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USGS2019

Prioritizing chemicals of ecological concern in Great Lakes tributaries using high-throughput screening data and adverse outcome pathways

Chemical monitoring data were collected in surface waters from 57 Great Lakes tributaries from 2010-13 to identify chemicals of potential biological relevance and sites at which these chemicals occur. Traditional water-quality benchmarks for aquatic life based on in vivo toxicity data were available for 34 of 67 evaluated chemicals. To expand evaluation of potential biological effects, measured chemical concentrations were compared to chemical-specific biological activities determined in high-throughput (ToxCast) in vitro assays. Resulting exposure-activity ratios (EARs) were used to prioritize the chemicals of greatest potential concern: 4-nonylphenol, bisphenol A, metolachlor, atrazine, DEET, caffeine, tris(2-butoxyethyl) phosphate, tributyl phosphate, triphenyl phosphate, benzo(a)pyrene, fluoranthene, and benzophenone. Water-quality benchmarks were unavailable for five of these chemicals, but for the remaining seven, EAR-based prioritization was consistent with that based on toxicity quotients calculated from benchmarks. Water-quality benchmarks identified three additional PAHs (anthracene, phenanthrene, and pyrene) not prioritized using EARs. Through this analysis, an EAR of 10-3 was identified as a reasonable threshold above which a chemical might be of potential concern. To better understand apical hazards potentially associated with biological activities captured in ToxCast assays, in vitro bioactivity data were matched with available adverse outcome pathway (AOP) information. The 49 ToxCast assays prioritized via EAR analysis aligned with 23 potentially-relevant AOPs present in the AOP-Wiki. Mixture effects at monitored sites were estimated by summation of EAR values for multiple chemicals by individual assay or individual AOP. Commonly predicted adverse outcomes included impacts on reproduction and mitochondrial function. The EAR approach provided a screening-level assessment for evidence-based prioritization of chemicals and sites with potential for adverse biological effects. The approach aids prioritization of future monitoring activities and provides testable hypotheses to help focus those efforts. This also expands the fraction of detected chemicals for which biologically-based benchmark concentrations are available to help contextualize chemical monitoring results.

Science of the Total Environment↗

USGS2017

In vivo isotopic fractionation of zinc and biodynamic modeling yield insights into detoxification mechanisms in the mayfly Neocloeon triangulifer

Diversity and biomass of aquatic insects decline in metal-rich aquatic environments, but the mechanisms by which insects from such environments cope with potentially toxic metal concentrations to survive through adulthood are less well understood. In this study, we measured Zn concentrations and isotopes in laboratory-reared diatoms and mayflies ( Neocloeon triangulifer ) from larval through adult stages. The larvae were fed Zn-enriched diatoms, and bio-concentrated Zn by a factor of 2.5–5 relative to the diatoms but maintained the same Zn-isotopic ratio. These results reflect the importance of dietary uptake and the greater rate of uptake relative to excretion or growth. Upon metamorphosis to subimago, Zn concentrations declined by > 70%, but isotopically heavy Zn remained in the subimago bodies. We surmised that the loss of isotopically light Zn during metamorphosis was due to the loss of detoxified Zn and retention of metabolically useful Zn. Through the transition from subimago to imago, Zn concentrations and isotope ratios were virtually unchanged. Because the decrease in Zn body concentration and increase in heavier Zn are seen in the subimagos relative to the larvae, the compartmentalization of Zn must be occurring within the larvae. A biodynamic model was constructed, allowing for isotopic fractionation and partitioning of Zn between metabolically essential and detoxified Zn reservoirs within larvae. The model provides a consistent set of rate and fractionation constants that successfully describe the experimental observations. Specifically, metabolically essential Zn is isotopically heavier and is tightly held once assimilated, and excess, isotopically light Zn is sequestered, detoxified, and ultimately lost during the metamorphosis of larvae to subimagos. To our knowledge, this is the first documentation of in vivo isotopic fractionation in insects, offering an improved understanding of the mechanisms and rates by which the N. triangulifer larvae regulate excess Zn in their bodies.

Science of the Total Environment↗

USGS2021

Time marches on, but do the causal pathways driving instream habitat and biology remain consistent?

