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OOD Ntegrity Andbook: Guide To Food Authenticity Issues and Analytical Solutions

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FOODINTEGRITY HANDBOOK

A GUIDE TO FOOD AUTHENTICITY ISSUES


AND ANALYTICAL SOLUTIONS

Editors: Jean-François Morin & Michèle Lees, Eurofins Analytics France

ISBN print version 978-2-9566303-0-2


electronic version 978-2-9566303-1-9

https://doi.org/10.32741/fihb

This book contains information obtained from authentic and highly regarded sources. Reasonable efforts have been made to
publish reliable data and information, but the authors, editors and publishers cannot assume responsibility for the validity of all
materials or the consequences of their use. The authors and editors have attempted to trace the copyright holders of all material
reproduced in this publication and apologise to copyright holders if permission to publish in this form has not been obtained. If any
copyright material has not been acknowledged, please write and let us know so we may rectify in any future reprint.

Disclaimer: The information expressed in this book reflects the authors’ views; the European Commission is not liable for the
information contained therein.
Coffee
Jean-François Morin*, Eric Jamin, Sophie Guyader, Freddy Thomas
Eurofins Analytics France, Nantes, France
*E-mail corresponding author: JeanFrancoisMorin@eurofins.com

General overview of the product


The coffee tree is a tropical evergreen shrub classified under the genus Coffea, and part of the
botanical family Rubiaceae. It grows between the Tropics of Cancer and Capricorn. Although more
than 100 species exist in this genus [1], only two of them are of real economic importance for the
production of the beverage coffee:
● C. arabica, called Arabica coffee: production area is mainly South and Central Americas,
with the exception of Ethiopia, the country of origin for coffee;
● C. canephora, called Robusta coffee: most of the world's Robusta is grown in Central and
Western Africa, parts of Southeast Asia and in Brazil.
The other species C. liberica (Liberian or Liberica coffee, or Excelsa coffee) is traded to a very
limited extent. The share of Arabica fell from about 80 % of world production in the 1960s to
around 60 % in the 2010s. Initially this was because of the strong growth of Robusta production in
Brazil and parts of Africa, but more recently because of the emergence of Asia as the world’s
leading Robusta producing region [2].
On the world market, Arabica coffees attract the highest prices. Arabica trees are costly to
cultivate because the ideal terrain tends to be steep and access is difficult. Also, because the trees
are more disease-prone than Robusta, they require additional care and attention. Robusta is
primarily used in blends and for instant coffees. The Robusta tree has the advantage of being able
to withstand warmer climates, which enables it to grow at far lower altitudes than Arabica.
Compared with Arabica, Robusta beans produce a coffee which has a distinctive taste and more
caffeine.
Coffee is grown globally in around 70 coffee producing countries. In 2016/17, coffee production
was 159.1 million bags (i.e. 9.5 millions of tonnes, each bag contains 60 kilograms of green coffee),
from which 98.8 were Arabica and 60.4 Robusta. Brazil is the largest producer: its coffee sector
contributes 35.2 % to the world’s total coffee production. Vietnam is the second largest producer
of coffee in the world, accounting for 16.8 % of global production. It is the main producer of
Robusta. Colombia is the second-largest supplier of Arabica coffee after Brazil, with respectively
15 % and 46 % of the worldwide production. Indonesia is the world’s second-largest exporter of
Robusta. Ethiopia is the largest coffee producer in Africa. The European Union (EU) is the primary
market, accounting for 40 % of the world’s coffee bean imports, followed by the United States
with 24 % [3].

https://doi.org/10.32741/fihb.16.coffee
Coffee

A great variety of coffee products can now be purchased. International coffee trade is conducted
almost exclusively in green coffee. However, consumers are nowadays offered roasted coffee
beans, roasted and ground coffee, as well as liquid and dried coffee extracts (soluble coffee).
Furthermore, coffee can be mixed with coffee substitutes, and also sold as roasted and ground
blends or as dried extracts. Whole-bean roasted coffee may also be soaked with liquid flavouring
agents to produce flavoured coffees. Finally, dried coffee extracts already containing milk solids
(café au lait, cappuccino) exist on the market. Decaffeinated forms of each of these coffee
products are also available.
The different varieties of coffee bean and the region where the coffee is grown may give rise to
products of different qualities that are more or less popular with the consumer. This in turns leads
to price differences on the market and the potential for adulteration or misrepresentation by a
dishonest trader. A popular component of the Western diet, coffee is also an important
commodity in international trade upon which the economies of a number of countries are
particularly dependent. In 2010 the International Coffee Organization (ICO) estimated total coffee
sector employment at about 26 million persons in 52 producing countries[4]. Thus, the coffee
industry itself has devoted considerable time and effort to ensuring both the quality and
authenticity of its product, and to developing suitable analytical techniques for this purpose.
In the last 30 years, the coffee market has seen the emergence of an increasing number of
initiatives related to fair-trade and sustainability. Often marked with a label on the coffee
packaging, these labels certify the sustainability of coffee production and the respect of
smallholder producers by improving their conditions of trade (e.g. more equitable and more stable
prices). In the coffee market, most extended programmes are UTZ Certified and the Rainforest
Alliance, which merged early 2018, and the Max Haavelar Foundation. According to Fairtrade
International, fair-trade coffee farmers produced an estimated 560 900 tonnes of coffee in 2015
(approximately 6 % of the worldwide production).

1. Product Identity
1.1. Definition of the product and manufacturing process
Green coffee may be produced by either a wet or dry process. The wet process involves washing
the coffee cherries and transferring them to depulping machines which remove the outer skin and
most of the pulp. This process leaves some of the pulp mucilage on the parchment shells which
encase the coffee bean and this remaining mucilage is fermented and washed away with clean
water. The beans are then dried and the inner husk known as 'parchment' is broken by rollers and
removed. Further rubbing removes the film or 'silverskin' which closely adheres to the coffee bean.
The dry process involves drying the fresh ripe cherries in the sun for up to three weeks. The dried
coffee cherries are dehulled mechanically to remove the outer skin, pulp, 'parchment' and the
'silverskin' to leave the clean, naked, green coffee beans.
Coffee is usually traded as green coffee beans, a state in which they can be kept without loss of
quality or taste. It is roasted and further processed in the purchasing country. Roasting brings out
the aroma and flavour that is locked inside the green coffee beans. The roasting process involves
the heating of the green beans at about 200 °C, followed by fast cooling to stop the process. Once
roasted, coffee should be used as quickly as possible before the fresh roast flavour begins to
diminish.

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Coffee

Instant coffee (soluble coffee) is also produced in the coffee growing countries and may be traded
packed ready for retail sale or in bulk for re-packaging in the country of receipt for national
consumption or for further export. Instant coffee is the dried water-extract of roasted, ground
coffee. Roasted, ground coffee is placed into columns known as percolators through which hot
water is fed in a counter-current process. The extract is further concentrated and may be traded in
bulk as such or dried to produce soluble coffee solids. Instant coffee is sold in three forms, which
relate to the drying process of the soluble coffee extract. Instant coffee powder is formed by spray
drying the extract; coffee granules are formed by agglomerating this powder with steam; and
freeze-dried coffee is formed by removing moisture from the extract under vacuum (sublimation)
at much lower temperatures than spray drying. Freeze-drying is more energy expensive but is
gentler on the product as less heat is applied to evaporate the water content. Consequently,
freeze-drying is used for the finer and more expensive blends of instant coffee.
Decaffeinated coffee is produced from green beans. Three different extraction processes slightly
differing from each other are in use in the industry. Basically a solvent is circulated around the
water soaked beans and this causes the caffeine to be released. The most widely used and less
costly is extraction with an organic solvent such as methylene chloride (also known as
dichloromethane) or ethyl acetate, an ester that is found naturally in fruits and vegetables. The
second method is water processing: water is used as a solvent to extract the caffeine. In the third
approach, carbon dioxide in supercritical state under a pressure of 250 to 300 bar circulates
through a bed of green beans. At the end of the process, caffeine content is usually reduced from
1–2 g% to 0.02–0.3 g% [5].

