Patterns in forage fish mercury concentrations across Northeast US estuaries.

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.

A National-Scale Assessment of Mercury Bioaccumulation in United States National Parks Using Dragonfly Larvae As Biosentinels through a Citizen-Science Framework.

We conducted a national-scale assessment of mercury (Hg) bioaccumulation in aquatic ecosystems, using dragonfly larvae as biosentinels, by developing a citizen-science network to facilitate biological sampling. Implementing a carefully designed sampling methodology for citizen scientists, we developed an effective framework for a landscape-level inquiry that might otherwise be resource limited. We assessed the variation in dragonfly Hg concentrations across >450 sites spanning 100 United States National Park Service units and examined intrinsic and extrinsic factors associated with the variation in Hg concentrations. Mercury concentrations ranged between 10.4 and 1411 ng/g dry weight across sites and varied among habitat types. Dragonfly total Hg (THg) concentrations were up to 1.8-fold higher in lotic habitats than in lentic habitats and 37% higher in waterbodies with abundant wetlands along their margins than those without wetlands. Mercury concentrations in dragonflies differed among families but were correlated (r2 > 0.80) with each other, enabling adjustment to a consistent family to facilitate spatial comparisons among sampling units. Dragonfly THg concentrations were positively correlated with THg concentrations in both fish and amphibians from the same locations, indicating that dragonfly larvae are effective indicators of Hg bioavailability in aquatic food webs. We used these relationships to develop an integrated impairment index of Hg risk to aquatic ecosytems and found that 12% of site-years exceeded high or severe benchmarks of fish, wildlife, or human health risk. Collectively, this continental-scale study demonstrates the utility of dragonfly larvae for estimating the potential mercury risk to fish and wildlife in aquatic ecosystems and provides a framework for engaging citizen science as a component of landscape Hg monitoring programs.

Dragonfly larvae as biosentinels of Hg bioaccumulation in Northeastern and Adirondack lakes: relationships to abiotic factors.

Mercury (Hg) is a toxic pollutant, widespread in northeastern US ecosystems. Resource managers' efforts to develop fish consumption advisories for humans and to focus conservation efforts for fish-eating wildlife are hampered by spatial variability. Dragonfly larvae can serve as biosentinels for Hg given that they are widespread in freshwaters, long-lived, exhibit site fidelity, and bioaccumulate relatively high mercury concentrations, mostly as methylmercury (88% ± 11% MeHg in this study). We sampled lake water and dragonfly larvae in 74 northeastern US lakes that are part of the US EPA Long-Term Monitoring Network, including 45 lakes in New York, 43 of which are in the Adirondacks. Aqueous dissolved organic carbon (DOC) and total Hg (THg) were strongly related to MeHg in lake water. Dragonfly larvae total mercury ranged from 0.016-0.918 µg/g, dw across the study area; Adirondack lakes had the minimum and maximum concentrations. Aqueous MeHg and dragonfly THg were similar between the Adirondack and Northeast regions, but a majority of lakes within the highest quartile of dragonfly THg were in the Adirondacks. Using landscape, lake chemistry, and lake morphometry data, we evaluated relationships with MeHg in lake water and THg in dragonfly larvae. Lakewater DOC and lake volume were strong predictors for MeHg in water. Dragonfly THg Bioaccumulation Factors (BAFs, calculated as [dragonfly THg]:[aqueous MeHg]) increased as lake volume increased, suggesting that lake size influences Hg bioaccumulation or biomagnification. BAFs declined with increasing DOC, supporting a potential limiting effect for MeHg bioavailability with higher DOC.

Mercury Levels in Freshwater Fish: Estimating Concentration with Fish Length to Determine Exposures Through Fish Consumption.

