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Baseline assessment of groundwater quality in Pike County, Pennsylvania, 2015

The Devonian-age Marcellus Shale and the Ordovician-age Utica Shale, which have the potential for natural gas development, underlie Pike County and neighboring counties in northeastern Pennsylvania. In 2015, the U.S. Geological Survey, in cooperation with the Pike County Conservation District, conducted a study that expanded on a previous more limited 2012 study to assess baseline shallow groundwater quality in bedrock aquifers in Pike County prior to possible extensive shale-gas development. Seventy-nine water wells ranging in depths from 80 to 610 feet were sampled during June through September 2015 to provide data on the presence of methane and other aspects of existing groundwater quality in the various bedrock geologic units throughout the county, including concentrations of inorganic constituents commonly present at low values in shallow, fresh groundwater but elevated in brines associated with fluids extracted from geologic formations during shale-gas development. All groundwater samples collected in 2015 were analyzed for bacteria, dissolved and total major ions, nutrients, selected dissolved and total inorganic trace constituents (including metals and other elements), radon-222, gross alpha- and gross beta-particle activity, dissolved gases (methane, ethane, and propane), and, if sufficient methane was present, the isotopic composition of methane. Additionally, samples from 20 wells distributed throughout the county were analyzed for selected man-made volatile organic compounds, and samples from 13 wells where waters had detectable gross alpha activity were analyzed for radium-226 on the basis of relatively elevated gross alpha-particle activity. Results of the 2015 study show that groundwater quality generally met most drinking-water standards for constituents and properties included in analyses, but groundwater samples from some wells had one or more constituents or properties, including arsenic, iron, manganese, pH, bacteria, sodium, chloride, sulfate, total dissolved solids, and radon-222, that did not meet (commonly termed failed or exceeded) primary or secondary maximum contaminant levels (MCLs) or Health Advisories (HA) for drinking water. Except for iron, dissolved and total concentrations of major ions and most trace constituents generally were similar. Only 1 of 79 well-water samples had any constituent that exceeded a MCL, with an arsenic concentration of about 30 micrograms per liter (µg/L) that was higher than the MCL of 10 µg/L. However, total arsenic concentrations were higher than the HA of 2 µg/L in samples from another 12 of 79 wells (about 15 percent). Secondary maximum contaminant levels (SMCLs) were exceeded most frequently by pH and concentrations of iron and manganese. The pH was outside of the SMCL range of 6.5–8.5 in samples from 24 of 79 wells (30 percent), ranging from 5.5 to 9.2; more samples had pH values less than 6.5 than had pH values greater than 8.5. Total iron concentrations typically were much greater than dissolved iron concentrations, indicating substantial presence of iron in particulate phase, and exceeded the SMCL of 300 µg/L more often [35 of 79 samples (44 percent)] than dissolved iron concentrations [samples from 8 of 79 wells (10 percent)]. Total manganese concentrations exceeded the SMCL of 50 µg/L in samples from 31 of 79 wells (39 percent) and the HA of 300 µg/L in samples from 13 of 79 wells (about 16 percent). A few (1–2) samples had concentrations of sodium, chloride, sulfate, or TDS higher than the SMCLs of 60, 250, 250, and 500 mg/L, respectively. However, dissolved sodium concentrations were higher than the HA of 20 mg/L in samples from 15 of 79 wells (nearly 20 percent). Total coliform bacteria were detected in samples from 25 of 79 wells (32 percent) but Escherichia coli were not detected in any sample. Radon-222 activities ranged from 11 to 5,100 picocuries per liter (pCi/L), with a median of 1,440 pCi/L, and exceeded the proposed and the alternate proposed drinking-water standards of 300 and 4,000 pCi/L, respectively, in samples from 60 of 79 wells (75 percent) and in samples from 2 of 79 wells (3 percent), respectively. Groundwater samples from all wells were analyzed for dissolved methane by one contract laboratory that determined water from 19 of the 79 wells (24 percent) had concentrations of methane greater than the reporting level of 0.010 milligrams per liter (mg/L) with a maximum methane concentration of 2.5 mg/L. Methane concentrations in 18 replicate samples submitted to a second laboratory for dissolved gas and isotopic analysis generally were higher by as much as a factor of 2.7 from those determined by the first laboratory, indicating potential bias related to combined sampling and analytical methods, and therefore, caution needs to be used when comparing methane results determined by different methods. The isotopic composition of methane in 9 of 10 samples with sufficient dissolved methane (about 0.3 mg/L) for isotopic analysis is consistent with values reported for methane of microbial origin produced through carbon dioxide reduction; an isotopic shift in 1 or 2 samples may indicate subsequent methane oxidation. The low concentrations of ethane relative to methane in these samples further indicate that the methane may be of microbial origin. Groundwater samples with relatively elevated methane concentrations (near or greater than 0.3 mg/L) also had chemical compositions that differed in some respects from groundwater with relatively low methane concentrations (less than 0.3 mg/L) by having higher pH (greater than 8) and higher concentrations of sodium, lithium, boron, fluoride, arsenic, and bromide and chloride/bromide ratios indicative of mixing with a small amount of brine of probable natural occurrence. The spatial distribution of groundwater compositions differs by topographic setting and lithology and generally shows that (1) relatively dilute, slightly acidic, oxygenated, calcium-carbonate type waters tend to occur in the uplands underlain by the undivided Poplar Gap and Packerton members of the Catskill Formation in southwestern Pike County; (2) waters of near neutral pH with the highest amounts of hardness (calcium and magnesium) generally occur in areas of intermediate altitudes underlain by other members of the Catskill Formation; and (3) waters with pH values greater than 8, low oxygen concentrations, and the highest arsenic, sodium, lithium, bromide, and methane concentrations can be present in deep wells in uplands but most frequently occur in stream valleys, especially at low altitudes (less than about 1,200 feet above North American Vertical Datum of 1988) where groundwater may be discharging regionally, such as to the Delaware River in northern and eastern Pike County. Thus, the baseline assessment of groundwater quality in Pike County prior to gas-well development shows that shallow (less than about 1,000 feet deep) groundwater generally meets primary drinking-water standards for inorganic constituents but varies spatially, with methane and some constituents present in high concentrations in brine (and connate waters from gas and oil reservoirs) present at low to moderate concentrations in some parts of Pike County.

Pennsylvania

Groundwater quality data in the Mojave study unit, 2008: Results from the California GAMA Program