The ICO was formed in 1962 under the auspices of the United Nations. It is a inter-government
body comprising 51 coffee importing and exporting countries which aims through international co-
operation on trade in coffee to achieve economic diversification and development of coffee-
producing countries, increased coffee consumption, price stabilisation and improved economic
relations between coffee exporting and importing countries. The ICO is well regarded for its
statistical services and its role as the international forum for discussing all issues affecting the
world coffee market. It also co-ordinates a number of projects (most of which deal with marketing,
pest/disease/quality problems or sustainability) and holds seminars on issues such as the
environmental aspects of coffee production and the use of the futures market.
The International Coffee Agreement 2007 is the legal agreement which sets out how these
objectives will be met [6]. In this document, the different coffee products are defined for
harmonising data collection, statistics and trade among producing and importing countries. On the
other side, the International Standard Organisation has issued a standard “Coffee and coffee
products – Vocabulary” (ISO 3509:2005) [7] also for setting the definitions of coffee products. The
same terms, such as “Roasted coffee” or “Decaffeinated coffee” can be found in both documents,
but definitions are largely consistent. Roughly ICO definitions are more statistically oriented
whereas ISO focuses more on quality and process.

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Coffee

Table 1: Comparison of the definition of coffee and coffee products between ICO and ISO

Product ICO Definition ISO 3509:2005 definition

Coffee General term for the fruits (cherries) and –


seeds (beans) of plants of the genus
Coffea, as well as products from these
fruits and seeds in different stages of
processing, such as dry cherry,
parchment, green, roasted, ground,
decaffeinated, liquid and soluble coffee
Green coffee All coffee in the naked bean before Commercial term designating the dried seed
roasting of the coffee plant
Roasted coffee Green coffee roasted to any degree and Coffee obtained by roasting green coffee
includes ground coffee
Ground coffee – Product obtained by grinding roasted coffee
Coffee extract – Product obtained exclusively from roasted
coffee by physical methods using water as
the only carrying agent which is not derived
from coffee
Soluble coffee Dried water-soluble solids derived from –
roasted coffee
Instant coffee – Dried, water-soluble product, obtained
Dried coffee extract exclusively from roasted coffee by physical
methods using water as the only carrying
agent which is not derived from coffee
Spray-dried instant coffee – Instant coffee obtained by a process in
which the coffee extract in the liquid state is
sprayed into a hot atmosphere and formed
into dried particles by evaporation of the
water
Agglomerated instant coffee – Instant coffee obtained by a process in
which the dried particles of instant coffee
are fused together to form larger particles
Freeze-dried coffee – Instant coffee obtained by a process in
Freeze-dried coffee extract which the product in the liquid state is
Freeze-dried instant coffee frozen and the ice removed by sublimation
Freeze-dried soluble coffee
Decaffeinated coffee Green, roasted or soluble coffee from Coffee from which caffeine has been
which caffeine has been extracted extracted

1.2. Current standards of identity or related legislation

1.2.1. Standards from ISO and the German organisation DIN


In 1980 the International Standard Organisation (ISO) created a sub-committee on coffee within its
Technical Committee on Food products (TC 34 / SC 15). The scope of its work is standardisation in
the field of coffee and coffee products, covering the coffee chain from green coffee to
consumption. Standardisation includes terminology, sampling, test methods and analysis, product
specifications and requirements for packaging, storage and transportation. About 30 standards
have been written and are available on the ISO website www.iso.org.

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Coffee

Among these standards, two of them have a special application to instant coffee authenticity. The
standard “Instant coffee - Criteria for authenticity” (ISO 24114:2011) [8] specifies criteria for
authenticity of soluble (instant) coffee. Its purpose is to identify adulterated soluble coffee,
defined as a “product prepared by the co‐extraction or the separate extraction of roasted coffee
beans and of raw or roasted materials other than coffee beans, where the product is sold as pure
soluble coffee and the addition of the non‐coffee bean material is not declared on the label”. The
aim is to avoid incorrect declarations that adulterated products with cheaper coffee substitutes
are 100 % pure soluble coffee. The standard focuses on two different parameters: total glucose
and total xylose, the values of which must not exceed certain limits (respectively 2.46 % and
0.45 %) for the instant coffee sample to be declared authentic.
The standard is based on a standardised method looking at the carbohydrate content of the
instant coffee, under the reference “Instant coffee - Determination of free and total carbohydrate
contents - Method using high-performance anion-exchange chromatography” (ISO 11292:1995)
[9]. The free and total carbohydrate profiles in soluble coffee are determined by anion exchange
chromatography with pulsed amperometric detection (AE-PAD).
For roasted coffee, the German standard method “Analysis of coffee and coffee products -
Determination of 16-O-methyl cafestol content of roasted coffee - HPLC-method” (DIN
10779:2011) [10] can also be used for authentication purposes. It is used to quantify the amount
of 16-O-methylcafestol (16-OMC) in roasted beans originally, even if applications to green coffee
beans and coffee brews have also been described in the literature [11]. It is based on the
observation that 16-OMC is present exclusively in Robusta.

1.2.2. EU legislation
Beyond general regulations on food products, such as the General Food Law (Regulation EC
178/2002), the European Union has set up several regulations dealing with coffee products.

The general EU Regulation 1169/2011 [12] on the provision of food information to consumers,
combines two Directives into one legislation: 2000/13/EC - Labelling, presentation and advertising
of foodstuffs, and 90/496/EEC - Nutrition labelling for foodstuffs. Among other themes, it deals
with the labelling of origin. No specific rules have been set up for coffee, the general principle that
“information shall not be misleading” applies. Voluntary provenance labels (i.e. indication where
the green coffee was grown) can be made in relation to product claims such as ‘100 % Brazilian
coffee’.
This regulation also stipulates a list of foods, including the following coffee products, which are
exempted from the requirement of the mandatory nutrition declaration:
● Products covered by Directive 1999/4/EC of the European Parliament and of the Council
of 22 February 1999 relating to coffee extracts and chicory extracts,
● Whole or milled coffee beans and whole or milled decaffeinated coffee beans.

Directive 1999/4/EC [13] relating to coffee extracts and chicory extracts determines which
substances may be added during manufacturing of these products, lays down common rules
concerning the packaging and labelling of such extracts and specifies the conditions under which
particular designations may be used for some of these products. It simplifies the legislation
previously regulated by Directive 77/436/EEC.

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Coffee

It defines coffee extracts as “the concentrated products obtained by extraction from roasted
coffee beans using only water as the medium of extraction and excluding any process of hydrolysis
involving the addition of an acid or a base”.
In particular it stipulates that “coffee extract must contain only the soluble and aromatic
constituents of coffee”, apart from those insoluble substances which it is technically impossible to
remove, and insoluble oils derived from coffee.
It controls the composition of three types of coffee extracts which differ in terms of their coffee-
based dry matter content:
● Dried coffee extract: not less than 95 % by weight,
● Coffee extract paste: from 70 % to 85 % by weight,
● Liquid coffee extract: from 15 % to 55 % by weight.
Liquid coffee extract is specifically allowed to contain edible sugar provided the sugar content in
the final product does not exceed 12 % by weight. The Directive does not permit coffee extract in
solid or paste to contain any substance other than those derived from its extraction.
This Directive also states that the term 'decaffeinated' can only be applied to coffee extracts which
have an anhydrous caffeine content of not more than 0.3 % by weight of its coffee-based dry
matter content.
The Directive does not cover roast and ground coffee.

According to Directive 2009/32/EC [14], solvents can be used for decaffeination of coffee in the
European Union. There are maximum residue limits restrictions for the extraction solvents such as
methyl acetate (20 mg/kg in the coffee), dichloromethane (2 mg/kg in the roasted coffee) and
ethylmethylketone (20 mg/kg in the coffee). In the United States, according to the FDA, methylene
chloride may be present in coffee as a residue from its use as a solvent at a level not to exceed 10
parts per million in decaffeinated roasted coffee and in decaffeinated soluble coffee extract
(instant coffee) [15].

Directive 2002/67/EC [16] on the labelling of foodstuffs containing quinine,and caffeine sets up
specific rules for protecting consumers and providing them with clear information on the presence
of these compounds.
Where a beverage which is intended for consumption without modification, or after reconstitution
of the concentrated or dried product, contains caffeine, from whatever source, in a proportion in
excess of 150 mg/l, the following message must appear on the label in the same field of vision as
the name under which the product is sold: "High caffeine content". This message shall be followed
by the caffeine content expressed in mg/100 ml.
However, this obligation does not apply to beverages based on coffee, tea or coffee or tea extract
where the name under which the product is sold includes the term "coffee" or "tea".

