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The truth is in the stream: Use of tracer techniques and synoptic sampling to evaluate metal loading and remedial options in a hydrologically complex setting

Two synoptic sampling campaigns were conducted to quantify metal loading to Illinois Gulch, a small stream affected by historical mining activities. The first campaign was designed to determine the degree to which Illinois Gulch loses water to the underlying mine workings, and to determine the effect of these losses on observed metal loads. The second campaign was designed to evaluate metal loading within Iron Springs, a subwatershed that was responsible for the majority of the metal loading observed during the first campaign. A continuous, constant-rate injection of a conservative tracer was initiated prior to both sampling campaigns and maintained throughout the duration of each study. Tracer concentrations were subsequently used to determine streamflow in gaining stream reaches using the tracer-dilution method, and as an indicator of hydrologic connections between Illinois Gulch and subsurface mine workings. Streamflow losses to the mine workings were quantified during the first campaign using a series of slug additions in which specific conductivity readings were used as a surrogate for tracer concentration. Data from the continuous injections and slug additions were combined to develop spatial streamflow profiles along each study reach. Streamflow estimates were multiplied by observed metal concentrations to yield spatial profiles of metal load that were in turn used to quantify and rank metal sources. Study results indicate that Illinois Gulch loses water to subsurface mine workings and suggest that remedial measures that reduce flow loss (e.g. channel lining) could lessen metal loading from the Iron Springs area. The primary sources of metals to Illinois Gulch include diffuse springs and groundwater, and a draining mine adit. Diffuse sources were determined to have a much larger effect on water quality than other sources that had been the subject of previous investigations due to their visual appearance, supporting the idea that “the truth is in the stream”. The overall approach of combining spatially intensive sampling with a rigorous hydrological characterization is applicable to non-mining constituents such as nutrients and pesticides.

Colorado↗

An assessment of the relation between metal contaminated sediment and freshwater mussel populations in the Big River, Missouri

The Big River in southeast Missouri drains the largest historical lead mining area in the United States. Ongoing releases of metal contaminated sediments into this river are well documented and are suspected of suppressing freshwater mussel populations. We characterized the spatial extent of metal contaminated sediments and evaluated its relationship with mussel populations in the Big River. Mussels and sediments were collected at 34 sites with potential metal effects and 3 reference sites. Analysis of sediment samples showed that lead (Pb) and zinc (Zn) concentrations were 1.5 to 65 times greater than background concentrations in the reach extending 168 km downstream from Pb mining releases. Mussel abundance decreased acutely downstream from these releases where sediment Pb concentrations were highest and increased gradually as Pb sediment concentrations attenuated downstream. We compared current species richness with historical survey data from three reference rivers with similar physical habitat characteristics and human effects, but without Pb-contaminated sediment. Big River species richness was on average about one-half that expected based on reference stream populations and was 70–75 % lower in reaches with high median Pb concentrations. Sediment Zn and cadmium, and particularly Pb, had significant negative correlations with species richness and abundance. The association of sediment Pb concentrations with mussel community metrics in otherwise high-quality habitat indicates that Pb toxicity is likely responsible for depressed mussel populations observed within the Big River. We used concentration-response regressions of mussel density verses sediment Pb to determine that the Big River mussel community is adversely affected when sediment Pb concentrations are above 166 ppm, the concentration associated with 50 % decreases in mussel density. Based on this assessment of metals concentrations sediment and mussel fauna, our findings indicate that sediment in approximately 140 km of the Big River with suitable habitat has a toxic effect to mussels.

Missouri↗

Energy-related wastewater contamination alters microbial communities of sediment, water, and amphibian skin

