Laura M. Bexfield

Per- and polyfluoroalkyl substances (PFAS), known colloquially as “forever chemicals,” have been associated with adverse human health effects and have contaminated drinking water supplies across the United States owing to their long-term and widespread use. People in the United States may unknowingly be drinking water that contains PFAS because of a lack of systematic analysis, particularly in domestic water supplies. We present an extreme gradient–boosting model for predicting the occurrence of PFAS in groundwater at the depths of drinking water supply for the conterminous United States. Our model results indicate that 71 million to 95 million people in the conterminous United States potentially rely on groundwater with detectable concentrations of PFAS for their drinking water supplies before any treatment.

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.

Groundwater-quality environmental data were collected from 983 wells as part of the National Water-Quality Assessment Project of the U.S. Geological Survey National Water Quality Program and are included in this report. The data were collected from six types of well networks: principal aquifer study networks, which are used to assess the quality of groundwater used for public water supply; land-use study networks, which are used to assess land-use effects on shallow groundwater quality; major aquifer study networks, which are used to assess the quality of groundwater used for domestic supply; enhanced trends networks, which are used to evaluate the time scales during which groundwater quality changes; vertical flow-path study networks, which are used to evaluate changes in groundwater quality from shallow to deeper depths; and modeling support studies, which are used to provide data to support groundwater modeling. Groundwater samples were analyzed for many water-quality indicators and constituents, including major ions, nutrients, trace elements, volatile organic compounds, pesticides, radionuclides, microbiological indicators, and some constituents of special interest (arsenic speciation, hexavalent chromium [chromium (VI)], and perchlorate). These groundwater-quality data, along with data from quality-control samples, are tabulated in this report and in an associated data release. Data for microbiological indicators for samples collected in 2016 are included in the companion data release.

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.

First posted December 2, 2020 Director, New England Water Science Center U.S. Geological Survey 10 Bearfoot Road Northborough, MA 01532 Water samples from 122 sites in the U.S. Geological Survey National Water Quality Network were collected in 2013–17 to document ambient water-quality conditions in surface water of the United States and to determine status and trends of loads and concentrations for nutrients, contaminants, and sediment to estuaries and streams. Quality-control (QC) samples collected in the field with environmental samples were combined with QC samples from laboratory processing to provide information and documentation about the quality of the environmental data. Quality assurance for inorganic and organic compounds assessed in the National Water Quality Network includes collection of field blanks to determine contamination bias and field replicates to determine variability bias. No contamination bias was found for 6 of the 13 nutrient compounds analyzed, and some potential contamination bias for some years was found for the other 7 nutrient compounds. Contamination bias was not found for carbon compounds or ultraviolet-absorbance measurements and was not assessed for sediment. All major ions and trace elements except potassium and lithium showed moderate contamination bias for at least 1 water year; generally, this bias was not at environmentally relevant concentrations. All compounds in the nutrient, carbon, and sediment group and in the major ions and trace elements group had low variability both in detection frequency and in concentration. Exceptions to this low variability were total particulate inorganic carbon and sediment for 2015, both of which are particulate substances with intrinsically high sampling variability. The risk of contamination bias for pesticides in National Water Quality Network samples was low, as indicated by very few detections in field blanks. Sixteen pesticide compounds showed potential contamination bias based on unexpected detections in third-party blind spikes (false-positive results for compounds that are not included in the spike mixture of a sample, where the identity as a QC sample is unknown to the analyst), and 47 different compounds (out of 225 pesticide compounds) showed potential contamination bias from laboratory blanks. However, when timing and relative magnitudes of detections in blank samples, environmental samples, and benchmark concentrations are considered, most of this potential contamination is not relevant to interpretation of published pesticide results. Overall variability in detection frequency for pesticides from field replicates was low or moderate. Also based on field replicates, 55 pesticides had overall high variability in concentrations for at least 1 water year, although these assessments likely overestimate high variability. At least 1 QC issue was found for 87 pesticides; however, most of the QC issues had no or little effect on the interpretation of environmental results because the U.S. Geological Survey National Water Quality Laboratory addressed the QC issue before publishing the environmental results, environmental results were almost entirely nondetections, concentrations of environmental results were higher than potential contamination bias, or benchmark concentrations were orders of magnitude higher than all environmental results. Eight compounds affected by two QC issues had a benchmark less than 100 nanograms per liter and warranted careful consideration of timing and magnitude of QC results in relation to surface-water results before interpretive use.

