USGS ScienceSearch

Geology topics

Collin A. Eagles-Smith

Publications and source records attributed to Collin A. Eagles-Smith.

At least 37 records · Page 2Linked to original sources

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.

Science of the Total Environment

Forest cover influences fish mercury concentrations in national parks of the western U.S.

The global prevalence of mercury (Hg) contamination and its complex biogeochemical cycling has resulted in elevated Hg concentrations in biota in remote and pristine environments. However, there is uncertainty in the relative importance of Hg deposition and landscape factors that control Hg cycling and bioaccumulation. To address this, we measured total mercury (THg) concentrations in 1344 fish across 60 subalpine lakes from 12 national parks (NPs). These parks represent three distinct high-elevation regions across the western U.S.: Cascades and Olympic Peninsula, Sierra Nevada and Great Basin, and Rocky Mountains. Within these regions, three NPs (Mount Rainier, Yosemite, and Rocky Mountain) were intensively studied representatives of each region. This study aimed to (1) assess the magnitude of mercury contamination in a collection of remote, small catchment lakes; (2) quantify the variability of fish THg concentrations among and within parks; and (3) test the relative importance of Hg inputs in comparison to landscape characteristics on lake-specific fish THg concentrations. The spatial variability in fish THg concentrations was 2.6-fold higher than variation in deposition to watersheds, suggesting that factors other than Hg delivery are important determinants of Hg accumulation in these environments. Spatially, fish THg concentrations (ng/g ww ± standard error) were lower in the Rockies (46.2 ± 5.0) and Sierra (56.5 ± 5.8) compared to the Cascades (67.8 ± 6.1). Additionally, fish THg concentrations increased with increasing conifer forest cover (Intensive parks: P < 0.0001, R 2 = 0.43; All parks: P = 0.0001, R 2 = 0.23) but were not correlated with wet Hg deposition across the catchment. These findings suggest that forest composition is likely an important aspect of Hg delivery to lake food webs, and although the mechanisms are unclear, could be tied to some combination of forest influences on catchment organic carbon and increased surface area for dry Hg deposition.

western United States

Reservoir stratification modulates the influence of impoundments on fish mercury concentrations along an arid land river system

Impoundment is among the most common hydrologic alterations with impacts on aquatic ecosystems that can include effects on mercury (Hg) cycling. However, landscape-scale differences in Hg bioaccumulation between reservoirs and other habitats are not well characterized nor are the processes driving these differences. We examined total Hg (THg) concentrations of Smallmouth Bass ( Micropterus dolomieu ) collected from reservoir, tailrace, and free-flowing reaches along an 863 km segment of the Snake River, USA, a semiarid river with 22 impoundments along its course. Across three size-classes (putative 1-year-old, first reproductive, and harvestable sized fish), THg concentrations in reservoirs and tailraces averaged 76% higher than those in free-flowing segments. Among reservoirs, THg concentrations were highest in reservoirs with inconsistent stratification patterns, 47% higher than annually stratified, and 144% higher than unstratified reservoirs. Fish THg concentrations in tailraces immediately downstream of stratified reservoirs were higher than those below unstratified (38–130%) or inconsistently stratified (32–79%) reservoirs. Stratification regimes influenced the exceedance of fish and human health benchmarks, with 52–80% of fish from stratifying reservoirs and downstream tailraces exceeding a human consumption benchmark, compared to 6–17% where stratification did not occur. These findings suggest that impoundment and stratification play important roles in determining the patterns of Hg exposure risk across the landscape.

Environmental Science & Technology

Broad-scale assessment of methylmercury in adult amphibians

Mercury (Hg) is a toxic contaminant that has been mobilized and distributed worldwide and is a threat to many wildlife species. Amphibians are facing unprecedented global declines due to many threats including contaminants. While the biphasic life history of many amphibians creates a potential nexus for methylmercury (MeHg) exposure in aquatic habitats and subsequent health effects, the broad-scale distribution of MeHg exposure in amphibians remains unknown. We used nonlethal sampling to assess MeHg bioaccumulation in 3,241 juvenile and adult amphibians during 2017–2021. We sampled 26 populations (14 species) across 11 states in the United States, including several imperiled species that could not have been sampled by traditional lethal methods. We examined whether life history traits of species and whether the concentration of total mercury in sediment or dragonflies could be used as indicators of MeHg bioaccumulation in amphibians. Methylmercury contamination was widespread, with a 33-fold difference in concentrations across sites. Variation among years and clustered subsites was less than variation across sites. Life history characteristics such as size, sex, and whether the amphibian was a frog, toad, newt, or other salamander were the factors most strongly associated with bioaccumulation. Total Hg in dragonflies was a reliable indicator of bioaccumulation of MeHg in amphibians (R 2 ≥ 0.67), whereas total Hg in sediment was not (R 2 ≤ 0.04). Our study, the largest broad-scale assessment of MeHg bioaccumulation in amphibians, highlights methodological advances that allow for nonlethal sampling of rare species and reveals immense variation among species, life histories, and sites. Our findings can help identify sensitive populations and provide environmentally relevant concentrations for future studies to better quantify the potential threats of MeHg to amphibians.