Stream ecosystems are complex networks of interacting terrestrial and aquatic drivers. To untangle these ecological networks, efforts evaluating the direct and indirect effects of landscape, climate, and instream predictors on biological condition through time are needed. We used structural equation modeling and leveraged a stream survey program to identify and compare important predictors driving condition of benthic macroinvertebrate and fish assemblages. We used data resampled 14 years apart at 252 locations across Maryland, USA. Sample locations covered a wide range of conditions that varied spatiotemporally. Overall, the relationship directions were consistent between sample periods, but their relative strength varied temporally. For benthic macroinvertebrates, we found that the total effect of natural landscape ( e.g ., elevation, longitude, latitude, geology) and land use ( i.e ., forest, development, agriculture) predictors was 1.4 and 1.5 times greater in the late 2010s compared to the 2000s. Moreover, the total effect of water quality ( e.g ., total nitrogen and conductivity) and habitat ( e.g ., embeddedness, riffle quality) was 1.2 and 4.8 times lower in the 2010s, respectively. For fish assemblage condition, the total effect of land use-land cover predictors was 2.3 times greater in the 2010s compared to the 2000s, while the total effect of local habitat was 1.4 times lower in the 2010s, respectively. As expected, we found biological assemblages in catchments with more agriculture and urban development were generally comprised of tolerant, generalist species, while assemblages in catchments with greater forest cover had more-specialized, less-tolerant species ( e.g., Ephemeroptera, Plecoptera, and Trichoptera taxa, clingers, benthic and lithophilic spawning fishes). Changes in the relative importance of landscape and land-use predictors suggest other correlated, yet unmeasured, proximal factors became more important over time. By untangling these ecological networks, stakeholders can gain a better understanding of the spatiotemporal relationships driving biological condition to implement management practices aimed at improving stream condition.

Maryland↗

USGS2016

Assessing potential health risks to fish and humans using mercury concentrations in inland fish from across western Canada and the United States

Fish represent high quality protein and nutrient sources, but Hg contamination is ubiquitous in aquatic ecosystems and can pose health risks to fish and their consumers. Potential health risks posed to fish and humans by Hg contamination in fish were assessed in western Canada and the United States. A large compilation of inland fish Hg concentrations was evaluated in terms of potential health risk to the fish themselves, health risk to predatory fish that consume Hg contaminated fish, and to humans that consume Hg contaminated fish. The probability that a fish collected from a given location would exceed a Hg concentration benchmark relevant to a health risk was calculated. These exceedance probabilities and their associated uncertainties were characterized for fish of multiple size classes at multiple health-relevant benchmarks. The approach was novel and allowed for the assessment of the potential for deleterious health effects in fish and humans associated with Hg contamination in fish across this broad study area. Exceedance probabilities were relatively common at low Hg concentration benchmarks, particularly for fish in larger size classes. Specifically, median exceedances for the largest size classes of fish evaluated at the lowest Hg concentration benchmarks were 0.73 (potential health risks to fish themselves), 0.90 (potential health risk to predatory fish that consume Hg contaminated fish), and 0.97 (potential for restricted fish consumption by humans), but diminished to essentially zero at the highest benchmarks and smallest fish size classes. Exceedances of benchmarks are likely to have deleterious health effects on fish and limit recommended amounts of fish humans consume in western Canada and the United States. Results presented here are not intended to subvert or replace local fish Hg data or consumption advice, but provide a basis for identifying areas of potential health risk and developing more focused future research and monitoring efforts.

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↗

USGS2017

Uptake and disposition of select pharmaceuticals by bluegill exposed at constant concentrations in a flow-through aquatic exposure system

The increasing use of pharmaceuticals has led to their subsequent input into and release from wastewater treatment plants, with corresponding discharge into surface waters that may subsequently exert adverse effects upon aquatic organisms. Although the distribution of pharmaceuticals in surface water has been extensively studied, the details of uptake, internal distribution, and kinetic processing of pharmaceuticals in exposed fish have received less attention. For this research, we investigated the uptake, disposition, and toxicokinetics of five pharmaceuticals (diclofenac, methocarbamol, rosuvastatin, sulfamethoxazole, and temazepam) in bluegill sunfish ( Lepomis macrochirus ) exposed to environmentally relevant concentrations (1000–4000 ng L –1 ) in a flow-through exposure system. Temazepam and methocarbamol were consistently detected in bluegill biological samples with the highest concentrations in bile of 4, 940, and 180 ng g –1 , respectively, while sulfamethoxazole, diclofenac, and rosuvastatin were only infrequently detected. Over 30-day exposures, the relative magnitude of mean concentrations of temazepam and methocarbamol in biological samples generally followed the order: bile ≫ gut > liver and brain > muscle, plasma, and gill. Ranges of bioconcentration factors (BCFs) in different biological samples were 0.71–3960 and 0.13–48.6 for temazepam and methocarbamol, respectively. Log BCFs were statistically positively correlated to pH adjusted log K ow (that is, log D ow ), with the strongest relations for liver and brain ( r 2 = 0.92 and 0.99, respectively), implying that bioconcentration patterns of ionizable pharmaceuticals depend on molecular status, that is, whether a pharmaceutical is un-ionized or ionized at ambient tissue pH. Methocarbamol and temazepam underwent rapid uptake and elimination in bluegill biological compartments with uptake rate constants ( K u ) and elimination rate constants ( K e ) at 0.0066–0.0330 h –1 and 0.0075–0.0384 h –1 , respectively, and half-lives at 18.1–92.4 h. Exposure to mixtures of diclofenac, methocarbamol, sulfamethoxazole, and temazepam had little or no influence on the uptake and elimination rates, suggesting independent multiple uptake and disposition behaviors of pharmaceuticals by fish would occur when exposed to effluent-influenced surface waters.

