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Characterization of Mercury as an Air Pollutant

ABSTRACT: Mercury is a naturally occurring metal found in air, water and soil.
Mercury exists in any of three valence states: Hg0 (elemental mercury), Hg2+2 (mercurous
mercury) and Hg+2 (mercuric mercury). These forms can be organized under three
headings: metallic mercury, inorganic mercury, and organic mercury. Metallic mercury is
present at liquid state in room temperature, and is used in thermometers and some
electrical switches. Inorganic mercury compounds occur when mercury combines with
elements such as chlorine, sulfur, or oxygen. These mercury compounds are also called
mercury salts. Most inorganic mercury compounds are white powders or crystals, except
for mercuric sulfide (also known as cinnabar), which is red and turns black after exposure
to light. Organic mercury compounds (or organomercurials) occur when mercury
combines with carbon. In the environment there is a large number of organic mercury
compounds; however, by far the most common organic mercury compound in the
environment is methyl mercury (or MeHg+). Methyl mercury is of particular concern
because it can build up in certain edible freshwater and saltwater fish and marine
mammals to levels that are many times greater than levels in the surrounding water.

INTRODUCTION
Mercury has been well known as an environmental pollutant for several decades. As
early as the 1950’s it was established that emissions of mercury to the environment could
have serious effects on human health. These early studies demonstrated that fish and
other wildlife from various ecosystems commonly attain mercury levels of toxicological
concern when directly affected by mercury-containing emissions from human-related
activities. Mercury in the air may settle into water bodies and affect water quality. This
airborne mercury can fall to the ground in raindrops, in dust, or simply due to gravity
(known as “air deposition”). After the mercury falls, it can end up in streams, lakes, or
estuaries. Over time, the mercury mostly precipitates to the red mineral cinnabar, HgS,
which is responsible for soil contamination. With the aid sulfate-reducing bacteria (SRB)
or iron-reducing bacteria (IRB), the cinnabar is converted to methyl mercury under
anaerobic and acidic conditions, which are typical of the well-buried muddy sediments of
rivers, lakes, and oceans. SRB and IRB use sulfur rather than oxygen as their cellular
energy-driving system.
HgS(s) ⎯SRB
⎯/⎯
IRB
⎯→ CH 3 Hg(II)X (aq ) + H 2 S(g )  
Where X is a ligand (an ion, a molecule, or a molecular group that binds to another
chemical entity to form a larger complex), typically Cl- or OH-, are the most toxic forms.
Upon methylation,
€ the SRB transport the new mercury complex back to the aquatic
environment, where it is taken up by other microorganisms. The conversion of inorganic
mercury to methyl mercury is important for two reasons:
(1) Methyl mercury is much more toxic than inorganic mercury.
(2) Organisms require a considerably longer period to eliminate methyl mercury.
At this point, the next higher level in the food chain may consume the methyl mercury-
containing bacteria, or the bacteria may release the methyl mercury to the water where it
can quickly adsorb to plankton. Plankton may also be consumed by the next level in the
food chain, or after dying, settle to the bottom of the lake and are incorporated into
bottom sediments. Studies of sediment cores show that younger sediments deposited
since industrialization have mercury concentrations that are about 3-5 times that of
historical sediments.
Mercury in aquatic environment
Most of the mercury entering aquatic environments is Hg+2. Methyl mercury
accumulates in fish at levels that may harm the fish and the other animals that eat them
via bioaccumulation and biomagnification. Bioaccumulation is the process by which
organisms (including humans) can take up contaminants more rapidly than their bodies
can eliminate them, thus the amount of mercury in their body accumulates over time. If
for a period of time an organism does not ingest mercury, its body burden of mercury will
decline. However, if an organism continually ingests mercury, its body burden can reach
toxic levels. The rate of increase or decline in body burden is specific to each organism.
Biomagnification is the incremental increase in concentration of a contaminant at each
level of a food chain. This phenomenon occurs because the food source for organisms
higher on the food chain is progressively more concentrated in mercury and other
contaminants, thus magnifying bioaccumulation rates at the top of the food chain. The
bioaccumulation effect is generally compounded the longer an organism lives, so that
larger predatory fish will likely have the highest mercury levels. In addition, unlike
organic contaminants (such as dioxin and PCBs) that concentrate in the skin and fat
tissues, mercury concentrates in muscle tissues. This implies that mercury cannot be
filleted or cooked out of consumable fish. Figure 1 illustrates the aquatic mercury cycle.

Figure 1. Mercury cycling pathways in aquatic environments. Reprinted with permission


from Mercury Pollution: Integration and Synthesis. Copyright Lewis Publishers, an
imprint of CRC Press.
Atmospheric Mercury
Mercury is a naturally occurring metal that is omnipresent in the environment.
Mercury is released to environmental media by both natural processes and anthropogenic
sources. Mercury ore is found in all classes of rocks including limestone, calcareous
shales, sandstones, serpentine, chert, andesite, basalt, and rhyolite. Mercury is released to
the atmosphere mostly by the burning of fossil fuels, which naturally contain mercury.
There are three main species of mercury occurring in the atmosphere: elemental mercury
vapor (Hg0), gaseous divalent mercury (Hg2+2 and Hg+2) and particulate mercury (Hgp).
Elemental mercury (Hg0)
Elemental mercury is the primary form of atmospheric mercury, accounting for 90%
in the atmosphere. In ambient air, elemental mercury is present globally at concentrations
of the order of 1.5-2.0 ng/m3. The fact that the reactivity of elemental mercury in water is
very low compared to the other forms of atmospheric mercury, allows it to persist in the
atmosphere with a lifetime of 1-2 years, as well as being capable to transport globally,
therefore making it a true global pollutant. Over the past century, it was shown that the
concentration of elemental mercury in the atmosphere has been increasing. It was
estimated that 50-75 percent of this increase originates from anthropogenic sources
(Expert Panel on Mercury Atmospheric Processes, 1994). Removal of elemental mercury
occurs by dry or wet deposition after oxidization by ozone (O3) to gaseous divalent
mercury, and is removed from the atmosphere by precipitation. The overall organic
peroxy compounds or radicals may also occur in the atmosphere. In clouds, however, a
fast oxidation reaction on the order of hours may occur between elemental mercury and
ozone, as described by the following reactions:

(1) Hg + hv (254nm) →Hg *


(2) Hg * + O2 →Hg + O2 *
(3) O2 * + O2 →O3 + O
 
(4) O + O2 →O3
(5) O3 + Hg →HgO + O2
(6) O + Hg →HgO

In the reactions above, under light of wavelength of 254 nm light, elemental mercury
is excited in reaction (1). The excited mercury reacts with oxygen in reaction (2) to

produce elemental mercury and an oxygen molecule in an excited state. The species
responsible for oxidation of elemental mercury are formed in reactions (3) and (4)
through the reaction of excited state oxygen with oxygen to form ozone and oxygen
radical, which also reacts with oxygen to form ozone. Both ozone and oxygen radicals
react with elemental mercury to form mercuric oxide (HgO) as shown in (5) and (6).
Most of the mercuric oxide is formed through the thermal reaction with ozone. The
overall reaction is obtained by adding reactions (1) through (5):

(7) Hg + 2O2 + hv →HgO + O3

Gaseous Divalent Mercury


€ (Hg2+2 and Hg+2)
+2 +2
Hg2 and Hg account for about 1-3 percent of total gaseous mercury in the
atmosphere (Lindberg and Stratton, 1998). It is believed that the most part of gaseous
divalent mercury consists of Hg2+2 (mercurous mercury) and Hg+2 (mercuric mercury),
but other divalent mercury species are also possible (like mercury dichloride HgCl2).
Gaseous divalent mercury is likely to be rapidly scavenged via dry and wet deposition
processes withing approximately 100 to 1000 kilometers as a result of its high water-
solubility and chemical reactivity, thus having much shorter life than elemental gaseous
mercury. Air concentrations of gaseous divalent mercury are likely to be highly related to
local sources, meteorological conditions and some other pollutants.
Particulate Mercury (Hgp)
Particulate mercury occurs in both gaseous and aqueous phases. It can be formed by
physical adsorption of gaseous divalent mercury to atmospheric particulate matter in
aqueous phase as the secondary particulate mercury. It can be emitted directly into the
atmosphere from anthropogenic and natural sources. Nevertheless, it is largely consisted
of anthropogenic origin. Background concentration of particulate mercury indicated that
it was a minor constituent – only 0.39 percent of total gaseous mercury. Particulate
mercury tends to be dry deposited at significant rates when and where measurable
concentrations of these mercury species exist.

