NUTRITION AND DIET RESEARCH PROGRESS

FISH AS A DIETARY SOURCE

OF MERCURY AND
METHYLMERCURY, RISKS
AND BENEFITS
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NUTRITION AND DIET

RESEARCH PROGRESS
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NUTRITION AND DIET RESEARCH PROGRESS

FISH AS A DIETARY SOURCE

OF MERCURY AND
METHYLMERCURY, RISKS
AND BENEFITS

AFNAN FREIJE
AND

MAYSOON AWADH

Nova Science Publishers, Inc.

New York

Copyright 2011 by Nova Science Publishers, Inc.

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CONTENTS
Preface

vii

Chapter 1

Chemical and Physical Properties of Mercury

Chapter 2

Inorganic Forms of Mercury

Chapter 3

Organic Forms of Mercury

Chapter 4

Sources of Mercury in the Environment

Chapter 5

Natural Sources

Chapter 6

Anthropogenic Releases from the Mobilization

of Mercury Impurities in Materials

11

Anthropogenic Releases from Mercury

Used in Products and Processes

13

Chapter 8

Emission of Mercury to the Air

15

Chapter 9

Emission of Mercury to the Water

17

Chapter 10

Emission of Mercury to the Soil

19

Chapter 11

Re-Mobilization of Historic
Anthropogenic Mercury

21

Global Cycling, Transport and Fate of

Mercury in the Environment

23

Mercury Species and Transformation in

Aquatic Environment

25

Chapter 7

Chapter 12
Chapter 13

vi
Chapter 14

Contents
Potential Sources of Exposure and Occurrence
of Mercury in Human Tissues

29

Chapter 15

Risks and Benefits of Eating Fish

31

Chapter 16

Fish Consumption Limits

33

Chapter 17

Toxicity of Mercury and Methylmercury

35

Chapter 18

Acute Toxicity

37

Chapter 19

Chronic Toxicity

39

Chapter 20

Developmental Toxicity

41

Chapter 21

Mutagenicity, Neurotoxicity and Cytotoxicity

43

Chapter 22

Distribution of Mercury in Fish Samples

45

Chapter 23

Human Health Risk Assessment

47

References

49

Index

61

PREFACE
This book is an overview that covers many aspects regarding
mercury and methylmercury. As a result, the findings of many recent
research studies have been incorporated in every chapter in this edition.
The chapters have been arranged in a logical way, taking the readers
through a journey beginning with basic information about mercury and
methylmercury, environmental sources, transport and fate, and ultimately
risks and awareness. A vast quantity of information about mercury and
methylmercury makes any attempt to collect such information a difficult
task.
The book is intended primarily for researchers that are interested in
the environmental pollutants mercury and methylmercury although it is
hoped to be appealing to other environmental researchers. It is based on
many years of research studies and reviews. We tried to stress the
importance of fish as a dietary source of mercury and methylmercury by
including details of many recent studies in this field.
We have tried to organized the chapters of this book in a way that
makes it easier to follow and understand if they are read in order. The
first part of the book is designed to take the reader step by step through
properties of mercury and its different forms, its deposition in the
environment and in the aquatic food chain. The latter part of the book
deals with risks and benefits associated with eating fish and therefore the
types of mercury toxicity that might be accompanied with fish
consumption.

Chapter 1

CHEMICAL AND PHYSICAL

PROPERTIES OF MERCURY
Mercury occurs naturally and distributed widely by human activities
in the environment. Mercury is a heavy metal, an element of the earth
with a molecular weight of 200.59g and an atomic number of 80. It is
one of the few elements that are mobile, shiny, silver-white, odorless
liquid at room temperatures, therefore it is called quicksilver. Mercury is
used to make thermometers, diffusion pumps, barometers, mercury
vapour lamps, mercury switches, pesticides, batteries, dental
preparations, antifouling paints, pigments, and catalysts (Boening, 2000;
Sanzo, 2001; UNEP, 2005).
Mercury in the environment exists in three forms, elemental or
metallic mercury (Hg0), inorganic and organic mercury compounds.
Mercury (Hg) can be bound to other compounds as monovalent Hg(I) or
divalent mercury (Hg(II) or Hg+). Both inorganic and organic chemical
compounds of mercury (II) are much more numerous than those of
mercury (I) (Qian, 2001; UNEP, 2005; Virtanen et al., 2006).
In addition to inorganic mercury salts, including mercurous chloride,
mercuric chloride, mercuric acetate, and mercuric sulfide, mercury (II)
forms an important class of organometallic compounds. The most toxic
organometallic compounds is the subclass of short-chain alkyl mercurials
in which mercury is attached to the carbon atom of a methyl, ethyl, or
propyl group (WHO, 1989; Clarkson, 1998; WHO, 2003; Dorea et al.,
2003).

Afnan Freije and Maysoon Awadh

The specific gravity of metallic mercury at 20C is 13.534 g/cm and

the vapour pressure is 0.16 Pa (0.0012 mmHg). However, a saturated
atmosphere at 20C contains approximately 15 mg/m, which is 300
times greater than the recommended health-based occupational exposure
limit of 0.05 mg/m.The boiling point of mercury is 356.73C (675F)
and it is a poor conductor of heat as compared with other metals but is a
good conductor of electricity (WHO, 1990; Wikipedia, 2006).
Mercury compounds differ greatly in their solubility values in water
in the order: elemental mercury < mercurous chloride < methylmercury
chloride < mercuric chloride (WHO, 1990). Due to the high solubility of
the methylmercury cation in water, the solubility of methylmercury
chloride in water is higher than that of mercurous chloride by about three
orders of magnitude (Clarkson, 1988). On the other hand elemental
mercury and the halide compounds of alkylmercurials are soluble in nonpolar solvents (Clarkson, 1988). Hursh (1985) showed that mercury
vapour is more soluble in plasma, whole blood, and haemoglobin than in
distilled water or isotonic saline.
Mercury readily forms alloys with other metals, such as gold, silver,
and tin. These alloys are called amalgams. Therefore, mercury is
amalgamated with gold to facilitate its recovery from its ores. Mercury
and its compounds are highly poisonous (Levy et al., 2003; UNEP,
2005).

