Environmental Health
BioMed Central
Open Access
Commentary
Mercury from chlor-alkali plants: measured concentrations in food
product sugar
Renee Dufault*1, Blaise LeBlanc2, Roseanne Schnoll3, Charles Cornett4,
Laura Schweitzer4, David Wallinga5, Jane Hightower6, Lyn Patrick7 and
Walter J Lukiw8
Address: 1United Tribes Technical College, Bismarck, ND, USA, 2Carl Hayden Bee Research Center, Tucson, AZ, USA, 3Department of Health and
Nutrition Sciences, Brooklyn College of CUNY, Brooklyn, NY, USA, 4Department of Chemistry and Engineering Physics, University of WisconsinPlatteville, Platteville, WI, USA, 5Institute for Agriculture and Trade Policy, Minneapolis, MN, USA, 6Department of Internal Medicine, California
Pacific Medical Center, San Francisco, CA, USA, 7Contributing Editor, Alternative Medicine Review, Durango, CO, USA and 8Professor of
Neuroscience and Ophthalmology, LSU Neuroscience Center. Louisiana State University Health Sciences Center, New Orleans, LA, USA
Email: Renee Dufault* - rdufault@uttc.edu; Blaise LeBlanc - blaise_ll@hotmail.com; Roseanne Schnoll - rschnoll@brooklyn.cuny.edu;
Charles Cornett - cornettc@uwplatt.edu; Laura Schweitzer - schweitl@uwplatt.edu; David Wallinga - lpatrick@frontier.net;
Jane Hightower - jhightowermd@aol.com; Lyn Patrick - dwallinga@iatp.org; Walter J Lukiw - wlukiw@lsuhsc.edu
* Corresponding author
Published: 26 January 2009
Environmental Health 2009, 8:2
doi:10.1186/1476-069X-8-2
Received: 9 September 2008
Accepted: 26 January 2009
This article is available from: http://www.ehjournal.net/content/8/1/2
© 2009 Dufault et al; licensee BioMed Central Ltd.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0),
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
Abstract
Mercury cell chlor-alkali products are used to produce thousands of other products including food
ingredients such as citric acid, sodium benzoate, and high fructose corn syrup. High fructose corn
syrup is used in food products to enhance shelf life. A pilot study was conducted to determine if
high fructose corn syrup contains mercury, a toxic metal historically used as an anti-microbial. High
fructose corn syrup samples were collected from three different manufacturers and analyzed for
total mercury. The samples were found to contain levels of mercury ranging from below a
detection limit of 0.005 to 0.570 micrograms mercury per gram of high fructose corn syrup.
Average daily consumption of high fructose corn syrup is about 50 grams per person in the United
States. With respect to total mercury exposure, it may be necessary to account for this source of
mercury in the diet of children and sensitive populations.
Background
Chlorine and caustic soda are produced at chlor-alkali
plants using mercury cells or the increasingly popular
membrane technology that is mercury free and more
energy-efficient. Worldwide there are approximately fifty
mercury cell chlor-alkali plants in operation [1]. Of those
there are eight in the United States (US) [2]. In 2003 the
EPA reported in the Federal Register that on average
approximately seven tons of mercury were missing from
each plant in the year 2000 [3]. These chlor-alkali plants
have an average of fifty-six cells, each containing as much
as 8,000 pounds of mercury [4] and, every year the chloralkali industry reports unaccounted for mercury losses to
the EPA [5]. Mercury is a danger to unborn children whose
developing brains can be damaged if they are exposed to
low dose microgram exposures in the womb [6]. Since
mercury is a potent neurological toxin, these unaccounted
for mercury losses from the chlor-alkali industry are of
concern as they could be a source of exposure for humans,
wildlife, and the environment. An Environmental Health
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Environmental Health 2009, 8:2
Officer (EHO) at the Food and Drug Administration
(FDA) conducted an investigation to find the missing
mercury in the chlor-alkali industry [7].
The path of the investigation
An employee of the Environmental Protection Agency
(EPA) suggested that the EHO contact the Wisconsin
Department of Natural Resources (DNR) for information
on Vulcan Chemicals' mercury balance sheet. Vulcan
Chemical was the only chemical company to find its missing mercury. Upon request, the Wisconsin DNR provided
the EHO with Vulcan Chemical's annual mercury balance
sheet that reported their mercury losses in their products
for the year that the mercury balance was done. Vulcan
Chemical submitted this mercury balance sheet to the
Wisconsin DNR in 2003 with their wastewater discharge
permit re-issuance application. This information led to
the realization that mercury residue may be found in all
products produced by the mercury cell chlor-alkali industry. A representative of the Chlorine Institute confirmed in
a telephone interview that the amount of mercury residue
in mercury cell chlor-alkali products varies, depending on
the manufacturing process at each plant. It is found in
mercury grade caustic soda according to product specification sheets [8].
