Experimental evidence for recovery of mercury-contaminated fish populations.

Anthropogenic releases of mercury (Hg)1-3 are a human health issue4 because the potent toxicant methylmercury (MeHg), formed primarily by microbial methylation of inorganic Hg in aquatic ecosystems, bioaccumulates to high concentrations in fish consumed by humans5,6. Predicting the efficacy of Hg pollution controls on fish MeHg concentrations is complex because many factors influence the production and bioaccumulation of MeHg7-9. Here we conducted a 15-year whole-ecosystem, single-factor experiment to determine the magnitude and timing of reductions in fish MeHg concentrations following reductions in Hg additions to a boreal lake and its watershed. During the seven-year addition phase, we applied enriched Hg isotopes to increase local Hg wet deposition rates fivefold. The Hg isotopes became increasingly incorporated into the food web as MeHg, predominantly from additions to the lake because most of those in the watershed remained there. Thereafter, isotopic additions were stopped, resulting in an approximately 100% reduction in Hg loading to the lake. The concentration of labelled MeHg quickly decreased by up to 91% in lower trophic level organisms, initiating rapid decreases of 38-76% of MeHg concentration in large-bodied fish populations in eight years. Although Hg loading from watersheds may not decline in step with lowering deposition rates, this experiment clearly demonstrates that any reduction in Hg loadings to lakes, whether from direct deposition or runoff, will have immediate benefits to fish consumers.

Mercury source changes and food web shifts alter contamination signatures of predatory fish from Lake Michigan.

To understand the impact reduced mercury (Hg) loading and invasive species have had on methylmercury bioaccumulation in predator fish of Lake Michigan, we reconstructed bioaccumulation trends from a fish archive (1978 to 2012). By measuring fish Hg stable isotope ratios, we related temporal changes in Hg concentrations to varying Hg sources. Additionally, dietary tracers were necessary to identify food web influences. Through combined Hg, C, and N stable isotopic analyses, we were able to differentiate between a shift in Hg sources to fish and periods when energetic transitions (from dreissenid mussels) led to the assimilation of contrasting Hg pools (2000 to present). In the late 1980s, lake trout δ202Hg increased (0.4‰) from regulatory reductions in regional Hg emissions. After 2000, C and N isotopes ratios revealed altered food web pathways, resulting in a benthic energetic shift and changes to Hg bioaccumulation. Continued increases in δ202Hg indicate fish are responding to several United States mercury emission mitigation strategies that were initiated circa 1990 and continued through the 2011 promulgation of the Mercury and Air Toxics Standards rule. Unlike archives of sediments, this fish archive tracks Hg sources susceptible to bioaccumulation in Great Lakes fisheries. Analysis reveals that trends in fish Hg concentrations can be substantially affected by shifts in trophic structure and dietary preferences initiated by invasive species in the Great Lakes. This does not diminish the benefits of declining emissions over this period, as fish Hg concentrations would have been higher without these actions.

Enhanced Susceptibility of Methylmercury Bioaccumulation into Seston of the Laurentian Great Lakes.

Mercury concentrations in the Laurentian Great Lakes waters are among the lowest reported in the literature, while game fish concentrations approach consumption advisory limits, particularly in Lakes Superior, Huron, and Michigan, indicating efficient methylmercury transfer from water to game fish. To determine if increased transfer efficiency is evident within the lower food web, we measured (2010-2018) mercury and dissolved organic carbon (DOC) in water, and in size-sieved seston, dietary tracers (carbon and nitrogen isotope ratios), phytoplankton methylmercury bioaccumulation, and methylmercury biomagnification between increasing seston size fractions. We observed consistently low filter-passing methylmercury (<0.010 ng L-1) and comparatively variable DOC (1.1 to 3.4 mg L-1) concentrations. Methylmercury biomagnification factors between size-sieved seston were similar between lakes. Bioaccumulation factors in phytoplankton were among the highest in the literature (log 5.5 to 6.1), exceeding those in oceans, smaller lakes, and streams, and was influenced by DOC. Higher bioaccumulation rates increase the susceptibility of methylmercury accumulation into the food web. Because mercury is dominantly delivered to the Great Lakes through the atmosphere and the biota therein is highly susceptible to methylmercury uptake, we propose that the Laurentian Great Lakes are excellent sentinels to trace the success of efforts to decrease global mercury emissions (e.g., Minamata Treaty) in the future.

