Wildfires Influence Mercury Transport, Methylation, and Bioaccumulation in Headwater Streams of the Pacific Northwest.

The increasing frequency and severity of wildfires are among the most visible impacts of climate change. However, the effects of wildfires on mercury (Hg) transformations and bioaccumulation in stream ecosystems are poorly understood. We sampled soils, water, sediment, in-stream leaf litter, periphyton, and aquatic invertebrates in 36 burned (one-year post fire) and 21 reference headwater streams across the northwestern U.S. to evaluate the effects of wildfire occurrence and severity on total Hg (THg) and methylmercury (MeHg) transport and bioaccumulation. Suspended particulate THg and MeHg concentrations were 89 and 178% greater in burned watersheds compared to unburned watersheds and increased with burn severity, likely associated with increased soil erosion. Concentrations of filter-passing THg were similar in burned and unburned watersheds, but filter-passing MeHg was 51% greater in burned watersheds, and suspended particles in burned watersheds were enriched in MeHg but not THg, suggesting higher MeHg production in burned watersheds. Among invertebrates, MeHg in grazers, filter-feeders, and collectors was 33, 48, and 251% greater in burned watersheds, respectively, but did not differ in shredders or predators. Thus, increasing wildfire frequency and severity may yield increased MeHg production, mobilization, and bioaccumulation in headwaters and increased transport of particulate THg and MeHg to downstream environments.

Geographic Drivers of Mercury Entry into Aquatic Food Webs Revealed by Mercury Stable Isotopes in Dragonfly Larvae.

Atmospheric mercury (Hg) emissions and subsequent transport and deposition are major concerns within protected lands, including national parks, where Hg can bioaccumulate to levels detrimental to human and wildlife health. Despite this risk to biological resources, there is limited understanding of the relative importance of different Hg sources and delivery pathways within the protected regions. Here, we used Hg stable isotope measurements within a single aquatic bioindicator, dragonfly larvae, to determine if these tracers can resolve spatial patterns in Hg sources, delivery mechanisms, and aquatic cycling at a national scale. Mercury isotope values in dragonfly tissues varied among habitat types (e.g., lentic, lotic, and wetland) and geographic location. Photochemical-derived isotope fractionation was habitat-dependent and influenced by factors that impact light penetration directly or indirectly, including dissolved organic matter, canopy cover, and total phosphorus. Strong patterns for Δ200Hg emerged in the western United States, highlighting the relative importance of wet deposition sources in arid regions in contrast to dry deposition delivery in forested regions. This work demonstrates the efficacy of dragonfly larvae as biosentinels for Hg isotope studies due to their ubiquity across freshwater ecosystems and ability to track variation in Hg sources and processing attributed to small-scale habitat and large-scale regional patterns.

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.

Stable Isotope Fractionation Reveals Similar Atomic-Level Controls during Aerobic and Anaerobic Microbial Hg Transformation Pathways.

Mercury (Hg) is a global pollutant and potent neurotoxin that bioaccumulates in food webs as monomethylmercury (MeHg). The production of MeHg is driven by anaerobic and Hg redox cycling pathways, such as Hg reduction, which control the availability of Hg to methylators. Anaerobes play an important role in Hg reduction in methylation hot spots, yet their contributions remain underappreciated due to how challenging these pathways are to study in the absence of dedicated genetic targets and low levels of Hg0 in anoxic environments. In this study, we used Hg stable isotope fractionation to explore Hg reduction during anoxygenic photosynthesis and fermentation in the model anaerobe Heliobacterium modesticaldum Ice1. We show that cells preferentially reduce lighter Hg isotopes in both metabolisms, leading to mass-dependent fractionation, but mass-independent fractionation commonly induced by UV-visible light is absent. Due to the variability associated with replicate experiments, we could not discern whether dedicated physiological processes drive Hg reduction during photosynthesis and fermentation. However, we demonstrate that fractionation is affected by the interplay between pathways controlling Hg recruitment, accessibility, and availability alongside metabolic redox reactions. The combined contributions of these processes lead to isotopic enrichment during anoxygenic photosynthesis that is in between the values reported for anaerobic respiratory microbial Hg reduction and abiotic photoreduction. Isotope enrichment during fermentation is closer to what has been observed in aerobic bacteria that reduce Hg through dedicated detoxification pathways. Our work suggests that similar controls likely underpin diverse microbe-mediated Hg transformations that affect Hg's fate in oxic and anoxic habitats. IMPORTANCE Anaerobic and photosynthetic bacteria that reduce mercury affect mercury delivery to microbes in methylation sites that drive bioaccumulation in food webs. Anaerobic mercury reduction pathways remain underappreciated in the current view of the global mercury cycle because they are challenging to study, bearing no dedicated genetic targets to establish physiological mechanisms. In this study, we used stable isotopes to characterize the physiological processes that control mercury reduction during photosynthesis and fermentation in the model anaerobe Heliobacterium modesticaldum Ice1. The sensitivity of isotope analyses highlighted the subtle contribution of mercury uptake to the isotope signature associated with anaerobic mercury reduction. When considered alongside the isotope signatures associated with microbial pathways for which genetic determinants have been identified, our findings underscore the narrow range of isotope enrichment that is characteristic of microbial mercury transformations. This suggests that there are common atomic-level controls for biological mercury transformations across a broad range of geochemical conditions.

