Geology topics

Michael T. Tate

Publications and source records attributed to Michael T. Tate.

At least 19 recordsLinked to original sources

USGS2026

Decoding the oxidative digestion mechanism for polystyrene nanoplastic detection in the Great Lakes using a customizable Raman spectral processing algorithm

Despite the concerns surging around nanoplastics (NPs) regarding their prevalence and bioavailability in freshwater systems, robust detection of NPs in complex environmental matrices is hindered by the lack of standardized sample pretreatment and a mechanistic understanding of oxidative digestion. Here, we systematically investigate the interaction between hydrogen peroxide (H 2 O 2 ) and polystyrene (PS) NPs during digestion in deionized (DI) water and four environmental matrices from in and around the Great Lakes Basin. To facilitate high-throughput analysis, we develop Pre_peak, a customizable Raman spectral processing algorithm that achieves >99% accuracy for both NP identification and interference rejection, allowing reliable NP quantification via pixel counting and systematic decoding of the oxidative digestion mechanisms. In DI water, varying H 2 O 2 doses from 0 to 30% has negligible effects on the recovery and Raman signal intensity of PS NPs over 24 hours of digestion. However, morphological changes and aggregation of PS NPs are observed when the H 2 O 2 dose exceeds 20%. Prolonged digestion further leads to progressive NP loss. In natural waters, the optimal dosage and digestion duration depend on matrix characteristics, including dissolved organic matter (DOM) and ion composition. This study provides mechanistic insights into NP–oxidant interactions and underscores the need for matrix-tailored digestion protocols to advance standardized NP detection in freshwater environments.

Great Lakes↗

USGS2026

Mercury mobilization and export from the Greenland Ice Sheet using an ice-to-ocean approach

The Greenland Ice Sheet (GrIS) is a poorly constrained source of mercury (Hg) to Arctic ecosystems. We measured Hg concentrations and stable isotopes along an ice-to-ocean continuum to identify controls on GrIS Hg export. Early-season permafrost melt and rainfall produced high filtered total mercury (fTHg, ~17 pM) and monomethylmercury (MMHg, ~2 pM). As subglacial drainage evolved, particulate Hg doubled (from ~8 to 17 pM) and MMHg production remained elevated, indicating Hg mobilization from subglacial environments. Shifts in Hg stable isotope ratios and Δ 199 Hg mass balance show supraglacial sources contribute 20–48% of exported Hg, suggesting subglacial inputs dominate the seasonal Hg flux. Fjord waters were enriched in fTHg ( ~ 10 pM) and MMHg ( ~ 2 pM) relative to rivers, consistent with particulate Hg transformations and terrestrial Hg inputs. The estimated GrIS Hg yield ( ~ 23 mmol km −2 yr −1 ) is similar to that of Arctic rivers and will likely increase with climate-driven mass loss.

Communications Earth & Environment↗

USGS2026

Comparing in vivo methylmercury detoxification in hunted duck: Implications for wildlife and human health

Great Salt Lake (GSL) waterfowl have elevated mercury (Hg) concentrations, and in vivo detoxification of neurotoxic and bioaccumulative methylmercury (MeHg) can occur through Hg-selenium (Se) complexation, influencing the suitability of Hg consumption advisories. Here, we present Hg chemical speciation and Hg stable isotope measurements of brain, breast muscle, liver, and kidney samples from two GSL duck species─northern shoveler ( Spatula clypeata ) and cinnamon teal (Spatula cyanoptera). Chemical and stable isotope measurements, along with high energy resolution fluorescence detected X-ray absorption near-edge structure (HERFD-XANES) spectroscopy, indicate the occurrence of in vivo MeHg demethylation in both bird species. The percentage of total Hg (THg) as MeHg (% MeHg) varied with tissue type (brain > breast muscle > kidney > liver), and differences between δ 202 THg and δ 202 MeHg were linearly correlated with % MeHg. Demethylated inorganic Hg was a mixture of Hg-dithiolate (Hg(SR) 2 ) and Hg-tetraselenolate (Hg(Sec) 4 ) in both bird species. Notably, liver THg concentrations were elevated in northern shoveler liver tissues relative to those of cinnamon teal (7.54 ± 4.69 mg/kg versus 2.19 ± 1.27 mg/kg, dry weight, respectively) and % MeHg liver values were significantly lower (40% ± 19% versus 68% ± 14%), indicating taxonomic differences in Hg detoxification and depuration. THg concentrations in waterfowl species from this study were comparable to previously reported levels, indicating that elevated Hg concentrations in northern shoveler and cinnamon teal at GSL have persisted over the past two decades. Due to in vivo demethylation, we show that THg is not an effective proxy for MeHg within duck species, carrying implications for current GSL waterfowl consumption advisories and assessments exposure risk. This study highlights important differences in MeHg detoxification between waterbird taxa and provides further insights into Hg toxicity risk to GSL waterbirds.