The National Water-Quality Assessment (NAWQA) Project of the U.S. Geological Survey (USGS) submitted nearly 1,900 samples collected from groundwater sites across the United States in 2013–18 for analysis of 225 pesticide compounds (pesticides and pesticide degradates, hereafter referred to as “pesticides”) by USGS National Water Quality Laboratory schedule 2437 (S2437). For the associated NAWQA study of pesticide occurrence and concentration in groundwater, and for other studies using pesticide results determined by S2437, it is necessary to assess the ability of reported results to meet data-quality requirements that will allow study objectives to be achieved. This assessment of the quality of S2437 results reported in 2013–18 examined data from field and laboratory quality-control samples, along with third-party performance assessment samples, to estimate bias and variability and to identify their potential sources, with an emphasis on implications for the interpretation of pesticide data for groundwater. Results indicate that measurements produced by the S2437 method for most pesticides have bias and variability that would be considered acceptable for many interpretative studies, which could therefore use the results without qualification or censoring. However, the reported data for a subset of pesticides have the potential for unacceptable contamination bias, high or low recovery bias, or high variability as a consequence of method performance and (or) nonlaboratory factors that could preclude their use for certain common objectives or could necessitate adjustment or qualification to meet those objectives.Based on data for laboratory blanks, censoring of some detections for a subset of pesticides reported by the laboratory in environmental samples might be necessary or desirable to avoid an unacceptably high likelihood of a false-positive result caused by laboratory contamination. The 90-percent upper confidence limit for the 95th percentile of laboratory blank concentration equals or exceeds the minimum reported groundwater concentration in at least 1 water year for 28 pesticides. During at least 1 water year, this upper confidence limit exceeds the maximum laboratory detection limit for 17 pesticides and exceeds the maximum laboratory reporting limit for 3 pesticides (ametryn, atrazine, and diazinon). The level of contamination indicated by this upper confidence limit should not substantially affect the suitability of reported environmental concentrations for any compound for comparison with corresponding human-health benchmarks.Despite being subjected to the same laboratory processes as laboratory blanks, field blanks indicated little evidence of contamination bias. This observation could largely be the consequence of data-reporting practices, which utilize detections in laboratory blanks to censor results in associated field samples (including blanks and environmental samples) when relative concentrations indicate that a result could have a substantial contribution from laboratory contamination. Laboratory censoring appears likely to reduce the risk of false-positive results in environmental samples below the level that laboratory blank results alone would imply.Whereas data available for third-party blind blank samples analyzed in 2018 indicate that only propoxur had any false-positive results, data for pesticides that were not spiked into blind spike samples analyzed in 2013–18 indicate that the false-positive rates for 31 pesticides exceeded 1 percent when considering only detections reported at concentrations greater than the maximum detection limit. Although about half of these pesticides lack substantial supporting evidence of contamination bias based on laboratory blank or field blank detections, indicating that spiking issues or degradation of parent compounds within the spiked samples might be a contributing factor to some false-positive results, these results indicate the need to closely examine detections reported for some pesticides in environmental samples analyzed during a similar period for possible contributions from contamination bias. Data for blind spike samples that were spiked at concentrations above the maximum reporting limit indicate that false-negative rates for eight pesticides exceed 10 percent; substantial low bias could affect results reported for these pesticides in environmental samples analyzed during a similar period.Data for laboratory reagent spikes, which measure recovery of pesticides in blank water, show little evidence for unacceptable recovery bias for S2437 pesticides. However, field matrix spikes, which measure recovery of pesticides in environmental matrices, indicate that degradation and (or) matrix effects could result in moderate to substantial low bias for groundwater results for several pesticides. Low bias could cause some reported concentrations to be categorized as being below a benchmark when the actual concentration in groundwater is greater than the benchmark. Occurrence and concentrations in groundwater could be substantially underrepresented for six pesticides with benchmarks (1H-1,2,4-triazole, asulam, bifenthrin, cis-permethrin, fenbutatin oxide, and naled) that have median recoveries between zero and 50 percent in field matrix spikes. Two compounds (didealkylatrazine and 2-hydroxy-6-ethylamino-4-amino-s-triazine) have median recoveries near or greater than 150 percent in field matrix spikes, indicating a substantial high bias. Plots of data for all spike types show clear changes in the typical recovery with time for some pesticides, which would require further examination for evaluation of temporal trends in environmental concentrations.Data for laboratory reagent spikes indicate that nearly all S2437 pesticides have acceptable variability resulting from random measurement error. Only two compounds (fenbutatin oxide and naled) have F-pseudosigma values greater than 30 percent for...