Chapter 2

INORGANIC FORMS OF MERCURY

Mercury is present in many chemical forms; it occurs naturally as
non toxic mercuric sulphide (HgS) cinnabar. Inorganic mercuric
compounds (mercury salts) include mercuric oxide (HgO), mercuric
chloride HgCl2 (corrosive sublimate - a violent poison), mercurous
chloride Hg2Cl2 (calomel, occasionally still used in medicine), mercury
fulminate Hg(ONC)2 (a detonator used in explosives), and mercuric
sulphide (vermillion, a high-grade paint pigment) (WHO, 1991; WHO,
2003; UNEP, 2005).
Most inorganic mercury salts are white powders or crystals, while
mercuric sulphide which is the most common form of mercury, is a red
insoluble salt which turns black after exposure to light. Some mercury
salts (such as HgCl2) are volatile to exist as an atmospheric gas.
However, the water solubility and chemical reactivity of these inorganic
(ionic) mercury gases lead to more rapid deposition from the atmosphere
than for metallic mercury. This results in shorter atmospheric lifetimes
for these divalent inorganic mercury gases than for the elemental
mercury gas (Qian, 2001; WHO, 2003).

Chapter 3

ORGANIC FORMS OF MERCURY

When mercury combines with carbon the compounds formed are
called organic mercury compounds or organomercurials. There are a
large number of organic mercury compounds (such as dimethylmercury,
phenylmercury, ethylmercury and methylmercury); however, the most
common organic mercury compound in the environment is
methylmercury. Methylmercury and phenylmercury exist as white
crystalline salts (for example, methylmercuric chloride or
phenylmercuric acetate). However, dimethylmercury is a colourless
liquid (WHO, 1990; UNEP, 2004).
Methylmercury (CH3Hg) is the most common organic mercury
compound that is generated by natural processes. Methylmercury can
build up (bioaccumulate and biomagnify) in fish and marine mammals to
levels that are many thousands of times greater than levels in the
surrounding water (USGS, 2000; USEPA, 2001; Mahaffey, 2004; Mora
et al., 2004; Voegborlo and Akagi, 2007). Methylmercury can be formed
in the environment mainly by microbial metabolism (biotic processes)
and by chemical processes that do not involve living organisms (abiotic
processes). Direct anthropogenic (or human-generated) sources of
methylmercury are currently not known. However, indirectly
anthropogenic releases contribute to the methylmercury levels found in
nature because of the transformation of other forms (USEPA, 2001;
UNEP, 2004).

Chapter 4

SOURCES OF MERCURY
IN THE ENVIRONMENT
Mercury occurs naturally and is distributed throughout the
environment by both natural processes and human activities (Qian, 2001;
FVSRC, 2005). The sources of mercury releases to biosphere as grouped
by the United Nations Environment Programme (UNEP, 2004; UNEP,
2005) in four categories were:

Chapter 5

NATURAL SOURCES
Natural sources of mercury releases by: volcanic activity, weathering
of rocks, evaporation from water and soil surfaces, forest fires and
degradation of minerals (FVSRC, 2005; UNEP, 2005).
The natural mercury emissions are beyond control, considered as a
part of the local and global living environment. Regions with high
concentrations in surface rocks are characterized by high mercury
emissions to the atmosphere. Emissions of mercury from water and soil
surfaces today, are composed of both natural sources and re-emission of
previous mercury deposition from both natural sources and
anthropogenic. This makes it very difficult to determine the actual
natural mercury emissions (UNEP, 2005).
There are indications that anthropogenic emissions of mercury
around the globe have resulted in deposition rates today which are 1.5 to
3 times higher than those during pre-industrial times. However, in and
around industrial areas the deposition rates have increased by 2 to 10
times during the last 200 years (Lindquist et al., 1984; Bergan et al.,
1999). The global natural emission was estimated by Mason et al. (1994)
at about 1650 metric tons/year. This estimate was updated by Lamborg et
al. (2002) to around 1400 metric tons/year. However, Bergan and Rohde
(2001) had estimated global natural emission of about 2400 metric tons,
in which 1100 was emitted from oceans and 1320 from land sources.

Chapter 6

ANTHROPOGENIC RELEASES FROM THE

MOBILIZATION OF MERCURY
IMPURITIES IN MATERIALS
Naturally, mercury is present in coal and other fossil fuels. On the
other hand, mercury present in minerals like lime for cement production
and soils (such as agricultural soils subject to acidification management)
and metal ores including for example zinc, copper and gold ore. Today
production of coal-fired power is deemed the single largest global source
of atmospheric mercury emissions (Pacyna and Pacyna, 2000).
In primary and recycled materials mercury impurities constitute
major contributions to the total global mercury burden. Processing of
secondary raw materials, like iron and steel for example, can also be a
significant source of mercury releases, and emission control technologies
are often necessary. In this case the origin of the mercury may be both
natural impurities and as a result of intentional use of mercury in
products/components in iron/steel scrap (switches, air-bag activators etc.)
(USGS, 2000; Qian, 2001; FVSRC, 2005).
The majority of atmospheric anthropogenic emissions are released as
gaseous elemental mercury (Hg). This is capable of being transported
over very long distances (USEPA, 1997).
The remaining part of air emissions are in the form of gaseous
divalent compounds (such as HgCl2) or bound to particles present in the
emission gas (UNEP, 2005).

