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USGS2019

A generically parameterized model of lake eutrophication (GPLake) that links field-, lab- and model-based knowledge

Worldwide, eutrophication is threatening lake ecosystems. To support lake management numerous eutrophication models have been developed. Diverse research questions in a wide range of lake ecosystems are addressed by these models. The established models are based on three key approaches: the empirical approach that employs field surveys, the theoretical approach in which models based on first principles are tested against lab experiments, and the process-based approach that uses parameters and functions representing detailed biogeochemical processes. These approaches have led to an accumulation of field-, lab- and model-based knowledge, respectively. Linking these sources of knowledge would benefit lake management by exploiting complementary information; however, the development of a simple tool that links these approaches was hampered by their large differences in scale and complexity. Here we propose a Generically Parameterized Lake eutrophication model (GPLake) that links field-, lab- and model-based knowledge and can be used to make a first diagnosis of lake water quality. We derived GPLake from consumer-resource theory by the principle that lacustrine phytoplankton is typically limited by two resources: nutrients and light. These limitations are captured in two generic parameters that shape the nutrient to chlorophyll- a relations. Next, we parameterized GPLake, using knowledge from empirical, theoretical, and process-based approaches. GPLake generic parameters were found to scale in a comparable manner across data sources. Finally, we show that GPLake can be applied as a simple tool that provides lake managers with a first diagnosis of the limiting factor and lake water quality, using only the parameters for lake depth, residence time and current nutrient loading. With this first-order assessment, lake managers can easily assess measures such as reducing nutrient load, decreasing residence time or changing depth before spending money on field-, lab- or model- experiments to support lake management.

Science of the Total Environment↗

USGS2020

De facto water reuse: Bioassay suite approach delivers depth and breadth in endocrine active compound detection

Although endocrine disrupting compounds (EDCs) have been detected in wastewater and surface waters worldwide using a variety of in vitro effects-based screening tools, e.g. bioassays, few have examined potential attenuation of environmental contaminants by both natural (sorption, degradation, etc) and anthropogenic (water treatment practices) processes. This study used several bioassays and quantitative chemical analyses to assess residence-time weighted samples at six sites along a river in the northeastern United States beginning upstream of a waste water treatment plant (WWTP) outfall and proceeding downstream along the stream reach to a drinking water treatment plant (DWTP). Known steroidal estrogens were quantified and changes in signaling pathway molecular initiating events (activation of estrogen, androgen, glucocorticoid, peroxisome proliferator-activated, pregnane X receptor, and aryl hydrocarbon receptor signaling networks) were identified in water extracts. In initial multi-endpoint assays geographic and receptor-specific endocrine activity patterns in transcription factor signatures and nuclear receptor activation were discovered. In subsequent single endpoint receptor-specific bioassays, estrogen (16 of 18 samples; 0.01 to 28 ng estradiol equivalents [E2Eqs]/L) glucocorticoid (3 of 18 samples; 1.8 to 21 ng dexamethasone equivalents [DexEqs]/L), and androgen (2 of 18 samples; 0.95 to 2.1 ng dihydrotestosterone equivalents [DHTEqs]/L) receptor transcriptional activation occurred above respective assay method detection limits (0.04 ng E2Eqs/L, 1.2 ng DexEqs/L, and 0.77 ng DHTEqs/L) in multiple sampling events. Estrogen activity, the most often detected, correlated well with measured concentrations of known steroidal estrogens (R2 = 0.890). Overall, activity indicative of multiple types of endocrine active compounds was highest in wastewater effluent samples, while activity downstream was progressively lower, and negligible in (unfinished) treated water. This multiple bioassay approach, in conjunction with targeted analytical chemistry methods, has gained acceptance among water quality screening programs. Not only was estrogenic and glucocorticoid activity confirmed in the effluent by utilizing multiple methods concurrently, but other activated signaling networks that historically received less attention (i.e. peroxisome proliferator-activated receptor) were also detected.