Utah↗

USGS2025

Quantifying depuration of methylmercury from fish consumption by travelers

During a two-week field sampling expedition in Gabon, two American scientists consumed fish daily from the Ogooué River watershed. We sampled their scalp and facial hair periodically to evaluate hair as a biomarker to track shifts in methylmercury (MeHg) exposure from diet. Each individual differed in the onset and extent of MeHg accumulation but showed similar depuration rates. Pretrip baseline Hg isotope values between participants were distinct from Gabonese fishes allowing us to detect shifts in MeHg sources in the hair of both individuals. δ 202 Hg values tracked the mass-dependent fractionation of MeHg depuration stemming from in vivo metabolism, leading to δ 202 Hg increases of 0.014 ± 0.001 per mille and total Hg losses of 8.3 ± 1.1 ng g –1 daily. While limited in scope due to minimal participants, our findings reveal a complex interaction between prior MeHg burdens, contemporary MeHg intakes, and sources of consumed fishes (locally caught versus market-sourced) in determining the dynamics of MeHg concentrations and δ 202 Hg in human hair. We also suggest that the offset in δ 202 Hg values used in literature between fish and human hair (1.75 ± 0.25‰) may overlook a time domain that increases starting fish-hair δ 202 Hg offsets (0.94‰), through time.

Agence Nationale des Parcs Nationaux↗

USGS2025

Regenerable membrane sensors for ultrasensitive nanoplastic quantification enabled by a data-driven Raman spectral processing algorithm

The detection of nanoplastics (NPs) in complex natural water systems is hindered by matrix interferences and limitations in current analytical techniques. This study presents Pre_seg, a Raman spectral processing algorithm integrated with regenerable anodic aluminum oxide (AAO) membrane sensors, for ultrasensitive, rapid, and quantitative NP detection at the single-particle level. The AAO membranes function as both filtration substrates and Raman sensors, reducing sample loss and contamination. Pre_seg incorporates statistically determined thresholds for signal-to-noise ratios (SNRs) and full width at half maximums (fwhms) across segmented spectral ranges, effectively minimizing noise and enhancing accuracy and sensitivity of NP detection. Pre_seg achieved 93.5% prediction accuracy of NPs and ≥90.4% rejection accuracy for non-NP entries. Mixed NPs were quantified at the lowest concentration of 0.5 μg L –1 . The robustness of Pre_seg was validated in eutrophic and oligotrophic lake matrices following oxidation digestion pretreatment to mitigate organic interferences. Furthermore, the AAO membrane sensors demonstrated stability through multiple regeneration and reuse cycles. This innovative approach advances NP detection by enabling scalable, customizable, and environmentally relevant monitoring.

