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Produced water geochemistry from hydraulically stimulated Niobrara Formation petroleum wells: Origin of salinity and temporal perspectives on treatment and reuse

Produced water (i.e., a mixture of returned injection fluids and geologic formation brines) represents the largest volumetric waste stream associated with petroleum production in the United States. As such, produced water has been the focus of intense study with emphasis on understanding the geologic origin of the fluids, environmental impacts of unintended or intentional release, disposal concerns, and their commodity (e.g., lithium) potential. However, produced water geochemistry from many active petroleum plays remain poorly constrained leading to knowledge gaps associated with the origin of brine salinity and parameters (e.g., radium levels) that can impact treatment, disposal, and possible reuse. Here we evaluate the major ion geochemistry, radium concentrations, and stable water isotope composition of ~120 produced water samples collected from 17 producing unconventional petroleum wells in Weld County, Colorado from the Late Cretaceous Niobrara Formation. This sample set encompasses eight produced water time series from four new wells across production days 0 to ~365 and from four established wells across production days ~1000 to ~1700. Additionally, produced water from nine other established Niobrara Formation wells were sampled at discrete time points ranging from day 458 to day 2256, as well as hydraulic fracturing input fluids. These results expand the available Niobrara Formation produced water geochemical data, previously limited to few wells sampled within the first year of production, allowing for the heterogeneity of major ions and radium to be evaluated. Furthermore, we explore the geochemical relationships between major ion ratios and stable water isotope composition to understand the origin of salinity in Niobrara Formation brines from the Denver-Julesburg Basin. These findings are discussed with perspective toward potential treatment and reuse of Niobrara produced water prior to disposal.

Colorado, Nebraska, Wyoming

Decadal trends in the quality of groundwater used for public drinking-water supply in California, 2004–2023, California groundwater ambient monitoring and assessment program, priority basin project

This study provides a comprehensive assessment of decadal changes in the quality of groundwater used for public drinking-water supply at 444 monitoring sites across California during 2004–2023. We assessed decadal step trends in groundwater quality for 145 water-quality constituents and geochemical indicators statewide and across geographic and land-use based network groups. We evaluated the statistical significance of directional changes (predominant increase or decrease of constituent concentrations) and the magnitude of those changes across all network groups. Uranium showed the most widespread directional and high-magnitude increases of all constituents with regulatory benchmarks statewide, particularly in the agriculture-dominated Central Valley as well as urban- and desert-dominated regions of Southern California. Fluoride and perchlorate showed the most widespread directional and high-magnitude decreases of all constituents with regulatory benchmarks statewide, which were also most pronounced in Southern California. Although arsenic and nitrate did not often register significant directional changes across network groups, they showed widespread, high-magnitude changes in both directions (increase and decrease) at levels often exceeding 10 percent of respective regulatory benchmarks statewide. Triazine herbicides (atrazine and simazine) and the gasoline oxygenate methyl tert-butyl ether (MTBE) showed significant directional decreases statewide, but not at levels considered to be of high magnitude compared to respective regulatory benchmarks. We observed significant directional and high-magnitude increases of total dissolved solids (TDS) statewide, which were most pronounced in agricultural areas. Analysis of explanatory geochemical indicators indicated that prevalent statewide increases of alkalinity and calcium were the predominant components of the observed statewide increases in TDS by mass. Widespread increases in groundwater alkalinity and calcium across agricultural and urban areas may be related, in part, to warm-season irrigation and other anthropogenic factors that have shifted soil weathering dynamics over the long term. Increasing alkalinity concentrations were related to increasing uranium concentrations, particularly in areas with aquifer materials derived from granitic rocks. Conversely, increasing calcium concentrations were related to decreasing fluoride concentrations, particularly in areas where fluoride occurred naturally at elevated concentrations. Decrease of perchlorate, triazine herbicides, and MTBE are likely related to decreased anthropogenic source inputs over time and natural attenuation in aquifers.

