The fate of mercury in the environment depends on the chemical form of
mercury released and the environmental conditions. Elemental mercury,
inorganic mercury, and methylmercury are the three most important forms of
mercury in natural aquatic environments. Most mercury is released into the
environment as inorganic mercury, which is primarily bound to particulates
and organic substances and may not be available for direct uptake by aquatic
organisms. The process of methylation of inorganic mercury to methylmercury,
which is highly bioavailable, is thus an important key to the fate of
mercury in the environment.
Elemental mercury has a high vapor pressure, a low solubility, does not
combine with inorganic or organic ligands, and is not available for
methylation. The mercurous ion (Hg[I]) combines with inorganic compounds
only and cannot be methylated. The mercuric ion (Hg[II]) combines with both
inorganic and organic ligands, and can be methylated. Methylation in aquatic
habitats is primarily a biological process. Mono- and dimethylmercury are
formed by microorganisms in both sediment and water through the methylation
of inorganic mercuric ions (Hg[II]). Dimethylmercury, which is highly
volatile, is generally not persistent in aquatic environments.
Methylation is influenced by environmental variables that affect both the
availability of mercuric ions for methylation and the growth of the
methylating microbial populations. Methylation rates are higher under anoxic
conditions, in freshwater compared to saltwater, and in low pH environments.
The presence of organic matter can stimulate growth of microbial populations
(and reduce oxygen levels), thereby enhancing the formation of
methylmercury. Sulfide can bind mercury and limit methylation. Methylmercury
production can vary due to seasonal changes in nutrients, oxygen,
temperature, and hydrodynamics. In most studies, methylation increased
during the summer months when biological productivity was high, and
decreased during the winter months.
Bioaccumulation
Mercury is accumulated by fish, invertebrates, mammals, and aquatic
plants and the concentration tends to increase with increasing trophic level
(mercury biomagnifies). Although inorganic mercury is the dominant form of
mercury in the environment and is easily taken up, it is also depurated
relatively quickly. Methylmercury accumulates quickly, depurates very
slowly, and therefore biomagnifies in higher trophic species. The percentage
of methylmercury, as compared to total mercury, also increases with age in
both fish and invertebrates. Due to its preferential uptake, ability to be
transferred among tissues, and slow depuration, most of the mercury in fish
muscle tissue (Å99%) is methylmercury.
Marine mammal tissues have some of the highest concentrations of mercury
found in all marine organisms, with the liver generally having the highest
total mercury concentration. Although many juvenile and adult marine mammals
primarily feed on fish, which contain high percentages of methylmercury,
high concentrations of inorganic mercury are found in adult specimens.
Apparently, adult marine mammals can
mineralize methylmercury into inorganic mercury. Juvenile marine
mammals have lower concentrations of total mercury than adults; but unlike
fish and invertebrates, the percentage of methylmercury is higher in
juvenile mammals.
Invertebrates generally have a lower percentage of methylmercury, as
compared to total mercury, in their tissues than do fish and marine mammals.
The percentage of methylmercury in invertebrates varies greatly and can
range from one percent in deposit-feeding polychaetes, to close to 100% in
crab.
Bioconcentration factors (BCFs) reflect uptake from water in laboratory
experiments. BCFs for mercury are variable, with the highest factors
determined for methylmercury. BCFs for methylmercury in brook trout range
from 69,000 to 630,000, depending on the tissue analyzed. BCFs for inorganic
mercury (mercuric chloride) in saltwater species range from 129 for adult
lobster (Homarus americanus) to 10,000 for oysters (Crassostrea virginica).
While sediment is usually the primary source of mercury in most aquatic
systems, the food web is the main pathway for accumulation. High trophic
level species tend to accumulate the highest concentrations of mercury, with
concentrations highest in fish-eating predators. Mercury concentrations in
higher trophic species often do not correlate with concentrations in
environmental media. Correlations have been made between sediment and lower
trophic species that typically have a high percentage of inorganic mercury,
and between mercury concentrations in higher trophic species and their prey
items.
Toxicity
Toxicity is influenced by the form of mercury, the environmental media,
environmental conditions, the sensitivity or tolerance of the organism, and
the life history stage. Inorganic mercury is less acutely toxic to aquatic
organisms than methylmercury, but the range in sensitivity among individual
species for either compound is large. Toxicity was found to be greater at
elevated temperatures, lower oxygen content, reduced salinities in marine
environments, and in the presence of metals such as zinc and lead.
In general, toxic effects occur because mercury binds to proteins and
alters protein production or synthesis. Toxicological effects include
reproductive impairment, growth inhibition, developmental abnormalities, and
altered behavioral responses. Reproductive endpoints are generally more
sensitive than growth or survival, with embryos and the early developmental
stages the most sensitive. Mercury can be transferred from tissues of the
adult female to developing eggs. Exposure to low concentrations of mercury
may not result in mortality directly, but may retard growth thereby
increasing the risk of predation.
Few studies report both tissue residues and effects in long-term exposure
to low concentrations of mercury. However, results from studies on different
freshwater species indicate that reproductive effects could be expected to
occur in sensitive fish species at tissue concentrations close to the FDA
action level of 1 mg/kg (ppm).
The interaction of mercury and other trace elements (e.g., cadmium,
copper, selenium, and zinc) can be both antagonistic and synergistic,
primarily depending on exposure concentrations and form of mercury. Effects
were generally less than additive (antagonistic) at lower exposure levels
and greater than additive (synergistic) at higher levels. Zinc and cadmium
were reported to reduce the teratogenic effects of methylmercury to
killifish while selenium reduced mercury's toxic effects on development in
medaka embryos.
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