Methylmercury (MeHg) is a neurotoxic pollutant that bioaccumulates and biomagnifies in aquatic food webs, impacting the health of piscivorous wildlife and human consumers of predatory fish. While fish mercury levels have been correlated with various biotic and abiotic factors, many studies only measure adults to characterize the health of locally fished populations, omitting information about how local fish bioaccumulate mercury relative to their growth. In this study, we sought to establish length: total mercury (THg) concentration relationships in juvenile and adult fish of four genera (sunfish, yellow perch, white perch, and killifish) across six freshwater pond systems of Nantucket Island to determine safe consumption sizes across species and environmental conditions. A wide length range (2-21 cm) was utilized to develop linear regression models of ln-THg versus fish length. In most cases, different genera within the same pond indicated similar slopes, supporting that all four genera share comparable features of feeding and growth. Comparing individual species across ponds, differences in ln-THg versus fish length were attributable to known environmental Hg-modulators including surface water MeHg levels, pH, and watershed area. Referencing human health and wildlife criteria, our results confirm that numerous Nantucket freshwater ecosystems contain elevated fish THg levels, which could impact the health of not only piscivorous wildlife in all measured ponds but also recreational fishers in at least two measured systems. Future studies should measure THg levels across juvenile and adult fish to detect potential differences in the slope of THg concentration across fish length relevant for local consumption advice.

Dynamics of Cadmium Acclimation in Daphnia pulex: Linking Fitness Costs, Cross-Tolerance, and Hyper-Induction of Metallothionein.

Acclimation increases tolerance to stress in individuals but is assumed to contribute fitness costs when the stressor is absent, though data supporting this widely held claim are sparse. Therefore, using clonal (i.e., genetically identical) cultures of Daphnia pulex, we isolated the contributions of acclimation to the regulation of the metal response gene, metallothionein 1 (MT1), and defined the reproductive benefits and costs of cadmium (Cd)-acclimation. Daphnia pulex were exposed for 50 parthenogenetic generations to environmentally realistic levels (1 µg Cd/L), and tolerance to Cd and other metals assessed during this period via standard toxicity tests. These tests revealed (1) increased tolerance to Cd compared to genetically identical nonacclimated cultures, (2) fitness costs in Cd-acclimated Daphnia when Cd was removed, and (3) cross-tolerance of Cd-acclimated Daphnia to zinc and silver, but not arsenic, thereby defining a functional role for metallothionein. Indeed, Cd-acclimated clones had significantly higher expression of MT1 mRNA than nonacclimated clones, when Cd exposed. Both the enhanced induction of MT1 and tolerant phenotype were rapidly lost when Cd was removed (1-2 generations), which is further evidence of acclimation costs. These findings provide evidence for the widely held view that acclimation is costly and are important for investigating evolutionary principles of genetic assimilation and the survival mechanisms of natural populations that face changing environments.

Factors affecting MeHg bioaccumulation in stream biota: the role of dissolved organic carbon and diet.

The bioaccumulation of the neurotoxin methylmercury (MeHg) in freshwater ecosystems is thought to be mediated by both water chemistry (e.g., dissolved organic carbon [DOC] and dissolved mercury [Hg]) and diet (e.g., trophic position and diet composition). Hg in small streams is of particular interest given their role as a link between terrestrial and aquatic processes. Terrestrial processes determine the quantity and quality of streamwater DOC, which in turn influence the quantity and bioavailability of dissolved MeHg. To better understand the effects of water chemistry and diet on Hg bioaccumulation in stream biota, we measured DOC and dissolved Hg in stream water and mercury concentration in three benthic invertebrate taxa and three fish species across up to 12 tributary streams in a forested watershed in New Hampshire, USA. As expected, dissolved total mercury (THg) and MeHg concentrations increased linearly with DOC. However, mercury concentrations in fish and invertebrates varied non-linearly, with maximum bioaccumulation at intermediate DOC concentrations, which suggests that MeHg bioavailability may be reduced at high levels of DOC. Further, MeHg and THg concentrations in invertebrates and fish, respectively, increased with δ15N (suggesting trophic position) but were not associated with δ13C. These results show that even though MeHg in water is strongly determined by DOC concentrations, mercury bioaccumulation in stream food webs is the result of both MeHg availability in stream water and trophic position.

Toenail mercury Levels are associated with amyotrophic lateral sclerosis risk.