Groundwater quality in the approximately 1,500 square-mile Mojave (MOJO) study unit was investigated from February to April 2008, as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). MOJO was the 23rd of 37 study units to be sampled as part of the GAMA Priority Basin Project. The MOJO study was designed to provide a spatially unbiased assessment of the quality of untreated ground water used for public water supplies within MOJO, and to facilitate statistically consistent comparisons of groundwater quality throughout California. Samples were collected from 59 wells in San Bernardino and Los Angeles Counties. Fifty-two of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (grid wells), and seven were selected to aid in evaluation of specific water-quality issues (understanding wells). The groundwater samples were analyzed for a large number of organic constituents [volatile organic compounds (VOCs), pesticides and pesticide degradates, and pharmaceutical compounds], constituents of special interest (perchlorate and N-nitrosodimethylamine [NDMA]) naturally occurring inorganic constituents (nutrients, dissolved organic carbon [DOC], major and minor ions, silica, total dissolved solids [TDS], and trace elements), and radioactive constituents (gross alpha and gross beta radioactivity, radium isotopes, and radon-222). Naturally occurring isotopes (stable isotopes of hydrogen, oxygen, and carbon, stable isotopes of nitrogen and oxygen in nitrate, and activities of tritium and carbon-14), and dissolved noble gases also were measured to help identify the sources and ages of the sampled ground water. In total, over 230 constituents and water-quality indicators (field parameters) were investigated. Three types of quality-control samples (blanks, replicates, and matrix spikes) each were collected at approximately 5–8 percent of the wells, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a significant source of bias in the data for the groundwater samples. Differences between replicate samples generally were within acceptable ranges, indicating acceptable analytical reproducibility. Matrix spike recoveries were within acceptable ranges for most compounds. This study did not attempt to evaluate the quality of water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, or blended with other waters to maintain water quality. Regulatory thresholds apply to water that is served to the consumer, not to untreated ground water. However, to provide some context for the results, concentrations of constituents measured in the untreated ground water were compared with regulatory and non-regulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Public Health (CDPH) and thresholds established for aesthetic and technical concerns by CDPH. Comparisons between data collected for this study and thresholds for drinking-water are for illustrative purposes only, and are not indicative of compliance or non-compliance with those thresholds. Most constituents that were detected in groundwater samples in the 59 wells in MOJO were found at concentrations below drinking-water thresholds. In MOJO’s 52 grid wells, volatile organic compounds (VOCs) were detected in 40 percent of the wells, and pesticides and pesticide degradates were detected in 23 percent of the grid wells. Results for health-based thresholds in MOJO grid wells showed that all of the detections of organic compounds in samples from MOJO grid wells were below health-based thresholds, with the exception of a single detection of NDMA above the California Department of Public Health notification level (NL-CA). Trace elements and radioactive constituents were sampled for at 19 MOJO grid wells and most detections were below health-based thresholds. Exceptions include: six detections of arsenic above the USEPA maximum contaminant level (MCL-US), two detections of boron and one detection of vanadium above the NL-CA, one detection each of molybdenum and strontium that were above the USEPA lifetime health advisory level (HAL-US), and one detection of fluoride just above the MCL-CA of 2 µg/L. Most detections of radioactive constituents in the MOJO grid wells were below health-based thresholds, with the exception of one detection of gross alpha radioactivity (72-hour count and 30-day count) above the MCL-CA, and 17 grid wells (of 19 sampled) that had activities of radon-222 above the proposed MCL-US of 300 pCi/L, but all were below the proposed alternative MCL-US of 4,000 pCi/L. All of the samples collected from the 19 MOJO grid wells for trace elements, and most of the samples for major ions and total dissolved solids (TDS), had measured concentrations below the non-enforceable thresholds set for aesthetic concerns. Four grid wells had TDS concentrations above the California Department of Public Health secondary maximum contaminant level (SMCL-CA) recommended threshold of 500 mg/L, and three of these wells were also above the SMCL-CA upper threshold of 1,000 mg/L. Four grid wells (of 19 sampled) had sulfate measured at concentrations above the recommended SMCL-CA threshold of 250 mg/L, and one of these detections was also above the upper SMCL-CA threshold of 500 mg/L. One grid well had chloride levels at a concentration above the upper SMCL-CA threshold of 500 mg/L. Eleven grid wells (of 52 sampled) had pH values outside of the SMCL-US range for pH.

California

Pesticides in surface water in the lower Illinois River basin, 1996-98

Surface-water quality samples were collected from April 1996 to September 1998 from eight locations in the Lower Illinois River Basin, a study unit of the U.S. Geological Survey?s National Water-Quality Assessment program. The study area is approximately 15,600 square miles and encompasses most of central and western Illinois. The dominant land use is agricultural and most land is used for the production of corn and soybeans. About 6.9 million acres of corn and soybeans are planted annually in the lower Illinois River Basin. Conservation tillage, defined as mulch-till and no-till, is used on about 40 percent of the cropland in the study area, similar to the statewide average. Nearly 90 percent of the samples for pesticide analyses were collected at four sites: the Illinois River at Ottawa, the Illinois River at Valley City, the La Moine River at Colmar, and the Sangamon River at Monticello. Two hundred fifty-eight samples were collected and analyzed for various herbicides, insecticides, and herbicide transformation products (also referred to as degradates). Thirty-one pesticides were detected at concentrations above their respective method detection limit: 23 herbicides and 8 insecticides. An additional set of 34 samples was collected in the summer of 1998 for the analysis of herbicide transformation products. Nine herbicide transformation products were detected, all belonging to the chloroacetanilide or the triazine chemical class. Two herbicides, atrazine and cyanazine, exceeded the associated human health drinking-water criteria and the aquatic health-criteria. Atrazine was detected in all samples. Sixty percent of the samples (48 of 80) collected in the months of May and June had atrazine concentrations that exceeded the clean drinking- water standard of 3 micrograms per liter (mg/L). The average atrazine concentration in the May to June samples was about 7.0 mg/L. The maximum atrazine concentrations were 110 mg/L in the La Moine River at Colmar and 32 mg/L in the Sangamon River at Monticello. The maximum atrazine concentration in the lower Illinois River was 20 mg/L, measured at Valley City, although most of the relatively elevated concentrations in the Illinois River sites were in the range from 5 to 8 mg/L. The concentrations of the herbicide cyanazine exceeded the health advisory guideline of 1 mg/L in about 19 percent (15 of 80) of the May to June samples. The pesticides chlorpyrifos, diazinon, metolachlor, and 2,4-D exceeded aquatic health guidelines at various times from May to August. Three dominant factors that affect the presence of pesticides in streams are identified: the pesticide usage, the time-of-year (or season), and the flow condition. The pesticides with the highest usage--atrazine, metolachlor, cyanazine, and acetochlor--generally were the pesticides detected most frequently and at the highest concentrations. Notable exceptions to this general observation are alachlor and simazine, which did not have high usage but were detected frequently. The elevated pesticide concentrations were most affected by seasonality--most of these elevated concentrations were observed across all flow conditions during May to June. Flow conditions also affect pesticide concentrations, but not as much as seasonality. The maximum pesticide loads were observed between March and July on the Illinois River. The net contribution of pesticides applied in the study area to net increases in load indicates that only about 1-2 percent of the pesticides applied exit the basin through the Illinois River at Valley City. The chloroacetanilide-class transformation products observed in samples collected in summer 1998 persistently contained elevated concentrations relative to the associated parent pesticide compound at all locations and for all streamflow conditions. The concentration of the transformation product metolachlor ethane sulfonic acid (ESA) usually was about 10 times higher than the parent compound in the mainstem of the lower

Water-Resources Investigations Report

Groundwater quality in relation to drinking water health standards and geochemical characteristics for 54 domestic wells in Clinton County, Pennsylvania, 2017