Figure 2. Transformation of mercury in air, water and sediments


Famous outbreaks of mercury poisoning
In the early days of the Industrial Revolution, mercury nitrate, Hg(NO3)2, was used to
soften rabbit fur to make felt hats. Mercury nitrate is a form of inorganic mercury that
isn’t absorbed by the body as easily as other species, but it was toxic enough to affect the
brains of many hat makers, that suffered from the toxic effect of mercury on their central
nervous system that eventually led to the death of many hat makers.
Over the history numerous cases of mercury contamination were reported. The
extensive toxicity of mercury was first revealed in 1955 in Minamata City in Japan,
where there was a mercury-poisoning outbreak as a result from a continuous poisoning of
the local bay by Chisso Corporation’s chemical factory. The outbreak was responsible to
the immediate death of 887 people, and to an overall death of 2,265 people (as of march
2001). The factory had been releasing methyl mercury to the Minamata Bay and the
Shiranui Sea between 1932 and 1968. Methyl mercury was then bio-accumulated in the
shellfish and fish in, which were then eaten by the local population, resulting in mercury
poisoning, also known as the Minamata disease, having similar symptoms in both
animals and humans. The neurological syndrome was characterized by a long list of
symptoms including prickling, tingling sensation in the extremities (paresthesia),
impaired peripheral vision, hearing, taste and smell, slurred speech, unsteadiness of gait
and limbs, muscle weakness, irritability, memory loss, depression, and sleeping
difficulties. The extensive mercury poisoning affected children and fetuses much more
than it affected adults, leading to severe brain damage in 22 infants whose mothers had
ingested fish contaminated with methyl mercury during pregnancy.
Another mercury poisoning outbreak also occurred in Iraq in 1971 and 1972, when
locals ate bread prepared from wheat and other cereals treated with a methyl mercury
fungicide. The outbreak caused to the hospitalization of more than 6,530 patients and 459
deaths occurred, probably due to central nervous system damage. In comparison to the
outbreak in Minamata Bay, the breast milk concentrations were reported to be as high as
200 ppb. Breast milk of individuals who lived in nearby areas to Minamata and had
consumed highly mercury-contaminated fish, had a total mercury concentrations on the
order of 63 ppb. Generally, breast milk with total mercury levels greater than 4 ppb
would exceed the safe level (2 μg methyl mercury/day for an average 5-kg infant).

Figure 3. Defects resulting from the


Minamata Bay mercury poisoning can be
observed at fisherman Akinori Mori’s hand
CHEMICAL AND PHYSICAL PROPERTIES OF MERCURY
Mercury has been recognized for decades as a persistent and bio-accumulative toxic
substance in the environment. It is the 6th most toxic in a universe of 6 million substances,
and the 16th most rare element of Earth. The origin of the name comes from the Latin
word hydrargyrum meaning liquid silver. It is a heavy, silver-white metal, liquid at room
temperature (250C), stable in air and water. Mercury is unreactive with alkalis and most
acids. It gives off poisonous elemental mercury vapor that has a chronic cumulative
effect. In the environment, mercury is a very persistent pollutant that is very mobile due
to its low vapor pressure (0.25 Pa at 250C), low melting point (-38.870C), and because of
among all metals, it has the highest solubility in water (56.1*10-6 g/L at 250C). The
physical properties of mercury allow it to be readily released from soil, water and plant
canopies; therefore it can be transported in the air and deposited back to the Earth’s
surface, as well as staying in the atmosphere for long time (up to two years). Mercury
also has a relatively poor thermal conductivity, good electric conductivity, and the ability
to expand and contract evenly with temperature changes. Its abilities to easily form alloys
with other metals and the high surface tension make it widely used in the manufacture of
industrial chemicals and electrical applications.
Inorganic mercury compounds include mercuric sulfide (HgS), mercurous chloride
(Hg2Cl2), mercuric chloride (HgCl2), mercuric nitrate (Hg(NO3)2) and mercuric oxide
HgO. Mercuric chloride is the major part of inorganic mercury compounds (U.S EPA,
1999). Most inorganic mercury compounds are white powders or crystals, unstable when
exposed to heat and light, and readily decompose to elemental mercury. Some mercury
salts such as mercuric chloride are volatile enough to evaporate into the atmosphere at
room temperature and pressure. However, their high water solubility and chemical
reactivity make them deposit from the atmosphere faster than elemental mercury.
Organic mercury compounds (also known as organomercurials) are differentiated from
inorganic mercury since they contain a covalent bond between carbon and mercury
atoms. Organic mercury compounds include methyl mercury, dimethyl-mercury and
methyl-mercury chloride. Organic mercury compounds include a large number of
compounds, however methyl mercury is by far the most toxic and prevalent form of
organic mercury compounds in the environment.
The toxicity of inorganic and organic mercury compounds is due to their strong
affinity for sulfur-containing organic compounds, such as enzymes and other proteins.
For this reason these compounds are extremely toxic to biological systems. Mercury is
unusual among metals because it tends to form covalent rather than ionic bonds. Most of
the mercury encountered in water/soil/sediments/biota (all environmental media except
the atmosphere) is in the form of inorganic mercuric salts and organomercurics. The
compounds most likely to be found under environmental conditions are: the mercuric
salts HgCl2, Hg(OH)2 and HgS; the methyl mercury compounds, methyl mercuric
chloride (CH3HgCl) and methyl mercuric hydroxide (CH3HgOH); and, in small fractions,
other organomercurics (for instance dimethylmercury and phenylmercury). Table 1
illustrates the difference in chemical properties of different mercury compounds.
Table 1. Properties of elemental mercury and selected mercury compounds
Hg0 HgCl2 HgS HgO (CH3)2Hg CH3HgCl

583 500
Melting Point (0C) -38.87 277 sublimation decomposition - 170

Boiling Point (0C) 356.72 302 - - 96 -

Water Solubility
(g/L) 56.1*10-6 66 2*10-24 5.3*10-2 2.95 <0.1

Density (g/cm3) 13.53 5.4 8.06-8.12 11.14 3.19 4.06

Vapor Pressure (Pa) 1.8*10-2 8.99*10-3 - 9.2*10-12 8.3*103 11.3*10-3

Properties of Mercury (203Hg):


Periodic Table Data:
Atomic number: 80  
Chemical Formula: Hg
Element category: Transition metal
Group numbers: 12
Period: 6
Electronic configuration: [Xe] 4f14 5d10 6s2
Molecular Weight / g*mol-1: 200.59 ± 0.02

Atomic Properties:
Formal Oxidation Number: +1 +2
Electronegativity: 1.9 (Pauling scale)
Atomic radius / pm: 150.3
Covalent radius / pm: 132±5
Van der Waals radius / pm: 155±5

Physical Properties:
Phase at room temperature: Liquid
Appearance: Silver-white, heavy, mobile, liquid metal. When heated it becomes a
colorless, odorless gas.
Odor: Odorless
pH: No information found
Melting point / °C: -38.83
Boiling point / °C: 356.73
Critical point / °C: 1476.85
Density / g*cm-3: 13.55 (293 K)
Molar volume / cm3*mol-1: 14.81 (293 K)
Electrical resistivity / μ*Ω*cm: 95.8 (20 °C)
Speed of sound / m/s: 1451.4 (liquid, 20°C)
Thermal Properties:
Thermal conductivity / W m-1K-1: 8.34  
Thermal expansion / µm m-1K-1: 60.4 --> constant rate over wide temperature range, thus
is used in thermometers and barometers
Heat of fusion / kJ mol-1: 2.331
Heat of vaporization / kJ mol-1: 59.11
Heat of atomization / kJ mol-1: 64.463