Resolving Atmospheric Mercury Loading and Source Trends from Isotopic Records of Remote North American Lake Sediments.

The strongest evidence for anthropogenic alterations to the global mercury (Hg) cycle comes from historical records of mercury deposition preserved in lake sediments. Hg isotopes have added a new dimension to these sedimentary archives, promising additional insights into Hg source apportionment and biogeochemical processing. Presently, most interpretations of historical changes are constrained to a small number of locally contaminated ecosystems. Here, we describe changes in natural Hg isotope records from a suite of dated sediment cores collected from various remote lakes of North America. In nearly all cases, the rise in industrial-use Hg is accompanied by an increase in δ202Hg and Δ199Hg values. These trends can be attributed to large-scale industrial emission of Hg into the atmosphere and are consistent with positive Δ199Hg values measured in modern-day precipitation and modeled increases in δ202Hg values from global emission inventories. Despite similar temporal trends among cores, the baseline isotopic values vary considerably among the different study regions, likely attributable to differences in the fractionation produced in situ as well as differing amounts of atmospherically delivered Hg. Differences among the study lakes in precipitation and watershed size provide an empirical framework for evaluating Hg isotopic signatures and global Hg cycling.

Isolation of methylmercury using distillation and anion-exchange chromatography for isotopic analyses in natural matrices.

The development of mercury (Hg) stable isotope measurements has enhanced the study of Hg sources and transformations in the environment. As a result of the mixing of inorganic Hg (iHg) and methylmercury (MeHg) species within organisms of the aquatic food web, understanding species-specific Hg stable isotopic compositions is of significant importance. The lack of MeHg isotope measurements is due to the analytical difficulty in the separation of the MeHg from the total Hg pool, with only a few methods having been tested over the past decade with varying degrees of success, and only a handful of environmentally relevant measurements. Here, we present a novel anion-exchange resin separation method using AG 1-X4 that further isolates MeHg from the sample matrix, following a distillation pretreatment, in order to obtain ambient MeHg stable isotopic compositions. This method avoids the use of organic reagents, does not require complex instrumentation, and is applicable across matrices. Separation tests across sediment, water, and biotic matrices showed acceptable recoveries (98 ± 5%, n = 54) and reproducible δ202Hg isotope results (2 SDs ≤ 0.15‰) down to 5 ng of MeHg. The measured MeHg pools in natural matrices, such as plankton and sediments, showed large deviations from the non-speciated total Hg measurement, indicating that there is an important isotopic shift during methylation that is not recorded by typical measurements, but is vital in order to assess sources of Hg during bioaccumulation. Graphical abstract.

Factors Affecting Mercury Stable Isotopic Distribution in Piscivorous Fish of the Laurentian Great Lakes.

Identifying the sources of methylmercury (MeHg) and tracing the transformations of mercury (Hg) in the aquatic food web are important components of effective strategies for managing current and legacy Hg sources. In our previous work, we measured stable isotopes of Hg (δ202Hg, Δ199Hg, and Δ200Hg) in the Laurentian Great Lakes and estimated source contributions of Hg to bottom sediment. Here, we identify isotopically distinct Hg signatures for Great Lakes trout ( Salvelinus namaycush) and walleye ( Sander vitreus), driven by both food-web and water-quality characteristics. Fish contain high values for odd-isotope mass independent fractionation (MIF) with averages ranging from 2.50 (western Lake Erie) to 6.18‰ (Lake Superior) in Δ199Hg. The large range in odd-MIF reflects variability in the depth of the euphotic zone, where Hg is most likely incorporated into the food web. Even-isotope MIF (Δ200Hg), a potential tracer for Hg from precipitation, appears both disconnected from lake sedimentary sources and comparable in fish among the five lakes. We suggest that similar to the open ocean, water-column methylation also occurs in the Great Lakes, possibly transforming recently deposited atmospheric Hg deposition. We conclude that the degree of photochemical processing of Hg is controlled by phytoplankton uptake rather than by dissolved organic carbon quantity among lakes.

Stable Mercury Isotopes in Polished Rice (Oryza sativa L.) and Hair from Rice Consumers.

