Sources and Transfers of Methylmercury in Adjacent River and Forest Food Webs

To study the sources and transformations of Hg in the rice plant ( Oryza sativa L.), stable Hg isotope variations in different tissues (foliage, root, stem, and seed) of rice which were collected from the Wanshan mercury mine (WSMM, Guizhou province, SW China) were investigated by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). In comparison, Hg isotope compositions of paddy soil, lichen, and direct ambient air samples in WSMM were also analyzed. We observed that mass dependent fractionation (MDF) of Hg differed by up to ∼ 3.0‰ in δ(202)Hg values and that mass independent fractionation (MIF) of Hg isotopes affected the odd Hg isotopes to produce a ∼ 0.40‰ range in Δ(199)Hg (and Δ(201)Hg) values in tissues of rice plant. The 1:1 Δ(199)Hg/Δ(201)Hg ratio in tissues of rice supported the hypothesis that a fraction of Hg in tissues of rice plants has undergone a photoreduction process prior to being accumulated by rice plants. We suggest that the variation of MIF represents a mixing between soil Hg and atmospheric Hg in rice plants. The estimated fraction of atmospheric Hg (f) in tissues of rice followed the trend of f leaf > f stem > f seed > f root. Finally, we demonstrated a significant MDF of >1.0‰ in δ(202)Hg during the processes of absorption of atmospheric Hg by leaf tissues and of absorption of soil Hg by roots. Our study demonstrated that Hg isotopes may represent an important contribution both to the study of Hg transportation in plants and to the understanding of sources of Hg contamination to critical food crops.

Mercury stable isotopes in flying fish as a monitor of photochemical degradation of methylmercury in the Atlantic and Pacific Oceans

Stable isotope composition of mercury forms in flue gases from a typical coal-fired power plant, Inner Mongolia, northern China

Inorganic mercury (iHg) methylation in aquatic environments is the first step leading to monomethylmercury (MMHg) bioaccumulation in food webs and might play a role in the Hg isotopic composition measured in sediments and organisms. Methylation by sulfate reducing bacteria (SRB) under sulfate-reducing conditions is probably one of the most important sources of MMHg in natural aquatic environments, but its influence on natural Hg isotopic composition remains to be ascertained. In this context, the methylating SRB Desulfovibrio dechloracetivorans (strain BerOc1) was incubated under sulfate reducing and fumarate respiration conditions (SR and FR, respectively) to determine Hg species specific (MMHg and IHg) isotopic composition associated with methylation and demethylation kinetics. Our results clearly establish Hg isotope mass-dependent fractionation (MDF) during biotic methylation (-1.20 to +0.58‰ for δ(202)Hg), but insignificant mass-independent fractionation (MIF) (-0.12 to +0.15‰ for Δ(201)Hg). During the 24h of the time-course experiments Hg isotopic composition in the produced MMHg becomes significantly lighter than the residual IHg after 1.5h and shows similar δ(202)Hg values under both FR and SR conditions at the end of the experiments. This suggests a unique pathway responsible for the MDF of Hg isotopes during methylation by this strain regardless the metabolism of the cells. After 9 h of experiment, significant simultaneous demethylation is occurring in the culture and demethylates preferentially the lighter Hg isotopes of MMHg. Therefore, depending on their methylation/demethylation capacities, SRB communities in natural sulfate reducing conditions likely have a significant and specific influence on the Hg isotope composition of MMHg (MDF) in sediments and aquatic organisms.

Denitrification devices in urban boilers change mercury isotope fractionation signatures of coal combustion products.