Mercury Isotope Fractionation by Internal Demethylation and Biomineralization Reactions in Seabirds: Implications for Environmental Mercury Science.

A prerequisite for environmental and toxicological applications of mercury (Hg) stable isotopes in wildlife and humans is quantifying the isotopic fractionation of biological reactions. Here, we measured stable Hg isotope values of relevant tissues of giant petrels (Macronectes spp.). Isotopic data were interpreted with published HR-XANES spectroscopic data that document a stepwise transformation of methylmercury (MeHg) to Hg-tetraselenolate (Hg(Sec)4) and mercury selenide (HgSe) (Sec = selenocysteine). By mathematical inversion of isotopic and spectroscopic data, identical δ202Hg values for MeHg (2.69 ± 0.04‰), Hg(Sec)4 (-1.37 ± 0.06‰), and HgSe (0.18 ± 0.02‰) were determined in 23 tissues of eight birds from the Kerguelen Islands and Adélie Land (Antarctica). Isotopic differences in δ202Hg between MeHg and Hg(Sec)4 (-4.1 ± 0.1‰) reflect mass-dependent fractionation from a kinetic isotope effect due to the MeHg → Hg(Sec)4 demethylation reaction. Surprisingly, Hg(Sec)4 and HgSe differed isotopically in δ202Hg (+1.6 ± 0.1‰) and mass-independent anomalies (i.e., changes in Δ199Hg of ≤0.3‰), consistent with equilibrium isotope effects of mass-dependent and nuclear volume fractionation from Hg(Sec)4 → HgSe biomineralization. The invariance of species-specific δ202Hg values across tissues and individual birds reflects the kinetic lability of Hg-ligand bonds and tissue-specific redistribution of MeHg and inorganic Hg, likely as Hg(Sec)4. These observations provide fundamental information necessary to improve the interpretation of stable Hg isotope data and provoke a revisitation of processes governing isotopic fractionation in biota and toxicological risk assessment in wildlife.

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.

Mercury Methylation Genes Identified across Diverse Anaerobic Microbial Guilds in a Eutrophic Sulfate-Enriched Lake.

Mercury (Hg) methylation is a microbially mediated process that converts inorganic Hg into bioaccumulative, neurotoxic methylmercury (MeHg). The metabolic activity of methylating organisms is highly dependent on biogeochemical conditions, which subsequently influences MeHg production. However, our understanding of the ecophysiology of methylators in natural ecosystems is still limited. Here, we identified potential locations of MeHg production in the anoxic, sulfidic hypolimnion of a freshwater lake. At these sites, we used shotgun metagenomics to characterize microorganisms with the Hg-methylation gene hgcA. Putative methylators were dominated by hgcA sequences divergent from those in well-studied, confirmed methylators. Using genome-resolved metagenomics, we identified organisms with hgcA (hgcA+) within the Bacteroidetes and the recently described Kiritimatiellaeota phyla. We identified hgcA+ genomes derived from sulfate-reducing bacteria, but these accounted for only 22% of hgcA+ genome coverage. The most abundant hgcA+ genomes were from fermenters, accounting for over half of the hgcA gene coverage. Many of these organisms also mediate hydrolysis of polysaccharides, likely from cyanobacterial blooms. This work highlights the distribution of the Hg-methylation genes across microbial metabolic guilds and indicate that primary degradation of polysaccharides and fermentation may play an important but unrecognized role in MeHg production in the anoxic hypolimnion of freshwater lakes.

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.