Environmental Science and Technology

Mercury isotope values in shoreline spiders reveal 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 δ 202 Hg 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 δ 202 Hg between tetragnathids and dragonfly larvae ( r 2 = 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.

Minnesota, Wisconsin

Complex life histories alter patterns of mercury exposure and accumulation in a pond-breeding amphibian

Quantifying how contaminants change across life cycles of species that undergo metamorphosis is critical to assessing organismal risk, particularly for consumers. Pond-breeding amphibians can dominate aquatic animal biomass as larvae and are terrestrial prey as juveniles and adults. Thus, amphibians can be vectors of mercury exposure in both aquatic and terrestrial food webs. However, it is still unclear how mercury concentrations are affected by exogenous (e.g., habitat or diet) vs endogenous factors (e.g., catabolism during hibernation) as amphibians undergo large diet shifts and periods of fasting during ontogeny. We measured total mercury (THg), methylmercury (MeHg), and isotopic compositions (δ 13 C, δ 15 N) in boreal chorus frogs ( Pseudacris maculata ) across five life stages in two Colorado (USA) metapopulations. We found large differences in concentrations and percent MeHg (of THg) among life stages. Frog MeHg concentrations peaked during metamorphosis and hibernation coinciding with the most energetically demanding life cycle stages. Indeed, life history transitions involving periods of fasting coupled with high metabolic demands led to large increases in mercury concentrations. The endogenous processes of metamorphosis and hibernation resulted in MeHg bioamplification, thus decoupling it from the light isotopic proxies of diet and trophic position. These step changes are not often considered in conventional expectations of how MeHg concentrations within organisms are assessed.

Environmental Science & Technology

Using mercury stable isotope fractionation to identify the contribution of historical mercury mining sources present in downstream water, sediment and fish

Ecosystems downstream of mercury (Hg) contaminated sites can be impacted by both localized releases as well as Hg deposited to the watershed from atmospheric transport. Identifying the source of Hg in water, sediment, and fish downstream of contaminated sites is important for determining the effectiveness of source-control remediation actions. This study uses measurements of Hg stable isotopes in soil, sediment, water, and fish to differentiate between Hg from an abandoned Hg mine from non-mine-related sources. The study site is located within the Willamette River watershed (Oregon, United States), which includes free-flowing river segments and a reservoir downstream of the mine. The concentrations of total-Hg (THg) in the reservoir fish were 4-fold higher than those further downstream (>90 km) from the mine site in free-flowing sections of the river. Mercury stable isotope fractionation analysis showed that the mine tailings (δ 202 Hg: −0.36‰ ± 0.03‰) had a distinctive isotopic composition compared to background soils (δ 202 Hg: −2.30‰ ± 0.25‰). Similar differences in isotopic composition were observed between stream water that flowed through the tailings (particulate bound δ 202 Hg: −0.58‰; dissolved: −0.91‰) versus a background stream (particle-bound δ 202 Hg: −2.36‰; dissolved: −2.09‰). Within the reservoir sediment, the Hg isotopic composition indicated that the proportion of the Hg related to mine-release increased with THg concentrations. However, in the fish samples the opposite trend was observed—the degree of mine-related Hg was lower in fish with the higher THg concentrations. While sediment concentrations clearly show the influence of the mine, the relationship in fish is more complicated due to differences in methylmercury (MeHg) formation and the foraging behavior of different fish species. The fish tissue δ 13 C and Δ 199 Hg values indicate that there is a higher influence of mine-sourced Hg in fish feeding in a more sediment-based food web and less so in planktonic and littoral-based food webs. Identifying the relative proportion of Hg from local contaminated site can help inform remediation decisions, especially when the relationship between total Hg concentrations and sources do not show similar covariation between abiotic and biotic media.

