Methylmercury formation in boreal wetlands in relation to chemical speciation of mercury(II) and concentration of low molecular mass thiols
Science of the Total Environment
Methylmercury (MeHg) is a neurotoxin formed from inorganic divalent mercury (HgII) via microbial methylation, and boreal wetlands have been identified as major sources of MeHg. There is however a lack of studies investigating the relationship between the chemical speciation of HgII and MeHg formation in such environments, in particular regarding to role of thiol compounds. We determined HgII methylation potentials, kmeth, in boreal wetland soils using two HgII isotope tracers: 198Hg(OH)2(aq)
... : 198Hg(OH)2(aq) and HgII bonded to thiol groups in natural organic matter, 200HgII-NOM(ads), representing HgII sources with high and low availability for methylation. The 198Hg(OH)2(aq) tracer was consistently methylated to a 5-fold higher extent than 200HgII-NOM(ads), independent of environmental conditions. This suggests that the concentration of HgII in porewater was a decisive factor for HgII methylation. A comprehensive thermodynamic speciation model (including HgII complexes with inorganic sulfide (H2S), polysulfides (H2Sn), thiols associated with natural organic matter (NOM-RSH) and specific low molecular mass thiols (LMM-RSH) provided new insights on the speciation of HgII in boreal wetland porewaters, but did not demonstrate any clear relationship between kmeth and the calculated chemical speciation. In contrast, significant positive relationships were observed between kmeth and the sum of LMM thiol compounds of biological origin. We suggest two possible mechanisms underlying these correlations: 1) LMM thiols kinetically control the size and composition of the HgII pool available for microbial uptake, and/or 2) LMM thiols are produced by microbes such that the correlation reflects a relation between microbial activity and MeHg formation.