/l of
inorganic As has been found in domestic water supplies in volcanic regions of South
America.75 In Taiwan the use of similarly contaminated water is believed to be
responsible for “blackfoot disease.”76 Levels of up to 100 µg As/l, and in some cases
even 1 mg/l, have been detected in water from deep tube wells in Bangladesh and
neighboring parts of India. It is estimated that up to 40% of the wells in some regions
of Bangladesh are contaminated.77
TABLE 10.5
Copper in Foods in the U.K.
Food Group Mean Concentration (mg/kg Fresh Weight)
Bread 1.6
Meat 1.4
Offal 40
Fish 1.1
Vegetables (green) 0.84
Potatoes 1.3
Beverages 0.10
Milk 0.05
Nuts 8.5
Levels in naturally occurring water supplies can vary widely. Public supplies should
normally not exceed the WHO standard of 50 µg/l, but this can sometimes be
exceeded in water that has passed through Cu pipes, especially if it is taken from
the hot tap. A study in Australia found that the daily consumption of 1.5 l of cold
tap water could give an intake of 80 µg of Cu, whereas from the hot tap the intake
was 12.3 mg, equivalent to a concentration of 8.2 mg Cu/l.89 Copper intoxication
has been reported in U.S. children who habitually drank water that contained 1.6
mg Cu/l (higher than the U.S. upper limit of 1.0 mg/l).90
Food cooked in a Cu saucepan can contain twice as much Cu as the same food
cooked in a stainless steel or Al utensil. The preparation of infant food in brass
utensils has been associated with Indian childhood cirrhosis (ICC), in which exces-
sive amounts of Cu accumulate in the liver.91 A study in Austria found an apparent
connection between the use of domestic water contaminated with Cu and outbreaks
of Tyrolean childhood cirrhosis.92
2234_C010.fm Page 376 Thursday, October 26, 2006 8:39 AM
TABLE 10.6
Zinc in Foods
Food Group Mean Concentration (mg/kg Fresh Weight)
Bread 9.0
Meat 51
Offal 43
Fish 9.1
Vegetables (green) 3.4
Potatoes 4.5
Beverages 0.3
Milk 3.5
Nuts 31
Depending on the quantity consumed, Zn salts can cause irritation of the intestine,
with nausea, vomiting, and abdominal pain. Consumption of about 1 g of a Zn salt
is required to produce these effects. Ingestion of 75 to 300 mg/d, in the form of
dietary supplements, has been shown to interfere with the absorption of other
essential trace elements, especially Cu and iron. A fall in levels of the enzyme Cu-
Zn superoxide dismutase has been observed after consumption of 50 mg of a Zn
supplement daily for 6 weeks. Other effects of chronic high intake include microcytic
anaemia, changes in immune function, and in lipoprotein metabolism.110
few expressions of concern, there is little evidence that tin is not a safe metal for
use in connection with food and beverages.
Organic compounds of Sn are found in some foods, especially fish. Their source
appears to be industrial pollution rather than, as in the case of Hg, natural methylation
of inorganic compounds. Dibutyltin salts are used as stabilizers in plastics and, until
recently, tributyl Sn was used extensively as marine antifouling agents. High levels
of organotin compounds have been reported in oysters in Australia,114 salmon in the
U.K.,115 and several species of fish in the River Ganges in India.116 Organotin has
been detected in wastewater and sewage sludge in Switzerland.117
TABLE 10.7
Tin in Foods
Food Group Mean Concentration (mg/kg Fresh Weight)
Bread 0.03
Meat 0.02
Offal 0.02
Fish 0.44
Vegetables (green) 0.02
Canned vegetables 44
Fresh fruit 0.03
Fruit products 17
Beverages 0.02
Milk 0.02
Nuts 0.03
TABLE 10.8
Aluminum in Foods
Food Group Mean Concentration (mg/kg Fresh Weight)
Bread 3.7
Miscellaneous cereals 78
Meat 0.49
Offal 0.35
Meat products 3.2
Fish 5.5
Vegetables (green) 1.8
Canned vegetables 1.1
Fresh fruit 0.57
Fruit products 1.0
Beverages 1.72
Milk < 0.27
Dairy products 0.64
Nuts 11
Processed foods are a major source, because Al compounds are used extensively
in food processing. Permitted food additives and processing aids in many countries
include sodium aluminosilicate and Al phosphate, Al stearate and sulphate, and many
others. Food containing these additives include processed cheese, confectionery,
dried milk, baked cereal goods, chewing gum, and extruded snack foods. Levels of
Al detected in some products include 224.8 mg/kg in chocolate cake, 274 mg/kg in
chewing gum,127 and 78 mg/kg in bakery products.41 Some beverages in Al cans
have been found to be relatively rich in Al, with 3.24 mg/l in a cola-based drink,128
and 10 mg/l in beer.129
Natural waters are generally low in Al because many of its compounds are relatively
insoluble. Concentrations in tap water are higher because it is normally treated to
remove turbidity and improve clarity and color. One of the most commonly used
coagulants is Al sulphate (alum). Reported levels of Al in treated water range from
10 to 2670 µg/l.130 The WHO recommend a maximum of 0.2 mg/l in domestic
water.131 Accidental addition of coagulants can increase Al levels considerably, as
occurred in the U.K., resulting in more than 100 mg/l.132
2234_C010.fm Page 382 Thursday, October 26, 2006 8:39 AM
REFERENCES
1. Sparks, D.L., Environmental Soil Chemistry, Academic Press, New York, 1995, p. 24.
2. Williams, C.H. and David, D.J., Heavy metals in Australian soils, Aust. J. Soil Res.,
11, 43, 1973.
3. Bakir, F., Damluji, S.F., and Amin-Zaki, L., Methylmercury poisoning in Iraq, Sci-
ence, 181, 230, 1973.
4. Ministry of Agriculture, Fisheries and Food, Survey of Arsenic in Food: the 8th Report
of the Steering Group on Food Surveillance, the Working Party on the Monitoring
of Foodstuffs for Heavy Metals, HMSO, London, 1982.
5. Pike, E.R., Graham, L.C., and Fogden, M.W., Metals in crops grown on sewage-
enriched soil, J. Am. Pediol. Assoc., 13, 19, 1975.
6. U.S. EPA, Clean Water Act, Section 503.58(2), U.S. Environmental Protection
Agency, Washington, D.C., 1993.
7. Ashami, M.O., Pollution of soils by cadmium, in Changing Metal Cycles and Human
Health, Nriagu, J.O. Ed., Springer-Verlag, Berlin, p. 9, 1984.
2234_C010.fm Page 383 Thursday, October 26, 2006 8:39 AM
33. Ministry of Agriculture, Fisheries and Food, 1994 Total Diet Study: Metals and Other
Elements, Food Surveillance Information Sheet No. 52, The Stationery Office, Lon-
don, 1997.
34. Craun, G.F. and McCabe, L.J., Lead in domestic water supplies, J. Am. Water Workers
Assoc., 67, 593, 1970.
35. Sherlock, J.C. and Quinn, M.J., Relationship between blood lead concentrations and
dietary lead intake by infants 0–1 year old, Food Addit. Contam., 3, 167, 1986.
36. FDA, Tin coated lead foil capsules for wine bottles, Fed. Reg., 58, 33860, Food and
Drug Administration, 1992.
37. EC, Council Regulation EEC2356/91 amending Council Regulation EEC 2392/89,
Off. J. Eur. Commun., I.261, 1, 1991.
38. DeLacey, E.A., Lead-crystal decanters — a health risk? Aust. Med. J., 147, 162, 1988.
39. Whitehead, T.P. and Prior, A.P., Lead poisoning from earthenware container, Lancet,
I, 1343, 1960.
40. Ysart, G. et al., Dietary exposure estimates of 30 elements from the U.K. Total Diet
Study, Food Addit. Contam., 16, 391, 1999.
41. GEMS/Food, Summary of 1986–1988 Monitoring Data, World Health Organization,
Geneva, 1991.
42. Gunderson, E.L., FDA Total Diet Study, July 1986–April 1991, dietary intakes of
pesticides, selected elements, and other chemicals, J. AOAC Int., 78, 1353, 1997.
43. Agricola, G., De Re Metallica, English translation by H.C. and L.H. Hoover, Dover,
New York, 1950.
44. Waldron, H.A., Did the Mad Hatter have mercury poisoning?, Br. Med. J., 287, 1961,
1983.
45. United Nations Environment Programme, International Labor Organization, World
Health Organization, Mercury — environmental aspects, Environmental Health Cri-
teria, 86, World Health Organization, Geneva, 1989.
46. World Health Organization, Environmental Health Criteria: Mercury, World Health
Organization, Geneva, 1976.
47. Bennet, B.G., Six most dangerous chemicals named, Monitoring and Assessment
Research Centre, London, on behalf of UNEP/PILO/WHO International Program on
Safety, Sentinel, 1, 3, 1984.
48. Marsh, D.O. et al., Fetal methylmercury poisoning: relationship between concentra-
tion in single strands of maternal hair and child effects, Arch. Neurol., 44, 1017, 1987.
49. Harada, M., Minamata disease: methyl mercury poisoning in Japan caused by envi-
ronmental pollution, Crit. Rev. Toxicol., 25, 1, 1995.
50. Vos, G., Hovens, J.P.C., and Delft, W.V., Arsenic, cadmium, lead and mercury in
meat, livers and kidneys of cattle slaughtered in the Netherlands during 1980–1985,
Food Addit. Contam., 4, 73, 1987.
51. Capon, C.J., Mercury and selenium content and chemical form in vegetable crops
grown on sludge-amended soil, Arch. Environ. Contam. Toxicol., 10, 673, 1981.
52. Moharram, Y.G. et al., Mercury content of some marine fish from the Alexandria
coast, Nahrung, 31, 899, 1987.
53. Food Standards Agency, Agency issues precautionary advice on eating shark, sword-
fish, and marlin, May 10, 2002, http://www.food.gov.uk/news/ressreleases/62503.
54. Clarkson, T.W. and Strain, J.J., Nutritional factors may modify the toxic action of
methyl mercury in fish-eating populations, J. Nutr., 133, 1S, 2003.
55. Asami, T., Cadmium pollution of soils and human health in Japan, in Human and
Animal Health in Relation to Circulation Processes of Selenium and Cadmium, Lag,
J., Norwegian Academy of Science and Letters, Oslo, 1991, p. 115.
2234_C010.fm Page 385 Thursday, October 26, 2006 8:39 AM
56. Buchet, J.P., Lauwerys, R., and Roels, H., Renal effects of cadmium, Lancet, 336,
699, 1990.
57. Dabeka, R.W., McKenzie, A.D., and Lacroix, G.M.A., Dietary intake of lead, cad-
mium, arsenic and fluoride by Canadian adults: a 24 h duplicate diet study, Food
Addit. Contam., 4, 89–102, 1987.
58. Hovinga, M.E., Sowers, M., and Humphrey, H.E.B., Environmental exposure and
lifestyle predictors of lead, cadmium, PCB, and DDT levels in great lakes fish eaters,
Arch. Environ. Health, 48, 98, 1993.
59. Asami, M.O., Pollution of soil by cadmium, in Changing Metal Cycles and Human
Health, Nriagu, J.O., Ed., Springer-Verlag, Berlin, 1984, p. 95.
60. Hoffmann, K. et al., The German environmental survey 1990/1992 (GerES II): cad-
mium in blood, urine and hair of adults and children, J. Expo. Anal. Environ. Epide-
miol., 10, 126, 2000.
61. MacIntosh, D.L. et al., Dietary exposure to selected metals and pesticides, Environ.
Health Perspect., 104, 202, 1996.
62. DeLaeter, J.R. et al., The cadmium content of rural tank water in Western Australia,
Search, 8, 85, 1976.
63. Rosman, K.J.R., Hosie, D.J., and De Laeter, J.R., The cadmium content of drinking
water in Western Australia, Search, 8, 85, 1977.
64. EC, Food Science and Techniques, report on Tasks for Scientific Cooperation, Dietary
Exposure to Cadmium, EUR 17527, Office for Official Publications of the European
Community, Luxumberg, 1997.
65. Ostergaard, K., Cadmium in cigarettes, Acta Med. Scand., 202, 193, 1977.
66. Hammer, D.I., Finklea, J.F., and Creason, J.P., Cadmium exposure and human health
effects, in Trace Substances in Environmental Health, Hempill, D.D., Ed., University
of Missouri Press, Columbia, MO, 1971, p. 269.
67. Carruthers, M.M. and Smith, B., Evidence of cadmium toxicity in a population living
in a zinc-mining area: pilot study of Shipham residents, Lancet, I, 663, 1979.
68. Piscator, M., Carcinogenicity of cadmium — review, presented at Third Int. Conf. on
Cadmium, Miami, FL, February 3–5, 1981.
69. Biswas, B.K. et al., Detailed study report of Samata, one of the arsenic affected
villages of Jessore district, Bangladesh, Curr. Sci., 74, 134, 1998.
70. Ministry of Agriculture, Fisheries and Food, Survey of Arsenic in Food, HMSO,
London.
71. Stijve, T. and Bourqui, B., Arsenic in edible mushrooms, Deutsche Lebensmittel-
Rundschau, 87, 307, 1991.
72. Jukes, D.J., Food Legislation in the U.K.: A Concise Guide, Butterworth/Heinemann,
Oxford, 1997, p. 137.
73. Bowen, H.J.M., Trace Elements in Biochemistry, Academic Press, London, 1966, p.
177.
74. Flowerdew, D.W., A Guide to the Food Regulations in the U.K., British Food Man-
ufacturing Industries Research Association, Leatherhead, Surrey, 1990, p. 156.
75. Queirolo, F. et al., Total arsenic, lead and cadmium levels in vegetables cultivated at
the Andean village of Northern Chile, Sci. Total Environ., 255, 75, 2000.
76. Shibata, A. et al., Mutational spectrum in the p53 gene in bladder tumors from the
endemic area of blackfoot disease in Taiwan, Carcinogenesis, 15, 1085, 1994.
77. Dhar, R.K. et al., Groundwater arsenic calamity in Bangladesh, Curr. Sci., 73, 48,
1997.
78. Wickstrom, G., Arsenic emission from the Novaky power station, Work Environ.
Health, 9, 2, 1982.
2234_C010.fm Page 386 Thursday, October 26, 2006 8:39 AM
79. Peach, D.F. and Lane, D.W., A preliminary study of geographic influence on arsenic
concentrations in human hair, Environ. Geochem. Health, 20, 231, 1998.
80. Tsuchiya, K., Arsenic contamination of infant formula, Environ. Health Perspect.,
19, 35, 1977.
81. Gunderson, E.L., Total Diet Study, July 1986–April 1991: dietary intakes of pesti-
cides, selected elements and other chemicals, J. AOAC. Int., 78, 1353, 1995.
82. Vannort, R.W., Hannah, M.L., and Pickston, L., New Zealand Total Diet Study: Part
2. Contaminant elements, New Zealand Health, Wellington, New Zealand, 1995.
83. Clarkson, T.W., Molecular targets of metal toxicity, in Chemical Toxicology and
Clinical Chemistry of Metals, Brown, S.S. and Savory, J., Eds., Academic Press,
London, 1983, p. 211.
84. Lafontaine, A., Health effects of arsenic, in CEC Trace Metals: Exposure and Health
Effects, Ferrante, E.D., Ed., Pergamon, Oxford, 1978, p. 107.
85. Chen, C.J., Kuo, T.L., and Wu, M.M., Arsenic and cancers, Lancet, I, 414, 1988.
86. Nielsen, F.H., Other trace elements, in Present Knowledge of Nutrition, Brown, M.I.,
Ed., International Life Sciences Institute, Washington, D.C., 1990, p. 294.
87. Department of Health, Dietary Reference Values for Food Energy and Nutrients in
the U.K., HMSO, London, 1991, p. 191.
88. Booth, C.K., Reilly, C., and Farmakalidis, E., Mineral composition of Australian
ready-to-eat breakfast cereals, J. Food Compos. Anal., 9, 135, 1996.
89. Reilly, C., The dietary significance of adventitious iron, zinc, copper and lead in
domestically-prepared food, Food Addit. Contam., 2, 209, 1985.
90. Spitalny, K.C. et al., Drinking-water-induced copper intoxication in a Vermont family,
Pediatrics, 74, 1103, 1984.
91. Pandit, A. and Bhave, S.A., Present interpretation of the role of copper in the Indian
childhood cirrhosis, Am. J. Clin. Nutr., 63, 830S, 1996.
92. Müller, T. et al., Endemic Tyrolean infantile cirrhosis: an ecogenic disorder, Lancet,
347, 877, 1996.
93. Pennington, J.A.T., Intakes of minerals from diets and foods: is there a need for
concern?, J. Nutr., 126, 2304S, 1996.
94. Food and Nutrition Board National Academy of Sciences, Dietary Reference Intakes:
Elements, 2003, http//www4.nationalacademies.org/10M/10Mhome.nst/pages/Food+
and+Nutrition+Board.
95. Turnland, J.R. et al., Copper absorption and retention in young men at three levels
of dietary copper by use of the stable isotope 65Cu, Am. J. Clin. Nutr., 49, 870, 1989.
96. Uauy, R., Olivares, M., and Gonzales, M., Essentiality of copper in humans, Am. J.
Clin. Nutr., 67, 952S, 1998.
97. Gitlin, J.D., The copper transporting ATPases in human disease, in Trace Elements
in Man and Animals 10, Roussel, A.M., Anderson, R.A., and Favier, A.E., Eds.,
Kluwer/Plenum, New York, 2000, p. 9.
98. Food and Agricultural Organization/WHO, Evaluations of Food Additives, WHO
Technical Reports Series No. 462, World Health Organization, Geneva, 1971.
99. Prasad, A.S., Discovery of human zinc deficiency and marginal deficiency of zinc,
in Trace Elements in Clinical Medicine, Tomita, H., Ed., Springer-Verlag, Tokyo,
1990, p. 3.
100. Ranum, P., Zinc enrichment of cereal staples, Food Nutr. Bull., 22, 169, 2001.
101. Welsh, S.O. and Marston, R.M., Zinc levels in the U.S. food supply: 1909–1980,
Food Technol., 36, 70, 1982.
102. Pennington, J.A.T. and Young, B., Iron, zinc, copper, manganese, selenium, and iodine
in foods from the U.S. Total Diet Study, J. Food Compos. Anal., 3, 166, 1990.
2234_C010.fm Page 387 Thursday, October 26, 2006 8:39 AM
103. Osendarp, S.J.M. et al., Zinc supplementation during pregnancy and effects on growth
and morbidity in low birthweight infants: a randomized placebo controlled trial,
Lancet, 357, 1080, 2001.
104. Prasad, A.S., Human zinc deficiency, in Biological Aspects of Metals and Metal-
Related Diseases, Sakar, A.B., Ed., Raven Press, New York, 1983, p. 107.