Science of the Total Environment↗

USGS2020

Spatial variability of phytoplankton in a shallow tidal freshwater system reveals complex controls on abundance and community structure

Estuaries worldwide are undergoing changes to patterns of aquatic productivity because of human activities that alter flow, impact sediment delivery and thus the light field, and contribute nutrients and contaminants like pesticides and metals. These changes can influence phytoplankton communities, which in turn can alter estuarine food webs. We used multiple approaches-including high-resolution water quality mapping, synoptic sampling, productivity and nitrogen uptake rates, Lagrangian parcel tracking, enclosure experiments and bottle incubations-over a short time period to take a “spatial snapshot” of conditions in the northern region of the San Francisco Estuary (California, USA) to examine how environmental drivers like light availability, nutrients, water residence time, and contaminants affect phytoplankton abundance and community attributes like size distribution, taxonomic structure, and nutrient uptake rates. Zones characterized by longer residence time (15–60 days) had higher chlorophyll-a concentrations (9 ± 4 µg L −1 ) and were comprised primarily of small phytoplankton cells (<5 µm, 74 ± 8%), lower ammonium concentrations (1 ± 0.8 µM), higher nitrate uptake rates, and higher rates of potential carbon productivity. Conversely, zones characterized by shorter residence time (1–14 days) had higher ammonium concentration (13 ± 5 µM) and lower chlorophyll-a concentration (5 ± 1 µg L −1 ) with diatoms making up a larger percent contribution. Longer residence time, however, did not result in the accumulation of large (>5 µm) cells considered important to pelagic food webs. Rather, longer residence time zones had a phytoplankton community comprised primarily of small cells, particularly picocyanobacteria that made up 38 ± 17% of the chlorophyll-a – nearly double the concentration seen in shorter residence time zones (22 ± 7% picocyanobacterial of chlorophyll-a). Our results suggest that water residence time in estuaries may have an effect as large or larger than that experimentally demonstrated for light, contaminants, or nutrients.

California↗

USGS2019

Dissolved organic matter in the deep TALDICE ice core: A nano-UPLC-nano-ESI-HRMS method

Trace organic compounds in deep ice cores supply important paleoclimatic information. Untargeted analyses of dissolved organic matter provide an overview of molecular species in ice samples however, sample volumes usually required for these analyses are generally not available from deep ice cores. Here, we developed an analytical method using a nano-UPLC-nano-ESI-HRMS to detect major molecular species in ice cores. Samples (4 µL) from the TALos Dome Ice CorE (TALDICE), allowed investigating molecular species across a range of depths including during glacial and interglacial periods. We detected 317 chemical species that were tentatively assigned to fatty acids, hydroxy fatty acids and their degradation products (oxo-fatty acids and dicarboxylic acids), as well as oxidation byproducts of isoprene and monoterpenes. These compounds indicate that the main sources of the organic fraction are microbes as well as primary and secondary aerosols. Interglacial samples encompass a wide range of species including compounds from the oxidation of isoprene and monoterpenes as well as unsaturated fatty acids, while the glacial samples contained less diverse species. This difference may be due to decreased temperatures during the glacial period inhibiting terrestrial vegetation growth and increasing the sea ice extent, thereby weakening the emission sources.

Science of the Total Environment↗

USGS2020

Could a freshwater fish be at the root of dystrophic crises in a coastal lagoon?

Eutrophication has a profound impact on ecosystems worldwide. Grass carp Ctenopharyngodon idella , an herbivorous fish, has been introduced to control aquatic plant overgrowth caused by eutrophication, but could have other, potentially detrimental, effects. We used the Po di Volano basin (south of the Po River delta, northern Italy) as a test case to explore whether grass carp effects on canal aquatic vegetation could be at the root of historical changes in N loads exported from the basin to the Goro Lagoon. We modeled the aquatic vegetation production and standing crop, its denitrification potential, and its consumption by introduced grass carp. We then examined whether changes in historical nitrogen loads matched the modeled losses of the drainage network denitrification function or other changes in agricultural practices. Our results indicate that introduced grass carp could completely remove submerged vegetation in the Po di Volano canal network, which could – in turn – lead to substantial loss of the denitrification function of the system, causing in an increase in downstream nitrogen loads. A corresponding increase, matching both timing and magnitude, was detected in historical nitrogen loads to the Goro Lagoon, which were significantly different before and after the time of modeled collapse of the denitrification function. This increase was not clearly linked to watershed use or agricultural practices, which implies that the loss of the denitrification function through grass carp overgrazing could be a likely explanation of the increase in downstream nitrogen loads. Perhaps for the first time, we provide evidence that a freshwater fish introduction could have caused long-lasting changes in nutrient dynamics that are exported downstream to areas where the fish is not present.