Despite the reliance on groundwater by approximately 2.4 million rural Pennsylvania residents, publicly available data to characterize the quality of private well water are limited. As part of a regional effort to characterize groundwater in rural areas of Pennsylvania, samples from 54 domestic wells in Clinton County were collected and analyzed in 2017. The samples were evaluated for a wide range of constituents and compared to drinking-water health standards and geochemical characteristics. The sampled wells were completed to depths ranging from 46 to 500 feet in bedrock that was of predominantly sandstone, shale, or carbonate lithology. Results of this study show that the sampled groundwater quality in Clinton County generally met most drinking-water standards that apply to public water supplies. However, a percentage of samples exceeded drinking-water maximum contaminant levels (MCLs) for total coliform bacteria (57.4 percent), Escherichia coli ( E. coli ) (25.9 percent), nitrate (1.9 percent), and arsenic (1.9 percent); and secondary maximum contaminant levels (SMCLs) for pH (31.5 percent), manganese (29.6 percent), iron (13 percent), total dissolved solids (7.4 percent), aluminum (1.9 percent), and chloride (1.9 percent). Sodium concentrations exceeded the U.S. Environmental Protection Agency drinking-water advisory recommendation in 16.7 percent of the samples. Radon-222 activities exceeded the proposed drinking-water standard of 300 picocuries per liter (pCi/L) in 59.3 percent of the samples. The only volatile organic compounds (VOCs) detected were acetone and methyl ethyl ketone in two separate samples; neither constituent exceeded drinking-water standards. Higher median nitrate concentrations were found in the carbonate (3.26 milligrams per liter [mg/L]) versus shale (less than 0.04 mg/L) and sandstone (0.27 mg/L) aquifer subsets. Most of the elevated nitrate concentrations were associated with E. coli detections in the carbonate aquifers, where transmissive bedrock can facilitate groundwater contamination by human activities at the land surface. The median pH of groundwater from the sandstone aquifers (6.53) was less than those for the shale aquifers (7.31) and carbonate aquifers (7.43). Generally, the lower pH samples had greater potential for elevated concentrations of dissolved metals, including beryllium, copper, lead, nickel, and zinc, whereas the higher pH samples had greater potential for elevated concentrations of total dissolved solids, sodium, fluoride, boron, and uranium. Near-neutral samples (pH 6.5 to 7.5) had greater hardness and alkalinity concentrations than other samples with pH outside this range. Many samples from the shale or sandstone aquifers, particularly those with pH less than 6.5, were identified as having serious potential corrosivity based on the combination of the calcite saturation index and the chloride to sulfate mass ratio; however, none of the samples from the carbonate aquifers was identified as seriously corrosive. Groundwater from 3.7 percent of the wells had concentrations of methane greater than the Pennsylvania action level of 7 mg/L, and 48 of the 54 wells (88.9 percent) had detectable concentrations of methane greater than the 0.0002 mg/L detection limit. Greater methane concentrations were found more frequently in groundwater sampled from the shale aquifers than the carbonate or sandstone aquifers in the study area. Most of the samples containing elevated methane (greater than 0.2 mg/L) were located outside the area of the Appalachian Plateaus. The elevated concentrations of methane generally were associated with suboxic groundwater (dissolved oxygen less than 0.5 mg/L) that had near-neutral to alkaline pH and were correlated with concentrations of iron, manganese, ammonia, sodium, lithium, barium, fluoride, and boron. The stable carbon and hydrogen isotopic compositions of methane in two of four samples analyzed for isotopes were consistent with compositions reported for mud-gas logging samples from gas-bearing geologic units (thermogenic gas) in the Appalachian Plateaus region, whereas two others were consistent with methane of microbial origin or a mixture of microbial and thermogenic gas. Forty-two percent of samples had chloride concentrations greater than 20 mg/L with variable bromide concentrations. Corresponding chloride/bromide ratios are consistent with low-bromide sources such as road-deicing salt and septic effluent or animal waste, or, in a few cases, high-bromide brine. Brines characterized by relatively high bromide are naturally present in deeper parts of the regional groundwater system and, in some cases, may be mobilized by gas drilling. The chloride, bromide, and other constituents in road-deicing salt or brine solutions tend to be diluted by mixing with fresh groundwater in shallow aquifers used for water supply. One of the four groundwater samples with methane concentrations greater than 4 mg/L had chloride and bromide concentrations and a chloride/bromide ratio that indicates mixing with a salinity source such as road-deicing salt, whereas the chloride and bromide concentrations and ratios for the other three high-methane samples indicate mixing with a small amount of brine (0.03 percent or less). In two other eastern Pennsylvania county studies where gas drilling is absent, groundwater with comparable chloride/bromide ratios, bromide, and chloride concentrations plus other element associations have been reported. Additional sampling and analysis, such as isotopic analysis of the dissolved gas, fracture analysis, and more detailed evaluation of surrounding land uses, may be warranted to better understand the origin of the methane and brine constituents in groundwater at specific locations.

Pennsylvania

Quality of water in domestic wells in the Chicot and Chicot equivalent aquifer systems, southern Louisiana and southwestern Mississippi, 2000-2001

In 2000-2001, water-quality data were collected from 60 randomly selected domestic wells in the Acadian-Pontchartrain Study Unit, as part of the National Water-Quality Assessment Program. The data were collected from wells screened in shallow sands (less than 350 feet below land surface) in two major aquifer systems--the Chicot aquifer system in southwestern Louisiana and the Chicot equivalent aquifer system in southeastern Louisiana and southwestern Mississippi. The Chicot equivalent aquifer system is part of the Southern Hills regional aquifer system, and both the Chicot aquifer system and the Southern Hills regional aquifer systems are designated as sole-source aquifers by the U.S. Environmental Protection Agency (USEPA). The well depths ranged from 40 to 340 feet below land surface with a median depth of 120 feet. The ground-water-quality data included 5 physiochemical properties, dissolved solids, 9 major inorganic ions, 24 trace elements, 6 nutrients, dissolved organic carbon, 109 pesticides and degradation products, and 85 volatile organic compounds (VOC's); and a subset of the wells were sampled for radon, chlorofluorocarbons, and stable isotopes. Water from 35 of the 60 domestic wells sampled had pH values less than the USEPA Seconday Maximum Contaminant Level (SMCL) range of 6.5 to 8.5 standard units. Specific conductance ranged from 17 to 1,420 microsiemens per centimeter at 25 degrees Celsius. Dissolved-solids concentrations in water from two wells exceeded the SMCL of 500 mg/L (milligrams per liter); the maximum concentration was 858 mg/L. Sodium and calcium were the dominant cations, and bicarbonate and chloride were the dominant anions. One chloride concentration (264 mg/L) exceeded the SMCL of 250 mg/L. One arsenic concentration (55.3 micrograms per liter) exceeded the USEPA Maximum Contaminant Level (MCL) of 10 micrograms per liter. Iron concentrations in water from 22 wells exceeded the SMCL of 300 micrograms per liter; the maximum concentration was 8,670 micrograms per liter. Manganese concentrations in water from 26 wells exceeded the SMCL of 50 micrograms per liter; the maximum concentration was 481 micrograms per liter. Health Advisories have been established for six of the trace elements analyzed; no concentrations were greater than these nonenforceable standards. Radon concentrations in water from 9 of 50 wells sampled were greater thanthe proposed USEPA MCL of 300 picocuries per liter. Concentrations of ammonia, ammonia plus organic nitrogen, and nitrite plus nitrate in water from four wells were greater than 2 mg/L, a level that might indicate anthropogenic influences. The median dissolved organic carbon concentration was an estimated 0.30 mg/L, which indicated naturally occurring dissolved organic carbon conditions in the study area. Eight pesticides and two degradation products were detected in water from five wells. Twenty-four VOC's were detected in water from 44 wells. All concentrations of pesticides and VOC's were less than USEPA drinking-water standards. Quality-control samples, which included field-blank samples, replicates, and field and laboratory spikes, indicated no bias in ground-water data from collection procedures or analyses. VAriance between the environmental sampls and he corresponding replicate samples was typically less than 5 percent, indicating and acceptable degree of laboratory precision and data collection reproducibility. The Mann-Whitney rank-sum test was used to compare depth to top of screen and selected physicochemical properties and chemical constituents between six groups of wells. Values for selected physicochemical and chemical constituents were typically greater in wells located in the Chicot aquifer system than in the Chicot equivalent aquifer system. Values for specific conductance, pH, calcium, sodium, bicarbonate, chloride, dis

Water-Resources Investigations Report

Pesticides in surface water of the Mid-Atlantic region

Water-quality data from 463 surface-water sites were compiled and analyzed to document the occurrence and distribution of pesticides in surface water of the Mid-Atlantic region as part of the Mid-Atlantic Integrated Assessment program of the U.S. Environmental Protection Agency. Those data collected by the U.S. Geological Survey from October 1973 through March 1997 were used in the analyses. Data are available for a large part of the Mid-Atlantic region, but large spatial gaps in the data do exist. USGS data bases contained analyses of surface-water samples for 127 pesticide compounds, including 12 degradates, but only 16 of the compounds were commonly detected. Atrazine, metolachlor, simazine, prometon, alachlor, tebuthiuron, cyanazine, diazinon, carbaryl, chlorpyrifos, pendimethalin, 2,4-D, dieldrin, DCPA, metribuzin, and desethylatrazine (an atrazine degradate) were detected in more than 100 of the samples analyzed. At least one pesticide was detected in about 75 percent of the samples collected and at more than 90 percent of the sites sampled. Concentrations greater than the Federal Maximum Contaminant Level (MCL) for drinking water of 3 micrograms per liter (ug/L) for atrazine were found in 67 of 2,076 samples analyzed; concentrations greater than the MCL of 2ug/L for alachlor were found in 13 of 1,693 samples analyzed, and concentrations greater than the MCL of 4 ug/L for simazine were found in 17 of 1,995 samples analyzed. Concentrations of four pesticides were greater than Federal Health Advisory levels for drinking water, and concentrations of nine pesticides were greater than Federal Ambient Water-Quality Criteria for the Protection of Aquatic Organisms. Streams draining basins with different land uses tend to have different pesticide detection frequencies and median concentrations. Median concentrations of herbicides tend to be highest in streams draining basins in which the major land use is agriculture, whereas median concentrations of insecticides tend to be highest in streams draining extensively urbanized basins. Concentrations of both herbicides and insecticides are usually highest during the spring and summer, although many pesticides are present at low concentrations in surface water throughout the year. Pesticide concentrations vary greatly seasonally and over different hydrologic conditions, with overall variation sometimes exceeding four orders of magnitude. During periods of pesticide application (typically spring and summer), the occurrence of selected pesticides in some streams in the Mid-Atlantic region is related to streamflow. Correlations between concentrations of selected pesticides and streamflow are statistically significant during spring and summer for small (draining less than 55 square miles) streams. Concentrations of selected pesticides in small streams increase during high flows in the growing season, up to 30 times the concentrations present during low-flow conditions in the growing season. In small streams draining urban areas, concentrations of atrazine decrease during high-flow events but concentrations of the insecticides diazinon and chlorpyrifos increase. This may be due to the differences in the pesticides used in agricultural and urban areas and the amounts applied.