105. Jackson, M.J., Physiology of zinc: general aspects, in Zinc in Human Biology, Mills,
C.F., Ed., Springer-Verlag, London, 1989, p. 1.
106. King, J.C., Shames, D.M., and Woodhouse, L.R., Zinc homeostasis in humans, J.
Nutr., 130, 1360S, 2000.
107. Berg, J.M. and Shi, Y., The galvanizing of biology: a growing appreciation of the
role of zinc, Science, 271, 1081, 1996.
108. Prasad, A.S. et al., Zinc metabolism in patients with the syndrome of iron deficiency
anemia, hepatosplenomegaly, dwarfism and hypogonadism, J. Lab. Clin. Med., 61,
537, 1963.
109. Walsh, C.T. et al., Zinc health effects and research priorities for the 1990s, Environ.
Health Perspect., 102, 5, 1994.
110. Yadrick, M.K., Kenney, M.A., and Winterfeldt, E.A., Iron, copper and zinc status:
responses to supplementation with zinc or zinc and iron in adult females, Am. J. Clin.
Nutr., 49, 145, 1989.
111. Biego, G.H. et al., Determination of dietary tin intake in an adult French citizen,
Arch. Environ. Contam. Toxicol., 36, 227, 1999.
112. Britton, S.C., Tin versus Corrosion, International Tin Research Institution Publication
No.510, ITRI, Greenford, Middlesex, U.K., 1975.
113. Bartsiokas, A., The Franklin expedition and lead poisoning, Eur. J. Oral. Sci., 108,
78, 2000.
114. Batley, G.E. et al., Accumulation of tributyltin in Sydney rock oysters, Saccostrea
commercialis, Aust. J. Mar. Freshwater Res., 40, 49, 1989.
115. Ministry of Agriculture, Fisheries and Food, Cadmium, Mercury and Other Metals
in Food. Food Surveillance Paper No. 53, The Stationery Office, London, 1998.
116. Kannan, K., Senthilkumar, K., and Sinha, R.K., Sources and accumulation of butyltin
compounds in Ganges river dolphin, Platanista gangetica, Appl. Organometallic
Chem., 11, 223, 1997.
117. Fent, K., Organotin compounds in municipal wastewater and sewage sludge: con-
tamination, fate in treatment process and ecological consequences, Sci. Total Environ.,
185, 151, 1996.
118. Newman, P., Tin enters the free market era, Metall., 50, 616, 1996.
119. Ministry of Agriculture, Fisheries and Food, MAFF U.K. 1997 — Total Diet Study,
Food Surveillance Information Sheet No. 191, http://www.foodstandards.gov.uk.
120. Shimbo, S. et al., Use of food composition database to estimate daily dietary intake
of nutrient or trace elements in Japan, with reference to limitation, Food Addit.
Contam., 13, 775, 1996.
121. DeGroot, A.P., Feron, V.J., and Til, H.P., Toxicology of tin compounds, Food Cosmet.
Toxicol., 11, 19, 1973.
122. Greger, J.L. and Johnson, M.A., Effect of dietary tin on zinc retention and excretion
by rats, Food Cosmet. Toxicol., 19, 163, 1981.
123. Baldwin, D.R. and Marshall, W.J., Heavy metal poisoning and its laboratory inves-
tigation, Ann. Clin. Chem., 36, 267, 1999.
124. Tylecote, R.F., A History of Metallurgy, The Metal Society, London, 1976, p. 195.
125. Jorhem, L. and Haegglund, G., Aluminium in foodstuffs and diets in Sweden, Z.
Lebens. Unters. Forsch., 194, 38, 1992.
2234_C010.fm Page 388 Thursday, October 26, 2006 8:39 AM
126. Ravichandran, R. and Parthiban, R., Aluminum content of South Indian teas and their
bioavailability, J. Food Sci. Technol., 35, 349, 1998.
127. Lione, A. and Smith, J.C., The mobilization of aluminum from three brands of
chewing gum, Food Cosmet. Toxicol., 22, 265, 1982.
128. Walton, J., Hams, G., and Wilcox, D., Bioavailability of Aluminum from Drinking
Water: Co-exposure with Foods and Beverages, Research Report No. 83, Urban Water
Research Association of Australia, Melbourne, Australia, 1994.
129. Williams, D., Aluminum in Beer, http://www.breworld.com/the-b/9603/br3.html.
130. Pennington, J.A.T., Aluminum content of foods and diets, Food Addit. Contam., 5,
161, 1987.
131. World Health Organization, Evaluation of Certain Additives and Contaminants, 33rd
Report of the Joint Expert Committee on Food Additives. WHO Technical Series
776. World Health Organization, Geneva, 1989.
132. Altmann, P. et al., Disturbance of cerebral function in people exposed to drinking
water contaminated with aluminium sulphate: retrospective study of the Camelford
water incident, Br. Med. J., 319, 807, 1999.
133. Pennington, J.A.T. and Schoen, S.A., Estimates of dietary exposure to aluminium,
Food Addit. Contam., 12, 119, 1995.
134. Ministry of Agriculture, Fisheries and Food, Aluminum in Food. Food Surveillance
Paper No. 39, HMSO, London, 1993.
135. Neelam, M., Bamji, S., and Kaladhar, M. Risk of increase aluminum burden in the
Indian population: contribution from aluminum cookware, Food Chem., 70, 57, 2000.
136. Alfrey, A.C., Physiology of aluminum in man, in Aluminum and Health: A Critical
Review, Gitelman, H.J., Ed., Dekker, New York, 1989, p. 101.
137. Moore, P.B. et al., Absorption of aluminium-26 in Alzheimer’s disease, measured
using accelerator mass spectrometry, Dementia Geriat. Cognit. Dis., 11, 66, 2000.
138. Platts, M.M., Goode, G.C., and Hislop, J.S., Composition of domestic water supply
and the incidence of fractures and encephalopathy in patients on home dialysis, Br.
Med. J., 2, 657, 1977.
139. McLachlan, D.R., Aluminum and the risk of Alzheimer’s disease, Environmetrics, 6,
233, 1995.
140. Doll, R., Review: Alzheimer’s disease and environmental aluminum, Age Ageing, 22,
138, 1993.
2234_C011.fm Page 389 Wednesday, October 18, 2006 7:40 AM
11 Pollutants in Food —
Radionuclides
Zitouni Ould-Dada
CONTENTS
11.1 INTRODUCTION
We have evolved in a naturally radioactive environment, and naturally radioactive
elements have always been present in our environment. They are present in the air
we breathe, the food we eat, the water we drink, and in all living organisms including
man. Natural sources include cosmic rays, gamma rays from the earth, radon decay
products in the air, and various radionuclides in food and drink. Artificial sources
include fallout from the testing of nuclear weapons in the atmosphere, discharges
of radioactive waste from the nuclear industry, and accidental releases.
389
2234_C011.fm Page 390 Wednesday, October 18, 2006 7:40 AM
TABLE 11.1
Symbols of Radionuclides Used in the Text
Element Radionuclides
Caesium 134Cs, 137Cs
Strontium 89Sr, 90Sr
Tritium 3H
Carbon 14C
Technetium 99Tc
Sulphur 35S
Phosphorus 32P
Americium 241Am
The most important radionuclides that contribute to human exposure via food
are generally those that are mobile in the environment. Radionuclides with a poten-
tially high environmental mobility are usually analogs of essential elements and
include 134/137Cs, 90Sr, 131I 14C, 3H, 35S, and 40K. Those with low environmental
mobility include radionuclides with large atomic weights such as P and Am.
Symbols of radionuclides used in the text are listed in Table. 11.1.
Food may become contaminated with radionuclides by a number of routes. These
include uptake of radionuclides by plants from the soil or from deposition onto the
upper parts of the plants. Radionuclides may be passed to humans directly from the
consumption of these food crops or indirectly via foods derived from animals feeding
on contaminated pastures or feedstuffs.
Natural and seminatural ecosystems (e.g., forests, uplands, heathlands, mountain
pastures, marshlands) provide a variety of wild foodstuffs such as mushrooms,
berries, honey, meat from game animals, and meat and milk from domestic ruminants
(e.g., sheep, goats). These foods are known to concentrate radioactive elements,
particularly 137Cs. Radionuclides incorporated into forest food products such as
mushrooms, berries, and grasses consumed by animals and humans can contribute
significantly to the radiation dose to humans.
Because agricultural products constitute the basic diet of most populations, the
fate and behavior of radionuclides in agricultural ecosystems are of primary impor-
tance when assessing radiation dose to humans from radioactivity released to the
environment. It is essential to understand the factors affecting the behavior and
transfer of radionuclides in the environment in order to accurately predict activity
concentrations in plant- and animal-derived food products, interpret monitoring
results, and develop appropriate and effective countermeasures.
TABLE 11.2
Average Annual Doses to the
U.K. Population from All
Sources of Radiation
Source Dose (mSv)
Natural
Cosmic 0.26
Gamma rays 0.35
Internal 0.3
Radon 1.3
Artificial
Medical 0.37
Occupational 0.007
Fallout 0.005
Products 0.0004
Discharges 0.0002
of patients accounts for 14% of the total, whereas all other artificial sources (e.g.
fallout, discharges from nuclear industry) account for about 0.5% of the total value.
When radionuclides are depositing from the atmosphere, by dry or wet deposi-
tion processes, a fraction of the depositing material will be intercepted by vegetation,
with the remainder reaching the ground. For the fraction intercepted by vegetation,
environmental removal processes (e.g., wind, rain, snow, abrasion between leaves,
leaf fall, shedding of cuticular wax) will combine with radioactive decay to reduce
the quantity of this initial contamination. The growth of vegetation also causes a
diluting effect on the retained contamination. Resuspension can occur due to the
action of the wind or by mechanical disruption of a surface.5,6 Resuspension can be
quite high during agricultural activities (e.g., ploughing, harvesting). However,
ploughing of fields reduces resuspension over a longer period as the surface layer
is mixed with the lower uncontaminated soil.
Radionuclides deposited in the soil can be transferred to plants through the
plant’s root system or by direct contamination of the plant’s surface with the soil
(e.g., soil resuspension). Surface contamination of plants by soil is generally less
important than root uptake because the material is less available for transfer within
the plant and can be removed by the action of wind and rain. However, in the case
of radionuclides with low soil-to-plant transfer factors (e.g., actinides), contamina-
tion by soil can have a significant effect on the activity in the plant.
2234_C011.fm Page 395 Wednesday, October 18, 2006 7:40 AM
Atmosphere
Dry deposition
Wet deposition
Land
Sea/River/Lake
Liquid radioactive effluents may be discharged into the marine environment, fresh-
water (lakes or rivers), or estuaries. Following the release to freshwater, the principal
pathways leading to the irradiation of people are ingestion of foods from the river,
drinking water from the river, drinking water used to irrigate crops and pasture and
for animals’ drinking, and external irradiation from sediments. In the case of releases
into the marine environment, a number of pathways may lead to the irradiation of
people, and these include ingestion of marine food, external irradiation from activity
on beaches, and inhalation of sea spray. The ingestion of fish and shellfish constitutes
an important pathway to humans for discharges of liquid effluent.
In some countries such as the U.K. there are also discharges of radionuclides to
the sewer system from hospitals, universities and research establishments, and a few
nuclear sites. This gives rise to possible routes of exposure to humans through the
ingestion of crops and animal products.37,38
Radionuclides released into seawater are dispersed through advection and dis-
persion of the water masses and are also absorbed by sediments. In the case of
discharges into the marine environment, the most exposed groups are likely to
include those individuals who consume higher-than-average amounts of locally
caught seafood, i.e., fish, crustaceans, and molluscs. Certain radionuclides dis-
charged into sea become strongly associated with sediments (e.g., plutonium), which
will be transported by tides and currents. Where pastures are inundated by seawater,
some of these sediments can be deposited on the surface of the soil or vegetation.
Animals grazing in such areas may therefore become contaminated with radionu-
clides as they inadvertently ingest sediment particles associated with vegetation. The
intake of radionuclides by inhalation would generally be insignificant compared to
the intake by ingestion, except possibly in winter when animals are given uncon-
taminated feed. Remobilization of radionuclides from sediments can be a source of
contamination resulting from past authorized discharges and is likely to be increas-
ingly important as authorized discharges decline.
Forests are an efficient reservoir for pollutants, and the long-term impact of
contaminated forests can be important.39,40 For example, radionuclides incorporated
2234_C011.fm Page 399 Wednesday, October 18, 2006 7:40 AM
into forest food products such as mushrooms, berries, and grasses consumed by
animals and humans can contribute significantly to the radiation dose to humans.
Interest in seaweed contamination has reemerged as a consequence of the release
of 99Tc from the Enhanced Actinide Removal Plant (EARP) plant at Sellafield. 99Tc
is highly concentrated by seaweeds such as Fucus sp. Seaweed is used as a fertilizer
and soil conditioner in the Sellafield area, leading to increased concentrations of
99Tc in soil and vegetable samples. In parts of northern Europe (e.g., northwest
France) it is gathered commercially for use in the alginate industry and represents
a potential pathway.
In addition to the internal irradiation from ingestion of contaminated food, radio-
nuclides released into the atmosphere can give rise to internal irradiation to man
following their inhalation, and external irradiation by photons and electrons emitted
as a result of the radioactive decay process. Following their deposition onto the ground,
radionuclides may lead to further irradiation of people by external irradiation, internal
irradiation of resuspended activity, and inadvertent ingestion of soil.
Marcoule the annual dose received from discharges in 1996 was estimated at 100
µSv and 30 µSv at 0.5 and 5 km, respectively, from the site. This was dominated
by discharges of 129I.
Radiation dose received by humans due to the ingestion of radionuclides in food
can be affected by a number of factors. For example, delays between production
and consumption of food results in the radioactive decay of short-lived radionuclides
(e.g., whether food is eaten fresh or frozen). Also, radionuclides may be removed
from foods prior to consumption during food preparation and processing. Washing
or peeling of vegetables grown in contaminated soils can significantly reduce the
potential intake of radioactivity.
restrictions covered 9036 farms with 4,278,000 sheep. Over the 18 years since the
accident, the areas under restrictions have been reduced as contaminated levels have
dropped. For example, in Northern Ireland restrictions were lifted in 2000.
It is essential to understand the factors affecting the behavior and transfer of
radionuclides in animals in order to accurately predict activity concentrations in
animal-derived food products, interpret monitoring results, and develop appropriate
and effective countermeasures. A review and summary of the advances in animal
radioecology since 1988 have been compiled by Howard and Beresford.44
evaporation of the whey until dryness, which increases the radiocesium activity
concentration by a factor of about 10.
The importance of the contribution of consumed natural food to the total radi-
ation dose has been clearly demonstrated following the Chernobyl accident. For
example, in Sweden the highest radiation doses were received by people living in
high deposition areas who consume large amounts of lake fish, meat from game
animals, and reindeer.53 Although in most countries the contribution of natural food
products to the total food consumption by humans is small, their contribution to the
long-term ingestion dose can be significant. Also, natural foods can become very
important under poor economic conditions. This was the case in Ukraine following
the Chernobyl accident, where the economic difficulties resulted in the increased
consumption of forest and natural foods (mushrooms, berries, meat of wild animals,
and local fish) that were highly contaminated by 137Cs.
3H in marine samples was found to be associated with organic matter. This form of
3H is strongly bound to organic matter and sediment and has the potential to transfer
through the marine foodchain from small organisms to accumulate in fish. Concen-
trations of 3H near Cardiff recorded in 2002 were 12,000 Bq/kg (wet) in sole, 2000
Bq/kg (wet) in cod, and 14,000 Bq/kg (wet) in mussels.2 The dose to the critical
group of fish and shellfish consumers for organic H was about 0.031 mSv (including
a contribution due to external radiation).
Technetium-99 has been the subject of considerable public concern in recent
years. Shellfish, especially lobsters, are well known to concentrate 99Tc.54,55 Recent
and current discharges of 99Tc contributed around 15% of the dose to the Sellafield
seafood consumers.2 Transuranics are less mobile than radiocesium in seawater and
have a high affinity for sediments. This was reflected in higher concentrations of
transuranics in shellfish compared with fish, and a rapid reduction in their concen-
trations, particularly in shellfish, with distance from Sellafield. Mussels can accu-
mulate high levels of radionuclides such as plutonium, americium, and polonium,
which are highly particle-reactive. This can be attributed to the filter feeding nature
of these organisms and the strong affinity of these radionuclides for fine particulate
matter. In a 3-year study of radionuclides in winkles near Sellafield, retained sedi-
ment was found to carry major fractions of 137Cs, 239+240Pu, and 241Am.56 The findings
of this study suggested that removing the sediment prior to cooking would reduce
the activity in these winkles by around 90%. The consumption of locally collected
winkles has been a major contributor to the radiation dose received by a group of
seafood consumers living near the Sellafield reprocessing plant in Cumbria, U.K.
The magnitude of this dose may depend on the proportion of the activity associated
with the sediments in the cooked winkles. Removing the sediments from these
winkles prior to cooking (e.g., by soaking the live winkles prior to boiling) would
substantially reduce the quantity of radionuclides consumed and hence the dose.
Atlantic salmon and rainbow trout are the main farmed fish species consumed
in the U.K. A study on radioactivity in fishmeal fed to fish had suggested from a
theoretical standpoint that farmed fish may contain enhanced levels of naturally
occurring radionuclides as a result of the fishmeal they were fed.57 Another study
sought to test this thesis by monitoring fish directly in fish farms in England,
Scotland, and Wales during 2001.58 The results of this study showed low levels of
radioactivity in farmed fish: 137Cs (0.23 to 0.53 Bq/kg), 14C (< 16 to 50 Bq/kg), 210Pb
(< 0.010 to 0.27 Bq/kg), and 210Po (0.016 to 0.29 Bq/kg). 99Tc was measured in one
set of Scottish salmon and fish feed samples, and the results were 0.24 Bq/kg and
1.3 Bq/kg, respectively. As a consequence of these low concentrations, estimated
doses to high-rate consumers of farmed fish were also low, ranging from 0.017
mSv/year for adults to 0.038 mSv/year for 1-year-old infants. Most of these doses
were due to naturally occurring 210Pb and 210Po.
The radiological impact on the European Community (EC) populations from
liquid discharges released into the Mediterranean Sea from European civil nuclear
plants during the period 1980–1991 has been assessed under a project called
MARINA-MED.59 Results showed that ingestion of molluscs was the dominant
pathway (60% of the collective dose) with 106Ru (62%), 241Am (22%), and 239Pu
(10%) being the main contributors to the dose. Ingestion of fish was also found to
2234_C011.fm Page 404 Wednesday, October 18, 2006 7:40 AM
be a significant pathway (20% of the collective dose) with 90Sr (51%) and 137Cs
(31%) being the most important contributors to the dose. Ingestion of crustaceans
was found to be a negligible contributor to the collective dose (< 2%).