Environmental groundwater-quality data were collected from 648 wells as part of the National Water-Quality Assessment Project of the U.S. Geological Survey National Water-Quality Program and are included in this report. Most of the wells (514) were sampled from January through December 2016, and 60 of them were sampled in 2013 and 74 in 2014. The data were collected from seven types of well networks: principal aquifer study networks, which are used to assess the quality of groundwater used for public-water supply; land-use study networks, which are used to assess land-use effects on shallow groundwater quality; major aquifer study networks, which are used to assess the quality of groundwater used for domestic supply; enhanced trends networks, which are used to evaluate the time scales during which groundwater quality changes; vertical flow-path study networks, which are used to evaluate changes in groundwater quality from shallow to deeper depths; flow-path study networks, which are used to evaluate changes in groundwater quality from shallow to deeper depths over a horizontal distance; and modeling support studies, which are used to provide data to support groundwater modeling. Groundwater samples were analyzed for many water-quality indicators and constituents, including major ions, nutrients, trace elements, volatile organic compounds, pesticides, radionuclides, and some constituents of special interest (arsenic speciation, chromium [VI], and perchlorate). These groundwater-quality data, along with data from quality-control samples, are tabulated in this report and in an associated data release. Some data from environmental samples collected in 2013–14 and quality-control samples collected in 2012–15 also are included in the associated data release. Data from samples collected in 2016 are associated with networks described in this report and have not been published previously; data from samples collected between 2012 and 2015 are associated with networks described in previous reports in this data series.

This is the first large-scale, systematic assessment of hormone and pharmaceutical occurrence in groundwater used for drinking across the United States. Samples from 1091 sites in Principal Aquifers representing 60% of the volume pumped for drinking-water supply had final data for 21 hormones and 103 pharmaceuticals. At least one compound was detected at 5.9% of 844 sites representing the resource used for public supply across the entirety of 15 Principal Aquifers, and at 11.3% of 247 sites representing the resource used for domestic supply over subareas of nine Principal Aquifers. Of 34 compounds detected, one plastics component (bisphenol A), three pharmaceuticals (carbamazepine, sulfamethoxazole, and meprobamate), and the caffeine degradate 1,7-dimethylxanthine were detected in more than 0.5% of samples. Hydrocortisone had a concentration greater than a human-health benchmark at 1 site. Compounds with high solubility and low K_oc were most likely to be detected. Detections were most common in shallow wells with a component of recent recharge, particularly in crystalline-rock and mixed land-use settings. Results indicate vulnerability of groundwater used for drinking water in the U.S. to contamination by these compounds is generally limited, and exposure to these compounds at detected concentrations is unlikely to have adverse effects on human health.