Environmental Science & Technology↗

USGS2023

Transcriptome signatures of wastewater effluent exposure in larval zebrafish vary with seasonal mixture composition in an effluent-dominated stream

Wastewater treatment plant (WWTP) effluent-dominated streams provide critical habitat for aquatic and terrestrial organisms but also continually expose them to complex mixtures of pharmaceuticals that can potentially impair growth, behavior, and reproduction. Currently, few biomarkers are available that relate to pharmaceutical-specific mechanisms of action. In the experiment reported in this paper, zebrafish ( Danio rerio ) embryos at two developmental stages were exposed to water samples from three sampling sites (0.1 km upstream of the outfall, at the effluent outfall, and 0.1 km below the outfall) during base-flow conditions from two months (January and May) of a temperate-region effluent-dominated stream containing a complex mixture of pharmaceuticals and other contaminants of emerging concern. RNA-sequencing identified potential biological impacts and biomarkers of WWTP effluent exposure that extend past traditional markers of endocrine disruption. Transcriptomics revealed changes to a wide range of biological functions and pathways including cardiac, neurological, visual, metabolic, and signaling pathways. These transcriptomic changes varied by developmental stage and displayed sensitivity to variable chemical composition and concentration of effluent, thus indicating a need for stage-specific biomarkers. Some transcripts are known to be associated with genes related to pharmaceuticals that were present in the collected samples. Although traditional biomarkers of endocrine disruption were not enriched in either month, a high estrogenicity signal was detected upstream in May and implicates the presence of unidentified chemical inputs not captured by the targeted chemical analysis. This work reveals associations between bioeffects of exposure, stage of development, and the composition of chemical mixtures in effluent-dominated surface water. The work underscores the importance of measuring effects beyond the endocrine system when assessing the impact of bioactive chemicals in WWTP effluent and identifies a need for non-targeted chemical analysis when bioeffects are not explained by the targeted analysis.

Iowa↗

USGS2001

The aquatic fate of triclopyr in whole-pond treatments

The aquatic fate of the triethylamine salt formulation of triclopyr (3,5,6-trichloro-2-pyridinyloxyacetic acid) was determined in whole-pond applications in closed (no water exchange) systems in California, Missouri and Texas in two studies conducted in 1995 and 1996. These studies determined dissipation rates of triclopyr and its principal metabolites, 3,5,6-trichloropyridinol (tcp) and 3,5,6-trichloro-2-methoxypyridine (tmp) in water, sediment and finfish. Ponds at each site containing a healthy biological community were treated at 2.5 mg AE litre-1 triclopyr. Water and sediment samples were collected through 12 weeks post-treatment, and non-target animals were collected through 4 weeks post-treatment. Dissipation rates for triclopyr, TCP and TMP were similar at each of the study sites, despite differences in weather, water quality, biotic community, light transmission and geographic location. Half-lives of triclopyr in water ranged from 5.9 to 7.5 days, while those of TCP and TMP ranged from 4 to 8.8 and 4 to 10 days, respectively. Levels of triclopyr and TCP declined in sediments at half-lives ranging from 2.8 to 4.6 days and 3.8 to 13.3 days, respectively. No TMP was detected in sediment. Triclopyr and TCP cleared from fish in relation to concentrations found in the water column. TMP levels in fish were generally an order of magnitude higher than levels of triclopyr and TCP, particularly in the visceral portion of the animals. No adverse effects on water quality or on the non-target biotic community were found following triclopyr applications. Results of these studies were comparable to those of triclopyr dissipation studies conducted in reservoirs, lakes and riverine systems in Georgia, Florida, Minnesota and Washington, indicating that the degradation and dissipation of triclopyr and its metabolites are similar in representative systems throughout the USA. ?? 2001 Society of Chemical Industry.