Oregon

Per- and polyfluoroalkyl substances (PFAS) in United States tapwater: Comparison of underserved private-well and public-supply exposures and associated health implications

Drinking-water quality is a rising concern in the United States (US), emphasizing the need to broadly assess exposures and potential health effects at the point-of-use. Drinking-water exposures to per- and poly-fluoroalkyl substances (PFAS) are a national concern, however, there is limited information on PFAS in residential tapwater at the point-of-use, especially from private-wells. We conducted a national reconnaissance to compare human PFAS exposures in unregulated private-well and regulated public-supply tapwater. Tapwater from 716 locations (269 private-wells; 447 public supply) across the US was collected during 2016–2021 including three locations where temporal sampling was conducted. Concentrations of PFAS were assessed by three laboratories and compared with land-use and potential-source metrics to explore drivers of contamination. The number of individual PFAS observed ranged from 1 to 9 (median: 2) with corresponding cumulative concentrations (sum of detected PFAS) ranging from 0.348 to 346 ng/L. Seventeen PFAS were observed at least once with PFBS, PFHxS and PFOA observed most frequently in approximately 15% of the samples. Across the US, PFAS profiles and estimated median cumulative concentrations were similar among private wells and public-supply tapwater. We estimate that at least one PFAS could be detected in about 45% of US drinking-water samples. These detection probabilities varied spatially with limited temporal variation in concentrations/numbers of PFAS detected. Benchmark screening approaches indicated potential human exposure risk was dominated by PFOA and PFOS, when detected. Potential source and land-use information was related to cumulative PFAS concentrations, and the number of PFAS detected; however, corresponding relations with specific PFAS were limited likely due to low detection frequencies and higher detection limits. Information generated supports the need for further assessments of cumulative health risks of PFAS as a class and in combination with other co-occurring contaminants, particularly in unmonitored private-wells where information is limited or not available.

U.S. Virgin Islands

Understanding drivers of mercury in lake trout (Salvelinus namaycush), a top-predator fish in southwest Alaska's parklands

Mercury (Hg) is a widespread element and persistent pollutant, harmful to fish, wildlife, and humans in its organic, methylated form. The risk of Hg contamination is driven by factors that regulate Hg loading, methylation, bioaccumulation, and biomagnification. In remote locations, with infrequent access and limited data, understanding the relative importance of these factors can pose a challenge. Here, we assessed Hg concentrations in an apex predator fish species, lake trout (Salvelinus namaycush), collected from 14 lakes spanning two National Parks in southwest Alaska, U.S.A. We then examined factors associated with the variation in fish Hg concentrations using a Bayesian hierarchical model. We found that total Hg concentrations in water were consistently low among lakes (0.11–0.50 ng L− 1). Conversely, total Hg concentrations in lake trout spanned a thirty-fold range (101–3046 ng g− 1 dry weight), with median values at 7 lakes exceeding Alaska’s human consumption threshold. Model results showed that fish age and, to a lesser extent, body condition best explained variation in Hg concentration among fish within a lake, with Hg elevated in older, thinner lake trout. Other factors, including plankton methyl Hg content, fish species richness, volcano proximity, and glacier loss, best explained variation in lake trout Hg concentration among lakes. Collectively, these results provide evidence that multiple, hierarchically nested factors control fish Hg levels in these lakes.

Alaska

A multi-level assessment of biological effects associated with mercury concentrations in smallmouth bass, Micropterus dolomieu

Total mercury (THg) was measured in muscle (fillet) and liver tissue of adult smallmouth bass Micropterus dolomieu collected at multiple sites in the Potomac and Susquehanna River drainages within the Chesapeake Bay watershed. Smallmouth bass in these drainages have experienced episodic mortality events, a high prevalence of skin lesions and reproductive endocrine disruption (intersex or testicular oocytes and plasma vitellogenin in males). A multi-level assessment of general and reproductive health including indicators at the organismal, organ, cellular and molecular levels was conducted on adult smallmouth bass during the spring (prespawn) season. Concentrations of THg were correlated with increased visible abnormalities, increased macrophage aggregates and tissue parasite burdens. In male bass positive correlations of THg were observed with plasma vitellogenin and hepatic transcript abundance of estrogen receptor β1 and androgen receptor α, while there was a negative association with estrogen receptors α and β2 and androgen receptors β. In female bass there was a negative correlation between THg and plasma vitellogenin as well as hepatic transcript abundance of vitellogenin, choriogenin, estrogen receptor β2 and 17β hydroxysteroid dehydrogenase. Associations of THg concentrations with various biological indicators suggest mercury may be an important environmental stressor contributing to the observed adverse effects in smallmouth bass populations.

