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Groundwater-quality data in the Western San Joaquin Valley study unit, 2010 - Results from the California GAMA Program

Groundwater quality in the approximately 2,170-square-mile Western San Joaquin Valley (WSJV) study unit was investigated by the U.S. Geological Survey (USGS) from March to July 2010, as part of the California State Water Resources Control Board (SWRCB) Groundwater Ambient Monitoring and Assessment (GAMA) Program's Priority Basin Project (PBP). The GAMA-PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001 and is being conducted in collaboration with the SWRCB and Lawrence Livermore National Laboratory (LLNL). The WSJV study unit was the twenty-ninth study unit to be sampled as part of the GAMA-PBP. The GAMA Western San Joaquin Valley study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the primary aquifer system, and to facilitate statistically consistent comparisons of untreated groundwater quality throughout California. The primary aquifer system is defined as parts of aquifers corresponding to the perforation intervals of wells listed in the California Department of Public Health (CDPH) database for the WSJV study unit. Groundwater quality in the primary aquifer system may differ from the quality in the shallower or deeper water-bearing zones; shallow groundwater may be more vulnerable to surficial contamination. In the WSJV study unit, groundwater samples were collected from 58 wells in 2 study areas (Delta-Mendota subbasin and Westside subbasin) in Stanislaus, Merced, Madera, Fresno, and Kings Counties. Thirty-nine of the wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and 19 wells were selected to aid in the understanding of aquifer-system flow and related groundwater-quality issues (understanding wells). The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOCs], low-level fumigants, and pesticides and pesticide degradates), constituents of special interest (perchlorate, N -nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), and naturally occurring inorganic constituents (trace elements, nutrients, dissolved organic carbon [DOC], major and minor ions, silica, total dissolved solids [TDS], alkalinity, total arsenic and iron [unfiltered] and arsenic, chromium, and iron species [filtered]). Isotopic tracers (stable isotopes of hydrogen, oxygen, and boron in water, stable isotopes of nitrogen and oxygen in dissolved nitrate, stable isotopes of sulfur in dissolved sulfate, isotopic ratios of strontium in water, stable isotopes of carbon in dissolved inorganic carbon, activities of tritium, and carbon-14 abundance), dissolved standard gases (methane, carbon dioxide, nitrogen, oxygen, and argon), and dissolved noble gases (argon, helium-4, krypton, neon, and xenon) were measured to help identify sources and ages of sampled groundwater. In total, 245 constituents and 8 water-quality indicators were measured. Quality-control samples (blanks, replicates, or matrix spikes) were collected at 16 percent of the wells in the WSJV study unit, and the results for these samples were used to evaluate the quality of the data from the groundwater samples. Blanks rarely contained detectable concentrations of any constituent, suggesting that contamination from sample collection procedures was not a significant source of bias in the data for the groundwater samples. Replicate samples all were within acceptable limits of variability. Matrix-spike recoveries were within the acceptable range (70 to 130 percent) for approximately 87 percent of the compounds. This study did not evaluate the quality of water delivered to consumers. After withdrawal, groundwater typically is treated, disinfected, and (or) blended with other waters to maintain water quality. Regulatory benchmarks apply to water that is delivered to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based benchmarks established by the U.S. Environmental Protection Agency (USEPA) and CDPH, and to non-regulatory benchmarks established for aesthetic concerns by CDPH. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. Most inorganic constituents detected in groundwater samples from the 39 grid wells were detected at concentrations less than health-based benchmarks. Detections of organic and special-interest constituents from grid wells sampled in the WSJV study unit also were less than health-based benchmarks. In total, VOCs were detected in 12 of the 39 grid wells sampled (approximately 31 percent), pesticides and pesticide degradates were detected in 9 grid wells (approximately 23 percent), and perchlorate was detected in 15 grid wells (approximately 38 percent). Trace elements, major and minor ions, and nutrients were sampled for at 39 grid wells; most concentrations were less than health-based benchmarks. Exceptions include two detections of arsenic greater than the USEPA maximum contaminant level (MCL-US) of 10 micrograms per liter (μg/L), 20 detections of boron greater than the CDPH notification level (NL-CA) of 1,000 μg/L, 2 detections of molybdenum greater than the USEPA lifetime health advisory level (HAL-US) of 40 μg/L, 1 detection of selenium greater than the MCL-US of 50 μg/L, 2 detections of strontium greater than the HAL-US of 4,000 μg/L, and 3 detections of nitrate greater than the MCL-US of 10 μg/L. Results for inorganic constituents with non-health-based benchmarks (iron, manganese, chloride, sulfate, and TDS) showed that iron concentrations greater than the CDPH secondary maximum contaminant level (SMCL-CA) of 300 μg/L were detected in five grid wells. Manganese concentrations greater than the SMCL-CA of 50 μg/L were detected in 16 grid wells. Chloride concentrations greater than the recommended SMCL-CA benchmark of 250 milligrams per liter (mg/L) were detected in 14 grid wells, and concentrations in 5 of these wells also were greater than the upper SMCL-CA benchmark of 500 mg/L. Sulfate concentrations greater than the recommended SMCL-CA benchmark of 250 mg/L were measured in 21 grid wells, and concentrations in 13 of these wells also were greater than the SMCL-CA upper benchmark of 500 mg/L. TDS concentrations greater than the SMCL-CA recommended benchmark of 500 mg/L were measured in 36 grid wells, and concentrations in 20 of these wells also were greater than the SMCL-CA upper benchmark of 1,000 mg/L.