Mercury (Hg) isotopic signatures were characterized in polished rice samples from China, U.S., and Indonesia (n = 45). Hg isotopes were also analyzed in paired hair samples for participants from China (n = 21). For the latter, we also quantified the proportion of methylmercury intake through rice (range: 31-100%), and the weekly servings of fish meals (range: 0-5.6 servings/weekly). For these participants, 29% (n = 6) never ingested fish, 52% (n = 11) ingested fish < twice/weekly, and 19% (n = 4) ingested fish ≥ twice/weekly. In rice and hair, both mass-dependent fractionation (MDF, reported as δ202Hg) and mass-independent fractionation (MIF, reported as Δ199Hg) of Hg isotopes were observed. Compared to rice, hair δ202Hg values were enriched on average (±1 standard deviation) by 1.9 ± 0.61‰, although the range was wide (range: 0.45‰, 3.0‰). Hair Δ199Hg was significantly inversely associated with %methylmercury intake from rice (Spearman's rho = -0.61, p < 0.01, n = 21), i.e., as the proportion of methylmercury intake from rice increased, MIF decreased. Additionally, hair Δ199Hg was significantly higher for participants ingesting fish ≥ twice/weekly compared to those who did not ingest fish or ingested fish < twice/weekly (ANOVA, p < 0.05, n = 21); Overall, results suggest that Hg isotopes (especially MIF) in human hair can be used to distinguish methylmercury intake from rice versus fish.

Production and retention of methylmercury in inundated boreal forest soils.

The Flooded Uplands Dynamics Experiment (FLUDEX) was an ecosystem-scale study examining the production of methylmercury (MeHg) and greenhouse gases from reservoirs constructed on an upland boreal forest landscape in order to quantify their dependence upon carbon stores. We detail the within-reservoir production and storage of MeHg before, during, and nine years after the experiment. The reservoirs were net MeHg producers during the first two years of flooding, and net demethylating systems afterward. During years 1-3, a rapid pulse of MeHg and total Hg was observed in floodwater, followed by substantial increases in MeHg in seston and sediment. Resampling of the dry reservoirs nine years after the experiment ended indicated that organic soil MeHg was still 8 to 52-fold higher than preflood conditions, and averaged 86% of the levels recorded at the end of the third flooding year. Both total Hg and MeHg retention in soil were a strong function of organic carbon content. The time scale of soil MeHg retention may help explain the decadal time lag frequently observed for the decrease of piscivorous fish Hg concentrations in new reservoirs. Predicted extreme precipitation events associated with climate change may serve to make landscapes more susceptible to this process.

Influence of Cladophora-Quagga Mussel Assemblages on Nearshore Methylmercury Production in Lake Michigan.

Recent spread of invasive mussels in Lake Michigan has altered primary productivity in the nearshore zone, resulting in proliferation of filamentous benthic green algae (Cladophora glomerata). In areas of dense Cladophora and quagga mussel (Dreissena bugensis) assemblages, as well as in regions where sloughed Cladophora accumulates, methylmercury (MeHg) production is enhanced. A shoreline transect from a river mouth through waters overlying Cladophora/quagga-rich zones showed that aqueous MeHg concentrations increased, despite river dilution. Cladophora, as primary producers, ranged from 0.6 to 7.5 ng g(-1) MeHg [4-47% of total mercury (Hg) as MeHg], and were higher than MeHg concentrations in offshore-collected seston. Concentrations of MeHg in decaying Cladophora accumulated onshore ranged from 2.6 to 18.0 ng g(-1) MeHg (18-41% as MeHg) and from 0.1 to 3.0 ng g(-1) MeHg (2-21% as MeHg) in deposits of recently sloughed and accumulated Cladophora in a nearshore topographical depression. Relative to offshore open waters, interstitial waters within decaying Cladophora from onshore and nearshore deposits were elevated in MeHg concentration, 1000- and 10-fold, respectively. Percent Hg as MeHg was also elevated (65-75% and 9-19%, respectively for onshore interstitial water and nearshore interstitial water, compared to 0.2-3.3% as MeHg for open water). Quagga mussels collected within growing Cladophora beds in the nearshore zone were significantly higher in MeHg than offshore counterparts. Our combined results suggest that recent changes in nearshore primary production contributes to MeHg production and bioaccumulation in Lake Michigan.

Competition between Dissolved Organic Matter and Freshwater Plankton Control Methylmercury Isotope Fractionation during Uptake and Photochemical Demethylation.