Po River basin↗

USGS2020

Nonlinear patterns in mercury bioaccumulation in American alligators are a function of predicted age

Mercury is a widespread, naturally occurring contaminant that biomagnifies in wetlands due to the methylation of this element by sulfate-reducing bacteria. Species that feed at the top trophic level within wetlands are predicted to have higher mercury loads compared to species feeding at lower trophic levels and are therefore often used for mercury biomonitoring. However, mechanisms for mercury bioaccumulation in sentinel species are often poorly understood, due to a lack of long-term studies or an inability to differentiate between confounding variables. We examined mercury bioaccumulation patterns in the whole blood of American alligators ( Alligator mississippiensis ) from a long-term mark-recapture study (1979–2017) in South Carolina, USA. Using a growth model and auxiliary information on predicted age at first capture, we differentiated between age- and size-related variation in mercury bioaccumulation, which are often confounded in alligators due to their determinate growth pattern. Contrary to predictions that the oldest or largest individuals were likely to have the highest mercury concentrations, our best-supported model indicated a peak in mercury concentration at 30–40 years of age, depending on the sex, and lower concentrations in the youngest and oldest animals. To evaluate the robustness of our findings, we re-analyzed data from a previously published study of mercury in alligators sampled at Merritt Island National Wildlife Refuge in Florida. Unlike the South Carolina data, the data from Florida contained minimal auxiliary information regarding age, yet the best supported model similarly indicated a peaked rather than increasing relationship between mercury and body size, a less-precise indicator of age. These findings highlight how long-term monitoring can differentiate between confounding variables (e.g., age and size) to better elucidate complex relationships between contaminant exposure and demographic factors in sentinel species.

Florida, South Carolina↗

USGS2020

Methylmercury exposure in wildlife: A review of the ecological and physiological processes affecting contaminant concentrations and their interpretation

Exposure to methylmercury (MeHg) can result in detrimental health effects in wildlife. With advances in ecological indicators and analytical techniques for measurement of MeHg in a variety of tissues, numerous processes have been identified that can influence MeHg concentrations in wildlife. This review presents a synthesis of theoretical principals and applied information for measuring MeHg exposure and interpreting MeHg concentrations in wildlife. Mercury concentrations in wildlife are the net result of ecological processes influencing dietary exposure combined with physiological processes that regulate assimilation, transformation, and elimination. Therefore, consideration of both physiological and ecological processes should be integrated when formulating biomonitoring strategies. Ecological indicators, particularly stable isotopes of carbon, nitrogen, and sulfur, compound-specific stable isotopes, and fatty acids, can be effective tools to evaluate dietary MeHg exposure. Animal species differ in their physiological capacity for MeHg elimination, and animal tissues can be inert or physiologically active, act as sites of storage, transformation, or excretion of MeHg, and vary in the timing of MeHg exposure they represent. Biological influences such as age, sex, maternal transfer, and growth or fasting are also relevant for interpretation of tissue MeHg concentrations. Wildlife tissues that represent current or near-term bioaccumulation and in which MeHg is the predominant mercury species (such as blood and eggs) are most effective for biomonitoring ecosystems and understanding landscape drivers of MeHg exposure. Further research is suggested to critically evaluate the use of keratinized external tissues to measure MeHg bioaccumulation, particularly for less-well studied wildlife such as reptiles and terrestrial mammals. Suggested methods are provided to effectively use wildlife for quantifying patterns and drivers of MeHg bioaccumulation over time and space, as well as for assessing the potential risk and toxicological effects of MeHg on wildlife.

Science of the Total Environment↗

USGS2019

Exposure and potential effects of pesticides and pharmaceuticals in protected streams of the US National Park Service southeast Region

Globally protected areas offer refugia for a broad range of taxa including threatened and endangered species. The United States National Park Service (NPS) manages public lands to preserve biodiversity, but increasing park visitation and development of surrounding landscapes increase exposure to and effects from bioactive contaminants. The risk (exposure and hazard) to NPS protected-stream ecosystems within the highly urbanized southeast region (SER) from bioactive contaminants was assessed in five systems based on 334 pesticide and pharmaceutical analytes in water and 119 pesticides in sediment. Contaminant mixtures were common across all sampled systems, with approximately 24% of the unique analytes (80/334) detected at least once and 15% (49/334) detected in half of the surface-water samples. Pharmaceuticals were observed more frequently than pesticides, consistent with riparian buffers and concomitant spatial separation from non-point pesticide sources in four of the systems. To extrapolate exposure data to biological effects space, site specific cumulative exposure-activity ratios (ΣEAR) were calculated for detected surface-water contaminants with available ToxCast data; common exceedances of a 0.001 ΣEAR effects-screening threshold raise concerns for molecular toxicity and possible, sub-lethal effects to non-target, aquatic vertebrates. The results illustrate the need for continued management of protected resources to reduce contaminant exposure and preserve habitat quality, including prioritization of conservation practices (riparian buffers) near stream corridors and increased engagement with upstream/up-gradient property owners and municipal wastewater facilities.

