Other Media.

Mercury emitted to the atmosphere is primarily in an inorganic form and it remains primarily in the
inorganic form when deposition occurs to water bodies. However, in water and sediments, inorganic
mercury can be transformed into methylmercury, which is very prone to bioaccumulate and biomagnify
as it moves through the food chain (Riisgard and Hansen 1990; UNEP 2018). In a study of
bioaccumulation of mercury in aquatic organisms, it was shown that fish had lower methylmercury
bioaccumulation factors in sites with high organic carbon, especially sites with large coastal wetlands and
large variability in dissolved organic carbon levels in the water column (Taylor et al. 2018b).
Methylmercury in surface waters is rapidly accumulated by aquatic organisms; concentrations in
carnivorous fish (e.g., pike, shark, and swordfish) at the top of both freshwater and marine food chains are
biomagnified on the order of 10,000–100,000 times the concentrations found in ambient waters (EPA
1979, 1984; WHO 1990, 1991). The range in experimentally determined bioconcentration factor (BCF)
values is shown in Table 5-9.

5.4.2 Transformation and Degradation

Mercury is transformed in the environment by biotic and abiotic oxidation and reduction, bioconversion
of inorganic and organic forms, and photolysis of organomercurials. Inorganic mercury can be methylated
by microorganisms indigenous to soils, fresh water, and salt water (Blanc et al. 2018). This process is
mediated by various microbial populations under both aerobic and anaerobic conditions. The most
probable mechanism for this reaction involves the nonenzymatic methylation of mercuric mercury ions by
methyl cobalamin compounds produced as a result of bacterial synthesis. Mercury forms stable
complexes with organic compounds. Monoalkyl mercury compounds (e.g., methylmercuric chloride) are
relatively soluble; however, the solubility of methylmercury is decreased with increasing dissolved
organic carbon content, indicating that it is bound by organic matter in water (Miskimmin 1991). Dialkyl
mercury compounds (e.g., dimethylmercury) are relatively insoluble (EPA 1979, 1984). Dimethyl-
mercury is volatile, although it makes up <3% of the dissolved gaseous mercury found in water
(Andersson et al. 1990; Vandal et al. 1991). The major pathways for transformation of mercury and
various mercury compounds in air, water, and soil are shown in Figure 5-4.

Water.
The most important transformation process in the environmental fate of mercury in surface waters is the
methylation and demethylation cycle. The methylation of mercury in surface waters is largely driven by
the presence of sulphate-reducing bacteria, and demethylation can occur through both abiotic and biotic
means (Ouddane et al. 2015). The photochemical degradation of methylmercury is the most important
process of the demethylation cycle at the surface or in shallow waters. Demethylation by biotic oxidation
and reduction reactions are the dominant pathways at deeper depths and in sediments.
Any form of mercury entering surface waters can be microbially converted to methylmercury, given
favorable conditions. The major factors that influence the rate of methylation are the abundance of
anaerobic microorganisms that have the biochemistry to methylate mercury and the bioavailability of
inorganic Hg(II) in these microorganisms (SERDP 2014). Sulfur-reducing bacteria are responsible for
most of the mercury methylation in the environment (Gilmour and Henry 1991; Ouddane et al. 2015),
Metrics of exposure (biomarkers). Humans are exposed to a mixture of methylmercury and inorganic
mercury (primarily mercuric and elemental) in their local environments, with either being more or less
pronounced under certain circumstances (e.g., occupational exposure to Hg 0 vapor, consumption of
methylmercury in fish).

Exposures of the general population to methylmercury can also occur as a result of methylation of
inorganic mercury released to local aquatic ecosystems (Ramirez et al. 2000).

Exposure to methylmercury in these populations derives primarily from methylation of inorganic

mercury released to local aquatic ecosystems from alluvial gold mining (Mergler 2002).

Most mercury in the atmosphere is in the gaseous elemental form, which can remain suspended in air for
long periods of time and is subject to long-range atmospheric transport. When released or deposited to
land or water, mercury can be transformed to methylated forms by anaerobic microorganisms.
Methylmercury is highly bioaccumulative and biomagnifies in the food chain.

Mercury occurs naturally as a mineral and is distributed throughout the environment by both natural
and anthropogenic processes. The natural global bio-geochemical cycling of mercury is characterized by
degassing of the element from soils and surface waters, followed by atmospheric transport, deposition
of mercury back to land, vegetation and surface water, and sorption of the compound to soil or
sediment particulates. Mercury deposited on land and open water is, in part, revolatilized back into the
atmosphere. This emission, deposition, and revolatilization creates difficulties in tracing the movement
of mercury to its sources. Major anthropogenic sources of mercury releases to the environment include
mining and smelting; industrial processes involving the use of mercury, including chloralkali production
facilities; combustion of fossil fuels, primarily coal; production of cement; and medical and municipal
waste incinerators and industrial/commercial boilers. Natural sources include volcanic activity, wildfires
that release sequestered mercury from biomass, and weathering of mercury-containing rocks.