Discharges of radioactivity into the Mediterranean Sea have been more than two
orders of magnitude lower than those made into the Northern European seas. Col-
lective doses to the EC population due to liquid discharges into the Northern Euro-
pean sea waters were assessed in another EC project, called MARINA.60 Results
from this project showed that the total collective dose to the EC population was
calculated to be more than nearly three orders of magnitude higher than that calcu-
lated for discharges into the Mediterranean.
Generally, doses to seafood consumers throughout Europe from naturally occur-
ring radionuclides are approximately two orders of magnitude higher than those
from anthropogenic radionuclides. For most people living in Europe, the majority
of the dose currently received from ingestion of food is due to natural radionuclides,
particularly 40K in terrestrial food and 210Po in fish and shellfish.
Collective and individual doses received as a result of routine radiological
discharges from nuclear power plants and nuclear fuel reprocessing plants in the EC
member states occurring between 1987 and 1996 has been assessed.61 Doses to
individuals residing near the Sellafield site have also decreased from 187 mSv in
1987 to 114 mSv in 1996. The contribution to the dose from various radionuclides
and exposure pathways varied considerably over the study period. However, impor-
tant radionuclides include 99Tc in crustaceans, 14C and 137Cs in fish, and 106Ru and
241Pu in molluscs. For liquid discharges, however, the more significant exposures
Operators of nuclear sites are required under their authorizations to carry out a
regular program of environmental monitoring to ensure that no unacceptable levels
of contamination appear in the local environment. Regulatory agencies also carry
out their own programs of environmental monitoring as part of their enforcement
responsibilities.
to the effective dose (Sv) and are available for a number of radionuclides and different
age groups.
11.8 CONCLUSION
Because radioactive materials occur everywhere in nature, it is inevitable that they
get into food. Human activities have added to the natural background of radioactivity
through civil and military uses of radiation. Under normal operation of nuclear power
plants, discharges of radioactive substances into the environment are controlled and
have been continually reduced. These releases are kept low in order to protect humans
and the environment, and the doses received from the normal operation of nuclear
plants are thus, in general, negligible.
For most people living in Europe, the majority of the dose currently received
from ingestion of food is due to natural radionuclides, particularly 40K in terrestrial
food and 210Po in fish and shellfish. In general, doses to consumers of seafood
throughout Europe from naturally occurring radionuclides are approximately two
orders of magnitude higher than those from anthropogenic radionuclides. Doses of
radionuclides from natural origin in terrestrial and marine foodstuffs are currently
much higher than those from artificial radionuclides. The highest concentrations of
anthropogenic radionuclides in seafood from the European seas are found in the
Northeastern Irish Sea near Sellafield.
It is essential to understand the factors affecting the behavior and transfer of
radionuclides in the environment in order to accurately predict activity concentra-
tions in crops and animal-derived food products, interpret monitoring results, and
develop appropriate and effective countermeasures.
2234_C011.fm Page 408 Wednesday, October 18, 2006 7:40 AM
REFERENCES
1. Thorne, M.C., Background radiation: natural and man-made, J. Radiol. Prot., 23, 29,
2003.
2. RIFE 4 to 9, Radioactivity in Food and the Environment (RIFE), Annual Reports
produced by Food Standards Agency (previously MAFF), Environment Agency, Scot-
tish Environment Protection Agency, and the Environment and Heritage Service of
Northern Ireland, 1999–2003.
3. Bexton, A.P., Radiological impact of routine discharges from U.K. civil nuclear sites
in the mid-1990s, National Radiological Protection Board, Chilton, NRPB-R312,
2000.
4. Naito M. and Smith G., Revised Sets of Example Assessment Contexts, BIOMASS
Theme 1, Task group 3, Note 1, Version 1.0, 1998.
5. Nicholson, K.W., A review of particle resuspension. Atmos. Environ., 22, 2639, 1988.
6. Ould-Dada, Z. and Baghini, N.M., Resuspension of small particles from tree surfaces,
Atmos. Environ., 35, 3799, 2001.
7. Shaw, G. and Bell, J.N.B, Transfer in agricultural and semi-natural environments, in
Radioecology: Radioactivity and Ecosystems, Van der Stricht E. and Kirchmann R.,
Eds., International Union of Radioecology, Fortemps, Liege, Belgium, 2001.
8. Murdock, R.N., Chemical Speciation of Radionuclides in the Terrestrial Environment,
Mouchel and Partners Ltd. LGM Report No. 48018.001-R1, 1996.
9. Bishop, G.P. and Cramp, T.J., The Effect of Chemical and Physical Form of Atmo-
spheric Releases of Radionuclides on Environmental Behavior, Associated Nuclear
Services Ltd. ANS Report No. 2132-1, 1988.
10. Warner, F. and Harrison, R.M., Radioecology after Chernobyl: Biogeochemical Path-
ways of Artificial Radionuclides, SCOPE 50, John Wiley & Sons, Chichester, 1993.
11. Sawidis T. et al., Caesium-137 accumulation in higher plants before and after Cher-
nobyl, Environ. Int., 16, 163, 1990.
12. Carini, F. et al., 134Cs foliar contamination of vine: translocation to grapes and
transfer to wine, in Proceedings of the International Symposium on Radioecology
Ten Years Terrestrial Radioecological Research following the Chernobyl Accident,
Austrian Soil Science Society and Federal Environment Agency, Vienna, 163, 1996.
13. Kopp, P. et al., Foliar uptake of radionuclides and their distribution in the plant, in
Proceedings of the Environment Contamination following a Major Nuclear Accident,
IAEA, Vienna, 2, 37, 1990.
14. Green, N., Wilkins, B.T., and Hammond, D.J., Transfer of radionuclides to fruit, J.
Radioanal. Nucl. Chem., 226, 195, 1997.
15. Cornell, R.M., Adsoption of caesium on minerals: a review, J. Radioanal. Nucl.
Chem., 171, 483, 1993.
16. Dumat, C. et al., The effect of removal of soil organic matter and iron on the adsorption
of radiocaesium, Eur. J. Soil Sci., 48, 675, 1997.
17. Valcke, E. and Cremers, A., Sorption-desorption dynamics of radiocaesium in organic
matter soils, Sci. Total Environ., 157, 275, 1994.
18. Carini, F. and Lombi, E., Foliar and soil uptake of 134Cs and 85Sr by grape vines,
Sci. Total Environ., 207, 157, 1997.
19. McCartney, M., Baxter, M.S., and Scott, E.M., Carbon-14 discharges from the nuclear
fuel cycle: 2. local effects, J. Environ. Radioact., 8, 157, 1988.
20. UNSCEAR, United Nations Scientific Committee on the Effects of Atomic Radiations
(UNSCEAR), Reports on Ionizing Radiation to General Assembly, New York, United
Nations, 1982, 1988, 1993.
2234_C011.fm Page 409 Wednesday, October 18, 2006 7:40 AM
21. Collins, C.D., The Movement of C-14 and S-35 in Crops Following Deposition from
the Atmosphere: A Review for the Ministry of Agriculture, Fisheries and Food, MAFF,
London, 1991.
22. Collins, C. and Gravett, A., The deposition of 14C, 3H, and 35S to vegetation in the
vicinities of a Magnox and an advanced gas cooled reactor, Sci. Total Environ.,
173–174, 399, 1995.
23. Morgan, J.E. and Beetham, C.J., Review of literature for radium, protactinium, tin
and carbon, Nirex Safety Studies, BSS/R220, UK Nirex, Harwell, UK, 1990.
24. Moorby, J., The production, storage and translocation of carbohydrates in developing
potato plants, Ann. Bot., 34, 297, 1970.
25. Benjamin, L.R. and Wren, M.J., Root development and source sink relations in carrot,
Daucas carrota L., J. Exp. Bot., 29, 425, 1978.
26. Bell, C.J. and Incoll, L.D., The redistribution of assimilate in field grown winter
wheat, J. Exp. Bot., 41, 949, 1990.
27. Murphy, C.E., Tritium transport and cycling in the environment, Health Phys., 65,
683, 1993.
28. Brudenell, A.J.P., Collins, C.D., and Shaw, G., Rain and the Effect of Washout of
Tritiated Water (HTO) on the Uptake and Loss of Tritium by Crops and Soils, MAFF
Report for Project RP 0175 produced by Imperial College, 1999.
29. Brudenell, A.J.P., Collins, C.D., and Shaw, G., Dynamic of tritiated water (HTO)
uptake and loss by crops after short-term atmospheric release, J. Environ. Radioact.,
36, 197, 1997.
30. Nicholson, K.W. and Dore, C.J., Factors affecting the variability of radionuclides in
terrestrial foodstuffs, MAFF Project Report produced by AEA Technology, Report
No. AEAT-2935 Issue 1, 1998.
31. Johnson, L.H. et al., Radiological assessment of Cl in the disposal of used CANDU
fuel, Atomic Energy of Canada Limited Report, AECL-11213, COG-94-527, 1995.
32. Coughtrey, P.J. and Thorne, M.C., Radionuclide Distribution and Transport in Ter-
restrial and Aquatic Environments, Vol. 1, A A Balkema, Rotterdam, 1983.
33. Sheppard, S.C. and Evenden, W.G., Response of some vegetable crop to soil applied
halides, Can. J. Soil Sci., 72, 555, 1992.
34. Sheppard, S.C., Eveden, W.G., and Amiro, B.D., Investigation of the soil-to-plant
pathway for I, Br, Cl, and F, J. Environ. Radioact., 21, 9, 1993.
35. Beresford, N.A. and Howard, B.J., The importance of soil adhered to vegetation as
a source of radionuclides ingested by grazing animals, Sci. Total Environ., 107, 237,
1991.
36. Hinton, T.G., Stoll, J.M., and Tobler, L., Soil contamination on plant surfaces from
grazing and rainfall interactions, J. Environ. Radioact., 29, 11, 1995.
37. Titley, J.G. et al., Investigation of the Sources and Fate of Radioactive Discharges to
Public Sewers, Environment Agency R&D Technical Report P288, 2000.
38. Ham, G.J. et al., Partitioning of radionuclides with sewage sludge and transfer along
terrestrial foodchain pathways from sludge-amended land — a review of data,
National Radiological Protection Board, Report No. NRPB-W32, 2003.
39. ANPA, SEMINAT Long-Term Dynamics of Radionuclides in Semi-Natural Environ-
ments: Derivation of Parameters and Modelling. Agenzia Nazionale Per La Protezione
Dell’Ambiente (ANPA), Final Report 1996–1999, Research contract No. FI4P-CT95-
0022, European Commission Nuclear Fission Safety Programme, 2000.
40. Ould-Dada, Z., Dry deposition profile of small particles within a model spruce
Canopy, Sci. Total Environ., 286, 83, 2002.
2234_C011.fm Page 410 Wednesday, October 18, 2006 7:40 AM
41. EC, Radiation Protection 128: Assessment of the Radiological Impact on the Popu-
lation of the European Union from European Union Nuclear Sites between 1987 and
1996. EC Luxembourg, 2002.
42. Kazakov, V.S., Demidchik, E.P., and Astakhova, L.N., Thyroid cancer after Cherno-
byl, Nature, 359, 21, 1992.
43. Likhtarev, I.A. et al., Thyroid dose assessment for the Chernigov region (Ukraine):
estimation based on 131I thyroid measurements and extrapolation of the results to
districts without monitoring, Radiat. Environ. Biophys., 33, 149, 1994.
44. Howard, B. and Beresford, N.A., Advances in animal radioecology, in Radioactive
Pollutants Impact on the Environment, Brechignac, F. and Howard, B. (Eds.), based
on invited papers at the ECORAD 2001 International Conference, EDP Sciences
2001.
45. IAEA, Modeling of Radionuclide Interception and Loss Processes in Vegetation and
of Transfer in Semi-natural Ecosystems, second report of the VAMP Terrestrial
Working Group, Part of the IAEA/CEC Co-ordinated Research Programme on the
Validation of Environmental Model Predictions (VAMP), International Atomic
Energy Agency, Vienna, Report No. IAEA-TECDOC-857, 1996.
46. Gruter, H., Radioactive fission product 137Cs in mushrooms in West Germany during
1963–1970, Health Phys., 20, 655, 1971.
47. Bakken, L.R. and Olsen, R., Accumulation of radiocaesium in fungi, Can. J. Micro-
biol., 36, 704, 1990.
48. MAFF and SEPA, Radioactivity in Food and the Environment (RIFE) 1998, Annual
report produced by the Ministry of Agriculture Fisheries and Food (MAFF) and the
Scottish Environment Protection Agency (SEPA), 1999.
49. Tataruch, F., Schonhofer, F., and Klansek, E., Studies in levels of radioactivity in
wildlife in Austria, in Transfer of Radionuclides in Natural and Semi-natural Envi-
ronments, Desmet, G., Nassimbeni, P., and Belli, M., Eds., Elsevier Applied Science,
London, 1990, p. 210.
50. Mascanzoni, D., Chernobyl’s challenge to the environment: a report of Sweden, Sci.
Total Environ., 67, 133, 1987.
51. Rissanen, K. and Rhola, T., 137Cs concentration in reindeer and its fodder plants, Sci.
Total Environ., 85, 199, 1989.
52. Hansen, H. S. and Hove, K., Radiocasium bioavailability: transfer of Chernobyl and
tracer radiocaesium to goat milk, Health Phys., 60, 665, 1991.
53. Mattsson, S. and Moberg, L., Fallout from Chernobyl and atmospheric nuclear weap-
ons tests, Chernobyl in perspective, in The Chernobyl fallout in Sweden, Moberg, L.,
Ed., Swedish Radiation Protection Institute, Stockholm, 1991, p. 591.
54. Swift, D.J., The accumulation of 95mTc from sea water by juvenile lobsters (Homarus
gammarus L.), J. Environ. Radioact., 2, 229, 1985.
55. Knowles, J.F., Smith, D.L., and Winpenny, K., A comparative study of the uptake,
clearance and metabolism of technetium in lobster (Homarus gammarus) and crab
(Cancer pagarus), Radiat. Prot. Dosimetry, 75, 125, 1998.
56. McKay, W.A. and Fox, A.A., Particulate-associated nuclides in Cumbrian Winkles -
implications for assessment of dose to man, J. Environ. Radioact., 14, 1, 1991.
57. Smith, B.D. and Jeffs, T.M., Transfer of Radioactivity from Fishmeal in Animal
Feeding Stuffs to Man Environmental Technical Note RL8/99. Centre for Environ-
ment, Fisheries, and Aquaculture Science, Lowestoft, UK (1999).
58. Smith, B.D., The Radiological Significance of Farmed Fish, Project R02015/C1289,
RL 19/02, CEFAS, Lowestoft, U.K., 2002.
2234_C011.fm Page 411 Wednesday, October 18, 2006 7:40 AM
59. Chartier, M. and Despres, A., Radiological impact on EC members states of routine
discharges into the Mediterranean sea, Radiat. Prot. Dosimetry, 75, 161, 1998.
60. CEC, The Radiological Exposure of the Population of the European Community from
Radioactivity in North European Waters — Project MARINA, report by a Group of
Experts Convened by the Commission of the European Communities, Report EUR
12483, Commission of the European Communities, Luxembourg, 1990.
61. EC, MARINA II project report Update of the MARINA project on the radiological
exposure of the European Community from Radioactivity in North European Water,
published by the European Commission at http://europa.eu.int/comm/environment/
radprot, August 2002.
62. Smith, K.R. et al., Uncertainties in the Assessment of Terrestrial Food Chain Doses,
NRPB-M922. NRPB, Chilton, Oxon, 1998.
63. Cabianca, T.R.A. et al., The Variability in Critical Group Doses from Routine Releases
of Radionuclides to the Environment, Chilton, NRPB-M952, London, HMSO, 1998.
64. Ould-Dada, Z. et al., Assessment of prospective foodchain doses from radioactive
discharges from BNFL Sellafield, J. Environ. Radioact., 59, 273, 2002.
2234_C011.fm Page 412 Wednesday, October 18, 2006 7:40 AM
2234_C012.fm Page 413 Wednesday, October 18, 2006 7:45 AM
12 Assessment of Exposure
to Chemical Pollutants in
Food and Water
Peter J. Peterson
CONTENTS
12.1 INTRODUCTION
Food and water are the major exposure routes for most chemicals that adversely
affect the health of nonoccupationally exposed people. Chemical contamination of
food and hence the potential for exposure to a wide variety of hazardous substances
can occur through the life cycle of foods, from cultivation through processing to
consumption. Indeed, the need to address chemical contamination of food and water
was recognized in Chapter Six of U.N. Agenda 21 as an important issue necessary
for the protection and promotion of human health.1 The World Summit on Sustain-
able Development, held 10 years after the Earth Summit, also called on governments,
industry, and all stakeholders to use and produce chemicals in ways that do not lead
to significant adverse effects on human health and the environment.2 The principal
aim of measuring concentrations of chemical contaminants in diets and dietary items
— the determination of exposure — is to be able to reduce health risks and the
social burden of food-borne diseases.
413
2234_C012.fm Page 414 Wednesday, October 18, 2006 7:45 AM
PTS in food and dietary intakes have been reported between 1990 and 2002, which
illustrates how the current emphasis has shifted away from mineral components in
foods. No international conventions have been adopted that address heavy metals,
although major national actions have been implemented around the world addressing
source reductions to reduce risk from such metals to human health.10
Risk
FIGURE 12.1 The relationship between chemicals in food, exposure, dose, and risk. (Mod-
ified from Huismans, J.W., Halpaap, A.A., and Peterson, P.J., International Environmental
Law: Hazardous Materials and Waste, 2nd revised ed., United Nations Institute for Training
and Research, Geneva, 2004.)
2234_C012.fm Page 416 Wednesday, October 18, 2006 7:45 AM
Exposure
In all three approaches the data used to determine exposure can be based either
on single-point data, as an initial analysis, or involving probabilistic methods using
data distributions for more refined evaluations.15
The first approach, the chemical concentration scenario,13 involves measure-
ments of the chemical in individual items including drinking water and the amounts
consumed followed by estimates of the frequency and duration of exposure to such
substances.
consumption rates, or, components to include within a total diet.16 The approach’s
main strength is that concentrations of different chemicals can be multiplied by the
amount of different food items consumed based on various exposure regimes, includ-
ing those in high-risk groups. In the case of a total diet study, one major benefit is
the small number of samples for analysis for the different populations studied. The
approach, which is population-based, is discussed in detail in Subsection 12.4.1 and
is the least expensive of the three.
