Global Groundwater Solute Composition and Concentrations.

Informed analysis of policies related to food security, global climate change, wetland ecology, environmental nutrient flux, element cycling, groundwater weathering, continental denudation, human health, and others depends to a large extent on quantitative estimates of solute mass fluxes into and out of all global element pools including the enigmatic global aquifer systems. Herein for the first time, we proffer the mean global solute concentration of all major and selected minor and trace solutes in the active groundwater that represents 99% of liquid fresh water on Earth. Concentrations in this significant element pool have yielded to a geospatial machine learning kNN-nearest neighbors' algorithm with numerous geospatial predictors utilizing a large new lithology/climate/aquifer age/elevation based solute database. The predicted concentrations are consistent with traditional solute ratios, concentrations, and thermodynamic saturation indices.

Volatile organic compounds in groundwater used for public supply across the United States: Occurrence, explanatory factors, and human-health context.

This systematic assessment of occurrence for 85 volatile organic compounds (VOCs) in raw (untreated) groundwater used for public supply across the United States (U.S.), which includes 43 compounds not previously monitored by national studies, relates VOC occurrence to explanatory factors and assesses VOC detections in a human-health context. Samples were collected in 2013 through 2019 from 1537 public-supply wells in aquifers representing 78% of the volume pumped for public drinking-water supply. Laboratory detection limits for VOCs generally were less than 0.1 µg/L. Detections were reported for 36% of the sampled principal-aquifer area (38% of sampled wells) and were most common in wells in shallow, unconfined aquifers in urban areas that produce high proportions of modern-age and oxic groundwater. The disinfection by-product trichloromethane (chloroform) was the most commonly detected VOC associated primarily with anthropogenic sources (24% of the sampled area, 25% of sampled wells), followed by the gasoline oxygenate methyl tert-butyl ether (8.4% of area, 11% of wells). Carbon disulfide (12% of area, 14% of wells) was examined separately because of likely substantial contributions from natural sources. Newly monitored VOCs were each detected in <1% of the sampled area. Although detections of 1,4-dioxane in this first national study of its occurrence in raw groundwater were rare, measured concentrations exceeded the most stringent (non-enforceable) human-health benchmark in 0.5% of the sampled area (9 wells). Two wells had exceedances of enforceable benchmarks for tetrachloroethylene and trichloroethylene, and 50 wells total (representing 2.0% of the sampled area, 3.3% of sampled wells) had combined VOC concentrations exceeding 10% of benchmarks of any type. Compared with previous national findings, this study reports lower rates of VOC detection, but confirms widespread anthropogenic influence on groundwater used for public supply, with relatively few concentrations of individual VOCs or mixtures that approach or exceed human-health benchmarks.

Perfluoroalkyl and Polyfluoroalkyl Substances in Groundwater Used as a Source of Drinking Water in the Eastern United States.

In 2019, 254 samples were collected from five aquifer systems to evaluate perfluoroalkyl and polyfluoroalkyl substance (PFAS) occurrence in groundwater used as a source of drinking water in the eastern United States. The samples were analyzed for 24 PFAS, major ions, nutrients, trace elements, dissolved organic carbon (DOC), volatile organic compounds (VOCs), pharmaceuticals, and tritium. Fourteen of the 24 PFAS were detected in groundwater, with 60 and 20% of public-supply and domestic wells, respectively, containing at least one PFAS detection. Concentrations of tritium, chloride, sulfate, DOC, and manganese + iron; percent urban land use within 500 m of the wells; and VOC and pharmaceutical detection frequencies were significantly higher in samples containing PFAS detections than in samples with no detections. Boosted regression tree models that consider 57 chemical and land-use variables show that tritium concentration, distance to the nearest fire-training area, percentage of urban land use, and DOC and VOC concentrations are the top five predictors of PFAS detections, consistent with the hydrologic position, geochemistry, and land use being important controls on PFAS occurrence in groundwater. Model results indicate that it may be possible to predict PFAS detections in groundwater using existing data sources.