EarthArXiv

Standardized method for logging drill core at the Idaho National Laboratory, Idaho

The U.S. Geological Survey’s (USGS) Lithologic Core Storage Library (CSL) at the Idaho National Laboratory stores more than 120,000 feet of drill core that is accessible to the public for research and sampling. To effectively convey the physical and descriptive properties of the drill core, USGS staff at the Idaho National Laboratory Project Office log the drill core and publish the lithologic logs as data releases. The logs provide essential data on the lithology, texture, mineralogy, alteration, and other physical properties of the core, which serve as valuable information for researchers to guide their research and sampling efforts. To ensure consistent, quality, and dependable lithologic logs, this document outlines the procedures and expectations for logging drill core at the CSL. This document describes the processes for storing, photographing, and logging core, and includes a variety of resources, reference materials, and appendixes designed to standardize and aid the logging process. Following the procedures outlined in this document will produce consistent, detailed logs that facilitate dependable observations and serve as an easy reference for researchers and other interested parties.

Idaho

Perspectives and insights gained from applying landscape ecological approaches to the Upper Mississippi riverscape

Advances in remote sensing, spatial data collection, hydraulic and geospatial models, and the maturation of landscape ecology during the early 2000s spurred the concept of rivers as landscapes or ‘riverscapes’. Since that time, the Upper Mississippi River Restoration (UMRR) Program - one of the world’s longest running large-river ecosystem restoration and monitoring programs - has applied landscape ecological principles to the Upper Mississippi River System (UMRS). I examine spatial patterns of aquatic nutrient concentrations, submersed aquatic vegetation, and fish and mussel communities, finding that within-river patterns are often patchy in nature, likely resulting from how nutrient processes and community traits interact with spatial variability in hydraulic exchange patterns. Local-scale patchy spatial patterns in the UMRS are embedded in system-scale longitudinal gradients and a hierarchical view of the river has provided a foundation for strategic river restoration planning. Key Words: Aquatic Habitat, hydraulic connectivity, patch, restoration, riverscape

BioScience

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

Complex hydrology and variability of nitrogen sources in a karst watershed

Streams draining karst areas with rapid groundwater transit times may respond relatively quickly to nitrogen reduction strategies, but the complex hydrologic network of interconnected sinkholes and springs is challenging for determining the placement and effectiveness of management practices. This study aims to inform nitrogen reduction strategies in a representative agricultural karst setting of the Chesapeake Bay watershed (Fishing Creek watershed, Pennsylvania) with known elevated nitrate contamination and a previous documented groundwater residence time of less than a decade. During baseflow conditions, streamflow did not increase with drainage area. Headwaters and the main stem lost substantial flow to sinkholes until eventually discharging along large springs downstream. Seasonal hydrologic conditions shift the flow and nitrogen load spatially among losing and gaining stream sections. A compilation of nitrogen source inputs with the geochemistry and the pattern of enrichment of δ 15 N and δ 18 O suggest that the nitrogen in streams and springs during baseflow represents a mixture of manure, fertilizer, and wastewater sources with low potential for denitrification. The pH and calcite saturation index increased along generalized flow paths from headwaters to springs and indicate shorter groundwater residence times in baseflow during the spring versus summer. Given the substantial investment in management practices, fixed monitoring sites could incorporate synoptic water sampling to properly monitor long-term progress and help inform management actions in karst watersheds. Although karst watersheds have the potential to respond to nitrogen reduction strategies due to shorter groundwater residence times, high nitrogen inputs, effectiveness of conservation practices, and release of legacy nutrients within the karst cavities could confound progress of water quality goals.