The second approach, the point of contact method13 in the case of food and
drinking water, applies to duplicate meal studies in which a proportion of the
customary meal is analyzed collectively whereas the remainder is eaten. Disadvan-
tages of the method relate to the relatively short-term sampling period, differences
in food items over the longer term, and the relationship between short-term exposure
studies and long-term low-level exposures typical of chronic health effects. This
approach also does not identify the contribution of particular contaminated dietary
items to the total dietary exposure. Its main advantage is that it measures exposure
directly over the period of time of the study. It is a household-based, or individual-
based, approach. It is especially relevant for accurately evaluating exposure where
major cultural differences in dietary patterns occur. The approach is expensive and
is further discussed in Subsection 12.4.2.
The third approach involves estimations of exposure from the dose through the
use of biological markers (biomarkers) of exposure.13 It is a reconstructive method
used to back-calculate dose and is individual-based. Biomarkers provide the link
between external exposure and internal dosimetry and depend upon the relationship
between the exposure and the health outcome.11 Biomarkers can reflect chemical
concentrations in tissues, organs, body fluids, excreta, etc., or what is bound to a
specific target molecule.5 They can represent past exposures (e.g., Pb in teeth), as
well as current exposures (e.g., As in urine). Arsenic in urine reflects exposure over
the last 1 to 3 d, and that in blood over a longer period, whereas contaminants in
hair reflect exposure over 1 or 2 months.5 Biomarkers of exposure can also help
identify groups at risk where analytical values differ from background concentra-
tions. The method is especially applicable for measuring the dietary intakes of
contaminants by infants consuming breast milk.17 A major disadvantage of breast
milk is that it is an evaluation of all exposure routes for the mother, not just food
and water. The method is expensive and is discussed further in Subsection 12.4.3.
Biomarkers are a specific group of indicators. In many cases, additional indica-
tors have been developed that reflect either exposure to a wide range of chemicals
or human health impacts (see Subsection 12.4.4).18
Each of the three scenarios outlined above, when compared with health out-
comes, has provided useful data helping to set standards and guideline values
designed to protect human health from chemical contaminants.15 Exposure measure-
ments are essential for the protection of populations and subgroups at high risk.15
exposure can be reevaluated in the light of new knowledge. For chemicals that have
been designated as carcinogens by the WHO’s International Agency for Research
on Cancer (IARC), no ADI is established.5 The Acute Reference Dose (RfD) for
humans is used in the U.S. and is comparable with the ADI, but it is weighted to
large portions in dietary intake.23
The determination of human exposure (dietary intake) and its risks to human
health, as mentioned above, all rely on accurate and reliable data quality on dietary
intakes, identification of foods that contribute substantially to the intake, and the
concentration of the chemical pollutants. Analytical Quality Assurance (AQA) and
Analytical Quality Control (AQC) initiatives organized for many years under the
GEMS/Food program are regularly published24 and have contributed to improving
national AQA capacity in many countries.25 In addition to the need for adoption of
standard AQA procedures, treatment of analytical data where the chemical is below
the detection limit also can affect exposure calculations. Different approaches within
total diet studies have been adopted, ranging from recording a zero value (often
referred to as a “lower bound”), some percentage of the detection limit, or the actual
detection limit (“upper bound”). Results may then be expressed as both the lower
bound measures and upper bound measures. It may not be clear in some studies
how samples that are below the detection limit were evaluated. These issues are
addressed further in Chapter 3.
not included and food was prepared using distilled water, so the adult exposure to
fluoride was 0.94 mg/d, which was compared with New Zealand and Canada total
diet studies of 2.65 and 1.76 mg/d, respectively. Fluoride from tea contributed
approximately 85% of the U.K. value. If drinking water was included in the U.K.
diet at an average of 1 mg/l, and the consumer drank 2 l, then the actual exposure
to F would be approximately 3 mg/d.
Boron can occur naturally in drinking water,29 ranging from < 0.3 to >100 mg/l
with average values of 0.5 mg/l. A daily drinking water intake of around 1 mg/d
(drinking 2 l of water a day) can be compared with the B intake from food, also of
approximately 1 mg/d, although specific country intakes can range to 10 mg/d,
especially for food grown in areas of volcanic activity.30
Bottled water constitutes a special case. The WHO guidelines on drinking water
apply to bottled drinking water, but bottled mineral waters are considered as food
items and evaluated within Codex standards.31
traditions and habits. Data are available on CD-ROM, e.g., from the U.S. Department
of Agriculture.35 In another example the 20th Australian total diet survey has been
completed36 and is available via http://www.anzfa.gov.au.
The Australian study36 reported the range of mean estimated dietary exposure
for metals, metalloids, several essential elements, and some pesticides, and compared
them with the PTWI or ADI separately for women and men, for infants (9 months),
children (2 years), teenagers (12 years), and adults (25–34 years). In all cases the
dietary exposures to Pb, Cd, Hg, and As were below the PTWI/PTDI, although the
highest mean exposure to Cd (13–69% PTWI), Pb (1–33%), Hg (1–35%), and As
(12–48%) were recorded in infants mainly influenced by their high food consumption
relative to body weight. Concern was expressed about the high potential Hg exposure
for pregnant women consuming large amounts of fish, because of the sensitivity of
the fetus to Hg.37 An advisory of one half of the health standard for pregnant women
compared with the general population was proposed in the Australian study.36
A comparable study — the 2000 U.K. Total Diet Study — has been reported38
following analysis of 12 elements. It involved 119 categories of food collected from
24 towns and grouped into 20 similar foods for analysis, and the results were
compared with the PTWI/PTDI. Diets were calculated to represent an elderly group
of citizens (> 64 years), vegetarians, as well as toddlers (1.5–4.5 years), young
people (4–18 years), and adults (16–64 years). The dietary exposure for toddlers for
all elements analyzed were in general higher than those for other age groups as with
the Australian study mentioned earlier, whereas the elderly had lower dietary expo-
sures. Measuring dietary exposure of the elements compared with PTWI represent
approximately 12% for Cd, 3% for Pb, and 12% for Hg, although high-level exposure
groups were two or three times these percentages. A comparison with the annual
U.K. population dietary exposures from 1976 to 2000 shows that concentrations of
As, Cd, Hg, and Pb have consistently decreased over time.
The high concentration of Hg in fish, predominantly as methyl-Hg,39,40 is the
major contributor to dietary Hg exposure. Reported Hg exposure differences between
countries are usually based on the amounts of fish consumed. Indigenous peoples
living in some countries where gold-mining activities have discharged Hg into soil
and rivers and who consume large amounts of fish,41,42 have Hg intakes that exceed
JECFA health guidelines.37 This issue is discussed further in Subsection 12.4.3.
Furthermore, in gold-mining areas, Hg in drinking water from boreholes and wells
may exceed the WHO limit,43 thus contributing to higher Hg exposures. Such results
can be compared with Hg concentrations in drinking water from nonpolluted areas
that are often below the limit of detection. Cd in drinking water is usually minimal,
whereas Pb in water reticulated through Pb-pipes may contribute considerably to
dietary exposure for many people including bottle-fed infants.44,45 Exposures to As
and F in drinking water are discussed in Subsection 12.4.4.
diet studies and analysis of fecal concentrations of Pb and Cd, food was shown to
be the main exposure route, although in areas where concentrations of Pb in air was
high, inhalation contributed significantly to exposure.46 In another study,47 large
interindividual and day-to-day variations were shown with respect to exposure to
Pb and Cd, which illustrates the usefulness of the duplicate diet approach. Concen-
trations of Cd in feces were again used to evaluate bioavailability of dietary Cd in
women consuming a mixed diet low in shellfish, a diet higher in shellfish (shellfish
accumulate Cd), or a vegetarian diet rich in fiber.48 Despite differences in Cd intakes
and a low absorption of dietary Cd, blood and urinary Cd values were similar.
A 7-d duplicate diet study of 12 elements and involving approximately 50
vegetarians in the U.K. has been reported49 and compared with results from the 1997
general U.K. Total Diet Study.50 As vegetarians do not eat fish, shellfish, or meat,
Hg that is accumulated in these food items was not determined. Dietary exposure
to As was lower in the vegetarian diet than in the general population (0.017 mg/d
compared with 0.065 mg/d) as fish also contributes substantially to the As intake.
With Cd, the intake was slightly higher in the vegetarian diet (0.015 mg/d compared
with 0.012 mg/d), which may relate to the higher dietary intake of nuts, pulses, and
vegetables (which contain high concentrations of Cd) thus offsetting Cd intakes by
the general population from meat, offal, and shellfish that are also known to contain
relatively high concentrations of Cd. With dietary exposure to Pb on the other hand,
exposure of the vegetarians was lower than that of the general population (0.015
mg/d compared with 0.026 mg/d). Specifically, beverages (i.e., based on drinking
water) that are major contributors to dietary exposures to Pb were not included in
the diet of the vegetarians.
Vegetarians also have a higher intake of B than the general population via
exposure from food because fruit, vegetables, pulses, legumes, and nuts have higher
concentrations of B.29 Average daily exposure of vegetarians to B, in EU countries
for example, range from 2.4 to 7 mg B/d compared with an average diet of 1.6 to
4.5 mg B/d.30
The point-of-contact approach, however, has some limitations. The number of
individuals participating in the studies is usually small, and errors with how the food
is split between what is analyzed and what is consumed have been reported. These
differences relate to behavioral differences and socioeconomic factors. In one study
in the U.S. that lasted for 28 d, although only 7 d of food collections were consec-
utive, food consumed in social settings was not collected, and noncollection of meals
and food increased after the third day of collection.51 In the duplicate diet study of
vegetarians mentioned earlier,49 underreporting of foods consumed was also recorded
based on diary records and mean daily energy intake calculations. As a result, more
than a dozen dietary results were not used by the researchers to calculate dietary
exposure.
Breast milk provides a rather different example of a duplicate diet approach.
Breast milk, which forms the major dietary intake of infants, has also been chemi-
cally analyzed for a range of pollutants as mentioned in the following subsection.
2234_C012.fm Page 423 Wednesday, October 18, 2006 7:45 AM
only the dietary intake but also nutritional factors.57 Generally, chemicals enter breast
milk by passive transfer from plasma, and their concentration in the milk is propor-
tional to their solubility and lipophilicity.58
In the case of breast-milk-fed infants whose mothers consumed large amounts
of fish, Hg concentrations were still below health guidelines.59,60 Concentrations of
Pb and Cd in breast milk were generally well below health guidelines.32 Lead and
Cd concentrations in breast milk are generally about 20% of the level in blood of
the same person, which is attributed to their low lipid-solubility and high binding
to erythrocytes.61 In the case of F, exposure via breast milk was substantially lower
than for formula-fed infants, which was largely determined by the concentration of
F in the drinking water used to reconstitute the milk.62
Hair is another useful biomarker for certain pollutants, although external con-
tamination can negate any dose–response relationship. Concentrations of As in
bunched strands of hair have been shown to reflect retrospective exposure, especially
to drinking water containing elevated concentrations of As, whereas patterns of
variations of concentration along single strands relate to shorter-term exposure.63
Mercury in hair is a good indicator of Hg in dietary intakes and blood Hg
concentrations.37 Hg concentrations in hair have been reported to be higher in
residents of areas41 contaminated by Hg as well as in villagers living on the coast
who eat fish compared with villagers living many kilometers inland.64 Hence, mea-
surements of methyl-Hg in hair reflect exposure to methyl-Hg in the diet being
proportional to its simultaneous concentration in blood.37 A blood–hair ratio for
methyl-Hg has been calculated37 as 1:250. Methyl-Hg exposure biomarkers as indi-
cators of neurotoxicity in children have been discussed.65 It has been considered by
some authors66 that although the JECFA PTWI for methyl-Hg (3.3 µg/kg body
weight/week) is sufficiently protective for the general population, it may not be
sufficiently protective for pregnant women due to the risk to the developing fetus.
A lower value of 0.7 µg/kg body weight/week, which corresponds to the U.S.
Environmental Protection Agency’s (EPA) Reference Dose, is more appropriate.
Again, as with As, concentrations of methyl-Hg have been shown to vary along
single strands of hair, reflecting a longitudinal history of blood methyl-Hg.67
Lead concentrations in shed teeth of children have also been used as an indicator
of exposure. Analyses of chemicals in fingernails and toenails have also been used
to indicate exposure.17
REFERENCES
1. U.N., Agenda 21: The United Nations Programme of Action from Rio, New York,
1993.
2. WSSD, World Summit on Sustainable Development, Johannesburg,
http://www.johannesburgsummit.org/html/documents/documents.html, 2002.
3. Goldman, L. and Tran, N., Toxics and Poverty: the Impact of Toxic Substances on
the Poor in Developing Countries, World Bank, Washington D.C., 2002.
4. WHO, Major Poisoning Episodes from Environmental Chemicals, Report
WHO/PEP/92, WHO, Geneva, 1992.
5. WHO/IPCS, Human Exposure Assessment, Environmental Health Criteria 214,
WHO, Geneva, 2000.
6. WHO, WHO Global Strategy for Food Safety: Safer Food for Better Health, WHO,
Geneva, 2002.
7. FAO/WHO, Codex Alimentarius Commission, Report of the Twenty-sixth Session,
Rome, June 30–July 7, 2003.
8. UNEP, Regionally Based Assessment of Persistent Toxic Substance: Global Report
2003, UNEP, Geneva, 2003.
9. UNEP, Stockholm Convention on Persistent Organic Pollutants (POPs), UNEP,
Geneva, 2001.
10. WHO, Health and Environment in Sustainable Development: Five Years after the
Earth Summit, WHO, Geneva, 1997.
11. U.S. NRC, Frontiers for Assessing Human Exposures to Environmental Toxicants,
U.S. National Research Council, National Academy Press, Washington D.C., 1991.
2234_C012.fm Page 428 Wednesday, October 18, 2006 7:45 AM
12. Huismans, J.W., Halpaap, A.A., and Peterson, P.J., International Environmental Law:
Hazardous Materials and Waste, 2nd revised ed., United Nations Institute for Training
and Research, Geneva, 2004.
13. WHO/IPCS, Principles for the Assessment of Risk to Human Health from Exposure
to Chemicals, Environmental Health Criteria 210, WHO, Geneva, 1999.
14. Peterson, P.J., Assessment of exposure to chemical contaminants in water and food,
Sci. Total Environ., 168, 123, 1995.
15. WHO, Food Consumption and Exposure Assessment of Chemicals, Report of a
FAO/WHO Consultation, Geneva February10–14, 1997.
16. EC, Report on Tasks for Scientific Co-operation: Improvement of Knowledge of Food
Consumption with a View to Protection of Public Health by Means of Exchanges
and Collaboration between Database Managers, Office for Official Publications of
the European Commission, Luxembourg, 1997.
17. WHO/IPCS, Biomarkers and Risk Assessment: Concepts and Principles, Environ-
mental Health Criteria 155, WHO, Geneva, 1993.
18. Von Shirnding, Y., Health in Sustainable Development Planning: the Role of Indica-
tors, WHO, Geneva, 2002.
19. WHO/IPCS, Principles for Evaluating Health Risks from Chemicals during Infancy
and Early Childhood, Environmental Health Criteria 59, WHO, Geneva, 1986.
20. WHO/IPCS, Principles for Evaluating the Effects of Chemicals on the Aged, Envi-
ronmental Health Criteria 144, WHO, Geneva, 1992.
21. Suk, W. A., Beyond the Bangkok Statement: research needs to address environmental
threats to children’s health, Environ. Health Perspect., 110, A284, 2002.
22. FAO/WHO, Summary of Evaluations by the Joint FAO/WHO Expert Committee on
Food Additives (JECFA 1956–2001) First through Fifty-seventh Meeting, Internet
Edition, FAO, Rome 2001.
23. U.S. EPA, Reference Dose (RfD): Description and Use in Health Risk Assessments,
Background document 1A, U.S. EPA, Springfield, 1993.
24. WHO, GEMS/Food Analytical Quality Assessment Study 2000, report of the
GEMS/Food Study of Food Analysis Performance of Heavy Metals, Report
WHO/PHE/FOS/01.2, WHO, Geneva, 2001.
25. Weigert, P. and Müller, J., Analytical quality assurance in the German food contam-
ination monitoring programme, Fresenius Z. Anal. Chem., 736, 737, 1988.
26. Mushak, P. and Crocetti, A.F., Risk and revision in arsenic cancer risk assessment,
Environ. Health Perspect,. 103, 684, 1995.
27. WHO, Guidelines for Drinking Water Quality, Vol. 1: Recommendations, WHO,
Geneva, 1993.
28. FSA, 1997 Total Diet Study — Fluorine, Bromine, and Iodine, Food Survey Infor-
mation Sheets 05/00, Food Standards Agency, London, 2000.
29. WHO/IPCS, Boron, Environmental Health Criteria 204, WHO, Geneva, 1998.
30. Mangas, S., Derivation of health investigation levels for boron and boron compounds,
in Health Risk Assessment of Contaminated Sites, Langley, A. et al., Contaminated
Sites Monograph Series 7, South Australian Health Commission, Adelaide, 1998, p.
229.
31. FAO, Codex Standards for National Mineral Water, Codex Alimentarius Commission
XI, (III), FAO, Rome, 1994.
32. Jelinek, C.F., Assessment of Dietary Intake of Chemical Contaminants, WHO,
Geneva, 1992.
33. WHO, GEMS/Food Total Diet Studies, Report of the Second International Workshop
on Total Diet Studies, Brisbane, Australia, February 4–15, 2002.
2234_C012.fm Page 429 Wednesday, October 18, 2006 7:45 AM
34. WHO, GEMS/Food Regional Diets: Regional Per Capita Consumption of Raw and
Semi-Processed Agricultural Commodities (revision September 2003), WHO,
Geneva, 2003.
35. USDA, CSFII 1994–1996: 1998 Data Set, National Technical Information Service
Accession No. PB 2000–500027, U.S. Department of Agriculture, Washington, D.C.,
2000.
36. FSANZ, The 20th Australian Total Diet Survey, Food Standards Australia New
Zealand, Canberra, 2003.
37. WHO/IPCS, Methyl mercury, Environmental Health Criteria 101, WHO, Geneva,
1990.
38. FSA, 2000 Total Diet Study of 12 Elements — Aluminum, Arsenic, Cadmium,
Chromium, Copper, Lead, Manganese, Mercury, Nickel, Selenium, Tin and Zinc,
Food Survey Information Sheets 48/04, Food Standards Agency, London 2004.
39. WHO/IPCS, Mercury: Environmental Aspects, Environmental Health Criteria 51,
WHO, Geneva, 1989.
40. Boudou, A., and Ribeyre, F., Mercury in the food web: accumulation and transfer
mechanisms, in Mercury and Its Effects on Environment and Biology, Sigel, A. and
Sigel, H., Eds., Marcel Dekker, New York, 1997, p. 289.
41. Fréry, N. et al., Gold mining activities and mercury contamination of native Amer-
indian communities in French Guiana: key role of fish in dietary uptake, Environ.
Health Perspect., 109, 449, 2001.
42. Grandjean, P. et al., Methyl mercury neurotoxicity in Amazonian children downstream
from gold mining, Environ. Health Perspect., 107, 589, 1999.