One Protected designation of origin (PDO) and one protected geographical indication (PGI) have
been granted by the European Union:
● Café de Colombia (PGI) in Regulation (EC) 1050/2007 of 12 September 2007 [17];
● Café de Valdesia (PDO) in Regulation (EU) 2016/1043 of 15 June 2016 [18].

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Coffee

1.2.3. Further legislation and standards regulating quality


In 2004, the International Coffee Organisation (ICO) has introduced voluntary targets for minimum
quality export standards for Arabica and Robusta under resolution 420 [19]. Thresholds for defects
(not more than 86 defects per 300 g sample for Arabica, not more than 150 defects per 300 g for
Robusta) and moisture (between 8 % and 12.5 %) are defined. The resolution aims to reduce the
export of inferior beans. Coffee exporters from ICO exporting Members are advised to closely
follow this resolution, except for the exports of specialty coffees which can be exempt from some
of the targets as long as this is clearly mentioned in the Certificate of Origin.
Different producing countries have differing quality control systems and attach differing values to
certain aspects of quality. Information is also available from coffee authorities in producing
countries. Some specific coffee products are also produced in some countries with specific
regulations, such as “Café torrefacto” in Spain and Portugal, which is a particular process to roast
coffee beans with sugar addition.
The Coffee Quality Institute, an independent organisation founded originally in the scope of the
Specialty Coffee Association of America (SCAA), has developed the Q Coffee System for Quality
Control. It is an initiative to introduce international standards for coffee quality. It is based on
trained and certified people in the supply chain (Q graders) who test coffee samples mainly from
an olfactory and sensory point of view according to SCAA protocols. Each sample is tested by three
local Q graders. Coffees that meet the standards for green, roasted, and cup quality are issued a Q
Certificate. Companies who wish to promote and sell Q coffee may use the Q certification marks
on their product packaging.

2. Authenticity issues
2.1. Identification of current authenticity issues
As mentioned previously the two coffee species of commercial importance are Arabica and
Robusta. Producer countries and coffee traders are mainly interested in being able to recognise
the country of origin of coffees, whereas food processors and regulatory authorities are interested
in checking on compliance of the declared composition in commercial blends and in the detection
of adulteration by addition of substitutes or other ingredients

2.1.1. Adulteration by addition of substitutes


Coffee substitutes may be added to the roasted and ground coffee if they are permitted and
declared on the label. However if these substitutes are not correctly labelled or not declared at all
then the consumer is being misled. In the case of roasted and ground coffee, inspection with a
microscope may help to determine the presence of non-coffee material. Possible ingredients that
may be found in ground coffee or coffee extracts include chicory, malt, figs, cereals such as corn
and barley, caramel, starch, maltodextrins or glucose syrups as well as roasted or even unroasted
coffee husks/parchment [20].
This problem is more important in soluble coffee extracts due to industrial processes which merge
Arabica and Robusta beans before several steps like lyophilisation. Consequently, the detection of
adulteration is no longer feasible by visual inspection, microscopy or other physical means
traditionally used to identify impurities or “defects” which can be present in green or roasted bean
or ground coffee.

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Coffee

2.1.2. Geographical origin


The taste and aroma of the coffee beverage is influenced by the country of origin, and even within
a certain geographical region or “terroir” some differences are to be expected as a function of
specific agro-climatic conditions. Some mild Arabicas of certain countries or regions attract high
prices on the world market raising the possibility of substitution with coffee of cheaper origin or
mislabelling. Geographic origin claims for middle range roasted coffees have begun to appear on
supermarket shelves. Geographic origin authentication is becoming increasingly of interest.
In the majority of coffee-producing countries as well as among coffee traders there are tasters
who can recognise the country of origin of the coffees they deal with, however none of them can
identify reliably a large number of coffee origins. Moreover the opinions of these tasters are
subjective, and in cases of arbitration, disagreements frequently occur between the tasters
appointed by the parties involved. Analytical techniques for checking geographical origin allow for
less subjective assessment.

2.1.3. Variety substitution and falsified proportion of inter-


specific blends
Arabica are more expensive than Robusta coffees. Arabica is generally viewed as superior in cup
quality to Robusta and is often sought exclusively by consumers. In these circumstances, addition
of Robusta coffee to Arabica offers the possibility of commercial gain to an unscrupulous dealer
and represents a fraud. Green and roasted beans normally may be recognised as Arabica or
Robusta by visual inspection and specifically because of their specific organoleptic characteristics,
however some washed Robusta coffees approach the taste quality of Arabica. As a result there is
still room for non-declared substitution. On the other hand it is important to confirm if the
proportions of Arabica and Robusta in the blend correspond to the price the consumer is paying.
Coffee breeding is still largely restricted to the two species, Coffea arabica and C. canephora, that
dominate world coffee production. Efforts have been greatly intensified through breeding
programmes in order to develop disease-resistant varieties, in anticipation of possible coffee leaf
rust (Hemileia vastatrix Berk. & Br.) epidemics that earlier in the century had devastated the C.
arabica plantations in Asia and Africa. Serious threats of coffee berry disease (Colletotrichum
coffeanum Noack sensu Hindorf) to Arabica coffee in the highlands of Eastern and Central Africa
prompted a number of entirely new breeding programmes in the early 1980s particularly in Kenya
and in Ethiopia [21].
Beyond the fight against diseases, coffee production is now threatened by climate change. Arabica
coffee is highly sensitive to elevated temperatures, drought, pest, and disease. The forecasted
consequences of climate change include changes in rainfall patterns, more frequent drought
periods, and elevated temperatures, as well as a shift in geographical coffee growing regions,
leading to environmental, economic and social threats in the coming years [22]. Since the second
th
half of the 20 century, most breeding programmes implemented throughout the world (Brazil,
Colombia, Kenya, Ethiopia, Costa Rica, Honduras, Tanzania, India, etc..) have transferred resistance
to the main diseases by introgression of C. canephora chromosomal fragments carrying resistance
genes. Today Arabica cultivars derived from C. canephora via the interspecific ‘Timor Hybrid’ (a
spontaneous cross between C. canephora x C. arabica) represent more than 30-40 % of the
Arabica trees cultivated around the world [23]. On the other hand, introgression via the Timor
Hybrid may carry not only resistance genes but also other undesirable genes involved in a
substantial drop in cup quality [24]. Consequently, complex and long term genetic selections have
been performed to eliminate these undesirable organoleptic properties, while keeping the plant
resistance to diseases.

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Coffee

Coffee buyers or roasters are paying more and more attention to the cultivar of the products they
buy. If some introgressed cultivars are preferred because of specific properties, coffee buyers want
to check if purchased coffee batches actually originate from the expected species. Secondly it has
been shown that introgression can have a negative impact on the cup quality of cultivars derived
from the Timor Hybrid. Consequently, coffee buyers or roasters may wish to assess whether the
coffee they are purchasing comes from introgressed varieties [25]. Finally it has been
demonstrated that the variety characteristics are not stable from one harvest to the next making it
necessary to use at least two harvest dates for each variety [26]. Therefore there might be a
concern about procurement quality and stability in time.

2.1.4. Counterfeiting of well-known brands of coffees


Some coffees have achieved a special reputation and notoriety based upon their rarity and overall
flavour. Jamaican Blue Mountain and Tanzanian Peaberry are notable examples. As such they
command a premium price [27]. Other examples are civet coffees, especially the Indonesian Kopi
Luwak coffee. Kopi Luwak coffee is produced from beans processed in the digestive tract of the
indigenous palm civet (Luwak) and then harvested. The action of microorganisms and enzymes
gives this coffee a specific taste which is highly valued by consumers. Annual production of Kopi
Luwak is estimated to be lower than 250 kg in 2004 [28] and the price is about USD 200 / lb
(approximately more than EUR 500 per kg) [29]. An important concern related to the price gap
between civet and regular coffees is the growing attempt of fraud involving illegal mixture of
cheaper coffee into premium civet coffee. This may be even considered as counterfeit in this case.

