Higher mass-independent isotope fractionation of methylmercury in the pelagic food web of Lake Baikal (Russia)

Mercury undergoes several transformations that influence its stable isotope composition during a number of environmental and biological processes. Measurements of Hg isotopic mass-dependent (MDF) and mass-independent fractionation (MIF) in food webs may therefore help to identify major sources and processes leading to significant bioaccumulation of methylmercury (MeHg). In this work, δ(13)C, δ(15)N, concentration of Hg species (MeHg, inorganic Hg), and stable isotopic composition of Hg were determined at different trophic levels of the remote and pristine Lake Baikal ecosystem. Muscle of seals and different fish as well as amphipods, zooplankton, and phytoplankton were specifically investigated. MDF during trophic transfer of MeHg leading to enrichment of heavier isotopes in the predators was clearly established by δ(202)Hg measurements in the pelagic prey-predator system (carnivorous sculpins and top-predator seals). Despite the low concentrations of Hg in the ecosystem, the pelagic food web reveals very high MIF Δ(199)Hg (3.15-6.65‰) in comparison to coastal fish (0.26-1.65‰) and most previous studies in aquatic organisms. Trophic transfer does not influence MIF signature since similar Δ(199)Hg was observed in sculpins (4.59 ± 0.55‰) and seal muscles (4.62 ± 0.60‰). The MIF is suggested to be mainly controlled by specific physical and biogeochemical characteristics of the water column. The higher level of MIF in pelagic fish of Lake Baikal is mainly due to the bioaccumulation of residual MeHg that is efficiently turned over and photodemethylated in deep oligotrophic and stationary (i.e., long residence time) freshwater columns.     

Absence of fractionation of mercury isotopes during trophic transfer of methylmercury to freshwater fish in captivity

We performed two controlled experiments to determine the amount of mass-dependent and mass-independent fractionation (MDF and MIF) of methylmercury (MeHg) during trophic transfer into fish. In experiment 1, juvenile yellow perch (Perca flavescens) were raised in captivity on commercial food pellets and then their diet was either maintained on unamended food pellets (0.1 μg/g MeHg) or was switched to food pellets with 1.0 μg/g or 4.0 μg/g of added MeHg, for a period of 2 months. The difference in δ(202)Hg (MDF) and Δ(199)Hg (MIF) between fish tissues and food pellets with added MeHg was within the analytical uncertainty (δ(202)Hg, 0.07 ‰; Δ(199)Hg, 0.06 ‰), indicating no isotope fractionation. In experiment 2, lake trout (Salvelinus namaycush) were raised in captivity on food pellets and then shifted to a diet of bloater (Coregonus hoyi) for 6 months. The δ(202)Hg and Δ(199)Hg of the lake trout equaled the isotopic composition of the bloater after 6 months, reflecting reequilibration of the Hg isotopic composition of the fish to new food sources and a lack of isotope fractionation during trophic transfer. We suggest that the stable Hg isotope ratios in fish can be used to trace environmental sources of Hg in aquatic ecosystems.     

Mercury stable isotopes in seabird eggs reflect a gradient from terrestrial geogenic to oceanic mercury reservoirs

Elevated mercury concentrations ([Hg]) were found in Alaskan murre (Uria spp.) eggs from the coastal embayment of Norton Sound relative to insular colonies in the northern Bering Sea-Bering Strait region. Stable isotopes of Hg, carbon, and nitrogen were measured in the eggs to investigate the source of this enrichment. Lower δ(13)C values in Norton Sound eggs (-23.3‰ to -20.0‰) relative to eggs from more oceanic colonies (-20.9‰ to -18.7‰) indicated that a significant terrestrial carbon source was associated with the elevated [Hg] in Norton Sound, implicating the Yukon River and smaller Seward Peninsula watersheds as the likely Hg source. The increasing [Hg] gradient extending inshore was accompanied by strong decreasing gradients of δ(202)Hg and Δ(199)Hg in eggs, indicating lower degrees of mass-dependent (MDF) and mass-independent Hg fractionation (MIF) (respectively) in the Norton Sound food web. Negative or zero MDF and MIF signatures are typical of geological Hg sources, which suggests murres in Norton Sound integrated Hg from a more recent geological origin that has experienced a relatively limited extent of aquatic fractionation relative to more oceanic colonies. The association of low δ(202)Hg and Δ(199)Hg with elevated [Hg] and terrestrial δ(13)C values suggested that Hg stable isotopes in murre eggs effectively differentiated terrestrial/geogenic Hg sources from oceanic reservoirs.     