43. Nyamah, D., Amonoo-Neizer, E.H., and Acheampong, K., Arsenic and mercury
pollution at the mining environs of Obuasi, Ghana, Ghana J. Chem., 1, 431, 2001.
44. FAO, Exposure of Infants and Children to Lead, FAO Food and Nutrition Paper 45,
FAO Rome, 1989.
45. MAFF, Lead in Food: Progress Report, Food Surveillance Paper 27, Ministry of
Agriculture, Fisheries and Food, Her Majesty’s Stationary Office, London, 1989.
46. Vahter, M. and Slorach, S., GEMS Exposure Monitoring of Lead and Cadmium: An
International Pilot Study within the WHO/UNEP Human Exposure Assessment Loca-
tion (HEAL) Project, WHO Geneva and UNEP Nairobi, 1990.
47. Slorach, S., Jorhem, J., and Becker, W., Dietary exposure to lead and cadmium in
Sweden, Chem. Speciation Bioavail., 3, 13, 1991.
48. Vahter, M. et al., Bioavailability of cadmium from shellfish and mixed diets in women,
Toxicol. Appl. Pharmacol., 136, 332, 1966.
49. MAFF, Duplicate Diet Study of Vegetarians — Dietary Exposure to 12 Metals and
Other Elements, MAFF Surveillance Information Sheet 193, Food Standards Agency,
London, 2000.
50. MAFF, 1997 Total Diet Study — Aluminum, Arsenic, Cadmium, Chromium, Copper,
Lead, Mercury, Nickel, Selenium, Tin and Zinc, Food Surveillance Information Sheet
191, The Stationary Office, London, 1999.
51. Thomas, K.W. et al., Testing duplicate diet sample collection methods for measuring
personal dietary exposure to chemical contaminants, J. Expo. Anal. Environ. Epide-
miol., 7, 17, 1997.
52. Bingham, S.A., Biomarkers used to validate dietary assessments in human population
studies, in Biomarkers in Food Chemical Risk Assessment, Crews, H.M. and Hanley,
A.B. Eds., Royal Society of Chemistry, Cambridge, MA, 1995, p. 20,
53. WHO/IPCS, Biomarkers in Risk Assessment: Validity and Validation, WHO, Geneva,
2001.
2234_C012.fm Page 430 Wednesday, October 18, 2006 7:45 AM
54. Buchet, J.P. et al., Consistency of biomarkers to exposure to inorganic arsenic: review
of recent data, in Arsenic Exposure and Health Effects, Chappell, W.R., Abernathy,
C.O., and Calderon, R.L., Eds., Elsevier, New York, 1999, p. 31.
55. Donohue, J.M., and Abernathy, C.O., Exposure to inorganic arsenic from fish and
shellfish, in Arsenic Exposure and Health Effects, Chappell, W.R., Abernathy, C.O.,
and Calderon, R.L., Eds., Elsevier, New York, 1999, p. 89.
56. Noonan, C.W. et al., Effects of exposure to low levels of environmental cadmium on
renal biomarkers, Environ. Health Perspect., 110, 151, 2002.
57. Sim, M.R. and McNeil, J.J., Monitoring chemical exposure using breast milk: a
methodological review, Am. J. Epidemiol., 136, 1, 1992.
58. Anderson, H.A. and Wolff, M.S., Environmental contaminants in human milk, J.
Expo. Anal. Environ. Epidemiol., 10, 755, 2000.
59. Skerfving, S., Mercury in women exposed to methyl mercury through fish consump-
tion and their newborn babies and breast milk, Bull. Environ. Contam. Toxicol., 41,
475, 1988.
60. UNEP, Global Mercury Assessment, UNEP, Geneva, 2002.
61. Needham, L.L. and Wang, R.Y., Analytic considerations for measuring environmental
chemicals in breast milk, Environ. Health Perspect., 110, A317, 2002.
62. Liteplo, R.G. et al., Inorganic fluoride: evaluation of risks to health from environ-
mental exposure to fluoride in Canada, Environ. Carcinog. Ecotoxicol. Rev., C12,
327, 1994.
63. Hindmarsh, J.T. et al., Hair arsenic as an index of toxicity, in Arsenic Exposure and
Health Effects, Chappell, W.R., Abernathy, C.O., and Calderon, R.L., Eds., Elsevier,
New York, 1999, p. 41.
64. Suzuki, T., Advances in Mercury Toxicology, Plenum Press, New York, 1991.
65. Grandjean, P. et al., Methylmercury exposure biomarkers as indicators of neurotox-
icity in children aged seven years, Am. J. Epidemiol., 150, 301, 1999.
66. COT, Statement on a Survey of Mercury in Fish and Shellfish, 2002/04, Committee
on Toxicology of Chemicals in Food, Consumer Products and the Environment, Food
Standards Agency, London, 2002.
67. Marsh, D.O. et al., Fetal MeHg poisoning: relationship between concentration in
single strands of maternal hair and child effects, Arch. Neurol., 44, 1017, 1997.
68. Peterson, P.J. et al., Development of indicators within different policy contexts for
endemic arsenic impacts in the People’s Republic of China, Environ. Geochem.
Health, 23, 159, 2001.
69. Yang, L.-S. et al., The relationship between exposure to arsenic concentrations in
drinking water and the development of skin lesions in farmers from Inner Mongolia,
China, Environ. Geochem. Health, 24, 293, 2002.
70. Peterson, P.J. and Li, R.-B., Endemic Fluorosis: A Global Health Issue, Report
UNEP/GEMS/92.H6, UNEP, Nairobi, 1992.
71. Yang, L.-S. et al., Developing environmental health indicators as policy tools for
endemic fluorosis management in the People’s Republic of China, Environ. Geochem.
Health, 25, 281, 2003.
72. Kjellström, T. and Corvalán, C., Framework for the development of environmental
health indicators, World Health Stat. Q., 48, 144, 1955.
73. WHO, Diet, Nutrition, and the Prevention of Chronic Diseases, Technical Report
797, WHO, Geneva, 1990.
2234_C012.fm Page 431 Wednesday, October 18, 2006 7:45 AM
13 Metal Contamination of
Dietary Supplements
Melissa J. Slotnick and Jerome O. Nriagu
CONTENTS
13.1 INTRODUCTION
The safety of over-the-counter dietary supplements is an issue of growing concern
given an increase in dietary supplement consumption, the vast range of products
available to consumers of all ages, and the resulting regulatory challenges. The
United States Food and Drug Administration (FDA) has estimated that over 29,000
different dietary supplements are available to consumers.1 Dietary supplements are
defined by the Dietary Supplement and Health Education Act of 1994 (DSHEA) as
containing one or more of the following: vitamins, minerals, herbs or other botan-
icals, amino acids, dietary supplements meant to increase total dietary intake, or a
combination of the above.1,2
The use of dietary supplements in the U.S. has been on the rise. Results from
the 1999–2000 National Health and Nutrition Examination Survey (NHANES),
conducted by the U.S. Centers for Disease Control and Prevention (CDC), indicate
that 52% of the adult population reported using any type of dietary supplement,
whereas 35% reported using a multivitamin or multimineral supplement.3 This is
over a 10% increase in dietary supplement use when compared with the previous
NHANES survey, conducted between 1988 and 1994.4 The increase in consumption
corresponds to a rise in dietary supplement sales from $10 million in 1996 to over
$17 million in 2000.1 Furthermore, use of dietary supplements is not limited to
adults; results from the 1988–1994 NHANES survey indicate that 51% of boys and
46% of girls aged 3 to 5 years use dietary supplements.4
433
2234_C013.fm Page 434 Thursday, October 26, 2006 8:50 AM
TABLE 13.1
Lead Concentrations in Calcium Supplements
Lead Concentration
(µg/g)
Supplement Study
Type Mean ± SDa Range Year Authors Location
d Mean and SD were derived from reported means. Levels below detection were assigned a value
providing an additional 7.7 µg of cadmium to the daily intake; the other elements
analyzed were not thought to be present at toxic levels.19 Roberts16 reported lead
levels in 7 brands of bonemeal supplements as well as 6 brands of dolomite sup-
plements. Results were averaged for comparison with other studies (Table 13.1).
Boulos and von Smolinski17 also analyzed one brand of dolomite tablets for lead,
as well as Al, As, Cd, Cr, Cu, Mn, Se, and Zn. Lead concentrations were similar to
previous studies (Table 13.1), but the low concentrations reported for other elements
were well below the current daily intake guidelines set by various regulatory agencies
(Table 13.2).17
Originally, lead levels were only thought to be elevated in dolomite and bone-
meal-based supplements;11 however, subsequent studies revealed lead contamination
of other types of calcium supplements. Bourgoin et al.10 measured lead and cadmium
in three types of calcium supplements available in North America. The calcium
supplements were either derived from calcium carbonate (CaCO3) or were composed
of chelate-bound calcium. The supplements were analyzed in four independent
laboratories using four different types of instrumentation. Mean lead concentration
ranged from 0.2 to 3.5 µg/g of supplement, and supplements derived from oyster
shells (CaCO3) contained the highest lead concentrations.10
In a later study, Bourgoin et al.11 measured lead concentration in 70 different
brands of supplements purchased in Canada and the U.S. The samples were cate-
gorized into five different types of calcium supplements: chelates, refined (CaCO3
synthesized in laboratory), dolomite, natural source (CaCO3 derived from limestone
rock/oyster shells), and bonemeal. Dolomite supplements had significantly higher
lead concentrations than chelates and refined supplements.11 Supplements derived
from bonemeal and natural CaCO3 had the highest levels of lead, but concentrations
were not significantly different from those of the dolomite supplements.11 Of the 70
different brands of calcium analyzed, 25% of them exceeded the total tolerable daily
intake for at risk populations of 6 µg lead/d.11 Hight et al.20 analyzed four types of
calcium supplements derived from dolomite, egg shell, and oyster shell. In addition
to lead, the supplements were analyzed for Al, Si, Sc, Tl, V, Fe, and Co.20 Lead
concentration ranged from 0.12 µg/g for the egg-shell based supplement to 1.9 µg/g
for the oyster shell supplement.20 These values are comparable to levels reported for
other natural source CaCO3 supplements analyzed around the same time period
(Table 13.1).
In the following year, Siitonen and Thompson18 published a report of lead content
in calcium supplements classified as oyster shell CaCO3, bone meal, dolomite,
calcium lactate, and “other.” Results from the first three types of supplements are
reported in Table 13.1. Mean concentrations for the calcium lactate supplements
ranged from nondetectable to 1.19 µg/g, whereas concentrations for the “other”
types of supplements ranged from nondetectable to 0.82 µg/g.18 Such continuation
of emerging evidence began to raise public awareness regarding the lead content of
calcium supplements.21–24 Consequently, legislation was passed in the State of Cal-
ifornia that required health advisory warnings to be put on products with lead doses
exceeding 1.5 µg/d.13
Given this growing concern over elevated lead concentrations, researchers have
continued to monitor the lead content of calcium supplements. Amarasiriwardena
2234_C013.fm Page 437 Thursday, October 26, 2006 8:50 AM
TABLE 13.2
Elemental Intake from Commonly Consumeda Herbal Supplements
Intake
Echinacea Gingko biloba Ginseng St. John’s Wort Valerian Guidelinesb
adults, and lower daily exposure levels are recommended for pregnant women (20 µg) and children under the age of six (6 µg).
c From ATSDR (Agency for Toxic Substances and Disease Registry), Minimum Risk Levels (MRLs) for Hazardous Substances, http://www.atsdr.cdc.gov/
2005.
e From Institute of Medicine, Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic, Boron, Chromium, Copper, Iodine, Iron, Manganese, Molybdenum,
Nickel, Silicon, Vanadium, and Zinc. A report of the Panel on Micronutrients, Subcommittees on Upper Reference Levels of Nutrients and the Interpretation
and Uses of Dietary Reference Intakes, and the Standing Committee on the Scientific Evaluation of Dietary Reference Intakes. Food and Nutrition Board,
Institute of Medicine. National Academy Press, Washington, D.C., 2001.
f From Farley, D., Dangers of Lead Still Linger, U.S Food and Drug Administration, FDA Consumer, January–February 1998.
Source: From Raman, P., Patino, L.C., and Nair, M.G., Evaluation of metal and microbial contamination in botanical supplements, J. Agric. Food Chem., 52,
7822, 2004; Dolan, S.P. et al., Analysis of dietary supplements for arsenic, cadmium, mercury, and lead using Inductively Coupled Plasma Mass Spectrometry,
J. Agric. Food Chem., 51, 1307, 2003; Huggett, D.B. et al., Organochlorine pesticides and metals in select botanical dietary supplements, Bull. Environ.
Contam. Toxicol., 66, 150, 2001; Hight, S.C. et al., Analysis of dietary supplements for nutritional, toxic, and other elements, J. Food Compos. Anal., 6, 121,
1993; Khan, I.A., Determination of heavy metals and pesticides in ginseng products, J. AOAC Int., 84, 936, 2001.
439
2234_C013.fm Page 440 Thursday, October 26, 2006 8:50 AM
0.10 µg/g of supplement for chelated calcium supplements to 2.15 µg/g of supple-
ment for calcium derived from algae.25
Cadmium has also been measured in calcium supplements from Canada.10,11
Supplements derived from oyster shell calcium carbonate (CaCO3) and supplements
classified as organic chelate-bound calcium were analyzed for cadmium in four
independent laboratories.10 Mean cadmium concentrations ranged from nondetect-
able for the oyster shell CaCO3 to approximately 3.5 µg/g for the chelate-bound
calcium.10
Outside of calcium supplements, there are few data assessing the metal content
of other mineral supplements. Krone et al.26 analyzed the cadmium content of six
different brands of zinc-containing mineral supplements obtained in the U.S. Cad-
mium levels in the supplements were estimated to contribute between 0.14 and 2.0
µg cadmium per day, a value that does not contribute significantly to the U.S. FDA’s
recommended maximum tolerable daily intake of 55 µg cadmium.26 Hight et al.20
also measured a variety of elements (Al, Si, Sc, Tl, V, Fe, Co, Pb) in four different
vitamin and mineral products. The products included the following: a supplement
with 7 minerals, 13 vitamins, and 50 other animal or botanical ingredients; a sup-
plement with 9 minerals and fish liver oil; a product with 8 different trace elements;
and zinc gluconate.20 Concentrations of elements in these products were comparable
to the herbal supplements analyzed by Hight et al.20 and discussed in the following
text, with the exception of thallium, which was reported to be 8400 µg/g in one
supplement.
the previous subsection, and synthetic extracts and oils such as aloe vera and fish
oil.20 One to two whole tablets were analyzed, with the serving weight ranging from
2 to 2.5 g.20 The authors estimated that, if the supplements were consumed as
recommended on the product label, roughly half of the supplements analyzed had
the potential to exceed the WHO 1989 PTTDI for lead.20 One product in particular,
bee propolis, was estimated to exceed the PTTDI for lead by a factor of ten.20 Of
the other elements analyzed, the supplements had the potential to exceed recom-
mended daily intake of Zn, Mn, Mg, Fe, and Ca.20
While it is important to monitor the dietary supplement content for a wide
spectrum of elements, as above, exposure to toxic metals is of particular concern.
Huggett et al.28 determined arsenic, cadmium, chromium, lead, and nickel concen-
trations in four different types of herbal dietary supplements (Valerian, St. John’s
wort, passion flower, and echinacea). Of these herbal supplements, three (Valerian,
St. John’s wort, and echinacea) are amongst the most commonly used herbal sup-
plements.6 A risk assessment considering the reported concentrations and calculated
intake resulted in a low hazard index (< 0.2), suggesting that carcinogenic effects
from metal intake from these particular supplements are unlikely.28 It should be
noted, however, that this risk assessment did not consider other exposure routes and
is limited to the concentrations reported in this study. Further studies reporting
concentrations in the context of risk assessment can help to better understand health
risks associated with metal contamination of dietary supplements.
Khan et al.29 reported chromium, mercury, arsenic, nickel, lead, and cadmium
concentrations of 21 ginseng products purchased in the U.S., Europe, and Asia. Both
solid (n = 13) and liquid (n = 8) supplements were analyzed. Chromium, mercury,
and arsenic were not detected in any of the samples (detection limits were 0.1 mg/l,
50–100 ng/l, and 0.5 mg/l, respectively).29 Nickel concentrations ranged from unde-
tectable to 20 µg/l, lead concentrations ranged from undetectable to 62.2 µg/l, and
cadmium concentrations ranged from 8.4 to 120.8 µg/l.29 These data were used to
calculate metal intake from the ginseng supplements, assuming the dose was 5 ml/d
for tinctures, 120 ml/d for beverages, and 1000 mg/d for solid samples.30 Average
daily intake, carcinogenic risk, and a noncancer hazard index were calculated; from
these calculations the authors determined that the metal concentrations from the
analyzed ginseng supplements did not pose any significant risks.30
Given the vast number of herbal supplements available to consumers, it is
important to continue monitoring a variety of different products. Dolan et al.31
assessed arsenic, cadmium, mercury, and lead concentration of 95 different herbal
supplements containing a variety of different extracts. Product components ranged
from a single herbal extract (e.g., echinacea or St. John’s wort) to combinations of
multiple extracts (e.g., St. John’s wort extract in combination with lecithin, kava
kava rhizome and root extract, vitamins and minerals).31 Concentrations reported for
commonly consumed herbal supplements are included in Table 13.2; however, this
table does not capture the complete range of concentrations found in all supplements
analyzed. For example, intake of 11 of the products sampled would result in expo-
sures that could exceed the tolerable intakes for sensitive populations, such as
pregnant women and children.31 Additionally, the highest arsenic concentration
reported was 3.77 µg/g; this value was measured in a supplement containing red
2234_C013.fm Page 442 Thursday, October 26, 2006 8:50 AM
clover blossoms, echinacea, licorice root, buckhorn bark, burdock root, and other
extracts, and therefore does not fall under the supplements classified as commonly
consumed.6 Given a recommended dose of 4.83 g/d,31 this translates into 0.0182 mg
of arsenic per day. This value slightly exceeds the chronic oral reference dose (RfD)
of 0.0003 mg inorganic As/kg/d34 for a 55-kg individual. This calculation assumes
that the arsenic concentration measured is inorganic arsenic only, and therefore may
be an overestimate of inorganic arsenic intake from this supplement; therefore, it
highlights the importance of understanding both concentration and chemical form
of metals in dietary supplements.