Lithium in groundwater used for drinking-water supply in the United States.

Lithium concentrations in untreated groundwater from 1464 public-supply wells and 1676 domestic-supply wells distributed across 33 principal aquifers in the United States were evaluated for spatial variations and possible explanatory factors. Concentrations nationwide ranged from <1 to 396 µg/L (median of 8.1) for public supply wells and <1 to 1700 µg/L (median of 6 µg/L) for domestic supply wells. For context, lithium concentrations were compared to a Health Based Screening Level (HBSL, 10 µg/L) and a drinking-water only threshold (60 µg/L). These thresholds were exceeded in 45% and 9% of samples from public-supply wells and in 37% and 6% from domestic-supply wells, respectively. However, exceedances and median concentrations ranged broadly across geographic regions and principal aquifers. Concentrations were highest in arid regions and older groundwater, particularly in unconsolidated clastic aquifers and sandstones, and lowest in carbonate-rock aquifers, consistent with differences in lithium abundance among major lithologies and rock weathering extent. The median concentration for public-supply wells in the unconsolidated clastic High Plains aquifer (central United States) was 24.6 µg/L; 24% of the wells exceeded the drinking-water only threshold and 86% exceeded the HBSL. Other unconsolidated clastic aquifers in the arid West had exceedance rates comparable to the High Plains aquifer, whereas no public supply wells in the Biscayne aquifer (southern Florida) exceeded either threshold, and the highest concentration in that aquifer was 2.6 µg/L. Multiple lines of evidence indicate natural sources for the lithium concentrations; however, anthropogenic sources may be important in the future because of the rapid increase of lithium battery use and subsequent disposal. Geochemical models demonstrate that extensive evaporation, mineral dissolution, cation exchange, and mixing with geothermal waters or brines may account for the observed lithium and associated constituent concentrations, with the latter two processes as major contributing factors.

Pesticides and Pesticide Degradates in Groundwater Used for Public Supply across the United States: Occurrence and Human-Health Context.

This is the first assessment of groundwater from public-supply wells across the United States to analyze for >100 pesticide degradates and to provide human-health context for degradates without benchmarks. Samples from 1204 wells in aquifers representing 70% of the volume pumped for drinking supply were analyzed for 109 pesticides (active ingredients) and 116 degradates. Among the 41% of wells where pesticide compounds were detected, nearly two-thirds contained compound mixtures and three-quarters contained degradates. Atrazine, hexazinone, prometon, tebuthiuron, four atrazine degradates, and one metolachlor degradate were each detected in >5% of wells. Detection frequencies were largest for aquifers with more shallow, unconfined wells producing modern-age groundwater. To screen for potential human-health concerns, benchmark quotients (BQs) were calculated by dividing concentrations by the human-health benchmark, when available. For degradates without benchmarks, estimated values (estimated benchmark quotients (BQE)) were first calculated by assuming equimolar toxicity to the most toxic parent; final analysis excluded degradates with likely overestimated toxicity. Six pesticide compounds and 1.6% of wells had concentrations approaching levels of potential concern (individual or summed BQ or BQE values >0.1), and none exceeded these levels (values >1). Therefore, although pesticide compounds occurred frequently, concentrations were low, even accounting for mixtures and degradates without benchmarks.

The relation of geogenic contaminants to groundwater age, aquifer hydrologic position, water type, and redox conditions in Atlantic and Gulf Coastal Plain aquifers, eastern and south-central USA.