Investigation of local mercury deposition from a coal-fired power plant using mercury isotopes

Coal combustion accounts for approximately two-thirds of global anthropogenic mercury (Hg) emissions. Enhanced deposition of Hg can occur close to coal-fired utility boilers (CFUBs), but it is difficult to link specific point sources with local deposition. Measurement of Hg stable isotope ratios in precipitation holds promise as a tool to assist in the identification of local Hg deposition related to anthropogenic emissions. We collected daily event precipitation samples in close proximity to a large CFUB in Crystal River, Florida. Precipitation samples collected in Crystal River were isotopically distinct and displayed large negative δ(202)Hg values (mean = -2.56‰, 1 SD = 1.10‰, n = 28). In contrast, precipitation samples collected at other sites in FL that were not greatly impacted by local coal combustion were characterized by δ(202)Hg values close to 0‰ (mean = 0.07‰, 1 SD = 0.17‰, n = 13). These results indicate that, depending on factors such as powdered coal isotopic composition and efficiency of Hg removal from flue gas, Hg deposited near CFUBs can be isotopically distinct. As this tool is further refined through future studies, Hg stable isotopes may eventually be used to quantify local deposition of Hg emitted by large CFUBs.     

Connecting breeding and wintering habitats of migratory piscivorous birds: implications for tracking contaminants (Hg) using multiple stable isotopes

Contaminant concentrations in migratory species are complicated by differential accumulation and elimination among geographically separated biomes. Double-crested cormorants ( Phalacrocorax auritus ) are used as monitors of Hg in North America; however, migration from northern breeding colonies to southern marine, freshwater, and aquaculture systems exposes individuals to spatiotemporal variations in contaminant uptake. We used stable isotopes (δ(34)S, δ(13)C, δ(15)N, δ(2)H) in primary feathers and a combined Bayesian assignment and isotopic threshold model to identify feather origins and the potential winter use of aquaculture (δ(34)S < 10‰, δ(13)C > -14‰), freshwater (δ(34)S < 10‰, δ(13)C < -20‰), and marine habitats (δ(34)S > 10‰). This approach allowed us to contrast body burden Hg derived from the breeding and wintering grounds, as well as from marine and freshwater habitats. We found feathers grown on Lake Winnipeg had greater Hg concentrations (mean = 4.26 ± 1.47 μg/g fresh weight; n = 20) than winter-grown feathers (3.19 ± 1.64 μg/g; n = 19), but Hg in winter-grown feathers was not related to any specific habitat. Isotopic assays of tissues of migratory birds allowed the source and degree of contaminant exposure to be identified throughout the annual cycle.     

Hg speciation and stable isotope signatures in human hair as a tracer for dietary and occupational exposure to mercury

Exposure of humans and wildlife to various inorganic and organometallic forms of mercury (Hg) may induce adverse health effects. While human populations in developed countries are mainly exposed to marine fish monomethylmercury (MMHg), this is not necessarily the case for developing countries and diverse indigenous people. Identification of Hg exposure sources from biomonitor media such as urine or hair would be useful in combating exposure. Here we report on the Hg stable isotope signatures and Hg speciation in human hair across different gold miner, indigenous and urban populations in Bolivia and France. We found evidence for both mass-dependent isotope fractionation (MDF) and mass-independent isotope fractionation (MIF) in all hair samples. Three limiting cases of dominant exposure to inorganic Hg (IHg), freshwater fish MMHg, and marine fish MMHg sources are used to define approximate Hg isotope source signatures. Knowing the source signatures, we then estimated Hg exposure sources for the Bolivian gold miner populations. Modeled IHg levels in hair correspond well to measured IHg concentrations (R = 0.9), demonstrating that IHg exposure sources to gold miners can be monitored in hair samples following either its chemical speciation or isotopic composition. Different MMHg and inorganic exposure levels among gold miners appear to correspond to living and working conditions, including proximity to small towns, and artisanal vs large scale mining activity.     