To inform responsible energy development, it is important to understand the ecological effects of contamination events. Wastewaters, a common byproduct of oil and gas extraction, often contain high concentrations of sodium chloride (NaCl) and heavy metals (e.g., strontium and vanadium). These constituents can negatively affect aquatic organisms, but there is scarce information for how wastewaters influence potentially distinct microbiomes in wetland ecosystems . Additionally, few studies have concomitantly investigated effects of wastewaters on the habitat (water and sediment) and skin microbiomes of amphibians or relationships among these microbial communities. We sampled microbiomes of water, sediment, and skin of four larval amphibian species across a gradient of chloride contamination (0.04–17,500 mg/L Cl) in the Prairie Pothole Region of North America. We detected 3129 genetic phylotypes and 68 % of those phylotypes were shared among the three sample types. The most common shared phylotypes were Proteobacteria, Firmicutes, and Bacteroidetes. Salinity of wastewaters increased dissimilarity within all three microbial communities, but not the diversity or richness of water and skin microbial communities. Strontium was associated with lower diversity and richness of sediment microbial communities, but not those of water or amphibian skin, likely because metal deposition occurs in sediment when wetlands dry. Based on Bray Curtis distance matrices, sediment microbiomes were similar to those of water, but neither had substantial overlap with amphibian microbiomes. Species identity was the strongest predictor of amphibian microbiomes; frog microbiomes were similar but differed from that of the salamander, whose microbiome had the lowest richness and diversity. Understanding how effects of wastewaters on the dissimilarity, richness, and diversity of microbial communities also influence the ecosystem function of communities will be an important next step. However, our study provides novel insight into the characteristics of, and associations among, different wetland microbial communities and effects of wastewaters from energy production.

Montana, North Dakota↗

Model-based assessment and mapping of total phosphorus enrichment in rivers with sparse reference data

Water nutrient management efforts are frequently coordinated across thousands of water bodies, leading to a need for spatially extensive information to facilitate decision making. Here we explore potential applications of a machine learning model of river low-flow total phosphorus (TP) concentrations to support landscape nutrient management. The model was trained, validated, and then applied for all rivers of Michigan, USA to identify potential drivers of nutrient variation, predict alteration in nutrient concentrations from minimally disturbed conditions, and explore reach specific sensitivity to riparian agricultural change. A boosted regression tree model of low-flow TP concentrations trained on natural and anthropogenic landscape predictors accounted for 53 % of variation in cross-validation data, had good accuracy, little bias, and plausible relationships between predictors and response. Percent riparian agricultural cover accounted for the greatest root mean square error reduction in the modeled response (33.2 %), followed by riparian soil permeability (12.9 %), watershed slope (9.6 %), and percent urban cover (9.6 %). An apparent non-linear relationship between TP concentrations and percent riparian agricultural cover suggested steep positive increases in stream TP concentrations between 10 and 30 % upstream riparian agricultural cover. Predicted minimally disturbed TP concentrations were spatially variable and ranged from 7.0 to 48.5 μg l −1 , with the highest concentrations in watersheds draining low-permeability lake plain soils. Comparison of minimally disturbed predictions to those from the early 2000s suggested that much of northern Michigan existed close to the reference condition, while lower Michigan streams were often substantially enriched. Our predicted values of minimally disturbed condition generally agree with previous studies but offer greater geographic specificity. Expanded application of machine learning modeling with landscape predictor data have great potential to inform large scale strategy development in landscapes with sparse reference data.

Michigan↗

Global review reveals how disparate study motivations, analytical designs, and focal ions limit understanding of salinization effects on freshwater animals

Global salinization of freshwaters is adversely affecting biotic communities and ecosystem processes. We reviewed six decades (1960–2020) of literature published on animal responses to increased salinities across different taxonomic and ecological contexts and identified knowledge gaps. From 585 journal articles, we characterized 5924 responses of mollusks, crustaceans, zooplankton, non-arthropod invertebrates (NAI), insects, fishes, and amphibians to salinization. Insects and fishes were the most studied taxa; Na + and Cl − were the most studied ions − . Collectively, concentrations of the ions examined typically spanned five orders of magnitude. Species' invasiveness was a key motivation for studying mollusks, crustaceans, and fishes; threats of urbanization and road salts were key motivations for studying NAI, zooplankton, and amphibians. Laboratory studies were more common than field studies for most taxa. Focal life stages in laboratory studies varied widely but juveniles and adults were represented similarly in field studies. Studies of mollusks, NAI, and crustacean focused on adults; studies of zooplankton, insects, fishes, and amphibians focused on juveniles. Organismal- and population-level responses measuring solute uptake, internal chemistry, body condition, or ion concentrations predominated laboratory studies; population- and assemblage-level responses measuring abundance, spatial distribution, or assemblage composition predominated field studies. Negative responses to salinization predominated but positive and unimodal responses were apparent across all taxa and organizational levels. Key topics for further research include a) salinity responses by more taxa, b) responses to especially toxic ions (i.e., potassium, bicarbonate, sulfate, magnesium), c) mechanisms causing positive and unimodal responses, d) traits underpinning responses, e) effects transcending organizational levels, f) ion-specific response thresholds, and g) interactions between salinity and other stressors. Our review suggests inter-taxa variation in sensitivity to salinization reflects occurrence of certain biological traits, including gill-breathing, semi-permeable skin, multiple life stages, and limited mobility. We propose a traits-based framework to predict salinization sensitivity from shared traits. This evolutionary approach could inform management aimed at preventing or reducing adverse impacts of freshwater salinization.