INTRODUCTION: Mercury is a neurotoxic metal that is potentially a risk factor for amyotrophic lateral sclerosis (ALS). Consumption of methylmercury contaminated fish is the primary source of US population exposure to mercury. METHODS: We used inductively coupled plasma mass spectrometry to measure levels of mercury in toenail samples from patients with ALS (n = 46) and from controls (n = 66) as a biomarker of mercury exposure. RESULTS: Patients with ALS had higher toenail mercury levels (odds ratio 2.49, 95% confidence interval 1.18-5.80, P = 0.024) compared with controls, adjusted for age and sex. We also estimated the amount of mercury consumed from finfish and shellfish and found toenail mercury levels elevated overall among patients with ALS and controls in the top quartile for consumption (P = 0.018). DISCUSSION: Biomarker data show that ALS is associated with increased with mercury levels, which were related to estimated methylmercury intake via fish. Replication of these associations in additional populations is warranted. Muscle Nerve, 2018.

Arsenic Reduces Gene Expression Response to Changing Salinity in Killifish.

Toxicogenomic approaches can detect and classify adverse interactions between environmental toxicants and other environmental stressors but require more complex experimental designs and analytical approaches. Here we use novel toxicogenomic techniques to analyze the effect of arsenic exposure in wild killifish populations acclimating to changing salinity. Fish from three populations were acclimated to full strength seawater and transferred to fresh water for 1 or 24 h. Linear models of gene expression in gill tissue identified 31 genes that responded to osmotic shock at 1 h and 178 genes that responded at 24 h. Arsenic exposure (100 µg/L) diminished the responses (reaction norms) of these genes by 22% at 1 h ( p = 1.0 × 10-6) and by 10% at 24 h ( p = 3.0 × 10-10). Arsenic also significantly reduced gene coregulation in gene regulatory networks ( p = 0.002, paired Levene's test), and interactions between arsenic and salinity acclimation were uniformly antagonistic at the biological pathway level ( p < 0.05, binomial test). Arsenic's systematic interference with gene expression reaction norms was validated in a mouse multistressor experiment, demonstrating the ability of these toxicogenomic approaches to identify biologically relevant adverse interactions between environmental toxicants and other environmental stressors.

A Critical Time for Mercury Science to Inform Global Policy.

Mercury is a global pollutant released into the biosphere by varied human activities including coal combustion, mining, artisanal gold mining, cement production, and chemical production. Once released to air, land and water, the addition of carbon atoms to mercury by bacteria results in the production of methylmercury, the toxic form that bioaccumulates in aquatic and terrestrial food chains resulting in elevated exposure to humans and wildlife. Global recognition of the mercury contamination problem has resulted in the Minamata Convention on Mercury, which came into force in 2017. The treaty aims to protect human health and the environment from human-generated releases of mercury curtailing its movement and transformations in the biosphere. Coincident with the treaty's coming into force, the 13th International Conference of Mercury as a Global Pollutant (ICMGP-13) was held in Providence, Rhode Island USA. At ICMGP-13, cutting edge research was summarized and presented to address questions relating to global and regional sources and cycling of mercury, how that mercury is methylated, the effects of mercury exposure on humans and wildlife, and the science needed for successful implementation of the Minamata Convention. Human activities have the potential to enhance mercury methylation by remobilizing previously released mercury, and increasing methylation efficiency. This synthesis concluded that many of the most important factors influencing the fate and effects of mercury and its more toxic form, methylmercury, stem from environmental changes that are much broader in scope than mercury releases alone. Alterations of mercury cycling, methylmercury bioavailability and trophic transfer due to climate and land use changes remain critical uncertainties in effective implementation of the Minamata Convention. In the face of these uncertainties, important policy and management actions are needed over the short-term to support the control of mercury releases to land, water and air. These include adequate monitoring and communication on risk from exposure to various forms of inorganic mercury as well as methylmercury from fish and rice consumption. Successful management of global and local mercury pollution will require integration of mercury research and policy in a changing world.

Spatial and taxonomic variation of mercury concentration in low trophic level fauna from the Mediterranean Sea.