Stable carbon isotope ratio analysis of anhydrosugars in biomass burning aerosol particles from source samples

A new method for stable carbon isotope ratio analysis of anhydrosugars from biomass burning aerosol particle source filter samples was developed by employing Thermal Desorption--2 Dimensional Gas Chromatography--Isotope Ratio Mass Spectrometry (TD-2DGC-IRMS). Compound specific isotopic measurements of levoglucosan, mannosan, and galactosan performed by TD-2DGC-IRMS in a standard mixture show good agreement with isotopic measurements of the bulk anhydrosugars, carried out by Elemental Analyzer--Isotope Ratio Mass Spectrometry (EA-IRMS). The established method was applied to determine the isotope ratios of levoglucosan, mannosan, and galactosan from source samples collected during combustion of hard wood, softwood, and crop residues. δ(13)C values of levoglucosan were found to vary between -25.6 and -22.2‰, being higher in the case of softwood. Mannosan and galactosan were detected only in the softwood samples showing isotope ratios of -23.5‰ (mannosan) and -25.7‰ (galactosan). The isotopic composition of holocellulose in the plant material used for combustion experiments was determined with δ(13)C values between -28.5 and -23.7‰. The difference in δ(13)C of levoglucosan in biomass burning aerosol particles compared to the parent fuel holocellulose was found to be -1.89 (±0.37)‰ for the investigated biomass fuels. Compound specific δ(13)C measurements of anhydrosugars should contribute to an improved source apportionment.     

Distribution and fluxes of total and methylmercury in Lake Superior

Despite the importance and size of Lake Superior, little is known regarding the biogeochemical cycling or distribution of mercury within its waters. We present the results from two research cruises on total Hg (HgT) and methylmercury (MeHg) distributions in aqueous and particulate phases, and in offshore sediments. Open waters of Lake Superior are similar in HgT content to Lakes Michigan and Ontario (sub-ng L(-1)), whereas MeHg was only 1% of HgT. Seasonality in aqueous HgT distribution was observed, most likely from tributary inputs during Spring snowmelt. Suspended particles were enriched in MeHg relative to water and surficial sediments, suggesting enhanced particle partitioning followed by demethylation in the water column and in surface sediments. Distribution coefficients for mercury in surficial sediments were lower than those in suspended material, likely due to remineralization. Preliminary estimates of mass balance indicate that air-water exchange processes such as evasion and wet deposition dominate the HgT budget, due to the basin's relatively small watershed area relative to lake area. In contrast, methylmercury cycling within Lake Superior is influenced more strongly by watershed sources, as well as by sedimentary sources and photodemethylation. The Hg cycle in Lake Superior is unique in that it is more similar in many aspects to that in marine systems than in small lakes, where management data for freshwaters typically originates.     

Online stable isotope analysis of dissolved organic carbon size classes using size exclusion chromatography coupled to an isotope ratio mass spectrometer