Mass dependent stable isotope fractionation of mercury during mer mediated microbial degradation of monomethylmercury

Isotopic study of mercury sources and transfer between a freshwater lake and adjacent forest food web

The photochemical reduction of Hg(II) is an important pathway in the environmental Hg cycle because it competes with Hg methylation and potentially limits the formation of bioaccumulative methylmercury. Hg stable isotope systematics have proven to be an effective tool for investigating the transport, transformation, and bioaccumulation of Hg. The dominant cause of mass independent isotope fractionation (MIF) of Hg in nature is the photochemical reduction of various species of Hg(II). However, it is difficult to fully interpret Hg stable isotope signatures due to the lack of mechanistic information about which Hg compounds are susceptible to MIF and why. This study investigates Hg isotope fractionation during the photochemical reduction of Hg(II) complexed to organic ligands, which are representative of the available binding sites in natural dissolved organic matter. The photochemical reduction of Hg(II) in the presence of cysteine resulted in both negative and positive MIF in residual Hg(II), where the sign depended on pH and dissolved oxygen level. In the presence of serine, either nuclear volume or magnetic isotope effects were observed depending on the wavelength of light and the extent of Hg(II) complexation by serine. In the presence of ethylenediamine, MIF was negative. Our Hg stable isotope results suggest that MDF and MIF are induced at different steps in the overall photochemical reduction reaction and that MIF does not depend on the rate-determining step but instead depends on photophysical aspects of the reaction such as intersystem crossing and hyperfine coupling. The behavior of Hg isotopes reported here will allow for a better understanding of the underlying reaction mechanisms controlling the Hg isotope signatures recorded in natural samples.

A hundred year record of industrial and urban development in French Alps combining Hg accumulation rates and isotope composition in sediment archives from Lake Luitel

Mass-dependent fractionation (MDF) and mass-independent fractionation (MIF) of Hg isotopes provides a new tool for tracing Hg in contaminated environments such as mining sites, which represent major point sources of Hg pollution into surrounding ecosystems. Here, we present Hg isotope ratios of unroasted ore waste, calcine (roasted ore), and poplar leaves collected at a closed Hg mine (New Idria, CA, U.S.A.). Unroasted ore waste was isotopically uniform with δ(202)Hg values from -0.09 to 0.16‰ (± 0.10‰, 2 SD), close to the estimated initial composition of the HgS ore (-0.26‰). In contrast, calcine samples exhibited variable δ(202)Hg values ranging from -1.91‰ to +2.10‰. Small MIF signatures in the calcine were consistent with nuclear volume fractionation of Hg isotopes during or after the roasting process. The poplar leaves exhibited negative MDF (-3.18 to -1.22‰) and small positive MIF values (Δ(199)Hg of 0.02 to 0.21‰). Sequential extractions combined with Hg isotope analysis revealed higher δ(202)Hg values for the more soluble Hg pools in calcines compared with residual HgS phases. Our data provide novel insights into possible in situ transformations of Hg phases and suggest that isotopically heavy secondary Hg phases were formed in the calcine, which will influence the isotope composition of Hg leached from the site.

Mercury (Hg) is assumed to be predominantly methylated by microorganisms in the environment. However, the mechanisms and extent of abiotic methylation are poorly appreciated. The understanding of the mechanisms leading to abiotic methylation and demethylation in the aquatic environment is of special concern since methylmercury (MeHg) biomagnifies in the food web. Bioaccumulating organisms have also been found to preserve specific Hg isotopic signatures that provide direct insight into aquatic Hg transformations. In this study we investigated the influence of chloride on the magnitude of Hg isotope fractionation during abiotic methylation of inorganic Hg (Hg(II)) using methylcobalamin as methyl donor compound. Coupling of gas chromatography with multi-collector inductively coupled plasma mass spectrometry has allowed to determine simultaneously isotopic ratios of inorganic and methyl-Hg species. Kinetic experiments demonstrated that the presence of chloride not only slowed the chemical alkylation of Hg(II) by methylcobalamin, but also decreased the extent of the methylation, which it is especially significant under visible light conditions due to the enhancement of MeHg photodecomposition. Abiotic methylation of Hg(II) by methylcobalamin in the presence of chloride caused significant Hg mass-dependent isotope fractionation (MDF) for both Hg(II) substrate (δ202Hg(II) from −0.74‰ to 2.48‰) and produced MeHg (δ202MeHg from −1.44‰ to 0.38‰) both under dark and visible light conditions. The value of this MDF under such saline conditions was higher than that previously reported (δ202MeHg from −0.73‰ to 0.09‰) in the absence of chloride and appeared mainly related to inorganic Hg speciation in solution, which is predominantly mercuric chloro-complexes (i.e. HgCl42−). Different isotopic signatures were observed for the different Hg species at the same time of reaction for either dark or visible light (450–650nm wavelengths) conditions. However, no significant mass-independent fractionation (MIF) was induced under any conditions within the analytical uncertainties (−0.17±0.31<∆201Hg<0.17±0.28‰), suggesting that photo-induced demethylation does not always involve MIF. These results also suggest that methylation by methylcobalamin can be an experimental model to study Hg isotope fractionation extent during elementary reaction of methyl transfer in biotic systems.