Chemical and Physical Controls on Mercury Source Signatures in Stream Fish from the Northeastern United States.

Streams in the northeastern U.S. receive mercury (Hg) in varying proportions from atmospheric deposition and legacy point sources, making it difficult to attribute shifts in fish concentrations directly back to changes in Hg source management. Mercury stable isotope tracers were utilized to relate sources of Hg to co-located fish and bed sediments from 23 streams across a forested to urban-industrial land-use gradient within this region. Mass-dependent isotopes (δ202Hg) in prey and game fish at forested sites were depleted (medians -0.95 and -0.83 ‰, respectively) in comparison to fish from urban-industrial settings (medians -0.26 and -0.38 ‰, respectively); the forested site group also had higher prey fish Hg concentrations. The separation of Hg isotope signatures in fish was strongly related to in-stream and watershed land-use indicator variables. Fish isotopes were strongly correlated with bed sediment isotopes, but the isotopic offset between the two matrices was variable due to differing ecosystem-specific drivers controlling the extent of MeHg formation. The multivariable approach of analyzing watershed characteristics and stream chemistry reveals that the Hg isotope composition in fish is linked to current and historic Hg sources in the northeastern U.S. and can be used to trace bioaccumulated Hg.

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.

Fractionation of Mercury Stable Isotopes during Microbial Methylmercury Production by Iron- and Sulfate-Reducing Bacteria.

The biological production of monomethylmercury (MeHg) in soils and sediments is an important factor controlling mercury (Hg) accumulation in aquatic and terrestrial food webs. In this study we examined the fractionation of Hg stable isotopes during Hg methylation in nongrowing cultures of the anaerobic bacteria Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132. Both organisms showed mass-dependent, but no mass-independent fractionation of Hg stable isotopes during Hg methylation. Despite differences in methylation rates, the two bacteria had similar Hg fractionation factors (αr/p = 1.0009 and 1.0011, respectively). Unexpectedly, δ(202)Hg values of MeHg for both organisms were 0.4‰ higher than the value of initial inorganic Hg after about 35% of inorganic Hg had been methylated. These results indicate that a (202)Hg-enriched pool of inorganic Hg was preferentially utilized as a substrate for methylation by these organisms, but that multiple intra- and/or extracellular pools supplied inorganic Hg for biological methylation. Understanding the controls of the Hg stable isotopic composition of microbially produced MeHg is important to identifying bioavailable Hg in natural systems and the interpretation of Hg stable isotopes in aquatic food webs.

Co-selection of Mercury and Multiple Antibiotic Resistances in Bacteria Exposed to Mercury in the Fundulus heteroclitus Gut Microbiome.

The emergence and spread of antibiotic-resistant pathogenic bacteria is currently one of the most serious challenges to human health. To combat this problem, it is critical to understand the processes and pathways that result in the creation of antibiotic resistance gene pools in the environment. In this study, we examined the effects of mercury (Hg) exposure on the co-selection of Hg and antibiotic-resistant bacteria that colonize the gastrointestinal tract of the mummichog (Fundulus heteroclitus), a small, estuarine fish. We examined this connection in two experimental systems: (i) a short-term laboratory exposure study where fish were fed Hg-laced food for 15 days and (ii) an examination of environmental populations from two sites with very different levels of Hg contamination. In the lab exposure study, fish muscle tissue accumulation of Hg was proportional to food Hg concentration (R 2 = 0.99; P < 0.0001). In the environmental study, fish from the contaminated site contained threefold more Hg compared to fish from the reference site (P < 0.05). Further, abundance of the Hg resistance gene mercuric reductase was more than eightfold higher (P < 0.0001) in DNA extracts of ingesta of fish from the contaminated site, suggesting adaptation to Hg. Finally, resistance to three or more antibiotics was more common in Hg-resistant as compared to Hg-sensitive bacterial colonies that were isolated from fish ingesta (P < 0.001) demonstrating co-selection of Hg and antibiotic resistances. Together, our results highlight the possibility for the creation of antibiotic resistance gene pools as a result of exposure to Hg in contaminated environments.

Hair mercury isotopes, a noninvasive biomarker for dietary methylmercury exposure and biological uptake.