Science of the Total Environment↗

Per- and polyfluorinated alkyl substances (PFAS) in Pennsylvania surface waters: A statewide assessment, associated sources, and land-use relations

The objectives of this study are to identify per- and polyfluoroalkyl substances (PFAS) in Pennsylvania surface waters, corresponding associations with potential sources of PFAS contamination (PSOC) and other parameters, and compare raw surface water concentrations to human and ecological benchmarks. Surface water samples from 161 streams were collected in September 2019 and were analyzed for 33 target PFAS and water chemistry. Land use and physical attributes in upstream catchments and geospatial counts of PSOC in local catchments are summarized. The hydrologic yield of the sum of 33 PFAS (∑PFAS) for each stream was computed by normalizing each site's load by the drainage area of the upstream catchment. Utilizing conditional inference tree analysis, the percentage of development (>7.58 %) was identified as a primary driver of the ∑PFAS hydrologic yields. When percentage of development was removed from analysis, ∑PFAS yields were closely related to surface water chemistry associated with landscape alteration (e.g., development or agricultural cropland), such as concentrations of total nitrogen, chloride, and ammonia, but also to count of water pollution control facilities (agricultural, industrial, stormwater, and/or municipal waste pollution abatement facilities). In oil and gas development regions, ∑PFAS yields were associated with combined sewage outfalls. Sites surrounded by ≥2 electronic manufacturing facilities had elevated ∑PFAS yields (median = 241 ng/s/km 2 ). Study results are critical to guide future research, regulatory policy, best practices that will mitigate PFAS contamination, and the communication of human health and ecological risks associated with PFAS exposure from surface waters.

Pennsylvania↗

Synergistic soil, land use, and climate influences on wind erosion on the Colorado Plateau: Implications for management

Two decades of drought in the southwestern USA are spurring concerns about increases in wind erosion, dust emissions, and associated impacts on ecosystems, agriculture, human health, and water supply. Different avenues of investigation into primary drivers of wind erosion and dust have yielded mixed results depending on the spatial and temporal sensitivity of the evidence. We monitored passive aeolian sediment traps from 2017 to 2020 across eighty-one sites near Moab UT to understand patterns of sediment flux. At measurement sites we collated climate, soil, topography and vegetation spatial layers to better understand the context of wind erosion and then combine these data with field observations of land use in models to characterize the influence of cattle grazing, oil and gas well pads, and vehicle/heavy equipment disturbance that potentially drive both exposure of bare soil and increases in erodible sediment supply that increase vulnerability to erosion. Disturbed areas with low soil calcium carbonate content yielded high sediment transport in dry years, but notably areas with little disturbance and low bare soil exposure had much less activity. Cattle grazing had the largest land use association with erosional activity with analyses suggesting that both herbivory and trampling from cattle could be drivers. The amount and distribution of bare soil exposure from new sub-annual fractional cover remote sensing products proved very helpful in mapping erosion, and new predictive maps informed by field data are presented to help depict spatial patterns of wind erosion activity. Our results suggest that despite the magnitude of current droughts, minimizing surface disturbance in vulnerable soils can mitigate a large portion of dust emissions. Results can help managers identify eroding areas where disturbance reduction and soil surface protection measures can be prioritized.