Studies of mercury (Hg) in the Mediterranean Sea have focused on pollution sources, air-sea mercury exchange, abiotic mercury cycling, and seafood. Much less is known about methylmercury (MeHg) concentrations in the lower food web. Zooplankton and small fish were sampled from the neuston layer at both coastal and open sea stations in the Mediterranean Sea during three cruise campaigns undertaken in the fall of 2011 and the summers of 2012 and 2013. Zooplankton and small fish were sorted by morphospecies, and the most abundant taxa (e.g. euphausiids, isopods, hyperiid amphipods) analyzed for methylmercury (MeHg) concentration. Unfiltered water samples were taken during the 2011 and 2012 cruises and analyzed for MeHg concentration. Multiple taxa suggested elevated MeHg concentrations in the Tyrrhenian and Balearic Seas in comparison with more eastern and western stations in the Mediterranean Sea. Spatial variation in zooplankton MeHg concentration is positively correlated with single time point whole water MeHg concentration for euphausiids and mysids and negatively correlated with maximum chlorophyll a concentration for euphausiids, mysids, and "smelt" fish. Taxonomic variation in MeHg concentration appears driven by taxonomic grouping and feeding mode. Euphausiids, due to their abundance, relative larger size, importance as a food source for other fauna, and observed relationship with surface water MeHg are a good candidate biotic group to evaluate for use in monitoring the bioavailability of MeHg for trophic transfer in the Mediterranean and potentially globally.

Influence of sample preparation on estuarine macrofauna stable isotope signatures in the context of contaminant bioaccumulation studies.

The ratios of stable isotopes of carbon and nitrogen provide important information on food sources of aquatic organisms and trophic structure of aquatic food webs. For many studies, trophic position and food source are linked to bioaccumulation and trophic transfer of contaminants from prey to predators. In these cases, it is useful to use measurements on whole organisms to make direct comparisons of contaminant bioaccumulation and food web attributes. There is a great deal of variation in methods used for stable isotope analysis, particularly in the selection of tissue type and sample preparation prior to stable isotope analysis. While there have been aquatic studies that examined methodological differences, few have focused on estuarine organisms. In this study, the effects of depuration and tissue dissection on the stable isotope enrichment of common estuarine invertebrates and fish were examined. Homogenized tissues of non-depurated whole organisms were compared to dissected muscle tissue or depurated whole organisms. A 24 h depuration did not change the mean δ15N and δ13C values for most species examined. Additionally, as expected, significant differences in carbon and nitrogen signatures were found when muscle tissues were compared to whole organisms. However, differences were small enough that food source as inferred by δ13C or trophic level as inferred from δ15N would not be inaccurately represented (differences of <1.9‰ for δ13C and <1.2‰ for δ15N). The results of this study suggest that for these common estuarine fish and macroinvertebrates, stable isotopes ratios of samples can be analyzed without depuration in the same way as samples for contaminant analysis, but differences in tissue types must be taken into account when combining data from different sources.

Dissolved organic carbon modulates mercury concentrations in insect subsidies from streams to terrestrial consumers.

Mercury (Hg) concentrations in aquatic environments have increased globally, exposing consumers of aquatic organisms to high Hg levels. For both aquatic and terrestrial consumers, exposure to Hg depends on their food sources as well as environmental factors influencing Hg bioavailability. The majority of the research on the transfer of methylmercury (MeHg), a toxic and bioaccumulating form of Hg, between aquatic and terrestrial food webs has focused on terrestrial piscivores. However, a gap exists in our understanding of the factors regulating MeHg bioaccumulation by non-piscivorous terrestrial predators, specifically consumers of adult aquatic insects. Because dissolved organic carbon (DOC) binds tightly to MeHg, affecting its transport and availability in aquatic food webs, we hypothesized that DOC affects MeHg transfer from stream food webs to terrestrial predators feeding on emerging adult insects. We tested this hypothesis by collecting data over 2 years from 10 low-order streams spanning a broad DOC gradient in the Lake Sunapee watershed in New Hampshire, USA. We found that streamwater MeHg concentration increased linearly with DOC concentration. However, streams with the highest DOC concentrations had emerging stream prey and spiders with lower MeHg concentrations than streams with intermediate DOC concentrations; a pattern that is similar to fish and larval aquatic insects. Furthermore, high MeHg concentrations found in spiders show that MeHg transfer in adult aquatic insects is an overlooked but potentially significant pathway of MeHg bioaccumulation in terrestrial food webs. Our results suggest that although MeHg in water increases with DOC, MeHg concentrations in stream and terrestrial consumers did not consistently increase with increases in streamwater MeHg concentrations. In fact, there was a change from a positive to a negative relationship between aqueous exposure and bioaccumulation at streamwater MeHg concentrations associated with DOC above ~5 mg/L. Thus, our study highlights the importance of stream DOC for MeHg dynamics beyond stream boundaries, and shows that factors modulating MeHg bioavailability in aquatic systems can affect the transfer of MeHg to terrestrial predators via aquatic subsidies.

