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David P. Krabbenhoft

Publications and source records attributed to David P. Krabbenhoft.

At least 37 records · Page 2Linked to original sources

Biogeochemical and hydrologic synergy control mercury fate in an arid land river-reservoir system

Reservoirs in arid landscapes provide critical water storage and hydroelectric power but influence the transport and biogeochemical cycling of mercury (Hg). Improved management of reservoirs to mitigate the supply and uptake of bioavailable methylmercury (MeHg) in aquatic food webs will benefit from a mechanistic understanding of inorganic divalent Hg (Hg( II )) and MeHg fate within and downstream of reservoirs. Here, we quantified Hg( II ), MeHg, and other pertinent biogeochemical constituents in water (filtered and associated with particles) at high temporal resolution from 2016–2020. This was done (1) at inflow and outflow locations of three successive hydroelectric reservoirs (Snake River, Idaho, Oregon) and (2) vertically and longitudinally within the first reservoir (Brownlee Reservoir). Under spring high flow, upstream inputs of particulate Hg (Hg( II ) and MeHg) and filter-passing Hg( II ) to Brownlee Reservoir were governed by total suspended solids and dissolved organic matter, respectively. Under redox stratified conditions in summer, net MeHg formation in the meta- and hypolimnion of Brownlee reservoir yielded elevated filter-passing and particulate MeHg concentrations, the latter exceeding 500 ng g −1 on particles. Simultaneously, the organic matter content of particulates increased longitudinally in the reservoir (from 9–29%) and temporally with stratified duration. In late summer and fall, destratification mobilized MeHg from the upgradient metalimnion and the downgradient hypolimnion of Brownlee Reservoir, respectively, resulting in downstream export of elevated filter-passing MeHg and organic-rich particles enriched in MeHg (up to 43% MeHg). We document coupled biogeochemical and hydrologic processes that yield in-reservoir MeHg accumulation and MeHg export in water and particles, which impacts MeHg uptake in aquatic food webs within and downstream of reservoirs.

Environmental Science: Processes & Impacts

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

Assessment of mercury in sediments and waters of Grubers Grove Bay, Wisconsin

Mercury is a global contaminant that can be detrimental to wildlife and human health. Anthropogenic emissions and point sources are primarily responsible for elevated mercury concentrations in sediments and waters. Mercury can physically move and chemically transform in the environment, resulting in biomagnification of mercury, in the form of methylmercury, in the food web and causing elevated mercury concentrations in upper trophic levels. The ability to measure total mercury concentrations in the environment has existed for several decades and makes it possible to detect hotspots that might exist because of ongoing or previous anthropogenic activity. However, recent (within the past 15 years) developments in mass spectrometry have made it possible to complete low level stable isotope analysis allowing for the determination of mercury sources—natural and anthropogenic—in the environment through “fingerprinting.” Grubers Grove Bay in Lake Wisconsin, the focus area of this study, was determined to have elevated mercury levels even after multiple remediation efforts, resulting in its listing on the Federal list of impaired waters pursuant to the Clean Water Act. Adjacent to the bay is the former Badger Army Ammunition Plant, which manufactured ammunition for the U.S. Army during the early and middle 20th century, after which it was put on standby before being fully decommissioned. This study assesses mercury concentrations in the sediments and suspended particulate matter of Grubers Grove Bay, Wiegands Bay, and upstream sites, and in adjacent soils on the former Badger Army Ammunition Plant site. This study confirmed that mercury contamination exists in the sediments of Grubers Grove Bay even after dredging attempts by the U.S. Army. Additionally, using isotope ratios and a two-endmember mixing model, it was determined that soil from within Badger Army Ammunition Plant’s former site contributed a substantial amount of mercury to the bay. This result was supported by an observed gradient of high to low mercury concentrations from the innermost (nearest Badger Army Ammunition Plant) to the outermost (farthest from Badger Army Ammunition Plant) part of the bay.