2.2. Potential threat to public health


Coffee has been known to have both beneficial and harmful effects upon health. Coffee
adulteration may therefore have harmful health consequences. In case of substitution of
decaffeinated coffee by genuine coffee, people suffering from caffeine dependency (caffeinism)
and who want to avoid caffeine may be misled. This is also the case of pregnant and breastfeeding
women who are recommended to limit coffee consumption during pregnancy, because excessive
caffeine consumption has been linked to stunted foetus development [30]. Caffeine intakes from
all sources up to 200 mg per day consumed throughout the day is considered to raise no safety
concern.
Another safety concern has arisen about the solvents used for decaffeination of coffee. In the early
th
20 century, benzene, known to cause severe illnesses when inhaled, even in small amounts, has
been widely used for this application. Today, coffee manufacturers have switched to safer
decaffeination methods, though many still use synthetic chemicals such as ethyl acetate (even if
naturally found in some fruits) and methylene chloride (commonly used in industrial applications)
to strip away caffeine. Even if authorities like the FDA or the European Commission have
promulgated regulations that require solvent levels, especially methylene chloride, to be below
specified thresholds in decaffeinated coffee [14,15], this question remains controversial. In organic
coffee, chemical solvents (e.g. methylene chloride) are not permitted for decaffeination, but the
water method or the supercritical carbon dioxide method may be used [2].

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Coffee

3. Analytical methods used to test for authenticity


3.1. Officially recognised methods
A few standardised methods have been developed to check the authenticity of coffee.

3.1.1. Detection of adulteration with carbohydrates


In the standard ISO 11292:1995 “Instant coffee - Determination of free and total carbohydrate
contents - Method using high-performance anion-exchange chromatography” [9], the free and
total carbohydrate profiles in soluble coffee can be determined by high-performance anion-
exchange chromatography with pulsed amperometric detection (HPAEC-PAD). The HPAEC-PAD
procedure enables the determination of all major carbohydrates present in soluble coffee in a
single run.
Using this analytical method, fraudulent addition of cheaper coffee substitutes in commercial
soluble coffee can be detected. High levels of total glucose and total xylose are good indicators of
adulteration. High levels of total xylose indicate the presence of coffee husks or parchments,
whereas the presence of cereals or caramelized sugar is detected by the very large amounts of
total glucose. This authenticity checking procedure has been officially approved for publication as
an ISO international standard ISO 24114:2011 “Instant coffee - Criteria for authenticity” [8]. Total
xylose and total glucose levels of 2.46 % and 0.45 % respectively are proposed by ISO as upper
limits, above which a soluble coffee should be considered as adulterated. The developed method
has been tested on more than 1.000 samples [31]. The procedure has also been officially adopted
as first action (Method 995.13) by the Association of Official Analytical Chemists (AOAC).
According to Thorburn Burns et al. [28], this method can also be applied to roasted ground coffee.
If a specific adulterant is sought, comparison has to be made between the coffee sample and
ground roasted coffee spiked with the sought adulterants.

3.1.2. Determination of substitutions with the caffeine content


The principle of the method ISO “Coffee and coffee products - Determination of the caffeine
content using high performance liquid chromatography (HPLC) - Reference method” [32] is a water
extraction of caffeine followed by detection and quantification by HPLC with UV detection. It can
be applied to green coffee; roasted coffee; soluble coffee, regular and decaffeinated; and mixed
instant coffee products (e. g. coffee/chicory mix or cappuccino-type coffee drink). The level of
caffeine, usually between 1 and 2 g% and also a little bit higher in Robusta coffees than in Arabica
can indicate substitution of coffee by other ingredients like husks or parchment.

3.1.3. Species determination with 16-O-methylcafestol content


of roasted coffee
Roasted coffee is subject to commercial fraud, because the high-quality C. arabica species,
described as 100 % Arabica, is often mixed with the less expensive C. canephora var. Robusta. A
German standard DIN 10779:2011 “Analysis of coffee and coffee products – Determination of 16-
O-methylcafestol content of roasted coffee – HPLC method” [10], being based on HPLC
measurements for the specific determination of 16-O-methylcafestol (16-OMC), has been
accepted. It is quite time expensive in sample preparation phases, even if at the end the
instrument required (HPLC-UV) can be considered cheap with respect to other analytical systems.
This method is tested for a mass fraction of 50 mg to 300 mg 16-OMC content per kg of roasted

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Coffee

coffee. It is based on the observation that 16-OMC is present exclusively in Robusta, whereas
other, more abundant diterpenes, such as cafestol and kahweol, cannot be used for this
discrimination.

3.2. Other commonly used methods

3.2.1. Detection of adulterations


Beyond the analysis of the carbohydrate profile (cf. § 3.1.1), other analytical techniques are
commonly used for detection of adulteration with cheaper ingredients.
Real-time PCR has been shown to be an alternative to chemical methods for identification of
diluents. DNA sequences corresponding to the endogenous genes for coffee, barley, corn and rice
have been selected for amplification. To verify the applicability of the method, 30 commercial
samples obtained in different countries were evaluated. Barley, corn and rice have been actually
detected in different samples [33].
Chromatographic or spectrometric techniques followed by statistical models have been described
in the literature for this application. UV-vis spectroscopy and the Successive Projections Algorithm
for variable selection in association with Linear Discriminant Analysis (SPA-LDA) showed complete
classification in both training and test sets (102 samples) [34]. Near Infra-Red (NIR) spectroscopy
has also been widely studied in this purpose for roasted ground coffee. A study based on 165
aqueous extracts of ground roasted coffee samples employed Diffuse Reflectance Infrared Fourier
Transform Spectroscopy (DRIFTS). A Linear Discriminant Analysis classification model provided
complete discrimination between roasted coffee, pure adulterants (corn and coffee husks) and
adulterated coffee samples [35]. However these proofs of concept are not yet available in routine
testing.
In the case of soluble coffee, analytical methods by NMR exist for detection of substitutions with
ingredients such as chicory, or mislabelling of coffee / chicory proportions in commercial blends
[36,37]. The presence of chicory in soluble coffee and conversely can be quantified at 10 % in
aqueous solution by NMR.

3.2.2. Authentication of the geographic origin


Several techniques have been explored by researchers in their attempt to discover a method, or
combination of methods, to authenticate the origin of any green or roasted coffee samples with
the highest degree of confidence possible.

3.2.2.1. Metabolomic profile with spectroscopic methods


One potential approach to the problem of geographical origin involves the use of spectroscopic
methods such as nuclear magnetic resonance (NMR) and near and mid-infrared techniques. They
have been used to measure spectroscopic “fingerprints” of known samples to which spectra of
unknowns are compared using a variety of statistical measurements for classification purposes.
These techniques generally have the advantage of speed, relatively simple sample preparation
requirements and are often non-destructive.
Multivariate data analysis of the phenolic and methylxanthine profiles obtained by liquid
chromatography coupled with UV spectrophotometry provided preliminary results that showed
their potential for the determination of the geographical origin of green coffees. Classification

― 11 ―
Coffee

models correctly identified all authentic Robusta green coffee beans from Cameroon and Vietnam
and 94 % of those from Indonesia. Moreover, PLS-DA afforded independent models for Robusta
samples from these three countries with sensitivities and specificities of classifications close to
100 % and for Arabica samples from America and Africa with sensitivities of 86 and 70 % and
specificities to the other class of 90 and 97 %, respectively [38].
1 13
Using both H-NMR and C-NMR spectroscopy, it has been shown that metabolite levels in coffee
were significantly different between the Arabica and Robusta species, and secondarily influenced
1
by geographical origins [39]. OPLS-DA models performed on H-NMR data led to a clear separation
of samples according to their origin: fatty acids, chlorogenic acids and lactate and finally acetate
and trigonelline were shown to be the main compounds characterising the American, African and
Asian samples respectively. The analytical approach presented here confirmed the potential of
joint NMR analysis and statistical treatment in coffee authentication [40]. Classification models
were built on aqueous NMR profiles allowing the distinction of 192 coffees on countries or
continents of origin [41]. More precisely, 50 samples of Colombian have been differentiated from
22 Asian, 12 African and 108 other American origins. Although the discrimination was based on the
global fingerprint, fatty acids, acetate and caffeine were identified to having a particular part in the
differentiation. However, some impacts of roasting processes were observed on spectral profile as
well as the post-harvest processes, the ripening periods and the year of harvest.
NIR spectroscopy has also demonstrated its potential in geographical origin authentication. Fourier
transform infrared spectroscopy (FTIR) following solvent extraction permits examination of
molecular variation to distinguish degrees of roast and country of origin, as between Columbia,
Costa Rica, Ethiopia and Kenya [42]. Near-infrared spectroscopy (NIR) has been used to distinguish
geographic origin and genotype of samples grown in Brazil [43].