Alabama, Florida, Georgia, Kentucky, Mississippi, ↗

USGS2020

Resolving selenium exposure risk: Spatial, temporal, and tissue-specific variability of an endemic fish in a large, dynamic estuary

Estuaries provide critical habitat for a vast array of fish and wildlife but are also a nexus for core economic activities that mobilize and concentrate contaminants that can threaten aquatic species. Selenium (Se), an essential element and potent reproductive toxin, is enriched in parts of the San Francisco Estuary (SFE) to levels known to cause toxicity, yet the risk of Se to species that inhabit the SFE is not well understood. We quantified Se concentrations in muscle, liver and ovary of the demersal cyprinid Sacramento Splittail from six regions in the SFE at three time points to evaluate Se exposure risk. Selenium levels exceeded proposed EPA criteria in ovary and thresholds of concern for liver in 15% and 20%, respectively, of fish collected in the fall of 2010, preceding the discovery of juvenile Splittail displaying a high incidence (>40%) of spinal deformities characteristic of Se toxicity, and again in 2011. No exceedances were detected in muscle tissue. Selenium concentrations varied significantly among regions for muscle (F 5,113 = 20.49, p < 0.0001), liver (F 5,113 = 28.4, p < 0.0001) and ovary (F 5,112 = 19.3, p < 0.0001) but did not vary between the wet and dry years, nor were they influenced by foraging trophic level or prey selection. Foraging location along the salinity gradient, defined by δ 34 S values, explained regional Se exposures in Splittail. Relationships between tissues varied among regions for muscle and liver and muscle and ovary, but a single global relationship could be defined for ovary and liver Se concentrations. Our results suggest that the proposed EPA Se criteria for muscle tissue in Splittail may be under-protective as it would not have predicted exceedances in liver or ovary tissue and that the relationship between muscle tissue and ovary and liver may be Se concentration and seasonal dependent.

California↗

USGS2020

Time scales of arsenic variability and the role of high-frequency monitoring at three water-supply wells in New Hampshire, USA

Groundwater geochemistry, redox process classification, high-frequency physicochemical and hydrologic measurements, and climate data were analyzed to identify controls on arsenic (As) concentration changes. Groundwater was monitored in two public-supply wells (one glacial aquifer and one bedrock aquifer), and one bedrock-aquifer domestic well in New Hampshire, USA, from 2014 to 2018 to identify time scales of and controls on As concentration changes. Concentrations of As and other geochemical constituents were measured bimonthly. Specific conductance (SC), pH, dissolved oxygen, and pumping rate/water level were measured at high frequency (every 5 to 15 min). Median (and 95% confidence interval) As concentrations at the three wells were 4.1 (3.7–4.6), 18.9 (17.2–23.6), and 37.5 (30.4–42.9) μg/L. Arsenic variability in each of the three wells, in relative standard deviation, ranged from 9 to 12%. Median quarterly As concentrations were highest in all wells in the spring. The bedrock-aquifer public-supply well As concentration increased over the period of study while pumping rate decreased. In the public-supply wells, As variability was correlated with SC and pH, and As species were related to SC, pH, pumping, precipitation, and changes in redox process. Specific conductance also had a seasonal pattern in the two public-supply wells and was correlated with Na and Cl. Excess Na in water samples suggests possible ion exchange with dissolved Ca, creating more capacity to dissolve CaCO 3 from calcareous rocks, which can increase pH and in turn, As concentrations in wells. High-frequency monitoring data are cost effective to collect, which could be advantageous in other parts of the United States and in the many parts of the world where glacial aquifers are in direct contact with other water supply aquifers or where water from different aquifers have potential to mix.

