Richard Blaine McCleskey

A random forest classification (RFC) model was developed to predict hydrochemical facies (HCFs) of groundwater in three dimensions across the conterminous United States (CONUS). Major‐ion data from 152,673 sites were used to categorize groundwater into one of six HCFs (CaMg‐HCO ₃ , NaK‐HCO ₃ , CaMg‐SO ₄ , NaK‐SO ₄ , Cl, or Mixed). These six HCFs were used as targets for RFC modeling. Model features that represent relevant geochemical processes and/or physical conditions were derived from previously published data. Additional model features were specifically engineered to support this analysis: elevation of the bottom of a well relative to the base of drinking water (ERDW) and six flags that relate geologic units to HCFs. The most important model feature was ERDW. The model was used to map HCFs at a 1‐km ² resolution across CONUS and to depths of 400 m below the base of drinking water (which varies from 22 m to 2 km). Model predictions are consistent with expectations. CaMg‐HCO ₃ is predicted to occur near the water table in more humid settings, and areas underlain by carbonate or crystalline rocks. At depths below the base of drinking‐water supplies, the model predicts a rapid transition from HCO ₃ HCFs to Cl. Model predictions are accurate based on point data, and data averaged across hydrogeologic regions and with depth. Model predictions of HCFs could be used for multiple purposes, including the mapping of salinity and other groundwater characteristics.

Groundwater is increasingly needed for water supplies but may have limited utility in some locations because of its salinity. Salinity, often expressed as total dissolved solid (TDS), is frequently estimated using specific conductance (SC) measurements. However, the commonly used proxy (0.65 multiplied by SC to indicate TDS, common in many handheld meters) can result in inaccurate TDS estimates. First, the TDS–SC relationship is not linear over the entire concentration range of groundwater. Furthermore, the TDS (and salinity)–SC relationships vary substantially depending on the major‐ion composition. Here we develop a proxy method utilizing SC and major‐ion water type to estimate TDS and salinity specifically for groundwaters. Compared to most surface waters, groundwater tends to have a wider range of salinity (fresh to highly saline) and higher concentrations of bedrock‐derived solutes such as carbonate ions, silica, and many other ions. The dataset used to develop the proxies includes water chemistry data from 149,059 discrete groundwater samples. The groundwater proxies, which employ nonlinear log–log relations, utilize five water types (HCO ₃ , Cl, Ca‐Mg‐SO ₄ , Na‐K‐SO ₄ , and mixed waters), are accurate (median percent difference between TDS and salinity determined using the proxy compared to discrete measurements was <±0.8%) over a wide range of SC (up to 200 mS/cm), rapid, cost‐effective, and can be measured on‐site.

In the United States (U.S.), waste byproducts generated from the treatment of municipal waste (biosolids), production of livestock (livestock waste), and drilling of oil and gas wells (drilling waste) are commonly applied to agricultural lands. Although this can be a cost-effective reuse/disposal practice, there is limited research on the potential for contaminant exposures and effects on ecosystems, wildlife, and human health from such land applications. In this study, we conducted extensive chemical, microbial, and toxicity analyses of biosolid, livestock, and drilling wastes just prior to land application on agricultural lands at 34 sites across the U.S. Twenty-two analytical methods were used to determine potential contaminant exposures profiles for 452 organic and 114 inorganic chemicals, nine microbial groups, estrogenicity, and cytotoxicity. Analytical results document unique and substantial chemical, microbial, and toxicity profiles for these land-applied wastes. Of the three waste byproducts, biosolids contained the greatest concentrations of household chemicals, pesticides, pharmaceuticals, per-/polyfluoroalkyl substances, calcium, and phosphorus. Livestock waste contained the greatest concentrations of total and leachable dissolved organic carbon, biogenic hormones, mycotoxins, plant estrogens, total inorganic nitrogen, and potassium. Drilling waste contained the greatest concentrations of BTEX compounds (benzene, toluene, ethylbenzene, and xylenes), polycyclic aromatic hydrocarbons, rare-earth elements, barium, strontium, and uranium–thorium series radioisotopes. Biosolid and livestock wastes had greater culturable heterotrophic bacteria, halophilic bacteria, Escherichia coli (E. coli), enterococci, and staphylococci concentrations, and greater microbial diversity than drilling waste. Bioassay analyses indicated that exposure to contaminants in livestock wastes and biosolids could result in estrogenic effects, whereas exposure to contaminants in drilling waste could result in cytotoxic effects. Our study documents that current reuse/disposal practices for biosolid, livestock, and drilling wastes on agricultural lands could provide a potential pathway for the redistribution of unique and complex contaminant mixtures into the environment that have bioactive, endocrine disrupting, and carcinogenic characteristics. Results of this study provide a snapshot of chemical compositions and concentrations that can be used to inform the development of best-management practices to help maximize beneficial reuse of these wastes and minimize risk to the environment and human health.