3.2.2.1. Isotopic ratios


The possibility of using the isotopic ratio of caffeine to distinguish between geographical origins
was investigated a few decades ago. Isotope ratio mass spectrometry (IRMS) was used to
13 12 15 14
determine the C/ C and N/ N isotope ratios and Site-Specific Isotopic Fractionation - Nuclear
2 1
Magnetic Resonance (SNIF-NMR) for the H/ H ratio [44]. However it was not possible to
discriminate within the African or the American group. Another study also reported the use of
13 12 2 1 18 16
C/ C, H/ H and O/ O ratios of the caffeine to check origins [45]. In addition using the carbon
and nitrogen isotopic ratios of caffeine it is possible to fully discriminate plant origins from
synthetic ones.
Some studies were performed directly on green coffee beans using multi-isotope analysis by IRMS
associated with elemental analysis (EA). A study applied on 68 green coffee beans has
13 15 18
demonstrated the potential of the combination of δ C (VPDB), δ N (VAIR), δ O (VSMOW) and
percentages of carbon and nitrogen in the discrimination of 20 different geographic origins
distributed over Central America, Pacific, South America, Africa, Asia and Oceania [46]. Another
study was applied to 54 samples of roasted coffee beans of 20 different countries of origin [47].
This second work combined stable isotope analysis by IRMS, Elemental Analysis by ICP-MS and an
13 13
analysis of δ C of extracted caffeine. It has demonstrated to some extent the potential of δ C and
15 13
δ N in the discrimination of coffees from Africa, Asia and Central / South America. Moreover δ C,
2 18
δ H and δ O combined with 5 elements (Ca, Ti, Fe, Ni, Zn) could discriminate all the considered
origins at 77 %.
As a conclusion, the direct multi-isotope analysis of green or roasted coffees (after grinding) is also
possible for a routine control of declared origins, provided that suitable databases are available.

― 12 ―
Coffee

3.2.2.2. Elemental analysis


Element-specific techniques, especially inductively coupled plasma emission spectroscopy (ICP-
OES), have been used to examine the trace element composition of coffee samples and have
shown interesting results.
In a survey including the major growing areas worldwide (Brazil, Ethiopia, Colombia, India, Mexico,
Honduras, Guatemala, Papua New Guinea, Kenya, Cuba, Timor, Mussulo and China), the variation
in trace element composition has been characterised and compared [48]. These mineral profiles
have also been used to differentiate coffee origins. Intercontinental and inter-country
discrimination between the major world coffee producers were achieved by applying canonical
discriminant analysis. Manganese and calcium were found to be the best chemical descriptors for
origin. This conclusion is consistent with the results obtained on green coffee by Krivan et al., who
analysed green Arabica coffees from eight different countries for twenty elements and found
manganese to be the best suited element for origin discrimination [49].
Although much attention has been given to patterns of amounts of trace elements, this technique
is not considered as robust enough by some authors due to the possibility of perturbations, for
example from the use of fertilizers [28].

3.2.2.3. Volatile compounds


Chemical profiles of volatile compounds have been studied to determine the geographical origin of
coffee. For instance changes in volatile components analysed by direct injection headspace
analysis by proton transfer reaction-time of flight mass spectrometry (PTR-TFMS) enable the
distinction between beans from Ethiopia, Columbia, Brazil and India [50].
An HS-SPME–GC–TOFMS methodology was developed by an academic laboratory for the purposes
of verifying its capability in terms of tracing back the coffee samples to their production area.
Acquired data related to naturally volatile and semi-volatile analytes from 47 samples was
submitted to principal component analysis and the corresponding geographical origin
discrimination of coffee from South and Central America, Africa and Asia was successfully
established [51].
However, many factors, such as the origin and the type of the coffee beans, roasting time and
temperature, and the degree and method of roasting, affect the resulting volatile profile.
Environmental factors like temperature during seed development also influence the sensory
profile, and consequently the volatile profile [52]. The variability of volatile constituents in coffee
caused by the different parameters do not appear to favour the volatile approach for the
identification of origin in roasted coffee samples.

3.2.3. Determination of Arabica and Robusta blends

3.2.3.1. NMR profiling


The need related to coffee species determination is first to discriminate between Arabica and
Robusta species and secondly to determine the proportion of Robusta and Arabica in commercial
blends.
The verification of species authenticity was well established in NMR spectroscopy on the lipid
fraction using the combination of two markers roughly specific to one species: 16-OMC for
Robusta and kahweol for Arabica [23]. Up until recently, it was believed that 16-OMC is exclusively
present in Robusta. This compound was therefore considered as an adequate marker in the

― 13 ―
Coffee

differentiation of Arabica and Robusta coffees. Indeed, the reference method DIN 10779:2011 [10]
has proven the existing correlation between the 16-OMC concentration and the Robusta rate in
Arabica roasted coffee. In parallel, kahweol was shown to be a key compound in species
differentiation and was considered as a marker of Arabica species, although this compound is
structurally very close to cafestol, compound present in both species.
1
Blend compositions were determined by H-NMR spectral fingerprints with a high accuracy for 56
mixtures in aqueous solution using Orthogonal - Partial Least Square (OPLS) regression models
[53]. This NMR method was proven to be a substitute for the official method because it requires
only limited preparation, thus avoiding the loss of analytes. It was also shown that this technique
could reach low limits of detection and quantification (5 and 20 mg/kg, respectively). This
performance is adequate to detect the presence of Robusta at percentages lower than 0.9 % and
down to 0.2 %, thus lower than the official method by HPLC (about 2 %) [11]. Furthermore, a
recent paper has proven the presence of 16-OMC, a marker of Robusta, in ground roasted Arabica
coffee in the order of 1-2 % [54]. Consequently the limit of quantification for Robusta content
must be defined at 5 % and 10 % respectively in roasted and green Arabica coffee, in order to
avoid false negative results. Moreover, this recent paper detected 2 doubtful market samples of
Arabica coffee with adulterations at levels up to 30 % (w/w) in a panel of 60 retail purchased
coffees using a limit of detection at 1 % and of quantification at 4 % [54].

3.2.3.2. NIR spectrometry


A near infrared spectroscopy signature, acquired over a set of harvests by keeping the most
heritable zones of the spectrum, can therefore effectively characterize a coffee variety [26]. In a
set of 191 roasted coffees from both pure Arabica and Robusta varieties and blends varying the
final Robusta content from 0 to 60 % (w/w), classification models were built using NIR
spectroscopy with Direct Orthogonal Signal Correction (DOSC) pre-processing method. It has been
demonstrated that classification between pure Arabica, Arabica-Robusta blends and pure Robusta
could be achieved.

3.2.3.3. Chemical compounds


The lipid content of Arabica coffee beans averages some 15 %, whilst Robusta coffees contain
much less, namely around 10 % lipid. By Principal Component Analysis, oleic, linolenic, linoleic, and
myristic acids used as chemical markers obtained by capillary gas chromatography were
demonstrated as useful for differentiating varieties [55]. Six fatty acids were also analysed by
Linear Discriminant Analysis (LDA) for a clear discrimination between Arabica and Robusta, green
and roasted, coffee samples. Total monounsaturated (MUFA) and saturated fatty acids (SFA) could
be used to determine amounts of Arabica and Robusta in a coffee blend [56].
Bertrand et al. compared the effectiveness of three chemical families, namely, chlorogenic acids,
fatty acids, and minerals, for the discrimination of Arabica varieties (traditional versus modern
introgressed lines) and potential terroir within a given coffee-growing area [57]. Although minerals
provided an excellent classification of three locations under study, they were useless for Arabica
variety discrimination. Chlorogenic acids gave satisfactory results, but fatty acids clearly offered
the best results for the determination of both varieties and environments, with very high
percentages of correct classification (79 and 90 %, respectively).
Roasted Arabica and Robusta coffees differ in their aroma as a consequence of their different
chemical composition. Robustas show (due to their high content of free amino acids and
chlorogenic acids) significantly higher concentrations of pyrazines, phenols and phenol ethers than
Arabicas. Direct correlations were established between individual amino acids of green coffee and

― 14 ―
Coffee

aroma compounds which are formed during roasting. Arabicas contain (due to their high sucrose
content) considerably higher amounts of steam-volatile furans, hydroxymethylfurfural and some
aliphatic sugar degradation products than Robustas [58]. In a recent paper, a comparison between
1
GC-C-IRMS, GC-MS, and H-NMR was carried out to discriminate coffees from Colombia versus
nearby countries (Brazil and Peru). According to the authors, results show that the quality of the
classifiers depends mainly on the number of variables included in the analysis, which does not
favour GC approaches [59].