12

Afnan Freije and Maysoon Awadh

These species have a shorter atmospheric lifetime than elemental

vapor and will deposit via wet or dry processes within roughly 100 to
1000 kilometers. However, significant conversion between mercury
species may occur during atmospheric transport, which will affect the
transport distance (UNEP, 2005).
The atmospheric residence time of elemental mercury is in the range
of months to roughly one year. Atmospheric residence time here
designates the time span from a given mercury molecule is emitted to the
atmosphere till it is deposited on land or in water. It does not include
subsequent re-emission to the atmosphere.
This makes transport on a hemispherical scale possible and
emissions in any continent can thus contribute to the deposition in other
continents. For example, contributions of external sources to
anthropogenic mercury depositions to Europe and Asia were estimated to
be about 20 percent and 15 percent, respectively. Similarly up to 50
percent of anthropogenic mercury deposited to North America is from
external sources (Travnikov and Ryaboshapko, 2002).
Furthermore, mercury is also capable of re-emissions from water and
soil surfaces. This process greatly enhances the overall residence time of
mercury in the environment. Recent findings indicate re-emission rates
of approximately 20 percent over a two-year period, based on stable
mercury isotope measurements in north-western Ontario, Canada
(Lindberg et al., 2001).

Chapter 7

ANTHROPOGENIC RELEASES
FROM MERCURY USED IN
PRODUCTS AND PROCESSES
Mercury is used in many products and industrial processes. Due to
releases during manufacturing, leaks, disposal or incineration of spent
products or other releases (UNEP, 2004; UNEP, 2005).

Chapter 8

EMISSION OF MERCURY TO THE AIR

The anthropogenic sources of mercury that releases to the air include
mining and smelting, industrial processes involving the use of mercury
such as chlor-alkali production facilities and production of cement
(UNEP, 2004; UNEP, 2005; McCrary et al., 2006).

Chapter 9

EMISSION OF MERCURY TO THE WATER

To the surface waters mercury is released from naturally occurring
mercury in soils and rocks and from industrial activities, including,
leather tanning, paper and pulp mills, electroplating, and chemical
manufacturing. On the other hand, wastewater treatment facilities may
also release mercury to water. Mercury in the air is an indirect source of
mercury to surface waters; it is deposited from rain and other processes
to water surfaces and to soils. Mercury may also be mobilized from
sediments if disturbed by flooding and/or dredging (Qian, 2001; UNEP,
2004; UNEP, 2005).

Chapter 10

EMISSION OF MERCURY TO THE SOIL

In soil the sources of mercury include direct application of fertilizers
and fungicides and disposal of solid waste, including batteries and
thermometers, to landfills. Municipal incinerator ash disposal in landfills
and the application of sewage sludge to crop land result in increased
levels of mercury in soil (UNEP, 2004; FVSRC, 2005; UNEP, 2005).

Chapter 11

RE-MOBILIZATION OF HISTORIC
ANTHROPOGENIC MERCURY
Mercury released previously can be deposited in soils, sediments,
water bodies landfills and waste/tailings piles (Boening, 2000; UNEP,
2004; UNEP, 2005).

Chapter 12

GLOBAL CYCLING, TRANSPORT

AND FATE OF MERCURY
IN THE ENVIRONMENT
Global cycling of mercury is a complex process. When mercury
evaporates from surface waters and soils to the atmosphere, is redeposited on land and surface water, and then is absorbed by soil or
sediments. After redeposition on land and water, mercury is commonly
volatilized back to the atmosphere as a gas, or as adherents to
particulates, or be methylated. Emitted mercury vapour is converted to
soluble forms (e.g. Hg II) and deposited by rain onto soil and water
(Boening, 2000; USGS, 2000; USEPA, 2001; Booth and Zeller, 2005).

Chapter 13

MERCURY SPECIES AND

TRANSFORMATION IN
AQUATIC ENVIRONMENT
In water methylmercury is the most common form of mercury,
quickly enters the aquatic food chain. In most adult fish, 90% to 100% of
the mercury is methylmercury (Bloom, 1992; Niencheski et al., 2001;
Mahaffey, 2004).
Marine aquatic organisms at all levels accumulate mercury in their
tissues, where organic mercury is retained for long periods. A number of
factors that affect the susceptibility of aquatic organisms to mercury,
include the life-cycle stage (the larval stage being particularly sensitive),
temperature, acidity, dissolved organic matter (DOC) and salinity of
surrounding water (Downs et al., 1998; Morel et al., 1998; Ikingura and
Akagi, 2003; Harding et al., 2006; Murphy et al., 2007). The ratio of the
methylmercury concentration in fish tissue to the concentration of
inorganic mercury in water is usually between 10,000 and 100,000 to one
(WHO, 1989).
The change of mercury from inorganic form to methylated forms is
the first step in the aquatic bioaccumulation process. This can occur by
microbial metabolism (biotic processes) such as by certain bacteria and
by chemical processes that do not involve living organisms (abiotic
processes). Bacteria that process sulfate (SO4)-2 take up mercury in its
inorganic form and convert it to methylmercury, through metabolic
processes. The conversion of inorganic mercury to methylmercury is