Wisconsin

Methylmercury stable isotopes: New insights on assessing aquatic food web bioaccumulation in legacy impacted regions

Through stable isotope measurements of total mercury (HgT), identification of crucial processes and transformations affecting different sources of mercury (Hg) has become possible. However, attempting to use HgT stable isotopes to track bioaccumulation of Hg sources among different food web compartments can be challenging, if not impossible, when tissues have varying methylmercury (MeHg) contents. We measured HgT and MeHg stable isotope ratios within the lower Fox River to examine how these values differed across the food web and if isotope values in biota were influenced by legacy contamination. We showed that seston, invertebrates, and fish had a large range of δ 202 HgT (−0.74 to 0.15 ‰, n = 11) due to varying MeHg contents in tissues but a commonly conserved MeHg isotope value (δ 202 MeHg ave = 0.01 ± 0.12 ‰, 1 standard deviation, n = 11). We also examined some mathematical approaches to estimate the MeHg isotope values, which were mostly comparable to measured MeHg isotope values in the Fox River, with some exceptions. In this study, we observed that the MeHg isotope values can elucidate links between different food web compartments and provide insight on aquatic Hg cycling that can be masked by the sole use of HgT isotopes in contaminated sites.

Wisconsin

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

Decadal trends of mercury cycling and bioaccumulation within Everglades National Park

Mercury (Hg) contamination has been a persistent concern in the Florida Everglades for over three decades due to elevated atmospheric deposition and the system's propensity for methylation and rapid bioaccumulation. Given declines in atmospheric Hg concentrations in the conterminous United States and efforts to mitigate nutrient release to the greater Everglades ecosystem, it was vital to assess how Hg dynamics responded on temporal and spatial scales. This study used a multimedia approach (water and biota) to examine Hg and methylmercury (MeHg) dynamics across a 76-site network within the southernmost portion of the region, Everglades National Park (ENP), from 2008 to 2018. Atmospheric Hg deposition was evaluated over time using a long-term monitoring station. Hg concentrations across matrices showed that air, water, and biota from the system were inextricably linked. Temporal patterns across matrices were driven primarily by hydrologic and climatic changes in the park and no evidence of a decline in atmospheric Hg deposition from 2008 to 2018 was observed, unlike other regions of the United States. In the Shark River Slough (SRS), excess dissolved organic carbon and sulfate were also consistently delivered from upgradient canals and showed no evidence of decline over the study period. Within the SRS a strong positive correlation was observed between MeHg concentrations in surface water and resident fish. Within distinct geographic regions of ENP (SRS, Marsh, Coastal), the geochemical controls on MeHg dynamics differed and highlighted regions susceptible to higher MeHg bioaccumulation, particularly in the SRS and Coastal regions. This study demonstrates the strong influence that dissolved organic carbon and sulfate loads have on spatial and temporal distributions of MeHg across the ENP. Importantly, improved water quality and flow rates are two key restoration targets of the nearly 30-year Everglades restoration program, which if achieved, this study suggests would lead to reduced MeHg production and exposure.

Florida

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 δ 202 Hg 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 δ 202 Hg 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 δ 202 Hg (+1.6 ± 0.1‰) and mass-independent anomalies (i.e., changes in Δ 199 Hg 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 δ 202 Hg 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.

Environmental Science and Technology

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

Long-term trends in regional wet mercury deposition and lacustrine mercury concentrations in four lakes in Voyageurs National Park

Although anthropogenic mercury (Hg) releases to the environment have been substantially lowered in the United States and Canada since 1990, concerns remain for contamination in fish from remote lakes and rivers where atmospheric deposition is the predominant source of mercury. How have aquatic ecosystems responded? We report on one of the longest known multimedia data sets for mercury in atmospheric deposition: aqueous total mercury (THg aq ), methylmercury (MeHg aq ), and sulfate from epilimnetic lake-water samples from four lakes in Voyageurs National Park (VNP) in northern Minnesota; and total mercury (THg) in aquatic biota from the same lakes from 2001–2018. Wet Hg deposition at two regional Mercury Deposition Network sites (Fernberg and Marcell, Minnesota) decreased by an average of 22 percent from 1998–2018; much of the decreases occurred prior to 2009, with relatively flat trends since 2009. In the four VNP lakes, epilimnetic MeHg aq concentrations declined by an average of 44 percent and THg aq by an average of 27 percent. For the three lakes with long-term biomonitoring, temporal patterns in biotic THg concentrations were similar to patterns in MeHg aq concentrations; however, biotic THg concentrations declined significantly in only one lake. Epilimnetic MeHg aq may be responding both to a decline in atmospheric Hg deposition as well as a decline in sulfate deposition, which is an important driver of mercury methylation in the environment. Results from this case study suggest that regional- to continental-scale decreases in both mercury and sulfate emissions have benefitted aquatic resources, even in the face of global increases in mercury emissions.

