[en] High-precision measurements of natural variations in the stable isotopic composition of mercury show great promise as a new tracer of mercury sources and chemical transformations in the environment. We strongly suggest that all laboratories adopt a common means of data correction, standardization, and nomenclature in order to ensure that data from various laboratories can be easily evaluated and compared. We make suggestions for mass bias correction, reporting of mass-dependent and mass-independent isotope variations, and a standard protocol for reporting analytical uncertainties. We also present our measured values for isotope ratios in several mercury standard solutions. (orig.)

[en] Highlights: • A small catchment lake preserves mercury isotopic signatures in sediments. • Atmospheric mercury deposition has increased 4-fold since 1850. • MDF and odd-MIF increase since 1850, reflecting increased photochemical reduction. -- Abstract: Mercury (Hg) deposition from the atmosphere has increased dramatically since 1850 and Hg isotope records in lake sediments can be used to identify changes in the sources and cycling of Hg. We collected a sediment core from a remote lake (Lost Lake, Wyoming, USA) and measured vertical variation of Hg concentration and isotopic composition as well as ²¹⁰Pb and ¹³⁷Cs activities to establish a chronology. We also analyzed vegetation and soil samples from the watershed which has a small ratio of watershed area to lake surface area (2.06). The Hg flux remains constant from ~1350 to 1850 before increasing steadily to modern values that are approximately four times pre-1850 values. The modern Hg isotopic composition preserved in the sediments is distinct from the Hg isotopic composition of pre-1850 samples with both δ²⁰²Hg and Δ¹⁹⁹Hg becoming progressively more positive through time, with shifts of +0.37‰ and +0.23‰ respectively. To explain temporal changes in δ²⁰²Hg, Δ¹⁹⁹Hg, and Hg concentration in the core segments, we estimated a present-day atmospheric endmember based on precipitation and snow samples collected near Lost Lake. The observed change in Hg isotopic values through time cannot be explained solely by addition of anthropogenic Hg with the isotopic composition that has been estimated by others for global anthropogenic emissions. Instead, the isotope variation suggests that the relative importance of redox transformations, whether in the atmosphere, within the lake, or both, have changed since 1850.

[en] There is a well documented accumulation of mercury in fish to concentrations of concern for human consumption. Variation in fish Hg burden between lakes is often high and may result from differences in Hg transfer through lower levels of the food web where mercury is bioconcentrated to phytoplankton and transferred to herbivorous zooplankton. Prior research derived patterns of mercury accumulation in freshwater invertebrates from field collected animals. This study provides results from controlled mesocosm experiments comparing the effects of zooplankton composition, algal abundance, and the chemical speciation of mercury on the ability of zooplankton to accumulate mercury from phytoplankton and transfer that mercury to planktivores. Experiments were conducted in 550-L mesocosms across a gradient of algal densities manipulated by inorganic nutrient additions. Enriched, stable isotopes of organic (CH₃²⁰⁰HgCl) and inorganic (²⁰¹HgCl₂) mercury were added to mesocosms and their concentrations measured in water, seston, and three common zooplankton species. After 2 weeks, monomethylmercury (MMHg) concentrations were two to three times lower in the two copepod species, Leptodiaptomus minutus and Mesocyclops edax than in the cladoceran, Daphnia mendotae. All three zooplankton species had higher MMHg concentrations in mesocosms with low versus high initial algal abundance. However, despite higher concentrations of inorganic mercury (Hg_I) in seston from low nutrient mesocosms, there were no significant differences in the Hg_I accumulated by zooplankton across nutrient treatments. Bioaccumulation factors for MMHg in the plankton were similar to those calculated for plankton in natural lakes and a four-compartment (aqueous, seston, macrozooplankton, and periphyton/sediments) mass balance model after 21 days accounted for ∼18% of the CH₃²⁰⁰Hg and ∼33% of the ²⁰¹Hg added. Results from our experiments corroborate results from field studies and suggest the importance of particular zooplankton herbivores (e.g., Daphnia) in the transfer of Hg to higher trophic levels in aquatic food webs

[en] Highlights: • Contrasting atmospheric processes control the Hg isotopic composition in snow. • Polar vortex snow progresses towards more negative odd-MIF when aged in sunlight. • Photoreduction of Hg(II) drives odd-MIF in mid-latitude snow. • Isotopic analysis of snowmelt is important for ecosystem Hg source identification. Atmospheric deposition of mercury (Hg) to terrestrial and aquatic ecosystems has significant implications for human and animal exposure. Measurements of Hg isotopic composition can be utilized to trace sources of Hg, but outside of the Arctic there has been little Hg isotopic characterization of snow. To better understand deposition pathways at mid-latitudes, five time series of snowfall were collected at two sites (Dexter and Pellston, Michigan, USA) to investigate the Hg isotopic composition of snowfall, how it changes after deposition, and how it compares to rain. The Hg isotopic composition of a subset of fresh snow samples revealed the influence of reactive surface uptake of atmospheric Hg(0). The first time series collected at Dexter occurred during a polar vortex, demonstrating Hg isotopic fractionation dynamics similar to those in Arctic snow, with increasingly negative Δ¹⁹⁹Hg as snow aged with exposure to sunlight. All other time series revealed an increase in Δ¹⁹⁹Hg as snow aged, with values reaching up to 3.5‰. This characterization of Hg isotopes in snow suggests a strong influence of oxidants and binding ligands in snow that may mediate Hg isotope fractionation. Additionally, isotopic characterization of Hg in snow deposited to natural ecosystems at mid-latitudes allows for better understanding of atmospheric mercury sources that are deposited to lakes and forests and that may become available for methylation and transfer to food webs.