According to an archived web page report initially produced by Vulcan Chemicals, mercury grade caustic soda
and hydrochloric acid are primarily used by the high fructose corn syrup industry [9]. Following this lead, the EHO
conducted an interview with an "organic" producer of
high fructose corn syrup (HFCS) in 2004 and was told
that the HFCS industry uses both mercury grade caustic
soda and membrane grade caustic soda in their manufacturing process to enhance product shelf life. A review of
the literature revealed that HFCS is indeed used as a sweetener by food manufacturers to stabilize food products and
enhance product shelf life [10]. HFCS is the end product
from a corn wet-milling process that involves a number of
steps in a product line that yields corn oil, animal feed,
starch products, and corn sweeteners. Several chemicals
are required to make HFCS, including caustic soda, hydrochloric acid, alpha-amylase, gluco-amylase, isomerase, filter aid, powdered carbon, calcium chloride, and
magnesium sulfate [11]. The caustic soda and hydrochloric acid are used throughout the milling process to adjust
the pH of the product line. The product line starts with
corn and the cornstarch molecule is then converted to different products by various methods that involve acids,
bases, sodium hypochlorite and enzymes [12]. Should
mercury grade caustic soda, hydrochloric acid, or sodium
hypochlorite (derived from mercury grade chor-alkali
chemicals) be used in the milling process, it seemed plausible to the EHO that mercury may well end up in the final
product – HFCS. A limited screening of HFCS samples for
http://www.ehjournal.net/content/8/1/2
mercury was initiated by the EHO and researchers at NIST
found low levels of total mercury. [13].
To determine the extent of total mercury in HFCS products, the EHO then used additional government resources
to collect HFCS samples from different manufacturers and
collaborate with individuals outside of the federal government to analyze the samples for total mercury content. It
should be noted that these activities occurred before the
EHO retired in January 2008.
HFCS sample collection and analytical method
The EHO working under the Office of the FDA Commissioner instructed an investigator in a FDA regional office
to collect HFCS samples from different manufacturers.
During the week of February 17–24, 2005, the FDA field
investigator successfully conducted three separate sampling events, one at each manufacturer. Prior to each sampling event, the FDA field investigator soaked the 20milliliter (mL) sample vials overnight in a 50 percent (%)
nitric acid solution and then rinsed them with distilled
water before allowing them to air dry. Per directed assignment from the FDA researcher, the FDA field investigator
collected five samples of 42% HFCS and five samples of
55% HFCS from Manufacturer A, five samples of 42%
HFCS from Manufacturer B, and five samples of 55%
HFCS from Manufacturer C. Each 20 mL sample vial contained approximately 10 mL of HFCS at the end of each of
the sampling events. Each sample vial was appropriately
labeled with the manufacturers name, % HFCS, date, and
the initials of the field investigator. All samples were kept
under lock and key prior to being shipped via FEDEX
overnight to a laboratory for analyses.
Researchers at the University of Wisconsin-Platteville
received the samples from a federal employee with chainof-custody intact and sub-sampled them for total mercury
analysis using NIST Oyster Tissue 1566 b as the standard
reference material. The NIST Certificate of Analysis for the
Oyster Tissue 1566 b stated that as a standard, it could validate the accuracy of the methods and instruments used to
analyze twenty-two different elements including total
mercury. All samples, blanks (water and acid matrix), and
NIST standard reference material Oyster Tissue 1566 b
were analyzed by the following method using Optima
Grade Fisher Scientific hydrochloric and nitric acids that
were certified to contain less than 0.0001 microgram (μg)
mercury per gram (g) reagent. Approximately 1.0 g (to
nearest 0.1 milligram) of a HFCS sample, blank, or reference material was accurately weighed into a clean 50 mL
XP1500 Plus microwave cell. Approximately 5 mL of
nitric acid (Optima Grade Fisher Scientific) was added to
the cell. The cell was sealed, and the contents were
digested in a high-pressure microwave oven (CEM Mars
5). The resulting solution was allowed to cool before
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http://www.ehjournal.net/content/8/1/2
gravimetrically diluting the sample to 50.0 grams (to nearest 0.1 milligram) with 2 Molar (M) hydrochloric acid
(Optima Grade Fisher Scientific; 18 MÙ-cm water). Each
sample was analyzed within three hours to minimize mercury loss.