Isotope fractionation related to photochemical reactions and planktonic uptake at the base of the food web is a major uncertainty in the biological application of mercury (Hg) stable isotopes. In freshwater systems, it is unclear how competitive interactions among methylmercury (MeHg), dissolved organic matter (DOM), and phytoplankton govern the magnitude of mass-dependent and mass-independent fractionation. This study investigated how DOM alters rates of planktonic MeHg uptake and photodegradation and corresponding Hg isotope fractionation in the presence of freshwater phytoplankton species, Raphidocelis subcapitata. Outdoor sunlight exposure experiments utilizing R. subcapitata were performed in the presence of different DOM samples using environmentally relevant ratios of MeHg-DOM thiol groups. The extent of Δ199Hg in phytoplankton incubations (2.99‰ St. Louis River HPOA, 1.88‰ Lake Erie HPOA) was lower compared to paired abiotic control experiments (4.29 and 2.86‰, respectively) after ∼30 h of irradiation, resulting from cell shading or other limiting factors reducing the extent of photodemethylation. Although the Δ199Hg/Δ201Hg ratio was uniform across experiments (∼1.4), Δ199Hg/δ202Hg slopes varied dramatically (from -0.96 to 15.4) across incubations with R. subcapitata and DOM. In addition, no evidence of Hg isotope fractionation was observed within R. subcapitata cells. This study provides a refined examination of Hg isotope fractionation markers for key processes occurring in the lower food web prior to bioaccumulation, critical for accurately accounting for the photochemical processing of Hg isotopes across a wide spectrum of freshwater systems.

Using carbon, nitrogen, and mercury isotope values to distinguish mercury sources to Alaskan lake trout.

Lake trout (Salvelinus namaycush), collected from 13 remote lakes located in southwestern Alaska, were analyzed for carbon, nitrogen, and mercury (Hg) stable isotope values to assess the importance of migrating oceanic salmon, volcanic activity, and atmospheric deposition to fish Hg burden. Methylmercury (MeHg) bioaccumulation in phytoplankton (5.0 - 6.9 kg L-1) was also measured to quantify the basal uptake of MeHg to these aquatic food webs. Hg isotope values in lake trout revealed that while the extent of precipitation-delivered Hg was similar across the entire study area, volcanic Hg is likely an important additional source to lake trout in proximate lakes. In contrast, migratory salmon (Oncorhynchus nerka) deliver little MeHg to lake trout directly, although indirect delivery processes via decay could exist. A high level of variability in carbon, nitrogen, and Hg isotope values indicate niche partitioning in lake trout populations within each lake and that a complex suite of ecological interactions is occurring, complicating the conceptually linear assessment of contaminant source to receiving organism. Without connecting energy and contaminant isotope axes, we would not have understood why lake trout from these pristine lakes have highly variable Hg burdens despite consistently low water Hg and comparable age-length dynamics.

Isotopic tracing of mercury sources in estuarine-inner shelf sediments of the East China Sea.

Large river estuarine-inner shelf systems play an important role in the coastal biogeochemical cycling of heavy metals; however, the source-to-sink of mercury (Hg) in these environments remain poorly understood. In this study, the Hg isotopic composition of surface sediments in the Yangtze River Estuary (YRE) and inner shelf of the East China Sea (ECS) were examined to quantitatively track Hg sources in this region. We detected large spatial variation in δ202Hg (-1.88 to -0.29‰) and Δ199Hg (-0.22 to 0.13‰) in sediments of the YRE-ECS inner shelf. The impact of sediment resuspension and transport from the YRE to the inner shelf of the ECS could have little effect on Hg isotopic composition, and the two regions shared similar Hg isotopic composition. An isotope-based triple mixing model further revealed major contributors to sediment Hg from industrial Hg discharge into water (51.8 ± 24.5%), soil Hg from surface runoff (29.2 ± 17.0%), and precipitation-derived atmospheric deposition Hg (19.1 ± 17.5%). The Hg isotopic compositions of the YRE sediments and other local river estuaries were similar to those of direct industrial Hg discharge, indicating that contaminated riverine discharge was the dominant Hg source for estuarine and adjacent shelf areas. Soil Hg delivered through surface runoff was the primary source of Hg to the coastal areas not near large river estuaries, whereas precipitation-derived atmospheric deposition had a greater influence on offshore sediment Hg content. Industrial Hg discharged to rivers had the highest mean depositional flux (35.0 ± 27.3 ng cm-2 yr-1) and mass inventory (25.6 t yr-1), accounting for 77.4% of the total Hg variance. The findings of this study demonstrate that large rivers such as the Yangtze River can supply substantial amounts of industrial Hg to the estuary and adjacent shelf.