[en] Highlights: • T-Hg, MMHg, and Hg isotopes were determined in Gulf of Mexico deep marine sediments. • Levels of mass independent fractionation of Hg isotopes varied from coastal sediments. • Levels of the MMHg were only slightly elevated at the cold seep site. • Cold seeps do not appear to be significant sources of MMHg to Gulf of Mexico waters. -- Abstract: Total-Hg, monomethylmercury (MMHg), and mercury isotopic composition was determined in sediment from a cold seep and background sites in the northern Gulf of Mexico (nGoM). Total-Hg averaged 50 ng/g (n = 28), ranged from 31 to 67 ng/g, and decreased with depth (0–15 cm). MMHg averaged 0.91 ng/g (n = 18), and ranged from 0.2 to 1.9 ng/g. There was no significant difference for total-Hg or MMHg between cold seep and background sites. δ²⁰²Hg ranged from −0.5 to −0.8‰ and becomes more negative with depth (r = 0.989). Mass independent fractionation (Δ¹⁹⁹Hg) was small but consistently positive (0.04–0.12‰); there was no difference between cold seeps (Δ¹⁹⁹Hg = +0.09 ± 0.03; n = 7, 1SD) and background sites (Δ¹⁹⁹Hg = +0.07 ± 0.02; n = 5, 1SD). This suggests that releases of hydrocarbons at the cold seep do not significantly alter Hg levels, and that cold seeps are likely not major sources of MMHg to nGoM waters

[en] The anthropogenic emission and subsequent deposition of heavy metals including mercury (Hg) and lead (Pb) present human health and environmental concerns. Although it is known that local and regional sources of these metals contribute to deposition in the Great Lakes region, it is difficult to trace emissions from point sources to impacted sites. Recent studies suggest that metal isotope ratios may be useful for distinguishing between and tracing source emissions. We measured Pb, strontium (Sr), and Hg isotope ratios in daily precipitation samples that were collected at seven sites across the Great Lakes region between 2003 and 2007. Lead isotope ratios ("2"0"7Pb/"2"0"6Pb = 0.8062 to 0.8554) suggest that Pb deposition was influenced by coal combustion and processing of Mississippi Valley-Type Pb ore deposits. Regional differences in Sr isotope ratios ("8"7Sr/"8"6Sr = 0.70859 to 0.71155) are likely related to coal fly ash and soil dust. Mercury isotope ratios (δ"2"0"2Hg = − 1.13 to 0.13‰) also varied among the sites, likely due to regional differences in coal isotopic composition, and fractionation occurring within industrial facilities and in the atmosphere. These data represent the first combined characterization of Pb, Sr, and Hg isotope ratios in precipitation collected across the Great Lakes region. We demonstrate the utility of multiple metal isotope ratios in parallel with traditional trace element multivariate statistical modeling to enable more complete pollution source attribution. - Highlights: • We measured Pb, Sr, and Hg isotopes in precipitation from the Great Lakes region. • Pb isotopes suggest that deposition was impacted by coal combustion and metal production. • Sr isotope ratios vary regionally, likely due to soil dust and coal fly ash. • Hg isotopes vary due to fractionation occurring within facilities and the atmosphere. • Isotope results support conclusions of previous trace element receptor modeling

[en] Monomethyl mercury (MMHg) and total mercury (THg) concentrations and Hg stable isotope ratios (δ"2"0"2Hg and Δ"1"9"9Hg) were measured in sediment and aquatic organisms from Cache Creek (California Coast Range) and Yolo Bypass (Sacramento Valley). Cache Creek sediment had a large range in THg (87 to 3870 ng/g) and δ"2"0"2Hg (− 1.69 to − 0.20‰) reflecting the heterogeneity of Hg mining sources in sediment. The δ"2"0"2Hg of Yolo Bypass wetland sediment suggests a mixture of high and low THg sediment sources. Relationships between %MMHg (the percent ratio of MMHg to THg) and Hg isotope values (δ"2"0"2Hg and Δ"1"9"9Hg) in fish and macroinvertebrates were used to identify and estimate the isotopic composition of MMHg. Deviation from linear relationships was found between %MMHg and Hg isotope values, which is indicative of the bioaccumulation of isotopically distinct pools of MMHg. The isotopic composition of pre-photodegraded MMHg (i.e., subtracting fractionation from photochemical reactions) was estimated and contrasting relationships were observed between the estimated δ"2"0"2Hg of pre-photodegraded MMHg and sediment IHg. Cache Creek had mass dependent fractionation (MDF; δ"2"0"2Hg) of at least − 0.4‰ whereas Yolo Bypass had MDF of + 0.2 to + 0.5‰. This result supports the hypothesis that Hg isotope fractionation between IHg and MMHg observed in rivers (− MDF) is unique compared to + MDF observed in non-flowing water environments such as wetlands, lakes, and the coastal ocean. - Highlights: • Mercury isotope ratios were measured in sediment and biota from Central California. • The isotopic composition of MMHg was estimated in streams and wetlands. • Mercury isotopes suggest multiple exposure pathways in these habitats. • Mass dependent fractionation between IHg and MMHg is different in streams.

