Mercury isotopic evidence for the importance of particles as a source of mercury to marine organisms.

The origin of methylmercury in pelagic fish remains unclear, with many unanswered questions regarding the production and degradation of this neurotoxin in the water column. We used mercury (Hg) stable isotope ratios of marine particles and biota to elucidate the cycling of methylmercury prior to incorporation into the marine food web. The Hg isotopic composition of particles, zooplankton, and fish reveals preferential methylation of Hg within small (< 53 µm) marine particles in the upper 400 m of the North Pacific Ocean. Mass-dependent Hg isotope ratios (δ202Hg) recorded in small particles overlap with previously estimated δ202Hg values for methylmercury sources to Pacific and Atlantic Ocean food webs. Particulate compound specific isotope analysis of amino acids (CSIA-AA) yield δ15N values that indicate more-significant microbial decomposition in small particles compared to larger particles. CSIA-AA and Hg isotope data also suggest that large particles (> 53 µm) collected in the equatorial ocean are distinct from small particles and resemble fecal pellets. Additional evidence for Hg methylation within small particles is provided by a statistical mixing model of even mass-independent (Δ200Hg and Δ204Hg) isotope values, which demonstrates that Hg within near-surface marine organisms (0-150 m) originates from a combination of rainfall and marine particles. In contrast, in meso- and upper bathypelagic organisms (200-1,400 m), the majority of Hg originates from marine particles with little input from wet deposition. The occurrence of methylation within marine particles is supported further by a correlation between Δ200Hg and Δ199Hg values, demonstrating greater overlap in the Hg isotopic composition of marine organisms with marine particles than with total gaseous Hg or wet deposition.

Ecological Traits of Fish for Mercury Biomonitoring: Insights from Compound-Specific Nitrogen and Stable Mercury Isotopes.

We coupled compound-specific isotopic analyses of nitrogen (N) in amino acids (δ15NGlu, δ15NPhe) and mercury stable isotopes (δ202Hg, Δ199Hg) to quantify ecological traits governing the concentration, variability, and source of Hg in largemouth bass (LB) and pike gudgeon (PG) across four rivers, South Korea. PG displayed uniform Hg concentration (56-137 ng/g), trophic position (TPcorrected; 2.6-3.0, n = 9), and N isotopes in the source amino acid (δ15NPhe; 7-13‰), consistent with their specialist feeding on benthic insects. LB showed wide ranges in Hg concentration (45-693 ng/g), TPcorrected (2.8-3.8, n = 14), and δ15NPhe (1.3-16‰), reflecting their opportunistic feeding behavior. Hg sources assessed using Hg isotopes reveal low and uniform Δ199Hg in PG (0.20-0.49‰), similar to Δ199Hg reported in sediments. LB displayed site-specific δ202Hg (-0.61 to -0.04‰) and Δ199Hg (0.53-1.09‰). At the Yeongsan River, LB displayed elevated Δ199Hg and low δ15NPhe, consistent with Hg and N sourced from the atmosphere. LB at the Geum River displayed low Δ199Hg and high δ15NPhe, both similar to the isotope values of anthropogenic sources. Our results suggest that a specialist fish (PG) with consistent ecological traits and Hg concentration is an effective bioindicator species for Hg. When accounting for Hg sources, however, LB better captures site-specific Hg sources.

Uptake Mechanisms of a Novel, Activated Carbon-Based Equilibrium Passive Sampler for Estimating Porewater Methylmercury.

We describe the validation of a novel polymeric equilibrium passive sampler comprised of agarose gel with embedded activated carbon particles (ag+AC), to estimate aqueous monomethylmercury (MeHg) concentrations. Sampler behavior was tested using a combination of idealized media and realistic sediment microcosms. Isotherm bottle experiments with ag+AC polymers were conducted to constrain partitioning to these materials by various environmentally relevant species of MeHg bound to dissolved organic matter (MeHgDOM) across a range of sizes and character. Log of partitioning coefficients for passive samplers (Kps ) ranged from 1.98 ± 0.09 for MeHg bound to Suwannee River humic acid to 3.15 ± 0.05 for MeHg complexed with Upper Mississippi River natural organic matter. Reversible equilibrium exchange of environmentally relevant MeHg species was demonstrated through a series of dual isotope-labeled exchange experiments. Isotopically labeled MeHgDOM species approached equilibrium in the samplers over 14 days, while mass balance was maintained, providing strong evidence that the ag+AC polymer material is capable of equilibrium measurements of environmentally relevant MeHg species within a reasonable deployment time frame. Samplers deployed across the sediment-water interface of sediment microcosms estimated both overlying water and porewater MeHg concentrations within a factor of 2 to 4 of measured values, based on the average measured Kps values for species of MeHg bound to natural organic matter in the isotherm experiments. Taken together, our results indicate that ag+AC polymers, used as equilibrium samplers, can provide accurate MeHg estimations across many site chemistries, with a simple back-calculation based on a standardized Kps. Environ Toxicol Chem 2022;41:2052-2064. © 2022 SETAC.