Pennsylvania

Review and synthesis of the applications of machine learning to coalbed methane recovery

Over the last 30 years, a substantial literature has evolved on the use of machine learning (ML) to assess, predict, and improve the efficiency of coalbed methane (CBM) recovery. In the United States, the production of CBM declined as shale gas production matured, but CBM continues to be an important energy resource in other parts of the world. ML applications that have the potential to improve CBM reservoir management and production forecasts, and to increase exploration and operational efficiency, are still of significant interest. The integration of geostatistical techniques into the CBM ML applications has been largely absent but represents an opportunity for improvement. The literature demonstrates the widespread interest in, and applicability of, ML algorithms applied to CBM problems, and that they continue to result in improvements in predictive performance. However, (1) much of the research is more academic than operational, (2) many results are based on simulations, or small or proprietary datasets, (3) ML performance information can be inconsistent and sometimes entirely omitted, (4) most methodologies are unique to the specific CBM situation and likely not generalizable, (5) no standard data repositories are available to directly compare the performance of competing algorithms, and (6) the spatial component is often omitted. Finally, relatively new ML protocols involving causality analysis and reinforced learning, as well as hybrid workflows combining both supervised and unsupervised learning, are anticipated to dominate the future investigations. Integration of geostatistical and geospatial analysis with ML should enhance performance.

Book chapter

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

Estimating agricultural irrigation water consumption for the High Plains aquifer region with integrated energy- and water-balance evapotranspiration modeling approaches

Estimation of irrigation water use provides essential information for the management and conservation of agricultural water resources. Conventionally, water use data are created based on reports and surveys from water users, whereas manual records may not be complete due to lacking flow meters, measurement gaps, inconsistent methods across regions, and time- and cost-consuming data processing. Alternatively, spatially explicit estimation of irrigation water use can be conducted efficiently using remote sensing evapotranspiration (ET) modeling approaches. In this study, we created a gridded blue water evapotranspiration (BWET) dataset to estimate historical irrigation water consumption (1986 – 2020) in the croplands across the United States High Plains aquifer region. The BWET data were generated by integrating an energy-balance ET model [Operational Simplified Surface Energy Balance model (SSEBop)] and a water-balance ET model [Vegetation ET model (VegET)]. BWET in croplands indicates crop consumptive use of irrigation water extracted from surface water and groundwater resources. The BWET estimates were compared with reported irrigation water use data for all counties within the aquifer region. The results revealed high agreement between growing season (May – September) BWET and annual water withdrawal at county level. Specifically, correlation coefficients of volumetric BWET and water withdrawal were 0.90 and 0.96, respectively, for the entire aquifer region and western Kansas. The timeseries of BWET and water withdrawal showed similar temporal trends and high covariations. The BWET estimates were systematically lower than the water withdrawal measurements, which was primarily attributed to blue water losses in the irrigation system. The irrigation efficiency, calculated as the ratio of BWET to water withdrawal depth, was 0.57 and 0.74 for the entire aquifer region and western Kansas, respectively. This study demonstrates the capability of using satellite-based ET models (e.g., SSEBop and VegET) to efficiently estimate crop water consumption and evaluate irrigation efficiency at landscape, county, and regional scales.

Colorado, Kansas, Nebraska, New Mexico, Oklahoma,

A conceptual framework to assess post-wildfire water quality: State of the science and knowledge gaps

Wildfire substantially alters aquatic ecosystems by inducing moderate to catastrophic physical and chemical changes. However, the relations of environmental and watershed variables that drive those effects are complex. We present a Driver-Factor-Stressor-Effect (DFSE) conceptual framework to assess the current state of the science related to post-wildfire water-quality. We reviewed 64 peer-reviewed papers using the DFSE framework to identify drivers, factors, stressors, and effects associated with each study. A total of five drivers were identified and ranked according to their frequency of occurrence in the literature: atmospheric processes > fire characteristics > ecologic processes and characteristics > land surface characteristics > soil characteristics. Commonly reported stressors include increased nutrients, runoff, and sediment transport. Furthermore, although several different factors have been used at least once to explain water-quality effects, relatively few factors outside of precipitation and fire characteristics are frequently studied. We identified several gaps indicating the need for long-term monitoring, multi-factor studies, consideration of organic contaminants, consideration of groundwater, and inclusion of soil characteristics. This assessment expands on other reviews and meta-analyses by exploring causal linkages between influential variables and overall effects in post-wildfire watersheds. Information gathered from our assessment and the framework itself can be used to inform future monitoring plans and as a guide for modeling efforts focused on better understanding specific processes or to mitigate potential risks of post-wildfire water quality.

Water Resources Research