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Dietary bioavailability of uranium to a model freshwater invertebrate

Uranium (U) mining increases environmental exposures. Understanding how U is taken up by organisms can aid in evaluating the potential for bioaccumulation and toxicity. Although the importance of aqueous geochemical speciation is well recognized for U bioavailability after dissolved exposures, far less is known about the processes controlling U bioavailability after dietary exposures. This study characterizes the biogeochemical drivers of dietary U uptake in the freshwater snail Lymnaea stagnalis in laboratory experiments. Solids tested included benthic diatoms pre-exposed to dissolved U(VI), soils from contaminated U mine sites, and colloidal hydrous ferric oxide (HFO) synthesized in the presence of dissolved U(VI) or with U complexed by natural organic matter (NOM). Results showed that U was bioavailable from all solids. Uranium assimilation efficiency (AE), a proxy for dietary U bioavailability, varied among solids. AE was lowest for the U-contaminated soils (25 ± 17%) and highest for the U-laden diatoms (71 ± 13%). AE varied slightly among HFO preparations, suggesting modest influences of NOM and iron on U bioavailability. Increases in dietary U exposures reduced feeding rates, and the extent of feeding inhibition appeared inversely related to U bioavailability. The high U assimilation and range of bioavailability have implications for toxicity risks inferred without considering dietary uptake.

Environmental Science and Technology

Cotton farming pesticides affect ileal microbiota activity expressions of virulome but not resistome or metabolic pathways in a sedentary wild passerine

The increased use of agrochemicals to enhance crop production has had detrimental environmental effects including implication in the sharp decline of North American farmland-breeding birds. Here, using a combination of deep shotgun metatranscriptomics and pesticide exposure data, we sought to assess whether exposure to cotton ( Gossypium spp.) production had a differential effect on ileum multi-kingdom microbial activity, metabolism, anti-microbial resistance, and virulence factors of sedentary northern mockingbirds ( Mimus polyglottos ) sampled from two cotton-producing areas (16 birds in total) and one uncultivated area (7 birds) in Texas, USA. Both Shannon Index values (Adj. r 2 = 0.174, F (1,21) = 5.633, p = 0.027) and a Mantel test (Spearman ρ = 0.184, p = 0.013) supported a relationship between metabolically active microbiota Bray–Curtis dissimilarities and differences in pesticide mixtures among study areas. Virulence factor richness (Adj. r 2 = 0.182, F (1,21) = 5.890, p = 0.024), Shannon Index (Adj. r 2 = 0.231, F (1,21) = 7.612, p = 0.012), and load (sum of virulence factor abundances; Adj. r 2 = 0.160, F (1,21) = 5.194, p = 0.033) were related to total pesticide load (total quantity of pesticides). We found no pesticide effects on expression of either antimicrobial resistance genes or metabolic pathways.

Texas

Vulnerability assessment of groundwater influenced ecosystems in the Northeastern United States

Groundwater-influenced ecosystems (GIEs) are increasingly vulnerable due to groundwater extraction, land-use practices, and climate change. These ecosystems receive groundwater inflow as a portion of their baseflow or water budget, which can maintain water levels, water temperature, and chemistry necessary to sustain the biodiversity that they support. In some systems (e.g., springs, seeps, fens), this connection with groundwater is central to the system’s integrity and persistence. Groundwater management decisions for human use often do not consider the ecological effects of those actions on GIEs. This disparity can be attributed, in part, to a lack of information regarding the physical relationships these systems have with the surrounding landscape and climate, which may influence the environmental conditions and associated biodiversity. We estimate the vulnerability of areas predicted to be highly suitable for the presence of GIEs based on watershed (U.S. Geological Survey Hydrologic Unit Code 12 watersheds: 24–100 km 2 ) and pixel (30 m × 30 m pixels) resolution in the Atlantic Highlands and Mixed Wood Plains EPA Level II Ecoregions in the northeastern United States. We represent vulnerability with variables describing adaptive capacity (topographic wetness index, hydric soil, physiographic diversity), exposure (climatic niche), and sensitivity (aquatic barriers, proportion urbanized or agriculture). Vulnerability scores indicate that ~26% of GIEs were within 30 m of areas with moderate vulnerability. Within these GIEs, climate exposure is an important contributor to vulnerability of 40% of the areas, followed by land use (19%, agriculture or urbanized). There are few areas predicted to be suitable for GIEs that are also predicted to be highly vulnerable, and of those, climate exposure is the most important contributor to their vulnerability. Persistence of GIEs in the northeastern United States may be challenged as changes in the amount and timing of precipitation and increasing air temperatures attributed to climate change affect the groundwater that sustains these systems.