In addition to assessing the metal content of the commonly used6 echinacea,
Gingko biloba, ginseng, and St. John’s wort, Raman et al.32 analyzed the metal
content for the following frequently used supplements: garlic, grape seed extract,
kava kava, and saw palmetto. Different brands of the supplements were purchased
from stores in Michigan, Illinois, and Indiana and analyzed for Pb, Cd, As, U, Cr,
V, Cu, Zn, Mo, Pd, Sn, Sb, Tl, and W.32 Concentrations of Cd, As, U, Cr, V, Cu, Zn,
Mo, Sn, and Pb were less than the guidelines used (Minimum Risk Level, Recom-
mended Dietary Allowance, No-Observed-Adverse-Effect Level); no reference val-
ues were available for Pd, Sb, Tl, and W.32 It is important to remember, however,
that additional exposure routes, such as diet or drinking water, may add to the total
daily intake of the metals. Additionally, the authors reported a large degree of
variability in lead concentrations for different batches of echinacea,32 reiterating the
importance of continued monitoring to ensure safety.
Oral chronic Reference Doses (RfDs) were reported for elements with no
ULDRI. RfDs are established by the U.S. Environmental Protection Agency (U.S.
EPA) and are defined as: “An estimate of a daily oral exposure for a given duration
to the human population (including susceptible subgroups) that is likely to be without
an appreciable risk of adverse health effects over a lifetime.”34 The RfDs are reported
by the U.S. EPA in units of mg/kg/day, but, for ease of comparison in this review,
were converted to µg/day based on a 55-kg individual.
For elements with no available ULDRI or RfD, the Minimum Risk Level (MRL)
was used. The MRL is established by the U.S. Agency for Toxic Substances and
Disease Registry (ATSDR), Centers for Disease Control, and is defined as the
following: “… an estimate of the daily human exposure to a hazardous substance
that is likely to be without appreciable risk of adverse noncancer health effects over
a specified duration of exposure.”35 As with the RfDs, the MRLs were converted to
µg/day, assuming a 55-kg individual. None of the above reference levels were
available for lead. Instead, the tolerable daily diet intake recommended by the U.S.
FDA36 was used for comparison. It should be noted that the level listed in the table
does not include sensitive populations; it is recommended that children under the
age of 6 years and pregnant women limit exposures to 6 µg/d and 25 µg/d, respec-
tively.36 Intake guidelines were not available for Pd, Sc, Sn, and W.
Means and ranges are well below the intake guidelines for most elements (Table
13.2). Lead, cadmium, and thallium concentrations in some supplements, however,
have the potential to exceed the daily reference dose for those metals. Specifically,
the mean cadmium intake for ginseng, an average of 29 different products from
three different studies, approximates half of the RfD set by the U.S. EPA (Table
13.2). Three products exceed the RfD, all of which were analyzed by Khan et al.29
Although no values for lead exceed the reference value stated, several values come
close to meeting or exceeding the tolerable daily diet intake for pregnant women
(20 µg/d) and children (6 µg/d) (Table 13.2). Lastly, the mean thallium concentration
(averaged from nine different ginseng products) is almost two times the RfD (Table
13.2). It should be noted that this mean appears to be driven by two extreme values
(63 µg/d and 12.8 µg/d20) that far exceed the results for the other products. Therefore,
additional sampling is necessary to determine the extent of thallium contamination
in ginseng and other herbal supplements.
REFERENCES
1. Gibson, J.E. and Taylor, D.A., Can claims, misleading information, and manufactur-
ing issues regarding dietary supplements be improved in the U.S.?, J. Pharmacol.
Exp. Ther., 314, 939, 2005.
2. Taylor, C.L., Regulatory frameworks for functional foods and dietary supplements,
Nutr. Rev., 62, 55, 2004.
3. Radimer, K. et al., Dietary supplement use by U.S. adults: data from the National
Health and Nutrition Examination Survey, 1999–2000, Am. J. Epidemiol., 160, 339,
2004.
4. Ervin, R.B., Wright, J.D., and Kennedy-Stephenson, J., Use of Dietary Supplements
in the U.S., 1988–1994. U.S. Department of Health and Human Services, Centers
for Disease Control and Prevention, National Center for Health Statistics. Hyattsville,
MD, DHHS Publication No. (PHS), 1999, p. 99–1694.
5. Schaffer, D.M. et al., Nonvitamin, nonmineral supplement use over a 12-month period
by adult members of a large health maintenance organization, J. Am. Diet. Assoc.,
103, 1500, 2003.
6. Kaufman, D.W. et al., Recent patterns of medication use in the ambulatory adult
population of the U.S.: the Slone survey, JAMA, 287, 337, 2002.
7. DeSmet, P., Herbal remedies, N. Engl. J. Med., 347, 2046, 2002.
8. Bent, S. and Ko, R., Commonly used herbal medicines in the U.S.: a review, Am. J.
Med., 116, 478, 2004.
9. Dorsch, K.D. and Bell, A., Dietary supplement use in adolescents, Curr. Opin.
Pediatr., 17, 653, 2005.
10. Bourgoin, B.P. et al., Instrumental comparison for the determination of cadmium and
lead in calcium supplements and other calcium-rich matrices, Analyst, 117, 19, 1992.
11. Bourgoin, B.P. et al., Lead content in 70 brands of dietary calcium supplements, Am.
J. Public Health, 83, 1155, 1993.
12. Amarasiriwardena, D., Sharma, K., and Barnes, R.M., Determination of lead con-
centration and lead isotope ratios in calcium supplements by inductively coupled
plasma mass spectrometry after high pressure, high temperature digestion, Fresenius
J. Anal. Chem., 362, 493, 1998.
13. Scelfo, G.M. and Flegal, A.R., Lead in calcium supplements, Environ. Health Per-
spect., 108, 309, 2000.
14. Kim, M., Kim, C., and Song, I., Analysis of lead in 55 brands of dietary calcium
supplements by graphite furnace atomic absorption spectrometry after microwave
digestion, Food Addit. Contam., 20, 149, 2003.
15. Ross, E.A., Szabo, N.J., and Tebbett, I.R., Lead content of calcium supplements,
JAMA, 284, 1425, 2000.
16. Roberts, J.H., Potential toxicity due to dolomite and bone meal, South. Med. J., 76,
556, 1983.
2234_C013.fm Page 446 Thursday, October 26, 2006 8:50 AM
17. Boulos, B.M. and von Smolinski, A., Alert to users of calcium supplements as antihy-
pertensive agents due to trace metal contaminants, Am. J. Hypertens., 1, 137S, 1988.
18. Siitonen, P.H. and Thompson, H.C., Analysis of calcium and lead in calcium supple-
ments by inductively coupled plasma-atomic emission spectrometry and graphite
furnace atomic absorption spectrophotometry, J. AOAC Int., 77, 1299, 1994.
19. Capar, S.G. and Gould, J.H., Lead, fluoride, and other elements in bone meal sup-
plements, J. Assoc. Off. Anal. Chem., 62, 1054, 1979.
20. Hight, S.C. et al., Analysis of dietary supplements for nutritional, toxic, and other
elements, J. Food Compos. Anal., 6, 121, 1993.
21. Whiting, S.J., Safety of some calcium supplements questioned, Nutrition Reviews,
52, 95, 1994.
22. Consumer Reports, Calcium supplements: hold the lead, please, Consumer Reports,
64, 9, 1997.
23. Barnum, A., Environmental group sues over lead in calcium supplements, The San
Francisco Chronicle, February 4, 1997.
24. Husted, A., Health watch: some calcium products may have excess lead, The Atlanta
Journal-Constitution, January 29, 1997.
25. Kim, M., Mercury, cadmium and arsenic contents of calcium dietary supplements,
Food Addit. Contam., 21, 763, 2004.
26. Krone, C.A., Wyse, E.J., and Ely, J.T.A., Cadmium in zinc-containing mineral sup-
plements, Int. J. Food Sci. Nutr., 52, 379, 2001.
27. Ponce de Leon, C.A., Bayon, M.M., and Caruso, J.A., Trace element determination
in vitamin E using ICP-MS, Anal. Bioanal. Chem., 374, 230, 2002.
28. Huggett, D.B. et al., Organochlorine pesticides and metals in select botanical dietary
supplements, Bull. Environ. Contam. Toxicol., 66, 150, 2001.
29. Khan, I.A., Determination of heavy metals and pesticides in ginseng products, J.
AOAC Int., 84, 936, 2001.
30. Huggett, D.B. et al., Environmental contaminants in the botanical dietary supplement
ginseng and potential human risk, Hum. Ecol. Risk Assess., 6, 767, 2000.
31. Dolan, S.P. et al., Analysis of dietary supplements for arsenic, cadmium, mercury,
and lead using inductively coupled plasma mass spectrometry, J. Agric. Food Chem.,
51, 1307, 2003.
32. Raman, P., Patino, L.C., and Nair, M.G., Evaluation of metal and microbial contam-
ination in botanical supplements, J. Agric. Food Chem., 52, 7822, 2004.
33. Institute of Medicine, Dietary Reference Intakes for Vitamin A, Vitamin K, Arsenic,
Boron, Chromium, Copper, Iodine, iron, Manganese, Molybdenum, Nickel, Silicon,
Vanadium, and Zinc, a report of the Panel on Micronutrients, Subcommittees on
Upper Reference Levels of Nutrients and the Interpretation and Uses of Dietary
Reference Intakes, and the Standing Committee on the Scientific Evaluation of
Dietary Reference Intakes, Food and Nutrition Board, Institute of Medicine, National
Academy Press, Washington, D.C., 2001.
34. IRIS (Integrated Risk Information System), U.S. Environmental Protection Agency,
http://www.epa.gov/iris/subst/0278.htm, accessed November 30, 2005.
35. ATSDR (Agency for Toxic Substances and Disease Registry), Minimum Risk Levels
(MRLs) for Hazardous Substances, http://www.atsdr.cdc.gov/mrls.html, accessed
December 3, 2005.
36. Farley, D., Dangers of Lead Still Linger, U.S. Food and Drug Administration, FDA
Consumer, January–February 1998.
37. Gulson, B.L. et al., Contribution of lead from calcium supplements to blood lead,
Environ. Health Perspect., 109, 283, 2001.
2234_Index.fm Page 447 Thursday, October 26, 2006 2:27 PM
Index
A Aluminum contamination of food 364
Aluminum potassium sulphate 138, 149
Absorption 10, 13, 14, 15, 16, 17, 18, 25, 33, 37, Aluminum sodium sulphate 138, 149
38, 71, 74, 109, 110, 111, 112, 125, Alzheimer’s disease 147, 353, 382
126, 127, 129, 130, 147, 152, 153, Amanita rubescens 148
154, 155, 156, 157, 164, 165, 195, American Society for Testing and Materials
213, 271, 330, 331, 332, 342, 343, (ASTM) 57
350, 363, 364, 367, 372, 374, 376, Americium isotope (241Am) 390, 403
377, 378, 380, 382, 396, 397, 400, Aminolevulinic acid 154
422, 423, 444, 445 Aminolevulinic acid dehydratase 154
Absorption and metabolism of arsenic 363, 374 Anaemia 367, 376, 378
Absorption and metabolism of copper 364, 376 Analysis of variance (ANOVA) 71, 90
Absorption and metabolism of tin 364, 380 Analytical Quality Assurance (AQA) 66, 419
Absorption and metabolism of zinc 364, 377 Animal radioecology 401
Acanthopleura haddoni 77 Anodic stripping voltammetry (ASV) 22, 25
Accelerated solvent extraction (ASE) 6, 25 Antagonism effect 155
Acceptable Daily Intake (ADI) 141, 341, 418
Anthocyanins 379
Accuracy 12, 21, 37, 52, 53, 57, 60, 61, 62, 64,
Antiacids 145
343
Anticaking agents 149, 156
Acid reacting ingredients in selfrising flour or
Antifouling paints 34
cornmeal 149, 156
Antifungal seed dressings 365
Acidic soils 327, 333, 352
AOAC 53, 57, 61, 350
Acrylonitrile-butadiene-styrene (ABS) 341
Arabica 96, 97, 99, 101
Actinides 394, 395, 397, 400, 402
Active charcoal 333 Arcachon Bay 77, 78, 79
Acute Reference Dose (RfD) 419 Arctic 80, 379, 400
Acute renal failure 374 Arsenic contamination of food 363
Adenosyl derivatives 36 Arsenicals 150, 151
Adjuncts of mal 109 Arsenobetaine 34, 35, 46, 47, 150, 151, 156, 165,
Adriatic Sea 73 196, 423
African diet 420 Arsenosugars 34, 44
African tea 95, 97, 260, 292, 305, 306 Artificial neural network (ANN) 88, 89, 91, 94,
AFS detector 39 96, 106
Agaricus 148, 289, 372 Artificial radionuclides 392, 393, 407
Agaricus bisporus 148 Ascorbate 127, 136, 138, 140
Agglomerative Hierarchical Clustering Asian tea 94, 95, 260, 292, 305, 306
(AHC) 96 Assessment of radiation doses 405
Agrochemicals 330, 363 Atomic Absorption Spectrometry (AAS) 10, 13,
Al phosphate 381 14, 15, 25, 37, 38, 71, 74, 83, 87, 89,
Al stearate 381 91, 93, 97, 100, 103, 106, 107, 108,
Al sulphate 381 109, 111, 342, 343, 350, 351, 353
Albumins 127, 136, 334, 372 Atomic absorption spectrometry with hydride
Ale 111 generation (HG-AAS) 15, 16, 25, 74,
Alginate 138, 139, 142, 399 80, 111
Alopecia 378 Atomic emission spectrometry (AES) 10, 11, 16,
Aluminum ammonium sulphate 138, 149 25, 37, 89, 91, 93, 95, 98, 103, 107,
Aluminum containers 147 109, 342
447
2234_Index.fm Page 448 Thursday, October 26, 2006 2:27 PM
Index 449
in cheeses 2, 19, 82, 83, 131, 134, 165, in animal foods 174
170, 171 in cheese 2, 170, 171, 174
in cocoa powder 233, 243 in dairy products 168, 169, 170, 174
in Egyptian sugar 233 in eggs 2, 171, 174
in fish 2, 72, 73, 76, 166 in fruits 100, 238, 239, 240
in fruit juices 15, 100, 240, 245 in honeys 90, 91, 92, 172, 173, 174
in green coffee 96, 97, 99, 101, 103, in luncheon meat 174
242 in meat products 166, 174
in green pepper 237 in milk 13, 131, 165, 169, 170, 174
in honeys 90, 92, 93, 113, 165, 172 in miscellaneous cereals 234, 235,
in maize products (flour, corn flour and 236, 247
grains) 233, 236 in nuts 131, 244, 247
in maple syrup 233, 245 in offal 166, 174
in milk 2, 13, 25, 82, 131, 165, 168, in plant foods see food crops
169, 170 in prepared frozen poultry 174
in miscellaneous cereals 2, 15, 19, 234 in ready-sliced ham 174
in nuts 233, 244 in tea leaves 241, 242, 247
in plant foods see food crops in vegetables 85, 86, 87, 88, 131, 141,
in pork loin 134, 165, 166 237, 238, 239, 240, 247
in potatoes 89, 90, 143, 238 Potassium (K)
in soya flour 233, 235 in animal foods 174
in spinach 89, 233, 239 in avocado 239, 247
in tea 13, 19, 93, 94, 95, 98, 241 in banana pulp 240, 247
in thyme honey 165 in beer 109, 110, 111, 113, 246, 247
in white flours fortified with additional in cheeses 83, 134, 170, 171, 174
calcium carbonate 233 in coffee 96, 97, 98, 99, 100, 101, 241,
in wholemeal flour 233, 234 242, 247
in wine 103, 105, 106, 107, 111, 246, in cow milk 13, 82, 131, 165, 169, 170,
323, 325, 327, 333 174
Magnesium (Mg) in dairy products 168
in alcoholic beverages 107, 109, 110, in fruits 15, 85, 237, 239, 240, 247
111, 113, 245, 246, 325, 332 in grain products 247
in beer 109, 110, 246 in honeydew 91, 94, 172, 174
in cactus pear juice 247 in honeys 90, 91, 93, 94, 172, 173, 174
in cocoa powder 247 in Idaho potatoes 247
in coffee 96, 97, 99, 101, 242 in nuts 2, 244, 247
in cow milk 13, 82, 165, 168, 170 in plant foods see food crops
in dairy products 82, 83, 165, 168, 170 in pork loin 134, 166, 174
in fish 72, 76, 166 in seafood 75, 80, 81, 166, 174, 407
in fruit juices 13, 100, 103, 240, 245 in seeds 134, 244, 247
in fruits 13, 233, 240, 333 in sesame honey 173, 174
in grain products 233, 234, 236 in syrup-feed honey 173
in honeys 90, 91, 92, 93, 172 in tea leaves 13, 19, 93, 94, 95, 96, 97,
in meat products 13, 165, 166 98, 241, 242, 247
in nuts 244 in vegetables 2, 19, 85, 86, 87, 88, 89,
in plant foods see food crops 90, 131, 237, 238, 239, 240, 247
in raw goat milk 165, 168, 169 in wine 103, 104, 105, 106, 107, 111,
in sheep milk 165, 168 113, 246, 247, 323, 325, 333
in syrup-feed honey 173, 174 Sodium (Na)
in tea leaves 93, 94, 98, 241 in animal foods 174