3.2.3.4. DNA-based methods


Identification of Arabica and Robusta coffee species, as well as the quantification of their relative
proportion in blends were performed by High Resolution Melting (HRM) analysis on green and
roasted coffee products [60]. For a more sensitive detection method, chloroplastic rather than
nuclear genetic variations were targeted, leading to the selection of 24 SNPs.

3.2.4. Detection of introgressed varieties


Introduction of new hydride varieties mostly induces an increase in the variability of the Arabica
species, making differentiation between the Arabica and Robusta species more and more difficult
for the analyst. For this purpose, chemometric approaches based on spectral profiles obtained by
NMR or IR screening are being increasingly developed. They enable the extraction and
combination of several species-characteristic signals from substantial datasets of coffee spectra.
Consequently, coffee buyers or roasters could assess whether the coffee they are purchasing
comes from traditional or introgressed Arabica varieties.
A chemometric method Independent Components - Discriminant Analysis (IC-DA) was applied to
1
the H-NMR fingerprints of lipophilic extracts from 272 authentic green coffees. Some signals of
terminal methyl group of the fatty acid chains were identified as possible markers for the
distinction between introgressed and native Arabica green coffee [61].
The NIR spectroscopy has also demonstrated its potential to be used to detect introgression in
C. arabica cultivars on a dataset composed of 62 samples from Nicaragua and 61 from Costa Rica
[25]. Moreover, particular metabolites were also identified such as fatty acids and caffeine, but
also chlorogenic acids.

3.2.5. Authentication of coffee cultivars


Visual inspection can authenticate green coffee species and varieties, but after roasting, and
particularly after grinding, this distinction becomes very difficult due to the morphological changes
of beans induced by the high temperatures. Therefore, more sophisticated techniques have been
developed, mainly based on genomics approaches, to check cultivars of roasted coffee, especially
after grinding.
PCR amplification techniques are generally sensitive, reproducible and routinely available in
testing laboratories. They can provide results even when testing very small amounts of degraded
DNA as in the case of roasted coffee [62]. They have been effectively employed in the
identification of roasted coffee species. An approach based on amplified fragment length
polymorphism (AFLP) and simple-sequence repeats (SSRs) has shown to be useful for calculating
genetic distance among 15 Arabica varieties from Yemen [63]. Applied to coffee species
authentication, the potential of 33 SSR markers was assessed in 24 accessions of the Coffea genus
[64]. The analysis included six Arabica (C. arabica) accessions, five Robusta accessions (C.
canephora), three Híbrido de Timor (C. arabica x C. canephora), three Triploids (C. arabica x C.

― 15 ―
Coffee

racemosa) and one Racemosa (C. racemosa) accession. Six leaf rust resistant Arabica were also
included. Authors concluded that that it is possible to use these SSRs for coffee variety
identification. Single Nucleotide Polymorphism (SNP) has also been studied for identification of
coffee germplasm with good results. A panel of 180 SNPs has been validated on 25 C. arabica and
C. canephora accessions from Puerto Rico [65]. All the Robusta accessions were differentiated, as
well as 10 out the 12 Arabica accessions (the 2 remaining ones were considered as synonymous).
All these tools are available for coffee players to assist in coffee germplasm management, quality
control of planting material propagation, coffee cultivar authentication and protection of varietal
rights in the international coffee community.

4. Overview of methods for authenticity testing


The following table provides a summary of the methods and the authenticity issues they address.

Analytical technique Indicative data or analyte Authenticity issue / information


1
NMR profiling H NMR spectrum Arabica-Robusta proportion in blends (green & roasted coffee)
Geographical origin
Adulteration with cheap ingredients
Chicory content confirmation
Identification of introgressed varieties
NIR spectroscopy and Substitution with cheaper ingredients (coffee husks, parchments)
profiling Geographical origin
Arabica-Robusta proportion in blends
Identification of introgressed varieties
UV-vis spectrometry Whole spectrum Substitution with cheaper ingredients (coffee husks, parchments)
Geographical origin of green coffee
HPAEC-PAD Carbohydrates Substitution with cheaper ingredients (coffee husks, parchments,
cereals, sugar)
HPLC Caffeine Substitution with cheaper ingredients (coffee husks, parchments)
HPLC 16-O-Methylcafestol Dilution of Arabica with Robusta
HPLC Chrologenic acids Identification of varieties
13 12 15 14 2 1
SNIF-NMR and IRMS C/ C and N/ N, H/ H, Geographical origin
18
O/16O, isotope ratios Naturality of caffeine
ICP-OES, ICP-AES Trace elements (minerals) Geographical origin
notably Mn and Ca Arabica-Robusta proportion in blends
Identification of varieties
Capillary GC Lipid content Arabica-Robusta proportion in blends
Identification of varieties
GC-MS Volatile compounds Geographical origin
Arabica-Robusta proportion in blends
Specialty coffee authentication
Real-time PCR Endogenous genes Dilution with barleycorn and rice
SSR fingerprinting Genome Varietal identification
Arabica / Robusta proportion in blends
SNP fingerprinting Genome EST transcriptome Varietal identification

― 16 ―
Coffee

5. Conclusion
Coffee authentication is a major concern for the coffee sector. The product itself, once roasted,
ground or processed as instant coffee, can be easily adulterated. Furthermore coffee is one of the
most appreciated and valued food commodities. Extensive research has been carried out on coffee
authentication over the last few decades with the results that robust authentications methods are
now available for the industry throughout the supply chain in order to ensure that genuine
products are delivered to consumers.
The problem of determining the proportion in blends or the adulteration of Arabica with Robusta
has been addressed and there are techniques that provide a good estimation of mixtures.
However, under pressure of changing climate conditions, new varieties are being created by
breeding Arabica and Robusta cultivars, for instance. Current differentiation between these two
species is becoming more and more complex. New knowledge is needed in the future to ensure
accurate results and to avoid false positives.

6. Bibliographic references
1. Davis A.P., Govaerts R., Bridson D.M. & Stoffelen P. (2006). – An annotated taxonomic conspectus of the genus
Coffea (Rubiaceae). Bot. J. Linn. Soc., 152 (4), 465–512. doi:10.1111/j.1095-8339.2006.00584.x.
2. International Trade Centre (ITC) (2012). – The Coffee Exporter’s Guide. 3rd ed., United Nations, Geneva. Available at:
http://www.intracen.org/WorkArea/DownloadAsset.aspx?id=58068.
3. United States, Department of & United States Department of Agriculture, Foreign Agricultural Service – Coffee:
World Markets and Trade. Available at: http://usda.mannlib.cornell.edu/usda/fas/tropprod//2010s/2017/tropprod-
06-16-2017.pdf.
4. International Coffee Council (2010). – Employment generated by the coffee sector. International Coffee Council,
London. Available at: http://www.ico.org/documents/icc-105-5e-employment.pdf.
5. Farah A. (2009). – 15 - Coffee as a speciality and functional beverage. . In Functional and Speciality Beverage
Technology (P. Paquin, ed), Woodhead Publishing. pp 370–395doi:10.1533/9781845695569.3.370.
6. ICO – International Coffee Agreement 2007. , 43. Available at: http://dev.ico.org/documents/ica2007e.pdf.
7. ISO Standard (1975). – Meat and meat products — Determination of nitrate content (Reference method). ISO
3091:1975. Available at: https://www.iso.org/standard/8231.html.
8. ISO Standard (2001). – Instant coffee — Criteria for authenticity. ISO 24114:2011. Available at:
https://www.iso.org/obp/ui/#iso:std:iso:20481:ed-1:v2:en.
9. ISO Standard (2001). – Instant coffee — Determination of free and total carbohydrate contents -- Method using high-
performance anion-exchange chromatography. ISO 11292:1995. Available at:
https://www.iso.org/standard/19270.html.
10. DIN (2011). – Analysis of coffee and coffee products - Determination of 16-O-methyl cafestol content of roasted
coffee - HPLC-method. DIN 10779:2011. Available at: https://www.beuth.de/en/standard/din-10779/137590328.
11. Schievano E., Finotello C., De Angelis E., Mammi S. & Navarini L. (2014). – Rapid Authentication of Coffee Blends and
Quantification of 16-O-Methylcafestol in Roasted Coffee Beans by Nuclear Magnetic Resonance. J. Agric. Food Chem.,
62 (51), 12309–12314. doi:10.1021/jf505013d.
12. Regulation (EU) No 1169/2011 of the European parliament and of The Council of 25 October 2011 on the
provision of food information to consumers (2011). Off. J. Eur. Union, L304, 18–63.
13. Directive 1999/4/EC of the European parliament and the Council of 22 February 1999 relating to coffee extracts and
chicory extracts (1999). Off. J. Eur. Union, L066, 26–29.
14. Regulation (EU) No 1379/2013 of the European Parliament and of the Council of 11 December 2013 on the common
organisation of the markets in fishery and aquaculture products, amending Council Regulations (EC) No 1184/2006
and (EC) No 1224/2009 and repealing Council Regulation (EC) No 104/2000 (2013). Off. J. Eur. Union, L354, 1–21.