Environmental Science and Technology↗

USGS2025

Application of mercury stable isotopes to examine sources and hydrologic factors impacting mercury bioaccumulation and cycling in invertebrates of a model saline lake

Invertebrates, such as brine shrimp and brine flies, are key prey items for millions of resident and migratory birds that utilize saline lakes such as Great Salt Lake (GSL). Elevated methylmercury (MeHg) in invertebrate and waterfowl species of GSL has been assumed to be linked to elevated MeHg in GSL’s anoxic Deep Brine Layer (DBL) where aqueous concentrations can exceed 30 ng/L. Here, we leverage mercury (Hg) concentration and stable isotope measurements on brine flies ( Ephydra hians and Ephydra cinerea ), brine shrimp ( Artemia franciscana ), and spider (western spotted orbweaver [ Neoscona oaxacensis ]) to examine temporal changes in Hg concentrations and sources during periods of DBL presence and absence. Mercury concentrations in brine flies were inversely correlated with lake level and directly correlated with salinity, possibly resulting from factors such as enhanced Hg bioaccumulation due to osmoregulatory stress and stunted growth and/or elevated salinities impacting composition, abundance, and Hg concentrations of food sources. DBL presence did not correspond to higher invertebrate Hg concentrations, highlighting that the DBL is not the primary source of MeHg to biota. Hg stable isotope signatures (Δ 199 Hg and δ 202 Hg) in brine shrimp varied seasonally and indicated greater cumulative photochemical Hg loss from the water column in late summer and fall months. Co-located brine fly and western spotted orbweaver samples show equivalent Δ 199 Hg and δ 202 Hg signatures, supporting Hg transfer from the aquatic to terrestrial food webs. Furthermore, Hg isotope results (Δ 200 Hg) indicate that the majority of Hg accumulating in GSL invertebrates is of atmospheric origin. This study highlights temporal controls on Hg bioaccumulation within GSL, which will help assess Hg cycling within the system in response to management actions and declining lake levels.

Utah↗

USGS2025

Ecological factors decouple Great Lakes fish mercury concentrations trends decadal declines in mercury emissions

Atmospheric mercury (Hg) deposition has been declining in North America but remains the dominant delivery mechanism to the Great Lakes. The Lakes are highly efficient at bioaccumulating methylmercury, making the fish excellent sentinels for tracking shifts in atmospheric Hg deposition. Invasive mussels have altered biogeochemical processes, prey populations and fish dietary strategies asynchronously and to varied extents across the lower four lakes, impacting fish Hg exposure. To test if fish are adapting to new biogeochemical conditions, we analyzed a 40 year fish archive for carbon and nitrogen isotope ratios and amino acid-specific nitrogen isotope ratios. To assess Hg sources, we measured Hg isotope ratios. We reconstructed and compared energetic pathways that impact fish Hg concentrations to Hg-source trends. We found fish-Hg concentrations are declining but not monotonically due to ecological disturbances. Fish-Hg isotope values, unimpacted by ecological disturbance, confirm that sources of bioaccumulated Hg shift contemporaneously with changes in atmospheric Hg concentrations. Across Lakes, the degree of responsiveness to changes in atmospheric Hg concentrations mirrors the proportion of atmospheric-delivered Hg we previously modeled. Changes in both fish concentrations and fish isotope values outpace paleolimnetic reconstructions suggesting declines in atmospheric Hg concentrations impact fish Hg more than sediment.

Great Lakes↗

USGS2025

A comprehensive sulfate and DOM framework to assess methylmercury formation and risk in subtropical wetlands

Wetlands play a vital role in contaminant cycling and uptake. Understanding how sulfate (SO 4 2‒ ) influences the conversion of inorganic mercury (Hg(II)) to toxic methylmercury (MeHg) is critical for predicting wetland responses to land use and climate change. Here, we sampled surface and pore waters across SO 4 2‒ gradients in three freshwater Everglades wetlands to assess linkages between SO 4 2‒ , MeHg, dissolved organic matter (DOM), and inorganic sulfide (S(‒II)). Increasing SO 4 2‒ concentrations increase S(‒II) and DOM concentrations and DOM aromaticity. MeHg concentration show a unimodal response to surface water SO 4 2‒ , which reflect high Hg(II) methylation at low-to-intermediate SO 4 2‒ concentration (2-12 mg/L) and low Hg(II) methylation at higher SO 4 2‒ concentrations ( > 12 mg/L). MeHg concentrations in surface waters correlate positively with MeHg concentrations in prey fish. The coherent biogeochemical relationships between SO 4 2‒ and MeHg concentrations and biologic uptake improve MeHg risk assessment for aquatic food webs and are globally relevant due to anthropogenic and climate-driven increases in SO 4 2‒ .