Connecticut, Delaware, District of Columbia, Maine

Guidelines for producing integrated 210Pb and 14C age-models

Accurate reconstructions of past environmental changes are crucial in paleoecological research and require reliable chronologies of sedimentary archives. Establishing robust age-models and obtaining the most appropriate proxies for analysis is a complex scientific endeavor, requiring extensive resources and collaboration among specialists, including radiochronologists. Radiometric dating methods, such as 210 Pb and radiocarbon ( 14 C), are frequently employed to establish chronologies in aquatic sedimentary deposits and peat bogs. In this study, we review key aspects of sampling, analysis, and the principles underlying 210 Pb and 14 C age-models, focusing on methods for developing robust joint chronologies for paleoenvironmental research. Drawing largely from the authors' experiences and group discussions during and after a scientific workshop in 2022, we discuss important considerations for site selection, sampling strategies, and radiometric dating to construct integrated 210 Pb and 14 C age-models. Using expert consensus, this group – called Paleostats – aims to provide a set of best practices for other geochronologists with this methods paper. Among our conclusions, we emphasize the importance of accounting for site-specific factors such as prior information on sedimentation rates to establish appropriate sampling and analytical strategies. The use of appropriate coring devices can minimize disturbance to sediments and ensure the core surface remains intact and preserved until sectioning. Where excess 210 Pb is expected, sectioning at intervals of ≤1 cm provides an adequate sampling resolution for 210 Pb dating. Exceptions are possible, allowing for ~2–3 cm sections in areas with confirmed high sedimentation rates (e.g., > 1 cm yr −1 ). Recovering deeper core sections for 14 C dating with sufficient overlap allows for accounting errors in depth estimates made in the field. Special attention is advised during time intervals where validation proxies, such as the human-made radionuclides 137 Cs or post-bomb 14 C, are expected, and to determine the depth of secular equilibrium between 210 Pb and 226 Ra. Radiocarbon analyses are commonly performed by accelerator mass spectrometry, and age models are constructed mainly using Bayesian statistics with Markov Chain Monte Carlo techniques (e.g., Bacon ). A Bayesian approach ( Plum ) is now available for producing 210 Pb age-models, which infers the 210 Pb ex flux, eliminates the need for selecting an equilibrium depth, and allows dating cores with incomplete 210 Pb ex inventory. Plum offers improved chronologies by integrating raw 210 Pb and 14 C data, and these age-models can be enriched with other dating methodologies, such as identifying tephras and other well-recorded historical events. Harmonized reporting would contribute to making radiometric age-models reproducible, which would benefit from an international effort. Using 210 Pb and 14 C to produce integrated age-models may yield better insights into the interplay between natural and recent anthropogenic forcings on ecosystems. This can enhance our understanding of environmental processes and their impacts on climate change, ultimately supporting science-based assessments and decisions.

Earth-Science Reviews

Integrating habitat suitability and climate constraints to predict nonnative fish invasion risk for U.S. streams and inland lakes

Introduction: Nonnative fishes in streams and inland lakes can substantially alter aquatic ecosystems by degrading habitat conditions, competing with native species, and restructuring food webs. Identifying invasion hotspots can inform proactive management and prevention of nonnative species establishment. Methods: In this study, we identified streams and lakes across the conterminous United States that are vulnerable to invasion by 18 nonnative stream and 28 nonnative lake fish species. Habitat suitability models were developed separately for stream and lake species across nine ecoregions using natural and anthropogenic predictors, and species occurrences were predicted by integrating model results with climate match scores based on comparisons between environmental conditions in species’ native and potential nonnative ranges. We classified areas with both high habitat suitability and strong climate similarity as having high invasion potential and generated hotspot maps by stacking species-level predictions. Results: Florida exhibits the highest invasion risk for both habitat types. Stream hotspots were concentrated near major metropolitan areas, whereas lake hotspots were more widely distributed across the Great Lakes basin and the northeastern U.S. Twelve species were predicted to invade both habitat types, with goldfish ( Carassius auratus ) and pirapitinga ( Piaractus brachypomus ) showing particularly high invasion potential. Discussion: These findings provide a comprehensive assessment of nonnative freshwater fish invasion risk and support targeted monitoring and management strategies.

