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Characterization of selected biological, chemical, and physical conditions at fixed sites in the Upper Colorado River Basin, Colorado, 1995-98

Biological community samples were collected at 15 sites in the Upper Colorado River Basin (UCOL) in Colorado as part of the National Water-Quality Assessment (NAWQA) Program. Sites sampled in two physiographic provinces, the Southern Rocky Mountains and the Colorado Plateau, represented agriculture, mining, urban and recreation, and mixed land uses and background conditions. Nine measures of water quality, which include information on nutrients, specific conductance (a surrogate for salinity), trace elements in streambed sediment, pesticides in fish tissue, fish communities, and macroinvertebrate richness and composition and stream habitat were used for comparisons among sites within the two physiographic provinces. Sampling sites from three other NAWQA study units—the Rio Grande Valley, the South Platte River Basin, and the Upper Snake River Basin study units—were categorized on the basis of land use and stream size in order to develop a larger data set for comparison to sites in the UCOL. Three categories of land use—forested (includes mining, urban and recreation, and background), agriculture, and mixed—were used for comparison to the UCOL fixed sites. Results indicated that all sites other than the Colorado River below Baker Gulch (a background site) showed some water-quality characteristics to be significantly affected. Results indicated that the concentrations of cadmium and zinc in streambed sediment at mining land-use sites in the Southern Rocky Mountains physiographic province generally were orders of magnitude higher than streambed-sediment concentrations at the background site. Streambed-sediment concentrations at mining land-use sites in the UCOL were greater than the 75 th percentile of concentrations from sites in the three other NAWQA study units. Fish communities and habitat conditions were degraded at mining land-use sites compared to the background site. Ephemeroptera, Plecoptera, and Trichoptera (EPT) richness and the percentage of EPT were lower at mining land-use sites than at the background site and were less than the 50 th percentile of those for sites from the three other NAWQA study units. Nutrient concentrations at urban and recreation sites in the Southern Rocky Mountain physiographic province generally were greater than concentrations at the background site and generally were between the 25 th and 90 th percentile of concentrations for sites from the three other NAWQA study units. Habitat conditions and fish communities at urban and recreation sites were slightly degraded compared to the background site. EPT richness and the percentage of EPT were lower at urban and recreation sites than at the background site and were between the 25 th and 75 th percentile of those for sites from the three other NAWQA study units. The percentage of Chironomidae, which may be indicative of pollutant-tolerant organisms, was higher at urban and recreation sites than at the background site. Mixed land-use sites in the Southern Rocky Mountains physiographic province had similar nutrient concentrations and similar cadmium and zinc streambed-sediment concentrations. Fish-community degradation index values were very different among the three mixed land-use sites in the Southern Rocky Mountains physiographic province. Larger percentages of omnivores and anomalies such as lesions and deformities at two mixed land-use sites resulted in higher degradation values of the fish community. Agriculture land-use sites had higher concentrations of nutrients and selenium than the background site in the Colorado Plateau physiographic province. Concentrations of p,p '-DDE in fish tissue at agriculture sites were higher than the 75 th percentile of concentrations for sites from the three other NAWQA study units. Fish communities had degradation values near the 75 th percentile for agriculture sites. The percentage of EPT was low at agriculture sites when compared to the background site. Two mixed land-use sites in the Colorado Plateau physiographic province had similar concentrations of nutrients, selenium, and p,p '-DDE, and similar EPT richness and composition. These two sites were located downstream from agricultural and urban activities. Some water-quality measures at these two sites indicated degradation compared to a mixed land-use site upstream from most of the agriculture and urban activities in the Colorado Plateau physiographic province.

Colorado

Non-destructive sampling of larval amphibians shows tail tissues reflect whole-body methylmercury concentrations and trophic-related differences in bioaccumulation

Mercury (Hg), and specifically methylmercury (MeHg), is a contaminant of global concern to humans and wildlife, but there is still limited understanding of its effects on many taxa. Amphibians are closely associated with water, where Hg is converted to MeHg, and high concentrations of MeHg can reduce survival of amphibians in the wild. However, limited non-lethal proxies exist for estimating MeHg bioaccumulation in amphibian larvae, which could be used to reduce destructive sampling and allow sampling of imperiled species. We evaluated whether tail clips were indicative of whole-body MeHg concentrations of larval amphibians, whether dragonflies were an effective bioindicator of Hg concentrations of larval amphibians, and compared MeHg bioaccumulation in predatory caudate (salamanders, newts) and non-predatory anuran (frogs, toads) larvae. Tail-clip and whole-body MeHg concentrations were strongly correlated, especially for caudates. There was high variability among sites and species, but caudates had higher MeHg than anurans, and MeHg concentrations of caudates and anurans were strongly correlated. Dragonflies were a weak indicator of MeHg for anurans but strong indicators for larval caudates, likely because caudates and dragonflies are carnivorous and occupy similar trophic positions. Our study revealed that sampling tails can be an effective non-destructive index of whole-body MeHg for larval amphibians and demonstrates differences in MeHg bioaccumulation related to trophic position in larval amphibians and dragonflies. All post-embryo life stages for a broad suite of amphibian species can now be sampled non-lethally for MeHg, allowing for a broader examination of population-level effects and focus on imperiled species that cannot be sampled destructively.