Science of the Total Environment↗

Cross-continental evaluation of landscape-scale drivers and their impacts to fluvial fishes: Understanding frequency and severity to improve fish conservation in Europe and the United States

Fluvial fishes are threatened globally from intensive human landscape stressors degrading aquatic ecosystems. However, impacts vary regionally, as stressors and natural environmental factors differ between ecoregions and continents. To date, a comparison of fish responses to landscape stressors over continents is lacking, limiting understanding of consistency of impacts and hampering efficiencies in conserving fishes over large regions. This study addresses these shortcomings through a novel, integrative assessment of fluvial fishes throughout Europe and the conterminous United States. Using large-scale datasets, including information on fish assemblages from more than 30,000 locations on both continents, we identified threshold responses of fishes summarized by functional traits to landscape stressors including agriculture, pasture, urban area, road crossings, and human population density. After summarizing stressors by catchment unit (local and network) and constraining analyses by stream size (creeks vs. rivers), we analyzed stressor frequency (number of significant thresholds) and stressor severity (value of identified thresholds) within ecoregions across Europe and the United States. We document hundreds of responses of fish metrics to multi-scale stressors in ecoregions across two continents, providing rich findings to aid in understanding and comparing threats to fishes across the study regions. Collectively, we found that lithophilic species and, as expected, intolerant species are most sensitive to stressors in both continents, while migratory and rheophilic species are similarly strongly affected in the United States. Also, urban land use and human population density were most frequently associated with declines in fish assemblages, underscoring the pervasiveness of these stressors in both continents. This study offers an unprecedented comparison of landscape stressor effects on fluvial fishes in a consistent and comparable manner, supporting conservation of freshwater habitats in both continents and worldwide.

Europe↗

Long short-term memory models to quantify long-term evolution of streamflow discharge and groundwater depth in Alabama

Long short-term memory (LSTM) models have been shown to be efficient for rainfall-runoff modeling, and to a lesser extent, for groundwater depth forecasting. In this study, LSTMs were applied to quantify the spatiotemporal evolution of surface and subsurface hydrographs in Alabama in the Southeastern United States, where water sustainability has not been fully quantified across spatiotemporal scales. First, the surface water LSTM model with extensive dynamic (precipitation and other weather variables) and static (basin characteristics) inputs predicted the main characteristics of streamflow for six years at 19 gauged basins in Alabama. The model tended to underestimate extremely high streamflow but adding drainage density as an input feature slightly improved the predictions of extreme events. Second, to predict the groundwater depth evolution, a groundwater LSTM (GW-LSTM) model was proposed and applied using static inputs capturing the aquifers' hydrogeological properties and dynamic inputs of meteorological information. Three precipitation scenarios were also explored to evaluate the groundwater hydrograph evolution in the next two decades. The GW-LSTM model predicted the general trend of daily groundwater depth fluctuations (at 21 wells distributed across Alabama from 1990 to 2021) including most extremely high groundwater levels, and recovered groundwater depth for locations withheld from model training and validation. This study, therefore, extended the application of LSTMs in quantifying the spatiotemporal evolution of surface water and groundwater, two manifestations of a single integrated resource.

Alabama↗

Multi-omic responses of fish exposed to complex chemical mixtures in the Shenandoah River watershed

To evaluate relationships between different anthropogenic impacts, contaminant occurrence, and fish health, we conducted in situ fish exposures across the Shenandoah River watershed at five sites with different land use. Exposure water was analyzed for over 500 chemical constituents, and organismal, metabolomic, and transcriptomic endpoints were measured in fathead minnows. Adverse reproductive outcomes were observed in fish exposed in the upper watershed at both wastewater treatment plant (WWTP) effluent- and agriculture-impacted sites, including decreased gonadosomatic index and altered secondary sex characteristics. This was accompanied with increased mortality at the site most impacted by agricultural activities. Molecular biomarkers of estrogen exposure were unchanged and consistent with low or non-detectable concentrations of common estrogens, indicating that alternative mechanisms were involved in organismal adverse outcomes. Hepatic metabolomic and transcriptomic profiles were altered in a site-specific manner, consistent with variation in land use and contaminant profiles. Integrated biomarker response data were useful for evaluating mechanistic linkages between contaminants and adverse outcomes, suggesting that reproductive endocrine disruption, altered lipid processes, and immunosuppression may have been involved in these organismal impacts. This study demonstrated linkages between human-impact, contaminant occurrence, and exposure effects in the Shenandoah River watershed and showed increased risk of adverse outcomes in fathead minnows exposed to complex mixtures at sites impacted by municipal wastewater discharges and agricultural practices.