26

Afnan Freije and Maysoon Awadh

important because its toxicity is greater and organisms require longer

time to eliminate methylmercury (Morel et al. 1998; USGS, 2000).
These methylmercury containing bacteria may be consumed by the
next higher level in the food chain, or excrete the methylmercury to the
water where it adsorb to plankton which are also consumed by the next
level in the food chain. Once methylmercury is released, it enters the
food chain by rapid diffusion and tight binding to proteins. Animals
consume higher concentrations of mercury at each successive level of the
food chain and accumulate methylmercury faster than they eliminate it.
Thus small environmental concentration of methylmercury can readily
accumulate to potentially harmful concentrations in fish, fish eating
wildlife and people (Nakagawa et al., 1997; Morel et al., 1998; USGS,
2000, Sehee et al., 2010).
The formation of methylmercury in aquatic systems is influenced by
a wide variety of environmental factors. The efficiency of microbial
mercury methylation generally depends on factors such as microbial
activity and the concentration of bioavailable mercury (rather than the
total mercury pool), which in turn are influenced by parameters such as
temperature, pH, redox potential and the presence of inorganic and
organic complexing agents. (Ullrich et al., 2001; Seiders, 2006)
Certain bacteria also demethylate mercury, thereby forming some
natural constraints on the build-up of methylmercury (MarvinDipasquale et al., 2000, Bailey et al., 2001). Since both methylation and
demethylation processes occur, environmental methylmercury
concentrations reflect net methylation rather than actual rates of
methylmercury synthesis. Numerous bacterial strains capable of
demethylating and methylmercury are known, including both aerobic and
anaerobic species, but demethylation appears to be predominantly
accomplished by aerobic organisms. Bacterial demethylation has been
demonstrated both in sediments and in the water column of freshwater
lakes. Degradation of methyl and phenyl mercury by fresh water algae
has also been described (Ullrich et al., 2001).
Purely chemical methylation of mercury is also possible if suitable
methyl donors are present. The relative importance of abiotic versus
biotic methylation mechanisms in the natural aquatic environment has
not yet been established, but it is generally believed that mercury
methylation is predominantly a microbially mediated process (Ullrich et
al., 2001).

Mercury Species and Transformation in Aquatic Environment

27

Mason and Fitzgerald (1996; 1997) have reviewed aspects of the

cycle of mercury in oceans and other waters. From open ocean studies, it
is apparent that elemental mercury, dimethylmercury and, to a lesser
extent, methylmercury are common constituents of the dissolved mercury
pool in deep ocean waters. In open ocean surface waters
dimethylmercury is lacking, maybe as a result of decomposition in the
presence of light and an additional potential loss via evaporation from the
water surface. Recent results suggest that low oxygen conditions are not
necessary for the formation of dimethylmercury in the open oceans. This
contrasts with temperate lake waters where methylmercury is more
commonly occurring than dimethylmercury. Studies in freshwater and
estuarine environments have shown that methylation of mercury is
primarily taking place under low oxygen conditions and mainly by
sulphate-reducing bacteria.

Chapter 14

POTENTIAL SOURCES OF EXPOSURE

AND OCCURRENCE OF MERCURY
IN HUMAN TISSUES
Humans are exposed to mercury from different sources. Dental
amalgam is the most important source for elemental mercury vapour
exposure. On the other hand, using skin-lightening creams and soaps that
contain mercury and using mercury for cultural/ritualistic purposes or in
traditional medicine, can also result in substantial exposure to inorganic
or elemental mercury (Levy et al., 2003; UNEP, 2004).
Dietary intake is the dominant source of exposure to mercury for the
general population. Fish and seafood products are the main source of
methylmercury in the diet; studies have shown that methylmercury
concentrations in fish and shellfish are approximately 1,000 to 10,000
times greater than in other foods (Rice et al., 2000; Dorea, 2009).
Once released into the environment, inorganic mercury is converted
to organic mercury (methylmercury) which is the primary form that
accumulates in fish and shellfish. Methylmercury biomagnifies up the
food chain as it is passed from a lower food chain level to a subsequently
higher food chain level through consumption of prey organisms or
predators. Fish at the top of the aquatic food chain, bioaccumulate
methylmercury approximately 1 to 10 million times greater than
dissolved methylmercury concentrations found in surrounding waters
(Lawrence and Mason, 2001; USEPA, 2001).

Chapter 15

RISKS AND BENEFITS OF EATING FISH

Fish and shellfish are an important part of a healthy diet. Fish and
shellfish contain high quality protein and other essential nutrients. They
are also low in saturated fat, and contain omega-3 fatty acids
eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA)
(Daviglus et al., 2002; Patterson, 2002; Burger and Gochfeld, 2006). A
variety of potential health benefits are associated with omega-3 fatty
acids, including prevention of cardiovascular disease (CVD), cardiac
autonomic nervous effect, hypertension, autoimmune diseases and
cancers (Connor, 2000; Kris, 2002; Burger and Gochfeld, 2004; Burger
and Gochfeld, 2006, Thurston et al., 2007; Yaginum-Sakurai et al., 2009;
Yourifuji et al., 2010).
In developing children, omega-3 fatty acids play a role in brain
development and visual acuity. A well-balanced diet that includes a
variety of fish and shellfish can contribute to heart health and children's
proper growth and development. So, women and young children in
particular should include fish or shellfish in their diets due to the many
nutritional benefits (Burger and Gochfeld, 2004; Oken et al., 2005; Kuntz
et al., 2009). The special requirements for the developing nervous system
in late gestation and early childhood make it important for pregnant and
lactating women to have sufficient dietary intake of omega-3 fatty acids,
which is most readily achieved by eating fish.
By including moderate amounts of a variety of fish in a balanced
diet, and choosing fish that are low in methylmercury, women can
provide these essential nutrients to their babies both in uterus and

32

Afnan Freije and Maysoon Awadh

through breast milk, while at the same time minimizing their exposure to
environmental pollutants (Mahaffey, 2004; Virtanen et al., 2006).
Nutritional benefits may be compromised by the health risks of toxic
contaminants in many fish. Potentially, some fish are sufficiently
contaminated with environmental pollutants, such as methylmercury
(Clarkson, 2002). Therefore, balancing the benefits and harm remains a
risk communication challenge (Knuth et al., 2003; Gochfeld, 2004;
Huang et al., 2005; Willett, 2005; Verger et al., 2007; Mahaffey et al.,
2008).