New Hampshire↗

USGS2020

The assessment and remediation of mercury contaminated sites: A review of current approaches

Remediation of mercury (Hg) contaminated sites has long relied on traditional approaches, such as removal and containment/capping. Here we review contemporary practices in the assessment and remediation of industrial-scale Hg contaminated sites and discuss recent advances. Significant improvements have been made in site assessment, including the use of XRF to rapidly identify the spatial extent of contamination, Hg stable isotope fractionation to identify sources and transformation processes, and solid-phase characterization (XAFS) to evaluate Hg forms. The understanding of Hg bioavailability for methylation has been improved by methods such as sequential chemical extractions and porewater measurements, including the use of diffuse gradient in thin-film (DGT) samplers. These approaches have shown varying success in identifying bioavailable Hg fractions and further study and field applications are needed. The downstream accumulation of methylmercury (MeHg) in biota is a concern at many contaminated sites. Identifying the variables limiting/controlling MeHg production—such as bioavailable inorganic Hg, organic carbon, and/or terminal electron acceptors (e.g. sulfate, iron) is critical. Mercury can be released from contaminated sites to the air and water, both of which are influenced by meteorological and hydrological conditions. Mercury mobilized from contaminated sites is predominantly bound to particles, highly correlated with total sediment solids (TSS), and elevated during stormflow. Remediation techniques to address Hg contamination can include the removal or containment of Hg contaminated materials, the application of amendments to reduce mobility and bioavailability, landscape/waterbody manipulations to reduce MeHg production, and food web manipulations through stocking or extirpation to reduce MeHg accumulated in desired species. These approaches often rely on knowledge of the Hg forms/speciation at the site, and utilize physical, chemical, thermal and biological methods to achieve remediation goals. Overall, the complexity of Hg cycling allows many different opportunities to reduce/mitigate impacts, which creates flexibility in determining suitable and logistically feasible remedies.

Science of the Total Environment↗

USGS2020

The method controls the story - Sampling method impacts on the detection of pore-water nitrogen concentrations in streambeds

Biogeochemical gradients in streambeds are steep and can vary over short distances often making adequate characterisation of sediment biogeochemical processes challenging. This paper provides an overview and comparison of streambed pore-water sampling methods, highlighting their capacity to address gaps in our understanding of streambed biogeochemical processes. This work reviews and critiques available pore-water sampling techniques to characterise streambed biogeochemical conditions, including their characteristic spatial and temporal resolutions, and associated advantages and limitations. A field study comparing three commonly-used pore-water sampling techniques (multilevel mini-piezometers, miniature drivepoint samplers and diffusive equilibrium in thin-film gels) was conducted to assess differences in observed nitrate and ammonium concentration profiles. Pore-water nitrate concentrations did not differ significantly between sampling methods ( p -value = 0.54) with mean concentrations of 2.53, 4.08 and 4.02 mg l − 1 observed with the multilevel mini-piezometers, miniature drivepoint samplers and diffusive equilibrium in thin-film gel samplers, respectively. Pore-water ammonium concentrations, however, were significantly higher in pore-water extracted by multilevel mini-piezometers (3.83 mg l − 1 ) and significantly lower where sampled with miniature drivepoint samplers (1.05 mg l − 1 , p -values <0.01). Differences in observed pore-water ammonium concentration profiles between active (suction: multilevel mini-piezometers) and passive (equilibrium; diffusive equilibrium in thin-film gels) samplers were further explored under laboratory conditions. Measured pore-water ammonium concentrations were significantly greater when sampled by diffusive equilibrium in thin-film gels than with multilevel mini-piezometers (all p -values ≤0.02). The findings of this study have critical implications for the interpretation of field-based research on hyporheic zone biogeochemical cycling and highlight the need for more systematic testing of sampling protocols. For the first time, the impact of different active and passive pore-water sampling methods is addressed systematically here, highlighting to what degree the choice of pore-water sampling methods affects research outcomes, with relevance for the interpretation of previously published work as well as future studies.