Florida↗

USGS2025

Seasonal stratification drives bioaccumulation of pelagic mercury sources in eutrophic lakes

Increased lake eutrophication, influenced by changing climate and land use, alters aquatic cycling and bioaccumulation of mercury (Hg). Additionally, seasonally dynamic lake circulation and plankton community composition can confound our ability to predict changes in biological Hg concentrations and sources. To assess temporal variation, we examined seasonal total Hg (THg) and methylmercury (MeHg) concentrations and stable isotope values in seston, waters, sediments, and fish from two adjacent urban eutrophic lakes in Madison, Wisconsin. In Lake Monona, surface sediment THg concentrations were elevated due to comparably higher urbanization and historical industrial inputs, whereas Lake Mendota sediments had lower concentrations corresponding with largely agricultural and suburban surrounding watershed. Surface water THg and MeHg were similar between lakes and seasonally dynamic, but water profiles exhibited elevated concentrations in the meta- and hypolimnion, highlighting water column MeHg production. Seston MeHg concentrations were often highest at shoulder seasons, possibly owing to metalimnetic MeHg delivery, but also differences in biomass and water clarity. The ∆199Hg and δ202Hg values in seston were similar between lakes, despite differing sediment THg concentrations and values, suggesting a shared bioaccumulated source of MeHg. Measurement of MeHg stable isotopes further elucidated that seston and fish predominantly bioaccumulated pelagic-sourced MeHg.

Wisconsin↗

USGS2025

Sulfate reduction drives elevated methylmercury formation in water column of eutrophic freshwater lake

Mercury (Hg) contamination of aquatic food webs is controlled in part by the formation and accumulation of toxic and bioaccumulative methylmercury (MeHg). MeHg production is mediated by metabolically diverse microorganisms carrying the hgcAB gene pair, while the demethylation reaction is mediated by several biotic and abiotic processes. However, the relative importance of these two processes on MeHg accumulation and the environmental factors that influence them are poorly characterized, especially in eutrophic environments. In this study, both Hg methylation and MeHg demethylation in a eutrophic freshwater lake were linked to ambient MeHg concentrations and hgcA abundance and expression. High methylation rate potentials indicated in situ MeHg formation was a key source of MeHg to the water column, driven by high hgcA abundance and transcription. Molybdate treatment decreased methylation rate potentials, highlighting the importance of sulfate reduction in driving MeHg formation. Sulfate-reducing bacteria accounted for over 50% of the hgcA gene transcription, despite representing less than 10% of the hgcA -carrying microbial community. An arsR -like transcriptional regulator preceded many hgcA sequences; these were transcriptionally active and linked to lower hgcA expression. Overall, this study elucidates the microbial and biogeochemical processes that influence the in situ formation of MeHg in understudied eutrophic freshwater environments.

Wisconsin↗

USGS2025

Contrasting magnitude and timing of pulsed aqueous methylmercury bioaccumulation across a reservoir food web

Water column hypoxia is a key process influencing methylmercury (MeHg) production and availability in waterbodies worldwide. During seasonal destratification, large, short-lived pulses of aqueous MeHg may be released into the subsequently mixed water column, but little is known about the fate of these pulses, particularly whether there are concomitant increases in MeHg uptake into aquatic food webs. We examined the magnitude and timing of MeHg uptake across several trophic guilds relative to the reservoir stratification status using biweekly mercury data from water, zooplankton, and fish (Bluegill, Lepomis macrochirus and Smallmouth Bass, Micropterus dolomieu ). Zooplankton MeHg concentrations increased by up to 250% during destratification, concurrent with increases in aqueous MeHg concentrations. Zooplankton and filter-passing MeHg concentrations were positively correlated when the reservoir was mixed ( R 2 = 0.95) and destratifying ( R 2 = 0.57) but not while the reservoir was stratified ( R 2 = 0.21). Mercury concentrations in adult bluegill and juveniles of both fish species increased 20–70% following destratification, with responses lagging 4–8 weeks behind those in water and zooplankton MeHg. Mercury concentrations in piscivorous adult bass varied little over the course of the study. Our findings demonstrate the responsiveness of reservoir food webs to pulses in MeHg availability, suggesting that these pulses could play an important role in biotic MeHg exposure within and downstream of reservoirs.