conterminous United States

Evaluation of daily stream temperature predictions (1979-2021) across the contiguous United States using a spatiotemporal aware machine learning algorithm

Stream temperature controls a variety of physical and biological processes that affect ecosystems, human health, and economic activities. We used 42 years (1979–2021) of data to predict daily summary statistics of stream temperature across >50,000 stream reaches in the contiguous United States using a recurrent graph convolution network. We comprehensively documented the performance – both across all reaches and by stream type (e.g., reservoir or groundwater influence) – as a baseline for future improvement. The model showed reach-level RMSE of <2 °C with 90 % prediction intervals that contain 90.7 % of observations. We also assessed how the model captured variability in ecologically relevant metrics (e.g., R 2 for annual 7-day maximum = 0.76; R 2 for days exceeding 25 °C = 0.75). This model does not outperform state-of-the-art machine learning efforts (e.g., RMSE ≤1.5 °C) due to a limited input set but does provide the most spatially complete modeling to date to support water availability assessments.

contiguous United States

The effect of temperature, flow, density and disease on smallmouth bass (Micropterus dolomieu) early life growth rate

Individual growth rates of fish are influenced by gradually changing environmental conditions and rapid-onset events. However, there is a paucity of information on drivers of spatiotemporal variability in growth rates of fishes across large spatial extents. Using a 36-year dataset of smallmouth bass ( Micropterus dolomieu ) length-at-age data across 10 river reaches in Pennsylvania, USA ( n = 54,068 individuals), we estimated annual early life growth rates (mm year −1 ) and assessed the effects of relative abundance, summer temperature, summer streamflow rate and a disease outbreak on growth rate. We found that temperature had a positive effect on growth rate, varied spatially, and had a stronger effect in diseased reaches. There was also evidence for an impact of disease on early life growth through density-dependent mechanisms, with growth rates increasing from ∼85 to 101 mm·year −1 following disease-related decreases in abundance. This study adds to our understanding of the factors that shape early life growth, including rapid-onset events like disease which can have immediate and lasting effects on growth rate trajectory.

Pennsylvania

Simulation of the impacts of projected climate change on groundwater resources in the urban, semiarid Yucaipa Valley watershed, southern California using an integrated hydrologic model

Managing water resources in semiarid watersheds is challenging due to limited supply and uncertain future climate conditions. This paper examines the impact of future climate changes on an urban watershed in southern California using an integrated hydrologic model. GSFLOW modeling software is used to simulate the nonlinear relationships between climate trends and precipitation partitioning into ET, runoff, and subsurface storage. Four global circulation models (GCMs), each with two greenhouse-gas scenarios, RCP45 and RCP85 are used to project future climate conditions. GCMs include the CanESM2, CNRM-CM5, HadGEM2-ES, and MIROC5 models. The model's simulated hydrologic conditions are compared with historical data to assess changes in water budgets and groundwater supply. Results indicate decreased groundwater storage in most scenarios due to increased natural evapotranspiration, vegetation consumptive use, and streamflow out of the watershed. Only scenarios with substantially increased future precipitation show increased groundwater storage. The study also highlights increased future aridity despite the rise in precipitation and large precipitation events forecast by GCMs, which increase the risk of urban floods and decrease stream leakage and water available to vegetation.

California

Properties of solid bitumen formed during hydrous, anhydrous, and brine pyrolysis of oil shale: Implications for solid bitumen reflectance in source-rock reservoirs