Pest Management Science↗

USGS2009

Ecological assessment of wadeable streams on O`ahu, Hawai'i, 2006-2007: A pilot study

In 2006–07, the U.S. Geological Survey (USGS) Pacific Islands Water Science Center (PIWSC), in cooperation with the Hawai‘i Department of Health (HDOH), conducted a pilot study as a participant in the U.S. Environmental Protection Agency’s (USEPA) Wadeable Streams Assessment (WSA) program. Forty randomly selected sites on perennial streams on O‘ahu, Hawai‘i, were surveyed for habitat characteristics, water chemistry, and benthic macroinvertebrate assemblages. Of the original sampling frame of approximately 505.2 miles of perennial stream, roughly 96.7±30.7 miles were found to be nonperennial or estuarine and another 200.5±64.7 miles were judged to be inaccessible. The scope of this report presents an assessment of the remaining 208±57.6 miles of accessible, wadeable, perennial stream length on O‘ahu. Benthic macroinvertebrate assemblages were used to determine the ecological condition at each site. Components of the benthic macroinvertebrate assemblages were assessed using the multimetric Preliminary–Hawaiian Benthic Index of Biotic Integrity (P–HBIBI) developed by Wolff (2005). Based on the P–HBIBI scores, an estimated 5.8±5.8 percent of the island’s total stream length is in most disturbed condition, 56±13.5 percent is in intermediately disturbed condition, and 38.2±13.2 percent is in least disturbed condition. Windward O‘ahu had the highest percentage of stream length in least disturbed biological condition at 56.7±20.8 percent. Using the relative abundance of insects, one of the core metrics that make up the P–HBIBI, 43.4±14.2 percent of the islandwide stream length was classified in the most disturbed condition—52±31.2 percent of the Honolulu region stream length and 51.4±23.3 percent of the windward O‘ahu stream length. An analysis of total nitrogen (N) estimated approximately 41.1±13.7 percent of the stream length on O‘ahu was in most disturbed condition. Regionally, the Honolulu region had the largest proportion, 61.3±28.6 percent, of most disturbed stream length in terms of total N. An analysis of total phosphorus (P) classified approximately 43.2±14 percent of the stream length on O‘ahu as most disturbed. Regionally, windward O‘ahu had the largest proportion, 78.4±19.5 percent, of stream length classified as most disturbed. An analysis of embeddedness classified 30.3±14.7 percent of O‘ahu’s stream length as most. Regionally, windward O‘ahu had the largest proportion, 43.3±17.1 percent, of stream length classified as most disturbed as compared to the reference condition. An analysis of riparian disturbance, an index of the in-channel, riparian, and near-stream human activities, classified 43±13 percent of stream length on O‘ahu as most disturbed. The Honolulu region had the largest proportion of stream length, 86.3±13.7 percent, classified as most disturbed. The information in this report is the first attempt in Hawai‘i to assess the islandwide ecological condition of wadeable, perennial streams on O‘ahu using the USEPA WSA probabilistic design. This study has demonstrated that such an assessment is practical and that it can provide information that may help the USEPA and HDOH in determining the status of aquatic ecosystems on O‘ahu, Hawai‘i. This study provides a baseline assessment of the current islandwide ecological condition and identifies potential environmental stressors. It can be used, with future WSA studies in Hawai‘i, to measure the changes in those conditions and the effectiveness of management efforts to protect, restore, and maintain Hawai‘i’s aquatic environment.

Hawaii↗

USGS2016

Reservoirs and water management influence fish mercury concentrations in the western United States and Canada

Anthropogenic manipulation of aquatic habitats can profoundly alter mercury (Hg) cycling and bioaccumulation. The impoundment of fluvial systems is among the most common habitat manipulations and is known to increase fish Hg concentrations immediately following impoundment. However, it is not well understood how Hg concentrations differ between reservoirs and lakes at large spatial and temporal scales or how reservoir management influences fish Hg concentrations. This study evaluated total Hg (THg) concentrations in 64,386 fish from 883 reservoirs and 1387 lakes, across the western United States and Canada, to assess differences between reservoirs and lakes, as well as the influence of reservoir management on fish THg concentrations. Fish THg concentrations were 1.4-fold higher in reservoirs (0.13 ± 0.011 μg/g wet weight ± standard error) than lakes (0.09 ± 0.006), though this difference varied among ecoregions. Fish THg concentrations were 1.5- to 2.6-fold higher in reservoirs than lakes of the North American Deserts, Northern Forests, and Mediterranean California ecoregions, but did not differ between reservoirs and lakes in four other ecoregions. Fish THg concentrations peaked in three-year-old reservoirs then rapidly declined in 4–12 year old reservoirs. Water management was particularly important in influencing fish THg concentrations, which were up to 11-times higher in reservoirs with minimum water storage occurring in May, June, or July compared to reservoirs with minimum storage occurring in other months. Between-year changes in maximum water storage strongly influenced fish THg concentrations, but within-year fluctuations in water levels did not influence fish THg concentrations. Specifically, fish THg concentrations increased up to 3.2-fold over the range of between-year changes in maximum water storage in all ecoregions except Mediterranean California. These data highlight the role of reservoir creation and management in influencing fish THg concentrations and suggest that water management may provide an effective means of mitigating Hg bioaccumulation in some reservoirs.