Minnesota

Demethylation of methylmercury in bird, fish, and earthworm

Toxicity of methylmercury (MeHg) to wildlife and humans results from its binding to cysteine residues of proteins, forming MeHg-cysteinate (MeHgCys) complexes that hinder biological functions. MeHgCys complexes can be detoxified in vivo, yet how this occurs is unknown. We report that MeHgCys complexes are transformed into selenocysteinate (Hg(Sec)4) complexes in multiple animals from two phyla (a waterbird, freshwater fish, and earthworms) sampled in different geographical areas and contaminated by different Hg sources. In addition, high energy-resolution X-ray absorption spectroscopy and chromatography-ICP mass spectrometry of the waterbird liver support the binding of Hg(Sec)4 to selenoprotein P and biomineralization of Hg(Sec)4 to chemically inert nanoparticulate mercury selenide (HgSe). The results provide a foundation for understanding mercury detoxification in higher organisms, and suggest that the identified MeHgCys to Hg(Sec)4 demethylation pathway is common in nature.

Environmental Science & Technology

Surface-air mercury fluxes and a watershed mass balance in forested and harvested catchments

Forest soils are among the world’s largest repositories for long-term accumulation of atmospherically deposited mercury (Hg), and understanding the potential for remobilization through gaseous emissions, aqueous dissolution and runoff, or erosive particulate transport to down-gradient aquatic ecosystems is critically important for projecting ecosystem recovery. Forestry operations, especially clear-cut logging where most of the vegetaiton is removed, can influence Hg mobility/fluxes, foodweb dynamics, and bioaccumulation processes. This paper measured surface-air Hg fluxes from catchments in the Pacific Northwest, USA, to determine if there is a difference between forested and logged catchments. These measurements were conducted as part of a larger project on the impact of forestry operations on Hg cycling which include measurements of water fluxes as well as impacts on biota. Surface-air Hg fluxes were measured using a commonly applied dynamic flux chamber (DFC) method that incorporated diel and seasonal variability in elemental Hg (Hg 0 ) fluxes at multiple forested and harvested catchments. The results showed that the forested ecosystem had depositional Hg 0 fluxes throughout most of the year (annual mean: −0.26 ng/m 2 /h). In contrast, the harvested catchments showed mostly emission of Hg 0 (annual mean: 0.63 ng/m 2 /h). Differences in solar radiation reaching the soil was the primary driver resulting in a shift from net deposition to emission in harvested catchments. The surface-air Hg fluxes were larger than the fluxes to water as runoff and accounted for 97% of the differences in Hg sequestered in forested versus harvested catchments.

Oregon

The influence of legacy contamination on the transport and bioaccumulation of mercury within the Mobile River Basin

Past industrial use and subsequent release of mercury (Hg) into the environment have resulted in severe cases of legacy contamination that still influence contemporary Hg levels in biota. While the bioaccumulation of legacy Hg is commonly assessed via concentration measurements within fish tissue, this practice becomes difficult in regions of high productivity and methylmercury (MeHg) production, like the Mobile River Basin, Alabama in the southeastern United States. This study applied Hg stable isotope tracers to distinguish legacy Hg from regional deposition sources in sediments, waters, and fish within the Mobile River. Sediments and waters displayed differences in δ 202 Hg between industrial and background sites, which corresponded to drastic differences in Hg concentration. Sites that were affected by legacy Hg, as defined by δ 202 Hg, produced largemouth bass with lower MeHg content (59–70%) than those captured in the main rivers (>85%). Direct measurements of Hg isotopes and mathematical estimates of MeHg isotope pools in fish displayed similar distinctions between legacy and watershed sources as observed in other matrices. These results indicate that legacy Hg can accumulate directly into fish tissue as the inorganic species and may also be available for methylation within contaminated zones decades after the initial release.

Alabama

Examining historical mercury sources in the Saint Louis River estuary: How legacy contamination influences biological mercury levels in Great Lakes coastal regions