Science of the Total Environment↗

USGS2020

Preferential elution of ionic solutes in melting snowpacks: Improving process understanding through field observations and modeling in the Rocky Mountains

The preferential elution of ions from melting snowpacks is a complex problem that has been linked to temporary acidification of water bodies. However, the understanding of these processes in snowpacks around the world, including the polar regions that are experiencing unprecedented warming and melting, remains limited despite being instrumental in supporting climate change adaptation. In this study, data collected from a snowmelt lysimeter and snowpits at meadow and forest-gap sites in a high elevation watershed in Colorado were combined with the PULSE multi-phase snowpack chemistry model to investigate the controls of meltwater chemistry and preferential elution. The snowdepth at the meadow site was 64% of that at the forest-gap site, and the snowmelt rate was greater there (meadow snowpit) due to higher solar irradiance. Cations such as Ca 2+ and NH 4 + "> 4+ were deposited mostly within the upper layers of both the meadow and forest-gap snowpacks, and acid anions such as NO 3 − "> 3− and SO 4 2 − "> 42− were more evenly distributed. The snow ion concentrations were generally greater at the forest-gap snowpit, except for NH 4 + "> 4+ , which indicates that wind erosion of wet and dry deposited ions from the meadow may have reduced concentrations of residual snow. Furthermore, at the forest-gap site, snow interception and scavenging processes such as sublimation, ventilation, and throughfall led to particular ion enrichment of Ca 2+ , Mg 2+ , K + , Cl − , SO 4 2 − "> 42− and NO 3 − "> 3− . Model simulations and observations highlight that preferential elution is enhanced by low snowmelt rates, with the model indicating that this is due to lower dilution rates and increased contact time and area between the percolating meltwater and the snow. Results suggest that low snowmelt rates can cause multiple early meltwater ionic pulses for ions subject to lower ion exclusion. Ion exclusion rates at the grain-size level have been estimated for the first time.

Colorado↗

USGS2020

Estimating burn severity and carbon emissions from a megafire in boreal forests of China

Wildfires, especially those of large size, worsen air quality and alter the carbon cycle through combustion of large quantities of biomass and release of carbon into the atmosphere. The Black Dragon fire, which occurred in 1987 in the boreal forests of China is among the top five of such megafires ever recorded in the world. With over 30 years of accumulation of data and availability of new greenhouse gas emission accounting methods, carbon emissions from this megafire can now be estimated with improved precision and greater spatial resolution. To do this, we combined field and remote sensing data to map four burn severity classes and calculated combustion efficiency in terms of the biomass immediately consumed in the fire. Results of the study showed that 1.30 million hectares burned and 52% of that area burned with high severity. The emitted carbon dioxide equivalents (CO2e), accounted for approximately 10% of total fossil fuel emissions from China in 1987, along with CO (2%–3% of annual anthropogenic CO emissions from China) and non-methane hydrocarbons (NMHC) contributing to the atmospheric pollutants. Our study provides an important basis for carbon emission estimation and understanding the impacts of megafires.

Science of the Total Environment↗

USGS2020

Fluxes of agricultural nitrogen and metolachlor metabolites are highly correlated in a first order stream in Maryland, USA

Nitrogen pollution in watersheds containing significant cropland area is generally problematic. Conservation practices intended to reduce nitrate-N (NO3--N) export from watersheds are being implemented by many regions without necessary tools to assess effectiveness of these abatement tools. A commonly used herbicide metolachlor degrades in the vadose zone of croplands to form two metabolites (metolachlor ethane sulfonic acid (MESA) and metolachlor oxanilic acid (MOXA)) which are both highly soluble in soils. Study of metabolite fates in a first order watershed provided evidence that transport of these metabolites to stream water is highly correlated to transport of the agricultural NO3--N that also forms in the cropland vadose zone. Linear models describing the relationships of stream flux of MESA and MOXA to NO3--N flux generated goodness of fit values of 0.93 and 0.82 respectively. These findings support a conclusion that both MESA and MOXA act as excellent transport analogs of NO3- and become strongly correlated to agricultural NO3--N leaching from the cropland vadose zone. Moreover, their use as conservative tracers in agricultural watersheds can provide valuable information concerning movement and fate of agricultural nitrogen at watershed scales of observation.