Environmental Pollution

Anticoagulant rodenticides are associated with increased stress and reduced body condition of avian scavengers in the Pacific Northwest

Anticoagulant rodenticides (AR) have been used globally to manage commensal rodents for decades. However their application has also resulted in primary, secondary, and tertiary poisoning in wildlife. Widespread exposure to ARs (primarily second generation ARs; SGARs) in raptors and avian scavengers has triggered considerable conservation concern over their potential effects on populations. To identify risk to extant raptor and avian scavenger populations in Oregon and potential future risk to the California condor ( Gymnogyps californianus ) flock recently established in northern California, we assessed AR exposure and physiological responses in two avian scavenger species (common ravens [ Corvus corax ] and turkey vultures [ Cathartes aura ]) throughout Oregon between 2013 and 2019. AR exposure was widespread with 51% (35/68) of common ravens and 86% (63/73) of turkey vultures containing AR residues. The more acutely toxic SGAR brodifacoum was present in 83% and 90% of AR exposed common ravens and turkey vultures. The odds of AR exposure in common ravens were 4.7-fold higher along the coastal region compared to interior Oregon. For common ravens and turkey vultures that were exposed to ARs, respectively, 54% and 56% had concentrations that exceeded the 5% probability of toxicosis (>20 ng/g ww; Thomas et al., 2011), and 20% and 5% exceeded the 20% probability of toxicosis (>80 ng/g ww; Thomas et al., 2011). Common ravens exhibited a physiological response to AR exposure with fecal corticosterone metabolites increasing with sum ARs (ΣAR) concentrations. Both female common raven and turkey vultures’ body condition was negatively correlated with increasing ΣAR concentrations. Our results suggest avian scavengers in Oregon are experiencing extensive AR exposure and the newly established population of California condors in northern California may experience similar AR exposure if they feed in southern Oregon. Understanding the sources of ARs across the landscape is an important first step in reducing or eliminating AR exposure in avian scavengers.

Oregon

The influence of short-term temporal variability on the efficacy of dragonfly larvae as mercury biosentinels

Mercury (Hg) exposure to fish, wildlife, and humans is widespread and of global concern, thus stimulating efforts to reduce emissions. Because the relationships between rates of inorganic Hg loading, methylmercury (MeHg) production, and bioaccumulation are extremely complex and challenging to predict, there is a need for reliable biosentinels to understand the distribution of Hg in the environment and monitor the effectiveness of reduction efforts. However, it is important to assess how temporal and spatial variation at multiple scales influences the efficacy of specific biosentinels. Seasonal and interannual variation in total Hg (THg) concentrations of dragonfly larvae were examined in relation to spatial variability among 21 sites in two U.S. national parks with contrasting ecologies and Hg deposition patterns. Dragonfly THg differed among sampling events at 17 of the 21 sites, but by an average of only 20.4 % across events, compared to an average difference of 52.7 % among sites. Further, THg concentrations did not follow consistent seasonal patterns across sites or years, suggesting that the observed temporal variation was unlikely to bias monitoring efforts. Importantly, for a specific site, there was no difference in % MeHg in dragonflies among sampling events. Finally, there was significant temporal variability in the biogeochemical factors (aqueous inorganic Hg, aqueous MeHg, DOC, SO 4 , and pH) influencing dragonfly THg, with the importance of individual factors varying by 2.4 to 4.3-fold across sampling events. Despite these results, it is noteworthy that the observed temporal variation in dragonfly THg concentrations was neither large nor consistent enough to bias spatial assessments. Thus, although this temporal variation may provide insights into the processes influencing biological Hg concentrations, it is unlikely to impair the use of dragonflies as biosentinels for monitoring spatial or temporal patterns at scales relevant to most mitigation efforts.