Industrial chemical contamination within coastal regions of the Great Lakes can pose serious risks to wetland habitat and offshore fisheries, often resulting in fish consumption advisories that directly affect human and wildlife health. Mercury (Hg) is a contaminant of concern in many of these highly urbanized and industrialized coastal regions, one of which is the Saint Louis River estuary (SLRE), the second largest tributary to Lake Superior. The SLRE has legacy Hg contamination that drives high Hg concentrations within sediments, but it is unclear whether legacy-derived Hg actively cycles within the food web. To understand the relative contributions of legacy versus contemporary Hg sources in coastal zones, Hg, carbon, and nitrogen stable isotope ratios were measured in sediments and food webs of SLRE and the Bad River, an estuarine reference site. Hg stable isotope values revealed that legacy contamination of Hg was widespread and heterogeneously distributed in sediments of SLRE, even in areas lacking industrial Hg sources. Similar isotope values were found in benthic invertebrates, riparian spiders, and prey fish from SLRE, confirming legacy Hg reaches the SLRE food web. Direct comparison of prey fish from SLRE and the Bad River confirmed that Hg isotope differences between the sites were not attributable to fractionation associated with rapid Hg bioaccumulation at estuarine mouths, but due to the presence of industrial Hg within SLRE. The Hg stable isotope values of game fish in both estuaries were dependent on fish migration and diet within the estuaries and extending into Lake Superior. These results indicate that Hg from legacy contamination is actively cycling within the SLRE food web and, through migration, this Hg also extends into Lake Superior via game fish. Understanding sources and the movement of Hg within the estuarine food web better informs restoration strategies for other impaired Great Lakes coastal zones.

Minnesota, Wisconsin

Observed and modeled mercury and dissolved organic carbon concentrations and loads at control structure S-12D, Florida Everglades, 2013–17

Mercury (Hg) has been a contaminant of concern for several decades in South Florida, particularly in the Florida Everglades. The transport and bioavailability of Hg in aquatic systems is intimately linked to dissolved organic carbon (DOC). In aquatic systems, Hg can be converted to methylmercury (MeHg), which is the form of Hg that bioaccumulates in food webs. The bioaccumulation of MeHg poses significant health risks to wildlife and humans. Fish consumption advisories triggered by elevated Hg levels first appeared in the 1980s in South Florida. Multiple structures regulate freshwater distribution to Everglades National Park, including S-12D. This report summarizes seasonal and annual concentration and load data from late September 2013 to April 2017 for the total of (1) filter-passing total mercury (FTHg), (2) filter-passing methylmercury (FMeHg), (3) particulate total mercury (PTHg), (4) particulate methylmercury (PMeHg) and, (5) DOC discharged through control structure S-12D. The loads of Hg fractions and DOC at control structure S-12D were determined by pairing discharge data with constituent concentrations estimated by empirical models based on surrogate in situ water-quality measurements. Calculated concentrations of DOC ranged from 12.8 milligrams per liter (mg/L) to 27.9 mg/L with a mean of 18.8 mg/L during the study period. Annual loads of DOC ranged from 3,950 tons in 2015 to 10,900 tons in 2016. DOC loads increased linearly with an increase in flow, and the highest monthly DOC load of 1,630 tons was observed in February 2016. Calculated concentrations of FTHg ranged from 0.35 to 1.55 nanograms per liter (ng/L) with a mean of 0.85 ng/L during the study period. Calculated concentrations of FMeHg ranged from 0.06 ng/L to 0.24 ng/L with a mean of 0.14 ng/L during the study period. Generally, FTHg and FMeHg con­centrations were lower during periods of decreased flow and higher during periods of increased flow. Calculated PTHg concentrations ranged from 0.09 ng/L to 4.19 ng/L with a mean of 0.58 ng/L during the study period. Calculated PMeHg concentrations ranged from below the limit of detection <0.01 ng/L to 0.29 ng/L with a mean of 0.03 ng/L during the study period. Loads of Hg were often zero or lowest from November to May, owing to the lack of flow or low-flow conditions. FTHg and FMeHg loads increased linearly with an increase in flow and typically were highest from June to October. During periods of increasing flow or following changes in gate operations, PTHg and PMeHg constituted a greater percentage of the total Hg load. Annual loads of total Hg (filter-passing and particulate) ranged from 254 grams in 2015 to 658 grams in 2016. FTHg was the predominant contributor to the total Hg load. Information presented herein provides the first assessment of DOC and Hg loads to Everglades National Park through control structure S-12D using continuous in situ measurements of discharge and constituent surrogates and compares the sur­rogate model approach to loads calculated from monthly sam­pling. Analysis of calculated and observed loads demonstrates the significance of flow data on calculating constituent loads.