Natural selection canalizes expression variation of environmentally induced plasticity-enabling genes.

Many organisms survive fluctuating and extreme environmental conditions by manifesting multiple distinct phenotypes during adulthood by means of developmental processes that enable phenotypic plasticity. We report on the discovery of putative plasticity-enabling genes that are involved in transforming the gill of the euryhaline teleost fish, Fundulus heteroclitus, from its freshwater to its seawater gill-type, a process that alters both morphology and function. Gene expression that normally enables osmotic plasticity is inhibited by arsenic. Gene sets defined by antagonistic interactions between arsenic and salinity show reduced transcriptional variation among individual fish, suggesting unusually accurate and precise regulatory control of these genes, consistent with the hypothesis that they participate in a canalized developmental response. We observe that natural selection acts to preserve canalized gene expression in populations of killifish that are most tolerant to abrupt salinity change and that these populations show the least variability in their transcription of genes enabling plasticity of the gill. We found that genes participating in this highly canalized and conserved plasticity-enabling response had significantly fewer and less complex associations with transcriptional regulators than genes that respond only to arsenic or salinity. Collectively these findings, which are drawn from the relationships between environmental challenge, plasticity, and canalization among populations, suggest that the selective processes that facilitate phenotypic plasticity do so by targeting the regulatory networks that gives rise to the response. These findings also provide a generalized, conceptual framework of how genes might interact with the environment and evolve toward the development of plastic traits.

The effect of sediment mixing on mercury dynamics in two intertidal mudflats at Great Bay Estuary, New Hampshire, USA.

Estuarine sediments store particulate contaminants including mercury (Hg). We studied Hg sediment dynamics in two intertidal mudflats at Great Bay estuary, NH, over multiple years. Sediments at both mudflats were physically mixed down to ~10 cm, as determined by 7Be measurements, albeit via different mechanisms. Portsmouth mudflat (PT) sediments were subject to bioturbation by infaunal organisms and Squamscott mudflat (SQ) sediments were subject to erosion and redeposition. The presence of higher concentrations of fresh Fe(III) hydroxide at PT suggested bioirrigation by the polychaetes (Nereis virens). At depths where infaunal bioirrigation was observed, pore-water inorganic Hg (Hgi) and methylmercury (MeHg) were lower potentially due to their interaction with Fe(III) hydroxide. Methylmercury concentrations increased immediately below this zone in some samples, suggesting that the observed increase in material flux in bioirrigated sediments may initiate from lower depths. Pore water in sediment at PT also had higher fractions of more protein-like and labile DOC than those at SQ that can lead to increased MeHg production in PT, especially at depths where Hgi is not removed from solution by Fe(III) hydroxide. Where sediment erosion and redeposition were observed at SQ, Hg species distribution was extended deeper into the sediment column. Moreover, methyl coenzyme M reductase (MCR) and mercury reductase (mer-A) genes were higher at SQ than PT suggesting differences in conditions for Hg cycling. Results showed that the near-surface region of high MeHg concentrations commonly observed in unmixed sediments does not exist in physically mixed sediments that are common in many estuarine environments.

Sources of water column methylmercury across multiple estuaries in the Northeast U.S.