conterminous United States

Factors contributing to pesticide contamination in riverine systems: The role of wastewater and landscape sources

Wastewater treatment plant (WWTP) discharges can be a source of organic contaminants, including pesticides, to rivers. An integrated model was developed for the Potomac River watershed (PRW) to determine the amount of accumulated wastewater percentage of streamflow (ACCWW) and calculate predicted environmental concentrations (PECs) for 14 pesticides in non-tidal National Hydrography Dataset Plus Version 2.1 stream segments. Predicted environmental concentrations were compared to measured environmental concentrations (MECs) from 32 stream sites that represented a range of ACCWW and land use to evaluate model performance and to assess possible non-WWTP loading sources. Statistical agreement between PECs and MECs was strongest for insecticides, followed by fungicides and herbicides. Principal component analysis utilizing optical fluorescence and ancillary water quality data identified wastewater and urban runoff sources. Pesticides that indicated relatively larger sources from WWTPs included dinotefuran, fipronil, carbendazim, thiabendazole, and prometon whereas imidacloprid, azoxystrobin, propiconazole, tebuconazole, and diuron were more related to urban runoff. In addition, PECs generally comprised a low proportion of MECs, which indicates possible dominant loading sources beyond WWTP discharges. Cumulative potential toxicity was higher for sites with greater ACCWW and/or located in developed areas. Imidacloprid, fipronil, and carbendazim accounted for the largest portion of predicted potential toxicity across sites. The chronic aquatic life toxicity benchmarks for freshwater invertebrates were exceeded for 82 % of the imidacloprid detections ( n = 28) and 47 % of the fipronil detections ( n = 19). These results highlight the ecological implications of pesticide contamination from WWTP discharges and also the potential legacy effects from accumulated soil and groundwater sources. Pesticide management strategies that mitigate both current and historical impacts may improve the health of aquatic ecosystems.

Potomac River watershed

Evidence of mineral alteration in a salt marsh subterranean estuary: Implications for carbon and trace element cycling

Subterranean estuaries (STE) in salt marshes are biogeochemically active zones where interactions between terrestrial groundwater and seawater drive complex cycling of carbon and trace elements, influenced by mineral dissolution. These systems, characterized by fine-grained organic-rich peat overlying permeable coastal aquifers, play a crucial role as a blue carbon sink, yet their geochemical dynamics remain poorly understood. We investigated dissolved trace elements, carbon, silica, and radium isotopes in a salt marsh STE (Sage Lot Pond, Waquoit Bay, MA) over seasonal and annual cycles. Our results reveal that groundwater and estuarine water circulation through marsh peat and aquifer sediments leads to enrichments of dissolved organic and inorganic carbon (DOC and DIC), Si, Ba, and Mn, with variable source/sink behavior of Fe and net removal of U. Submarine groundwater discharge dominated Ba fluxes, whereas pore water drainage from marsh peat acted as the main sink for U and source of Si. Fe cycling was variable, with terrestrial Fe largely removed as groundwater passed through the STE, consistent with Fe-sulfide and amorphous phase formation. Radium isotope ratios identified two distinct subsurface flow pathways, influenced by metal-oxide cycling and organic matter breakdown. Si production was decoupled from DIC, suggesting Si originates from mineral alteration, whereas DIC results from both mineral weathering and microbial respiration. Silicate mineral alteration, coupled with marsh pore water drainage, accounts for up to 16% of annual DIC exports (66 g C m −2 y −1 ), highlighting the importance of STEs in coastal carbon and trace element cycling, especially as marshes face environmental change.

Massachusetts

Are the horizontal-to-vertical spectral ratios of earthquakes and microtremors the same?