Science of the Total Environment↗

USGS1998

Palynology of latest Neogene (Middle Miocene to late Pliocene) strata in the Delmarva Peninsula of Maryland and Virginia

Palynology of Miocene and Pliocene formations in the Delmarva Peninsula of Maryland and Virginia reveals a significant representation of exotic pollen interspersed in pollen assemblages that are otherwise comparable to those from the modern vegetation of the Mid-Alantic coastal plain region. The late Tertiary arboreal pollen (AP) assemblages are dominated by oak, hickory, pine, birch and alder with minor amounts of mid- and southern coastal tree taxa, as well as minor spruce and hemlock and a trace of fir. Nonarboreal pollen (NAP) include grass, sedge, composite and aquatic taxa. Exotic pollen in these assemblages represent plants now foreign to this region. They may be placed in three categories. First, there are extinct forms, such as Labrapollis, Plicatopollis, and Multiporopollenites, that can be traced from the Cretaceous or Early Tertiary into the Late Tertiary. The second group includes forms, such as Podocarpus, Engelhardtia, Pterocarya, Ephedra, Eucommia, Ulmus-Zelkova, Glyptostrobus, Palmae, and Cyathea, that are not found in this region today and not found in early Pleistocene sediments in the eastern United States. Many of these taxa are subtropical or greatly restricted in geographic range. A third group of exotics, mainly Cyrilla, Planera, Gordonia, Jussiaea, and Sapotacaea, including Minusops, are generally found south of the study area or have their northern limit here at this time. The lack of the extinct or distant exotics in early to mid-Pleistocene sediments in the mid-Atlantic coastal plain and the last appearance of Pterocarya, as the last exotic taxon in the early Pleistocene of western Europe, support the stratigraphic assignment of the Pliocene units. The number of exotic taxa diminish markedly between the Miocene pollen assemblages and those of the Late Pliocene. Climatic fluctuations characterize the Late Tertiary environments. The Miocene, for example, incorporates a warming trend between the upper, middle Miocene and the Manokin beds and the late Miocene of the Pokomoke beds. The late Miocene was probably somewhat warner than the present climate in the Delmarva region. This trend is based on the presence of colder climate indicators, mainly spruce and hemlock, in the Manokin pollen record. The two distinct pollen assemblages constitute two pollen zones. Similarly, the Pliocene pollen record also shows a warming trend. The pollen zone of the Yorktown Formation of the early Pliocene age contains the colder climate indicators spruce and hemlock. The Beaverdam and Walston formation of late Pliocene age contain pollen assemblages that reflect climatic conditions warmer than the present time.

Northeastern Geology and Environmental Sciences↗

USGS2022

Restoring aquatic habitats through dam removal

This report presents results from a four-year project (2018–2022) to document the effects of small, run-of-river dams and dam removal on water quality (stream temperature and dissolved oxygen (DO)), aquatic macroinvertebrates, and fishes. Temperature and DO are critical water quality parameters that shape biogeochemical processes and biotic assemblages in streams. Macroinvertebrate and fish assemblages can be reflective of habitat and water quality due to their diversity and sensitivity to high temperatures and low DO and are often used as indicators of ecosystem health (e.g., Clean Water Act Section 401). This study aimed to better explain the responses of these important ecological parameters to small dam removals, which may support a more comprehensive understanding of the benefits of restoration to aquatic ecosystems. We collected pre- and post-restoration water quality data and macroinvertebrate samples at 16 small dams in Massachusetts that have been removed (10 sites) or are currently being considered for removal (6 sites). General results from these monitoring efforts indicate that: ● 15 of 16 small dams increased impoundment water temperatures and warming persisted downstream at 11 of those sites, relative to upstream. Dam removal reduced summer impoundment warming at 7 of 10 removal sites and reduced downstream warming at 5 of 10 sites. These in-stream temperature improvements occurred within 5 years after dam removal. ● 13 of 16 small dams negatively impacted dissolved oxygen (DO) concentrations within the impoundments, but the magnitude of impact varied across sites. Negative impoundment DO impacts did not consistently translate downstream, and downstream responses to dam removal were generally minimal and variable across sites. Dam removal significantly reduced negative impoundment DO impacts within 1 year after removal at 7 of 10 sites, and sites with greater pre-removal impacts experienced the greatest magnitude of DO recovery after dam removal. ● Interannual variability in dam impacts on water quality across sites suggests periods of extreme weather (i.e., droughts or high precipitation) due to climate change may exacerbate adverse impacts from run-of-river dams. ● Macroinvertebrate assemblages within dam impoundments differed from assemblages in adjacent un-impounded stream sections and exhibited a loss of sensitive organisms (an average of 17% fewer). Dam removal led to more similar macroinvertebrate assemblages throughout most stream sections, and recovery of sensitive taxa occurred relatively quickly (1-3 years). ● Fish species richness increased upstream at 2 of 10 removal sites, suggesting potential increases in fish passage from downstream reaches. However, particular species, such as American Eel ( Anguilla rostrata ), exhibited both positive and negative responses to dam removal across study sites. Incorporating more sites with pre-and post-dam removal fish data could allow for better understanding factors explaining site-specific differences.