To improve our understanding of hydrothermal activity on the Yellowstone Plateau volcanic field, we collected and analyzed a large data set of δ²H, δ¹⁸O, and the ³H concentrations of circum‐neutral and alkaline waters. We find that (a) hot springs are fed by recharge throughout the volcanic plateau, likely focused through fractured, permeable tuff units. Previous work had stressed the need for light δ²H water recharge restricted to the northern part of the plateau or recharge during past cold periods. However, new data from the Y‐7 drill hole suggests that recharge is not restricted to a certain area or a cold period. (b) δ¹⁸O values of thermal waters in the geyser basins are shifted from the global meteoric water line by temperature‐dependent water‐rock reactions with higher subsurface temperatures resulting in a greater shift. (c) Large temporal variations in the isotopic composition of meteoric water recharge and small temporal variability in the isotopic composition of hot spring discharge implies that the volume of groundwater in, and around the Yellowstone caldera is substantially larger than the volume of annual water recharge. (d) Hot springs discharged through different rhyolitic units correlate with identifiable differences in δ²H and δ¹⁸O compositions, ³H concentrations, and water chemistry that imply equilibration at different temperatures and travel along different flow paths. (e) Based on measured ³H concentrations, we calculate that hot spring waters in the central part of the geyser basins mostly contain <2% post‐1950 meteoric water, whereas waters discharged at the basin margins contain larger fractions of post‐1950s meteoric water.

Tapwater (TW) safety and sustainability are priorities in the United States. Per/polyfluoroalkyl substance(s) (PFAS) contamination is a growing public-health concern due to prolific use, widespread TW exposures, and mounting human-health concerns. Historically-rural, actively-urbanizing communities that rely on surficial-aquifer private wells incur elevated risks of unrecognized TW exposures, including PFAS, due to limited private-well monitoring and contaminant-source proliferation in urbanizing landscapes. Here, a broad-analytical-scope TW-assessment was conducted in a hydrologically-vulnerable, Mississippi River alluvial-island community, where PFAS contamination of the shallow-alluvial drinking-water aquifer has been documented, but more comprehensive contaminant characterization to inform decision-making is currently lacking. In 2021, we analyzed 510 organics, 34 inorganics, and 3 microbial groups in 11 residential and community locations to assess (1) TW risks beyond recognized PFAS issues, (2) day-to-day and year-to-year risk variability, and (3) suitability of the underlying sandstone aquifer as an alternative source to mitigate TW-PFAS exposures. Seventy-six organics and 25 inorganics were detected. Potential human-health risks of detected TW exposures were explored based on cumulative benchmark-based toxicity quotients (∑_TQ). Elevated risks (∑_TQ ≥ 1) from organic and inorganic contaminants were observed in all alluvial-aquifer-sourced synoptic samples but not in sandstone-aquifer-sourced samples. Repeated sampling at 3 sites over 52–55 h indicated limited variability in risk over the short-term. Comparable PFAS-specific ∑_TQ for spatial-synoptic, short-term (3 days) temporal, and long-term (3 years quarterly) temporal samples indicated that synoptic results provided useful insight into the risks of TW-PFAS exposures at French Island over the long-term. No PFAS detections in sandstone-aquifer-sourced samples over a 3 year period indicated no PFAS-associated risk and supported the sandstone aquifer as an alternative drinking-water source to mitigate community TW-PFAS exposures. This study illustrated the importance of expanded contaminant monitoring of private-well TW, beyond known concerns (in this case, PFAS), to reduce the risks of a range of unrecognized contaminant exposures.

Stream discharge is often determined by wading the stream and measuring the point velocity at fixed widths and depths. However, there are conditions when wading measurements are not safe or the measurements are poor because of high turbulence, rocky streambeds, non‐standard velocity distributions, shallow or sheet flow, aquatic plants, or inaccessibility due to ice. Under these conditions, it is often preferable to determine discharge using salt slug addition and downstream measurement of salt concentration with time. A new method for determining stream discharge using specific conductance as a surrogate for salt concentrations is presented. The method adapts an approach that accurately calculates the specific conductance by utilizing ionic molal conductivities to determine the concentration of salt. The method was applied at four mountainous stream sites where a total of twenty‐nine slug‐additions were performed. The discharge determined from the new method was compared to four alternative methods including discharge from continuous injection, slug addition with discrete sample calibration, wading measurements with velocity measurement, and a stream gage. The discharge ranged from 21.5 to 778 L/s and the median difference between the new method and the traditional methods was −0.01%. Additionally, the p‐value (0.75) determined from a paired t ‐test indicates that there is no significant difference between the discharge determined from the new and alternative discharge methods. The primary advantage of the new method is that it obviates the need to collect and analyze discrete samples to accurately quantify the specific conductance‐salt surrogate relationship, allowing for rapid, low‐cost determination of discharge.