Background. Fish and rice are the main dietary sources of methylmercury (MeHg); however, rice does not contain the same beneficial nutrients as fish, and these differences can impact the observed health effects of MeHg. Hence, it is important to validate a biomarker, which can distinguish among dietary MeHg sources. Methods. Mercury (Hg) stable isotopes were analyzed in hair samples from peripartum mothers in China (n = 265). Associations between mass dependent fractionation (MDF) (δ202Hg) and mass independent fractionation (MIF) (Δ199Hg) (dependent variables) and dietary MeHg intake (independent variable) were investigated using multivariable regression models. Results. In adjusted models, hair Δ199Hg was positively correlated with serum omega-3 fatty acids (a biomarker for fish consumption) and negatively correlated with maternal rice MeHg intake, indicating MIF recorded in hair can be used to distinguish MeHg intake predominantly from fish versus rice. Conversely, in adjusted models, hair δ202Hg was not correlated with measures of dietary measures of MeHg intake. Instead, hair δ202Hg was strongly, negatively correlated with hair Hg, which explained 27-29% of the variability in hair δ202Hg. Conclusions. Our results indicated that hair Δ199Hg can be used to distinguish MeHg intake from fish versus rice. Results also suggested that lighter isotopes were preferentially accumulated in hair, potentially reflecting Hg binding to thiols (i.e., cysteine); however, more research is needed to elucidate this hypothesis. Broader impacts include 1) validation of a non-invasive biomarker to distinguish MeHg intake from rice versus fish, and 2) the potential to use Hg isotopes to investigate Hg binding in tissues.

National-Scale Assessment of Total Gaseous Mercury Isotopes Across the United States.

With the 2011 promulgation of the Mercury and Air Toxics Standards by the U.S. Environmental Protection Agency, and the successful negotiation by the United Nations Environment Program of the Minamata Convention, emissions of mercury (Hg) have declined in the United States. While the declines in atmospheric Hg concentrations in North America are encouraging, linking the declines to changing domestic and global source portfolios remains challenging. To address these research gaps, the U.S. Geological Survey initiated the first national-scale effort to establish a baseline of total gaseous mercury stable isotope values at 31 sites distributed across the United States. Results indicated that unique Hg sources, such as Hg evasion from an elemental Hg contaminated site or free tropospheric intrusions in high altitude sites, were distinguishable from background atmospheric values. Minor gradients were observed across the nation, with regions of heavy industrial activity demonstrating lower δ202Hg, but no consistent changes in other isotopes such as Δ199Hg and Δ200Hg were observed. Furthermore, δ202Hg was impacted by foliar uptake and senescence but trends varied between forested regions in the northeastern and midwestern United States. These data demonstrate regional emission sources and other environmental variables can impact total gaseous Hg (TGM) isotope values, highlighting the need to characterize atmospheric Hg isotopes over larger geographical areas to evaluate changes related to national and international Hg regulations.

Mercury Isotope Values in Shoreline Spiders Reveal the Transfer of Aquatic Mercury Sources to Terrestrial Food Webs.

The transfer of aquatic contaminants, including mercury (Hg), to terrestrial food webs is an often-overlooked exposure pathway to terrestrial animals. While research has implemented the use of shoreline spiders to assess aquatic to terrestrial Hg transfer, it is unclear whether Hg sources, estimated from isotope ratios, can be successfully resolved to inform site assessments and remedy effectiveness. To examine aquatic to terrestrial Hg transfer, we collected shoreline spiders (Tetragnatha spp.) and aquatic insect larvae (suborder Anisoptera) across a mosaic of aquatic and shoreline habitats in the St. Louis River and Bad River, tributaries to Lake Superior. The fraction of industrial Hg in sediments was reflected in the δ202Hg values of aquatic dragonfly larvae and predatory fish, connecting benthic Hg sources to the aquatic food web. Shoreline spiders mirrored these aquatic Hg source signatures with highly positive correlations in δ202Hg between tetragnathids and dragonfly larvae (r2 = 0.90). Further assessment of different spider taxa (i.e., araneids and pisaurids) revealed that differences in prey consumption and foraging strategies resulted in isotope differences, highlighting the importance of spider taxa selection for Hg monitoring efforts.

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.

Can preserved museum specimens be used to reconstruct fish mercury burden and sources through time?