Solid bitumen reflectance (BR o in %) is widely used as a thermal maturity proxy in source-rock reservoirs, yet solid bitumen texture and physical attributes may be affected by varying environmental constraints during its formation, e.g., water saturation, mineral catalysis, or salinity. Herein we investigated the development of solid bitumen properties during artificial maturation using three diverse (lacustrine to marine) oil shale samples containing abundant amorphous H-rich sedimentary organic matter (bituminite). The oil shales were treated via pyrolysis (320 °C, 72 h) using hydrous, anhydrous, and brine conditions, causing the development of a newly formed solid bitumen in the experiment residues from the thermal conversion of bituminite. The properties of the newly formed solid bitumen then were evaluated via geochemical screening tests, optical and electron microscopy, and infrared spectroscopy. Experimental residues also were treated via solvent extraction, allowing characterization of the effects of extraction on solid bitumen. Results showed that bituminite with higher resin and asphaltene components evolved to a solid bitumen with higher reflectance (as a percentage of the original value) when exposed to the same heat treatment, relative to bituminite with higher saturate and aromatic components. Aromatization of solid bitumen also was generally more pronounced in the presence of deionized water relative to anhydrous conditions, supporting prior observations. These results suggest the compositions of primary sedimentary organic matter, and the local concentration of water, affect the development of solid bitumen during thermal advance, potentially explaining the origin of multiple solid bitumen populations with varying reflectance in source-rock reservoir samples or in a single microscope field. Experiments using brine were inconclusive regarding enhanced/decreased aromatization, which could be attributed to the salinities of the brines used in the tests. Extraction of residues caused a consistent increase in BR o values, suggesting that migrating or expelled oils could cause an increase in BR o via natural solvation and absent an increase in temperature. This work provides insights into the development and evolution of BR o in source-rock reservoirs as a function of the composition of the original bituminite and changing environmental conditions, with potentially broad application for petroleum prospecting and resource estimation.

Colorado

PFAS mixture composition and internal exposure profiles shape biological responses under field-realistic exposure

Per- and polyfluoroalkyl substances (PFAS) occur as complex mixtures, yet mixture-dependent biological effects under environmentally realistic exposure conditions remain poorly understood. We conducted multiyear (2018, 2019, 2021) continuous-flow, field-based exposures of male fathead minnows ( Pimephales promelas ) using a low-PFAS reference well (REF; sum of measured PFAS (∑PFAS) 0.1–0.2 μg L –1 ) and PFAS-contaminated groundwater from a fire-training area (FTA) at Joint Base Cape Cod, Massachusetts. Dilution treatments enabled separation of concentration and mixture effects. Groundwater from well FTA1 was perfluorooctanesulfonate (PFOS) dominated (∑PFAS 10–31 μg L –1 ), whereas groundwater from well FTA2 had higher concentrations and was enriched in perfluorooctanoate (PFOA) and diverse precursors (∑PFAS ∼ 80 μg L –1 ). Despite comparable plasma ∑PFAS and PFOS in FTA1–100% and FTA2–50% on day-7, cumulative mortality reached approximately 35% in FTA2–50% and 17% in FTA2–100%, and secondary sex trait expression was reduced by approximately 65–80% relative to REF, whereas sperm motility effects were mixture- and time-dependent. Plasma PFAS profiles were dominated by perfluorohexanesulfonate (PFHxS), PFOS, and sulfonamide precursors. Liver transcriptomics from REF-acclimated fish revealed robust disruption of metabolic, mitochondrial, and endocrine pathways that link PFAS mixture chemistry and internal exposure profiles to organismal outcomes, and testis transcriptomics provided complementary insight into reproductive impairment. These results indicate that PFAS mixture composition and internal exposure profiles, including precursor-associated differences, are important determinants of ecotoxicological outcomes under field-realistic conditions.

Massachusetts

Hydrologic response of groundwater and streamflow to natural and anthropogenic drivers of change in headwaters of the upper Colorado River basin during recent wet (1982–1999) and drought (2000–2022) conditions

Study region: Headwaters of the upper Colorado River basin (UCOL), USA Study focus: Surface-water and groundwater numerical models incorporating water-use information were used to investigate changes in climate, water use, and simulated hydrologic responses of snow processes, evapotranspiration, groundwater, and streamflow during recent wet (1982–1999) and drought (2000–2022) periods in the headwater subregions of the upper Colorado River basin. New hydrologic insights for the region: Decreases in average streamflow between wet and drought periods ranged from 20 % in the Colorado River headwaters subregion to 23 % in the Gunnison River headwaters subregion. Like streamflow, average surface runoff was statistically less during the drought than the wet period, with decreases from 24–31 % in the headwaters. On a volume basis, runoff decreases were greater than streamflow decreases in both the Colorado River and Gunnison River headwaters. Although the amount of water-year groundwater discharge to streams remained nearly the same between the wet and drought periods, groundwater as a percentage of streamflow increased between the wet and drought periods, highlighting the importance of groundwater in sustaining streamflow during drought conditions. Multiple linear regression analyses revealed that snowmelt-only models were better than the best precipitation and temperature models at explaining streamflow variability from all headwater subregions for both the wet and drought periods.