Science of the Total Environment

In-reservoir physical processes modulate aqueous and biological methylmercury export from a seasonally anoxic reservoir

Anoxic conditions within reservoirs related to thermal stratification and oxygen depletion lead to methylmercury (MeHg) production, a key process governing the uptake of mercury in aquatic food webs. Once formed within a reservoir, the timing and magnitude of the biological uptake of MeHg and the relative importance of MeHg export in water versus biological compartments remain poorly understood. We examined the relations between the reservoir stratification state, anoxia, and the concentrations and export loads of MeHg in aqueous and biological compartments at the outflow locations of two reservoirs of the Hells Canyon Complex (Snake River, Idaho-Oregon). Results show that (1) MeHg concentrations in filter-passing water, zooplankton, suspended particles, and detritus increased in response to reservoir destratification; (2) zooplankton MeHg strongly correlated with MeHg in filter-passing water during destratification; (3) reservoir anoxia appeared to be a key control on MeHg export; and (4) biological MeHg, primarily in zooplankton, accounted for only 5% of total MeHg export from the reservoirs (the remainder being aqueous compartments). These results improve our understanding of the role of biological incorporation of MeHg and the subsequent downstream release from seasonally stratified reservoirs and demonstrate that in-reservoir physical processes strongly influence MeHg incorporation at the base of the aquatic food web.

Idaho, Oregon

Using carbon, nitrogen, and mercury isotope values to distinguish mercury sources to Alaskan lake trout

Lake trout ( Salvelinus namaycush ), collected from 13 remote lakes located in southwestern Alaska, were analyzed for carbon, nitrogen, and mercury (Hg) stable isotope values to assess the importance of migrating oceanic salmon, volcanic activity, and atmospheric deposition to fish Hg burden. Methylmercury (MeHg) bioaccumulation in phytoplankton (5.0–6.9 kg L –1 ) was also measured to quantify the basal uptake of MeHg to these aquatic food webs. Hg isotope values in lake trout revealed that while the extent of precipitation-delivered Hg was similar across the entire study area, volcanic Hg is likely an important additional source to lake trout in proximate lakes. In contrast, migratory salmon ( Oncorhynchus nerka ) deliver little MeHg to lake trout directly, although indirect delivery processes via decay could exist. A high level of variability in carbon, nitrogen, and Hg isotope values indicates niche partitioning in lake trout populations within each lake and that a complex suite of ecological interactions is occurring, complicating the conceptually linear assessment of the contaminant source to the receiving organism. Without connecting energy and contaminant isotope axes, we would not have understood why lake trout from these pristine lakes have highly variable Hg burdens despite consistently low water Hg and comparable age-length dynamics.

Alaska

Collateral damage: Anticoagulant rodenticides pose threats to California condors

Anticoagulant rodenticides (ARs) are widespread environmental contaminants that pose risks to scavenging birds because they routinely occur within their prey and can cause secondary poisoning. However, little is known about AR exposure in one of the rarest avian scavengers in the world, the California condor ( Gymnogyps californianus ). We assessed AR exposure in California condors and surrogate turkey vultures ( Cathartes aura ) to gauge potential hazard to a proposed future condor flock by determining how application rate and environmental factors influence exposure. Additionally, we examined whether ARs might be correlated with prolonged blood clotting time and potential mortality in condors. Only second-generation ARs (SGARs) were detected, and exposure was detected in all condor flocks. Liver AR residues were detected in 42% of the condors (27 of 65) and 93% of the turkey vultures (66 of 71). Although concentrations were generally low (<10 ng/g ww), 48% of the California condors and 64% of the turkey vultures exposed to ARs exceeded the 5% probability of exhibiting signs of toxicosis (>20 ng/g ww), and 10% and 13% exceeded the 20% probability of exhibiting signs toxicosis (>80 ng/g ww). There was evidence of prolonged blood clotting time in 16% of the free-flying condors. For condors, there was a relationship between the interaction of AR exposure index (legal use across regions where condors existed) and precipitation, and the probability of detecting ARs in liver. Exposure to ARs may complicate recovery efforts of condor populations within their current range and in the soon to be established northern California experimental population. Continued monitoring of AR exposure using plasma blood clotting assays and residue analysis would allow for an improved understanding of their hazard to condors, particularly if paired with recent movement data that could elucidate exposure sources on the landscape occupied by this endangered species.

