Mercury methylation/demethylation and volatilization pathways in estuarine sediment slurries using species-specific enriched stable isotopes

• Published in: Marine chemistry 2004-11, Vol.90 (1), p.107-123
• Main Authors: Rodrı́guez Martı́n-Doimeadios, R.C., Tessier, E., Amouroux, D., Guyoneaud, R., Duran, R., Caumette, P., Donard, O.F.X.
• Format: Article
• Language: English
• Subjects: Analytical chemistry; Brackish; Chemical Sciences; Demethylation; Earth sciences; Earth, ocean, space; Engineering and environment geology. Geothermics; Enriched stable isotopes; Estuarine sediments; Exact sciences and technology; External geophysics; Geochemistry; Mercury; Methylation; Methylmercury; Mineralogy; Physical and chemical properties of sea water; Physics of the oceans; Pollution, environment geology; Silicates; Volatilization; Water geochemistry
• ISSN: 0304-4203; 1872-7581
• DOI: 10.1016/j.marchem.2004.02.022

Species-specific enriched stable isotopes have been used to study mercury transformations (methylation, demethylation and volatilization) in estuarine sediments under different environmental conditions (both biotic and abiotic and oxic and anoxic). These experiments have demonstrated the potential for the isotopically enriched species in combination with highly sensitive measurement methods (ICP MS) to facilitate the study of mercury speciation and reactivity. Sediments (sterilized and nonsterilized) were spiked with both isotopically enriched inorganic ( 199Hg) and monomethylmercury (MM 201Hg) at environmental levels to avoid perturbing the system and incubated under both aerobic and anaerobic conditions. The formation of MM 199Hg and the degradation of MM 201Hg were measured simultaneously during time series experiments by capillary gas chromatography-inductively coupled mass spectrometry. Specific methylation and demethylation rate constants ( K m and K d) were calculated. Results clearly showed that methylmercury levels in sediments are controlled by competing and simultaneous methylation and demethylation reactions. Operating conditions, likely to drastically modify the reactivity of the media, were of primary importance to assess the relative significance of each mechanism. In estuarine sediments, mercury methylation was enhanced under anaerobic nonsterile conditions, whereas other environmental conditions were either less favorable for monomethylmercury production or more effective for its degradation. The production of total gaseous mercury was found to be minimal, although it could be demonstrated that it was related to the fate and transformation of methylmercury.