Ionization Energy:
1st ionization energy / kJ mol-1: 1007.07
2nd ionization energy / kJ mol-1: 1809.69
3rd ionization energy / kJ mol-1: 3299.82

Isotopes:
Isotope Relative atomic mass Mass percent Stable with
196
Hg 195.965815(4) 0.15(1) 116 neutrons
198
Hg 197.966752(3) 9.97(8) 118 neutrons
199
Hg 198.968262(3) 16.87(10) 119 neutrons
200
Hg 199.968309(3) 23.10(16) 120 neutrons
201
Hg 200.970285(3) 13.18(8) 121 neutrons
202
Hg 201.970626(3) 29.86(20) 122 neutrons
204
Hg 203.973476(3) 6.87(4) 124 neutrons

Radiological Data of 203Hg:


Nuclear and Emissions:
Half-life: 47 days
Beta particles: 0.210 MeV maximum energy (100 %) and 0.070 MeV average energy.
Gamma rays: 0.279 MeV (100%).
Beta Maximum Range: 34 cm in air; 0.04 cm in tissue; 0.04 cm in Plexiglas

Dose and Shielding


Dose rate to the skin at 30 cm: 15.2 mrem/hour/mCi (for an unshielded point source)
Gamma Dose rate (deep tissue dose) at 30 cm: 1.63 mrem/hour/mCi (for an unshielded
point source).
Dose rate to epidermal basal cells from skin contamination of 1 μCi/cm2: 3296
mrem/hour
Shielding: Shield stock vials with lead.
Half-Value Layer: 0.2 cm lead The half-value layer is the amount of material required to
reduce the radiation intensity by 50%.
Annual Limit on Intake (ALI): 500 microcuries via ingestion and 800 microcuries via
inhalation. The intake of one ALI will produce a dose of 5 rem.
Crystallography of Mercury:

Crystal structure: rhombohedral


Unit-cell dimensions / pm: a=299.25, α=70°44.6'

Space group: R 3 m
Classification of Mercury in Hazardous Materials Identification System (HMIS):

Figure 4. Elemental mercury at room Figure 5. Density of mercury is high


temperature looks like liquid water enough to allow an adult to sit on it
Physical and Chemical Transformations of Mercury in the Atmosphere
Gas phase reactions
The only important gaseous reaction globally identified so far is that between
Hg0 and O3 (marked in green), with an expected lifetime of 1.4 years at an ozone
concentration of 30 ppb.
Reaction Rate (cm−3*molec−1*s−1) Reference
Hg (g) + O3(g) → HgO(g,s)
0
3.0 ± 2 × 10−19
Hall, 1995
Hg (g) + H2O2(g) → HgOH2(g,s)
0
8.5 × 10−19
Tokos et al., 1998
Hg0(g) + Cl2(g) → HgCl2(g,s) 4.8 × 10−18 Calhoun & Prestbo, 2001
Hg (g) + HO• → Hg
0 +2
8.7 × 10−14
Sommar et al.,2001
Hg0(g) + HCl(g) → products 1.0 × 10−19 Hall et al., 1993
Hg (g) + NO3•(g) → products
0
4.0 × 10−15
Sommar et al., 1997
Br(g) + Hg0(g) → products 4.0 × 10−15 Sommar et al., 1997
Br2(g) + Hg (g) → products
0
4.0 × 10−15
Sommar et al., 1997
BrO(g) + Hg0(g) → products 4.0 × 10−15 Sommar et al., 1997

Aquatic phase reactions


Aqueous phase reactions of mercury or mercury compounds occur in rainwater, cloud-
water or fog-water in the atmosphere. In aqueous phase, the chemical conversion of Hg+2
to Hg0 takes place. The proposed reaction mechanism involves a formation of an
intermediate HgSO3 that decomposes to produce Hg+2, which in turn is rapidly reduced to
Hg0. The overall rate of the reaction is inversely dependent on the sulfite concentration.
This reaction may influence the concentration of mercury in cloud and rain water by
reducing water soluble Hg+2 to volatile Hg0. Hg+2 and the hydroxide ion, OH−, form
HgOH+ and Hg(OH)2, and the divalent mercury bound as Hg(OH)2 can be reduced back
to Hg0(aq) by photolysis.
Reaction Rate Reference
Hg (aq) + O3(aq) → Hg (aq) + products
0 +2 7 −1 −1
4.7 × 10 M s Munthe(1991)
HgSO3(aq) → Hg0(aq) + products Texp((31.971T)−12595T)Ts−1 Van Loon (2000)
Hg(OH)2(aq) + hν → Hg0(aq) + products 6.0 × 10−7 s−1(maximum)a Xiao et al.,(1994)
Hg0(aq) + OH(aq) → Hg+2(aq) + products 2.0 × 109 M−1s−1 Lin (1997)
Hg+2 + HO2(aq) → Hg0(aq) + products 4.7 × 107 M−1s−1 Lin (1998)
Hg0(aq) + HOCl(aq) → Hg+2(aq) + products 2.09 × 106 M−1s−1 Lin (1998)
Hg0(aq) + OCl−(aq) → Hg+2(aq) + products 1.99 × 106 M−1s−1 Lin (1998)
Hg0(aq) + H2O2(aq) →
HgO(s) + Hg+2 + products 6.0 M−1s−1 Lin (1998)
Hg+2 + SO−2 ↔ HgSO3 2.0 × 10−13 M Smith (1976)
HgSO3 + SO-2 ↔ Hg(SO)2-2 4.0 × 10−12 M Smith (1976)
Hg+2 + 2Cl− ↔ HgCl2 1.0 × 10−14 M2 Smith (1976)
Hg+2 + OH− ↔ HgOH+ 2.51 × 10−11 M Lin (1999)
HgOH+ + OH− ↔ Hg(OH)2 6.31 × 10−12 M Smith (1976)
HgOH+ + Cl− ↔ HgOHCl 3.72 × 10−8 M Smith (1976)
Hg(OH)2(s) ↔ Hg(OH)2(aq) 3.5 × 10−4 M Smith (1976)
HgCl2(s) ↔ HgCl2(aq) 0.27 M Smith (1976)

Dissolved Hg0 in cloud droplets is oxidized by O3, hydroxyl radical (HO•) and
chlorine (HOCl/OCl−), leading to the formation of Hg+2 in rain or cloud water, which may
then be removed from the atmosphere on shorter time scales due to the increase in water
solubility. After oxidized by Ozone, elemental mercury in cloud droplets mainly forms
HgO(aq), which reacts further to divalent mercury, Hg2+2 or Hg+2. Another oxidant of
potential significance is OH(aq), which is also capable of oxidizing elemental mercury in
cloud droplets to divalent mercury. A modeling study involving known atmospheric
reactions of mercury concluded that the two most important oxidation reactions of
elemental mercury in aqueous phase involve hydroxyl group (OH) in daytime and
chlorine atom (Cl) at nighttime.

Figure 6. Physical and chemical transformation of mercury in the atmosphere (Bullock,


2003)
The complexity of the various atmospheric chemical reactions is not fully understood
yet. It is evident that mercury is emitted and returns to the ground by precipitation, yet the
conditions at which the transformations among the different mercury types are not
known. Further explanation on the environmental fate of mercury is presented later on in
this project.
SOURCES OF MERCURY IN THE ENVIRONMENT
Mercury is released to the environment by both natural processes and anthropogenic
sources. Natural mercury emission is defined as the mobilization or release of
geologically bound mercury by natural processes, with mass transfer of mercury to the
atmosphere (e.g., volcanic activity and weathering of mercury-containing rocks);
Anthropogenic mercury emission is the mobilization or release of the mercury by human
activities, with mass transfer of mercury to the atmosphere. Currently, the average
mercury level in the atmosphere is about 3 to 6 times higher than the estimated level in
the preindustrial atmosphere. However, a degree of uncertainty exists with respect to
estimates of the relative contributions of natural and anthropogenic sources of mercury
emissions to the environment due to the fact that no previous data was collected in the
past.
Anthropogenic Sources
Approximately 25% of atmospheric mercury is attributed to the continuous releasing
of mercury in different anthropogenic activities. The natural component of the total
atmospheric burden is difficult to estimate, although anthropogenic releases of mercury to
the atmosphere were estimated to cause triple its concentration in air and marine surface
waters since the pre-industrial era. Recent estimates of anthropogenic releases of mercury
to the atmosphere range from 2,000-4,500 metric tons/year, mostly from the mining and
smelting of mercury and other metal sulfide ores. An estimated 10,000 metric tons of
mercury are mined each year, although there is considerable year-to-year variation (WHO
1990).