Virginia, West Virginia↗

Changes in chemical occurrence, concentration, and bioactivity in the Colorado River before and after replacement of the Moab, Utah wastewater treatment plant

Long-term (2010–19) water-quality monitoring on the Colorado River downstream from Moab Utah indicated the persistent presence of Bioactive Chemicals (BC), such as pesticides and pharmaceuticals. This stream reach near Canyonlands National Park provides critical habitat for federally endangered species. The Moab wastewater treatment plant (WWTP) outfall discharges to the Colorado River and is the nearest potential point-source to this reach. The original WWTP was replaced in 2018. In 2016–19, a study was completed to determine if the new plant reduced BC input to the Colorado River at, and downstream from, the outfall. Water samples were collected before and after the plant replacement at sites upstream and downstream from the outfall. Samples were analyzed for as many as 243 pesticides, 109 pharmaceuticals, 20 hormones, 51 wastewater indicator chemicals, 20 metals, and 8 nutrients. BC concentrations, hazard quotients (HQs), and exposure activity ratios (EARs) were used to identify and prioritize contaminants for their potential to have adverse biological effects on the health of native and endangered wildlife. There were 22 BC with HQs >1, mostly metals and hormones; and 23 BC with EARs >0.1, mostly hormones and pharmaceuticals. Most high HQs or EARs were associated with samples collected at the WWTP outfall site prior to its replacement. Discharge from the new plant had reduced concentrations of nutrients, hormones, pharmaceuticals, and other BC. For example, all 16 of the hormones detected at the WWTP outfall site had maximum concentrations in samples collected prior to the WWTP replacement. The WWTP replacement had less effect on instream concentrations of metals and pesticides, BC whose sources are less directly tied to domestic wastewater. Study results indicate that improved WWTP technology can create substantial reductions in concentrations of non-regulated BC such as pharmaceuticals, in addition to regulated contaminants such as nutrients.

Utah↗

Fluid migration pathways to groundwater in mature oil fields: Exploring the roles of water injection/production and oil-well integrity in California, USA

Mature oil fields potentially contain multiple fluid migration pathways toward protected groundwater (total dissolved solids, TDS, in nonexempted aquifer <10,000 mg/L) because of their extensive development histories. Time-series data for water use, fluid pressures, oil-well construction, and geochemistry from the South Belridge and Lost Hills mature oil fields in California are used to explore the roles of injection/production of oil-field water and well-integrity issues in fluid migration. Injection/production of oil-field water modified hydraulic gradients in both oil fields, resulting in chemical transport from deeper groundwater and hydrocarbon-reservoir systems to aquifers in the oil fields. Those aquifers are used for water supply outside the oil-field boundaries. Oil wells drilled before 1976 can be fluid migration pathways because a relatively large percentage of them have >10 m of uncemented annulus that straddles oil-well casing damage and/or the base of groundwater with TDS <10,000 mg/L. The risk of groundwater-quality degradation is higher when wells with those risk factors occur in areas with upward hydraulic gradients created by positive net injection, groundwater withdrawals, or combinations of these variables. The complex changes in hydrologic conditions and groundwater chemistry likely would not have been discovered in the absence of years to decades of monitoring data for groundwater elevations and chemistry, and installation of monitoring wells in areas with overlapping risk factors. Important monitoring concepts based on results from this and other studies include monitoring hydrocarbon-reservoir and groundwater systems at multiple spatiotemporal scales and maintaining transparency and accessibility of data and analyses. This analysis focuses on two California oil fields, but the methods used and processes affecting fluid migration could be relevant in other oil fields where substantial injection/production of oil-field water occurs and oil-well integrity is of concern.

California↗

Spectral characterization of dissolved organic matter in groundwater to assess mixing with oil-field water near selected oil fields, southern California

Samples of oil-field water (oil wells, injectate, disposal ponds) and groundwater near selected oil and gas fields in southern California were analyzed for dissolved organic carbon (DOC) concentration and by optical spectroscopic techniques (i.e., absorbance and fluorescence) to assess whether these measurements can be used to distinguish between oil-field water (Oil Field), native groundwater (WGnat), and native groundwater mixed with oil-field water from surface (WGsurf) or subsurface sources (WGsub), and if so whether commonly reported optical measurements can be used as a screening tool to identify such water. Concentrations of DOC were significantly (p < 0.0001) higher (67 to 2934 mg C L−1) in oil-field water compared to native groundwater samples (<5.0 mg C L−1). Individual optical properties varied by water category and frequently overlapped. However, multivariate statistical analysis showed that when evaluated in combination, 10 optical properties were determined by discriminant analysis to be significant (p < 0.05) in distinguishing among water categories. Principal component analysis of those 10 optical properties showed that these properties can be used to successfully distinguish Oil Field samples from WGnat, WGsurf, and WGsub even when mixing fractions are low (approximately 10 %).