The element has three valence states and is found in the environment in the metallic form and in the form
of various inorganic and organic complexes. The major features of the bio-geochemical cycle of mercury
include degassing of mineral mercury from the lithosphere and hydrosphere, long-range transport in the
atmosphere, wet and dry deposition to land and surface water, sorption to soil and sediment particulates,
revolatilization from land and surface water, and bioaccumulation in both terrestrial and aquatic food
chains.

Potential sources of general population exposure to mercury include inhalation of mercury vapors in
ambient air, ingestion of drinking water and foodstuffs contaminated with mercury, and exposure to
mercury through dental and medical treatments. Dietary intake is the most important source of
nonoccupational exposure to mercury, with fish and other seafood products being the dominant source of
mercury in the diet. Most of the mercury consumed in fish or other seafood is the highly absorbable
methylmercury form. Consumption of rice can also make a substantial contribution to dietary mercury
intake. Intake of elemental mercury from dental amalgams is another important contributing source to the
total mercury body burden in humans in the general population. This is expected to decline as use of
dental amalgams is being phased-out in many countries.

Additional anthropogenic releases of mercury to soil are expected as a result of the disposal of industrial
and domestic solid waste products (e.g., thermometers, electrical switches, and batteries) to landfills
(see Table 5-8). Another source of mercury releases to soil is the disposal of municipal incinerator ash in
landfills (Mumma et al. 1990). In 1987, nationwide concentrations of mercury present in the ash from
municipal waste incineration ranged from 0.03 to 25 ppm (Mumma et al. 1990). Such releases may
exhibit a seasonal variability. For example, fly ash collected prior to Christmas in December of 1989
contained significantly less mercury (6.5 ppm) than ash collected after Christmas in January of 1990 (45–
58 ppm), possibly as a result of the increased use and disposal of batteries containing mercury in toys
and other equipment used during this season (Mumma et al. 1991). Emission sources include stack
emissions, ashes collected at the stack, ashes from electrostatic precipitators, and slags (Morselli et al.
1992). An analysis of mercury concentrations in soil, refuse combustibles, and bottom and fly ash from
incinerators showed increasing concentrations of 0, 2, 4, and 100 mg/kg (ppm), respectively (Goldin et
al. 1992).

Sediment and Soil. The sorption process has been found to be related to the organic matter content of the
soil or sediment. Mercury is strongly sorbed to humic materials and sesquioxides in soil at a pH >4
(Blume and Brummer 1991) and to the surface layer of peat (Lodenius and Autio 1989). Mercury has
been shown to volatilize from the surface of more acidic soils (i.e., soil pH <3.0) (Warren and Dudas
1992). Adsorption of mercury in soil is decreased with increasing pH and/or chloride ion concentrations
(Schuster 1991). Mercury is sorbed to soil with high iron and aluminum content up to a maximum loading
capacity of 15 g/kg (15,000 ppm) (Ahmad and Qureshi 1989). Inorganic mercury sorbed to particulate
material is not readily desorbed. Thus, freshwater and marine sediments are important repositories for
inorganic forms of the element, and leaching is a relatively insignificant transport process in soils.
However, surface runoff is an important mechanism for moving mercury from soil to water, particularly
for soils with high humic content (Meili 1991). Mobilization of sorbed mercury from

5.4.2 Transformation and Degradation

Mercury is transformed in the environment by biotic and abiotic oxidation and reduction, bioconversion
of inorganic and organic forms, and photolysis of organomercurials. Inorganic mercury can be methylated
by microorganisms indigenous to soils, fresh water, and salt water (Blanc et al. 2018). This process is
mediated by various microbial populations under both aerobic and anaerobic conditions. The most
probable mechanism for this reaction involves the nonenzymatic methylation of mercuric mercury ions by
methyl cobalamin compounds produced as a result of bacterial synthesis. Mercury forms stable
complexes with organic compounds. Monoalkyl mercury compounds (e.g., methylmercuric chloride) are
relatively soluble; however, the solubility of methylmercury is decreased with increasing dissolved
organic carbon content, indicating that it is bound by organic matter in water (Miskimmin 1991). Dialkyl
mercury compounds (e.g., dimethylmercury) are relatively insoluble (EPA 1979, 1984). Dimethyl-
mercury is volatile, although it makes up <3% of the dissolved gaseous mercury found in water
(Andersson et al. 1990; Vandal et al. 1991).