in vegetables 85, 86, 87, 88, 89, 131, in beer 109, 110, 111, 113, 246, 247
237, 238, 239, 240 in cereals 19, 234, 235, 236, 247
in wine 103, 104, 105, 106, 107, 111, in cheeses 83, 84, 113, 170, 171, 174
113, 246, 323, 325, 332 in coffee 96, 97, 98, 99, 100, 101, 241,
Phosphorus (P) 242, 247
2234_Index.fm Page 450 Thursday, October 26, 2006 2:27 PM
in fruit juices 100, 245, 247 in fruit juices 100, 267, 269
in meat products 166, 174 in Galician honey 91, 93, 175, 194
in milk 82, 131, 165, 169, 170 in grain 247, 248, 249, 250, 251, 252,
in plant foods see food crops 269
in pork loin 90, 166, 174 in honeys 90, 91, 92, 93, 94, 175, 193,
in sesame honey 173, 174 194
in syrup-feed honey 173, 174 in human milk 183, 184
in tea leaves 13, 19, 93, 94, 95, 96, 97, in Marmite yeast extract 269
98, 241, 242, 247 in meat 71, 132, 175, 176, 177, 178,
in thyme honey 173, 174 180, 181
in vegetables 2, 19, 85, 88, 89, 90, 131, in milk 175, 182, 183, 184, 185, 186,
143, 237, 238, 239, 240, 247 187, 188
in wine 103, 104, 105, 106, 107, 111, in offal 175, 177
113, 246, 247, 325, 323, 333 in orange honey 194
Micronutrients in plant foods see food crops
Chromium (Cr) in raw goat milk 184, 185
in acid food preserved in stainless steel in sesame honey 175, 194
269 in sheep milk 184
in beer 111, 247, 268 in tartary buckwheat grain 252, 269
in black pepper 269 in tartary buckwheat leaf flour 251,
in Brewer’s yeast 131, 247, 440 269
in dairy products (cheeses) 3, 19, 131, in tea leaves 93, 94, 95, 96, 97, 260,
135, 188, 189, 190, 191 261, 262, 269
in fresh vegetable 269 in Vegemite yeast extract 269
in fruits 247, 254, 255, 256, 257, 258, in vegetables 19, 85, 86, 87, 88, 89,
259, 267 90, 254, 255, 256, 257, 257, 258, 269
in grain products 247 in wine 103, 104, 105, 106, 107, 268
in honeys 13, 90, 91, 92, 93, 94, 135, in yeast extract 175, 269
174, 175, 193, 194 Copper (Cu)
in meat and meat products 13, 71, 72, in animal foods 175
131, 174, 175, 176, 177, 178, 180, in bovine muscle 175, 176
181 in cereals 19, 248, 249, 250, 251, 252,
in milk and its products 13, 174, 182, 269, 375
183, 184, 185 in cheese 83, 84, 175, 188, 189, 190,
in nuts 3, 247, 264, 265, 266 191
in pine tree honey 175, 194 in coffee beans 96, 97, 98, 99, 101,
in plant foods see food crops 260, 261, 262, 269
in processed food 247 in cow milk 13, 83, 175, 182, 183, 184,
in red cabbage pickled in vinegar 269 185, 186
in tartary buckwheat grain 252 in crab meat 175, 180
in vegetables 15, 85, 86, 87, 88, 89, in currants 258, 269
90, 131, 247, 254, 255, 256, 257, in fruits 15, 100, 132, 188, 254, 256,
258, 269 258, 259, 267, 269
in wine 103, 104, 105, 107, 108, 247, in geese muscle meat 175, 178
268, 323, 325, 328 in goat milk 184, 185
Cobalt (Co) in grain products 269
in acacia honey 193 in grits 249, 269
in alcoholic beverages 103, 104, 105, in hen kidney 178
106, 107, 111, 112, 268, 269 in hen liver 178
in animal foods 269 in honeys 13, 90, 91, 92, 93, 135, 175,
in beer 268, 269 193, 194
in cereal products 269 in human milk 184, 187
in cheese 19, 175, 188, 189, 190, 191 in legumes 132, 255, 269
in common buckwheat bran 251, 269 in lythrum honey 175
in flour 19, 248, 249, 250, 251, 269 in maize flour 250, 269
2234_Index.fm Page 451 Thursday, October 26, 2006 2:27 PM
Index 451
in mammalian liver 175 in tea leaves 13, 93, 94, 95, 96, 97, 98,
in milk infant formula 185, 186 260, 261, 262
in nuts 15, 132, 264, 265, 266, 269, in vegetables 85, 86, 87, 88, 89, 90,
375 132, 143, 254, 255, 256, 257, 258,
in offal 175, 177, 375 269
in pine tree honey 175, 194 in wild rice 249
in plant foods see food crops in wine 103, 104, 105, 106, 107, 108,
in ready-to eat Australian breakfast 109, 110, 111, 112, 113, 175, 176,
cereals 269 268, 270, 329, 330
in sheep milk 184 Manganese (Mn)
in soya flour 250, 269 in acacia tree honey 192, 193
in sultanas 258 in animal foods 192
in tea leaves 13, 19, 93, 94, 95, 96, 97, in Apiaceae honey 192, 193
98, 260, 261, 262, 269
in beer 109, 110, 111, 112, 268
in Turkish hazelnut 269
in bovine muscle 176
in vegetables 2, 19, 85, 86, 88, 89, 143,
in British dry tea leaves 270
254, 256, 257, 258, 269
in citrus honey 193
in wheat bran 251, 269
in wholegrain 269, 375 in coffee 96, 97, 98, 99, 100, 101, 261,
in wild rice 249, 269 262, 270
Iron (Fe) in cow milk 13, 83, 182, 183, 184, 185,
in acacia honey 192, 193 186, 187, 188, 192
in animal foods 175 in crab meat 180, 192
in animal liver 192 in elk muscle 177, 192
in beer 109, 110, 111, 112, 268 in eucalyptus honey 91, 92, 193
in breakfast cereals 249, 270 in fruit juices 100, 267, 270
in canned blackcurrants 270 in fruits 15, 100, 132, 188, 249, 258,
in canned food 192 259, 267, 270
in cereal products 13, 112, 270, 248, in hazelnuts 270
249, 250, 251, 252 in honeys 13, 90, 91, 92, 93, 94, 192,
in cocoa powder 263, 270 193, 194
in cow milk 13, 182, 183, 184, 185, in human milk 184, 187
187, 188, 197 in infant formula 185, 186, 187, 192
in crab meat 180, 192 in instant coffee 261, 270
in curry powder 270 in meat 13, 71, 72, 132, 176, 177, 178,
in eggplant 89, 254, 269 180, 181
in flour 19, 248, 249, 250, 251 in milk products 82, 83, 84, 182, 183,
in fruit juices 100, 267 184, 185, 186, 187, 187, 188, 189,
in fruits 15, 100, 113, 132, 249, 254, 190, 191
256, 257, 258, 259, 267, 269, 270 in nuts 132, 264, 265, 266, 270
in grain coffee 96, 97, 98, 99, 100, 101,
in plant foods see food crops
260, 261, 262, 270
in soy-based milk infant formula 186
in hen kidney 178
in stabilized wheatgerm 251, 270
in hen liver 178
in tea beverage 13, 93, 95, 261, 270
in honeys 13, 90, 91, 92, 93, 94, 193,
194 in tea leaves 13, 19, 93, 94, 95, 96, 97,
in meat products 71, 177, 192 98, 132, 260, 261, 262, 270
in miscellaneous products 270 in vegetables 19, 85, 88, 89,
in nuts 2, 15, 264, 265, 266 in wheat bran 251, 270
in offal 2, 177, 192 in wine 103, 104, 105, 106, 107, 111,
in plant foods see food crops 113, 268, 332
in rye flour 251, 270 Molybdenum (Mo)
in sesame honey 192, 194 in animal foods 192
in tartary buckwheat leaf flour 251, in canned vegetables 143
270 in carcass meat 176
2234_Index.fm Page 452 Thursday, October 26, 2006 2:27 PM
in dairy products 82, 83, 84, 182, 183, in selenium-rich yeast 271
184, 185, 186, 187, 188, 189, 190, in sheep milk 195
191 in soybean 271
in milk 13, 83, 132, 182, 183, 184, 185, in vegetables 143, 254, 255, 256, 257,
186, 187, 188, 192 258, 271
in offal 177, 192 in wheat enriched 271
in peas 85, 85, 86, 135, 256, 270 Zinc (Zn)
in plant foods see food crops in acacia tree honey 193, 195
in wine 103, 104, 105, 268, 270 in almond 264
Nickel (Ni) in beef meat 176
in animal foods 192 in beer 109, 110, 111, 112, 268
in British instant tea 271 in carcass meat 176, 195
in cacao bean 271 in cheeses 19, 82, 83, 84, 134, 188,
in chocolate 271 189, 190, 191
in clover honey 192, 193 in clover honey 193, 195
in cocoa 263, 271 in cocoa powder 263, 272
in dairy products 82, 83, 182, 183, 184, in cow milk 13, 182, 184, 187, 195
185, 186, 187, 188, 192 in currants 259
in fruits 254, 258, 259 in dried apple 258, 272
in grain products 248, 249, 250, 251, in fresh fruit 258, 272
252, 253, 271 in fruit juices 100, 267, 272
in honeys 13, 90, 91, 92, 93, 94, 192, in honeys 13, 91, 92, 93, 134, 193, 194,
193, 194 195
in meat and its products 71, 72, 176, in human milk 184, 187
177, 178, 179, 180, 181, 192 in Indian honey 194, 195
in milk 13, 182, 183, 184, 185, 186, in infant formula 185, 186, 187, 195
187, 188, 192 in mammalian liver 195
in nuts 3, 264, 265, 266, 271 in milk 133, 182, 183, 184, 185, 186,
in plant foods see food crops 187, 188, 195
in sugar 102, 104, 107, 108, 262, 263, in nuts 133, 264, 265, 266, 272
265, 271 in offal 177, 195
in tea leaves 93, 94, 95, 96, 97, 98, in plant foods see food crops
260, 261, 262, 271 in pork loin 176, 195
in vegetables 85, 86, 87, 88, 89, 90, in seafoods 73, 74, 75, 76, 77, 78, 79,
254, 255, 256, 257, 258, 271 80, 81, 82, 179
Selenium (Se) in seeds 264, 265, 266, 272, 377
in beets 271 in stabilized wheatgerm 251, 272
in broccoli 42, 133, 271 in sultanas 258, 272
in cabbage 133, 254, 271 in sunflower seed 265
in cooked cod 195 in wheat bran 272
in cow milk 182 in wine 103, 104, 105, 106, 107, 268,
in dairy products 82, 182, 183, 184, 324, 334, 325
185, 186, 187, 188, 189, 190, 195 Non-toxic and non-essential elements
in fruit products 100, 188, 249, 258, Aluminum (Al)
271 in animal foods 196
in garlic 271 in beer 109, 110, 111, 273, 282, 381
in goat milk 184, 185 in cocoa powder 273, 280
in grain products 271, 248, 249, 250, in cow milk 13, 148, 196, 198
251, 252, 253, 254, 255, 256, 257 in dairy products 82, 156, 196, 198,
in milk 13, 135, 195 199, 200, 381
in nuts 264, 265, 266, 271 in dried tea leaves 273, 380
in plant foods see food crops in fish 13, 73, 76, 106, 148, 196, 197
in offal 177, 195 in fresh fruit 273, 278, 381
in onion 85, 86, 255, 271 in herbs 273, 380
in seafood 15, 16, 76, 78, 80, 81, 195 in honeys 90, 92, 196, 202
2234_Index.fm Page 453 Thursday, October 26, 2006 2:27 PM
Index 453
in infant formulas 196, 199, 273 in cow milk 13, 82, 215, 216
in legumes 273, 276 in dairy products 82, 213, 215, 216,
in meat offal 196, 380 217
in miscellaneous cereals 273, 274, in fruit juices 100, 293, 309
275, 381 in goat milk 215, 216, 217
in plant foods see food crops in milk-based powder formulas 213,
in soy-base infant formulas 196 215
in sultanas 273, 278 in miscellaneous cereals 293, 296
in tea leaves 13, 19, 93, 94, 95, 96, 98, in nuts 308
273, 279, 280 in plant foods see food crops
in vegetables 85, 86, 88, 143, 273, 276, in roasted coffee 293, 305, 307
277 in sheep milk 213, 215, 216, 217
in wine 103, 104, 105, 106, 107, 273, in tea leaves 13, 93, 94, 95, 98, 305,
282, 324, 325 306
Tin (Sn) in vegetables 217, 293, 300
in canned food 197, 379, 380 in wine 103, 105, 106, 107, 293, 309
in canned products 273 Bismuth (Bi)
in canned vegetables 273, 276, 379 in cream skimmed 213, 216
in eggs 197, 201 in dairy products 213, 215, 216, 217
in fish 106, 197 in eggs 213, 215, 216, 217
in fresh tomatoes 273 in meat products 213, 214
in fruit products 273, 278, 379 in milk 215, 216
in grain products 273, 275 Caesium (Cs)
in honeys 13, 197, 202 in animal foods 221
in Italian peaches 273 in beer 111
in meat and offal 197 in plant foods see food crops
in milk 13, 198 in rice 296
in plant foods see food crops in vegetables 300, 399, 400
in poultry 197 in wine 106, 107
in seafood 197 Cerium (Ce)
in tartary buckwheat leaf flour 273, in animal foods see food crops 213
275 Germanium (Ge)
in tomatoes in lacquered and in alcoholic beverages 293, 310
unlacquered cans 273 in animal foods 221
in vegetables 85, 86, 87, 88, 273, 276, in beer 293, 309, 311
277, 278 in bread 296
Other elements in dairy products 215, 216, 217, 221
Antimony (Sb) in eggs 221
in animal foods 213 in fish 221
in grain products 283, 298 in grain products 297
in meat 213, 214 in milk 215, 216, 221
in milk 13 in miscellaneous cereals 296
in offal 213, 214 in offal 214
in plant foods see food crops in plant foods see food crops
in vegetables 283, 298 in poultry 214, 221
in vegetal- and milk-based formulas in wine 293, 311
213 Gold (Au)
in wines 324 in animal foods 221
Barium (Ba) in bread 296, 299
in animal foods 213 in dairy products 215, 216, 221
in beer 109, 293, 309 in eggs 216, 221
in Brazil nut 293 in fish 214, 221
in cheese 213, 215, 216, 217 in meat 214
in contaminated salt in a Chinese in milk 215, 216
community 213 in miscellaneous cereals 296, 299
2234_Index.fm Page 454 Thursday, October 26, 2006 2:27 PM
Index 455
Index 457
in dairy products 202, 208, 209, 210 in seafoods 15, 16, 73, 74, 75, 80, 81,
in fruits 3, 281, 289, 290, 349 82, 206, 212, 213, 283, 426
in green leaf vegetables 281 in South America tuna 213
in honeys 13, 90, 92, 202, 212 Chernobyl accident 221, 393, 400, 401, 402
in lettuce and spinach 3, 89, 287, 288 Chewing gum 381
in meat 3, 71, 202, 203, 204, 205, 206, Chewing gum 381
371 Chinese tea 94, 241, 260, 261, 279, 292, 305, 306,
in milk 13, 202, 208, 209, 371 313
in plant foods see food crops Chlorine isotope (36Cl) 397
in rice 24, 281, 284, 294, 365, 370 Chocolate cake 381
in sheep offal 202 Chondroitin 434
in shellfish 202, 422 Chronic public health effects 418
in vegetables 85, 86, 87, 88, 89, 281, Citric acid 330, 351, 352
286, 287, 288, 371 Citric complex of Fe (III) 330
Lead (Pb) Clearance half-time 152
in alcoholic beverages 103,104, 105, Cluster analysis (CA) 70, 73, 82, 87, 88, 89, 90,
106, 107, 283, 295, 330, 331, 368, 93, 94, 95, 96, 98, 99, 100, 104, 106,
369 107, 111, 113
in animal foods 202, 212 CO2-cooled reactors 397
in cereals 3, 111, 112, 283, 284, 285, Coated squid rings 81
368 Cobalt isotope (60Co) 402
in dairy products 3, 82, 208, 209, 210 Codex Alimentarius Commission FAO/WHO 52,
in foods in lead-soldered cans 283 56, 66, 67, 141, 339, 414
Codex Alimentarius Commission Procedure
in fruits 283, 284, 289, 290, 349
Manual 339
in honeys 13, 90, 212
Coffee bean from:
in Italian canned vegetables 283
Indonesia 96
in meat 71, 202, 203, 204, 205, 206,
East Africa 96
368
Central/South America 96
in milk 13, 53, 202, 208, 209
Cola-based drink 381
in offal 202, 204
Cold vapor atomic absorption spectrometry (CV-
in plant foods see food crops
AAS) 15, 16, 25, 80, 342, 351
in Saudi Arabia honey 212
Colorants 344, 345, 349
in sesame honey 212
Committee of the Life Sciences Research Office
in syrup-feed honey 212 of the Federation of American
in tea 93, 94, 95, 96, 97, 283, 292, 293 Societies for Experimental Biology
in vegetables 3, 85, 86, 87, 88, 89, 283, 149
286, 287, 288, 368 Components in bleaching agents 149
in wines 13, 103, 104, 105, 106, 107, Confectionery 366, 381
295, 325, 330, 331, 369 Continuous flow isotope ratio mass spectrometry
Mercury (Hg) (CFIRMS) 71, 82, 83, 107
in animal foods 212 Cookware 147, 348, 352
in beer 111, 283, 295 Copper casse 328, 329
in canned vegetables 283, 286 Copper contamination of food 364
in cattle 203, 204, 212 Copper sulphate 328
in dairy products 208, 209, 210 Copper sulphide 127, 328
in fish 3, 15, 73, 151, 157, 205, 212, Cosmic rays 389, 391,
213, 283, 370 Crab 81, 82, 166, 175, 180, 192, 206, 372
in fruits 283, 289, 290 Creatine 434
in honeys 90, 212 Crustaceans 81, 82, 148, 197, 398, 404, 423
in lettuce 283, 287, 370 Cumbria 400, 403
in meat 203, 204, 205, 206, 212, 370 Curing agents 149, 156
in milk 13, 208, 209, 210, 370 Cyanide 18, 22, 330, 334, 426
in organ meat 212 Cyanogenic glycosides 426
in plant foods see food crops Cysteine 36, 42, 128, 136, 152, 271
2234_Index.fm Page 458 Thursday, October 26, 2006 2:27 PM
Index 459
Factor analysis (FA) 70, 71, 72, 73, 77, 79, 80, G
83, 87, 88, 89, 90, 106, 107, 111, 112
FAO/WHO Codex Alimentarius Commission’s Galician honey 91, 93, 172, 173, 175, 194, 222
Food Standards Programme 414 Galician potatoes 89
FAO/WHO Expert Committee 67, 125, 138, 140, Gamma rays 20, 389, 391, 392
141, 150, 158, 414 Gas chromatography with electron capture
Far Eastern diet 420 detector (GC-ECD) 16, 25
Fava beans 426 GC - EI MS 38
Fermentation 136, 138, 324, 326, 327, 328, 329, GC - FPD 38
330, 331, 333, 334, 373 GC - ICP MS 38
Ferritin 136, 153 GC - MIP AED 38
Ferroxidases 137 GC-AAS 38