Tissue 1566 b (0.036 ± 0.006 μg/g mercury) exhibited
good agreement with certified values (0.037 ± 0.001 μg/g
mercury). The NIST Oyster Tissue 1566 b analyses were
performed prior to samples, between samples, and postsamples with no significant difference (p < 0.05) in the
total mercury content between these analyses.
A Leeman Labs Hydra AA cold vapor atomic absorption
spectrometer (CVAAS) was used for the total mercury
analysis. A calibration curve ranging from 10 to 200 picograms mercury/g was constructed using gravimetric dilutions (2 M hydrochloric acid described above) of a
primary standard mercury solution (GFS Chemicals).
Samples, blanks, and reference materials were introduced
along with stannous chloride (GFS Chemicals) reductant
at a rate of 5 mL/minute. Each sample and reference material was analyzed in triplicate.
Mercury was detected in nine of the twenty samples analyzed (Table 1). Of ten samples from manufacturer "A",
nine were below the 0.005 μg mercury/g sample detection
limit with the sole exception being a sample that was
0.012 μg mercury/g HFCS. Of the remaining ten samples
from two other manufacturers, two were below the detection limit and the mercury content of the other eight samples ranged from 0.065 μg to 0.570 μg mercury/g HFCS
(Table 1).
Results of analyses
Implications
Inter-sample blanks displayed no mercury signal above
the method detection limit of 0.005 μg mercury/g sample.
Mercury recovery of spiked reference materials (GFS
Chemicals) averaged 98.8 ± 0.3 %. The results from the
total mercury analysis of NIST reference material Oyster
Mercury was not detected in eleven out of twenty HFCS
samples analyzed (detection limit 0.005 μg mercury/g). A
single manufacturer produced nine of these eleven samples. These samples were likely manufactured using caustic soda produced by a membrane chlor-alkali plant
Table 1: total mercury (Hg) in high fructose corn syrup (HFCS) samples
Sample Name
Hg content (μg Hg/g HFCS)
Sample Name
Hg content (μg Hg/g HFCS)
MANUFACTURER A
HFCS 42% (sample 1)
< DL (0.005)
MANUFACTURER B
HFCS 42% (sample 1)
< DL (0.005)
MANUFACTURER A
HFCS 42% (sample 2)
< DL (0.005)
MANUFACTURER B
HFCS 42% (sample 2)
< DL (0.005)
MANUFACTURER A
HFCS 42% (sample 3)
0.012
MANUFACTURER B
HFCS 42% (sample 3)
0.350
MANUFACTURER A
HFCS 42% (sample 4)
< DL (0.005)
MANUFACTURER B
HFCS 42% (sample 4)
0.390
MANUFACTURER A
HFCS 42% (sample 5)
< DL (0.005)
MANUFACTURER B
HFCS 42% (sample 5)
0.065
MANUFACTURER A
HFCS 55% (sample 1)
< DL (0.005)
MANUFACTURER C
HFCS 55% (sample 1)
0.130
MANUFACTURER A
HFCS 55% (sample 2)
< DL (0.005)
MANUFACTURER C
HFCS 55% (sample 2)
0.400
MANUFACTURER A
HFCS 55% (sample 3)
< DL (0.005)
MANUFACTURER C
HFCS 55% (sample 3)
0.570
MANUFACTURER A
HFCS 55% (sample 4)
< DL (0.005)
MANUFACTURER C
HFCS 55% (sample 4)
0.110
MANUFACTURER A
HFCS 55% (sample 5)
< DL (0.005)
MANUFACTURER C
HFCS 55% (sample 5)
0.240
DL – Detection Limit
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Environmental Health 2009, 8:2
which does not use mercury in its manufacturing process.
