Specific characters of mercury

Boiling point is 629.88K (356.73C, 674.11F) The melting point is 234.32K (-38.83C, -37.89F) Exists with three valence states Hg0, Hg1+, and Hg2+ Only trace element which volatilizes at ambient temperature Occurs in the environment in its metallic form as well as in various inorganic and organic complexes With an aqueous solubility that is comparable to that of oxygen, elemental Hg (Hg0) is a ubiquitous component of natural waters

Sources Of Total Hg In Aquatic Environment Natural Sources:

Volcanoes
Evaporation from soil and water surfaces Degradation of minerals

Forest fires
Flooding

Anthropogenic Sources:

Atmospheric deposition Urban discharges

Agricultural material runoff

Mining Fossil fuel use and industrial discharges Pharmaceutical production

Fig. Anthropogenic sources of Hg

Mercury Cycle

Fate Of Mercury In Water

Exists in all the oxidation states, Hg0, Hg1+, and Hg2+

Hg0 is insoluble,HgSO4 most soluble, Hg(II) chloride is readily soluble, Hg(I) chloride is much less soluble and mercury sulfide has a very low solubility.

Chloro-complexes of Hg are most abundant in sea water at pe + pH>12, especially in oxic waters

 Hg0

is found at all depths in the oceans, supersaturated, especially in surface waters

Increase

in salinity enhance HgCl42concentration while a decrease favors HgCl3species anoxic sea water (pe + pH <3) Hg-S complexes are the major species of dissolved inorganic mercury

In

Effect Of Sulphur

Controls chemistry of mercury in anaerobic sites

Dominant mercury species in the anaerobic conditions are mono- and bi-sulphide complexes such as HgS, HgS2H2, HgS2H
HgS (Cinnabar) is poorly water soluble, precipitates in sediments and determines the solubility of Hg(II) compounds Organic matter plays an important role in release of Hg from HgS, inhibited by Ca2+ HgS is strongly bound with the sediments, it can be partly dissolved by bacteria or under oxidizing conditions (bioturbation)

Diagram of hydroxo-, chloro- and sulfide complexes of MeHg at pH= 7 as a function of chloride and total sulfide S (II) concentration

Methylation of Hg

Marine and estuary sediments, CH3Hg ~ 0.5% of total Hg whereas in fresh water sediments it usually reaches 1-1.5% Abiotic methylation, which generally occurs in anoxic sediments, is not considered very important in freshwater environments (Berman and Bartha 1986; Miskimmin et al. 1992). Biotic methylation occurs through the action of sulphur reducing bacteria (SRBs) (Gilmour et al. 1992; Benoit et al. 2003)

Group of SRB: Clostridium butyricum, Desulfobulbus propionicus, Desulfovibrio desulfuricans, Desulfococcus multivorans, Desulfobacter sp.,Desulfobacterium sp

Methylation requires a suitable CH3 donor, and methylcobalamin (vitamin B12) is believed to be the only natural methylating agent capable of transferring methyl groups

Factors affecting rate of Hg methylation includes pH

Presence of sulphur DOC Microbial respiration,

Water temperature, and lake surface area

(Miskimmin et al 1992)

Effect of pH

Acidic conditions favor mercury methylation in the water column and at the sediment-water interface Microbial activity is enhanced in low pH waters Low pH also favors the production of monomethylmercury over dimethylmercury (McMurtry et al. 1989) At higher pH, the processes of mercury demethylation (volatile) is favored

Effect Of Redox Conditions

Surface layers of the bottom sediments (oxidizing conditions) make a geochemical barrier for diffusion of methylmercury from the deeper layers (reducing conditions) to the water column

Minimum conc. of Hg is expected around the suboxic to anoxic interface

Hg concentration increases as redox shifts to both extremes

Effects of D.O.C

Organic matter can bind up to 95% of the divalent Hg species Serves as a carrier to transport Hg(II) into a water body from catchment area Grieb et al. (1990) found a positive correlation between Hg in fish tissue and DOC in drainage lakes, but a negative relationship in seepage lakes High DOC (10.5 mg/L) and low pH (<6.0) favour methylation of inorganic mercury over gaseous evasion in aquatic cycling of mercury (Miskimmin et al. 1992; Watras et al. 1995)

Effect Of Salinity

Rate of mercury methylation decreases with increasing concentration of salt At higher salinity neutral species of Hg(II) such as HgCl2 or Hg(OH)2 are present instead of HgCl3 or HgCl42-

The oxidation of elementary mercury ,Hg0 to Hg(II) is significantly lower in fresh water than in marine water

Effects Of Temperature and Lake Surface Area

Rate of mercury methylation was greatest in the epilimnion during summer stratification and demethylation rate was greatest in the hypolimnion during winter stratification, Ramalal et al. (1993)

Increased temperature increases metabolic rate, leading to increased uptake of food and water, leads to an increased rate of MeHg uptake (Bodaly et al. 1993)
Smaller lakes tend to be shallower and therefore warmer in summer than larger, deeper lakes

Factors Affecting Bioaccumulation Of Hg In Fish

Among various species of Hg found in water bodies, only MeHg bioaccumulated Hg accumulation is affected by Dissolved Hg conc. Position of an organism in food web Geographic location Sea water salinity and Temperature

Average proportion of MeHg over total Hg is 10% in water column ,15% in phytoplankton, 30% in zooplankton, and 95% in fish

Hg conc. in fish species generally increase with increasing age and body size (Lange et al. 1993; Weiner and Spry 1996)

Piscivorous species such as lake trout acquire more Hg than other species

Desorption

pH:- Lower pH enhances desorption of Hg Redox:- In anoxic sediment more Hg will be complexed by sulphur ions (HS- ,S2- ,S2-)

Salinity:- Increase in salinity forms mercury chloro complexes , brings more Hg to sea water , enhances desorption.

Demethylation
CH3-Hg+ + H+ CH4 + Hg2+ Catalysed by Pseudomonas group of bacteria

Hg demethylation are more effective in the marine ecosystems with relatively high salinity than in the fresh waters Methylmercury can be lost through microbial demethylation and photodegradation Iron and manganese hydroxides, catalyse demethylation of Hg in aerobic conditions