Groundwater age distributions developed from carbon-14 (14C), tritium (3H), and helium-4 (4He) concentrations, along with aquifer hydrologic position, water type, and redox conditions, were compared to geogenic contaminants of concern (GCOC) from 252 public-supply wells in six Atlantic and Gulf Coastal Plain unconsolidated-sediment aquifers. Concentrations of one or more GCOCs in 168 (67%) wells exceeded MCLs (maximum contaminant levels), SMCLs (secondary MCLs), or HBSLs (health-based screening levels). Human-health benchmark thresholds (MCLs or HBSLs) were exceeded in 31 (12%) wells, and included 0.8% for fluoride (F), 2.4% for arsenic (As), 4% for lead-210 (210Pb), and 6.7% for polonium-210 (210Po). Values of pH increase with age and were outside the SMCL in 31% of wells (23% < 6.5 and 7.5% > 8.5, SMCL). Among GCOCs with concentrations that increased significantly with groundwater age, the frequency of sentry threshold exceedances (i.e., one-half of MCL, SMCL, or HBSL) included 40% for dissolved solids (DS), 12% for chloride (Cl), 3.6% for F, 4.4% for As, and 9.5% for 210Po. Iron (Fe) concentrations did not correlate with groundwater age, but exceeded sentry thresholds in 29% of wells. Groundwater age, water types, redox, pH, and GCOCs varied because of unique hydrogeologic features of the aquifers (recharge locations and geometry). As expected, primarily confined aquifers had young, oxic, low to near-neutral pH water near the outcrop (recharge area), and older, reduced, high pH water deeper and farther along flow paths. However, unique aquifer hydrogeologic conditions, such as multiple-recharge zones produced anomalous patterns of young and old groundwater at varying depths and locations along flow paths. Evidence for this variability is seen in disequilibrium patterns in the progression of the chemical evolution of groundwater with hydrologic position. When hydrogeologic differences are considered, groundwater age combined with hydrologic-position data, can provide a strong basis for inferring potential occurrence of GCOCs.

Fluoride occurrence in United States groundwater.

Data from 38,105 wells were used to characterize fluoride (F) occurrence in untreated United States (U.S.) groundwater. For domestic wells (n = 11,032), water from which is generally not purposely fluoridated or monitored for quality, 10.9% of the samples have F concentrations >0.7 mg/L (U.S. Public Health Service recommended optimal F concentration in drinking water for preventing tooth decay) (87% are <0.7 mg/L); 2.6% have F > 2 mg/L (EPA Secondary Maximum Contaminant Level, SMCL); and 0.6% have F > 4 mg/L (EPA MCL). The data indicate the biggest concern with F in domestic wells at the national scale could be one of under consumption of F with respect to the oral-health benchmark (0.7 mg/L). Elevated F concentrations relative to the SMCL and MCL are regionally important, particularly in the western U.S. Statistical comparisons of potentially important controlling factors in four F-concentration categories (<0.1-0.7 mg/L; >0.7-2 mg/L; >2-4 mg/L; >4 mg/L) at the national scale indicate the highest F-concentration category is associated with groundwater that has significantly greater pH values, TDS and alkalinity concentrations, and well depths, and lower Ca/Na ratios and mean annual precipitation, than the lowest F-concentration category. The relative importance of the controlling factors appears to be regionally variable. Three case studies illustrate the spatial variability in controlling factors using groundwater-age (groundwater residence time), water-isotope (evaporative concentration), and water-temperature (geothermal processes) data. Populations potentially served by domestic wells with F concentrations <0.7, >0.7, >2, and >4 mg/L are estimated to be ~28,200,000, ~3,110,000; ~522,000; and ~172,000 people, respectively, in 40 principal aquifers with at least 25 F analyses per aquifer.