Estuarine water column methylmercury (MeHg) is an important driver of mercury (Hg) bioaccumulation in pelagic organisms and thus it is necessary to understand the sources and processes affecting environmental levels of MeHg. Increases in water column MeHg concentrations can ultimately be transferred to fish consumed by humans, but despite this, the sources of MeHg to the estuarine water column are still poorly understood. Here we evaluate MeHg sources across 4 estuaries and 10 sampling sites and examine the distributions and partitioning of sediment and water column MeHg across a geographic range (Maine to New Jersey). Our study sites present a gradient in the concentrations of sediment, pore water and water column Hg species. Suspended particle MeHg ranged from below detection to 187 pmol g-1, dissolved MeHg from 0.01 to 0.68 pM, and sediment MeHg from 0.01 to 109 pmol g-1. Across multiple estuaries, dissolved MeHg correlated with Hg species in the water column, and sediment MeHg correlated with sediment total Hg (HgT). Water column MeHg did not correlate well with sediment Hg across estuaries, indicating that sediment concentrations were not a good predictor of water MeHg concentrations. This is an unexpected finding since it has been shown that MeHg production from inorganic Hg2+ within sediment is the primary source of MeHg to coastal waters. Additional sources of MeHg regulate water column MeHg levels in some of the shallow estuaries included in this study.

Pathways of CH3Hg and Hg ingestion in benthic organisms: an enriched isotope approach.

Mercury is a widespread contaminant in marine food webs, and identifying uptake pathways of mercury species, CH3Hg(+) and Hg(2+), into low trophic level organisms is important to understanding its entry into marine food webs. Enriched stable isotope tracers were used to study benthic vs. pelagic pathways of CH3Hg(+) and Hg(2+) uptake via food to the infaunal estuarine amphipod, Leptocheirus plumulosus. Algal cells differentially labeled with isotopically enriched CH3Hg(+) or Hg(2+) were added simultaneously to the sediment and water column of microcosms, and Hg species were monitored in amphipods and in sediment and water compartments. Methylation of Hg(2+) occurred during the course of the experiment, enhancing the uptake of Hg(2+) spikes. Trophic transfer of Hg from algae added to the water column was determined to be the major uptake route for amphipods, suggesting inputs of contaminated organic matter from the pelagic zone are important to mercury bioaccumulation even in organisms living in sediments.

Mercury isotope study of sources and exposure pathways of methylmercury in estuarine food webs in the Northeastern U.S.

We measured mercury (Hg) isotope ratios in sediments and various estuarine organisms (green crab, blue mussel, killifish, eider) to investigate methylmercury (MMHg) sources and exposure pathways in five Northeast coast (U.S.) estuaries. The mass independent Hg isotopic compositions (MIF; Δ(199)Hg) of the sediments were linearly correlated with the sediment 1/Hg concentrations (Δ(199)Hg: r(2) = 0.77, p < 0.05), but the mass dependent isotope compositions (MDF; δ(202)Hg) were not (r(2) = 0.26, p = 0.16), reflecting inputs of anthropogenic Hg sources with varying δ(202)Hg. The estuarine organisms all display positive Δ(199)Hg values (0.21 to 0.98 ‰) indicating that MMHg is photodegraded to varying degrees (5-12%) prior to entry into the food web. The δ(202)Hg and Δ(199)Hg values of most organisms can be explained by a mixture of MMHg and inorganic Hg from sediments. At one contaminated site mussels have anomalously high δ(202)Hg, indicating exposure to a second pool of MMHg, compared to sediment, crabs and fish. Eiders have similar Δ(199)Hg as killifish but much higher δ(202)Hg, suggesting that there is an internal fractionation of δ(202)Hg in birds. Our study shows that Hg isotopes can be used to identify multiple anthropogenic inorganic Hg and MMHg sources and determine the degree of photodegradation of MMHg in estuarine food webs.

Habitat and dissolved organic carbon modulate variation in the biogeochemical drivers of mercury bioaccumulation in dragonfly larvae at the national scale.