California↗

Impacts of acute and chronic suspended solids exposure on juvenile freshwater mussels

Construction activities may affect adjacent water systems by introducing increased levels of suspended solids into the water body and may subsequently affect the survival and growth of freshwater mussels. We tested three sediment types from sites in Missouri, including Spring River sediment (SRS), Osage River bank clay soil (ORC), and quarried limestone from Columbia (LMT). We prepared series of suspensions of each sediment with total suspended solids concentrations ranging from 0 to 5000 mg/L. Juveniles from three mussel species, Fatmucket ( Lampsilis siliquoidea ), Arkansas Brokenray ( Lampsilis reeveiana ), and Washboard ( Megalonaias nervosa ) were exposed to these suspensions in both acute (96-h) and chronic (28-d) tests. No clear impact on survival was observed from the acute or chronic exposures, but chronic test showed that juvenile mussels' growth was strongly affected. Interestingly, growth was enhanced at lower levels of SRS and ORC (≤500 mg/L, p < 0.05), and the juvenile mussels exposed to 500 mg/L SRS exhibited approximately 60 % more dry weight than those reared in the control. LMT did not enhance growth. Growth was slowed by high concentrations (>1000 mg/L) of all three sediments, implying that high suspended solids levels could reduce survival in the long term. Our findings may help to inform regulations and guidelines for construction activities to minimize adverse effects on juvenile mussels.

Science of the Total Environment↗

Recent, widespread nitrate decreases may be linked to persistent dissolved organic carbon increases in headwater streams recovering from past acidic deposition

Long-term monitoring of water quality responses to natural and anthropogenic perturbation of watersheds informs policies for managing natural resources. Dissolved organic carbon (DOC) and nitrate (NO 3 − ) in streams draining forested landscapes provide valuable information on ecosystem function due to their biogeochemical reactivity and solubility in water. Here we evaluate a 20-year record (2001−2021) of biweekly stream-water samples ( n > 3000) and continuous discharge in three forested catchments in the Adirondack region of New York to investigate and interpret long-term trends in DOC and NO 3 − concentrations. Results from the intensively monitored catchments were compared with data from synoptic surveys of streams throughout the Adirondack region. A weighted regressions on time, discharge, and season (WRTDS) model, used to estimate daily flow-normalized concentrations, determined that DOC increased by ~30 to 50 % while NO 3 − decreased by ~50 to 70 % over the study period. The large amount of data from catchments with different soil properties permitted us to assess the relative effects of hydrology, season, and land cover factors on temporal trends in DOC and NO 3 − concentrations. We found weak evidence of climatic forcing of long-term increases in DOC, and instead contend that declining ionic strength in precipitation linked to declining anthropogenic acid deposition is driving DOC trends in stream waters. Nitrate concentrations were more variable but clearly decreased in recent years possibly related to declining N deposition. The recent increase in DOC:NO 3 − in all catchments indicates a major shift in stream stoichiometry that reflects changes in ecosystem functioning that may have important biogeochemical implications for terrestrial as well as aquatic ecosystems.

Science of the Total Environment↗

Target and suspect per- and polyfluoroalkyl substances in fish from an AFFF-impacted waterway