Stable isotopic content of dissolved organic carbon (δ(13)C-DOC) provides valuable information on its origin and fate. In an attempt to get additional insights into DOC cycling, we developed a method for δ(13)C measurement of DOC size classes by coupling high-performance liquid chromatography (HPLC)-size exclusion chromatography (SEC) to online isotope ratio mass spectrometry (IRMS). This represents a significant methodological contribution to DOC research. The interface was evaluated using various organic compounds, thoroughly tested with soil-water from a C3-C4 vegetation change experiment, and also applied to riverine and marine DOC. δ(13)C analysis of standard compounds resulted in excellent analytical precision (≤0.3‰). Chromatography resolved soil DOC into 3 fractions: high molecular weight (HMW; 0.4-10 kDa), low molecular weight (LMW; 50-400 Da), and retained (R) fraction. Sample reproducibility for measurement of δ(13)C-DOC size classes was ±0.25‰ for HMW fraction, ± 0.54‰ for LMW fraction, and ±1.3‰ for R fraction. The greater variance in δ(13)C values of the latter fractions was due to their lower concentrations. The limit of quantification (SD ≤0.6‰) for each size fraction measured as a peak is 200 ng C (2 mg C/L). δ(13)C-DOC values obtained in SEC mode correlated significantly with those obtained without column in the μEA mode (p < 0.001, intercept 0.17‰), which rules out SEC-associated isotopic effects or DOC loss. In the vegetation change experiment, fractions revealed a clear trend in plant contribution to DOC; those in deeper soils and smaller size fractions had less plant material. It was also demonstrated that the technique can be successfully applied to marine and riverine DOC without further sample pretreatment.     

Mercury in soils, lakes, and fish in Voyageurs National Park (Minnesota): importance of atmospheric deposition and ecosystem factors

Concentrations of methylmercury in game fish from many interior lakes in Voyageurs National Park (MN, U.S.A.) substantially exceed criteria for the protection of human health. We assessed the importance of atmospheric and geologic sources of mercuryto interior lakes and watersheds within the Park and identified ecosystem factors associated with variation in methylmercury contamination of lacustrine food webs. Geologic sources of mercury were small, based on analyses of underlying bedrock and C-horizon soils, and nearly all mercury in the 0- and A-horizon soils was derived from atmospheric deposition. Analyses of dated sediment cores from five lakes showed that most (63% +/- 13%) of the mercury accumulated in lake sediments during the 1900s was from anthropogenic sources. Contamination of food webs was assessed by analysis of whole, 1-year-old yellow perch (Perca flavescens), a regionally important prey fish. The concentrations of total mercury in yellow perch and of methylmercury in lake water varied substantially among lakes, reflecting the influence of ecosystem processes and variables that affect the microbial production and abundance of methylmercury. Models developed with the information-theoretic approach (Akaike Information Criteria) identified lake water pH, dissolved sulfate, and total organic carbon (an indicator of wetland influence) as factors influencing methylmercury concentrations in lake water and fish. We conclude that nearly all of the mercury in fish in this seemingly pristine     

Contribution of coexisting sulfate and iron reducing bacteria to methylmercury production in freshwater river sediments

We investigated microbial methylmercury (CH(3)Hg) production in sediments from the South River (SR), VA, an ecosystem contaminated with industrial mercury (Hg). Potential Hg methylation rates in samples collected at nine sites were low in late spring and significantly higher in late summer. Demethylation of (14)CH(3)Hg was dominated by (14)CH(4) production in spring, but switched to producing mostly (14)CO(2) in the summer. Fine-grained sediments originating from the erosion of river banks had the highest CH(3)Hg concentrations and were potential hot spots for both methylation and demethylation activities. Sequencing of 16S rRNA genes of cDNA recovered from sediment RNA extracts indicated that at least three groups of sulfate-reducing bacteria (SRB) and one group of iron-reducing bacteria (IRB), potential Hg methylators, were active in SR sediments. SRB were confirmed as a methylating guild by amendment experiments showing significant sulfate stimulation and molybdate inhibition of methylation in SR sediments. The addition of low levels of amorphous iron(III) oxyhydroxide significantly stimulated methylation rates, suggesting a role for IRB in CH(3)Hg synthesis. Overall, our studies suggest that coexisting SRB and IRB populations in river sediments contribute to Hg methylation, possibly by temporally and spatially separated processes.     