California

Geographic drivers of mercury entry into aquatic food webs revealed by mercury stable isotopes in dragonfly larvae

Atmospheric mercury (Hg) emissions and subsequent transport and deposition are major concerns within protected lands, including national parks, where Hg can bioaccumulate to levels detrimental to human and wildlife health. Despite this risk to biological resources, there is limited understanding of the relative importance of different Hg sources and delivery pathways within protected regions. Here, we used Hg stable isotope measurements of a single aquatic bioindicator, dragonfly larvae, to determine if these tracers can resolve spatial patterns in Hg sources, delivery mechanisms, and aquatic cycling at a national scale. Mercury isotope values in dragonfly tissues varied among habitat types (e.g., lentic, lotic, wetland) and geographic location. Photochemical-derived isotope fractionation was habitat-dependent and influenced by factors that impact light penetration directly or indirectly, including dissolved organic matter, canopy cover, and total phosphorus. Strong patterns for Δ 200 Hg emerged in the western US, highlighting the relative importance of wet deposition sources in arid regions in contrast to dry deposition delivery in forested regions. This work highlights the efficacy of dragonfly larvae as biosentinels for Hg isotope studies due to their ubiquity across freshwater ecosystems and ability to track variation in Hg sources and processing attributed to small-scale habitat and large-scale regional patterns.

Environmental Science and Technology

Groundwater-quality data in the Bear Valley and Selected Hard Rock Areas study unit, 2010: Results from the California GAMA Program