Eight of the nine HFCS samples exhibiting mercury levels
between 0.065 μg to 0.570 μg mercury/g HFCS were produced by the other two manufacturers. This could indicate
the use of mercury grade caustic soda or hydrochloric acid
in the manufacturing processes used by these two manufacturers. Such use would account for the mercury in these
HFCS products. With key aspects of the HFCS manufacturing process considered proprietary information, we
could not confirm the composition of the raw materials
used by the individual HFCS manufacturers and the subsequent source of the mercury. While more sophisticated
methods produce lower detection limits, the CVAAS
method used in these analyses was sufficient as it clearly
and reliably demonstrated significant levels of mercury in
45% of the HFCS samples analyzed. Clearly the sample
size of this preliminary trial is too small but there was no
support to collect additional samples for analyses. When
university researchers outside of the government
attempted to obtain additional HFCS samples direct from
the manufacturer they were unable to get them. However,
with 45% of the HFCS samples containing mercury in this
small study, it would be prudent and perhaps essential for
public health that additional research be conducted by the
FDA or some other public health agency to determine if
products containing HFCS also contain mercury. In 2004,
several member states of the European Union reported
finding mercury concentrations in beverages, cereals and
bakery ware, and sweeteners [14] – all of which may contain HFCS. FDA does not currently have a mercury surveillance program for food ingredients such as added sugars
or preservatives manufactured with mercury grade chloralkali products.
The FDA does analyze some foods for mercury through
the ongoing surveillance program known as the Total Diet
Study (TDS). The TDS, however, does not test all foods for
mercury. Mercury is routinely detected by the TDS in fish,
liver, and poultry because farmers routinely use fishmeal
and/or fish oil as feed for certain livestock to include
chickens, swine, dairy cows, and farmed fish. Animals that
are fed fishmeal can bioconcentrate monomethyl mercury
in protein matrices that are then passed on to the consumer in the fat components of derived foods [15]. A list
of the foods that were recently tested for total mercury
along with the results of the analyses may be found at the
FDA website [16]. In 2003, FDA tested 48 foods for mercury during the TDS and of those only three may have
contained HFCS. Average daily US consumption of HFCS
for the year 2007 was approximately 49.8 g per person
according to the US Department of Agriculture website
[17]. High-end consumers of beverages sweetened with
HFCS could easily be ingesting more HFCS than the average person. Results of a recent study of dietary fructose
consumption among US children and adults indicate that
http://www.ehjournal.net/content/8/1/2
fructose consumption by Americans represents ten percent (10%) of calories consumed in a 24-hour period
[18]. Seventy four percent (74%) of this fructose came
from foods and beverages other than fruits and vegetables.
With respect to product labeling, FDA requires food manufacturers to list on the food product label ingredients in
descending order of weight from most to least [19]. For
example, HFCS is commonly listed as the first ingredient
in chocolate syrup on the product label, therefore all that
can be known is that of all the ingredients in chocolate
syrup, there is more HFCS in the product than any other
ingredient. Product labels listing HFCS as a first or second
ingredient may contain detectable levels of mercury if the
HFCS was manufactured with mercury grade chlor-alkali
chemicals. As part of the review process for this article, the
authors contacted manufacturers for more information
on the % concentration of HFCS in their products and the
common response back from manufacturers was that this
information is proprietary. With the reported average
daily consumption of 49.8 g HFCS per person, however,
and our finding of mercury in the range of 0.00 to 0.570
μg mercury/g HFCS, we can estimate that the potential
average daily total mercury exposure from HFCS could
range from zero to 28.4 μg mercury. This range can be
compared to the range of total mercury exposure from
dental amalgam in children reported by Health Canada
[20]. In the report issued by Canada, daily estimates of
total mercury exposure from dental amalgam in children
ages 3–19 ranged on average from 0.79 to 1.91 μg mercury. Canada and other countries do not recommend the
use of mercury amalgam in pregnant women or children.
Current international food processing standards allow 1.0
μg mercury/g caustic soda [21,22] and there is no standard for mercury in food grade hydrochloric acid. Both of
these chemicals may be used to make HFCS. The FDA has
approved HFCS for use as an added sugar in food products but a review of food product labels reveals that it is
often added to a product in addition to sugar presumably
to enhance product shelf life. Regardless of its intended
use, it is imperative that public health officials evaluate
this potential source of mercury exposure, as HFCS is presently ubiquitous in processed foods and therefore significantly consumed by people all over the world.
Mercury in any form – either as water-soluble inorganic
salt, a lipid-soluble organic mercury compound, or as
metallic mercury- is an extremely potent neurological
toxin [23]. Organic mercury compounds such as methylmercury that are fat-soluble and readily cross the blood
brain barrier are especially damaging to developing nervous tissues [24,25]. For example, prenatal exposure as low
as 10 mg/kg methylmercury, as measured in maternal hair
growing during pregnancy, may adversely affect the devel-
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Environmental Health 2009, 8:2
opment of the fetal brain [25,26]. Confounding associations and concerns with various stages of brain
development related to cumulative early life exposure to
mercury include the following sources of mercury: maternal fish consumption during pregnancy, the thimerosal
(sodium ethylmercurithiosalicylate, approximately 49%
mercury weight) content of certain vaccines and dental
amalgam [27].