Water-Resources Investigations Report

Water-quality characteristics and ground water quantity of the Fraser River watershed, Grand County, Colorado, 1998-2001

The U.S. Geological Survey, in cooperation with the Grand County Board of County Commissioners, conducted a 4-year study to assess ground- and surface-water-quality conditions and ground-water quantity in the 302-square-mile Fraser River watershed in north-central Colorado. The Fraser River flows north about 28 miles from the headwaters near the Continental Divide, through the towns of Winter Park, Fraser, Tabernash, and Granby, and is one of the major tributaries to the Upper Colorado River. Increasing urban development, as well as the seasonal influx of tourists, is placing more demands on the water resources in the Fraser River watershed. A ground-water sampling network of 11 wells was established to represent different aquifer systems (alluvial, Troublesome Formation, Precambrian granite), land uses (urban, nonurban), and areas with or without individual septic disposal system use. The well network was sampled for ground-water quality on a semiannual basis from August 1998 through September 2001. The sampling included field properties and the collection of water samples for analysis of major ions, trace elements, nutrients, dissolved organic carbon, bacteria, methylene blue active substances, and radon-222. One surface-water site, on the Fraser River just downstream from the town of Tabernash, Colorado, was sampled bimonthly from August 1998 through September 2001 to assess the cumulative effects of natural and human processes on water quality in the upper part of the Fraser River watershed. Surface-water-quality sampling included field properties and the collection of water-quality samples for analysis of major ions, trace elements, nutrients, organic carbon, and bacteria. Ground water was a calcium-bicarbonate type water and is suitable as a drinking-water, domestic, municipal, industrial, and irrigation source. In general, no widespread ground-water-quality problems were indicated. All pH values and concentrations of dissolved solids, chloride, fluoride, sulfate, nitrite, and nitrate in the ground-water samples met or were substantially less than U.S. Environmental Protection Agency drinking-water standards and health advisories or State of Colorado water-quality standards. Federal standards for turbidity and concentrations of iron, manganese, methylene blue active substances, and radon-222 were not met in water samples from at least one well. The only ground-water-quality concern assessed by this study is radon-222, which was detected in all radon- analyzed samples from 10 wells at levels exceeding the proposed U.S. Environmental Protection Agency drinking-water standard of 300 picocuries per liter. Concentrations of chloride, magnesium, and sulfate were statistically different (higher) in ground-water samples from wells completed in the alluvial aquifer, urbanized areas, and areas with individual septic disposal system use than those from wells completed in the Troublesome Formation, nonurban areas, and areas without individual septic disposal system use. Dissolved organic carbon concentrations were statistically higher in ground-water samples from wells completed in the alluvial aquifer and areas without individual septic disposal system use than those from wells completed in the Troublesome Formation and areas with individual septic disposal system use. Differences in dissolved organic-carbon concentrations between the latter category and areas without septic systems likely had no environmental significance. Surface water at the site Fraser River below Crooked Creek at Tabernash was a calcium-bicarbonate type water and is suitable as a drinking-water, residential, commercial, and irrigation resource. All pH values and concentrations of dissolved oxygen were within the State of Colorado instream water-quality standards, and all concentrations of chloride, sulfate, iron, manganese, un-ionized ammonia, nitrite, nitrate, and fecal coliform bacteria met State standards. Seasonal changes in the values or conc

Colorado

Ground-water quality data in the Southern Sacramento Valley, California, 2005 — Results from the California GAMA Program

Ground-water quality in the approximately 2,100 square-mile Southern Sacramento Valley study unit (SSACV) was investigated from March to June 2005 as part of the Statewide Basin Assessment Project of Ground-Water Ambient Monitoring and Assessment (GAMA) Program. This study was designed to provide a spatially unbiased assessment of raw ground-water quality within SSACV, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 83 wells in Placer, Sacramento, Solano, Sutter, and Yolo Counties. Sixty-seven of the wells were selected using a randomized grid-based method to provide statistical representation of the study area. Sixteen of the wells were sampled to evaluate changes in water chemistry along ground-water flow paths. Four additional samples were collected at one of the wells to evaluate water-quality changes with depth. The GAMA Statewide Basin Assessment project was developed in response to the Ground-Water Quality Monitoring Act of 2001 and is being conducted by the California State Water Resources Control Board (SWRCB) in collaboration with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory (LLNL). The ground-water samples were analyzed for a large number of man-made organic constituents (volatile organic compounds [VOCs], pesticides and pesticide degradates, pharmaceutical compounds, and wastewater-indicator constituents), constituents of special interest (perchlorate, N -nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, and carbon-14, and stable isotopes of hydrogen, oxygen, and carbon), and dissolved noble gases also were measured to help identify the source and age of the sampled ground water. Quality-control samples (blanks, replicates, matrix spikes) were collected at ten percent of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Assessment of the quality-control data resulted in censoring of less than 0.03 percent of the analyses of ground-water samples. This study did not evaluate the quality of water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to treated water that is served to the consumer, not to raw ground water. However, to provide some context for the results, concentrations of constituents measured in the raw ground water were compared with health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and California Department of Health Services (CADHS) (Maximum Contaminant Levels [MCLs], notification levels [NLs], or lifetime health advisories [HA-Ls]) and thresholds established for aesthetic concerns (Secondary Maximum Contaminant Levels [SMCLs]). All wells were sampled for organic constituents and selected general water quality parameters; subsets of wells were sampled for inorganic constituents, nutrients, and radioactive constituents. Volatile organic compounds were detected in 49 out of 83 wells sampled and pesticides were detected in 34 out of 82 wells; all detections were below health-based thresholds, with the exception of 1 detection of 1,2,3-trichloropropane above a NL. Of the 43 wells sampled for trace elements, 27 had no detections of a trace element above a health-based threshold and 16 had at least one detection above. Of the 18 trace elements with health-based thresholds, 3 (arsenic, barium, and boron) were detected at concentrations higher an MCL. Of the 43 wells sampled for nitrate, only 1 well had a detection above the MCL. Twenty wells were sampled for radioactive constituents; only 1 (radon-222) was measured at activities higher than the proposed MCL. Radon-222 was detected below the threshold in 7 wells and above the threshold in 13 wells. SMCLs have been established for nine constituents or parameters analyzed in SSACV. Six were measured at levels higher than an SMCL: chloride, iron, manganese, pH, specific conductance, and total dissolved solids. Chloride, iron, manganese, pH, and total dissolved solids were measured in 43 wells: 27 wells had no measurements above a threshold and 16 wells had a measurement above a threshold. Specific conductance was measured in 83 wells. In 68 wells, specific conductance was measured lower than the threshold and in 15 wells it was measured above the threshold.

