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Article

Importance of Dissolved Neutral Mercury Sulfides for Methyl Mercury Production in Contaminated Sediments

Supporting Info

Andreas Drott,^† Lars Lambertsson,^‡ Erik Björn,^‡ and Ulf Skyllberg*^†

Department of Forest Ecology, Swedish University of Agricultural Sciences, S-90183 Ume, Sweden, and Department of Chemistry, Ume University, S-90187 Ume, Sweden

Environ. Sci. Technol., 2007, 41 (7), pp 2270–2276

DOI: 10.1021/es061724z

Publication Date (Web): February 28, 2007

†

Swedish University of Agricultural Sciences.

‡

Umeå University.

Corresponding author phone: +46(0)90-7868460; fax: +46(0)90-7868163; e-mail: ulf.skyllberg@sek.slu.se.

Abstract

Biotic transformation of inorganic mercury, Hg(II), to mono methyl mercury (MeHg) is proposed to be largely controlled by passive uptake of neutral Hg complexes by sulfate reducing bacteria (SRB). In this study, the chemical speciation of Hg(II) in seven locally contaminated sediments covering environments such as (i) brackish water, (ii) low-productivity freshwater, and, (iii) high-productivity freshwater was related to potential Hg methylation rates, determined by incubation at 23 °C for 48 h under N₂(g), and to total MeHg concentrations in sediments. Pore water speciation was modeled considering Hg complexes with halides, organic thiols [Hg(SR)₂(aq), associated to dissolved organic matter], monosulfides, and bisulfides. The sum of neutral mercury sulfides [Hg(SH)₂⁰(aq)] and [HgS⁰(aq)] was significantly, positively (p < 0.001, n = 20) correlated to the specific methylation rate constant (K_m, day^-1) at depths of 5−100 cm in two brackish water sediments. Total Hg, total mercury sulfides or Hg(SR)₂(aq) in pore water gave no significant relationships with K_m. In two sub-sets of freshwater sediments, neutral mercury sulfides were positively correlated to total Hg in pore water, and therefore, total Hg also gave significant relationships with K_m. The sum of [Hg(SH)₂⁰(aq)] and [HgS⁰(aq)] was significantly, positively correlated to total sediment MeHg (μg kg^-1) in brackish waters (p < 0.001, n = 23), in southern, high-productivity freshwaters (p < 0.001, n = 20), as well as in northern, low-productivity freshwater (p = 0.048, n = 6). The slopes (b, b‘) of the relationships K_m (day^-1) = a + b([Hg(SH)₂⁰(aq)] + [HgS⁰(aq)]) and MeHg (μg kg^-1) = a‘ + b‘([Hg(SH)₂⁰(aq)] + [HgS⁰(aq)]) showed an inverse relationship with the C/N ratio, supposedly reflecting differences in primary production and energy-rich organic matter availability among sites. We conclude that concentrations of neutral inorganic mercury sulfide species, together with the availability of energy-rich organic matter, largely control Hg methylation rates in contaminated sediments. Furthermore, Hg(SH)₂⁰(aq) is suggested to be the dominant species taken up by MeHg producing bacteria in organic-rich sediments without formation of HgS(s).