Figure 7. Industrial power plant is the primary source of anthropogenic mercury


Emission to the atmosphere
In the past, chlor-alkali plants were thought to be the single largest source category of
anthropogenic mercury emissions to the environment in many industrialized countries
until the 1970s. After that, its ranking among the remaining source categories has been
substantially changed due to antipollution measures. Coal combustion, waste
incineration, metal smelting, refining and manufacturing are currently major source
categories in the industrialized world. Until few years ago, mercury was commonly used
in thermometers and barometers due to its high rate of thermal expansion that is fairly
constant over a wide temperature range. Other potential emission sources include copper
and zinc smelting operations, paint applications, waste oil combustion, geothermal
energy plants, crematories, and incineration of agricultural wastes. The incineration of
medical equipment has also been found to be a significant source of atmospheric
mercury, releasing up to 12.3 mg/m3 of mercury. Medical wastes release approximately
110 mercury mg/kg of uncontrolled emissions from medical waste incinerators,
compared with 25.5 mercury mg/kg general municipal waste. Table 2 shows the different
anthropogenic source types of mercury in the US.
Table 2. Atmospheric mercury emission inventory for the US by anthropogenic source
type (Bullock, 2003)

Anthropogenic mercury emission has been a global issue, forcing the leading countries
to innovate new technologies in order to reduce the environmental effect resulted to
aquatic environments. In Canada, anthropogenic mercury emissions were reduced from
approximately 32 to 8 metric tons from 1990 to 2000. The largest source of mercury prior
to 1995 was base metal mining industry. From 1995 to 2000, electricity generation and
metal smelting were equally the largest sources of mercury into the atmosphere, each
accounting for 25% of Canadian emissions. In the US, emissions of mercury to the air
from anthropogenic sources have fallen by more than 45% since passage of the 1990
Clean Air Act Amendments, which provided new authority to EPA to reduce emissions
of mercury and other toxic pollutants to the air (U.S. EPA, 2006). Figure 8 shows the
anthropogenic mercury emissions in the US over the past decade.

Figure 8. U.S. anthropogenic mercury emissions over past decades (U.S. EPA, 2006)
Anthropogenic emissions from a number of major sources have been estimated to be
decreasing in North America and Europe due to reduction efforts during the last decade,
while the anthropogenic emissions from some developing countries have been increasing
dramatically over past ten years (Figure 9). In recent years, Asia was the biggest
anthropogenic mercury emission region, accounting for about 52% of the global
anthropogenic emission.

Figure 9. Anthropogenic mercury emissions: distributed by region in 1990 and 2000


(Cain, 2006)
Natural Sources
Mercury is a naturally occurring element that is present in the Earth’s crust, with an
average abundance of 0.5 ppm (μg/g). It is considered to have been a component of the
lithosphere since the planet was formed approximately 4.5 billion years ago. Low levels
of mercury can be found everywhere in the environment - in rocks, plants, animals, water
and the air. Mercury ore is found in all classes of rocks, including limestone, calcareous
shales, sandstone, serpentine, chert, andesite, basalt, and rhyolite. The normal
concentration of mercury in igneous and sedimentary rocks and minerals appears to be
10-50 ppb; however, the mineral cinnabar (mercuric sulfide, HgS) contains 86.2%
mercury.
The high temperature in the Earth’s mantle layer results in high mercury mobility,
allows mercury to continuously diffuse to the Earth’s surface. Elemental and some forms
of oxidized mercury come to the atmosphere due to their volatility. In the environment,
mercury is emitted naturally in the form of volcanic activity, deposition of mercury,
weathering of mercury-containing rocks, degassing of the earth’s mantle/crustal material,
evasion from soil, water, vegetation surfaces, wild fires, and geothermal sources. All of
which result in higher concentrations of mercury in certain compartments within the
natural environment.
Active volcanoes release substantial quantities of volatile materials into the
atmosphere in the form of gases and aerosol. It was estimated that that the time-averaged
volcanic mercury emission is about 700 Mg/yr, or 20-40% of total natural emissions
(Pyle and Mather, 2003). Continuous degassing accounts for only 10% of this flux, while
75% of volcanic mercury is released during smaller sporadic eruptions (<10-102
Mg/event). Rare, large (>103 Mg) explosive eruptions overwhelm the total atmospheric
burden several times per century, and account for about 15% of total volcanic mercury
emissions. However, the extent of the volcanic contribution to global mercury emission
remains highly uncertain, therefore current atmospheric mercury modeling studies
ignored the volcanic contribution of mercury to the atmosphere.
Emission from soil, water and vegetation surfaces is another important pathway.
Several estimates of natural mercury emission have been made, but the estimates differ
significantly. Earth surfaces might act as dynamic exchange interfaces which can be
sources or sinks of atmospheric mercury depending on the ambient mercury
concentration, mercury deposition velocities, micro-meteorological conditions and
mercury concentration in the transpiration stream, water or soil.
Roots of trees are also considered as a natural source of mercury emission. Mercury
can be taken up by the roots of trees and later released to the environment when that
wood is burned in a stove or a forest fire. Emission of mercury due to biomass burning is
currently being studied. In 2001, a scholar names Brunke measured mercury in the plume
of a wild land fire in South Africa and estimated the global contribution to the
atmospheric emission to be as high as 1×106 kg/yr.
Other pathways of evasion of mercury include emission from the bottom of the oceans
and from geothermal or tectonically active areas. To date, considerable uncertainties still
remain in the estimations of the quantitative significance of evasion. Very little is known
about the amounts of mercury evading from soil, water and vegetation.
Re-Emission Sources
Re-emitted mercury is defined as the mass transfer of mercury to the atmosphere by the
processes drawing on mercury that was deposited to the earth’s surface after initial
mobilization by either anthropogenic or natural activities. To date, very little is known
about the natural emissions and re-emissions of mercury. Current emissions of mercury
from soil, water and vegetation not only include emission of naturally occurring mercury
that exists in the substrates but also include re-emission of previously deposited mercury
from anthropogenic sources. This makes it very difficult to discriminate actual natural
emissions from re-emission. Currently, there is still no effective way to strictly
distinguish between natural emissions and re-emissions, except in cases where there is a
strong natural source signal (e.g., areas geologically enriched in mercury such as
volcanoes). In addition, there are few measurements available and current estimates are to
a large extent extrapolated from a few data points and constrained by global mass balance
estimates.
MEASUREMENT OF ATMOSPHERIC MERCURY
Attempts to measure atmospheric mercury have been established globally in order to
forecast mercury contamination that may alter life quality, as well as to predict movement
of atmospheric mercury to different regions through wind and precipitation. Elemental
mercury is not soluble in water, however gaseous divalent mercury, Hg+2 and Hg2+2, are
very water-soluble, making the measurement of atmospheric mercury more challenging.
Currently there are a number of experimental methods used in the measurement of
atmospheric mercury deposition. Some of the methods include the dynamic flux
chambers (DFC), surrogate tanks (SS), micrometeorological methods like the modified
Brown ratio (MBR), the aerodynamic (AER) and the relaxed eddy accumulation (REA).
The degree of uncertainty in the measurement varies considerably with the measurement
method used. The use of two systems of the same method reduces the degree of
uncertainty, like in Fritscher et.al (2008a), a research that measured elemental
atmospheric mercury air-surface exchange over grassland, used two micrometeorological
methods simultaneously.
The DFC measurement method employs flux chambers to measure the fluxes. DFC
methods have been used in wetlands in Quebec, Ontario, the Florida Everglades, forest
areas in Tennessee, in background soils across the US, and in over lakes and forest soils
in southwestern Sweden. DFC can provide immediate results and are relatively simple to
use, however they can alter local conditions such as temperature, humidity and
turbulence.
A surrogate surface is a surface composed of a material such as Teflon or polysulfone
that is placed at a site for a designated amount of time, allowing mercury to deposit onto
it. The surface is then washed and analyzed. Drawbacks to the use of surrogate surfaces
include the need to cover the surfaces during rain showers, therefore it creates gaps in the
data collection and a difficulty in determining the speciation of mercury (gaseous vs.
particulate) and the uncertainties associated with the fact that these surfaces are not real
life and therefore cannot accurately duplicate every aspect of deposition. Surrogate
surfaces and water surface samplers have been used to measure mercury at a hardwood
forest site in Michigan, over wetlands in Florida and over arid lands in south central New
Mexico. Surrogate surfaces have also been used to observe dew over wetland vegetation
in Florida and to measure particulate mercury on rooftops in Tokyo.
Micrometeorological methods have been used to measure fluxes for several different
surface types. The modified Brown ratio (MBR) method provides relatively accurate
results but is complicated by the fact that it requires measurements of a second gas in
addition to mercury. The MBR method has been used over wetlands in Quebec and
Florida, forests and their background soils within the Walker Branch Watershed, young
pine plantation in Tennessee, boreal forest floor in Sweden, grassland sites in the US,
Austria and Switzerland and pavement surfaces in Indiana. The flux measured when
using micrometeorological methods is higher than flux measured in enclosure methods
that may encounter condensation building up inside the bag during the nighttime.
The REA method is a relatively new method that has been used for flux measurement
of RGM over snow in Alaska, modified soil surfaces in Sweden, hardwood forest in
Connecticut and over a cornfield in Minnesota. The REA method is attractive since it
requires measurements at only one height and for only one gas. However, its accuracy
can be decreased by small gradients.
The AER method has been used to measure total gaseous mercury fluxes over a rice
paddy field in Korea, elemental mercury fluxes over a snow surface in Nunavut, an
agricultural field in Ontario and subalpine grassland sites in Austria and Switzerland. The
AER method requires measurements at various heights, thereby increasing the amount of
data analysis required.
An additional measurement, known as the 222Rn/Hg0 method, has recently been used
for the measurement of fluxes of elemental mercury at a grassland site in Seebodenalp,
Switzerland. It was used during periods with a stable nocturnal boundary layer and was
found to be an effective method for the measurement of elemental mercury fluxes in
situations where the atmospheric conditions are non-turbulent, the fluxes are small, or the
surface is highly heterogeneous.
In the measurement of mercury, two kinds of denuders are used: tubular and annular:
1) Tubular denuder consists of 6 mm quartz tubes coated with KCl. During sampling, the
denuders are electrically heated to approximately 450C to avoid water vapor
condensation. The sampling flow rate is of 1 L/min. Analysis is made using thermal
desorption and CVAFS detection (Cold Vapor Atomic Fluorescence Spectrophotometry).
The denuders is heated to 450oC and purged with N2 in order to remove any traces of
mercury associated with the coating procedure. Mercury released from the denuder is
collected on a gold trap, which then is analyzed using CVAFS. The detection limit is of 5
pg/m3 for a 24 hours integrated sample.
2) Annular denuder consists of a 15 mm outer diameter quartz tube with an inner,
enclosed 8 mm tube. Air is pulled through the space between the two tubes. Both the
inner surface of the outer tube and the outer surface of the inner tube are coated with KCl.
The sampling flow rate is of 5-10 L/min. In the analysis step the denuder is heated to
5000C, which converts the adsorbed RGM to elemental mercury vapor, which is pre-
concentrated on a gold trap. The gold trap is then analyzed using the normal desorption
and CVAFS detection procedure. The detection limit for a measurement with 2 hours
sampling time is under 2-3 pg/m3.

