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Brett A. Poulin

Publications and source records attributed to Brett A. Poulin.

30 records · Page 2Linked to original sources
USGS2023

Mercury sources and budget for the Snake River above a hydroelectric reservoir complex

Understanding sources of mercury (Hg) and methylmercury (MeHg) to a water body is critical for management but is often complicated by poorly characterized Hg inputs and in situ processes, such as inorganic Hg methylation. In this study, we determined inorganic Hg and MeHg concentrations and loads (filter-passing and particulate fractions) for a semi-arid 164-kilometer stretch of the Snake River above the Hells Canyon Complex, a Hg-impaired hydroelectric reservoir complex on the Idaho-Oregon border, and used water quality measurements and Hg stable isotope ratios to create a comprehensive Hg source budget for the river. Results show that whereas most of the streamflow to the study reach comes from the main branch of the Snake River (i.e., the upstream watershed), major tributaries within the study reach contribute a greater proportion of inorganic Hg and MeHg loads. Mercury stable-isotope analyses highlight that Hg within the tributaries is predominantly associated with geologic deposits and snowmelt sources, the latter reflecting wet deposition. Surprisingly, irrigation return drains contribute 40–50 % of particulate inorganic Hg loads despite being ≤4.3 % of the overall water budget. Together, tributaries and irrigation return drains account for 97–100 % of the inorganic Hg and streamflow to the study reach, but ~65 % of the MeHg, indicating in-stream and riparian methylation may be an important and previously unrecognized source of MeHg. Streamflow, total suspended solids, dissolved organic carbon, and agricultural land cover were found to be important controls on the mobilization and transport of different Hg species and fractions. This study represents the first fluvial budget for Hg in the Snake River that accounts for particulate and filter-passing Hg species from both major tributaries and irrigation return drains, and expands our understanding of Hg sources and methylation processes within semi-arid environments. This information is critical to inform management decisions related to elevated Hg burdens in biota.

Idaho, Nevada, Oregon↗
USGS2023

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↗
USGS2022

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↗
USGS2022

How beavers are changing Arctic landscapes and Earth’s climate

Beavers build dams that change the way water moves between streams, lakes, and the land. In Alaska, beavers are moving north from the forests into the Arctic tundra. When beavers build dams in the Arctic, they cause frozen soil, called permafrost, to thaw. Scientists are studying how beavers and the thawing of permafrost are impacting streams and rivers in Alaska’s national parks. For example, permafrost thaw from beavers can add harmful substances like mercury to streams. Mercury can be taken up by stream food webs, including fish, which then become unhealthy to eat. Permafrost thaw can also move carbon (from dead plants) to beaver ponds. When this carbon decomposes, it can be released from beaver ponds into the air as greenhouse gases, which cause Earth’s climate to warm. Scientists are trying to keep up with these busy beavers to better understand how they are changing Arctic landscapes and Earth’s climate.

Alaska↗
USGS2022

Multi-year, spatially extensive, watershed-scale synoptic stream chemistry and water quality conditions for six permafrost-underlain Arctic watersheds

Repeated sampling of spatially distributed river chemistry can be used to assess the location, scale, and persistence of carbon and nutrient contributions to watershed exports. Here, we provide a comprehensive set of water chemistry measurements and ecohydrological metrics describing the biogeochemical conditions of permafrost-affected Arctic watersheds. These data were collected in watershed-wide synoptic campaigns in six stream networks across northern Alaska. Three watersheds are associated with the Arctic Long-Term Ecological Research site at Toolik Field Station (TFS), which were sampled seasonally each June and August from 2016 to 2018. Three watersheds were associated with the National Park Service (NPS) of Alaska and the U.S. Geological Survey (USGS) and were sampled annually from 2015 to 2019. Extensive water chemistry characterization included carbon species, dissolved nutrients, and major ions. The objective of the sampling designs and data acquisition was to characterize terrestrial–aquatic linkages and processing of material in stream networks. The data allow estimation of novel ecohydrological metrics that describe the dominant location, scale, and overall persistence of ecosystem processes in continuous permafrost. These metrics are (1) subcatchment leverage, (2) variance collapse, and (3) spatial persistence. Raw data are available at the National Park Service Integrated Resource Management Applications portal (O'Donnell et al., 2021, https://doi.org/10.5066/P9SBK2DZ ) and within the Environmental Data Initiative (Abbott, 2021, https://doi.org/10.6073/pasta/258a44fb9055163dd4dd4371b9dce945 ).

Alaska↗
USGS2022

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↗
USGS2021

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↗
USGS2021

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↗
USGS2021

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↗
USGS2020

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↗
USGS2017

Spatial dependence of reduced sulfur in Everglades dissolved organic matter controlled by sulfate enrichment

Sulfate inputs to the Florida Everglades stimulate sulfidic conditions in freshwater wetland sediments that affect ecological and biogeochemical processes. An unexplored implication of sulfate enrichment is alteration of the content and speciation of sulfur in dissolved organic matter (DOM), which influences the reactivity of DOM with trace metals. Here, we describe the vertical and lateral spatial dependence of sulfur chemistry in the hydrophobic organic acid fraction of DOM from unimpacted and sulfate-impacted Everglades wetlands using X-ray absorption spectroscopy and ultrahigh-resolution mass spectrometry. Spatial variation in DOM sulfur content and speciation reflects the degree of sulfate enrichment and resulting sulfide concentrations in sediment pore waters. Sulfur is incorporated into DOM predominantly as highly reduced species in sulfidic pore waters. Sulfur-enriched DOM in sediment pore waters exchanges with overlying surface waters and the sulfur likely undergoes oxidative transformations in the water column. Across all wetland sites and depths, the total sulfur content of DOM correlated with the relative abundance of highly reduced sulfur functionality. The results identify sulfate input as a primary determinant on DOM sulfur chemistry to be considered in the context of wetland restoration and sulfur and trace metal cycling.

Florida↗