California

Informing Lake Erie agriculture nutrient management via scenario evaluation

Harmful algal blooms (HABs) have been increasing in extent and intensity in the western basin of Lake Erie. The cyanobacteria Microcystis produces toxins that pose serious threats to animal and human health, resulting in beach closures and impaired water supplies, and have even forced a “do not drink” advisory for the City of Toledo water system for several days in the summer of 2014. The main driver of Lake Erie HABs is elevated phosphorus loading from watersheds draining to the western basin, particularly from the Maumee River watershed (Obenour et al. 2014). Through the 2012 Great Lakes Water Quality Agreement (GLWQA), the U.S. and Canadian governments agreed to revise Lake Erie phosphorus loading targets to decrease HAB severity below levels representing a hazard to ecosystem and human health. New targets limit March-July loadings from the Maumee River to 186 metric tonnes of dissolved reactive phosphorus (DRP) and 860 metric tonnes of total phosphorus (TP) – a 40% reduction from 2008 loads (GLWQA 2016). The Great Lakes region must now determine what policy options are most effective and feasible for meeting those targets. While all sources are important, our focus is on agriculture because it overwhelms other sources. In a conservative ballpark estimate we found that 85% of the Maumee River’s load to Lake Erie comes from farm fertilizers and manures, even though this is only 10% of farmland fertilizer applications (Figure 1). Load targets will not be met without reductions from agriculture. Therefore, the overall goal of this study was to identify potential options for agricultural management to reduce phosphorus loads and lessen future HABs in Lake Erie. We applied multiple watershed models to test the ability of a series of land management scenarios, developed in consultation with agricultural and environmental stakeholders, to reach the proposed targets.

Indiana, Michigan, Ohio

Overview of the Texas Source Water Assessment Project

The 1996 Amendments to the Safe Drinking Water Act require, for the first time, that each state prepare a source water assessment for all PWS. Previously, Federal regulations focused on sampling and enforcement with emphasis on the quality of delivered water. These Amendments emphasize the importance of protecting the source water. States are required to determine the drinking-water source, the origin of contaminants monitored or the potential contaminants to be monitored, and the intrinsic susceptibility of the source water. Under the amendments to the Act, States must create SWAP Programs. The programs must include an individual source water assessment for each public water system regulated by the State. These assessments will determine whether an individual drinking water source is susceptible to contamination. During 1997?99, TNRCC and USGS staff met as subject-matter working groups to develop an approach to conducting Source Water Susceptibility Assessments (SWSA) and a draft workplan. The draft workplan was then presented to and reviewed by various stakeholder and technical advisory groups. Comments and suggestions from these groups were considered, and a final workplan was produced and presented to the EPA. After EPA approval, work formally began on the Texas SWAP Project. The project has an expected completion date of September 2002. At that time, initial SWSA of all Texas public water supplies should be complete. Ground-water supplies can be considered susceptible if a possible source of contamination (PSOC) exists in the contributing area for the public-supply well field or spring, the contaminant travel time to the well field or spring is short, and the soil zone, vadose zone, and aquifer-matrix materials are unlikely to adequately attenuate the contaminants associated with the PSOC. In addition, particular types of land use/cover within the contributing area may cause the supply to be deemed more susceptible to contamination. Finally, detection of various classes of constituents in water from wells in the vicinity of a public supply well may indicate susceptibility of the public-supply well even though there may be no identifiable PSOC or land use activity. Surface-water supplies are by nature susceptible to contamination from both point and non-point sources. The degree of susceptibility of a PWS to contamination can vary and is a function of the environmental setting, water and wastewater management practices, and land use/cover within a water supply's contributing watershed area. For example, a PWS intake downstream from extensive urban development may be more susceptible to non-point source contamination than a PWS intake downstream from a forested, relatively undeveloped watershed. Surface-water supplies are also susceptible to contamination from point sources, which may include permitted discharges, as well as accidental spills or other introduction of contaminants.

Texas

Groundwater-quality characteristics for the Wyoming Groundwater-Quality Monitoring Network, November 2009 through September 2012

Groundwater samples were collected from 146 shallow (less than or equal to 500 feet deep) wells for the Wyoming Groundwater-Quality Monitoring Network, from November 2009 through September 2012. Groundwater samples were analyzed for physical characteristics, major ions and dissolved solids, trace elements, nutrients and dissolved organic carbon, uranium, stable isotopes of hydrogen and oxygen, volatile organic compounds, and coliform bacteria. Selected samples also were analyzed for gross alpha radioactivity, gross beta radioactivity, radon, tritium, gasoline range organics, diesel range organics, dissolved hydrocarbon gases (methane, ethene, and ethane), and wastewater compounds. Water-quality measurements and concentrations in some samples exceeded numerous U.S. Environmental Protection Agency (EPA) drinking water standards. Physical characteristics and constituents that exceeded EPA Maximum Contaminant Levels (MCLs) in some samples were arsenic, selenium, nitrite, nitrate, gross alpha activity, and uranium. Total coliforms and Escherichia coli in some samples exceeded EPA Maximum Contaminant Level Goals. Measurements of pH and turbidity and concentrations of chloride, sulfate, fluoride, dissolved solids, aluminum, iron, and manganese exceeded EPA Secondary Maximum Contaminant Levels in some samples. Radon concentrations in some samples exceeded the alternative MCL proposed by the EPA. Molybdenum and boron concentrations in some samples exceeded EPA Health Advisory Levels. Water-quality measurements and concentrations also exceeded numerous Wyoming Department of Environmental Quality (WDEQ) groundwater standards. Physical characteristics and constituents that exceeded WDEQ Class I domestic groundwater standards in some samples were measurements of pH and concentrations of chloride, sulfate, dissolved solids, iron, manganese, boron, selenium, nitrite, and nitrate. Measurements of pH and concentrations of chloride, sulfate, dissolved solids, aluminum, iron, manganese, boron, and selenium exceeded WDEQ Class II agriculture groundwater standards in some samples. Measurements of pH and concentrations of sulfate, dissolved solids, aluminum, boron, and selenium exceeded WDEQ Class III livestock groundwater standards in some samples. The concentrations of dissolved solids in two samples exceeded the WDEQ Class IV industry groundwater standard. Measurements of pH and concentrations of dissolved solids, aluminum, iron, manganese, and selenium exceeded WDEQ Class special (A) fish and aquatic life groundwater standards in some samples. Stable isotopes of hydrogen and oxygen measured in water samples were compared to the Global Meteoric Water Line and Local Meteoric Water Lines. Results indicated that recharge to all of the wells was derived from precipitation and that the water has undergone some fractionation, possibly because of evaporation. Concentrations of organic compounds did not exceed any State or Federal water-quality standards. Few volatile organic compounds were detected in samples, whereas gasoline range organics, diesel range organics, and methane were detected most frequently. Concentrations of wastewater compounds did not exceed any State or Federal water-quality standards. The compounds N,N-diethyl-meta-toluamide (DEET), benzophenone, and phenanthrene were detected most frequently. Bacteria samples were collected, processed, incubated, and enumerated in the field or at the U.S. Geological Survey Wyoming-Montana Water Science Center. Total coliforms and Escherichia coli were detected in some samples.