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

Groundwater geochemistry, redox process classification, high-frequency physicochemical and hydrologic measurements, and climate data were analyzed to identify controls on arsenic (As) concentration changes. Groundwater was monitored in two public-supply wells (one glacial aquifer and one bedrock aquifer), and one bedrock-aquifer domestic well in New Hampshire, USA, from 2014 to 2018 to identify time scales of and controls on As concentration changes. Concentrations of As and other geochemical constituents were measured bimonthly. Specific conductance (SC), pH, dissolved oxygen, and pumping rate/water level were measured at high frequency (every 5 to 15 min). Median (and 95% confidence interval) As concentrations at the three wells were 4.1 (3.7-4.6), 18.9 (17.2-23.6), and 37.5 (30.4-42.9) µg/L. Arsenic variability in each of the three wells, in relative standard deviation, ranged from 9 to 12%. Median quarterly As concentrations were highest in all wells in the spring. The bedrock-aquifer public-supply well As concentration increased over the period of study while pumping rate decreased. In the public-supply wells, As variability was correlated with SC and pH, and As species were related to SC, pH, pumping, precipitation, and changes in redox process. Specific conductance also had a seasonal pattern in the two public-supply wells and was correlated with Na and Cl. Excess Na in water samples suggests possible ion exchange with dissolved Ca, creating more capacity to dissolve CaCO3 from calcareous rocks, which can increase pH and in turn, As concentrations in wells. High-frequency monitoring data are cost effective to collect, which could be advantageous in other parts of the United States and in the many parts of the world where glacial aquifers are in direct contact with other water supply aquifers or where water from different aquifers have potential to mix.

Using Age Tracers and Decadal Sampling to Discern Trends in Nitrate, Arsenic, and Uranium in Groundwater Beneath Irrigated Cropland.

Repeat sampling and age tracers were used to examine trends in nitrate, arsenic, and uranium concentrations in groundwater beneath irrigated cropland. Much higher nitrate concentrations in shallow modern groundwater were observed at both the Columbia Plateau and High Plains sites (median values of 10.2 and 15.4 mg/L as N, respectively) than in groundwater that recharged prior to the onset of intensive irrigation (median values of <1 and <4 mg/L as N, respectively). Repeat sampling of these well networks indicates that high nitrate concentrations in modern, shallow groundwater have been sustained for decades, posing a future risk to older, deeper groundwater used for drinking water. In fact, nitrate concentrations in older modern water (30-60 years since recharge) at the High Plains site have increased in the past decade. Groundwater irrigated areas in the Columbia Plateau tend to have higher nitrate concentrations in groundwater than surface water irrigated areas, suggesting repeated dissolution of land applied fertilizer during recirculation may be an important factor causing high nitrate concentrations in groundwater. Mobilization of uranium and arsenic by land surface activities is suggested by the higher concentrations of these constituents in modern, shallow groundwater than in older, deeper groundwater at the Columbia Plateau site. Bicarbonate concentrations in modern groundwater are positively correlated with uranium (r = 0.72, p < 0.01), suggesting bicarbonate may mobilize uranium in this system. A positive correlation between arsenic and phosphorus concentrations in modern groundwater (r = 0.55, p < 0.01) suggests that phosphate from fertilizer outcompetes arsenate for sorption sites, mobilizing sorbed arsenic derived from past pesticide use or other sources.

Hydrocarbons in Upland Groundwater, Marcellus Shale Region, Northeastern Pennsylvania and Southern New York, U.S.A.

Water samples from 50 domestic wells located <1 km (proximal) and >1 km (distal) from shale-gas wells in upland areas of the Marcellus Shale region were analyzed for chemical, isotopic, and groundwater-age tracers. Uplands were targeted because natural mixing with brine and hydrocarbons from deep formations is less common in those areas compared to valleys. CH4-isotope, predrill CH4-concentration, and other data indicate that one proximal sample (5% of proximal samples) contains thermogenic CH4 (2.6 mg/L) from a relatively shallow source (Catskill/Lock Haven Formations) that appears to have been mobilized by shale-gas production activities. Another proximal sample contains five other volatile hydrocarbons (0.03-0.4 µg/L), including benzene, more hydrocarbons than in any other sample. Modeled groundwater-age distributions, calibrated to 3H, SF6, and 14C concentrations, indicate that water in that sample recharged prior to shale-gas development, suggesting that land-surface releases associated with shale-gas production were not the source of those hydrocarbons, although subsurface leakage from a nearby gas well directly into the groundwater cannot be ruled out. Age distributions in the samples span ∼20 to >10000 years and have implications for relating occurrences of hydrocarbons in groundwater to land-surface releases associated with recent shale-gas production and for the time required to flush contaminants from the system.