Idaho, Oregon↗

USGS2025

Connecting tributary mercury loads to nearshore and offshore sediments in Lake Superior

Lake Superior has a vast and largely undeveloped watershed in comparison to the other Great Lakes, which makes it challenging to study mercury (Hg) sources and cycling. To examine Hg inputs to Lake Superior, we conducted an expansive binational assessment in 40 watersheds from a diverse range of landcover types. We further paired tributary Hg data to sediment source portfolios in the nearshore and offshore zones of Lake Superior through partnership with the Great Lakes Sediment Surveillance Program. We observed that total Hg loads were highest in the spring driven by the combination of elevated Hg concentrations and increased water discharge from snowmelt. In addition, total Hg concentrations in tributaries from remote, heavily forested regions, such as Pukaskwa National Park and the Minnesota Northshore, were higher than the Southshore and Thunder Bay regions. Methylmercury concentrations and loads were more spatially dependent, often corresponding to regions with more wetlands (e.g., Michigan Upper Peninsula). We estimated that the total Hg tributary load to Lake Superior in 2021 was 126 kg per year. To further examine the fate of watershed Hg sources, we examined sediments from 28 sites in Lake Superior using Hg stable isotopes. At open water sites, precipitation was the primary Hg source to sediments, but within nearshore sites Hg originated predominantly from watershed runoff. This work further defines the sources and fate of Hg within Lake Superior and highlights how Hg delivery is intrinsically tied to varying hydrologic regimes.

Michigan, Minnesota, Ontario, Wisconsin↗

USGS2024

Adaptable plasmonic membrane sensors for fast and reliable detection of trace low micrometer microplastics in lake water

In freshwater environments, low-micrometer microplastics (LMMPs) have captured significant attention due to their prevalence and toxicity. Yet, rapid detection of LMMPs (1–10 μm) at the single-particle level within complex freshwater matrices remains a hurdle. We developed an adaptable plasmonic membrane sensor for fast detection of individual LMMPs in eutrophic lake waters. The plasmonic membrane sensor functions both as a membrane filter and as a sensor for LMMP collection and analysis. Among the four types of membrane sensors, polycarbonate track-etch (PCTE) membrane sensors exhibit superior imaging quality for LMMPs due to their flat and homogeneous surfaces. Besides the significantly improved imaging contrast and reduced background interferences, the Raman intensity of LMMPs is enhanced by 48% ± 25% on PCTE membrane sensors compared to unmodified membranes. The increased Raman intensities of a chemical probe with an increasing gold layer thickness and a decreasing membrane pore size suggest a surface-enhanced Raman scattering effect from the membrane sensors. The membrane sensors achieve a detection limit of 1 μg/L and an ultrafast scanning time of 0.01 s for individual LMMPs across natural eutrophic lake water. The developed membrane sensors offer an adaptable tool for the swift and reliable detection of individual LMMPs in complex environmental matrices.

Environmental Science and Technology↗

USGS2024

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 protected regions. Here, we used Hg stable isotope measurements of 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, 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 Δ 200 Hg emerged in the western US, highlighting the relative importance of wet deposition sources in arid regions in contrast to dry deposition delivery in forested regions. This work highlights 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.