Groundwater quality in the 112-square-mile Bear Valley and Selected Hard Rock Areas (BEAR) study unit was investigated by the U.S. Geological Survey (USGS) from April to August 2010, as part of the California State Water Resources Control Board (SWRCB) Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project (PBP). The GAMA-PBP was developed in response to the California Groundwater Quality Monitoring Act of 2001 and is being conducted in collaboration with the SWRCB and Lawrence Livermore National Laboratory (LLNL). The BEAR study unit was the thirty-first study unit to be sampled as part of the GAMA-PBP. The GAMA Bear Valley and Selected Hard Rock Areas study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the primary aquifer system and to facilitate statistically consistent comparisons of untreated groundwater quality throughout California. The primary aquifer system is defined as the zones corresponding to the perforation intervals of wells listed in the California Department of Public Health (CDPH) database for the BEAR study unit. Groundwater quality in the primary aquifer system may differ from the quality in the shallow or deep water-bearing zones; shallow groundwater may be more vulnerable to surficial contamination. In the BEAR study unit, groundwater samples were collected from two study areas (Bear Valley and Selected Hard Rock Areas) in San Bernardino County. Of the 38 sampling sites, 27 were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the primary aquifer system in the study unit (grid sites), and the remaining 11 sites were selected to aid in the understanding of the potential groundwater-quality issues associated with septic tank use and with ski areas in the study unit (understanding sites). The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOCs], pesticides and pesticide degradates, pharmaceutical compounds, and wastewater indicator compounds [WICs]), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-trichloropropane [1,2,3-TCP]), and inorganic constituents (trace elements, nutrients, dissolved organic carbon [DOC], major and minor ions, silica, total dissolved solids [TDS], alkalinity, and arsenic and iron species), and uranium and other radioactive constituents (radon-222 and activities of tritium and carbon-14). Isotopic tracers (of hydrogen and oxygen in water, of nitrogen and oxygen in dissolved nitrate, of dissolved boron, isotopic ratios of strontium in water, and of carbon in dissolved inorganic carbon) and dissolved noble gases (argon, helium-4, krypton, neon, and xenon) were measured to help identify the sources and ages of sampled groundwater. In total, groundwater samples were analyzed for 289 unique constituents and 8 water-quality indicators in the BEAR study unit. Quality-control samples (blanks, replicate pairs, or matrix spikes) were collected at 13 percent of the sites in the BEAR study unit, and the results for these samples were used to evaluate the quality of the data from the groundwater samples. Blank samples rarely contained detectable concentrations of any constituent, indicating that contamination from sample collection or analysis was not a significant source of bias in the data for the groundwater samples. Replicate pair samples all were within acceptable limits of variability. Matrix-spike sample recoveries were within the acceptable range (70 to 130 percent) for approximately 84 percent of the compounds. This study did not evaluate the quality of water delivered to consumers. After withdrawal, groundwater typically is treated, disinfected, and (or) blended with other waters to maintain water quality. Regulatory benchmarks apply to water that is delivered to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based benchmarks established by the U.S. Environmental Protection Agency (USEPA) and CDPH, and to non-health-based benchmarks established for aesthetic concerns by CDPH. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. All concentrations of organic and special-interest constituents from grid sites sampled in the BEAR study unit were less than health-based benchmarks. In total, VOCs were detected in 17 of the 27 grid sites sampled (approximately 63 percent), pesticides and pesticide degradates were detected in 4 grid sites (approximately 15 percent), and perchlorate was detected in 21 grid sites (approximately 78 percent). Inorganic constituents (trace elements, major and minor ions, nutrients, and uranium and other radioactive constituents) were sampled for at 27 grid sites; most concentrations were less than health-based benchmarks. Exceptions include one detection of arsenic greater than the USEPA maximum contaminant level (MCL-US) of 10 micrograms per liter (μg/L), three detections of uranium greater than the MCL-US of 30 μg/L, nine detections of radon-222 greater than the proposed MCL-US of 4,000 picocuries per liter (pCi/L), and one detection of fluoride greater than the CDPH maximum contaminant level (MCL-CA) of 2 milligrams per liter. Concentrations of inorganic constituents with non-health-based benchmarks (iron, manganese, chloride, and TDS) were less than the CDPH secondary maximum contaminant level (SMCL-CA) in most grid sites. Exceptions include two detections of iron greater than the SMCL-CA of 300 μg/L and one detection of manganese greater than the SMCL-CA of 50 μg/L.

California

Ground-water quality data in the coastal Los Angeles Basin study unit, 2006: Results from the California GAMA Program