Hg0 measurements
The gaseous elemental mercury vapor exits in the largest portion in the atmosphere
(95-99%), making the measurement techniques crucial to protect the welfare of the public
and the environment. Measurements of elemental mercury are conducted by using CEMS
(continuous emission monitoring systems) as of the beginning of the third millennia. The
measurement of elemental mercury is done by “gold trap”. Gold traps consist of a wafer
thin ceramic tube, which has been carefully crafted to achieve minimum thermal inertia.
The tube has been packed with pure gold and supports a heating coil on its outside. The
mercury gold trap reveals sharp and high peaks and an excellent long-term stability. As
air is used for purging the trap during the heating step, possible contaminations are
oxidized and swept off thus preventing from passivation.
The primary reason why gold traps work is because mercury sticks to gold at room
temperature. A flue gas used in the measurement of elemental mercury is carrying
gaseous mercury (mostly elemental mercury and mercuric chloride). In order to convert
the other mercury species into an elemental form, there is a use in thermo-catalytic
converter that uses wet chemical reactions that converts mercuric chloride to elemental
mercury vapor. Commonly used reagents to accomplish the conversion to elemental
mercury were Stannous Chloride, Sodium Tetrahydroborate and Ascorbic Acid. Due to
the presence of reactors and tubings associated with wet chemistry, first generations of
the CEMS suffered from problems related to tubing pluggage, corrosion and inefficient
conversion of mercuric chloride to mercury.
Once solely elemental mercury is present in the flue gas (typically between 50C and
0
35 C), it is then pulled through the trap, the gas continues to flow through the trap but the
mercury stays behind since it got trapped on the gold. After the mercury is captured, the
gold trap is rapidly heated to approximately 2000C. As a result, the mercury is released as
a gas (thermal desorption). The gaseous mercury is then swept by the flow of purified
mercury free air (composed of a very high content of nitrogen gas) into the optical cell of
the detector, which measures the mercury in a UV Atomic Absorption Spectrometry
(AAS) operating at 253.7 nm.
  It is essential that the trap is free of mercury before sampling. This is ensured by a
cleaning step, which is automatically performed. To keep particles out of the system and
to protect the trap from passivation, an easily replaceable filter is installed upstream the
sample inlet. The filter is made of low-interactive material; the filter membrane has a
porosity of 0.45 µm and is made of PTFE. It is possible to control sample volume based
on the expected mercury concentration. An illustration of the measurement of elemental
mercury is shown in figure 10.

Figure 10 – Process flow diagram of the measurement of elemental mercury

Hg+2 / Hg2+2 (HgII) measurements


In spite of the fact that atmospheric mercury mostly consists in an elemental form, the
remainder is mostly attributed to particulate and gaseous HgII species.
Gaseous HgII species, termed Reactive Gaseous Mercury (RGM), are approximately 105
more soluble than elemental mercury, mostly composed of HgCl2 and HgO in minute
amounts (pg/m3). This fact strongly influences the extent of removal from the atmosphere
and subsequent deposition to the biosphere, which may affect marine aquatics once
deposited and methylated into toxic methyl mercury.
Measurements of RGM are more complicated than of elemental mercury that uses
gold trap. Due to the minute amounts of mercury, there is a use in an apparatus called
denuder. The denuder is an apparatus that separates gases and aerosols (over a given
diameter) based upon the difference in diffusion velocity between gases and aerosol
particles. Usually, a denuder apparatus contains tubes with selective internal wall coating
that removes the gaseous compounds at the wall (IUPAC Compendium of Chemical
Terminology, 1997). In general, an adsorbent is used to trap reactive polar gases that
diffuse along its surface. In measurement of RGM, the chosen sorbent must solely sorbs
the reactive form of mercury, Hg+2 and Hg2+2 and not the elemental mercury. The most
common sorbent that is used in this case is 2M of potassium chloride solution (KCl) due
to its high tendency to absorb the RGM species from the gas stream to its surface.
However, the use of KCl is subject to high maintenance when used for extended periods
of time.
A third, less used method of RGM measurement (after tubular and annular denuders)
is called “Mist Chamber” (MC) technique that was developed in 1995 by Lindberg and
Stratton. In this technique, air is drawn through a Pyrex glass chamber of 100 ml total
volume containing 30 ml diluted HCl solution. Part of the MC solution is dispersed as a
fine aerosol, by a nebulizer (a device for producing a fine spray of liquid) inside the
chamber. A hydrophobic filter at the top of the MC separates the droplets from the air
and allows the liquid to drain back into the chamber. SnCl2 and CVAFS detection analyze
HgII species adsorbed in the MC solution after reduction to elemental mercury. The air
sampling flow rate is 10-15 L/min and the detection limit for a 6-hour sample is 1 pg/m3.
In the measurements of RGM, annular denuders are found to be more suitable for
mercury monitoring efforts than tubular denuders since the improved surface area can
facilitate larger sampling times that allows sufficient amounts of samples collected.