A major source of toxic per - and polyfluoroalkyl substances (PFAS) is aqueous film-forming foams (AFFF) used in firefighting and training at airports and military installations, however, PFAS have many additional sources in consumer products and industrial processes. A field study was conducted on fish tissues from three reaches of the Columbia Slough, located near Portland International Airport, OR, that are affected by AFFF and other PFAS sources. Fishes including largescale sucker ( Catostomus macrocheilus ), goldfish ( Carassius auratus ), and largemouth bass ( Micropterus salmoides ) were collected in 2019 and 2020. Fish blood, liver, and fillet (muscle) were analyzed for target and suspect PFAS by liquid chromatography high resolution mass spectrometry (LC-HRMS). Data were analyzed for patterns by fish species, tissue type, and river reach. Thirty-three out of 50 target PFAS and additional suspect compounds were detected at least once during the study, at concentrations up to 856 ng/g. Seven carboxylic acids (PFOA, PFNA, PFDA, PFUdA, PFDoA, PFTrDA, PFTeDA), three sulfonates (PFHxS, PFOS, PFDS), three electrofluorination-based compounds (FBSA, FHxSA, FOSA), and two fluorotelomer-based compounds (8:2 FTS, 10:2 FTS) were the most frequently detected compounds in all tissue types. The C6 (PFHxS) to C10 (PFDS) homologs were detected with PFOS and FHxSA at concentrations 1–3 orders of magnitude greater than the other PFAS detected. This is the first report of Cl-PFOS, FPeSA, and FHpSA detected in fish tissue. In all fish samples, fillet concentrations of PFAS were the lowest, followed by liver, and blood concentrations of PFAS were the highest. Differences in PFAS concentrations were driven primarily by tissue types and to a lesser extent fish species, but weakly by river reach. The Oregon Health Authority modified an existing fish consumption advisory on the Columbia Slough to recommend no whole-body consumption of most fish to avoid elevated levels of PFOS in fish liver. Measured PFAS concentrations in fish tissues indicate the potential for adverse ecological effects.

Oregon↗

Assessing the added value of antecedent streamflow alteration information in modeling stream biological condition

In stream systems, disentangling relationships between biology and flow and subsequent prediction of these relationships to unsampled streams is a common objective of large-scale ecological modeling. Often, streamflow metrics are derived from aggregating continuous streamflow records available at a subset of stream gages into long-term flow regime descriptors. Despite demonstrated value, shortcomings of these long-term approaches include spatial restriction to locations with long-term continuous flow records (commonly, biased toward larger systems) and omission of potentially ecologically important short-term (i.e., ≤1 year) antecedent streamflow information. We used long-term flow regime and short-term antecedent streamflow alteration information to evaluate relative performance in modeling stream fish biological condition. We compared results to understand whether short-term antecedent streamflow information improved models of fish biological condition. Results indicated that models incorporating short-term antecedent data performed better than those relying solely on long-term flow regime data (kappa statistic = 0.29 and 0.23, respectively) and improved prediction accuracy among stream sizes and in six of nine ecoregions. Additionally, models relying solely on short-term streamflow information performed similarly to those with only long-term streamflow information (kappa = 0.23). Incorporating short-term antecedent streamflow metrics may provide added ecological information not fully captured by long-term flow regime summaries in macroscale modeling efforts or perform similarly to long-term streamflow data when long-term data are not available.

Science of the Total Environment↗

Legacy sediment as a potential source of orthophosphate: Preliminary conceptual and geochemical models for the Susquehanna River, Chesapeake Bay watershed, USA

Nutrient pollution from agriculture and urban areas plus acid mine drainage (AMD) from legacy coal mines are primary causes of water-quality impairment in the Susquehanna River, which is the predominant source of freshwater and nutrients entering the Chesapeake Bay. Recent increases in the delivery of dissolved orthophosphate (PO 4 ) from the river to the bay may be linked to long-term increases in pH, decreased acidity of precipitation, and decreased acidity, iron, and aluminum loading from widespread AMD. Since the 1950s, baseline pH increased from ~6.5 to ~8 in the West Branch and “North Branch” of the Susquehanna River, which drain bituminous and anthracite coalfields of Pennsylvania. A current baseline pH of ~8 and daily maxima exceeding 9 have been documented along the lower Susquehanna River. In response to improved river quality, bioavailable PO 4 now may be released into solution from legacy sediment that has filled major impoundments in lower reaches of the river. At typical pH (5–8) of natural water, aqueous PO 4 species tend to be adsorbed by hydrous iron, aluminum, and manganese oxides that coat soil and sediment particles; however, PO 4 may be substantially desorbed at pH >8. We created a geochemical model that simulates equilibrium aqueous/solid distributions of PO 4 as pH and other solution characteristics change. Considering current conditions in the lower Susquehanna River, the model demonstrates potential for extensive release of adsorbed PO 4 at pH >8. Empirical data from laboratory experiments corroborate model results. The transfer of PO 4 into the water column may increase algae growth, which removes CO 2 and drives pH to higher values, facilitating additional PO 4 release and exacerbating the potential for harmful algal blooms. Thus, legacy sediment is a currently unquantified source of PO 4 that warrants consideration by resource managers and programs collaborating to reduce phosphorus loads to the bay and similar settings worldwide.

Chesapeake Bay watershed↗