Using groundwater age distributions to understand changes in methyl tert-butyl ether (MtBE) concentrations in ambient groundwater, northeastern United States.

Temporal changes in methyl tert-butyl ether (MtBE) concentrations in groundwater were evaluated in the northeastern United States, an area of the nation with widespread low-level detections of MtBE based on a national survey of wells selected to represent ambient conditions. MtBE use in the U.S. peaked in 1999 and was largely discontinued by 2007. Six well networks, each representing specific areas and well types (monitoring or supply wells), were each sampled at 10year intervals between 1996 and 2012. Concentrations were decreasing or unchanged in most wells as of 2012, with the exception of a small number of wells where concentrations continue to increase. Statistically significant increasing concentrations were found in one network sampled for the second time shortly after the peak of MtBE use, and decreasing concentrations were found in two networks sampled for the second time about 10years after the peak of MtBE use. Simulated concentrations from convolutions of estimates for concentrations of MtBE in recharge water with age distributions from environmental tracer data correctly predicted the direction of MtBE concentration changes in about 65% of individual wells. The best matches between simulated and observed concentrations were found when simulating recharge concentrations that followed the pattern of national MtBE use. Some observations were matched better when recharge was modeled as a plume moving past the well from a spill at one point in time. Modeling and sample results showed that wells with young median ages and narrow age distributions responded more quickly to changes in the contaminant source than wells with older median ages and broad age distributions. Well depth and aquifer type affect these responses. Regardless of the timing of decontamination, all of these aquifers show high susceptibility for contamination by a highly soluble, persistent constituent.

Holding-time and method comparisons for the analysis of fecal-indicator bacteria in groundwater.

As part of the US Geological Survey National Water-Quality Assessment Program, groundwater samples from domestic- and public-supply wells were collected and analyzed for fecal-indicator bacteria. A holding time comparison for total coliforms, Escherichia coli, and enterococci was done by analyzing samples within 8 h using presence/absence methods and within 18-30 h using quantitative methods. The data indicate that results obtained within 18-30 h were not significantly different from those obtained within 8 h for total coliforms and enterococci, by Colilert® and Enterolert® methods (IDEXX Laboratories Inc., Westbrook, ME), respectively. Quantitative laboratory methods for samples analyzed within 18-30 h showed a statistically significant higher detection frequency when compared to presence/absence methods done within 8 h for the following methods, E. coli by Colilert and enterococci by membrane filtration on mEI agar. Additionally, a comparison of methods for the enumeration of enterococci was done. Using non-parametric statistical analyses, results from the two methods were statistically different. In this study, the membrane filtration method on mEI agar was more sensitive, resulted in more detections of enterococci, and results were easier to interpret than with the quantitative Enterolert method. The quantitative Enterolert method produced varying levels of fluorescence, which required additional verification steps to eliminate false-positive results. It may be more advantageous to analyze untreated groundwater for enterococci using the membrane filtration method on mEI agar.

Factors affecting temporal variability of arsenic in groundwater used for drinking water supply in the United States.