Figure 11 – Annular denuder Figure 12 – Mist Chamber in ambient air at the


Florida Everglades
Hgp measurements
The total mercury content of airborne particles (TPM) in ambient air is in the range of
less than 1 pg/m3 to some hundreds of pg/m3. The low concentrations level makes
adequate quantification difficult. The traditional procedure is to sample particles on fiber
or membrane filters. The filters are made of glass fiber and quartz. To remove larger
particles to the upstream of the filter, collection time should be longer (around 24 hours)
and with a relatively larger ambient air flow rate (10-30 L/min) compared to the
measurement of RGM. Following sampling, the filters are placed into acid digestion (20
mLs of a 10% dilution of concentrated nitric acid (HNO3) with a concentration of 1.6M)
followed by digestion of the filter in a vessel made of Teflon for 20 minutes at 160°C and
4.7 atmospheres that uses CEM computer that controls microwave unit. The mercury
forms in the nitric acid solution is then oxidized by bromine monochloride (BrCl) and is
left overnight. The mercury content of the digestion solution is determined by standard
methods, using SnCl2 for reduction (of HgII to an elemental form) and pre-concentration
via gold amalgamation followed by CVAFS or CVAAS (Cold Vapor Atomic Absorption
Spectrometry) detection. The method allows large air volumes to be sampled in a
relatively short time thereby collecting enough mercury to improve analysis accuracy.
The disadvantage of this traditional method of sampling particles on fiber or membrane
filters is the risk of contamination in combination with sample handling. The analysis
procedure requires a fair amount of time and involves treatment with chemicals that are
not totally free of mercury, hence limiting the detection limit of the method.
Another method to measure particulate mercury is the Miniaturised TPM-traps. This
new technique does not require treatment with chemicals, no manual sample transfer or
sample handling and has a low total cost per sample. Hence, the risk of contamination is
low. In contrast to the previous technique, the airflow of the sample is limited to only 4-5
L/min. These traps serve as both particulate trap and pyrolyzer that converts any mercury
form to a gaseous elemental form. The trap consists of a small quartz glass fiber filter
supported in a small quarts glass tube. After sampling the device is analyzed by pyrolyzis
followed by either amalgamation, thermal desorption or CVAFS as the detection step.
The detection limit for a 24-hour measurement is close to 1 pg/m3.
MEASUREMENT DATA OF ATMOSPHERIC MERCURY
Using the measurement techniques previously described, measurements of
atmospheric mercury are conducted across the world to monitor its levels. Mercury
interacts, transforms and transports in the atmosphere from very short (e.g.1–2 days in the
spring time in a gaseous divalent form) to very large time and space scales (1–2 years
lifetime of elemental mercury). Therefore, multi-scale atmospheric models are needed to
understand mercury cycling in the atmosphere. During the last decade, a number of
numerical regional models and a few global models with varying degrees of complexity
have been developed for the transport and transformation of mercury in the atmosphere.
Nevertheless, the complete understanding of mercury sources is not fully understood. In
order to improve the quantitative environmental fate component of the risk assessment
for mercury and mercury compounds, more and better mercury emissions data are
needed. Measured mercury data near sources of concern, as well as a better quantitative
understanding of mercury chemistry in the atmosphere are essential for future prediction
of atmospheric mercury. Examples of future measurement fields include:
• Aqueous oxidation-reduction kinetics in atmospheric water droplets
• Physical adsorption and condensation of divalent mercury gas to ambient
particulate matter
• Photolytic reduction of particle-bound divalent mercury by sunlight
• Convincing evidence that gas-phase oxidation of mercury is insignificant
From figure 9 it was concluded that Asia, North America and Europe emitted the
largest quantity of atmospheric mercury at the end of the 20th century. Figure 13 shows
the 1990 Global Emission Inventory Activity of atmospheric mercury.

Figure 13. Global anthropogenic emission of atmospheric mercury in 1990 (Dastoor and
Larocque, 2003)
The three major source areas are Europe, China and North America but, There are also
significant emissions in South Africa. The total global anthropogenic emission for 1990,
according to EPA, was 1881 tons/year which approximately 33% was from Europe, 38%
from China and Japan and 14% from North America. More recent global emissions are
being compiled and they show that the geographical distribution is changing. However,
the total global emissions of atmospheric mercury are not declining. Figure 14 shows the
distribution of the total gaseous mercury on the surface in 1997 at the North Hemisphere
(NH), the South Hemisphere (SH) and globally.

Figure 14. Monthly mean total gaseous mercury surface average air concentrations in
1997 (Dastoor and Larocque, 2003)
Figure 14 shows an average seasonal cycle in Northern and Southern Hemispheres with
higher concentrations in fall and winter due to the increase in coal combustion to provide
electricity and heat. Conversely, during the spring and summer there are lower
concentrations, as the weather gets warmer.
From table 2 previously presented, the major anthropogenic sources of atmospheric
mercury were medical waste incineration (26%), municipal waste collection (22%),
electric utility boilers (22%) and power & heat generation plants (13%). Figures 14-16
illustrate the emission of elemental mercury, RGM and particulate mercury into the
atmosphere across the US in 1990, respectively:
Figure 13. Elemental mercury emissions (tons per year) from anthropogenic sources at
the US in 1990 (EPA: 1997)

Figure 14. Reactive gaseous mercury emissions (tons per year) from anthropogenic
sources at the US in 1990 (EPA: 1997)
Figure 15. Particulate mercury emissions (tons per year) from anthropogenic sources at
the US in 1990 (EPA: 1997)
From observation of figures 13, 14 and 15, it is evident that the eastern side of the US
contains more point sources of atmospheric mercury emission. This is due to the presence
of coal-burning power plants that generate electricity that are mostly at the northeastern
side of the US. Most of the emission of reactive gaseous mercury and particulate mercury
are due to medical waste incineration facilities and municipal waste collections.
The EPA model, IEM-2M, was presented to the congress in 1997. The model divided
the US into Western and Eastern halves along the line of 90 degrees west longitude. IEM-
2M is composed of two integrated modules that simulate mercury fate using mass
balance equations describing watershed soils and a shallow lake. The results of these
terrestrial and aquatic models were used to predict mercury exposure to hypothetical
humans through inhalation, consumption of drinking water, and ingestion of soil, farm
products (e.g., beef products and vegetables), and fish. These models were also used to
predict mercury exposure in hypothetical fish-eating birds and mammals through their
consumption of fish. The model compared pre-industrialized atmospheric mercury
emission with industrialized ones. It was estimate that pre-industrial (starting
approximately around the 17th century) atmospheric mercury levels were roughly one
third of current levels. Table 3 presents the inputs to the IEM-2M models on both the
Western and Eastern sides of the 90 degrees west longitude, comparing the emission of
mercury from the pre-industrial and the industrial eras. Once the input to the model has
been inserted, an atmospheric model for mercury transportation can be made.
Table 3. Inputs to IEM-2M model obtained from atmospheric mercury measurements

As expected, once the industrial era started, all measurement parameters across the US
have increased considerably. From the atmospheric modeling analyses of mercury
deposition and on a comparative basis, a facility located in a humid climate has a higher
annual rate of mercury deposition than a facility located in an arid climate. Precipitation
removes various forms of mercury from the atmosphere and deposits mercury to the
surface of the earth. Of the species of mercury that are emitted, divalent mercury is
predicted to generally deposit to local environments near sources. Elemental mercury is
predicted to generally remain in the atmosphere for longer periods until atmospheric
conversion to divalent species occurs.
Given the simulated deposition efficiencies for each form of mercury air emission
(elemental mercury – 1%, divalent mercury vapor – 70%, and particulate mercury – 38%)
the relative source contributions to the total anthropogenic mercury deposited to the
continental U.S. are strongly and positively correlated to the mass of emissions in
oxidized form. This oxidized mercury occurs in both gaseous (Hg+2) and particulate (Hgp)
forms. While coal combustion is responsible for more than half of all emissions of
mercury in the inventory of U.S. anthropogenic sources, the fraction of coal combustion
emissions in oxidized form is thought to be less than that from waste incineration and
combustion. The true speciation of mercury emissions from the various source types
modeled is still uncertain and is thought to vary, not only among source types, but also
for individual plants as feedstock and operating conditions change. With further research,
it may be possible to make a confident ranking of relative source contributions to
mercury deposition in the continental U.S. Table 4 shows a comparison of mercury
concentrations between rural and urban areas.
Table 4. Summary of measures mercury concentrations in rural and urban areas