Ground-water quality in the approximately 860 square-mile Coastal Los Angeles Basin study unit (CLAB) was investigated from June to November of 2006 as part of the Statewide Basin Assessment Project of the Ground-Water Ambient Monitoring and Assessment (GAMA) Program. The GAMA Statewide Basin Assessment was developed in response to the Ground-Water 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). The Coastal Los Angeles Basin study was designed to provide a spatially unbiased assessment of raw ground-water quality within CLAB, as well as a statistically consistent basis for comparing water quality throughout California. Samples were collected from 69 wells in Los Angeles and Orange Counties. Fifty-five of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (?grid wells?). Fourteen additional wells were selected to evaluate changes in ground-water chemistry or to gain a greater understanding of the ground-water quality within a specific portion of the Coastal Los Angeles Basin study unit ('understanding wells'). Ground-water samples were analyzed for: a large number of synthetic organic constituents [volatile organic compounds (VOCs), gasoline oxygenates and their degradates, pesticides, polar pesticides, and pesticide degradates, pharmaceutical compounds, and potential wastewater-indicators]; constituents of special interest [perchlorate, N-nitrosodimethylamine (NDMA), 1,4-dioxane, and 1,2,3-trichloropropane (1,2,3-TCP)]; inorganic constituents that can occur naturally [nutrients, major and minor ions, and trace elements]; radioactive constituents [gross-alpha and gross-beta radiation, radium isotopes, and radon-222]; and microbial indicators. Naturally occurring isotopes [stable isotopic ratios of hydrogen and oxygen, 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. Quality-control samples (blanks, replicates, and samples for matrix spikes) were collected at approximately one-fourth of the wells, and the results for these samples were used to evaluate the quality of the data for the ground-water samples. Field blanks rarely contained detectable concentrations of any constituent, suggesting that contamination was not a significant source of bias. Differences between replicate samples were within acceptable ranges, indicating acceptably low variability. Matrix spike recoveries were within acceptable ranges for most compounds. Assessment of the quality-control information resulted in applying ?V? codes to approximately 0.1 percent of the data collected for ground-water samples (meaning a constituent was detected in blanks as well as the corresponding environmental data). This study did not attempt to evaluate the quality of drinking water delivered to consumers; after withdrawal from the ground, water typically is treated, disinfected, and (or) blended with other waters to maintain acceptable drinking-water quality. Regulatory thresholds are applied to the treated drinking 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 regulatory and non-regulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA), California Department of Public Health (CDPH, formerly California Department of Health Services [CADHS]) and thresholds established for aesthetic concerns (secondary maximum contaminant levels, SMCL-CA) by CDPH. Comparisons between data collected for this study and drinking-water thresholds are for illustrative purposes only, and are not indicative of compliance or non-compliance with those thresholds. VOCs were detected in alm

California

Groundwater-quality data in the South Coast Range-Coastal study unit, 2008: Results from the California GAMA Program