We paired mercury (Hg) concentrations in dragonfly larvae with water chemistry in 29 U.S. national parks to highlight how ecological and biogeochemical context (habitat, dissolved organic carbon [DOC]) influence drivers of Hg bioaccumulation. Although prior studies have defined influences of biogeochemical variables on Hg production and bioaccumulation, it has been challenging to determine their influence across diverse habitats, regions, or biogeochemical conditions within a single study. We compared global (i.e., all sites), habitat-specific, and DOC-class models to illuminate how these controls on biotic Hg vary. Although the suite of important biogeochemical factors across all sites (e.g., aqueous Hg, DOC, sulfate [SO42-], and pH) was consistent with general findings in the literature, contrasting the restricted models revealed more nuanced controls on biosentinel Hg. Comparing habitats, aqueous (filtered) total mercury (THg) and SO42- were important in lentic systems whereas aqueous (filtered) methylmercury (MeHg), DOC, pH, and SO42- were important in lotic and wetland systems. The ability to identify important variables varied among habitats, with less certainty in lentic (model weight (W) = 0.05) than lotic (W = 0.11) or wetland habitats (W = 0.23), suggesting that biogeochemical drivers of bioaccumulation are more variable, or obscured by other aspects of Hg cycling, in these habitats. Results revealed a contrast in the importance of aqueous MeHg versus aqueous THg between DOC-classes: in low-DOC sites (<8.5 mg/L), availability of upstream inputs of MeHg appeared more important for bioaccumulation; in high-DOC sites (>8.5 mg/L) THg was more important, suggesting a link to in-situ controls on bioavailability of Hg for MeHg production. Mercury bioaccumulation (indicated by bioaccumulation factor) was more efficient in low DOC-class sites, likely due to reduced partitioning of aqueous MeHg to DOC. Together, findings highlight substantial variation in the drivers of Hg bioaccumulation and suggest consideration of these factors in natural resource management and decision-making.

Methylmercury production in estuarine sediments: role of organic matter.

Methylmercury (MeHg) affects wildlife and human health mainly through marine fish consumption. In marine systems, MeHg is formed from inorganic mercury (Hg(II)) species primarily in sediments, then accumulates and biomagnifies in the food web. Most of the fish consumed in the United States are from estuarine and marine systems, highlighting the importance of understanding MeHg formation in these productive regions. Sediment organic matter has been shown to limit mercury methylation in estuarine ecosystems, as a result it is often described as the primary control over MeHg production. In this paper, we explore the role of organic matter by looking at the effects of its changing sediment concentrations on the methylation rates across multiple estuaries. We measured sedimentary MeHg production at eleven estuarine sites that were selected for their contrasting biogeochemical characteristics, mercury (Hg) content, and location in the Northeastern U.S. (ME, NH, CT, NY, and NJ). Sedimentary total Hg concentrations ranged across 5 orders of magnitude, increasing in concentration from the pristine, sandy sediments of Wells (ME), to industrially contaminated areas such as Portsmouth (NH) and Hackensack (NJ). We find that methylation rates are the highest at locations with high Hg content (relative to carbon), and that organic matter does not hinder mercury methylation in estuaries.

Spatial variability of metal bioaccumulation in estuarine killifish (Fundulus heteroclitus) at the Callahan mine superfund site, Brooksville, ME.

The former Callahan Mine Site in Brooksville, ME, is an open-pit, hardrock mine site in an intertidal system, thus providing a unique opportunity to evaluate how metal-enriched sediments and overlying water impact estuarine food webs. Copper, zinc, cadmium, and lead concentrations in sediment, whole water, and Atlantic killifish (Fundulus heteroclitus) were evaluated at sites in Goose Pond (GP; Callahan Mine Site) and at reference sites. The metal concentrations of sediment, water, and fish were spatially distinct and significantly greater at the mine site than in the reference estuary. Sediment concentrations were particularly elevated and were above probable effects levels for all four metals adjacent to the tailings pile. Even in this well-mixed system, water metal concentrations were significantly elevated adjacent to the tailings pile, and concentrations of Cu and Zn were above ambient water-quality criteria for chronic marine exposure. Neither organic matter in the sediment nor salinity or pH of the water explained the metal concentrations. Adjacent to the tailings pile, killifish metal body burdens were elevated and were significantly related to both sediment and aqueous concentrations. In conclusion, (1) the contaminated sediment and seepage from the tailings impoundment and waste rock pile no. 3 create a continual flux of metals into the water column, (2) the metals are bioavailable and bioconcentrating as evident in the killifish tissue concentrations, and (3) Callahan Mine is directly affecting metal bioaccumulation in fauna residing in the GP estuary and, potentially, in Penobscot Bay by the way of "trophic nekton relay."