Table 4 shows that the measured U.S. atmospheric mercury concentrations are generally
very low. The dominant form in the atmosphere is vapor-phase elemental mercury,
although close to emission sources, higher concentrations of the divalent form may be
present due to its strong ability to dissolve in water. Small fractions of particulate
mercury and methyl mercury may also be measured in ambient air. The formation of
methyl mercury in the atmosphere still remains a great unknown. In rural areas, airborne
particulate mercury is typically 4% or less of the total (particulate + gas phase) mercury
in air
From the modeling analysis and a review of field measurement studies, it is concluded
that mercury deposition appears to be ubiquitous across the continental U.S. and at, or
above, detection limits when measured with current analytic methods. Due to the use of
atmospheric models to detect atmospheric mercury, it was discovered that of the total
amount of elemental mercury vapor that is emitted, about 1 percent (0.9 metric tons/yr)
may be atmospherically transformed into divalent mercury by tropospheric ozone and
adsorbed to particulate soot in the air and subsequently deposited in rainfall and snowfall
to the surface of the continental U.S. The vast majority of emitted elemental mercury
does not become part of the global mercury cycle due to the fact that it does not diffuse
vertically to the free atmosphere. However, nearly all of the elemental mercury vapor
emitted from other sources around the globe also enters the global cycle and can be
deposited slowly to the U.S. Over 30 times as much elemental mercury vapor is deposited
from these other sources than from stationary point sources and area sources within the
U.S.
ENVIRONMENTAL FATE OF ATMOSPHERIC MERCURY
Mercury is emitted to the environment by both anthropogenic and natural processes.
Due to its chemical properties, mercury is thought to move through various
environmental compartments, possibly changing form and species during process.
Mercury, like other elements such as nitrogen, sulfur and carbon, has a cycle that
describes its environmental fate. The mercury cycle has been studies by many scholars
over the years, and the understanding of it continues to undergo refinement. The
movement and distribution of mercury in the environment can be confidentially described
in general terms, since not all its details are agreed due to lack of information. Currently
it is estimated that about half of total anthropogenic mercury emissions eventually enter
the global atmospheric cycle. The remainder is removed through local or regional cycles.
An estimated 5 to 10 percent of primary RGM emissions are deposited within 100 km of
the point of emission and a larger fraction on a regional scale. Elemental mercury that is
emitted may be removed on a local and regional scale to the extent that it is oxidized to
RGM. Some elemental mercury may also be taken up directly by plants and trees.
However, most elemental mercury that is not oxidized will undergo long-range transport
due to its insolubility in water. In general, primary RGM emissions will be deposited on a
local and regional scale to the degree that wet deposition processes remove the soluble
RGM. The wet and dry deposition phenomena will be discussed in this section. Figure 16
below illustrates the mercury cycle, illustrating the natural and anthropogenic sources of
mercury in the environment.

Figure 16. Global mercury cycle schematic (Bullock, 2000a)


From figure 16 it can be seen that the atmospheric mercury is continuously
transforming to different forms and deposited at land and aquatic sources. Of the total
amount of global divalent mercury vapor that is emitted, about 70 percent (36.8 metric
tons/year) deposits to the surface through wet or dry processes within the U.S. The
remaining 30 percent is transported outside the U.S. or is vertically diffused to the free
atmosphere to become part of the global cycle. Of the total amount of particulate mercury
that is emitted, about 38 percent (10.0 metric tons/year) deposits to the surface through
wet or dry processes within the U.S. The remaining 62 percent is transported outside the
U.S. or is vertically diffused to the free atmosphere to become part of the global cycle.
All three major forms of mercury can be dry deposited and the rates of deposition vary
depending upon surface characteristics and meteorological conditions. The dry deposition
velocity of a gaseous pollutant is governed by three factors: turbulent diffusive transport
in the atmosphere, molecular diffusive transport through the quasi-laminar sublayer
(boundary level resistance) at the ground surface and uptake by the surface or plants.
Elemental mercury is relatively inert, therefore it is likely that elemental mercury
deposits with a small dry deposition velocity. Due to high background concentration of
elemental mercury, the total dry deposition of mercury is sensitive to dry deposition
velocity of elemental mercury. Both particulate and gaseous divalent mercury (RGM) are
thought to dry deposit at large rates, where measurable concentrations of these mercury
species exist. The deposition velocity of particulate mercury is dependent on atmospheric
conditions and particle size.
Wet deposition is often parameterized through the precipitation rate and the washout
ratio, which is the ratio of the mercury concentration in rainwater divided by the mercury
concentration in air. Scavenging of mercury by precipitation varies considerably. It is
generally accepted that elemental mercury is not susceptible to any major process of
direct wet deposition. Precipitation is the major way the gaseous divalent mercury is
readily expected to be collected. Due to its higher solubility, divalent mercury is thought
to wet deposit at much higher rates than that of elemental mercury vapor. The washout
ratio used for divalent mercury vapor is based on an assumed similarity between divalent
mercury and nitric acid. Particulate mercury is also subject to wet deposition due to
scavenging by cloud microphysics and precipitation. Roughly half of particulate mercury
may be scavenged by atmospheric water.

Transport and transformation of mercury in the environment


Atmospheric emissions are a major concern with respect to the mercury entering the
environment. Mercury that is released to the atmosphere is transported, transformed, and
deposited back to the earth’s surface as can be seen from figure 16. The distance of
mercury transport depends upon the chemical form of the emitted mercury, the height of
the emissions, the chemical and physical processes, and the atmospheric conditions (e.g.,
wind speeds, precipitation, composition of oxidizing and reducing species). Among the
three forms of atmospheric mercury, an atmospheric transport is likely to be the primer
mechanism by which elemental mercury is distributed throughout the environment.
However, there is an indirect pathway by which elemental mercury vapor released into
the atmosphere may be removed and deposited to the earth's surface. Chemical reactions
occur in the aqueous phase (cloud droplets) that both oxidize elemental mercury to
divalent mercury and reduce the divalent mercury to elemental mercury. The most
important reactions in this aqueous reduction-oxidation balance are thought to be
oxidation of elemental mercury with ozone, reduction of divalent mercury by sulfite
(SO3-2) ions, or complexation of divalent mercury with soot to form particulate divalent
mercury:
Hg0(g) → Hg0(aq)
Hg0(aq) + O3(aq) → Hg+2(aq)
Hg+2(aq) + soot/possible evaporation → Hg+2(p)
Hg+2(aq) + SO3-2(aq) → Hg0(aq)
The RGM produced from oxidation of elemental mercury by ozone can be reduced
back to elemental mercury by sulfite ion. However, the oxidation of elemental mercury
by ozone is a much faster reaction than the reduction of RGM by sulfite. The RGM(aq)
produced would then be susceptible to atmospheric removal via wet deposition. The third
reaction, however, may transform most of the RGM(aq) into the particulate form, due to
the much greater amounts of soot than mercury in the atmosphere. The resulting RGM(p)
can then be removed from the atmosphere by wet deposition (if the particle is still
associated with the cloud droplet) or dry deposition (following cloud droplet
evaporation).
Airborne mercury can also undergo chemical reactions, which may significantly affect
the lifetime of atmospheric mercury. Particulate mercury is likely to be transported and
deposited at an intermediate distances depending on aerosol diameter or mass.
Before mercury is deposited back to the earth’s surfaces, a series of complex physical and
chemical transformations of mercury can take place in the atmosphere as was illustrated
in figure 6. The transformations include the equilibriums of mercury species among
gaseous, aqueous and solid phases, the aqueous phase chemistry of mercury, and the
gaseous phase chemistry of mercury. Often the equilibrium relationship between the
partial pressure in the gas phase and the mole fraction in the liquid phase can be
expressed by a straight-line Henry’s law equation at low concentrations:
pA=H*xA
Where: pA is the partial in the gas, H is the Henry’s law constant in atm/mole fraction for
the given system and xA is the mole fraction in the liquid phase.