Chapter 16

FISH CONSUMPTION LIMITS

Levels of methylmercury, measured in parts per million (ppm) or
(mg/Kg) wet weight, vary greatly, based upon the species, size and age
of the fish (Kureishy, 1993; Al-Majed and Perston, 2000 a,b; Sadiq et al.,
2002; Kehrig et al, 2007; Magalhaes et al., 2007).
In general, methylmercury levels for most fish range from less than
0.01 to 0.5 mg/kg, according to the Food and Drug Administration
(FDA). The average concentration for commercially important species is
less than 0.3 mg/kg. However, in large predator fish, methylmercury
levels can reach up to 1 mg/kg, which is the limit allowed by the FDA in
fish intended for human consumption (Lacerda et al., 2000; USEPA,
2001; Chen et al., 2004; Voegborlo and Akagi, 2007; USFDA, 2006).
The risks from mercury in fish and shellfish depend on the amount of
fish and shellfish eaten and the level of mercury in the fish and shellfish.
Therefore, the FDA and the Environmental Protection Agency (EPA) are
advising women who may become pregnant, pregnant women, nursing
mothers, and young children to avoid some types of fish and eat fish and
shellfish that are lower in mercury (Mahaffey, 2004; USFDA, 2006).

Chapter 17

TOXICITY OF MERCURY
AND METHYLMERCURY
PHARMACOKINETICS EFFECTS
Methylmercury carries the largest risk due to its high mobility in the
body. Approximately 95% of methylmercury ingested is absorbed
through the gastrointestinal tract, and is distributed to all tissues in about
30 hours. Methylmercury is somewhat lipophilic, allowing it to pass
through lipid membranes of cells and facilitating its distribution to all
tissues, where it binds readily to proteins fish muscle tissue. Skinning,
trimming and cooking the fish do not significantly reduce the mercury
concentration in the fillet. Since moisture is lost during cooking, the
concentration of mercury after cooking is actually higher than it is in the
fresh uncooked fish (USEPA, 2001; Clarkson, 2002; Mahaffey, 2004;
Virtanen et al., 2006).
On the other hand, Methylmercury is present in the body as watersoluble complexes mainly, if not exclusively, attached to the sulphur
atom of thiol ligands. It enters the endothelial cells of the blood brain
barrier as a complex with L-cysteine. The process is so specific that the
complex with the optical isomer D-cysteine is not transported.
Structurally, the L-complex is similar to the large neutral amino acid Lmethionine and is carried across the cell membrane on the large neutral
amino acid carrier (Clarkson, 2002).
Following ingestion and distribution, about 5% of the
methylmercury is found in blood and 10% in the brain. The

36

Afnan Freije and Maysoon Awadh

methylmercury concentration in red blood cells is approximately 20

times that in the plasma (Clarkson, 2002). On the other hand,
methylmercury can accumulate in hair and toenails and can be used as
indicators for long term mercury exposure. In hair, mercury levels about
250 times larger than blood levels (WHO, 1990). Methylercury is also
distributed to the fur and feathers of wild life. The highest mercury levels
in humans are generally found in the kidneys (Levy et al., 2003).
Methylmercury crosses the placental barrier with cord blood levels
similar or slightly higher than levels in maternal blood. Fetal brain
mercury levels are approximately 5-7 times higher than in maternal
blood. The excretion process for methylmercury involves its
demethylation, converting it (half life in body is about 70-80 days) to
inorganic form, then elimination from the body in the feces (UNEP,
2005).

Chapter 18

ACUTE TOXICITY
The estimated lethal dose of methylmercury is 10 to 60 mg/kg. Acute
high-level exposures to methylmercury may result in impaired central
nervous system function, damage of kidney and failure, gastrointestinal
damage, cardiovascular collapse, shock, and death (Harda, 1995;
USEPA, 2001).

Chapter 19

CHRONIC TOXICITY
Both elemental mercury and methylmercury produce a variety of
health effects at relatively high exposures. While recent studies indicate
that lower dose exposure can have effects on the cardiovascular and
immune systems, neurotoxicity is the effect of greatest concern. This is
true whether exposure occurs to the developing embryo or fetus during
pregnancy or to adults and children (Grandjean et al., 1997; Gulson et al.,
1998; Hites et al., 2004).
Two major episodes of long-term methylmercury poisoning through
fish consumption has been recorded in Japan. The first occurred in the
early 1950s among people, fish consuming domestic animals such as
cats, and wildlife living near Minamata City on the shores of Minamata
Bay, Kyushu, Japan. The source of the methylmercury contamination
was effluent from a chemical factory that used mercury as a catalyst and
discharged wastes into the bay where it accumulated in fish and shellfish
that were a dietary staple of this population (Qian, 2001, UNEP, 2005).
In 1965, another methylmercury poisoning incident occurred in the
area of Niigata, Japan. The signs and symptoms of the disease in Niigata
were similar to those of methylmercury poisoning in Minamata (JECFA,
2003; UNEP, 2005).
Methylmercury poisoning also occurred in Iraq following
consumption of seed grain that had been treated with a fungicide
containing methylmercury. The first outbreak occurred prior to 1960; the
second occurred in the early 1970s (USEPA, 2001; UNEP, 2005).

40

Afnan Freije and Maysoon Awadh

In this case, imported mercury-treated seed grains that arrived after

the planting season were ground into flour and baked into bread. Unlike
the long-term exposures in Japan, the epidemic of methylmercury
poisoning in Iraq was short in duration lasting approximately 6 months.
The signs and symptoms of methylmercury poisining disease in Iraq
were predominantly in the nervous system, including difficulty with
peripheral vision or blindness, sensory disturbances, incoordination,
impairment of walking, and slurred speech. Both children and adults
were affected (Shao et al., 2006).