The occurrence of arsenic in groundwater is a recognized environmental hazard with worldwide importance and much effort has been focused on surveying and predicting where arsenic occurs. Temporal variability is one aspect of this environmental hazard that has until recently received less attention than other aspects. For this study, we analyzed 1245 wells with two samples per well. We suggest that temporal variability, often reported as affecting very few wells, is perhaps a larger issue than it appears and has been overshadowed by datasets with large numbers of non-detect data. Although there was only a slight difference in arsenic concentration variability among samples from public and private wells (p=0.0452), the range of variability was larger for public than for private wells. Further, we relate the variability we see to geochemical factors-primarily variability in redox-but also variability in major-ion chemistry. We also show that in New England there is a weak but statistically significant indication that seasonality may have an effect on concentrations, whereby concentrations in the first two quarters of the year (January-June) are significantly lower than in the second two quarters (July-December) (p<0.0001). In the Central Valley of California, the relation of arsenic concentration to season was not statistically significant (p=0.4169). In New England, these changes appear to follow groundwater levels. It is possible that this difference in arsenic concentrations is related to groundwater level changes, pumping stresses, evapotranspiration effects, or perhaps mixing of more oxidizing, lower pH recharge water in wetter months. Focusing on the understanding the geochemical conditions in aquifers where arsenic concentrations are concerns and causes of geochemical changes in the groundwater environment may lead to a better understanding of where and by how much arsenic will vary over time.

Pesticides in groundwater of the United States: decadal-scale changes, 1993-2011.

The national occurrence of 83 pesticide compounds in groundwater of the United States and decadal-scale changes in concentrations for 35 compounds were assessed for the 20-year period from 1993-2011. Samples were collected from 1271 wells in 58 nationally distributed well networks. Networks consisted of shallow (mostly monitoring) wells in agricultural and urban land-use areas and deeper (mostly domestic and public supply) wells in major aquifers in mixed land-use areas. Wells were sampled once during 1993-2001 and once during 2002-2011. Pesticides were frequently detected (53% of all samples), but concentrations seldom exceeded human-health benchmarks (1.8% of all samples). The five most frequently detected pesticide compounds-atrazine, deethylatrazine, simazine, metolachlor, and prometon-each had statistically significant (p < 0.1) changes in concentrations between decades in one or more categories of well networks nationally aggregated by land use. For agricultural networks, concentrations of atrazine, metolachlor, and prometon decreased from the first decade to the second decade. For urban networks, deethylatrazine concentrations increased and prometon concentrations decreased. For major aquifers, concentrations of deethylatrazine and simazine increased. The directions of concentration changes for individual well networks generally were consistent with changes determined from nationally aggregated data. Altogether, 36 of the 58 individual well networks had statistically significant changes in concentrations of one or more pesticides between decades, with the majority of changes attributed to the five most frequently detected pesticide compounds. The magnitudes of median decadal-scale concentration changes were small-ranging from -0.09 to 0.03 µg/L-and were 35- to 230,000-fold less than human-health benchmarks.

Influence of fracture anisotropy on ground water ages and chemistry, Valley and Ridge province, Pennsylvania.

Model ground water ages based on chlorofluorocarbons (CFCs) and tritium/helium-3 (3H/3He) data were obtained from two arrays of nested piezometers located on the north limb of an anticline in fractured sedimentary rocks in the Valley and Ridge geologic province of Pennsylvania. The fracture geometry of the gently east plunging fold is very regular and consists predominately of south dipping to subhorizontal to north dipping bedding-plane parting and east striking, steeply dipping axial-plane spaced cleavage. In the area of the piezometer arrays, which trend north-south on the north limb of the fold, north dipping bedding-plane parting is a more dominant fracture set than is steeply south dipping axial-plane cleavage. The dating of ground water from the piezometer arrays reveals that ground water traveling along paths parallel to the dip direction of bedding-plane parting has younger 3H/3He and CFC model ages, or a greater component of young water, than does ground water traveling along paths opposite to the dip direction. In predominantly unmixed samples there is a strong positive correlation between age of the young fraction of water and dissolved sodium concentration. The travel times inferred from the model ages are significantly longer than those previously calculated by a ground water flow model, which assumed isotropically fractured layers parallel to topography. A revised model factors in the directional anisotropy to produce longer travel times. Ground water travel times in the watershed therefore appear to be more influenced by anisotropic fracture geometry than previously realized. This could have significant implications for ground water models in other areas underlain by similarly tilted or folded sedimentary rock, such as elsewhere in the Valley and Ridge or the early Mesozoic basins.