Massachusetts↗

USGS2010

Assessment of PDMS-water partition coefficients: implications for passive environmental sampling of hydrophobic organic compounds

Solid-phase microextraction (SPME) has shown potential as an in situ passive-sampling technique in aquatic environments. The reliability of this method depends upon accurate determination of the partition coefficient between the fiber coating and water (K f ). For some hydrophobic organic compounds (HOCs), K f values spanning 4 orders of magnitude have been reported for polydimethylsiloxane (PDMS) and water. However, 24% of the published data examined in this review did not pass the criterion for negligible depletion, resulting in questionable K f values. The range in reported K f is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these questionable values are removed. Other factors that could account for the range in reported K f , such as fiber-coating thickness and fiber manufacturer, were evaluated and found to be insignificant. In addition to accurate measurement of K f , an understanding of the impact of environmental variables, such as temperature and ionic strength, on partitioning is essential for application of laboratory-measured K f values to field samples. To date, few studies have measured K f for HOCs at conditions other than at 20 degrees or 25 degrees C in distilled water. The available data indicate measurable variations in K f at different temperatures and different ionic strengths. Therefore, if the appropriate environmental variables are not taken into account, significant error will be introduced into calculated aqueous concentrations using this passive sampling technique. A multiparameter linear solvation energy relationship (LSER) was developed to estimate log K f in distilled water at 25 degrees C based on published physicochemical parameters. This method provided a good correlation (R2 = 0.94) between measured and predicted log K f values for several compound classes. Thus, an LSER approach may offer a reliable means of predicting log K f for HOCs whose experimental log K f values are presently unavailable. Future research should focus on understanding the impact of environmental variables on K f . Obtaining the data needed for an LSER approach to estimate K f for all environmentally relevant HOCs would be beneficial to the application of SPME as a passive-sampling technique.

Environmental Science & Technology↗

USGS2019

A novel method to characterise levels of pharmaceutical pollution in large scale aquatic monitoring campaigns

Much of the current understanding of pharmaceutical pollution in the aquatic environment is based on research conducted in Europe, North America and other select high-income nations. One reason for this geographic disparity of data globally is the high cost and analytical intensity of the research, limiting accessibility to necessary equipment. To reduce the impact of such disparities, we present a novel method to support large-scale monitoring campaigns of pharmaceuticals at different geographical scales. The approach employs the use of a miniaturised sampling and shipping approach with a high throughput and fully validated direct-injection High-Performance Liquid Chromatography-Tandem Mass Spectrometry method for the quantification of 61 active pharmaceutical ingredients (APIs) and their metabolites in tap, surface, wastewater treatment plant (WWTP) influent and WWTP effluent water collected globally. A 7-day simulated shipping and sample stability assessment was undertaken demonstrating no significant degradation over the 1–3 days which is typical for global express shipping. Linearity (r 2 ) was consistently ≥0.93 (median = 0.99 ± 0.02), relative standard deviation of intra- and inter-day repeatability and precision was <20% for 75% and 68% of the determinations made at three concentrations, respectively, and recovery from Liquid Chromatography Mass Spectrometry grade water, tap water, surface water and WWTP effluent were within an acceptable range of 60–130% for 87%, 76%, 77% and 63% of determination made at three concentrations respectively. Limits of detection and quantification were determined in all validated matrices and were consistently in the ng/L level needed for environmentally relevant API research. Independent validation of method results was obtained via an interlaboratory comparison of three surface-water samples and one WWTP effluent sample collected in North Liberty, Iowa (USA). Samples used for the interlaboratory validation were analysed at the University of York Centre of Excellence in Mass Spectrometry (York, UK) and the U.S. Geological Survey National Water Quality Laboratory in Denver (Colorado, USA). These results document the robustness of using this method on a global scale. Such application of this method would essentially eliminate the interlaboratory analytical variability typical of such large-scale datasets where multiple methods were used.