Arizona, Colorado, New Mexico, Utah, Wyoming

Natural source zone depletion of crude oil in the subsurface: Processes controlling mass losses of individual compounds

At many petroleum hydrocarbon spill sites, residual spilled product forms a long-term source of groundwater contamination. The phrase source zone natural depletion is used to refer to the mass loss rates. Overall mass lost under environmental conditions was analyzed using conservative biomarker concentrations for a 1979 oil spill in northern Minnesota, USA. After 40–41 years, an average of 50% of the mass was lost with values ranging from 22% to 57% depending on location. It is also important to understand the composition changes in the source. To understand controls on the losses of individual compounds, concentrations of volatile hydrocarbons in oil samples were compared with aqueous solubilities, and pore-space oil saturations. The results of the comparison show that losses of the oil compounds were controlled by pore-space oil saturations, solubility, and susceptibility to degradation under methanogenic conditions. Compounds that degrade under methanogenic conditions, including toluene, o -xylene, and n -alkanes are more depleted compared to benzene, ethylbenzene, and m - and p -xylene for which losses are dominated by dissolution. These rates and compound-specific behaviors form a foundation for improved modeling approaches and risk analyses.

Minnesota

Wetter winters, drier summers: Quantifying the change in hydrological response around the Puget Sound area using the wflow_sbm hydrological model and CMIP6 projections

Climate change is expected to impact hydrological regimes worldwide, including the Pacific Northwest of the United States. This study investigates how climate change will affect river discharge in the Puget Sound region of the State of Washington, with a focus on King and Pierce Counties. We simulated river discharge under historical and future conditions using the physically based, spatially distributed wflow_sbm hydrological model, which was calibrated and validated against U.S. Geological Survey discharge records. Future forcing was based on an ensemble of six high-resolution CMIP6 climate models, which were bias corrected using empirical quantile mapping. The results indicate a decrease in summer discharges (5–10%) and an increase in winter discharges (5–10%) across the study region. The high discharges (90th percentile) are projected to increase in winter, and the low discharges are projected to decrease in summer, due to shifts in precipitation regimes, snowpack hydrology, and evapotranspiration. However, variability between individual CMIP6 models often exceeds the magnitude of ensemble mean changes, underscoring substantial uncertainty in climate projections and the importance of including multiple climate models in climate change analysis. Furthermore, model consensus increased with elevation, which could be the result of the higher elevation areas being driven by less diverse hydrological processes. These findings highlight potential challenges for regional water management, ecosystem health, and flood risk mitigation in the Puget Sound region under future climate conditions.

EarthArXiv

Comparative assessment of a restored and natural wetland using 13C-DNA SIP reveals a higher potential for methane production in the restored wetland

Wetlands are the largest natural source of methane (CH 4 ), a potent greenhouse gas produced by methanogens. Methanogenesis rates are controlled by environmental factors such as redox potential, temperature, and carbon and electron acceptor availability and are presumably dependent on the composition of the active methanogen community. We collected intact soil cores from a restored and natural freshwater depressional wetland on Maryland’s Delmarva Peninsula (USA) to assess the effects of wetland restoration and redox shifts on microbial processes. Intact soil cores were incubated under either saturated (anoxic) or unsaturated (oxic) conditions and amended with 13 C-acetate for quantitative stable isotope probing (qSIP) of the 16S rRNA gene. Restored wetland cores supported a distinct community of methanogens compared to natural cores, and acetoclastic methanogens putatively identified in the genus Methanosarcina were among the most abundant taxa in restored anoxic and oxic cores. The active microbial communities in the restored wetland cores were also distinguished by the unique presence of facultatively anaerobic bacteria belonging to the orders Firmicutes and Bacteroidetes . In natural wetland incubations, methanogen populations were not among the most abundant taxa, and these communities were instead distinguished by the unique presence of aerobic bacteria in the phyla Acidobacteria , Actinobacteria , and class Alphaproteobacteria . Iron-reducing bacteria, in the genus Geobacter , were active across all redox conditions in both the restored and the natural cores, except the natural oxic–anoxic condition. These findings suggest an overall higher potential for methanogenesis in the restored wetland site compared to the natural wetland site, even when there is evidence of Fe reduction.