Biogenic carbonate mercury and marine temperature records reveal global influence of Late Cretaceous Deccan Traps.

The climate and environmental significance of the Deccan Traps large igneous province of west-central India has been the subject of debate in paleontological communities. Nearly one million years of semi-continuous Deccan eruptive activity spanned the Cretaceous-Paleogene boundary, which is renowned for the extinction of most dinosaur groups. Whereas the Chicxulub impactor is acknowledged as the principal cause of these extinctions, the Deccan Traps eruptions are believed to have contributed to extinction patterns and/or enhanced ecological pressures on biota during this interval of geologic time. We present the first coupled records of biogenic carbonate clumped isotope paleothermometry and mercury concentrations as measured from a broad geographic distribution of marine mollusk fossils. These fossils preserve evidence of simultaneous increases in coastal marine temperatures and mercury concentrations at a global scale, which appear attributable to volcanic CO2 and mercury emissions. These early findings warrant further investigation with additional records of combined Late Cretaceous temperatures and mercury concentrations of biogenic carbonate.

Changes in the mercury isotopic composition of sediments from a remote alpine lake in Wyoming, USA.

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.

Isotopic evidence for mercury photoreduction and retention on particles in surface waters of Central California, USA.

Cache Creek (Coast Range, California) and the Yuba River (Sierra Nevada Foothills, California) are two river systems affected by extensive mercury (Hg) contamination due to legacy sources of Hg related to mining. Stable Hg isotope techniques have proven useful for elucidating the complex cycling of Hg within aquatic ecosystems, and we applied these techniques to improve understanding of Hg and methylmercury (MeHg) transformations in these watersheds. Total mercury (THg) concentrations and Hg stable isotope ratios were measured in filtered surface waters and suspended particulate matter collected from 14 sites within the Cache Cr. and Yuba R. watersheds. Filtered surface waters from both watersheds exhibited values of ∆199Hg (0.37‰ to 0.71‰), consistently elevated above those observed in sediments (∆199Hg average = 0.07‰). Associated suspended particulates from these surface water samples displayed a much greater range of values for ∆199Hg (-0.61‰ to 0.70‰), although suspended particulates from the Yuba R. exhibited mostly negative ∆199Hg values (-0.61‰ to 0.10‰). The relationship between ∆199Hg and ∆201Hg in the filtered surface waters and associated suspended particulates was calculated using a bivariate York regression, yielding a slope of 1.57 ±â€¯0.49 (±2SE) for the Yuba R. and 1.40 ±â€¯0.27 (±2SE) for Cache Cr., both within error of the previously reported experimentally-derived slopes for MeHg- and inorganic Hg(II)-photoreduction. This provides isotopic evidence that Hg photoreduction is occurring within these surface waters to a significant degree, and suspended particulate phases are retaining the reduced product of Hg photoreduction, particularly within the Yuba R. The isotopic compositions of filtered surface waters are consistent with the isotopic signatures recorded in biota at low trophic positions within these watersheds, suggesting that the reservoir of Hg incorporated within the biota of these systems is similar to the filter-passing Hg fraction in surface waters.

Isotopic Characterization of Mercury Downstream of Historic Industrial Contamination in the South River, Virginia.

Historic point source mercury (Hg) contamination from industrial processes on the South River (Waynesboro, Virginia) ended decades ago, but elevated Hg concentrations persist in the river system. In an effort to better understand Hg sources, mobility, and transport in the South River, we analyzed total Hg (THg) concentrations and Hg stable isotope compositions of streambed sediments, stream bank soils, suspended particles, and filtered surface waters. Samples were collected along a longitudinal transect of the South River, starting upstream of the historic Hg contamination point-source and extending downstream to the confluence with the South Fork Shenandoah River. Analysis of the THg concentration and Hg isotopic composition of these environmental samples indicates that the regional background Hg source is isotopically distinct in both Δ199Hg and δ202Hg from Hg derived from the original source of contamination, allowing the tracing of contamination-sourced Hg throughout the study reach. Three distinct end-members are required to explain the Hg isotopic and concentration variation observed in the South River. A consistent negative offset in δ202Hg values (∼0.28‰) was observed between Hg in the suspended particulate and dissolved phases, and this fractionation provides insight into the processes governing partitioning and transport of Hg in this contaminated river system.