Chapter 20

DEVELOPMENTAL TOXICITY
Data are available on developmental effects in animals. Also,
convincing data from a number of human studies (i.e., Minamata and
Iraq) indicate that methylmercury causes subtle to severe neurological
effects depending on dose and individual susceptibility. EPA considers
methylmercury to have sufficient human and animal data to be classified
as a developmental toxicant. Methylmercury accumulates in body tissue;
consequently, maternal exposure occurring prior to pregnancy can
contribute to the overall maternal body burden and result in exposure to
the developing fetus. In addition, infants may be exposed to
methylmercury through breast milk (Ubillus et al., 2000; USEPA, 2001;
Renee et al., 2006; Davidson et al., 2008; Fonseca et al., 2008; Sakamoto
et al., 2008, Rand et al. 2009).
Some infants born to mothers who had consumed methylmercury
contaminated grain (particularly during the second trimester of
pregnancy) showed nervous system damage even though the mother was
only slightly affected or asymptomatic (Carrington, 2004).

Chapter 21

MUTAGENICITY, NEUROTOXICITY
AND CYTOTOXICITY
Methylmercury appears to be clastogenic but not to be a point
mutagen; that is, mercury causes chromosome damage but not small
heritable changes in DNA. EPA has classified methylmercury as being of
high concern for potential human germ cell mutagenicity (USEPA,
2001).
Chronic exposure to Methylmercury may lead to inducedneurotoxicity that can be identified by three major mechanisms resulting
in neural cell death as well as cytoarchitectural alterations in the nervous
system. The major three mechanisms include calcium homeostasis
disruption, overproduction of reactive protein species inducing oxidative
stress or reduction of antioxidative defenses, and interactions with
sulfhydryl groups (Rice, 2008; Ceccatelli et al., 2010).
Morphological and cytotoxic effects has also being associated with
feeding on fish contaminated with Methylmercury. The liver of exposed
individuals showed infiltration of leukocytes, increased number of
melano-macrophage centers, lesions and necrotic areas in Disses space,
chaos and disorder in cytoskeleton organization suggesting toxic effect in
hepatocytes. Head kidney showed increased necrotic areas, increased
centers of melano-macrophages, increased phagocytic areas suggesting
too slow mechanisms of defense to Methylmercury (Mela et al., 2007).

Chapter 22

DISTRIBUTION OF MERCURY
IN FISH SAMPLES
Several factors are associated with the variation in Hg concentrations
in fish including trophic level, age, and size of fish (Kureishy, 1993; AlMajed and Preston, 2000a; Billard and Lecointre, 2001). Higher
concentrations of Hg are usually detected in larger fish than smaller fish
especially within a species. Fish that are high in the food chain
biomagnify contaminant such as Hg and accumulate them in higher
concentrations (Nakagawa et al., 1997; Al-Majed and Preston, 2000a;
Mora et al., 2004; Freije and Awadh; 2009). Carnivores fish can
sometimes be an exception, having higher concentrations due to their
trophic position. Those carnivores fish can be used as a good indicator
of mercury pollution monitoring (Vigh et al., 1996).
Several studies on mercury accumulation in fish have shown a
significant positive correlation between T-Hg and MeHg suggesting that
more organic mercury (MeHg) accumulate in fish muscles than inorganic
mercury (Hg) (Akagi et al., 1995; Al-Majed and Preston, 2000a; Mora et
al., 2004; Freije and Awadh, 2009).
MeHg is one of the most toxic forms of Hg in aquatic ecosystems
which is bioavailable and biomagnify in the food chain resulting in
relatively high levels in large fish. The proportion of MeHg relative to
Hg in fish species studied ranged from 87.5 to 97.6% (Chvojka et al.,
1990; Anderson and Depledge, 1997; Kannan et al., 1998; Al-Majed and
Preston, 2000a; Campbell et al., 2003; Freije and Awadh, 2009).

46

Afnan Freije and Maysoon Awadh

The T-Hg and MeHg concentrations of fish muscles also correlate

positively with fish weight and forklength which also represent the age
and hence exposure (Allen-Gil et al., 1997; Phillips et al., 1997; Stafford,
1997; Romeo et al., 1999; Al-Majed and Preston, 2000a; Billard and
Lecointre, 2001; Agusa et al., 2004; Freije and Awadh, 2009).
Generally, diet and living environment influence mercury and
methylmercury content in muscle tissues of fish (Vigh et al., 1996;
Svobodoval et al., 2004; Sarica et al., 2005; Sehee et al., 2010). It is well
established that nearly all of mercury in fish muscles (95%) occur as
methylmercury and is mostly transferred to fish through their food.
Therefore, fish species that feed on other fish have higher mercury
concentrations which increases in these predators as they age (Gray,
2002).In general, muscles of predatory fish contain higher concentrations
of T-Hg and MeHg, than nonpredatory fishes. The lowest concentrations
of T-Hg and MeHg recorded were in the muscles of fish which primarily
feed on plankton, whereas the highest concentrations were detected in
long-lived top predator fish (Al-Arrayed et al., 1999; Fishbase, 2006;
Freije and Awadh, 2009).
The trophic positions of the different species should also be taken in
consideration when comparing T-Hg and MeHg in fish. Fish that are at
the top of the food chain as well as being an epiplagic and a demersal
fish feeding respectively on Small fish show a relatively higher T-Hg and
MeHg contents in comparison with other fish species. On the other hand,
fish that are predominantly planktonic surface feeder have the lowest
concentrations of T-Hg and MeHg. (Carpenter et al., 1997; Fisher and
Bianchi, 1984; Anderson and Depledge, 1997; Al-Majed and Preston,
2000a; Surette et al., 2006; Freije and Awadh; 2009). Anderson and
Depledge (1997) reported an obvious difference between the
contaminant distribution in epipelagic, mesopelagic and demersal fish.
They have suggested that the epipelagic fish are more exposed to
atmospheric inputs and photochemical production of MeHg, wheres
demersal fish are more influenced by sediment conditions (Surette et al.,
2006).