Wyoming

Groundwater quality in West Virginia, 1993-2008

Approximately 42 percent of all West Virginians rely on groundwater for their domestic water supply. However, prior to 2008, the quality of the West Virginia’s groundwater resource was largely unknown. The need for a statewide assessment of groundwater quality prompted the U.S. Geological Survey (USGS), in cooperation with West Virginia Department of Environmental Protection (WVDEP), Division of Water and Waste Management, to develop an ambient groundwater-quality monitoring program. The USGS West Virginia Water Science Center sampled 300 wells, of which 80 percent were public-supply wells, over a 10-year period, 1999–2008. Sites for this statewide ambient groundwater-quality monitoring program were selected to provide wide areal coverage and to represent a variety of environmental settings. The resulting 300 samples were supplemented with data from a related monitoring network of 24 wells and springs. All samples were analyzed for field measurements (water temperature, pH, specific conductance, and dissolved oxygen), major ions, trace elements, nutrients, volatile organic compounds, fecal indicator bacteria, and radon-222. Sub-sets of samples were analyzed for pesticides or semi-volatile organic compounds; site selection was based on local land use. Samples were grouped for comparison by geologic age of the aquifer, Groups included Cambrian, Ordovician, Silurian, Devonian, Pennsylvanian, Permian, and Quaternary aquifers. A comparison of samples indicated that geologic age of the aquifer was the largest contributor to variability in groundwater quality. This study did not attempt to characterize drinking water provided through public water systems. All samples were of raw, untreated groundwater. Drinking-water criteria apply to water that is served to the public, not to raw water. However, drinking water criteria, including U.S. Environmental Protection Agency (USEPA) maximum contaminant level (MCL), non-enforceable secondary maximum contaminant level (SMCL), non-enforceable proposed MCL, or non-enforceable advisory health-based screening level (HBSL), were used as benchmarks against which to compare analytical results. Constituent concentrations were less than the MCLs in most samples. However, some samples exceeded non-enforceable SMCLs, proposed MCLs, or advisory HBSLs. Radon-222 concentrations exceeded the proposed MCL of 300 pCi/L in 45 percent of samples, and iron concentrations exceeded the SMCL of 300 µg/L in 57 percent of samples. Manganese concentrations were greater than the SMCL (50 µg/L) in 62 percent of samples and greater than the HBSL (300 µg/L) in 25 percent of the samples. Other sampled constituents, including organic compounds and trace elements, exceeded drinking-water criteria at much lower frequencies. The radon-222 median concentrations in samples from Cambrian, Ordovician, Silurian, Permian, and Quaternary aquifers exceeded the proposed 300 pCi/L MCL. Although median radon concentrations for wells in Devonian, Mississippian, and Pennsylvanian aquifers were less than the proposed MCL, radon concentrations greater than the proposed MCL were measured in samples from aquifers of all geologic ages. The median iron concentrations for samples from Devonian and Pennsylvanian aquifers were greater than the 300 µg/L SMCL. Iron concentrations exceeded the SMCL in aquifers of all geologic ages, except Cambrian. Median concentrations of manganese exceeded the SMCL in samples from Devonian, Pennsylvanian, and Quaternary aquifers. As with iron, manganese concentrations were found to exceed the SMCL in at least one sample from aquifers of all geologic ages, except Cambrian. Pesticides were detected most frequently and in higher concentrations in limestone-dominated areas. Most of West Virginia’s agriculture is concentrated in those areas. This study, the most comprehensive assessment of West Virginia groundwater quality to date, indicates the water quality of West Virginia’s groundwater is generally good; in the majority of cases raw-water samples met primary drinking water-criteria. However, some constituents, notably iron and manganese, exceeded the secondary drinking criteria in more than half the samples.

West Virginia

Hydrogeology and water quality of sand and gravel aquifers in McHenry County, Illinois, 2009–14, and comparison to conditions in 1979

Baseline conditions for the sand and gravel aquifers (groundwater) in McHenry County, Illinois, were assessed using data from a countywide network of 44 monitoring wells collecting continuous water-level data from 2009–14. In 2010, water-quality data were collected from 41 of the monitoring wells, along with five additional monitoring wells available from the U.S. Geological Survey National Water Quality Assessment Program. Periodic water-quality data were collected from 2010–14 from selected monitoring wells. The continuous water-level data were used to identify the natural and anthropogenic factors that influenced the water levels at each well. The water-level responses to natural influences such as precipitation, seasonal and annual variations, barometric pressure, and geology, and to anthropogenic influences such as pumping were used to determine (1) likely hydrogeologic setting (degree of aquifer confinement and interconnections) that, in part, are related to lithostratigraphy; and (2) areas of recharge and discharge related to vertical flow directions. Water-level trends generally were determined from the 6 years of data collection (2009–14) to infer effects of weather variability (drought) on recharge. Precipitation adds an estimated 2.4 inches per year of recharge to the aquifer. Some of this recharge is subsequently discharged to streams and some is discharged to supply wells. A few areas in the eastern half of the county had higher average recharge rates, indicating a need for adequate protection of these recharge areas. Downward vertical flow gradients in upland areas indicate that recharge to the confined aquifer units occurs near upland areas. Upward vertical flow gradients in lowland areas indicate discharge at locations of surface water and groundwater interaction (wetlands, ponds, and streams). Monitoring wells were sampled for major and minor ions, metals, and nutrients and a subset of wells was sampled for trace elements, dissolved gases, pesticides, and volatile organic compounds. The results were compared to health ‑ based and aesthetically based standards, which include the U.S. Environmental Protection Agency Maximum Contaminant Level (EPA MCL), and EPA Secondary Maximum Contaminant Levels (SMCL), as well as EPA Health-based Standards Drinking Water Advisories. Health‑based standards were exceeded for arsenic in 22 percent, sodium in 20 percent, and nitrates in 2 percent of the monitoring wells sampled. Aesthetically based standards were exceeded for total dissolved solids in 33 percent, chloride in 11 percent, iron in 85 percent, and manganese in 30 percent of the wells sampled. Many of these same constituents, such as arsenic, iron, and manganese, are naturally occurring but become elevated in areas that have anoxic, mixed, and suboxic conditions. Some areas of potential vulnerability to anthropogenic-sourced constituents in the sand and gravel aquifers were evidenced by trace amounts of volatile organic compounds and pesticides detected in water-quality samples from shallow wells (total depth less of than 46 feet below land surface) near urban settings, and by the detection of elevated major ions (chloride, sodium, magnesium, and calcium) associated, in part, with road-salt applications. Source analysis for chloride indicates mixtures of road salt, water softeners, and sewage. Continuously measured specific conductance values were used as a surrogate for continuously measured chloride concentrations in the groundwater. The estimated chloride concentrations generally were highest in spring and lowest in summer, and occasionally peak during spring melt. Overall, the range of concentrations varied depending on the local thickness and hydraulic conductivity of the aquifer. Water levels and water quality from the countywide groundwater monitoring network were compared to water levels and water-quality results in 1979 from a previous U.S. Geological Survey study. Potentiometric surface maps show areas with inferred decreases of water levels near the southern and southeastern areas of McHenry County. Significant increases were noted for total dissolved solids and specific conductance. Chloride concentrations increased as much as 521 percent in three of six wells resampled in 2015 from the previous study.

Illinois

Isolation and identification of microcystin-degrading bacteria in Lake Erie source waters and drinking-water plant sand filters

The increasing prevalence of cyanobacterial harmful algal blooms and the toxins they produce is a global water-quality issue. In the Western Basin of Lake Erie, high microcystin concentrations have led to water-quality advisories, process adjustments for treating drinking water, and increased water-quality monitoring. Biodegradation is an environmentally friendly and cost-effective way to reduce concentrations of microcystins in drinking water; however, few studies have been done to determine biodegradation potential of bacteria indigenous to the Lake Erie watershed. As part of a cooperative program between the U.S. Geological Survey and the U.S. Environmental Protection Agency, this study aimed to identify naturally occurring microcystin-degrading bacteria in source waters and in the sand filters of drinking-water treatment plants in the Western Basin of Lake Erie. Biodegradation of microcystin-LR was found to occur in microcosms developed with three different Lake Erie-area sources—Lake Erie water, water from storage reservoirs supplied by inland streams, and water or solid medium from sand/anthracite filters at drinking-water plants. In microplates with microcystin-LR as the sole carbon source, 10 isolates exhibited cellular respiration and were, therefore, identified as promising microcystin biodegraders; 4 of those isolates subsequently were found to have potential to form biofilms. The 10 promising isolates along with 14 additional isolates from the microcosms were identified by 16S ribosomal RNA sequencing: 15 isolates were γ-proteobacteria, 6 isolates were β-proteobacteria, 1 isolate was an α-proteobacterium, 1 isolate was a flavobacterium in the phylum Bacteroidetes , and 1 isolate was in the phylum Actinobacteria . Isolates were screened for possession of the mlrA gene (found to encode for the protein responsible for cleaving the cyclic structure of microcystin), and results indicate that, for Lake Erie source waters and elsewhere, more work would be required to identify microcystin-biodegradation pathways and products and to confirm biodegradation rates in pure culture isolates.