― 17 ―
Coffee

15. Methylene chloride (2017). US Food Drug Adm., 21CFR173.255. Available at:
https://www.accessdata.fda.gov/scripts/cdrh/cfdocs/cfcfr/CFRSearch.cfm?fr=173.255.
16. Regulation (EC) No 853/2004 of the European Parliament and of the Council of 29 April 2004 laying down specific
hygiene rules for food of animal origin (2004). Off. J. Eur. Union, L139, 55–205.
17. Commission Regulation (EC) No 1050/2007 of 12 September 2007 registering certain names in the Register of
protected designations of origin and protected geographical indications (Mejillón de Galicia or Mexillón de Galicia
(PDO) — Café de Colombia (PGI) — Castagna Cuneo (PGI) — Asparago Bianco di Bassano (PDO)) (2007). Off. J. Eur.
Union, L240, 7–8.
18. Commission Implementing Regulation (EU) 2016/1043 of 15 June 2016 entering a name in the register of protected
designations of origin and protected geographical indications (Café de Valdesia (PDO)) (2016). Off. J. Eur. Union,
L170, 3.
19. International Coffee Organisation (2004). – Coffee Quality Improvement Programme – Modifications - Resolution
420. Available at: http://www.ico.org/documents/iccres420e.pdf.
20. Alves R.C., Oliveira M.B.P.P. & Casal S. (2011). – Coffee authenticity. . In Current Topics on Food Authentication,
Transworld Research Network, Kerala, India. pp 57–72
21. Vossen H.A.M. (1985). – Coffee Selection and Breeding. . In Coffee: Botany, Biochemistry and Production of Beans
and Beverage (M.N. Clifford, ed), Springer USAvailable at: //www.springer.com/la/book/9781461566595.
22. Bunn C., Läderach P., Pérez Jimenez J.G., Montagnon C. & Schilling T. (2015). – Multiclass Classification of Agro-
Ecological Zones for Arabica Coffee: An Improved Understanding of the Impacts of Climate Change. PLoS ONE, 10
(10). doi:10.1371/journal.pone.0140490.
23. Monakhova Y.B., Ruge W., Kuballa T., Ilse M., Winkelmann O., Diehl B., Thomas F. & Lachenmeier D.W. (2015). –
Rapid approach to identify the presence of Arabica and Robusta species in coffee using 1H NMR spectroscopy. Food
Chem., 182, 178–184. doi:10.1016/j.foodchem.2015.02.132.
24. Bertrand B., Guyot B., Anthony F. & Lashermes P. (2003). – Impact of the Coffea canephora gene introgression on
beverage quality of C. arabica. Theor. Appl. Genet., 107 (3), 387–394. doi:10.1007/s00122-003-1203-6.
25. Bertrand B., Etienne H., Lashermes P., Guyot B. & Davrieux F. (2005). – Can near-infrared reflectance of green coffee
be used to detect introgression in Coffea arabica cultivars? J. Sci. Food Agric., 85 (6), 955–962. doi:10.1002/jsfa.2049.
26. Posada H., Ferrand M., Davrieux F., Lashermes P. & Bertrand B. (2009). – Stability across environments of the coffee
variety near infrared spectral signature. Heredity, 102 (2), 113–119. doi:10.1038/hdy.2008.88.
27. Marcone M.F. (2004). – Composition and properties of Indonesian palm civet coffee (Kopi Luwak) and Ethiopian civet
coffee. Food Res. Int., 37 (9), 901–912. doi:10.1016/j.foodres.2004.05.008.
28. Thorburn Burns D., Tweed L. & Walker M.J. (2017). – Ground Roast Coffee: Review of Analytical Strategies to
Estimate Geographic Origin, Species Authenticity and Adulteration by Dilution. Food Anal. Methods, 10 (7), 2302–
2310. doi:10.1007/s12161-016-0756-3.
29. Jumhawan U., Putri S.P., Yusianto null, Bamba T. & Fukusaki E. (2016). – Quantification of coffee blends for
authentication of Asian palm civet coffee (Kopi Luwak) via metabolomics: A proof of concept. J. Biosci. Bioeng., 122
(1), 79–84. doi:10.1016/j.jbiosc.2015.12.008.
30. European Food Safety Authority (2015). – EFSA explains risk assessment - Caffeine. EFSA, Parma. Available at:
http://www.efsa.europa.eu/sites/default/files/corporate_publications/files/efsaexplainscaffeine150527.pdf.
31. Girard P., Stöber P., Blanc M. & Prodolliet J. (2006). – Carbohydrate specification limits for the authenticity
assessment of soluble (instant) coffee: statistical approach. J. AOAC Int., 89 (4), 999–1003.
32. ISO Standard (2008). – Coffee and coffee products — Determination of the caffeine content using high performance
liquid chromatography (HPLC) — Reference method. ISO 20481:2008. Available at:
https://www.iso.org/obp/ui/#iso:std:iso:20481:ed-1:v2:en.
33. Ferreira T., Farah A., Oliveira T.C., Lima I.S., Vitório F. & Oliveira E.M.M. (2016). – Using Real-Time PCR as a tool for
monitoring the authenticity of commercial coffees. Food Chem., 199, 433–438. doi:10.1016/j.foodchem.2015.12.045.
34. Souto U.T. de C.P., Barbosa M.F., Dantas H.V., Pontes A.S. de, Lyra W. da S., Diniz P.H.G.D., Araújo M.C.U. de & Silva
E.C. da (2015). – Identification of adulteration in ground roasted coffees using UV–Vis spectroscopy and SPA-LDA.
LWT - Food Sci. Technol., 63 (2), 1037–1041. doi:10.1016/j.lwt.2015.04.003.
35. Reis N., Franca A.S. & Oliveira L.S. (2013). – Discrimination between roasted coffee, roasted corn and coffee husks by
Diffuse Reflectance Infrared Fourier Transform Spectroscopy. LWT - Food Sci. Technol., 50 (2), 715–722.
doi:10.1016/j.lwt.2012.07.016.