Applied Sciences↗

USGS2018

Chesapeake Bay dissolved oxygen criterion attainment deficit: Three decades of temporal and spatial patterns

Low dissolved oxygen (DO) conditions are a recurring issue in waters of Chesapeake Bay, with detrimental effects on aquatic living resources. The Chesapeake Bay Program partnership has developed criteria guidance supporting the definition of state water quality standards and associated assessment procedures for DO and other parameters, which provides a binary classification of attainment or impairment. Evaluating time series of these two outcomes alone, however, provides limited information on water quality change over time or space. Here we introduce an extension of the existing Chesapeake Bay water quality criterion assessment framework to quantify the amount of impairment shown by space-time exceedance of DO criterion (“attainment deficit”) for a specific tidal management unit (i.e., segment). We demonstrate the usefulness of this extended framework by applying it to Bay segments for each 3-year assessment period between 1985 and 2016. In general, the attainment deficit for the most recent period assessed (i.e., 2014–2016) is considerably worse for deep channel (DC; n = 10) segments than open water (OW; n = 92) and deep water (DW; n = 18) segments. Most subgroups – classified by designated uses, salinity zones, or tidal systems – show better (or similar) attainment status in 2014–2016 than their initial status (1985–1987). Some significant temporal trends (p < 0.1) were detected, presenting evidence on the recovery for portions of Chesapeake Bay with respect to DO criterion attainment. Significant, improving trends were observed in seven OW segments, four DW segments, and one DC segment over the 30 3-year assessment periods (1985–2016). Likewise, significant, improving trends were observed in 15 OW, five DW, and four DC segments over the recent 15 assessment periods (2000–2016). Subgroups showed mixed trends, with the Patuxent, Nanticoke, and Choptank Rivers experiencing significant, improving short-term (2000–2016) trends while Elizabeth experiencing a significant, degrading short-term trend. The general lack of significantly improving trends across the Bay suggests that further actions will be necessary to achieve full attainment of DO criterion. Insights revealed in this work are critical for understanding the dynamics of the Bay ecosystem and for further assessing the effectiveness of management initiatives aimed toward Bay restoration.

Maryland, Virginia↗

USGS2007

Comparison of ion-exchange resin counterions in the nutrient measurement of calcareous soils: Implications for correlative studies of plant-soil relationships

For more than 40 years, ion-exchange resins have been used to characterize nutrient bioavailability in terrestrial and aquatic ecosystems. To date, however, no standardized methodology has been developed, particularly with respect to the counterions that initially occupy resin exchange sites. To determine whether different resin counterions yield different measures of soil nutrients and rank soils differently with respect to their measured nutrient bioavailability, we compared nutrient measurements by three common counterion combinations (HCl, HOH, and NaHCO 3 ). Five sandy calcareous soils were chosen to represent a range of soil characteristics at Canyonlands National Park, Utah, and resin capsules charged with the different counterions equilibrated in saturated pastes of these soils for one week. Data were converted to proportions of total ions of corresponding charge for ANOVA. Results from the different methods were not comparable with respect to any nutrient. Of eleven nutrients measured, all but iron (Fe 2+ ), manganese (Mn 2+ ), and zinc (Zn 2+ ) differed significantly ( p ≤0.05) as a function of soil×counterion interactions; Fe 2+ and Zn 2+ varied as functions of counterion alone. Of the counterion combinations, HCl-resins yielded the most net ion exchange with all measured nutrients except Na + , and the three of which desorbed in the greatest quantities from HOH-resins. Conventional chemical extractions using ammonium acetate generally yielded high proportional values of Ca 2+ , K + , and Na + . Further, among-soil rankings of nutrient bioavailability varied widely among methods. This study highlights the fact that various ion-exchange resin techniques for measuring soil nutrients may have differential effects on the soil-resin environment and yield data that should not be compared nor considered interchangeable. The most appropriate methods for characterizing soil-nutrient bioavailability depends on soil characteristics and likely on the physiological uptake mechanisms of plants or functional groups of interest. The effects of different extraction techniques on nutrient measures should be understood before selecting an extraction method. For example, in the calcareous soils used for this experiment, nutrient extraction methods that alter soil carbonates through dissolution or precipitation could compromise the accurate measurement of plant-available nutrients. The implications of this study emphasize the universal importance of understanding the differential effects of alternate methods on soil chemistry.