Maryland↗

USGS2020

Estimation of nonlinear water-quality trends in high-frequency monitoring data

Recent advances in high-frequency water-quality sensors have enabled direct measurements of physical and chemical attributes in rivers and streams nearly continuously. Water-quality trends can be used to identify important watershed-scale changes driven by natural and anthropogenic influences. Statistical methods to estimate trends using high-frequency data are lacking. To address this gap, an evaluation of the generalized additive model (GAM) approach to test for trends in high-frequency data was conducted. Our proposed framework includes methods for handling serial correlation, trend estimation and slope-change detection, and trend interpretation at arithmetic scale for log-transformed variables. Water-temperature and turbidity data, representing two analytes with different temporal patterns, collected from the James River at Cartersville, Virginia, USA, were chosen for this analysis. Results indicated that the model, including flow, season, time covariates, and interaction between flow and season performed well for both analytes. The same model structure was applied to specific conductance data, collected from a small highly urbanized watershed, with satisfactory model performance. The water temperature GAM results indicated that the significant decreasing-then-increasing patterns after 2012 were mainly driven by air temperature changes. The turbidity trend was not significant over time. The specific conductance results showed a consistently upward trend over the last decade due to ever-increasing urbanization in the small watershed. This study suggests that the GAM method has great potential as a useful tool for trend analysis on high-frequency data, and for informing watershed managers of hydro-climatic and human influences on water quality by detecting crucial signal variation over time.

Chesapeake Bay watershed↗

USGS2020

Daily stream samples reveal highly complex pesticide occurrence and potential toxicity to aquatic life

Transient, acutely toxic concentrations of pesticides in streams can go undetected by fixed-interval sampling programs. Here we compare temporal patterns in occurrence of current-use pesticides in daily composite samples to those in weekly composite and weekly discrete samples of surface water from 14 small stream sites. Samples were collected over 10–14 weeks at 7 stream sites in each of the Midwestern and Southeastern United States. Samples were analyzed for over 200 pesticides and degradates by direct aqueous injection liquid chromatography with tandem mass spectrometry. Nearly 2 and 3 times as many unique pesticides were detected in daily samples as in weekly composite and weekly discrete samples, respectively. Based on exceedances of acute-invertebrate benchmarks (AIB) and(or) a Pesticide Toxicity Index (PTI) >1, potential acute-invertebrate toxicity was predicted at 11 of 14 sites from the results for daily composite samples, but was predicted for only 3 sites from weekly composites and for no sites from weekly discrete samples. Insecticides were responsible for most of the potential invertebrate toxicity, occurred transiently, and frequently were missed by the weekly discrete and composite samples. The number of days with benthic-invertebrate PTI ≥0.1 in daily composite samples was inversely related to Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness at the sites. The results of the study indicate that short-term, potentially toxic peaks in pesticides frequently are missed by weekly discrete sampling, and that such peaks may contribute to degradation of invertebrate community condition in small streams. Weekly composite samples underestimated maximum concentrations and potential acute-invertebrate toxicity, but to a lesser degree than weekly discrete samples, and provided a reasonable approximation of the 90th percentile total concentrations of herbicides, insecticides, and fungicides, suggesting that weekly composite sampling may be a compromise between assessment needs and cost.

Science of the Total Environment↗

USGS2020

The response of stream ecosystems in the Adirondack region of New York to historical and future changes in atmospheric deposition of sulfur and nitrogen

The present-day acid-base chemistry of surface waters can be directly linked to contemporary observations of acid deposition; however, pre-industrial conditions are key to predicting the potential future recovery of stream ecosystems under decreasing loads of atmospheric sulfur (S) and nitrogen (N) deposition. The integrated biogeochemical model PnET-BGC was applied to 25 forest watersheds that represent a range of acid sensitivity in the Adirondack region of New York, USA to simulate the response of streams to past and future changes in atmospheric S and N deposition, and calculate the target loads of acidity for protecting and restoring stream water quality and ecosystem health. Using measured data, the model was calibrated and applied to simulate soil and stream chemistry at all study sites. Model hindcasts indicate that historically stream water chemistry in the Adirondacks was variable, but inherently sensitive to acid deposition. The median model-simulated acid neutralizing capacity (ANC) of the streams was projected to be 55 μeq L −1 before the advent of anthropogenic acid deposition (~1850), decreasing to minimum values of 10 μeq L −1 around the year 2000. The median simulated ANC increased to 13 μeq L −1 by 2015 in response to decreases in acid deposition that have occurred over recent decades. Model projections suggest that simultaneous decreases in sulfate, nitrate and ammonium deposition are more effective in restoring stream ANC than individual decreases in sulfur or nitrogen deposition. However, the increases in stream ANC per unit equivalent decrease in S deposition is greater compared to decreases in N deposition. Using empirical algorithms, fish community density and biomass are projected to increase under several deposition-control scenarios that coincide with increases in stream ANC. Model projections suggest that even under the most aggressive deposition-reduction scenarios, stream chemistry and fisheries will not fully recover from historical acidification by 2200.

New York↗