Maryland

Critical review of mercury methylation and methylmercury demethylation rate constants in aquatic sediments for biogeochemical modeling

Mercury is a toxin that causes neurological impairments in adults, is particularly harmful for fetuses and children, and is deadly in severe cases, making it a worldwide health concern. Methylmercury (MeHg) is the environmentally relevant form of mercury (Hg) because it biomagnifies along the food chain. Methylmercury is mainly produced in aquatic sediments via methylation of inorganic Hg (Hg(II)) and transformed back via demethylation. Because transformation rates determine MeHg concentrations, quantification of methylation and demethylation rates is needed to inform management of MeHg. Published rate constants for Hg(II) methylation ( 𝑘 𝑚 ) and MeHg demethylation ( 𝑘 𝑑 ) vary greatly, stemming partly from differences in experimental methods. We conducted a comprehensive review of rate laws, evaluated published rate constants, and performed biogeochemical simulations to assess variability in reported 𝑘 𝑚 and 𝑘 𝑑 . Based on selected studies employing the same pseudo-first-order rate law and similar experimental methods, we found that 𝑘 𝑚 = 0.04 ± 0.03 d −1 is a reasonable range for wetland sediments. Over a number of environments, maximum 𝑘 𝑑 was smaller at sites without Hg source ( 𝑘 𝑑 = 0.5 d −1 ) than at sites with identified Hg source ( 𝑘 𝑑 = 1.8 d −1 ). Larger variability and higher uncertainty in 𝑘 𝑑 compared to 𝑘 𝑚 highlight the need for more research on MeHg demethylation rates. This critical review: (a) aids the design of future experimental studies of 𝑘 𝑚 and 𝑘 𝑑 ; (b) provides guidance for comparing rate constants from different studies; (c) presents a biogeochemical reaction model to assess rate constants; and (d) informs selection of 𝑘 𝑚 and 𝑘 𝑑 values from the literature for use in model simulations.

Critical Reviews in Environmental Science and Tech

Remote sensing enables basin-scale inventories of coal mine methane

Underground coal mines are important global sources of methane, but emission estimates are uncertain. We show that emission estimates for individual mines from aircraft remote-sensing surveys in the United States agree within 40% with direct measurements used for national emission reporting (IPCC Tier 3 estimate). Such direct measurements are unavailable in most countries, which rely on estimated emission factors (EFs) applied to coal-production rates. We find that EFs from IPCC Tier 1 and the Model for Calculating Coal Mine Methane (MC2M) methods overestimate U.S. emissions 3-fold due to incorrect dependence on mine depth. An IPCC Tier 2 method using measured basin-specific mine gas content agrees with direct emission measurements but does not account for gob well emissions and requires gas content data that are generally unavailable. We show that aircraft remote sensing for a small sample of mines can successfully estimate basin-specific EFs for ventilation shafts and gob wells, enabling estimates of basin- and national-scale emissions. We discuss how the method can be applied with satellite remote sensing to quantify coal emissions worldwide.

Alabama, Colorado, Kentucky, New Mexico, Ohio, Pen

Observing northern high-latitude river systems to understand changes in a warming Arctic

Purpose of Review Streams and rivers are undergoing rapid change as the Arctic warms and thaws. We review recent observations in Arctic stream systems to identify ubiquitous changes and the most useful tools for observing change and exploring the underlying processes. Recent Findings Recent literature indicates increasingly significant trends in river hydrology and chemistry due to persistent warming in the Arctic and longer observational records for analysis. However, regional differences in the magnitude and direction of these trends persist. We also observe thresholds in ground thaw and surface–groundwater interactions that can impact river hydrology and chemistry. Summary Warming and thaw are occurring rapidly at high latitudes, resulting in increasing, yet variable responses in stream systems across regions and scales. These differences highlight the need for long-term records and an interdisciplinary approach to explain trends and predict future states. Stream systems respond to multiple landscape changes related to hydrology (changing precipitation and subsurface flow), geology (ground thaw dynamics), and ecology (vegetation change).

Current Climate Change Reports

Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques

The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.

Environmental Science and Technology