― 18 ―
Coffee

36. Campo G. del, Berregi I., Caracena R. & Zuriarrain J. (2010). – Quantitative determination of caffeine, formic acid,
trigonelline and 5-(hydroxymethyl)furfural in soluble coffees by 1H NMR spectrometry. Talanta, 81 (1), 367–371.
doi:10.1016/j.talanta.2009.12.010.
37. Charlton A.J., Farrington W.H.H. & Brereton P. (2002). – Application of 1H NMR and Multivariate Statistics for
Screening Complex Mixtures: Quality Control and Authenticity of Instant Coffee. doi:10.1021/jf011539z.
38. Alonso-Salces R.M., Serra F., Reniero F. & HÉberger Ká. (2009). – Botanical and Geographical Characterization of
Green Coffee (Coffea arabica and Coffea canephora): Chemometric Evaluation of Phenolic and Methylxanthine
Contents. doi:10.1021/jf8037117.
39. Wei F., Furihata K., Koda M., Hu F., Miyakawa T. & Tanokura M. (2012). – Roasting Process of Coffee Beans as Studied
by Nuclear Magnetic Resonance: Time Course of Changes in Composition. J. Agric. Food Chem., 60 (4), 1005–1012.
doi:10.1021/jf205315r.
40. Consonni R., Cagliani L.R. & Cogliati C. (2012). – NMR based geographical characterization of roasted coffee. Talanta,
88, 420–426. doi:10.1016/j.talanta.2011.11.010.
41. Arana V.A., Medina J., Alarcon R., Moreno E., Heintz L., Schäfer H. & Wist J. (2015). – Coffee’s country of origin
determined by NMR: The Colombian case. Food Chem., 175, 500–506. doi:10.1016/j.foodchem.2014.11.160.
42. Wang N., Fu Y. & Lim L.T. (2011). – Feasibility Study on Chemometric Discrimination of Roasted Arabica Coffees by
Solvent Extraction and Fourier Transform Infrared Spectroscopy. J. Agric. Food Chem., 59 (7), 3220–3226.
doi:10.1021/jf104980d.
43. Marquetti I., Link J.V., Lemes A.L.G., Scholz M.B. dos S., Valderrama P. & Bona E. (2016). – Partial least square with
discriminant analysis and near infrared spectroscopy for evaluation of geographic and genotypic origin of arabica
coffee. Comput. Electron. Agric., 121, 313–319. doi:10.1016/j.compag.2015.12.018.
44. Danho D., Naulet N. & Martin G.J. (1992). – Deuterium, carbon and nitrogen isotopic analysis of natural and synthetic
caffeines. Authentification of coffees and coffee extracts. Analusis Fr. Available at: http://agris.fao.org/agris-
search/search.do?recordID=FR9202331.
45. Weckerle B., Richling E., Heinrich S. & Schreier P. (2002). – Origin assessment of green coffee (Coffea arabica) by
multi-element stable isotope analysis of caffeine. Anal. Bioanal. Chem., 374 (5), 886–890. doi:10.1007/s00216-002-
1560-z.
46. Rodrigues C.I., Maia R., Miranda M., Ribeirinho M., Nogueira J.M.F. & Máguas C. (2009). – Stable isotope analysis for
green coffee bean: A possible method for geographic origin discrimination. J. Food Compos. Anal., 22 (5), 463–471.
doi:10.1016/j.jfca.2008.06.010.
47. Carter J.F., Yates H.S.A. & Tinggi U. (2015). – Isotopic and Elemental Composition of Roasted Coffee as a Guide to
Authenticity and Origin. J. Agric. Food Chem., 63 (24), 5771–5779. doi:10.1021/acs.jafc.5b01526.
48. Oliveira M., Ramos S., Delerue-Matos C. & Morais S. (2015). – Espresso beverages of pure origin coffee: Mineral
characterization, contribution for mineral intake and geographical discrimination. Food Chem., 177, 330–338.
doi:10.1016/j.foodchem.2015.01.061.
49. Krivan V., Barth P. & Morales A.F. (1993). – Multielement analysis of green coffee and its possible use for the
determination of origin. Microchim. Acta, 110 (4–6), 217–236. doi:10.1007/BF01245106.
50. Yener S., Romano A., Cappellin L., Granitto P.M., Aprea E., Navarini L., Märk T.D., Gasperi F. & Biasioli F. (2015). –
Tracing coffee origin by direct injection headspace analysis with PTR/SRI-MS. Food Res. Int., 69, 235–243.
doi:10.1016/j.foodres.2014.12.046.
51. Risticevic S., Carasek E. & Pawliszyn J. (2008). – Headspace solid-phase microextraction–gas chromatographic–time-
of-flight mass spectrometric methodology for geographical origin verification of coffee. Anal. Chim. Acta, 617 (1–2),
72–84. doi:10.1016/j.aca.2008.04.009.
52. Bertrand B., Boulanger R., Dussert S., Ribeyre F., Berthiot L., Descroix F. & Joët T. (2012). – Climatic factors directly
impact the volatile organic compound fingerprint in green Arabica coffee bean as well as coffee beverage quality.
Food Chem., 135 (4), 2575–2583. doi:10.1016/j.foodchem.2012.06.060.
53. Cagliani L.R., Pellegrino G., Giugno G. & Consonni R. (2013). – Quantification of Coffea arabica and Coffea canephora
var. robusta in roasted and ground coffee blends. Talanta, 106, 169–173. doi:10.1016/j.talanta.2012.12.003.
54. Gunning Y., Defernez M., Watson A.D., Beadman N., Colquhoun I.J., Le Gall G., Philo M., Garwood H., Williamson D.,
Davis A.P. & Kemsley E.K. (2018). – 16-O-methylcafestol is present in ground roast Arabica coffees: Implications for
authenticity testing. Food Chem., 248, 52–60. doi:10.1016/j.foodchem.2017.12.034.
55. Martı ́n M.J., Pablos F., González A.G., Valdenebro M.S. & León-Camacho M. (2001). – Fatty acid profiles as
discriminant parameters for coffee varieties differentiation. Talanta, 54 (2), 291–297. doi:10.1016/S0039-
9140(00)00647-0.

― 19 ―
Coffee

56. Romano R., Santini A., Le Grottaglie L., Manzo N., Visconti A. & Ritieni A. (2014). – Identification markers based on
fatty acid composition to differentiate between roasted Arabica and Canephora (Robusta) coffee varieties in
mixtures. J. Food Compos. Anal., 35 (1), 1–9. doi:10.1016/j.jfca.2014.04.001.
57. Bertrand B., Villarreal D., Laffargue A., Posada H., Lashermes P. & Dussert S. (2008). – Comparison of the
Effectiveness of Fatty Acids, Chlorogenic Acids, and Elements for the Chemometric Discrimination of Coffee (Coffea
arabica L.) Varieties and Growing Origins. J. Agric. Food Chem., 56 (6), 2273–2280. doi:10.1021/jf073314f.
58. Silwar R. & Lüllman C. (1993). – The aroma composition of the coffee beverage. Quantitative determination of
steam-volatile aroma constituents. Proc 15th Coll ASIC Montp., , 873–879.
59. Arana V.A., Medina J., Esseiva P., Pazos D. & Wist J. (2016). – Classification of Coffee Beans by GC-C-IRMS, GC-MS,
and 1H-NMR. J. Anal. Methods Chem., 2016. doi:10.1155/2016/8564584.
60. Combes M.C., Joët T. & Lashermes P. (2018). – Development of a rapid and efficient DNA-based method to detect
and quantify adulterations in coffee (Arabica versus Robusta). Food Control, 88, 198–206.
doi:10.1016/j.foodcont.2018.01.014.
61. Guyader S., Thomas F., Jamin E., Bertrand B. & Remaud G. (2018). – Impact of introgression in coffee for the control
of Arabica/Robusta species studied by a combination of 1H-NMR and chemometrics. Submitted.
62. Martellossi C., Taylor E.J., Lee D., Graziosi G. & Donini P. (2005). – DNA Extraction and Analysis from Processed Coffee
Beans. J. Agric. Food Chem., 53 (22), 8432–8436. doi:10.1021/jf050776p.
63. Anthony F., Combes M., Astorga C., Bertrand B., Graziosi G. & Lashermes P. (2002). – The origin of cultivated Coffea
arabica L. varieties revealed by AFLP and SSR markers. Theor. Appl. Genet., 104 (5), 894–900. doi:10.1007/s00122-
001-0798-8.
64. Missio R.F., Caixeta E.T., Zambolim E.M., Zambolim L., Cruz C.D. & Sakiyama N.S. (2010). – Polymorphic information
content of SSR markers for Coffea spp. Cropp Breed. Appl. Biotechnol., 10 (1), 89–94. doi:10.12702/1984-
7033.v10n01a12.
65. Zhou L., Vega F.E., Tan H., Lluch A.E.R., Meinhardt L.W., Fang W., Mischke S., Irish B. & Zhang D. (2016). – Developing
Single Nucleotide Polymorphism (SNP) Markers for the Identification of Coffee Germplasm. Trop. Plant Biol., 9 (2),
82–95. doi:10.1007/s12042-016-9167-2.

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