Consistent trace element distribution and mercury isotopic signature between a shallow buried volcanic-hosted epithermal gold deposit and its weathered horizon.

Trace elements and Hg isotopic composition were investigated in mineralized rocks, barren rocks, and mineral soils in the Xianfeng prospect, a shallow buried epithermal gold deposit in northeastern China, to understand whether this deposit has left a diagnostic geochemical fingerprint to its weathered horizon. All the rocks and soils display congruent patterns for immobile elements (large ion lithophile elements, high field strength elements, and rare earth elements), which reflect the subduction-related tectonic setting. Both mineralized rocks and soils showed common enrichment of elemental suite As-Ag-Sb-Hg, suggesting that the Xianfeng gold deposit has released these elements into its weathered horizon. Similar mercury isotopic composition was observed between mineralized rocks (δ202Hg: -0.21 ± 0.70‰; Δ199Hg: -0.02 ± 0.12‰; 2SD) and barren rocks (δ202Hg: -0.46 ± 0.48‰; Δ199Hg: 0.00 ± 0.10‰; 2SD), suggesting that mercury in the Xianfeng deposit is mainly derived from the magmatic rocks. Mineralized soils (δ202Hg: -0.44 ± 0.60‰; -0.03 ± 0.14‰; 2SD) and barren soils (δ202Hg: -0.54 ± 0.68‰; Δ199Hg: -0.05 ± 0.14‰; 2SD) displayed congruent Hg isotopic signals to the underlying rocks, suggesting limited Hg isotope fractionation during the release of Hg from ore deposit to soils via weathering. This study reveals evidence of a simple and direct geochemical link between this shallow buried hydrothermal deposit and its weathered horizon, and highlights that the weathering of shallow-buried hydrothermal gold deposits can release a substantial amount of heavy metals (e.g. Hg, As and Sb) to surface soil.

Mercury risk in poultry in the Wanshan Mercury Mine, China.

In this study, total mercury (THg) and methylmercury (MeHg) concentrations in muscles (leg and breast), organs (intestine, heart, stomach, liver) and blood were investigated for backyard chickens, ducks and geese of the Wanshan Mercury Mine, China. THg in poultry meat products range from 7.9 to 3917.1 ng/g, most of which exceeded the Chinese national standard limit for THg in meat (50 ng/g). Elevated MeHg concentrations (0.4-62.8 ng/g) were also observed in meat products, suggesting that poultry meat can be an important human MeHg exposure source. Ducks and geese showed higher Hg levels than chickens. For all poultry species, the highest Hg concentrations were observed in liver (THg: 23.2-3917.1 ng/g; MeHg: 7.1-62.8 ng/g) and blood (THg: 12.3-338.0 ng/g; MeHg: 1.4-17.6 ng/g). We estimated the Hg burdens in chickens (THg: 15.3-238.1 µg; MeHg: 2.2-15.6 µg), ducks (THg: 15.3-238.1 µg; MeHg: 3.5-14.7 µg) and geese (THg: 83.8-93.4 µg; MeHg: 15.4-29.7 µg). To not exceed the daily intake limit for THg (34.2 µg/day) and MeHg (6 µg/day), we suggested that the maximum amount (g) for chicken leg, breast, heart, stomach, intestine, liver, and blood should be 1384, 1498, 2315, 1214, 1081, 257, and 717, respectively; the maximum amount (g) for duck leg, breast, heart, stomach, intestine, liver, and blood should be 750, 1041, 986, 858, 752, 134, and 573, respectively; and the maximum amount (g) for goose leg, breast, heart, stomach, intestine, liver, and blood should be 941, 1051, 1040, 1131, 964, 137, and 562, respectively.

Influences of iron, manganese, and dissolved organic carbon on the hypolimnetic cycling of amended mercury.