Chapter 23

HUMAN HEALTH RISK ASSESSMENT

The benefits of fish consumption are well documented in the
literature. Fish is an excellent source of omega-3 fatty acids that reduce
cholesterol levels and the incidence of stroke, heart disease and pre-term
delivery (Daviglus et al., 2002; Patterson, 2002; Conner, 2000; Whelton
et al., 2004; Gochfeld and Burger, 2005; Fernandes and Venkatraman,
2006). Despite these benefits, fish consumption is the main pathway for
human exposure for MeHg (Rice et al., 2000). MeHg can cross the
placenta posing a direct effect on the developing fetus. Chronic exposure
of fetus to MeHg can cause infants to be born with mental retardation
and to exhibit cerebral palsy like symptoms (Gulson et. al., 1998). The
ingestion of mercury contaminated fish for long term induce numbness in
extremities, tremors, spasms, personality and behavioral changes,
difficulty in walking, defenses, blindness, and finally lead to death (IOM,
1991).
The action level of T-Hg and MeHg in fish (0.5-1.0 mg/kg wet
weight) is considered as the upper tolerance limit for human
consumption by several authorities including the United States Food and
Drug Administration (USFDA), the Australian National Health and
Medical Research Council (NHMRC), the Common-wealth and
Victorian Statutory, and the USEPA (Al-Hashimi and Al-Zorba, 1991,
USFDA, 2006). However the WHO permissible limits is 0.5 mg/kg wet
weight for T-Hg and 0.3 mg/kg wet weight for Me-Hg (WHO, 1990),
whereas Burger and Gochfeld (2006) considered this limit as a regulatory
level rather than risk level.

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INDEX
A
absorption, 52, 58, 59
acid, 35, 54
acidity, 25
Africa, 50
air emissions, 11
Alaska, 50
algae, 26
amalgam, 29, 54
anthropogenic sources, 15
apoptosis, 50
aquatic bioaccumulation, 25
aquatic ecosystems, 45
aquatic systems, 26
ASI, 55
Asia, 12
assessment, 49, 52, 58
asymptomatic, 41
atmosphere, 2, 3, 9, 12, 23, 50
atomic number, 1
authorities, 47
autoimmune diseases, 31

B
bacteria, 25, 26, 27
bacterial strains, 26
Bahrain, 49, 50, 52, 60

barometers, 1
batteries, 1, 19
behavioral change, 47
bioaccumulation, 25, 51, 54, 55
bioavailability, 52
biological systems, 55
biomarkers, 57
biosphere, 7
biotic, 5, 25, 26
blindness, 40, 47
blood pressure, 57
brain, 31, 35
Brazil, 49, 56
breast milk, 32, 41

C
calcium, 43
carbon, 1, 5
cardiovascular collapse, 37
cardiovascular disease, 31, 53, 59
carp, 58
Caspian Sea, 49
catalyst, 39
cation, 2
cell death, 43
cement, 11, 15
central nervous system, 37
cerebral palsy, 47

62

Index

chaos, 43
chemical reactivity, 3
child development, 53
childhood, 31, 57
chlor-alkali production facilities, 15
cholesterol, 47
chromatography, 51
chromosome, 43
City, 39
class, 1
climate, 50
climate change, 50
coal, 11
cognition, 56
compounds, 1, 2, 3, 5, 11, 59
conductor, 2
conservation, 50
consumption, vii, 29, 33, 39, 47, 51, 52,
53, 54, 56, 57
contaminant, 45, 46
contamination, 39, 52, 56, 57, 59
cooking, 35
copper, 11
coronary heart disease, 59
correlations, 57
crystalline, 5
crystals, 3
CVD, 31
cycles, 55
cycling, 23, 55
cytoskeleton, 43
cytotoxic effects, 43

D
D-cysteine, 35
decomposition, 27
deficit, 52
degradation, 9
deposition, vii, 3, 9, 12
deposition rate, 9
diet, 29, 31, 46, 50
dietary intake, 31
diffusion, 1, 26

digestion, 51
discharges, 56
disorder, 43
dissolved organic matter (DOC), 25
distilled water, 2
disturbances, 40
DNA, 43
docosahexaenoic acid, 31
donors, 26
Drosophila, 56

E
effluent, 39
eicosapentaenoic acid, 31
electricity, 2
electroplating, 17
elemental, 1, 2, 3, 11, 12, 27, 29, 39, 50,
55
emission, 9, 11, 12
endothelial cells, 35
environmental factors, 26
environmental pollutants, vii, 32
Environmental Protection Agency, 33,
54, 58
environmental sources, vii
EPA, 31, 33, 41, 43, 58
epidemic, 40
estuarine environments, 27
evaporation, 9, 27
excretion, 36
exertion, 54
explosives, 3
exposure, 2, 3, 29, 32, 36, 39, 41, 43, 46,
47, 51, 52, 53, 54, 57, 58, 59
extraction, 51