Evaluation of stable isotope tracing for ZnO nanomaterials--new constraints from high precision isotope analyses and modeling

This contribution evaluates two possible routes of stable isotope tracing for ZnO nanomaterials. For this we carried out the first high precision Zn isotope analyses of commercially available ZnO nanomaterials, to investigate whether such materials exhibit isotope fractionations that can be exploited for tracing purposes. These measurements revealed Zn isotopic compositions (of δ(66/64)Zn = +0.28 to -0.31‰ relative to JMC Lyon Zn) that are indistinguishable from "normal" natural and anthropogenic Zn in environmental samples. Stable isotope tracing therefore requires the application of purpose-made isotopically enriched ZnO nanoparticles. A detailed evaluation identified the most suitable and cost-effective labeling isotopes for different analytical requirements and techniques. It is shown that, using relatively inexpensive (68)Zn for labeling, ZnO nanoparticles can be reliably detected in natural samples with a Zn background of 100 μg/g at concentrations as low as about 5 ng/g, if the isotopic tracing analyses are carried out by high precision mass spectrometry. Stable isotope tracing may also be able to differentiate between the uptake by organisms of particulate ZnO and Zn(2+) ions from the dissolution of nanoparticles.     

Biotic and abiotic pathways of phosphorus cycling in minerals and sediments: insights from oxygen isotope ratios in phosphate

A key question to address in the development of oxygen isotope ratios in phosphate (δ(18)O(p)) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here, we present experimental results aimed at understanding the biotic and abiotic pathways of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of sedimentary phosphate phases by Escherichia coli and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction of phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (<50 h) due to efficient O-isotope exchange (between O in PO(4) and O in water; that is, actual breaking and reforming of P-O bonds) (biotic pathway). The difference in isotopic composition between newly equilibrated aqueous and residual sorbed phosphate groups promoted the ion exchange (analogous to isotopic mixing) of intact phosphate ions (abiotic pathway) so that this difference gradually became negligible. In sediment containing different P phases, E. coli extracted loosely sorbed phosphate first, whereas M. aquaeolei preferred Fe-oxide-bound phosphate. The presence of bacteria always imprinted a biotic isotopic signature on the P phase that was taken up and cycled. For example, the δ(18)O(p) value of loosely sorbed phosphate shifted gradually toward equilibrium isotopic composition. The δ(18)O(p) value of Fe-oxide-bound phosphate, however, showed only slight changes initially but, when new Fe-oxides were formed, coprecipitated/occluded phosphate retained δ(18)O values of the aqueous phosphate at the time of formation of new Fe oxides. Concentrations and isotopic compositions of authigenic and detrital phosphates did not change, suggesting that these phosphate phases were not utilized by bacteria. These findings support burgeoning applications of δ(18)O(p) as a tracer of phosphorus cycling in sediments, soils, and aquatic environments and as an indicator of paleo- environmental conditions.     

Historical variations in the stable isotope composition of mercury in Arctic lake sediments

The stable isotope composition of mercury (Hg) in a dated core from the anoxic zone of a saline, meromictic Arctic lake was found to vary as a complex function of the age and chemical composition of the sediment. Throughout the stratigraphic sequence, which spans the years 1899-1997, the ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg, and 204Hg/202Hg expressed as delta-values (per mil deviations relative to a standard) reveal enrichment in 198Hg, 199Hg, 200Hg, and 201Hg, with depletion in 204Hg, the degree of enrichment varying inversely with atomic mass. A plot of delta198Hg, delta199Hg, delta200Hg, and delta201Hg against depth gave parallel profiles characterized by large, regular undulations superimposed on an overall trend toward increase with depth (i.e. age), and the delta204Hg profile is a mirror image of them. The delta198Hg, delta199Hg, delta200Hg, and delta201Hg values of the oldest (1899-1929) strata vary inversely with NH2OH.HCl/HNO3-extractable manganese concentration, but those of the youngest (1963-1997) strata give a positive correlation; intermediate (1936-1956) strata show no correlation and negligible variation in delta-values, possibly signifying a transition phase in which the two opposite trends offset each other. The delta-values show similar but weaker relationships with organic carbon. The results strongly suggest fractionation of Hg isotopes by microbial activities linked to oxidation-reduction reactions in the lake, although effects of isotopic signatures indicative of the sources of the Hg have not been ruled out. The radical change in the nature of the relationship between 6-values and sediment chemistry over time may reflect environmental and biotic changes that altered the isotope-fractionating processes. These findings imply that variations in the isotopic makeup of Hg, together with related physical, chemical, and biological data, could yield important new information about the biogeochemical cycle of Hg.     