Mercury (Hg) isotopes can be used as tracers of Hg biogeochemical pathways in the environment. The photochemical reduction of aqueous Hg species by natural sunlight leads to both mass-dependent fractionation (MDF) of Hg isotopes and mass-independent fractionation (MIF) of the odd-mass isotopes, with the relation between the MIF for the two odd isotopes being distinct for different photoreduction pathways. Large variations in MDF and MIF are observed in fish and provide new insights into the sources and bioaccumulation of Hg in food webs. MIF in fish can also be used to estimate the loss of methylmercury via photoreduction in aquatic ecosystems.

Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound Hg. Hg(II) chloride and nitrate solutions were equilibrated in parallel batches with varying amounts of thiol resin resulting in different fractions of thiol-bound and free Hg. Mercury isotope ratios in both fractions were analyzed by multiple collector inductively coupled plasma mass spectrometry (MC-ICPMS). Theoretical equilibrium Hg isotope effects by mass-dependent fractionation (MDF) and nuclear volume fractionation (NVF) were calculated for 14 relevant Hg(II) species. The experimental data revealed that thiol-bound Hg was enriched in light Hg isotopes by 0.53 per thousand and 0.62 per thousand (delta(202)Hg) relative to HgCl(2) and Hg(OH)(2), respectively. The computational results were in excellent agreement with the experimental data indicating that a combination of MDF and NVF was responsible for the observed Hg isotope fractionation. Small mass-independent fractionation (MIF) effects (<0.1 per thousand) were observed representing one of the first experimental evidences for MIF of Hg isotopes by NVF. Our results indicate that significant equilibrium Hg isotope fractionation can occur without redox transition, and that NVF must be considered in addition to MDF to explain Hg isotope variations.

Mercury isotopic composition of hydrothermal systems in the Yellowstone Plateau volcanic field and Guaymas Basin sea-floor rift

Due to the advent of cold vapor-multicollector-inductively coupled plasma mass spectrometry (CV-MC-ICP-MS) in the past two decades, many research groups studying mercury (Hg) biogeochemistry have integrated stable Hg isotopes into their research. Currently, >200 studies using this technique have been published and this has greatly enhanced our understanding of the Hg biogeochemical cycle beyond what Hg concentration and speciation analyses alone can provide. These studies are largely divided into two groups: (i) controlled experiments investigating fractionation of Hg isotopes and refining tools of isotopic analyses, and (ii) studies of natural variations of Hg isotopes. It is now known that Hg isotopes undergo both mass dependent fractionation (MDF; reported as the ratio of mass 202Hg to 198Hg) and mass independent fractionation (MIF), with MIF occurring at odd masses (199Hg, 201Hg) to a larger magnitude and at even masses (200Hg, 204Hg) to a much smaller magnitude. The two types of MIF are controlled by different photochemical processes. The range of isotopic variations of MDF, odd-MIF, and even-MIF are now well documented in a diverse set of environmental samples, and researchers are continuing to explore how the field of Hg isotope biogeochemistry can be further developed and taken to the next level of understanding. One application that has received considerable attention is the use of Hg isotopes to examine the environmental controls on the production and degradation of methylmercury (MeHg), the most toxic and bioaccumulative form of Hg. Since MeHg is efficiently assimilated and biomagnified along food chains, MeHg has the potential to be a robust ecological tracer. In this review, we give an updated overview of the field of Hg isotopes and focus on how Hg isotopes of MeHg can be used to address fundamental ecological questions, including energy transfer across ecosystem interfaces and as a tracer for animal movements.