Groundwater quality in the approximately 766-square-mile South Coast Range–Coastal (SCRC) study unit was investigated from May to December 2008, as part of the Priority Basins Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basins Project was developed in response to legislative mandates (Supplemental Report of the 1999 Budget Act 1999-00 Fiscal Year; and, the Groundwater Quality Monitoring Act of 2001 [Sections 10780-10782.3 of the California Water Code, Assembly Bill 599]) to assess and monitor the quality of groundwater in California, and is being conducted by the U.S. Geological Survey (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The SCRC study unit was the 25th study unit to be sampled as part of the GAMA Priority Basins Project. The SCRC study unit was designed to provide a spatially unbiased assessment of untreated groundwater quality in the primary aquifer systems and to facilitate statistically consistent comparisons of untreated groundwater quality throughout California. The primary aquifer systems (hereinafter referred to as primary aquifers) were defined as that part of the aquifer corresponding to the perforation interval of wells listed in the California Department of Public Health (CDPH) database for the SCRC study unit. The quality of groundwater in shallow or deep water-bearing zones may differ from the quality of groundwater in the primary aquifers; shallow groundwater may be more vulnerable to surficial contamination. In the SCRC study unit, groundwater samples were collected from 70 wells in two study areas (Basins and Uplands) in Santa Barbara and San Luis Obispo Counties. Fifty-five of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study unit (grid wells), and 15 wells were selected to aid in evaluation of specific water-quality issues (understanding wells). In addition to the 70 wells sampled, 3 surface-water samples were collected in streams near 2 of the sampled wells in order to better comprehend the interaction between groundwater and surface water in the area. The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, polar pesticides and metabolites, and pharmaceutical compounds), constituents of special interest (perchlorate, N-nitrosodimethylamine [NDMA], and 1,2,3-TCP), naturally occurring inorganic constituents (trace elements, nutrients, dissolved organic carbon [DOC], major and minor ions, silica, total dissolved solids [TDS], and alkalinity), and radioactive constituents (gross alpha and gross beta radioactivity). Naturally occurring isotopes (stable isotopes of hydrogen and oxygen in water, stable isotopes of nitrogen and oxygen in dissolved nitrate, stable isotopes of sulfur in dissolved sulfate, stable isotopes of carbon in dissolved inorganic carbon, activities of tritium, and carbon-14 abundance), and dissolved gases (including noble gases) also were measured to help identify the sources and ages of the sampled groundwater. In total, 298 constituents and field water-quality indicators were investigated. Three types of quality-control samples (blanks, replicates, and matrix-spikes) were collected at approximately 3 to 12 percent of the wells in the SCRC study unit, 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 from sample collection procedures was not a significant source of bias in the data for the groundwater samples. Differences between replicate samples generally were less than 10 percent relative and/or standard deviation, indicating acceptable analytical reproducibility. Matrix-spike recoveries were within the acceptable range (70 to 130 percent) for approximately 84 percent of the compounds. This study did not attempt to evaluate the quality of drinking water delivered to consumers; after withdrawal from the ground, untreated groundwater typically is treated, disinfected, and/or blended with other waters to maintain water quality. Regulatory thresholds apply to water that is served to the consumer, not to untreated groundwater. However, to provide some context for the results, concentrations of constituents measured in the untreated groundwater were compared with regulatory and non-regulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and CDPH, and to non-regulatory thresholds established for aesthetic 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 noncompliance with those thresholds. Most organic and inorganic constituents that were detected in groundwater samples from the 55 grid wells in the SCRC study unit were detected at concentrations less than drinking-water thresholds. In addition, all detections of organic constituents in SCRC grid well samples were less than health-based thresholds. In total, VOCs were detected in 33 percent of the 55 grid wells sampled and pesticides and pesticide degradates were detected in 27 percent of grid wells sampled in the SCRC study unit. In the Basins study area, VOCs and pesticides and pesticide degradates were detected in approximately 33 percent of the 39 grid wells. In the Uplands study area, VOCs were detected in approximately 31 percent and pesticides and pesticide degradates were detected in approximately 13 percent of the 16 grid wells. Trace elements and minor ions were sampled for at 32 grid wells and nutrients at 33 grid wells in the SCRC study unit, and most detections were less than health-based thresholds. Exceptions in the Basins study area include one detection of arsenic greater than the USEPA maximum contaminant level (MCL-US) of 10 µg/L and three detections of nitrite plus nitrate, as nitrogen (NO2-+NO3-) greater than the MCL-US of 10 mg/L. Exceptions in the Uplands study area include two detections of arsenic greater than the MCL-US and eight detections of molybdenum greater than the USEPA lifetime health advisory level (HAL-US) of 40 µg/L. All detections of major and minor ions and gross alpha and gross beta radioactivity from the SCRC grid wells were less than health-based thresholds. Results for trace elements, major ions, and TDS with non-enforceable thresholds set for aesthetic concerns from 16 Basins study area grid wells showed that iron concentrations greater than the CDPH secondary maximum contaminant level (SMCL-CA) of 300 µg/L were detected in grid wells. Manganese concentrations greater than the SMCL-CA of 50 µg/L were detected in six grid wells. Chloride concentrations greater than the recommended SMCL-CA threshold of 250 mg/L were detected in one grid well. Sulfate concentrations greater than the recommended SMCL-CA threshold of 250 mg/L were measured in 12 grid wells and 3 of these wells also were greater than the upper SMCL-CA threshold of 500 mg/L. TDS concentrations greater than the SMCL-CA recommended threshold of 500 mg/L were measured in 14 of the 16 Basins study area grid wells and concentrations in 5 of these wells also were greater than the SMCL-CA upper threshold of 1,000 mg/L. In the Uplands study area, iron concentrations greater than the SMCL-CA were detected in 2 of 16 grid wells and manganese concentrations greater than the SMCL-CA were detected in 3 grid wells. TDS and sulfate concentrations greater than the recommended SMCL-CA thresholds were detected in 11 and 2 grid wells, respectively, but none of these concentrations were greater than the SMCL-CA upper thresholds.