Mercury regulation varies from country to country. While
the US government only regulates methylmercury in fish,
several other governments regulate all forms of mercury in
all foodstuffs. In the US, the current action level of 1 μg
methylmercury/g fish or seafood was set in 1977 during
court proceedings of the United States of American v.
Anderson Seafoods, Inc. [28]. The data used to determine
the action level in fish came from a poisoning incident
that occurred in Iraq under Saddam Hussein's regime in
1971–1972. There was not a chain of custody for the specimens taken from the victims of that poisoning that were
tested by World Health Organization or American
researchers, and an appropriate epidemiological study
was not undertaken [29]. Further risk assessment for
methylmercury has been conducted using human data
from the massive episodes of mercury poisoning in the
tragic Minimata Bay incident in Japan, as well as from
large scale epidemiological studies concerning childhood
neurodevelopment and neurotoxicity in relation to fetal
exposure in various fish eating communities around the
world [24,25]. There has never been a blinded, placebo,
controlled study published giving humans mercury or
methylmercury, nor would this kind of study be ethically
considerable. Quantitative information on long-term
effects of inorganic mercury compounds on humans does
not exist [30]. Inorganic mercury compounds react with
DNA and are clastogenic [30]. Because the mechanisms of
these reactions remain unknown, it is currently impossible to establish a no adverse-effect-level for mercury in
humans. Sensitive populations such as neonates lacking
the ability to efficiently excrete mercury or individuals
that retain mercury in their body due to impairments in
detoxification pathways may not be protected by any
exposure limit. The implications for mercury in ingested
HFCS are not known and clearly more epidemiological
and neurotoxicological studies are required.
http://www.ehjournal.net/content/8/1/2
system development [6]. Current international food
processing standards allow 1.0 μg mercury/g caustic soda
[21,22] and there is no standard for mercury in food grade
hydrochloric acid. Both of these chemicals may be used to
make HFCS. Mercury contamination of food products as
a result of the use of mercury contaminated HFCS seems
like a very real possibility. With daily per capita consumption of HFCS in the US averaging about 50 grams and
daily mercury intakes from HFCS ranging up to 28 μg, this
potential source of mercury may exceed other major
sources of mercury especially in high-end consumers of
beverages sweetened with HFCS. Food products that contain a significant amount of HFCS should be tested for
mercury contamination in the end product and the public
should be informed of any detections. Clearly, more
research is needed to determine the extent of mercury
exposure in children from mercury contaminated HFCS in
food products.
Abbreviations
AA: Atomic Absorption; CEM: Corporation that makes
microwave accelerated reaction systems; CVAAS: Cold
Vapor Atomic Absorption Spectrometer; DNR: Department of Natural Resources; EHO: Environmental Health
Officer; EPA: Environmental Protection Agency; FDA:
Food and Drug Administration; GFS: Grade Fisher Scientific; HFCS: High Fructose Corn Syrup; M: Molar; MARS:
Microwave Accelerated Reaction System; NIST: National
Institute of Standards and Technology; TDS: Total Diet
Study; US: United States; XPI: Cross Polar Isolation
Competing interests
The authors declare that they have no competing interests.
Authors' contributions
RD carried out the environmental investigation, conceived the study, acquired the samples for analyses, and
was involved in drafting the manuscript. BL provided
assistance in the study design and was involved in drafting
the manuscript. CC and LS analyzed the samples,
acquired the data and were involved in drafting the manuscript. RS, LP, JH, DW and WJL were all instrumental in
drafting the manuscript and revising it critically for intellectual content. All authors read and approved the final
manuscript.
Conclusion
Acknowledgements
An EHO at the FDA conducted an investigation of the
chlor-alkali industry in 2004 and found mercury residue
in all of the mercury cell chlor-alkali products including
caustic soda, chlorine, potassium hydroxide, and hydrochloric acid. Mercury is widely accepted to be a neurotoxic
heavy metal [23]. The American Academy of Pediatrics
has recommended that minimizing any form of mercury
exposure is essential for optimal child health and nervous
This research article is based on the views of the authors and does not represent an official FDA position. Thanks to Dr. Isaac Pessah and Dr. Howard
Hu for their helpful reviews and feedback on the way to present this information to the public. Thanks to Dr. Barry Lai for providing assistance with
sample transportation.
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