The biogeochemical cycling of iron, manganese, sulfide, and dissolved organic carbon were investigated to provide information on the transport and removal processes that control the bioavailability of isotopic mercury amended to a lake. Lake profiles showed a similar trend of hypolimnetic enrichment of Fe, Mn, DOC, sulfide, and the lake spike ((202)Hg, purity 90.8%) and ambient of pools of total mercury (HgT) and methylmercury (MeHg). Hypolimnetic enrichment of Fe and Mn indicated that reductive mobilization occurred primarily at the sediment-water interface and that Fe and Mn oxides were abundant within the sediments prior to the onset of anoxia. A strong relationship (r(2)=0.986, n=15, p<0.001) between filterable Fe and Mn indicated that reduction of Fe and Mn hydrous oxides in the sediments is a common in-lake source of Fe(II) and Mn(II) to the hypolimnion and that a consistent Mn:Fe mass ratio of 0.05 exists in the lake. A strong linear relationship of both the filterable [Fe] (r(2)=0.966, n=15, p<0.001) and [Mn] (r(2)=0.964, n=15, p<0.001) to [DOC] indicated a close linkage of the cycles of Fe and Mn to DOC. Persistence of iron oxides in anoxic environments suggested that DOC was being co-precipitated with Fe oxide and released into solution by the reductive dissolution of the oxide. The relationship between ambient and lake spike HgT (r(2)=0.920, n=27, p<0.001) and MeHg (r(2)=0.967, n=23, p<0.001) indicated that similar biogeochemical processes control the temporal and spatial distribution in the water column. The larger fraction of MeHg in the lake spike compared to the ambient pool in the hypolimnion suggests that lake spike may be more available for methylation. A linear relationship of DOC to both filterable ambient HgT (r(2)=0.406, n=27, p<0.001) and lake spike HgT (r(2)=0.314, n=15, p=0.002) suggest a role of organic matter in Hg transport and cycling. However, a weak relationship between the ambient and lake spike pools of MeHg to DOC indicated that other processes have a major role in controlling the abundance and distribution of MeHg. Our results suggest that Fe and Mn play important roles in the transport and cycling of ambient and spike HgT and MeHg in the hypolimnion, in part through processes linked to the formation and dissolution of organic matter-containing Fe and Mn hydrous oxides particles.

Subsurface sources of methyl mercury to Lake Superior from a wetland-forested watershed.

Identification of sites of methyl mercury (MeHg) production is critical to predicting long-term fate of bioaccumulative Hg in the aquatic environment. During baseflow, when groundwater sources dominate, we observed consistently elevated levels of MeHg (0.1-0.4 ng L(-1)) at the mouth and in several tributaries to the Tahquamenon River in the Lake Superior watershed. MeHg concentrations in groundwater observation wells exceeded 0.6 ng L(-1) in a coniferous catchment with highly conductive sandy surficial deposits. Furthermore, we identified MeHg concentrations as high as 12 ng L(-1) in the hyporheic zone of East Creek, a tributary to the Tahquamenon. This study confirms the importance of groundwater as a source of MeHg in watersheds of the Great Lakes. Indirect groundwater discharge represents a major component of flow in rivers of the basin, further emphasizing the need to better understand subsurface MeHg production and transport processes when modeling watershed responses and biogeochemical fate of Hg in the Great Lakes.

Speciation of aqueous methylmercury influences uptake by a freshwater alga (Selenastrum capricornutum).

Uptake of methylmercury (MeHg) by the alga Selenastrum capricornutum was measured in freshwater batch culture bioassays. The concentration of MeHg in the alga increased rapidly (within 15 min), reached a maximum by 6 h, and then declined because of growth dilution. The alga's rapid growth rate (doubling time, approximately 10 h) contributed to the importance of growth dilution. Conditional first-order rate constants were calculated for uptake (k1 = 6.95 x 10(-9) L/cell/h) and growth (kG = 0.07/h). A competitive synthetic ligand, disodium ethylenediaminetetra-acetate, formed strong complexes with MeHg and reduced MeHg uptake, consistent with the biotic ligand model. A conditional equilibrium formation constant (K) for the MeHg-algae complex was estimated to be approximately 10(16) and was used to model the influence of natural ligands on MeHg bioavailability. Model results suggested MeHg would be most bioavailable at concentrations of dissolved organic matter (DOM) less than 10 mg/L and increasingly unavailable at higher DOM concentrations for the specific humic acid modeled. Similarly, at molar concentrations of sulfide (and, possibly, metal-sulfide clusters) equal to approximately half the MeHg concentration, MeHg was predicted to be unavailable to algae because of the formation of strong 2:1 MeHg-sulfide complexes.