Lake Erie

Results of 2018–19 water-quality and hydraulic characterization of aquifer intervals using packer tests and preliminary geophysical-log correlations for selected boreholes at and near the former Naval Air Warfare Center Warminster, Bucks County, Pennsylvania

The U.S. Geological Survey (USGS) collected data on the vertical distribution of hydraulic head, specific capacity, and water quality using aquifer-interval-isolation tests and other vertical profiling methods in 15 boreholes completed in fractured sedimentary bedrock in Northampton, Warminster, and Warwick Townships, Bucks County, Pennsylvania during 2018–19. This work was done, in cooperation with the U.S. Navy, to support detailed investigations at and near the former Naval Air Warfare Center (NAWC) Warminster, where groundwater contamination with per- and polyfluoroalkyl substances (PFAS) had become a concern since 2014. Two PFAS compounds, perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), have been measured in groundwater samples from supply and monitoring wells at or near NAWC Warminster in concentrations above U.S. Environmental Protection Agency health advisory levels for drinking water. The area is underlain by the Triassic Stockton Formation, which predominantly consists of sandstone interbedded with shale and siltstone beds and forms a layered fractured-rock aquifer used for private, industrial, and public drinking water supply. The vertical distribution of aquifer properties and water quality was assessed through hydraulic tests and sampling of aquifer intervals using a straddle-packer system (13 boreholes) or depth-discrete point sampling under known borehole-flow conditions (2 boreholes). Geophysical and video logs collected by USGS during 2017–19 were used to identify potential water-bearing fractures in 15 boreholes, which ranged in depth from 210 to 604 feet (ft) and included 6 boreholes drilled in 2018 and 9 existing wells on or near the former NAWC Warminster. Measured borehole flow was predominantly downward in most of the deepest boreholes (greater than 400 ft), which were commonly located at the highest land-surface elevations, with inflow from fractures at relatively shallow depths and outflow through fractures near or below depths of 500 ft below land surface. Hydraulic head differences measured during packer tests were up to about 60 ft between shallow and deep intervals. Borehole flow was predominantly upward in most boreholes less than 400 ft in depth and farther from, and at lower land-surface elevations than, the former NAWC Warminster. Total borehole specific capacity ranged from about 0.07 to 41 gallons per minute per foot [(gal/min)/ft]. Specific-capacity values for individual intervals ranged from 0.02 to 40.0 (gal/min)/ft, with a median of 1.14 (gal/min)/ft and a large range in values at most depths. Differences in water quality of samples as indicated by field properties (pH, dissolved oxygen, and specific conductance) and concentrations of dissolved major ions, PFOA, and PFOS were apparent among isolated intervals in the boreholes. Summed concentrations of PFOA and PFOS ranged from about 11 to 10,780 nanograms per liter (ng/L) and were greater than the 2016 U.S. Environmental Protection Agency health advisory of 70 ng/L for summed PFOA and PFOS concentrations in 62 of 104 intervals and discrete depths tested. The mass ratio of PFOS to PFOA was generally higher than 1.0 in samples with summed PFOA and PFOS concentrations greater than 70 ng/L, with ratio values as high as 8.7. In many boreholes, summed concentrations of PFOA and PFOS were positively related to chloride concentrations, which were elevated above natural-background values [less than 10 milligrams per liter] in most samples and as high as 717 milligrams per liter. Sources of the elevated chloride other than, or in addition to, common rock salt (sodium chloride) were indicated by chloride to sodium molar ratios greater than 1.0. Water-quality data indicated that sampled water from some intervals with lower hydraulic heads may be affected by water from intervals with higher hydraulic heads because of vertical flow in open boreholes; samples from these intervals with lower hydraulic heads may not be fully representative due to some component of cross contamination and should be interpreted with caution. Through a preliminary correlation of natural gamma and resistivity logs of boreholes drilled at and near the former NAWC Warminster, 11 lithologic units were identified and interpreted to strike northeast and dip to the northwest. Hydraulic heads were generally highest in isolated intervals that intercepted beds which, when projected up dip, crop out at the highest land-surface elevation on the former NAWC Warminster, indicating that the dipping-bed structure and topography are factors affecting the distribution of hydraulic head in the aquifer. The hydrogeologic framework in conjunction with the vertical distribution of hydraulic heads and water quality may assist in evaluating the locations of various PFAS sources and potential migration pathways of PFAS in groundwater at and near NAWC Warminster.

Pennsylvania

Arsenic, iron, lead, manganese, and uranium concentrations in private bedrock wells in southeastern New Hampshire, 2012-2013

Trace metals, such as arsenic, iron, lead, manganese, and uranium, in groundwater used for drinking have long been a concern because of the potential adverse effects on human health and the aesthetic or nuisance problems that some present. Moderate to high concentrations of the trace metal arsenic have been identified in drinking water from groundwater sources in southeastern New Hampshire, a rapidly growing region of the State (Montgomery and others, 2003). During the past decade (2000–10), southeastern New Hampshire, which is composed of Hillsborough, Rockingham, and Strafford Counties, has grown in population by nearly 48,700 (or 6.4 percent) to 819,100. These three counties contain 62 percent of the State’s population but encompass only about 22 percent of the land area (New Hampshire Office of Energy and Planning, 2011). According to a 2005 water-use study (Hayes and Horn, 2009), about 39 percent of the population in these three counties in southeastern New Hampshire uses private wells as sources of drinking water, and these wells are not required by the State to be routinely tested for trace metals or other contaminants. Some trace metals have associated human-health benchmarks or nonhealth guidelines that have been established by the U.S. Environmental Protection Agency (EPA) to regulate public water supplies. The EPA has established a maximum contaminant level (MCL) of 10 micrograms per liter (μg/L) for arsenic (As) and a MCL of 30 μg/L for uranium (U) because of associated health risks (U.S. Environmental Protection Agency, 2012). Iron (Fe) and manganese (Mn) are essential for human health, but Mn at high doses may have adverse cognitive effects in children (Bouchard and others, 2011; Agency for Toxic Substances and Disease Registry, 2012); therefore, the EPA has issued a lifetime health advisory (LHA) of 300 μg/L for Mn. Recommended secondary maximum contaminant levels (SMCLs) for Fe (300 μg/L) and Mn (50 μg/L) were established primarily as nonhealth guidelines—based on aesthetic considerations, such as taste or the staining of laundry and plumbing fixtures—because these contaminants, at the SMCLs, are not considered to present risks to human health. Because lead (Pb) contamination of drinking water typically results from corrosion of plumbing materials belonging to water-system customers but still poses a risk to human health, the EPA established an action level (AL) of 15 μg/L for Pb instead of an MCL or SMCL (U.S. Environmental Protection Agency, 2012). The 15-μg/L AL for Pb has been adopted by the New Hampshire Department of Environmental Services for public water systems, and if exceeded, the public water system must inform their customers and undertake additional actions to control corrosion in the pipes of the distribution system (New Hampshire Department of Environmental Services, 2013). Unlike the quality of drinking water provided by public water suppliers, the quality of drinking water obtained from private wells in New Hampshire is not regulated; consequently, private wells are sampled only when individual well owners voluntarily choose to sample them. The U.S. Geological Survey (USGS), in cooperation with the EPA New England, conducted an assessment in 2012–13 to provide private well owners and State and Federal health officials with information on the distribution of trace-metal (As, Fe, Pb, Mn, and U) concentrations in groundwater from bedrock aquifers in the three counties of southeastern New Hampshire. This fact sheet analyzes data from water samples collected by a randomly selected group of private well owners from the three-county study area and describes the major findings for trace-metal concentrations.

New Hampshire

Investigations by the U.S. Geological Survey of soil and moisture conservation on public domain lands, 1941-1964