GC-AFS 38
Fertilizer superphosphate 330
Genotoxicity 380
Filter pads 330
Germany 83, 106, 273
Filtering aids 327
Gingko biloba extract 434
Fining agents 327, 332, 333
Ginseng 434, 438, 439, 441, 442, 443
Finland 83, 240, 258, 290, 400 Ginseng supplements 441
‘Fino’ sherry wine 332 Glass 5, 7, 8, 13, 54, 71, 326, 328, 330, 332, 340,
Firming agents 139, 149 348, 349, 350, 351, 366
Fish liver oil 440 Global Environment Monitoring System (GEMS)
Fisher discrimination method 106 66
Flame atomic absorption spectrometry (FAAS) Glucosamine 434, 442
14, 25, 38, 350 Glucose Tolerance Factor (GTF) 126
Flame atomic emission spectrometry (FAES) 11, Glycolytic cycle 332
25 Good Laboratory Practice (GLP) 5, 25, 56
Flame photometric detection (FPD) 38 Good manufacturing practice (GMP) 141, 346
Flame photometry (FP) 11, 25 Grape maturity 103, 326
Flavonoids 136 Grape ripening 327
Flounder 73, 76 Grape seed extract 442
Grapevines 330
Fluroborate 326
Graphite furnace atomic absorption spectrometry
Folic acid 434
(GF-AAS) 14, 25, 80, 107, 343
Food additives 51, 67, 125, 136, 138, 140, 141,
Gravimetric methods 6
145, 146, 149, 150, 158, 269, 340,
Greek red wines 106
344, 349, 352, 381, 414
Green coffees from:
Food and Nutrition Board of the US National
Brazil 96, 242, 261
Academy of Science 125
Cameroon 96
Food Contact Materials 339, 340, 347, 348, 349,
Colombia 96, 100, 242, 261, 280
352, 353
Costa Rica 96, 100, 261, 280
Food Packaging 339, 340, 341, 342, 343, 344,
Guatemala 96, 242, 262, 280
345, 346, 347, 349, 353
Honduras 96
Food Performance Assessment Scheme (FAPAS)
Indonesia 96
63
Ivory Coast 96
Food stimulants 341, 342, 343, 344, 353
Nicaragua 96
Food wrappings 147 Salvador 96
Foodchain 403, 406 Thailand 96
France 80, 83, 90, 92, 172, 193, 202, 212, 222, Uganda 96
274, 379, 399 Vietnam 96
Frozen dough 149 Green tea 16, 98, 242, 261, 279, 305, 306
Frozen rolls 149 Greenland 148, 167, 180, 181, 206, 207
Fucus vesiculosus 399 Gulf of Aden 77
Fungicide copper sulphate 330 Gulf of Gdask 77, 78, 79
2234_Index.fm Page 460 Thursday, October 26, 2006 2:27 PM
Index 461
Mushrooms 2, 43, 69, 98, 99, 133, 148, 237, 238, Optical emission spectrometry with inductively
239, 240, 254, 256, 257, 258, 272, coupled plasma excitation (ICP-
273, 278, 286, 288, 289, 290, 300, OES) 13, 25, 106, 343
302, 304, 390, 399, 401, 402, 405 Organic mercurials 365
Mussels 40, 41, 71, 73, 74, 75, 76, 77, 78, 79, 80, Organoarsenic 34, 40, 43, 46, 150, 151, 156, 165,
81, 82, 403 196
Must 69, 111, 112, 113, 323, 324, 326, 327, 328, Organolead 38, 331
329, 330, 332, 333, 334 Organoleptical properties 328
MW digestion techniques 343 Organometallic species 38
Myanmar 426 Organoselenium 34, 40, 46
Mytilus edulis 75, 79, 80 Osteodystrophy 156
Mytilus galloprovincialis 77 Osteomalacia 131, 146, 157, 352, 382
Mytilus trossulus 79 Ostrea cucullata 77
Overglaze paints 349
Öxelosund, Sweden 79
N Oxygen flask combustion procedures (OFC) 343
Oysters 132, 133, 135, 157, 164, 377, 379
NADH 136
NADPH 136
National Radiological Protection Board (NRPB) P
392, 393
Nebulization 6 Package films 342
Packaging inks 344
Neurologic syndrome 145
‘Packaging grade’ plastics 341
Neurotoxicity 156, 380, 424
Pakistan 83, 85, 234, 249, 274, 297, 314
Neurotransmitter serotonin 154
Pancake 149
Neurotransmitter aminobutyric acid 154
Pancake mixes 149
Neutralizing agents 149
Paperboard 339, 340, 342, 345, 346, 347, 349
Neutron activation analysis (NAA) 7, 17, 18, 20,
Paraffin waxes 340
25, 26, 100, 342, 343
Passion Flower 441
New Zealand 81, 232, 374, 420
Pb arsenate insecticides 365
Nitrate 7, 8, 18, 22, 23, 132, 275, 351, 366, 379 Pea 85, 272, 285
Non-dairy creams 149 Pectic polysaccharides 43, 44
Non-Galician honey 91, 93 Pectinase 43
Nonheme iron 137, 192 Pectinolysis 41, 43
No-observed-adverse-effect-level (NOAEL) 418 Pectinolytic enzymes 43, 44, 45
Nordihydroguaiaretic acid 137 Penédes brandies 107
North Sea 80, 148 Peptides 34, 43
Northeast Atlantic 148 Perfluoroalkoxy (PFA) 5, 26
Northern European seas 404 Peripheral neuritis 374
Northern Ireland 400, 401 Peroxidation products 136
Norway 81, 148, 275, 400, 401 Peroxidative reaction 136
Nuclear magnetic resonance (NMR) 83, 107 Phenyltin 34
Nuclear weapons 389, 391, 392, 393, 399 Phosphorus isotope (32P) 390
Phosphorus supplements 434
Phytase 44
O Phytates 127, 195, 372, 376, 377
Pickled vegetables
Octopus 81, 82, 167, 181, 207 Pineapple juice 100, 245, 267, 348
Octyltin 34 Plastic Packaging Materials 339, 341
Odorous substances 347 Plasticized PVC 342
Onion 85, 86, 89, 133, 238, 255, 271, 276, 277, Pleuronectes ferruginea 76
281, 287, 300, 301, 302, 303, 304, Plutonium isotopes (238Pu, 239Pu, 240Pu, 241Pu) 390,
313 393, 395, 397, 398, 399, 403
Oolong tea 94, 98 Point of contact method 413, 416, 417
2234_Index.fm Page 463 Thursday, October 26, 2006 2:27 PM
Index 463
Poland 80, 81, 99, 101, 102, 176, 177, 178, 179, Provisional tolerably weekly intake (PTWI) 125,
182, 184, 188, 189, 191, 203, 204, 158, 349, 351, 353, 368, 414, 418,
205, 211, 214, 239, 248, 251, 252, 420, 421, 424
257, 266, 268, 282, 284, 289, 294, Provisional Total Tolerable Daily Intake (PTTDI)
295, 300, 309, 310, 311, 312, 314, 441
315 Pulsed flame photometric detector (PFPD) 38
Polonium isotope (210Po) 399, 401, 402, 403, 404, Purine 136
407
Polyamide (PA) 341
Polyanions 142 Q
Polycarbonate (PC) 341
Polyethylene (PE) 341 QM restriction quality limits 345
Polyethylene terephtalate (PET) 341 Quadratic discriminant analysis (QDA) 108
Polyolefins 343 Quality Assurance (QA) 5, 26, 33, 46, 55, 56, 57,
Polyphenolic compounds 136, 329, 332 62, 64, 66, 419
Polypropylene (PP) 341 Quality control 47, 52, 55, 56, 57, 61, 75, 97, 100,
Polystyrene (PS) 341 107, 109, 343, 351, 353, 419
Polytetrafluoroethylene (PTFE) 5, 8, 9, 26 Quality measurement system 55
Polyuronic acids 327
Polyvinyl chloride (PVC) 341
Portugal 207, 246, 268, 311, 312 R
Potable waters 373
Potassium bitartrate 333 Radiation dose to man 399, 400, 401
Potassium caseinate 333 Radiation units 389, 390
Potassium isotope (40K) 399, 404, 407 Radioactive half-lives 392
Potassium metabisulfite 139, 333 Radioactive waste 389, 391, 393, 394,
Potassium tartrate 327 402, 404
Potatoes (Solanum tuberosum) 2, 88, 89, 90, 143, Radioactivity in ‘free’ food 389, 401
232, 233, 247, 256, 273, 277, 288, Radioactivity in animal food 399, 400
299, 300, 301, 302, 303, 352, 365, Radioactivity in aquatic food 389, 402
371, 373, 375, 377, 397 Radioactivity in crops 389, 399
Powdered products 149 Radioactivity in Food and the Environment
Prawns 372 (RIFE) 393
Precision 11, 12, 23, 57, 58, 59, 60, 64 Radioactivity in terrestrial food 389, 399
Preeclampsia in pregnancy 444 Radiocaesium (137Cs) 221, 396, 400, 401, 402,
Premium long rice 85 403, 404
Principal components analysis (PCA) 70, 71, 72, Radiocesium
73, 74, 75, 76, 78, 82, 83, 85, 86, 87, in apple 396, 397
88, 89, 90, 91, 93, 94, 96, 97, 99, in gooseberries 396
100, 103, 104, 105, 106, 107, 108, in melon 396
111, 112, 113 in redcurrants 396
Printing Inks 339, 344, 345, 346 in rhubarb 396
Processed cheeses 149, 156, 381, 382 in strawberries 396
Processing aids 149, 381 in wild boar 401
Procyanidins 331 in wildfowl 401
Proficiency testing (PT) 51, 55, 62, 63, 64 Radiochemical methods 1, 17
Propylgallate 137 Radiochemical neutron activation analysis
Proteins 34, 39, 41, 42, 43, 44, 127, 128, 129, 130, (RNAA) 20, 26
136, 142, 144, 152, 155, 329, 331, Radioiodine 395, 400
376, 378, 423 Radionuclides
Proteolytic enzymes 43 in berries 390, 396, 399, 401, 402, 405
Provisional maximum tolerably daily intake in cod 403
(PMTDI) 125, 138, 140, 141 in cooked winkles 403
Provisional Tolerable Daily Intake (PTDI) 418, in crustaceans 404, 423
421 in fish 399, 402, 403, 404, 407
2234_Index.fm Page 464 Thursday, October 26, 2006 2:27 PM
ingoats 390, 401 Seafood 2, 3, 15, 16, 34, 38, 41, 42, 69, 73, 75,
ingrasses 390, 399 76, 80, 81, 82, 113, 131, 133, 148,
inhoney 390, 401 151, 156, 164, 165, 166, 174, 179,
inmeat and milk from domestic ruminants 195, 196, 197, 206, 212, 213, 223,
390, 401 273, 283, 371, 372, 398, 402, 403,
in meat from game animals 390, 401, 402 404, 405, 407, 423, 426
in milk 390, 395, 399, 400, 401, 405 Seafood from:
in molluscs 403, 404 Canada 81
in mushrooms 390, 399, 401, 402, 405 Great Britain 81
in reindeer 400, 401, 402, 405 India 81
in sheep 390, 400, 401 New Zealand 81
in shellfish 399, 402, 403, 404, 407, 422 Norway 81, 148
Radionuclides in food 389, 391, 400 Philippines 81
Radium isotope (226Ra) 399 Spain 81
Radon 389, 391, 392 Thailand 81
Radon decay products 389, 391 Se-cystine 46
Recommended daily intake (RDA) 125, 126, 376, Selectivity/specificity 59
378 Selenate 36, 271
Recycled fiber 345, 346, 347 Selenite 36, 271
Red wines 104, 106, 246, 268, 311, 312, 326, 331, Selenized yeast 42, 43, 44
333 Selenoaminoacids 34, 42
Reduced immunity 378 Selenocysteine 36, 271
Reference material (RM) 20, 46, 47, 51, 53, 55, Selenomethionine 36, 43, 46, 47, 271
56, 57, 58, 60, 61, 62, 63, 66, 343, Self-organizing with adaptive neighbourhood
351 network (SOAN) 89, 114
Reference Materials and Measurements (IRMM) Sellafield plant 395, 399, 401, 402, 403, 404, 407
63, 351 SeMet 47
Regenerated cellulose 340 Se-methionine 44, 46
Repeatability 58, 59, 64 Se-methylselenocysteine 36, 42
Repeatability conditions 58 Sensitivity 11, 17, 21, 24, 37, 38, 59, 60, 106, 133,
Reproducibility conditions 58 343, 353, 421
Rhamnogalacturonan-II 43 Serenoa repens 434
Rheological properties 123, 142 Shelf life 124, 136, 144, 342, 348
Ribonucleic acid (RNA) 26, 131, 155 Shellfish 132, 135, 148, 150, 151, 156, 157, 202,
Risk management 425 372, 398, 399, 402
Risk-reduction strategies 425 Sherry brandies 107
RNA polymerase 155 Sherry wine vinegars 113
Robusta 96, 97, 99, 101 Shrimp 15, 81, 82, 135, 166, 179, 180, 196, 206
Rubbers 340 Sievert (Sv) 391
Russia 80, 365 Simplified mode of potential curves (SMPC) 89
Russula ochroleuca 148 Skeletal fluorosis disease 425
Skin lesions 2, 4, 378, 425
Slovenian wines 107
S SML restrictions 345
SOAN-MLF-ANN 89
Safe and adequate daily intake (SAI) Sodium aluminosilicate 381
125, 126 Sodium aluminum phosphate 140, 149
Saganoseki, Japan 79 Sodium aluminum phosphate acidic and basic 140
Salmon 131, 135, 179, 205, 379, 402, 403 Sodium bicarbonate 149, 426
Salvador 96 Sodium borate 326
Saw palmetto 442 Sodium borotartrate 326
Scientific Committee on Food (SCF) 341 Sodium chloride 137, 144, 174
Scotch Whiskies 69, 107 Sodium citrate 137
Scotland 246, 268, 295, 393, 400, 403 Sodium oxalate 137
2234_Index.fm Page 465 Thursday, October 26, 2006 2:27 PM
Index 465
Soft independent modeling-class analogy Tea from Sri Lanka 94, 96, 260, 279, 305, 306
(SIMCA) 89, 91, 93, 104, 106, 111 Technetium isotope (99Tc) 397, 399, 403, 404
Sole 372, 403 Teflon coated aluminum-pans 148
Solid phase extraction (SPE) 6, 26 Temporary ADI (TADI) 138, 140, 141, 341
Sources of radioactivity 389, 391 Tetraalkylated lead 34
South Africa 366 Tetrabutyltin 41
South America 96, 213, 271, 373 Tetramethylarsonium 35, 46
Spain 80, 81, 87, 90, 104, 105, 106, 111, 112, 166, Textile products 340
172, 173, 176, 177, 179, 180, 181, Texturized milk products 142
184, 189, 190, 194, 198, 199, 200,
Texturizers 149
201, 203, 204, 206, 216, 218, 219,
Thailand 81, 96, 426
220, 222, 238, 246, 249, 254, 256,
Thermal ionization isotope dilution mass
264, 265, 268, 274, 286, 287, 288,
spectrometry (TI-IDMS) 343
294, 301, 302, 308, 310, 311, 374
Thermoplastic polymers 341
Spanish wines 104, 106
Speciation analysis 6, 34, 37, 38, 39, 41, 45, 46, Thickeners 149, 156
145, 165, 195 Thiobarbituric acid 137
Spectrophotometric methods 1, 10, 11 Thiols 136
Spirituous beverages 69, 108 Tin contamination of food 364
Squids 81, 82, 164 Titrimetric methods 6,7
St. John’s wort 434, 438, 441, 442 TMSe+ 47
Stabilization stages 327 Tokay wines 107
Stabilizers 149, 156, 341, 342, 379 Tomatoes 87, 239, 257, 273, 352, 379, 397
Stainless steel-pans 348 Torpedo shrimp 81
Standard Operating Procedures (SOP’s) 5 Total reflection X-ray fluorescence analysis
Stockholm Convention on Persistent Organic (TXRF) 96
Pollutants (POPs) 414 Toxic Effects 154, 156, 374, 418
Stout 109, 110, 111 Toxic psychosis 367
Stronitium (90Sr) 390, 393, 394, 396, 399, 440 Toxicity of tin 364, 380
Sub-Arctic regions 400 Traceability 55, 58, 61
Succinyl dehydrogenase 146 Transferrins 127, 136
Suillus 148 Transuranics 403
Suitable and reference materials 55 Tributyltin 41, 46, 165, 197
Sulfur dioxide 139, 141, 324, 328 Trimethyl/triethyl lead 331
Sulphur 151, 390, 397 Triphenyltin 41
Sulphur isotope (35S) 397
Tripropyltin 41
Supercritical fluid extraction (SFE) 6, 26
Tritium (3H) 390, 392, 393, 396, 397, 492
Superoxide dismutase (SOD) 136, 137, 333, 376
True value 53, 57, 58, 59, 60, 61
Supervised learning PR methods 109
Trueness 58, 59, 62
Supplement for calcium derived from algae 440
Tryptophan pyrollase 154
Surimi crab 81
Sweden 79, 80, 168, 182, 250, 251, 275, 285, 367, Tyrolean childhood cirrhosis 375
400, 402
Switzerland 83, 148, 176, 177, 178, 379
Synergistic effect 155 U
U.S. Food and Drug Administration (U.S. FDA)
433, 434, 440, 443
T U.S.A. 72, 85
Taiwan 179, 180, 181, 206, 373 Ukraine 393, 402
Tannates 129 Ultraviolet (UV) 14, 17, 26
Tannins 329, 330, 331 Unbleached fiber material 345
Tanzania 426 Uncoated Al-pans 352
Tea from India 96, 241, 260, 261, 279, 292, 305, Uncoated aluminum utensils 353
306 United Nations Environment Program (UNEP) 66
2234_Index.fm Page 466 Thursday, October 26, 2006 2:27 PM
United Nations Scientific Committee on the Wheat 2, 62, 109, 110, 111, 112, 134, 135, 153,
Effects of Atomic Radiations 235, 236, 250, 251, 252, 253, 269,
(UNSCEAR) 392 270, 271, 272, 273, 274, 275, 284,
United States see U.S.A. 285, 425
Univariate tests of normality (Kolmogorov- Wheat beer 109, 111
Smirnov) 71 White wines 106, 246, 324, 326, 328, 329, 330,
Unlacquered tin cans 129 331, 332
Upper Level Dietary Reference Intake (ULDRI) Wilson’s disease 376
442, 443 Wine tanks 348
Uranium isotopes (233U, 234U, 235U, 238U) 390, 391, Wines from El Hierro 105
402 Wines from La Palma 105
U.S. Bureau of Alcohol, Tobacco and Firearms Wines from Lanzarote 105
(BATF) 368 Wines from the Canary Islands 105, 106
U.S. EPA’s Reference Dose 424 Wines from the Tenerife Island 106
Utensils 147, 148, 222, 233, 269, 334, 348, 351, Wood, including cork 340
352, 353, 363, 366, 375, 378 World Trade Organization (WTO) 414
V X
Valerian 438, 440, 442 Xerocomus badius (caps and stalks) from north-
Validations of methods 56 eastern Poland 98, 101, 102
Vegetarian diet 422 X-ray energy spectroscopy (XES) 73
Vietnam 96, 426
Vine growth 327
Vineyards 326, 327, 330 Y
Vinification equipment 329, 330, 334
Yeast doughs 149
Visible (VIS) 14, 17, 24, 25, 26, 109
Yellowtail flounder 73, 76
Vitamin A 133, 434, 439, 440
Yemen 80
Vitamin B12 126, 132, 175, 434, 440
Yushan salt 426
Vitamin C 143, 434, 440
Vitamin D 129, 155, 157, 382, 434, 440
Vitamin E 434, 440
Vitamin Supplements 433, 440
Z
Zinc contamination of food 364
‘Zinc finger protein’ 378
W Zinc gluconate 440
Zinc thiocarbamate 328, 334
Waffle 149
Zinc toxicity 364, 378
Wales 393, 400, 403
Ward hierarchical clustering method 106