California

Mercury exposure of tidal marsh songbirds in the northeastern United States and its association with nest survival

The biogeochemistry of tidal marsh sediments facilitates the transformation of mercury (Hg) into the biologically available form methylmercury (MeHg), resulting in elevated Hg exposures to tidal marsh wildlife. Saltmarsh and Acadian Nelson’s sparrows ( Ammospiza caudacutua and A. nelsoni subvirgatus , respectively) exclusively inhabit tidal marshes, potentially experiencing elevated risk to Hg exposure, and have experienced range-wide population declines. To characterize spatial and temporal variation of Hg exposure in these species, we sampled total mercury (THg) in blood collected from 9 populations spanning 560 km of coastline, including individuals resampled within and among years. Using concurrent nesting studies, we tested whether THg was correlated with nest survival probabilities, an index of fecundity. Blood THg ranged from 0.074–3.373 µg/g ww across 170 samples from 127 individuals. We detected high spatial variability in Hg exposure, observing differences of more than 45-fold across all individuals and 8-fold in mean blood THg among all study plots, including 4-fold between study plots within 4 km. Intraindividual changes in blood Hg exposure did not vary systematically in time but were considerable, varying by up to 2-fold within and among years. Controlling for both species differences and maximum water level, the dominant driver of fecundity in this system, nest survival probability decreased by 10% across the full range of female blood THg concentrations observed. We conclude that Hg has the potential to impair songbird reproduction, potentially exacerbating known climate-change driven population declines from sea-level rise in saltmarsh and Acadian Nelson’s sparrows.

Connecticut, Maine, New Hampshire, New Jersey

Small mammal shooting as a conduit for lead exposure in avian scavengers

Lead (Pb) exposure is a widespread wildlife conservation threat. Although commonly associated with Pb-based ammunition from big-game hunting, small mammals (e.g., ground squirrels) shot for recreational or pest-management purposes represent a potentially important Pb vector in agricultural regions. We measured the responses of avian scavengers to pest-shooting events and examined their Pb exposure through consumption of shot mammals. There were 3.4-fold more avian scavengers at shooting fields relative to those at fields with no recent shooting, and avian scavengers spent 1.8-fold more time feeding after recent shooting events. We isotopically labeled shot ground squirrels in the field with an enriched 15N isotope tracer; 6% of avian scavengers sampled within a 39 km radius reflected this tracer in their blood. However, 33% of the avian scavengers within the average foraging dispersal distance of nests (0.6−3.7 km) were labeled, demonstrating the importance of these shooting fields as a source of food for birds nesting in close proximity. Additionally, Pb concentrations in 48% of avian scavengers exceeded subclinical poisoning benchmarks for sensitive species (0.03−0.20 μg/g w/w), and those birds exhibited reduced δ-aminolevulinic acid dehydratase activity, indicating a biochemical effect of Pb. The use of shooting to manage small mammal pests is a common practice globally. Efforts that can reduce the use of Pb-based ammunition may lessen the negative physiological effects of Pb exposure on avian scavengers.

Oregon

Isotope fractionation from In Vivo methylmercury detoxification in waterbirds

The robust application of stable mercury (Hg) isotopes for mercury source apportionment and risk assessment necessitates the understanding of mass-dependent fractionation (MDF) due to internal transformations within organisms. Here, we used high energy-resolution XANES spectroscopy and isotope ratios of total mercury (δ202THg) and methylmercury (δ202MeHg) to elucidate the chemical speciation of Hg and the resultant MDF due to internal MeHg demethylation in waterbirds. In three waterbirds (Clark’s grebe, Forster’s tern, south polar skua), between 17-86% of the MeHg was demethylated to inorganic mercury (iHg) species primarily in the liver and kidneys as Hg-tetraselenolate (Hg(Sec)4) and minor Hg-dithiolate (Hg(SR)2) complexes. Tissular differences between δ202THg and δ202MeHg correlated linearly with %iHg (Hg(Sec)4 + Hg(SR)2), and were interpreted to reflect a kinetic isotope effect during in vivo MeHg demethylation. The product-reactant isotopic enrichment factor (εp/r) for the demethylation of MeHg  Hg(Sec)4 was −2.2 ± 0.1‰. δ202MeHg values were unvarying within each bird regardless of Hg(Sec)4 abundance, indicating fast internal cycling or replenishment of MeHg relative to demethylation. Our findings document a universal selenium-dependent demethylation reaction in birds, provide new insights on the internal transformations and cycling of MeHg and Hg(Sec)4, and allow for mathematical correction of δ202THg values due to the MeHg  Hg(Sec)4 reaction.

ACS Earth and Space Chemistry