A detailed understanding of the formation of the potent neurotoxic methylmercury is neededto explain the large observed variability in methylmercury levels in aquatic systems. While it is known that organic matter interacts strongly with mercury, the role of organic matter composition in the formation of methylmercury in aquatic systems remains poorly understood. Here we show that phytoplankton-derived organic compounds enhance mercurymethylation rates in boreal lake sediments through an overall increase of bacterial activity. Accordingly, in situ mercury methylation defines methylmercury levels in lake sediments strongly influenced by planktonic blooms. In contrast, sediments dominated by terrigenous organic matter inputs have far lower methylation rates but higher concentrations of methylmercury, suggesting that methylmercury was formed in the catchment and imported into lakes. Our findings demonstrate that the origin and molecular composition of organic matter are critical parameters to understand and predict methylmercury formation and accumulation in boreal lake sediments.
ABSTRACT: Methylmercury is a potent human neurotoxin which biomagnifies in aquatic food webs. Although anaerobic microorganisms containing the hgcA gene potentially mediate the formation of methylmercury in natural environments, the diversity of these mercury-methylating microbial communities remains largely unexplored. Previous studies have implicated sulfate-reducing bacteria as the main mercury methylators in aquatic ecosystems. In the present study, we characterized the diversity of mercury-methylating microbial communities of boreal lake sediments using high-throughput sequencing of 16S rRNA and hgcA genes. Our results show that in the lake sediments, Methanomicrobiales and Geobacteraceae also represent abundant members of the mercury-methylating communities. In fact, incubation experiments with a mercury isotopic tracer and molybdate revealed that only between 38% and 45% of mercury methylation was attributed to sulfate reduction. These results suggest that methanogens and iron-reducing bacteria may contribute to more than half of the mercury methylation in boreal lakes.
IMPORTANCE: Despite the global awareness that mercury, and methylmercury in particular, is a neurotoxin to which millions of people continue to be exposed, there are sizable gaps in the understanding of the processes and organisms involved in methylmercury formation in aquatic ecosystems. In the present study, we shed light on the diversity of the microorganisms responsible for methylmercury formation in boreal lake sediments. All the microorganisms identified are associated with the processing of organic matter in aquatic systems. Moreover, our results show that the well-known mercury-methylating sulfate-reducing bacteria constituted only a minor portion of the potential mercury methylators. In contrast, methanogens and iron-reducing bacteria were important contributors to methylmercury formation, highlighting their role in mercury cycling in the environment.
An important issue in mercury (Hg) biogeochemistry is to explore the influence of aqueous Hg(II) forms on bacterial uptake, and subsequent methyl mercury formation, under iron(III) and sulfate reducing conditions. The success of this is dependent on relevant information on the thermodynamic stability of Hg-sulfides. In the present study, we determined the solubility of a commercially available HgS(s) phase, which was shown by X-ray diffraction to be a mixture of 83% metacinnabar and 17% cinnabar. At aqueous sulfide concentrations between 0.060 and 84 µM, well below levels in previous studies, we report a solubility product (log Ksp±SE) of -36.8±0.3 (HgS(s) + H+ = Hg2+ + HS-, I=0, T=25°C, pH 6-10, n=20) for metacinnabar. This value is 0.7 log units higher than previous estimates. Complementing our data with data from Paquette and Helz (1997), we took advantage of a large data set (n=65) covering a wide range of aqueous sulfide (0.06 µM-140 mM), and pH (1-11). Based on this we report refined formation constants (±SE) for the three aqueous Hg(II)-sulfide species proposed by Schwarzenbach and Widmer (1963): Hg2+ + 2HS- = Hg(SH)20; log K = 39.1±0.1, Hg2+ + 2HS- = HgS2H- + H+; log K = 32.5±0.1, Hg2+ + 2HS- = HgS22- + 2H+; log K = 23.2±0.1. Our refined log K values differ from previous estimates by 0.2-0.6 log units. Furthermore, at the low sulfide concentrations in our study we could rule out the value of -10.0 for the reaction HgS(s) + H2O = HgOHSH(aq), as reported by Dyrssén and Wedborg (1991). By establishing a solubility product for the most environmentally relevant HgS(s) phase, metacinnabar, and extending the range of aqueous sulfide concentrations to sub-µM levels, relevant for soils, sediments and waters, this study decreases the uncertainty in stability constants for Hg-sulfides, thereby improving the basis for understanding the bioavailability and mobility of Hg(II) in the environment.
We investigated the concentration levels, fractionation and molecular weight distribution (MWD) of dissolved organic matter (DOM) and metals (V, Cr, Co, Ni, Cu, Zn, As, Cd, Sn, Ba, Hg and Pb) in a polluted groundwater from an industrial area in Northern Sweden. DOM was mainly recovered in the hydrophobic acidic and hydrophobic neutral sub-fractions (45 and 35%, respectively) while most metals were found in the acidic sub-fractions (46–93%) except for V, Fe and As, which were predominant in the basic sub-fractions (74–93%) and Cd in the neutral ones (50%). DOM exhibited a broad MWD in groundwaters, usually from 5 to 200 kDa and was dominated by high molecular weight hydrophobic acids, low molecular weight hydrophilic acids and hydrophilic neutral compounds. Most of the studied metals (Fe, Cr, Co, Sn, Ba, Hg) were associated with the high molecular weight DOM fraction (ca. 40–100 kDa). Cu, Pb, Zn, Cd and Ni interacted with a broad range of DOM size fractions but were still most abundant in the high molecular weight fraction. Few metal/metalloids (As, V and Cr in some cases) presented a very weak affinity for DOM and presumably existed predominantly as “free” inorganic ions in solution.