Florida

Seasonal dynamics and interannual variability in mercury concentrations and loads through a three-reservoir complex

The Hells Canyon Complex (HCC) along the Snake River (Idaho-Oregon border, USA) encompasses three successive reservoirs that seasonally stratify, creating anoxic conditions in the hypolimnion that promote methylmercury (MeHg) production. This study quantified seasonal dynamics and interannual variability in mercury concentrations (inorganic divalent mercury (IHg) and MeHg) and loads at four reservoir inflow and outflow locations through the HCC (2014-2017). We observed (1) that the HCC is a net sink for both IHg and MeHg, (2) interannual variability in IHg and MeHg loads largely reflecting streamflow conditions, and (3) seasonal variability in particulate IHg loading at the inflow (greatest from February to April) and MeHg export from the outflow (greatest from September to December) of the HCC. Seasonal export of MeHg was evidenced by increases in monthly mean concentrations of unfiltered MeHg (approximately twofold) and the percentage of total mercury (THg) as MeHg (≥ fourfold) coincident with reservoir destratification. Despite evidence of seasonal export of MeHg from the HCC, annual loads indicate a 42% decrease in unfiltered MeHg from HCC inflow to outflow. Results from this study improve the understanding of seasonal variability in mercury transport through and transformation within a reservoir complex.

Idaho, Oregon

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 landscape-level inquiry that might otherwise be resource limited. We assessed variation in dragonfly Hg concentrations across >450 sites spanning 100 US National Park Service units, and examined intrinsic and extrinsic factors associated with variation in Hg concentrations. Mercury concentrations ranged between 10.4-1,411 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 in both fish and amphibians from the same locations, indicating that dragonfly larvae are effective indicators of Hg bioavailability in aquatic food webs. Collectively, this continental-scale study demonstrates the utility of dragonfly larvae for estimating 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.

Environmental Science and Technology

Insights into mercury source identification and bioaccumulation using stable isotope approaches in the Hannibal Pool of the Ohio River

Mercury contamination in river systems due to historic and current Hg releases is a persistent concern for both wildlife and human health. In larger rivers, like the Ohio River, USA, it is difficult to directly link Hg discharges to bioaccumulation due to the existence of multiple industrial Hg sources as well as the varied dietary and migratory habits of biota. To better understand how industrial effluent influences the cycling and bioaccumulation of Hg within the Ohio River, Hg stable isotope analysis was applied to various nonbiological and biological media. High Hg concentrations in suspended particulate matter suggest this vector was the largest contributor of Hg to the water column, and distinct Hg source signatures were observed in effluent particulates from different industrial processes, such as chlor‐alkali activity (δ 202 Hg = −0.52‰) and coal power plant discharge (δ 202 Hg = −1.39‰). Despite this distinction, average sediments (δ 202 Hg = −1.00 ± 0.23‰) showed intermediate isotopic signatures that suggest the accumulation of a mixed Hg source driven by multiple industrial discharges. Biota in the system were shown to have a conserved range of δ 202 Hg and estimation approaches related these signatures back to particulate matter within Hannibal Pool. Mussels were found to conserve Hg isotopes signatures independently of food web drivers and served as ideal water column indicators of bioaccumulated Hg sources. This study highlights the complexity of Hg cycling within an industrialized river and shows that an isotope tracer approach can provide insight to water column sources of Hg. Integr Environ Assess Manag 2021;17:233−242. Published 2020. This article is a US Government work and is in the public domain in the USA.

Ohio

Mercury export from Arctic great rivers

Land–ocean linkages are strong across the circumpolar north, where the Arctic Ocean accounts for 1% of the global ocean volume and receives more than 10% of the global river discharge. Yet estimates of Arctic riverine mercury (Hg) export constrained from direct Hg measurements remain sparse. Here, we report results from a coordinated, year-round sampling program that focused on the six major Arctic rivers to establish a contemporary (2012–2017) benchmark of riverine Hg export. We determine that the six major Arctic rivers exported an average of 20 000 kg y –1 of total Hg (THg, all forms of Hg). Upscaled to the pan-Arctic, we estimate THg flux of 37 000 kg y –1 . More than 90% of THg flux occurred during peak river discharge in spring and summer. Normalizing fluxes to watershed area (yield) reveals higher THg yields in regions where greater denudation likely enhances Hg mobilization. River discharge, suspended sediment, and dissolved organic carbon predicted THg concentration with moderate fidelity, while suspended sediment and water yields predicted THg yield with high fidelity. These findings establish a benchmark in the face of rapid Arctic warming and an intensifying hydrologic cycle, which will likely accelerate Hg cycling in tandem with changing inputs from thawing permafrost and industrial activity.

Environmental Science & Technology