We consider the similarities and differences between earthquake and microtremor horizontal‐to‐vertical spectral ratios (eHVSR and mHVSR, respectively) using a dataset of 161 sites in southern California. Quantitative comparisons are made in terms of the eHVSR and mHVSR lognormal median curves, as well as the frequencies and amplitudes associated with the fundamental‐ and higher‐mode resonances where present. The results show only 58% of the eHVSR–mHVSR pairs agree in terms of their median curve and only 25% of the eHVSR–mHVSR pairs agree in terms of shared resonances, which increases to 68% if flat HVSRs are considered equivalent. Furthermore, while the shared resonances match very well in terms of frequency (root mean square error, RMSE, <0.11 Hz), the amplitudes of those resonances do not agree (RMSE >1.6). These findings demonstrate that while eHVSR and mHVSR agree at some sites, they are not equivalent at all sites. To investigate if the agreement between eHVSR and mHVSR could be related to features of the microtremor data, earthquake recordings, and/or the site conditions, three machine learning (ML) models at varying levels of interpretability are presented. The ML models—which include multivariate logistic regression, gradient‐boosted trees, and support vector machines—show only partial success at using site‐specific data to predict whether eHVSR and mHVSR will likely agree in terms of their median curve (accuracy of 78%) and number of resonances (accuracy of 84%). Therefore, we conclude that while eHVSR and mHVSR can be quite similar in terms of resonant frequencies at some sites, they are not identical at all sites. Furthermore, preliminary evidence shows that the agreement of eHVSR and mHVSR can be predicted a priori given features of the microtremor measurements, earthquake recordings, and site conditions, although a larger dataset will be necessary for developing a robust predictive model.

California

Modeling seawater intrusion along the Alabama coastline using physical and machine learning models to evaluate the effects of multiscale natural and anthropogenic stresses

Seawater intrusion threatens groundwater resources in coastal regions, including southern Baldwin County, Alabama, where the freshwater-saltwater interface dynamics remain poorly understood. To address this gap, this study uses combined physics-based and machine-learning models to quantify seawater intrusion caused by natural (storm surges) and anthropogenic (human activities) perturbations. The long short-term memory network and wavelet analysis were used to assess vertical aquifer vulnerabilities, revealing that the shallow part of the Coastal lowlands aquifer system (CL1) in the southern Baldwin County region is more susceptible to sea level rise and groundwater extraction than deeper aquifers. Based on these findings, a cross-sectional numerical model (physics approach) for the CL1 aquifer was developed to evaluate tidal and storm surge effects, using Tropical Storm Claudette (June 2021) as a case study. Results showed that tidal fluctuations had a minimal impact on the saltwater-freshwater interface location, whereas storm surges caused substantial inland movement, with effects lasting for nine months. The steady-state version of the three-dimensional (3D) physical model predicted seawater intrusion across the entire area, and convolutional neural network-based modeling further validated the model results. The 3D physical model was also applied to a smaller area to assess human impact on the saltwater interface due to two groundwater pumping scenarios (± 50% of the baseline pumping rate). Results revealed that a 50% increase in groundwater withdrawals caused seawater to advance ~ 320 m inland, whereas a 50% reduction led to a ~ 270-meter retreat. This study highlights the vulnerability of Alabama’s shallow coastal aquifers to seawater intrusion due to storm surges and human activities, and demonstrates that combining physics-based models with machine learning approaches can improve groundwater predictions, though its accuracy depends on the availability of site-specific data.

Alabama

Stream sediment sources in Medicine Creek, northern Missouri and southern Iowa

This report presents the results of a cooperative study by the U.S. Geological Survey and Missouri Department of Natural Resources to quantify sediment transport source contributions in the Medicine Creek drainage basin. Understanding relative source contributions provides valuable information for selecting the conservation practices that may be most effective in reducing sediment and sediment-associated nutrient transport in the Medicine Creek drainage basin and similar areas of the Lower Grand River drainage basin. Sediment samples were collected from potential contributing areas (source samples) and from fluvial-transported samples (target samples). Source sample types included streambanks, row crop fields, and a combined pastures and forests category. Samples were analyzed for particle size and quantity of carbon, nitrogen, stable isotopes of carbon and nitrogen, and 49 mineral elements as potential tracers. Results for the carbon stable isotope ratio of carbon-13/carbon-12 (δ 13 C) and concentrations of total carbon, total nitrogen, calcium, potassium, and copper were selected by discriminant function analysis as the best combination of multiple tracers to differentiate each source type. The discriminant function analysis poorly differentiated pastures and forests, so these source types were combined. The sources defined by the discriminant function analysis were then used in an unmixing model to apportion sources for each target sample. In the study area, transported sediment was predominantly bank sediment, with an overall average of 86.9 percent of suspended-sediment samples and depositional streambed samples attributed to bank material. Suspended-sediment samples from the mainstem of Medicine Creek were dominated by bank sediments (average of 95.8 percent), and depositional streambed samples from throughout the drainage basin had more variable source contributions with an average of 71.1 percent attributed to bank material. The relative importance of upland sources (row crop fields and the combined pastures and forests category) varied seasonally and with streamflow but was not related to land use or drainage basin size. Relative contributions from upland sources were greater in the summer through winter rather than spring and during lower streamflow, though this may be driven by the seasonality of streamflow. These results indicate management practices that reduce bank erosion could be effective strategies for managing the dominant source of sediment and sediment-associated phosphorus.

