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Biogeochemical conditions and landscape can have strong influences on mercury bioaccumulation in fish, but these effects across regional scales and between sites with and without point sources of contamination are not well understood. Normal means clustering, a type of unsupervised machine learning, was used to analyze relationships between forage fish (Fundulus heteroclitus and Menidia menidia) mercury (Hg) concentrations and sediment and water column Hg and methylmercury (MeHg) concentrations, ancillary variables, and land classifications within the sub-watershed. The analysis utilized data from 38 sites in 8 estuarine systems in the Northeast US, collected over five years. A large range of mercury concentrations and land use proportions were observed across sites. The cluster correlations indicated that for Fundulus, benthic and pelagic Hg and MeHg concentrations were most related to tissue concentrations, while Menidia Hg was most related to water column MeHg, reflecting differing feeding modes between the species. For both species, dissolved MeHg was most related to tissue concentrations, with sediment Hg concentrations influential at contaminated sites. The models considering only uncontaminated sites showed reduced influence of bulk sediment MeHg for both species, but Fundulus retained sediment drivers at some sites, with dissolved MeHg still highly correlated for both. Dissolved organic carbon (DOC), chlorophyll, land use, and other ancillary variables were of lesser importance in driving bioaccumulation, though DOC was strongly related within some clusters, likely in relation to dissolved Hg. Land use, though not of primary importance, showed relationships opposite to those observed in freshwater, with development positively correlated and forests and agriculture negatively correlated with tissue concentrations across clusters and species. Clusters were composed of sites from geographically distinct systems, indicating the greater importance of small scale drivers of MeHg formation and uptake into the food web over system or region-wide influences., (Copyright © 2020 Elsevier Inc. All rights reserved.)

High exposures of mammalian species to inorganic mercury (Hg II ) and methylmercury (MeHg) have been associated with adverse effects on behavior and reproduction. Different mammalian species exhibit varying responses to similar external exposure levels, reflecting potential differences in Hg toxicokinetics. Here, we use Hg stable isotopes, total Hg, MeHg and selenium (Se) concentrations measured in multiple tissues of North Atlantic pilot whales (Globicephala melas) to investigate processes affecting the distribution and accumulation of Hg II and MeHg. We find that simple mixing of two distinct isotopic end-members: MeHg (1.4‰) and Hg II (-1.6‰) can explain the observed variability of δ 202 Hg in brain tissue. A similar isotopic composition for the MeHg end-member in the brain, muscle, heart, and kidney suggests efficient exchange of MeHg in blood throughout the body. By contrast, the Hg isotopic composition of the liver of adult whales is different from younger whales and other tissues that follow the two-end member mixing model. Measured Se:Hg ratios are lowest in adult whales with the highest levels of MeHg exposure. In these individuals, Se availability is likely reduced by complexation with demethylated Hg II . We speculate that this results in a higher fraction of labile Hg II eliminated from the liver of adult whales compared to young whales and subsequent redistribution to other tissues, potentially affecting toxicity., Competing Interests: Declaration of competing interest All authors declare no competing financial interest., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Our previous work has documented a correlation between Hg concentrations and (210)Pb activity measured in wet deposition that might be used to help apportion sources of Hg in precipitation. Here we present the results of a 27-month precipitation collection effort using co-located samplers for Hg and (210)Pb designed to assess this hypothesis. Study sites were located on the east and west coasts of North America, in the continental interior, and on the Florida Peninsula. Relatively high variability in Hg/(210)Pb ratios was found at all sites regionally and seasonally (e.g., overall: 0.99-9.13ngdpm(-1)). The ratio of average volume-weighted Hg concentrations and (210)Pb activities showed consistent trends (higher in impacted area), with Glacier Bay in southeast Alaska, exhibiting the lowest value. Assuming that Glacier Bay represents a benchmark for a site with no regional contribution, we estimate less than 50% of the Hg input was "global" at the Seattle and Florida sites. Differences in Hg/(210)Pb in wet deposition could be due to either a regional/local source contribution of Hg, or a regional/local enhancement in the removal of Hg from the atmosphere (i.e., oxidants), however, this approach is not capable of discerning between these two possibilities. Thus, this method of source apportionment represents an estimate of the maximal amount of Hg contributed by regional sources and may be limited in regions of deep convective mixing., (Copyright © 2012 Elsevier B.V. All rights reserved.)