F
fatty acids, 31, 47, 51, 53, 54
FDA, 33
feces, 36
fertilizers, 19

63

Index
fetus, 39, 41, 47
fish, vii, 5, 25, 26, 29, 31, 32, 33, 35, 39,
43, 45, 46, 47, 49, 50, 51, 52, 53, 54,
55, 56, 57, 58, 59
fish oil, 53
fishing, 57
flooding, 17
flour, 40
fluorescence, 57
food additives, 53
fossil fuels, 11
France, 58
freshwater, 26, 27, 49, 52, 57

incidence, 47
industrial processes, 13, 15
infants, 41, 47
ingestion, 35, 47
inorganic, 1, 3, 25, 26, 29, 36, 45, 57, 58,
59
Inorganic mercuric compounds, 3
invertebrates, 50
ions, 55
Iraq, 39, 40, 41
iron, 11
isotonic saline, 2
isotope, 12

gastrointestinal damage, 37
gastrointestinal tract, 35
gestation, 31, 57
Global cycling, 23
gold, 2, 11
grass, 58

H
haemoglobin, 2
hair, 36, 49, 56, 57
health effects, 39
heart disease, 47
heavy metal, 1, 54, 55
heavy metals, 54, 55
hepatocytes, 43
heptane, 51
high mercury emissions, 9
histology, 55
homeostasis, 43
human exposure, 47
hypertension, 31, 59

I
immune system, 39
impurities, 11

Japan, 39, 40, 52

K
Kenya, 50
kidney, 37, 43, 55
kidneys, 36
Korea, 57
Kuwait, 49, 50

L
lakes, 26, 49, 50, 55, 57
landfills, 19, 21
Latvia, 52
L-complex, 35
L-cysteine, 35
leaks, 13
lesions, 43
lifetime, 12
liver, 43, 55
living environment, 9, 46
low oxygen conditions, 27

64

Index

M
macrophages, 43
Maine, 57
majority, 11
management, 11
manufacturing, 13, 17
marine environment, 55
markers, 51
mass spectrometry, 51
Mauritania, 56
membranes, 35
mental retardation, 47
mercuric acetate, 1
mercuric chloride, 1, 2, 3
mercuric oxide (HgO), 3
mercuric sulfide, 1
mercuric sulphide (HgS) cinnabar, 3
mercury fulminate, 3
mercury switches, 1
mercury vapour, 1, 2, 23, 29, 51
metabolism, 5, 25
metallic mercury, 1, 2, 3
metals, 2
methylation, 26, 27
methylmercury, i, iii, vi, vii, 2, 5, 25, 26,
27, 29, 31, 32, 33, 35, 36, 37, 39, 40,
41, 43, 46, 50, 51, 52, 53, 54, 55, 56,
57, 58, 59
Minamata Bay, 39
mining, 15, 49
modeling, 50
moisture, 35
molecular weight, 1
monitoring, 45, 51, 55
Moon, 57
Moscow, 58
Municipal incinerator ash disposal, 19
muscles, 45, 46
mutagen, 43

N
National Health and Medical Research
Council (NHMRC), 47
NATO, 55
nervous system, 31, 40, 41, 43
Netherlands, 55
neural development, 56
neurotoxicity, 39, 43, 50, 56
New South Wales, 51
North America, 12
Norway, 56
nursing, 33
nutrients, 31, 56

O
oceans, 9, 27
oil, 54
oil spill, 54
omega-3, 31, 47, 51, 53, 54
ores, 2, 11
organ, 1
organic matter, 25
organic mercury compounds, 1, 5
organometallic compounds, 1
overproduction, 43
oxidation, 57
oxidative stress, 43
oxygen, 27

P
paints, 1
pesticides, 1
pigments, 1
pilot study, 49
placenta, 47
placental barrier, 36
planktonic surface feeder, 46
plasma, 2, 36
poison, 3
pollution, 45, 49, 52, 58

65

Index
polyunsaturated fat, 49
polyunsaturated fatty acids, 49
positive correlation, 45
precipitation, 51
pregnancy, 39, 41, 51, 52
prevention, 31
project, 52, 57
proteins, 26, 35
pulp, 17
pumps, 1

Q
Qatar, 50, 54
quicksilver, 1

R
raw materials, 11
recommendations, iv
red blood cells, 36
resources, 50
rocks, 9, 17
room temperature, 1
Russia, 58

S
salinity, 25
salmon, 52
salts, 1, 3, 5
saturated fat, 31
Saudi Arabia, 50
scavengers, 57
seafood, 29, 56, 59
sediment, 46, 49, 53
sediments, 17, 21, 23, 26, 55, 57
seed, 39, 40
selenium, 51
sewage, 19
Seychelles, 53
shellfish, 29, 31, 33, 39, 54, 55, 58
shock, 37

shores, 39
short-chain alkyl mercurials, 1
signs, 39, 40
silver, 1, 2
skeleton, 52
skin, 29
sludge, 19
smelting, 15
social environment, 56
sodium, 51
solid waste, 19
solubility, 2, 3
solvents, 2
Spain, 57
species, 12, 26, 33, 43, 45, 46, 50, 52,
54, 56
specific gravity, 2
speech, 40
stable isotopes, 57
steel, 11
streams, 52
stroke, 47
sulphate-reducing bacteria, 27
sulphur, 35
supermarkets, 50
survey, 50
susceptibility, 25, 41
Sweden, 56
Switzerland, 58, 59
symptoms, 39, 40, 47
synthesis, 26

T
Tanzania, 53
temperature, 25, 26
thermometers, 1, 19
tin, 2
tissue, 25, 35, 41, 49, 50
toxic effect, 43
toxic metals, 51
toxicity, vii, 26
trace elements, 49
transformation, 5

66

Index

transformations, 50
transport, vii, 12, 50, 58

vapor, 12
vision, 40
visual acuity, 31

U
W
U.S. Geological Survey, 58
United Arab Emirates, 50
United Nations, 7, 58
United States Food and Drug
Administration (USFDA), 47
urine, 54
uterus, 31

walking, 40, 47
waste, 21, 54
wastewater, 17, 56
wealth, 47
wildlife, 26, 39
World Health Organisation, 59

V
validation, 57
valuation, 53

Z
zinc, 11
zooplankton, 49