Henry’s law governs the gas-liquid equilibriums of mercury species. The Henry’s law
constant for elemental mercury is quite small in the atmosphere, which lowers its partial
pressure; therefore it can travel for long distances. Although elemental mercury is the
dominant constitute of atmospheric mercury, the cloud-water concentration of elemental
mercury in Henry’s equilibrium with gaseous elemental mercury range only from 1.3 to
5.3 ×10-14 M, which is relatively low compared to the total dissolved and absorbed reactive
gaseous mercury. In contrast, the Henry’s law constants for Hg(OH)2 and HgCl2 are 4 and
6 orders of magnitude bigger than that for elemental mercury. Solid mercury species are
not likely present in atmospheric water given the low atmospheric concentration of
mercury. The quantitative description of gas-solid equilibriums is rather limited due to
uncertain nature of atmospheric particles.
In the aqueous phase, mercury compounds often remain as not disassociated
molecules, and the reported solubility values reflect this. Most organomercurics are not
soluble and do not react with weak acids or bases due to the low affinity of the mercury
for oxygen bonded to carbon. Hydroxy methyl mercury, CH3HgOH, however, is highly
soluble due to the strong hydrogen bonding capability of the hydroxide group. The
mercuric salts vary widely in solubility. For example HgCl2 is readily soluble in water,
and HgS is as unreactive as the organomercurics due to the high affinity of mercury for
sulfur.
The phenomenon of re-emission of deposited mercury results most significantly from
the evasion of elemental mercury from the oceans. In this process, anthropogenically
emitted mercury is deposited to the oceans as reactive gaseous mercury and then reduced
to volatile elemental mercury and re-emitted. According to one estimate, this process
accounts for approximately 30% (10 Mmol/year) of the total mercury flux to the
atmosphere. The slow release of mercury from terrestrial sinks to freshwater and coastal
waters will likely persist for much longer, though, effectively increasing the lifetime of
anthropogenic mercury further. This may be particularly significant considering that
surface soils currently contain most of the pollution-derived mercury of the industrial
period. However, recently published studies indicate that mercury in soil may be reduced
and re-volatilized, in that the capacity of soils to isolate airborne mercury must be
reconsidered. Thus, re-emissions of anthropogenic mercury will contribute to long-term
influences on the global biogeochemical cycle for mercury.

Environmental fate of mercury in marine environment


There are a number of pathways by which mercury can enter the freshwater
environment: RGM and methyl mercury from atmospheric deposition (wet and dry) can
enter water bodies directly; RGM and methyl mercury can be transported to water bodies
when it is bound to suspended soil or attached to dissolved organic carbon; or RGM and
methyl mercury can leach into the water body from groundwater flow in the upper soil
layers. Once in the freshwater system, mercury can remain in the water column, be lost
from the lake through drainage water, re-volatilize into the atmosphere, settle into the
sediment or be taken up by aquatic biota. After entry, the movements of mercury through
any specific water body may be unique. Mercury in the water, in the sediment, and in
other aquatic biota appears to be available to aquatic organisms for uptake. However, not
all mercury compounds entering an aquatic ecosystem are methylated by sulfur reducing
bacteria, and demethylation reactions as well as volatilization of dimethyl mercury
decrease the amount of methyl mercury available in the aquatic environment. There is a
large degree of scientific uncertainty and variability among water bodies concerning the
processes that methylate mercury.
Bacterial methylation rates appear to increase under anaerobic conditions, high
temperatures and low pH – a relationship exists between methyl mercury content in fish
and lake pH, with higher methyl mercury content in fish tissue typically found in more
acidic lakes. In addition, anthropogenic acidification of lakes appears to increase
methylation rates, as well increased quantities of the mercuric species, the proper biologic
community, adequate suspended soil load and sedimentation rate. Methyl mercury
accumulates in fish through the aquatic food web. Nearly 100% of the mercury found in
fish muscle tissue is methylated. Methyl mercury appears to be primarily passed to
planktivorous and piscivorous fish via their diets. Larger, longer-lived fish species at the
upper end of the food web typically have the highest concentrations of methyl mercury in
a given water source. Most of the total methyl mercury production ends up in biota,
particularly fish. Methyl mercury appears to be efficiently passed through the aquatic
food web to the highest tropic level consumers in the community (for instance the
piscivorous fish). At this point, humans and fish-consuming wildlife may ingest fish
contaminated with methyl mercury. The mechanisms for the behavior of methyl mercury
and the increased biomagnifications are still unknown.
This bioaccumulation of methyl mercury in fish muscle tissue occurs in water bodies
that are remote from emission sources and seemingly immaculate, as well as in water
bodies that are less isolated. Methyl mercury appears to pass from the gastrointestinal
tract into the bloodstream more efficiently than the divalent species. In humans,
consumption of fish contaminated with methyl mercury is particularly dangerous for
pregnant women, infants and young children. Once consumed into the body, the human
body degrades slowly methyl mercury (with half-life of 45 to 70 days). It builds up in the
brain and is secreted in breast milk. Potential consequences of methyl mercury include
death, kidney toxicity, cardiovascular toxicity, immunotoxicity and neurotoxicity (the
development of the fetus is the most sensitive). Figure 17 illustrates the mercury cycle in
the environment.

Figure 17. Environmental fate of mercury

By considering the current global mercury budget and estimates of the preindustrial
mercury fluxes, it was estimated that total emissions have increased by a factor of
approximately 4.5 since preindustrial times, which has subsequently increased the
atmospheric and oceanic reservoirs by a factor of 3. The difference is attributed to local
deposition near anthropogenic sources. Although the estimated residence time of
elemental mercury in the atmosphere is about 1 year, the equilibrium between the
atmosphere and ocean waters results in a longer time period needed for overall change to
take place for reservoir amounts. Therefore, by substantially increasing the size of the
oceanic mercury pool, anthropogenic sources have introduced long-term perturbations
into the global mercury cycle. Modeled results estimated that if all anthropogenic
emissions were ceased today, it would take about 15 years for mercury pools in the
oceans and the atmosphere to return to pre-industrial conditions. However, The Science
Advisory Board concluded that it could take significantly longer.

CONCLUSION
Mercury is an element that is naturally present in the environment. Mercury is
persistent pollutant that is released to the atmosphere mostly by coal-burning power
plants. Atmospheric mercury is characterized into three types: elemental, reactive
gaseous and particulate. Elemental mercury is insoluble in water and can be transported
for long distances, whereas the reactive gaseous form is highly soluble in water and as a
result lands in nearby areas to the pollution sources via wet deposition.
When enters to aquatic systems, mercury is transformed by sulfur and iron reducing
bacteria to an organic form – methyl mercury, the most toxic form of mercury. In aquatic
systems, fish eat different foods that were contaminated with methyl mercury, staying in
their body for long periods of time. Human consuming fish containing methyl mercury
experience a biomagnification of methyl mercury in their body, resulting in severe
diseases and eventually - death. Up to date, it is still unknown how mercury is
transformed form its inorganic form to the organic one, in both aquatic and atmospheric
matrices.
Currently, mercury is monitored in many areas around the world, trying to predict or
model future transportation or behavior of the pollutant in the atmosphere. Understanding
the movement of mercury in the atmosphere will help to alert populations with different
health risks that are associated with mercury. Future research in the investigation of
mercury as an atmospheric pollutant can focus on understanding to greater details how to
analyze obtained data within three or four years since measurement dates instead of eight
or nine years as it stands now. In addition, more accurate equipments generating less
uncertainty per given measurement will greatly help in the future understanding and
prediction of atmospheric mercury pollution.
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