Iowa, Missouri

Models no not provide proof: An example of model ambiguity and application of isotopic data in a mine pit lake

Geochemical and hydrologic models of pit lakes are commonly used in environmental regulatory decisions to predict future water quality and hydrologic conditions and to understand existing pit lakes. Models may be used to quantify sulfide oxidation, predict thermal/chemical stratification and mixing, and better understand connections between pit lakes and aquifers. One concern related to the hydrologic character of pit lakes is if they are terminal (a groundwater sink with no outflow) or flowthrough (both receiving groundwater inflow and discharging to groundwater). This question was pertinent to the Liberty pit lake, a small acidic pit lake formed in a former Cu deposit in south-central Nevada where potentiometric and geochemical data potentially indicate pit-lake outflow. Potential discharge to groundwater from the pit lake was evaluated using a water-balance model, but uncertainty in hydraulic parameters led to ambiguity in the hydrologic character. Stable isotopes of water were then sampled from the pit lake and adjacent groundwater wells, which unambiguously indicated the lack of an evaporative signature in downgradient groundwater because the groundwater did not plot on a hypothetical mixing line between evaporated pit lake water and observed meteoric recharge. This methodology provided a more effective and more data-driven approach for understanding pit-lake hydrology. Although predictive models are required to quantify reasonable bounds on future conditions, many models contain substantial uncertainty and are not well suited in some environments. Datasets that provide more clear lines of evidence could be collected from existing pit lakes whenever possible to inform water-rock interaction, limnological behavior, and connectivity to adjacent groundwater.

Nevada

The use of fluorite geochemistry and machine learning to identify critical mineral systems

Fluorite (CaF 2 ) is a potential pathfinder to critical mineral and rare earth element (REE) deposits but its application has been limited to a narrow range of mineralization types. I show that fluorite is a robust recorder of mineralization fertility by applying statistical and machine-learning methods to a new global fluorite geochemical database. Distinct median rare earth and trace element patterns are observed among deposit types and genetic environments. Fluorite associated with carbonatites and REE deposits are relatively enriched in Sr and have minimal Eu anomalies. These characteristics define new bivariate discrimination diagrams that correctly identify 78% of carbonatite-related fluorite and 88% of fluorite from REE deposits. Random forest classifiers were developed for a wide range of mineralization types and genetic settings. Trained solely on rare earth element patterns, these models achieve accuracies of 77–79%. Higher classification accuracies (up to 88–96%) are obtained when including elements such as Sr, highlighting the significance of trace elements for optimal fluorite classification. The recognition of diagnostic fluorite compositional fingerprints, particularly in REE-fertile systems, underscores its potential as a pathfinder and indicator for critical mineral exploration in F-bearing environments.

Mineralium Deposita

USGS addresses needs for lithium calibration and quality control materials for pLIBS analysis

Lithium (Li) is a globally important commodity used for energy storage, national defense, human health, and advanced technologies. Lithium resource development requires identifying deposits with elevated concentrations and optimal mineralogy, typically associated with select clays and pegmatites. Lithium is a light, highly reactive alkali metal with low atomic mass that is difficult to detect and quantify using conventional portable geochemical techniques such as X-ray fluorescence (XRF). However, portable laser-induced breakdown spectroscopy (pLIBS) is a powerful analytical technique for lithium exploration due to its ability to analyze solids quickly with minimal preparation. The expanded utility of pLIBS is hampered by the lack of matrix-matched calibration and quality control (QC) materials. The United States Geological Survey (USGS) has developed in-house lithium calibration and QC materials for lithium in clay and pegmatite matrices to address this limitation. We present the workflow and implementation of a custom-built matrix specific calibration on a SciAps Z-300 pLIBS, using proprietary Profile Builder software. The implementation of the custom calibration and quality control standards enables us to collect semiquantitative results directly from the pLIBS while in the field. Ultimately, this calibration has improved confidence in sample selection and collection in the field, providing more efficient site characterization.

Conference Paper