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.     

Deposition and cycling of sulfur controls mercury accumulation in Isle Royale fish

Mercury contamination of fish is a global problem. Consumption of contaminated fish is the primary route of methylmercury exposure in humans and is detrimental to health. Newly mandated reductions in anthropogenic mercury emissions aim to reduce atmospheric mercury deposition and thus mercury concentrations in fish. However, factors other than mercury deposition are important for mercury bioaccumulation in fish. In the lakes of Isle Royale, U.S.A., reduced rates of sulfate deposition since the Clean Air Act of 1970 have caused mercury concentrations in fish to decline to levels that are safe for human consumption, even without a discernible decrease in mercury deposition. Therefore, reductions in anthropogenic sulfur emissions may provide a synergistic solution to the mercury problem in sulfate-limited freshwaters.     

Level and degradation of Deepwater Horizon spilled oil in coastal marsh sediments and pore-water

This research investigates the level and degradation of oil at ten selected Gulf saltmarsh sites months after the 2010 BP Macondo-1 well oil spill. Very high levels (10-28%) of organic carbon within the heavily oiled sediments are clearly distinguished from those in pristine sediments (<3%). Dissolved organic carbon in contaminated pore-waters, ranging up to hundreds of mg/kg, are 1 to 2 orders of magnitude higher than those at pristine sites. Heavily oiled sediments are characterized by very high sulfide concentrations (up to 80 mg/kg) and abundance of sulfate reducing bacteria. Geochemical biomarkers and stable carbon isotope analyses fingerprint the presence of oils in sediments. Ratios of selected parameters calculated from the gas chromatograph spectra are in a remarkable narrow range among spilled oils and initial BP crude. At oiled sites dominated by C(4) plants, δ(13)C values of sediments (-20.8 ± 2.0‰) have been shifted significantly lower compared to marsh plants (-14.8 ± 0.6‰) due to the inflow of isotopically lighter oil (-27 ± 0.2‰). Our results show that (1) lighter compounds of oil are quickly degraded by microbes while the heavier fractions of oil still remain and (2) higher inputs of organic matter from the oil spill enhance the key microbial processes associated with sulfate reducing bacteria.     

Methylmercury in freshwater fish linked to atmospheric mercury deposition

A connection between accumulation of methylmercury (MeHg) in wild fish populations and atmospheric mercury deposition has not been made. Large databases for both MeHg in fish and atmospheric mercury deposition have been assimilated from monitoring efforts spanning the contiguous United States. Here, we compare results of these data sets and show that state-wide average concentrations of MeHg in a cosmopolitan freshwater fish, the largemouth bass Micropterus salmoides, are related positively to wet atmospheric Hg fluxes among most of the 25 states that are analyzed, which span a 5-fold range in Hg deposition. Differences in largemouth bass MeHg concentrations among states are unrelated to average precipitation depth, wet atmospheric acid deposition, or interstate variations in the type of water body (river, lake, reservoir) from which the fish were sampled. There are modest correlations between MeHg in bass and surface water pH, temperature, and wet atmospheric deposition of sulfate. However, when fish and atmospheric mercury results are combined at the state level, wet atmospheric Hg deposition accounts for about two-thirds of the variation in bass MeHg among most states, and stepwise multiple regression analysis reveals thatthese variables do not improve the linear model significantly. This suggests the accumulation of MeHg in wild fish populations is linked to atmospheric Hg loadings, two-thirds of which are estimated to be from anthropogenic sources.