Environmental Science and Technology↗

USGS2024

Using mercury and lead stable isotopes to assess mercury, lead, and trace metal source contributions to Great Salt Lake, Utah, USA

Great Salt Lake is a critical habitat for migratory birds that is threatened by elevated metal concentrations, including mercury (Hg) and lead (Pb), and is subject to severe hydrologic changes, such as declining lake level. When assessing metal profiles recorded in Great Salt Lake sediment, a large data gap exists regarding the sources of metals within the system, which is complicated by various source inputs to the lake and complex biogeochemistry. Here, we leverage Hg and Pb stable isotopes to track relative changes in metal source contributions to Great Salt Lake over time. Mercury and Pb concentrations increase in sediments deposited after 1920 and peak between 1965 and 1995, following closure of several local smelters and the onset of increased emission controls. The nominal associations above are confirmed via Hg stable isotopes in pre-1920 background sediments, which reflect atmospheric inputs from regional and global origin, whereas Hg and Pb stable isotopes together indicate that elevated metal concentrations in mid-late 20th century sediments reflect increased mining/smelting inputs. The observed minimal rebound towards pre-1920 Pb isotope signatures in 21st century sediments indicates that mining/smelting inputs, though reduced, remain a primary source of Pb to Great Salt Lake. In contrast, the more pronounced rebound of Hg stable isotope signatures to pre-1920 values indicate a greater contribution of atmospheric inputs of regional/global origin to current Hg inputs, though Hg concentrations are ∼10 times greater than pre-1920 background values due to global increases in atmospheric Hg concentrations or possibly slow recovery from local contamination. The importance of regional/global Hg sources to the system suggests that reductions in Hg bioaccumulation in the open water food webs of Great Salt Lake are more dependent on national and global reductions in Hg emissions and management strategies to limit methylmercury production within system. This work highlights the utility of using coupled Hg and Pb stable isotope values to assess trace metal pollution sources and pathways in aquatic systems.

Utah↗

USGS2024

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) ( δ 202 Hg) and mass independent fractionation (MIF) ( Δ 199 Hg) (dependent variables) and dietary MeHg intake (independent variable) were investigated using multivariable regression models. Results . In adjusted models, hair Δ 199 Hg 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 δ 202 Hg was not correlated with measures of dietary measures of MeHg intake. Instead, hair δ 202 Hg was strongly, negatively correlated with hair Hg, which explained 27–29% of the variability in hair δ 202 Hg. Conclusions . Our results indicated that hair Δ 199 Hg 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.

Environmental Science: Processes & Impacts↗

USGS2023

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 Δ 199 Hg 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 Δ 199 Hg/Δ 201 Hg ratio was uniform across experiments (∼1.4), Δ 199 Hg/δ 202 Hg 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.

ACS Earth and Space Chemistry↗

USGS2023

Metabolically diverse microorganisms mediate methylmercury formation under nitrate-reducing conditions in a dynamic hydroelectric reservoir

Brownlee Reservoir is a mercury (Hg)-impaired hydroelectric reservoir that exhibits dynamic hydrological and geochemical conditions and is located within the Hells Canyon Complex in Idaho, USA. Methylmercury (MeHg) contamination in fish is a concern in the reservoir. While MeHg production has historically been attributed to sulfate-reducing bacteria and methanogenic archaea, microorganisms carrying the hgcA gene are taxonomically and metabolically diverse and the major biogeochemical cycles driving mercury (Hg) methylation are not well understood. In this study, Hg speciation and redox-active compounds were measured throughout Brownlee Reservoir across the stratified period in four consecutive years (2016–2019) to identify the location where and redox conditions under which MeHg is produced. Metagenomic sequencing was performed on a subset of samples to characterize the microbial community with hgcA and identify possible links between biogeochemical cycles and MeHg production. Biogeochemical profiles suggested in situ water column Hg methylation was the major source of MeHg. These profiles, combined with genome-resolved metagenomics focused on hgcA -carrying microbes, indicated that MeHg production occurs in this system under nitrate- or manganese-reducing conditions, which were previously thought to preclude Hg-methylation. Using this multidisciplinary approach, we identified the cascading effects of interannual variability in hydrology on the redox status, microbial metabolic strategies, abundance and metabolic diversity of Hg methylators, and ultimately MeHg concentrations throughout the reservoir. This work expands the known conditions conducive to producing MeHg and suggests that the Hg-methylation mitigation efforts by nitrate or manganese amendment may be unsuccessful in some locations.

Idaho↗