[en] Total mercury (Hg) concentrations in hair and urine are often used as biomarkers of exposure to fish-derived methylmercury (MeHg) and gaseous elemental Hg, respectively. We used Hg stable isotopes to assess the validity of these biomarkers among small-scale gold mining populations in Ghana and Indonesia. Urine from Ghanaian miners displayed similar Δ"1"9"9Hg values to Hg derived from ore deposits (mean urine Δ"1"9"9Hg=0.01‰, n=6). This suggests that urine total Hg concentrations accurately reflect exposure to inorganic Hg among this population. Hair samples from Ghanaian miners displayed low positive Δ"1"9"9Hg values (0.23–0.55‰, n=6) and low percentages of total Hg as MeHg (7.6–29%, n=7). These data suggest that the majority of the Hg in these miners' hair samples is exogenously adsorbed inorganic Hg and not fish-derived MeHg. Hair samples from Indonesian gold miners who eat fish daily displayed a wider range of positive Δ"1"9"9Hg values (0.21–1.32‰, n=5) and percentages of total Hg as MeHg (32–72%, n=4). This suggests that total Hg in the hair samples from Indonesian gold miners is likely a mixture of ingested fish MeHg and exogenously adsorbed inorganic Hg. Based on data from both populations, we suggest that total Hg concentrations in hair samples from small-scale gold miners likely overestimate exposure to MeHg from fish consumption. - Highlights: • Mercury isotopes were measured in hair and urine from small-scale gold miners. • Mercury isotopes indicate that Hg in urine comes from mining activity. • Mercury isotopes suggest Hg in hair is a mixture of fish MeHg and inorganic Hg. • A large percentage of Hg in miner’s hair is released during amalgam burning and adsorbed

[en] Studies of monomethylmercury (MMHg) sources and biogeochemical pathways have been extensive in aquatic ecosystems, but limited in forest ecosystems. Increasing evidence suggests that there is significant mercury (Hg) exchange between aquatic and forest ecosystems. We use Hg stable isotope ratios (δ"2"0"2Hg and Δ"1"9"9Hg) to investigate the relative importance of MMHg sources and assess Hg transfer pathways between Douglas Lake and adjacent forests located at the University of Michigan Biological Station, USA. We characterize Hg isotopic compositions of basal resources and use linear regression of % MMHg versus δ"2"0"2Hg and Δ"1"9"9Hg to estimate Hg isotope values for inorganic mercury (IHg) and MMHg in the aquatic and adjacent forest food webs. In the aquatic ecosystem, we found that lake sediment represents a mixture of IHg pools deposited via watershed runoff and precipitation. The δ"2"0"2Hg and Δ"1"9"9Hg values estimated for IHg are consistent with other studies that measured forest floor in temperate forests. The Δ"1"9"9Hg value estimated for MMHg in the aquatic food web indicates that MMHg is subjected to ~ 20% photochemical degradation prior to bioaccumulation. In the forest ecosystem, we found a significant negative relationship between total Hg and δ"2"0"2Hg and Δ"1"9"9Hg of soil collected at multiple distances from the lakeshore and lake sediment. This suggests that IHg input from watershed runoff provides an important Hg transfer pathway between the forest and aquatic ecosystems. We measured Δ"1"9"9Hg values for high trophic level insects and compared these insects at multiple distances perpendicular to the lake shoreline. The Δ"1"9"9Hg values correspond to the % canopy cover suggesting that forest MMHg is subjected to varying extents of photochemical degradation and the extent may be controlled by sunlight. Our study demonstrates that the use of Hg isotopes adds important new insight into the relative importance of MMHg sources and complex Hg transfer pathways across ecosystem boundaries. - Highlights: • Hg isotope ratios were measured in basal resources and lake and forest biota. • IHg & MMHg isotopic compositions were estimated for biota with varying % MMHg. • MMHg isotopic compositions suggest that MMHg is produced in situ before photodegradation. • IHg isotopic compositions suggest that soil is the dominant IHg source to lake & forest. • Watershed runoff is the primary Hg transfer pathway between lake & forest