Communications in Soil Science and Plant Analysis↗

USGS2021

Co-occurring lotic crayfishes exhibit variable long-term responses to extreme-flow events and temperature

Crayfish serve critical roles in aquatic ecosystems as engineers, omnivores, and prey. It is unclear how increasingly frequent extreme-flow events and warming air temperatures will affect crayfish populations, partly because there are few long-term crayfish monitoring datasets. Using a unique 10-y dataset, we asked 1) whether recruitment of crayfishes in summer responded to extreme-flow events and air temperature during spring brooding and summer growing periods and 2) whether responses were similar among 3 co-occurring crayfish species. Golden ( Faxonius luteus [Creaser, 1933]), Ozark ( Faxonius ozarkae [Williams, 1952]), and Spothand ( Faxonius punctimanus [Creaser, 1933]) crayfishes were sampled in quadrats at 2 sites each in the Big Piney (1993–2000) and Jacks Fork (1992–2001) rivers (Missouri, USA; n = 3355 1-m 2 quadrats). We used zero-inflated generalized linear models to relate variability in quadrat-level age-0 counts to mean daily maximum air temperatures and flow metrics (variability, magnitude, and frequency of extreme high- and low-flow events). Species ranged from a small-bodied, abundant habitat generalist (Golden Crayfish) to large-bodied, uncommon habitat specialists (Ozark and Spothand crayfishes). Golden Crayfish occurred in higher-velocity habitats (riffles, runs) and had variable recruitment that increased during years with few spring and summer high-flow events and summers with lower flows and warmer temperatures. In contrast, annual recruitment variability of Ozark and Spothand crayfishes was low and explained by positive effects of cooler summers and by different flow metrics. Spothand Crayfish recruitment decreased in years with frequent spring and summer high-flow events, whereas lower summer minimum flow was the only flow metric that explained slight increases in Ozark Crayfish recruitment. Relationships with the preceding year’s recruitment were quadratic for Ozark and Spothand crayfishes, suggesting potential density dependence at higher recruitment levels. Species-specific responses suggest that closely related crayfishes could respond idiosyncratically to changes in temperature and flow. Temperature- and flow-related disturbances may be key mechanisms mediating competition and, thus, may help maintain crayfish diversity. However, warming air temperatures and increasingly frequent extreme-flow events could disadvantage some species, thereby altering future crayfish assemblages.

Missouri↗

USGS2023

Dissolved organic carbon dynamics and fluxes in Mississippi-Atchafalaya deltaic system impacted by an extreme flood event and hurricanes: A multi-satellite approach using Sentinel-2/3 and Landsat-8/9 data

Transport of riverine and wetland-derived dissolved organic carbon (DOC) spanning tidal wetlands, estuaries, and continental shelf waters functionally connects terrestrial and aquatic carbon reservoirs, yet the magnitude and ecological significance of this variable and its spatiotemporal linkage remains uncertain for coastal deltaic regions, such as Mississippi River Delta Plain, which includes Mississippi (MR) and Atchafalaya (AR) rivers and estuaries with vast expanses of wetlands and coastal forests. We examined DOC dynamics and fluxes in this large river-dominated wetland-estuarine system for the period between 2019 and 2021 that included an extreme river flood event in 2019, two major hurricanes (Barry in 2019 and Ida in 2021), and cold front passage using an improved adaptive quasi-analytical algorithm (QAA-AD) applied to multi-satellite sensors (Sentinel 3A/B OLCI, Landsat-8/OLI and Sentinel-2A/B MSI) with varying spectral and spatial (10/30/300 m) resolutions. The DOC estimates from multi-satellite sensors in combination with water fluxes were used to assess DOC fluxes from two large rivers (MR and AR) and small channels across the delta plain. Overall, this system delivered a total of 6.7 Tg C yr -1 (1 Tg = 10 12 g) into the estuarine zone and the northern Gulf of Mexico (nGoM) during 2019. High DOC fluxes from the AR (1.3 Tg C yr -1 ) and MR (4.5 Tg C yr -1 ) were associated with the extreme flood event in 2019. Hurricanes that occurred in the study period also contributed to the wetland and estuarine DOC fluxes into continental shelf waters; for example, the passage of Hurricane Barry in July 2019, delivered over a 3-day period ~1.33 ×10 9 g DOC from Barataria Basin into the nGoM. Sentinel 2-MSI land and water classification revealed that Hurricane Ida eroded a total of 1.34×10 8 m 2 of marshes in middle Barataria Basin, converting those habitats into open water with 3.0 m inundation depth and high DOC concentrations (16.4 mg L -1 ), a potentially large DOC source to the coastal waters. Overall, storms and flood events are major sources of DOC flux that facilitate transport of upstream carbon as well as transformation of carbon in the wetlands, through the conversion of vegetated wetland to open water.

Louisiana↗