To evaluate the utility of preserved fishes for reconstructing historical and spatial patterns of mercury (Hg) exposure, we experimentally tested the stability of Hg concentrations and Hg stable isotope ratios under standard museum practices of specimen preservation. We found that loss of unidentified constituents during preservation increased Hg concentrations in fish muscle. Low-Hg fish reared in the laboratory were susceptible to exogenous contamination with inorganic mercury (iHg) when preservative fluids were intentionally spiked or iHg leached passively from contaminated wild fishes in the same container. This contamination impacted Hg isotope values of total Hg, but the conservative nature of methylmercury allows us to quantitatively correct for iHg contamination. Our findings validate the potential to use fishes from the world's museums to generate spatiotemporal baselines for the Minamata Convention on Mercury, but we recommend a set of precautions to maximize inference strength. Selecting the largest specimens of a target species helps dilute any iHg contamination. Specimens should be drawn from lots that were not comingled with fishes from other collections to minimize risk of iHg transfer among fish with different contamination histories. Finally, focusing on low-lipid species will enhance the comparability of Hg concentrations between historical and contemporary collections.

Tracing the sources and depositional history of mercury to coastal northeastern U.S. lakes.

Mercury (Hg) deposition was reconstructed in sediment cores from lakes in two coastal U.S. National Parks: Acadia National Park (ANP) and Cape Cod National Seashore (CCNS), to fill an important spatial gap in Hg deposition records and to explore changing sources of Hg and processes affecting Hg accumulation in these coastal sites. Recent Hg deposition chronology was assessed using (1) a newly developed lead-210 (210Pb) based sediment age model which employs 7Be to constrain deposition and sediment mixing of 210Pb-excess, (2) coinciding Pb flux and isotope ratios (206Pb/207Pb), and (3) Hg isotope ratios and their response to changes in Hg flux. At both sites, Hg flux increased substantially from pre-1850 levels, with accumulation in ANP peaking in the 1970s, whereas in CCNS, Hg levels were highest in recent sediments. Negative values of δ202Hg and Δ199Hg indicated terrestrially-derived Hg was a major constituent of Hg flux to Sargent Mountain Pond, ANP, although recent decreases in Hg flux were in agreement with precipitation Hg records, indicating a rapid watershed response. By contrast, δ202Hg and Δ199Hg profiles in Long Pond, CNNS reflect direct Hg deposition, but disturbances in the sedimentary record were indicated by bomb fallout radionuclide inventories and by peaks in both Pb and Hg isotope depth profiles. These cores provided poor reconstructions of atmospheric deposition and reveal responses that are decoupled from emissions reduction due to complex post-depositional redistribution of atmospheric metals including Hg. The application of multiple tracers of Hg deposition provide insight into the sources and pathways governing Hg accumulation in these lakes.

Elevated Mercury Concentrations and Isotope Signatures (N, C, Hg) in Yellowfin Tuna (Thunnus albacares) from the Galápagos Marine Reserve and Waters off Ecuador.

We examined how dietary factors recorded by C and N influence Hg uptake in 347 individuals of yellowfin tuna (Thunnus albacares), an important subsistence resource from the Galápagos Marine Reserve (Ecuador) and the Ecuadorian mainland coast in 2015-2016. We found no differences in total Hg (THg) measured in red muscle between the two regions and no seasonal differences, likely due to the age of the fish and slow elimination rates of Hg. Our THg concentrations are comparable to those of other studies in the Pacific (0.20-9.60 mg/kg wet wt), but a subset of individuals exhibited the highest Hg concentrations yet reported in yellowfin tuna. Mercury isotope values differed between Δ199 Hg and δ202Hg in both regions (Δ199 Hg = 2.86 ± 0.04‰ vs. Δ199 Hg = 2.33 ± 0.07‰), likely related to shifting food webs and differing photochemical processing of Hg prior to entry into the food web. There were significantly lower values of both δ15 N and δ13 C in tuna from Galápagos Marine Reserve (δ15 N: 8.5-14.2‰, δ13 C: -18.5 to -16.1‰) compared with those from the Ecuadorian mainland coast (δ15 N: 8.3-14.4‰, δ13 C: -19.4 to -11.9‰), of which δ13 C values suggest spatially constrained movements of tuna. Results from the pooled analysis, without considering region, indicated that variations in δ13 C and δ15 N values tracked changes of Hg stable isotopes. Our data indicate that the individual tuna we used were resident fish of each region and were heavily influenced by upwellings related to the eastern Pacific oxygen minimum zone and the Humboldt Current System. The isotopes C, N, and Hg reflect foraging behavior mainly on epipelagic prey in shallow waters and that food web shifts drive Hg variations between these populations of tuna. Environ Toxicol Chem 2022;41:2732-2744. © 2022 SETAC.