The report focuses on the screening of previously published concentration data associated with 12 elements of concern (aluminum, arsenic, cadmium, chromium, copper, iron, mercury, manganese, lead, selenium, uranium, and zinc) measured in stream surface waters of three hydrologic basins (Delaware River Basin, Illinois River Basin, and the Upper Colorado River Basin). The purpose of this analysis is to determine what subsets of the original dataset (containing more than 1,500,000 observations) may be most suitable for each of two types of modeling efforts. The first type of modeling envisions a machine learning approach to determine which geospatial attributes are most significant in describing the spatial distribution of elemental concentrations within a basin. The second type of modeling envisions a stepwise regression approach to develop multivariable models that can be used to determine high resolution time-series estimates of elemental concentrations or loads at discrete U.S. Geological Survey real-time stream surface water sites. These site-specific temporal models are based on continuous measurements of available discharge and (or) in situ sensor data (temperature, pH, turbidity, dissolved oxygen, specific conductance, and (or) fluorescent dissolved organic matter) as the explanatory variables. The data screening for both model types considered historical trends in analytical methods and detection quantitation limits, the extent of censored data, data density, and environmental relevance with respect to three U.S. Environmental Protection Agency water quality thresholds (drinking water guidelines, human health criteria, and aquatic life criteria). The result of this analysis was the production of a final list of potential models deemed suitable for further development based upon the data exclusion (or inclusion) scheme developed herein for each model type. In both cases, the final models included mostly the three crustal elements (iron, manganese, and aluminum) that are found at comparatively high concentrations in surface water, whereas most of the more pernicious elements were excluded from the final model lists owing to various data limitations. The one exception to this was arsenic, for which the existing data were sufficient at three U.S. Geological Survey real-time sites for potential further development of time-series models.

Natural radiogenic isotopes (primarily ⁸⁷Sr/⁸⁶Sr) from hot springs in the Upper Geyser Basin of the Yellowstone Plateau volcanic field and associated rocks were used to evaluate groundwater flow patterns, water‐rock reactions, and the extent of mixing between various groundwater sources. Thermal waters have very low uranium concentrations and ²³⁴U/²³⁸U activity ratios near 1.0, which limit their utility as tracers in this reducing setting. Thermal waters have higher Sr concentrations (87Sr/⁸⁶Sr values that vary both temporally at individual discharge sites and between adjacent springs, indicating that conduits tap different subsurface reservoirs to varying degrees. Sr from local rhyolites have ⁸⁷Sr/⁸⁶Sr compositions that bound the range of values observed in groundwater throughout the basin. Non‐boiling springs on the west flank of the basin discharge water with low ⁸⁷Sr/⁸⁶Sr consistent with flow through young volcanic rocks exposed at the surface. Boiling springs in the central basin have higher ⁸⁷Sr/⁸⁶Sr values reflecting interactions with older, more radiogenic volcanic rocks. Variability in upwelling thermal waters requires mixing with a low ⁸⁷Sr/⁸⁶Sr component derived from young lava or glacial sediments, or more likely, from deeper sources of hot groundwater circulating through buried Lava Creek Tuff having intermediate ⁸⁷Sr/⁸⁶Sr. Isotope data constrain basin‐wide output of thermal water to 110–140 kg·s⁻¹. Results underscore the utility of radiogenic Sr isotopes as valuable tracers of hydrothermal flow patterns and improve the understanding of temperature‐dependent water‐rock reactions in one of the largest continental hydrothermal systems on Earth.

Less than a year after the 2018 Kīlauea caldera collapse and eruption, water appeared in newly deepened Halemaʻumaʻu crater. The lake—unprecedented in the written record—grew to a depth of ∼50 m before lava from the December 2020 eruption boiled it away. Surface water heightened concerns of potential phreatic or phreatomagmatic explosions but also offered a new means of possibly identifying eruption precursors. The U.S. Geological Survey Hawaiian Volcano Observatory (HVO) monitored the lake via direct visual observation, webcams, thermal imaging, colorimetry, and laser rangefinders. HVO also employed uncrewed aircraft systems to sample the water and measure near‐lake gas composition. The lake's δD and δ¹⁸O indicate a groundwater source with substantial evaporation. The initial sample had a salinity (total dissolved solids concentration) of 71,000 mg/L and was rich in sulfate (∼53,000 mg/L), iron (∼500 mg/L), and magnesium (∼10,000 mg/L). Subsequent samples were slightly more dilute. The water's pH (∼4), δ³⁴S (+4.3‰), and surface temperatures (up to 85°C) suggest, rather than significant scrubbing of magmatic volatiles, leaching of basalt and reactions with sulfate minerals resulted in high concentrations of sulfate and other solutes. Thermodynamic modeling and precipitate mineralogy indicate that water composition was controlled by iron oxidation and sulfate dissolution. Although the lake exhibited no detectable precursors before the next eruption, and phreatic or phreatomagmatic explosions did not materialize, our multi‐parameter approach to monitoring yielded an enhanced understanding of the hydrologic, geologic, and magmatic conditions that led to the formation of the unique and short‐lived lake.