Sediment and Soil. Mercury compounds in soils may undergo the same chemical and biological
transformations described for surface waters. Mercuric mercury usually forms various complexes with
chloride and hydroxide ions in soils; the specific complexes formed depend on the pH, salt content, and
composition of the soil solution. Formation and degradation of organic mercurials in soils appear to be
mediated by the same types of microbial processes occurring in surface waters and may also occur
through abiotic processes (Andersson 1979). Elevated levels of chloride ions reduce methylation of
mercury in river sediments, sludge, and soil (Olson et al. 1991), although increased levels of organic
carbon and sulfate ions increase methylation in sediments (Gilmour and Henry 1991). In freshwater and
estuarine ecosystems, the presence of chloride ions (0.02 M) may accelerate the release of mercury from
sediments (Wang et al. 1991). Cesario et al. (2017) studied the methylation and demethylation kinetics of
mercury in sediments, with and without salt-marsh plant vegetation, obtained from the Guadiana and
Tagus Estuaries, Portugal. Methylation and demethylation rates varied between sediments of the estuaries
depending upon the presence of vegetation and the macrophyte species present

Water. The most important transformation process in the environmental fate of mercury in surface
waters is the methylation and demethylation cycle. The methylation of mercury in surface waters is
largely driven by the presence of sulphate-reducing bacteria, and demethylation can occur through both
abiotic and biotic means (Ouddane et al. 2015). The photochemical degradation of methylmercury is the
most important process of the demethylation cycle at the surface or in shallow waters. Demethylation by
biotic oxidation and reduction reactions are the dominant pathways at deeper depths and in sediments.
Any form of mercury entering surface waters can be microbially converted to methylmercury, given
favorable conditions. The major factors that influence the rate of methylation are the abundance of
anaerobic microorganisms that have the biochemistry to methylate mercury and the bioavailability of
inorganic Hg(II) in these microorganisms (SERDP 2014). Sulfur-reducing bacteria are responsible for
most of the mercury methylation in the environment (Gilmour and Henry 1991; Ouddane et al. 2015),
with anaerobic conditions favoring their activity (Regnell and Tunlid 1991). Yeasts, such as Candida
albicans and Saccharomyces cerevisiae, whose growth is favored by low pH conditions, are able to
methylate mercury and are also able to reduce ionic mercury to elemental mercury (Yannai et al. 1991).
Methyl cobalamin compounds produced by bacterial synthesis appear to be involved in the nonenzymatic
methylation of inorganic mercury ions (Regnell and Tunlid 1991). The rate of methylmercury formation
by this process is largely determined by the concentration of methyl cobalamin compounds, inorganic
mercuric ions, and the oxygen concentration of the water, with the rate increasing as the conditions
become anaerobic. Volatile elemental mercury may be formed through the demethylation of
methylmercury or the reduction of inorganic mercury, with anaerobic conditions again favoring the
demethylation of the methylmercury. At a pH of 4–9 and a normal sulfide concentration, mercury will
form mercuric sulfide. This compound is relatively insoluble in aqueous solution (11x10 -17 ppb), and it
will therefore precipitate out and remove mercury ions from the water, reducing the availability of
mercury to fish. Under acidic conditions, however, the activity of the sulfide ion decreases, thus
inhibiting the formation of mercuric sulfide and favoring the formation of methylmercury (Bjornberg et
al. 1988). Low pH and high mercury sediment concentrations favor the formation of methylmercury,
which has greater bioavailability potential for aquatic organisms than inorganic mercury compounds.
Methylmercury may be ingested by aquatic organisms lower in the food chain, such as yellow perch,
which in turn are consumed by piscivorous fish higher in the food chain (Cope et al. 1990; Wiener et al.
1990). Mercury cycling occurs in freshwater lakes, with the concentrations and speciation of the
mercury being dependent on limnological features and water stratification. Surface waters may be
saturated with volatile elemental mercury, whereas sediments are the primary source of the mercury in
surface waters. During the summer months, surface concentrations of methyl and elemental mercury
decline as a result of evaporation, although they remain relatively constant in deeper waters (Bloom and
Effler 1990).

621
 Elemental Mercury Inorganic Mercury (II)
Sources Anthropogenic: gold mining Anthropogenic:
and fossil fuel burning Industrial discharge,
Dental amalgams, chloralkali Industrial processes;
process Mercury containing products
Mercury recycling and (Skin lightening cream and
reprocessing facilities soaps), wastewater,

Natural: volcanoes, wildfires, Natural: Microbial

weathering of mercury- Conversion (e.g.,
containing rocks Methylmercury), Natural
Weathering of Mercury-
Containing Deposits
Primary mode/s of transport Long-range atmospheric Biomagnification,
transport (Bioaccumulation in food
webs), Sorption Process,
Wet and Dry deposition,
Surface Runoff
Factors that affect its Wet and dry deposition (?) Volatilization
dissipation (removal) in the Bio-geochemical cycling of
environment mercury?

Not incinerated (elemental

form so no break down +
toxic vapor)

Inorganic Mercury
Sources :
Anthropogenic: Industrial discharge, Industrial processes; Mercury containing
products (Skin lightening cream and soaps), wastewater,
Natural: Microbial Conversion (e.g., Methylmercury), Natural Weathering of
Mercury-Containing Deposits
Primary mode/s of transport:
s, (Bioaccumulation in food webs), Sorption Process, Wet and Dry deposition,
Surface Runoff
Factors that affect its dissipation in the environment:
Bioconversion to Volatile forms, Abiotic Reduction, Methylation reduction
Mercury exists abundantly in the environment in its inorganic form, or as
impurities in other minerals. Inorganic mercury can easily combine with elements
like chlorine and sulfur, forming salts that can be transported through water and
soil.