Historical Records of Mercury Stable Isotopes in Sediments of Tibetan Lakes.

The Tibetan Plateau (TP), known as the "Third Pole", is a critical zone for atmospheric mercury (Hg) deposition. Increasing anthropogenic activities in the globe leads to environmental changes, which may affect the loading, transport and deposition of Hg in the environment. However, the deposition history and geochemical cycling of Hg in the TP is still uncertain. Our records of Hg and Hg isotopes in sediment profiles of the two largest lakes in the TP, Lake Qinghai and Nam Co, show increased Hg influx since last century, with the maximum Hg influx enrichment ratios of 5.4 and 3.5 in Lake Qinghai and Nam Co, respectively. Shifts in negative δ (202)Hg in Lake Qinghai (-4.55 to -3.15‰) and Nam Co (-5.04 to -2.16‰) indicate increased atmospheric Hg deposition through rainfall, vegetation and runoff of soils. Mass independent fractionation of both even-Hg (∆ (200)Hg: +0.05 to +0.10‰) and odd-Hg (∆ (199)Hg: +0.12 to +0.31‰) isotopes were observed. Positive Δ (200)Hg suggest high proportion of precipitation-derived Hg in the TP, whereas the positive Δ (199)Hg results from Hg(II) photo-reduction. Both lakes show increasing Δ (199)Hg since the 1900 s, and we conclude that with the decrease of ice duration, Hg(II) photo-reduction may have been accelerated in these TP lakes.

Mercury Isotopes as Proxies to Identify Sources and Environmental Impacts of Mercury in Sphalerites.

During the past few years, evidence of mass independent fractionation (MIF) for mercury (Hg) isotopes have been reported in the Earth's surface reservoirs, mainly assumed to be formed during photochemical processes. However, the magnitude of Hg-MIF in interior pools of the crust is largely unknown. Here, we reported significant variation in Hg-MIF signature (Δ(199)Hg: -0.24 ~ + 0.18‰) in sphalerites collected from 102 zinc (Zn) deposits in China, indicating that Hg-MIF can be recorded into the Earth's crust during geological recycling of crustal material. Changing magnitudes of Hg-MIF signals were observed in Zn deposits with different formations, evidence that Hg isotopes (especially Hg-MIF) can be a useful tracer to identify sources (syngenetic and epigenetic) of Hg in mineral deposits. The average isotopic composition in studied sphalerites (δ(202)Hg average: -0.58‰; Δ(199)Hg average: +0.03‰) may be used to fingerprint Zn smelting activities, one of the largest global Hg emission sources.

Application of ultrafiltration and stable isotopic amendments to field studies of mercury partitioning to filterable carbon in lake water and overland runoff.

Results from pilot studies on colloidal phase transport of newly deposited mercury in lake water and overland runoff demonstrate that the combination of ultrafiltration, and stable isotope amendment techniques is a viable tool for the study of mercury partitioning to filterable carbon. Ultrafiltration mass balance calculations were generally excellent, averaging 97.3, 96.1 and 99.8% for dissolved organic carbon (DOC), total mercury (Hg(T)), and methylmercury (MeHg), respectively. Sub nanogram per liter quantities of isotope were measurable, and the observed phase distribution from replicate ultrafiltration separations on lake water agreed within 20%. We believe the data presented here are the first published colloidal phase mercury data on lake water and overland runoff from uncontaminated sites. Initial results from pilot-scale lake amendment experiments indicate that the choice of matrix used to dissolve the isotope did not affect the initial phase distribution of the added mercury in the lake. In addition there was anecdotal evidence that native MeHg was either recently produced in the system, or at a minimum, that this 'old' MeHg partitions to the same subset of DOC that binds the amended mercury. Initial results from pilot-scale overland runoff experiments indicate that less than 20% of newly deposited mercury was transported in the filterable fraction (<0.7 microm). There is some indication of colloidal phase enrichment of mercury in runoff compared to the phase distribution of organic carbon, but the mechanism of this enrichment is unclear. The phase distribution of newly deposited mercury can differ from that of organic carbon and native mercury, suggesting that the quality of the carbon (available ligands), not the quantity of carbon, regulates partitioning. Further characterization of DOC is needed to clarify the underlying mechanisms.