The passage of the Taylor Grazing Act in 1934 marked the end of an era in the land policies in the United States in that disposal of the public lands by homesteading was terminated except under rigidly prescribed procedures, and the remaining public lands covering about 175 million acres in the western conterminous states were brought under regulatory authority for grazing use. In 1934 the lands were mostly in a severe state of deterioration as a result of overgrazing and drought. In addition to reducing numbers of livestock using the lands, successive programs of conservation practices were established of which the Soil and Moisture Conservation Program of the Department of the Interior is of particular interest here. The services of the Geological Survey, in an investigational and advisory capacity were enlisted in this program. The work of the Geological Survey has consisted of the collection of hydrologic data, investigations of range-water supplies to facilitate management and provide information for design of structures and land-treatment measures. Appraisal of the effects of treatment practices has also been an important activity. Conservation on the public domain involves mainly growing vegetation for forage and reducing erosion. The two elements are intimately related--accomplishment in one is usually reflected by an improvement in the other. Erosion is a serious problem on most of the public domain, but particularly in the Colorado River and Rio Grande basins where, despite low annual water yields, the public domain and similar lands on the Indian reservations contribute the major part of the sediment measured at the downstream gaging stations. In parts of the Missouri River basin also, erosion is obviously very active but the sediment yield contributed by the public domain cannot be as readily isolated. The reasons for the erosion are generally evident--the erodibility of the rock and soils and the sparsity of vegetation as a result of low precipitation, unfavorable soils, or past land use. How much is due to the land use is still controversial, resulting in many questions relative to planning corrective measures. The problem facing the early administrators of the Taylor Grazing Act to bring about proper use and conservation of the public domain was a difficult one because of the lack of records on actual grazing use in animal-unit months of the qualified allottees and the lack of data on treatment practices in an arid area. Reduction of grazing was imperative in some localities, but generally, it could not be brought about as rapidly as it should have been. Numbers of animal units in the grazing districts were reduced from about 3.6 million in 1941 to about 3.2 million in 1964, whereas the areas included in districts was increased about 3 percent. Reductions are still being made in certain areas where deterioration is evident. One of the earliest activities connected with management of the range was the development of water supplies to facilitate the distribution of grazing. The investigations needed for such development formed a large part of the early work in the Soil and Moisture program of the Geological Survey and has continued to be a major activity to the present time. Most of the work has involved investigations of sites for wells but has included also the investigation of proposed spring developments and collection of hydrologic data for use in reservoir design. Well-site investigations have been of two general types: (1) the investigation of a site selected by the land administration agency, and (2) an areal investigation covering entire grazing districts or units thereof. In each type of investigation, a study is made of the geology and the recharge conditions. Reports are prepared giving estimates of the depth of drilling required, the depth to water, the yield, and the quality of the water, together with other information on drilling conditions and developing. Springs are a significant so

Open-File Report

Quality of water from crystalline rock aquifers in New England, New Jersey, and New York, 1995-2007

Crystalline bedrock aquifers in New England and parts of New Jersey and New York (NECR aquifers) are a major source of drinking water. Because the quality of water in these aquifers is highly variable, the U.S. Geological Survey (USGS) statistically analyzed chemical data on samples of untreated groundwater collected from 117 domestic bedrock wells in New England, New York, and New Jersey, and from 4,775 public-supply bedrock wells in New England to characterize the quality of the groundwater. The domestic-well data were from samples collected by the USGS National Water-Quality Assessment (NAWQA) Program from 1995 through 2007. The public-supply-well data were from samples collected for the U.S. Environmental Protection Agency (USEPA) Safe Drinking Water Act (SDWA) Program from 1997 through 2007. Chemical data compiled from the domestic wells include pH, specific conductance, dissolved oxygen, alkalinity, and turbidity; 6 nitrogen and phosphorus compounds, 14 major ions, 23 trace elements, 222 radon gas (radon), 48 pesticide compounds, and 82 volatile organic compounds (VOCs). Additional samples were collected from the domestic wells for the analysis of gross alpha- and gross beta-particle radioactivity, radium isotopes, chlorofluorocarbon isotopes, and the dissolved gases methane, carbon dioxide, nitrogen, and argon. Chemical data compiled from the public-supply wells include pH, specific conductance, nitrate, iron, manganese, sodium, chloride, fluoride, arsenic, uranium, radon, combined radium ( 226 radium plus 228 radium), gross alpha-particle radioactivity, and methyl tert -butyl ether (M t BE). Patterns in fluoride, arsenic, uranium, and radon distributions were discernable when the data were compared to lithology groupings of the bedrock, indicating that the type of bedrock has an effect on the quality of groundwater from NECR aquifers. Fluoride concentrations were significantly higher in groundwater samples from the alkali granite, peraluminous granite, and metaluminous granite lithology groups than from samples in the other lithology groups. Water samples from 1.4 percent of 2,167 studied wells had fluoride concentrations that were equal to or greater than the maximum contaminant level (MCL) of 4 milligrams per liter (mg/L) and 7.5 percent of the wells had fluoride concentrations that were equal to or greater than the secondary MCL of 2 mg/L. For arsenic, groundwater samples from the calcareous metasedimentary rocks in the New Hampshire-Maine geologic province, peraluminous granite, and pelitic rocks lithology groups had higher concentrations than did samples from the other lithology groups. Water samples from 13.3 percent of 2,054 studied wells had arsenic concentrations that were equal to or greater than the MCL of 10 micrograms per liter (μg/L), about double the national rate of occurrence in community-supply systems and in domestic wells of the United States. Uranium concentrations were significantly higher in groundwater samples from the peraluminous granite, alkali granite, and calcareous metasedimentary rocks in the New Hampshire-Maine geologic province lithology groups than from samples in the other lithology groups. Water samples from 14.2 percent of 556 studied wells had uranium concentrations equal to or greater than the MCL of 30 μg/L. Radon activities were equal to or greater than the proposed MCL of 300 picocuries per liter (pCi/L) in 95 percent of 943 studied wells, and 33 percent of the wells had radon activities were equal to or greater than the proposed alternative maximum contaminant level (AMCL) of 4,000 pCi/L. Radon activities exceeded the proposed AMCL in 20 percent or more of groundwater samples in each of the studied lithology groups with a minimum of 9 samples, but radon activities were significantly higher in groundwater samples from the alkali granite, peraluminous granite, and Narragansett basin metasedimentary rocks lithology groups. Water samples from 3.2 percent of 564 studied wells had combined radium activities equal to or greater than the MCL of 5 pCi/L; however, combined radium activities were not significantly different among the studied lithology groups. Land use and population density also were evaluated to explain patterns in water quality. Concentrations of nitrate, sodium, chloride, and MtBE from the studied wells were significantly greater in areas of high population density (≥50 persons per square kilometer) than in areas of low population density (<50 persons per square kilometer). Concentrations of sodium, chloride, and M t BE from the studied wells were significantly greater in areas classified as developed (urban lands) than in areas classified as undeveloped (forested), agricultural, or mixed (no dominant land use). Nitrate concentrations from the public-supply wells were not significantly different among the four land use categories, but nitrate concentrations from the domestic wells were significantly greater in areas classified as developed than in areas classified as undeveloped, agricultural, or mixed. Chloride to bromide mass ratios in the domestic well samples indicate that the groundwater was probably affected by at least three halogen sources: local precipitation and recharge waters, remnant seawater and connate waters evolved from seawater, and recharge waters affected by road salt. The groundwater in the NECR aquifers generally contained low concentrations of nitrate, VOCs, and pesticides. Less than 1 percent of water samples from 4,781 studied wells had concentrations of nitrate greater than the MCL of 10 mg/L. Less than 1 percent of water samples from 1,299 studied wells exceeded the USEPA advisory level of 20 to 40 μg/L for M t BE. None of the other studied VOCs exceeded a human health benchmark. M t BE (36 percent frequency detection) and chloroform (32.9 percent frequency detection) were the most frequently detected (>0.02 μg/L) VOCs in the domestic wells. M t BE was detected more often in water samples with apparent ages of less than 25 years than in water samples with apparent ages greater than 25 years. This finding is consistent with the time period of high M t BE use in areas in the United States where reformulated gasoline was mandated. The largest pesticide concentration was an estimated concentration of 0.06 μg/L for the herbicide metolachlor. Deethylatrazine, a degradate of atrazine, (18 percent frequency detection) and atrazine (8 percent frequency detection) were the only pesticide compounds detected (>0.001 μg/L) in more than 3 percent of the domestic wells. None of the detected pesticide compounds exceeded human health benchmarks. Concentrations of nitrate and gross alpha-particle activities were significantly greater in the water samples from the domestic wells than in samples from the public-supply wells. Concentrations of sodium, chloride, iron, manganese, and uranium were significantly greater in the water samples from the public-supply wells than in the samples from the domestic wells. One possible explanation may be related to differences in field processing (filtered samples from the domestic wells compared to unfiltered samples from the public-supply wells). The high frequency of detections for a wide variety of manmade and naturally occurring contaminants in both domestic and public-supply wells shows the vulnerability of NECR aquifers to contamination. The highly variable water quality and the association with highly variable lithology of crystalline bedrock underscores the importance of testing individual wells to determine if concentrations for the most commonly detected contaminants exceed human health benchmarks.

Connecticut, Maine, Massachusetts, New Hampshire,