California

Use of radium isotopes to determine the age and origin of radioactive barite at oil-field production sites

Radium-bearing barite (radiobarite) is a common constituent of scale and sludge deposits that form in oil-field production equipment. The barite forms as a precipitate from radium-bearing, saline formation water that is pumped to the surface along with oil. Radioactivity levels in some oil-field equipment and in soils contaminated by scale and sludge can be sufficiently high to pose a potential health threat. Accurate determinations of radium isotopes (226Ra+228Ra) in soils are required to establish the level of soil contamination and the volume of soil that may exceed regulatory limits for total radium content. In this study the radium isotopic data are used to provide estimates of the age of formation of the radiobarite contaminant. Age estimates require that highly insoluble radiobarite approximates a chemically closed system from the time of its formation. Age estimates are based on the decay of short-lived 228Ra (half-life=5.76 years) compared to 226Ra (half-life=1600 years). Present activity ratios of 228Ra/226Ra in radiobarite-rich scale or highly contaminated soil are compared to initial ratios at the time of radiobarite precipitation. Initial ratios are estimated by measurements of saline water or recent barite precipitates at the site or by considering a range of probable initial ratios based on reported values in modern oil-field brines. At sites that contain two distinct radiobarite sources of different age, the soils containing mixtures of sources can be identified, and mixing proportions quantified using radium concentration and isotopic data. These uses of radium isotope data provide more description of contamination history and can possibly address liability issues. Copyright ?? 2000 .

Environmental Pollution

Altitude, age, and quality of groundwater, Papio-Missouri River Natural Resources District, eastern Nebraska, 1992 to 2009

The U.S. Geological Survey, in cooperation with the Papio-Missouri River Natural Resources District (PMRNRD), conducted this study to map the water-level altitude of 2009 within the Elkhorn River Valley, Missouri River Valley, and Platte River Valley alluvial aquifers; to present the predevelopment potentiometric-surface altitude within the Dakota aquifer; and to describe the age and quality of groundwater in the five principal aquifers of the PMRNRD in eastern Nebraska using data collected from 1992 to 2009. In addition, implications of alternatives to the current PMRNRD groundwater-quality monitoring approach are discussed. In the PMRNRD, groundwater altitude, relative to National Geodetic Vertical Datum of 1929, ranged from about 1,080 feet (ft) to 1,180 ft in the Elkhorn River Valley alluvial aquifer and from about 960 ft to 1,080 ft in the Missouri River Valley and Platte River Valley alluvial aquifers. In the PMRNRD, the estimated altitude of the potentiometric surface of the Dakota aquifer, predevelopment, ranged from about 1,100 ft to 1,200 ft. To assess groundwater age and quality, groundwater samples were collected from a total of 217 wells from 1992 to 2009 for analysis of various analytes. Groundwater samples collected in the PMRNRD from 1992 to 2009 and interpreted in this report were analyzed for age-dating analytes (chlorofluorocarbons), dissolved gases, major ions, trace elements, nutrients, stable isotope ratios, pesticides and pesticide degradates, volatile organic compounds, explosives, and 222radon. Apparent groundwater age was estimated from concentrations of chlorofluorocarbons measured in samples collected in 2000. Apparent groundwater-recharge dates ranged from older than 1940 in samples from wells screened in the Missouri River Valley alluvial aquifer to the early 1980s in samples from wells screened in the Dakota aquifer. Concentrations of major ions in the most recent sample per well collected from 1992 to 2009 indicate that the predominant water type was calcium bicarbonate. Samples from 4 wells exceeded the U.S. Environmental Protection Agency (USEPA) Secondary Drinking Water Regulation (SDWR) for sulfate [250 milligrams per liter (mg/L)], and samples from 4 wells exceeded the USEPA Drinking Water Advisory Table for sodium (30-60 mg/L). Eighteen of the 21 trace elements analyzed in samples from PMRNRD wells have USEPA drinking-water standards. Sixteen of the trace elements with USEPA standards were detected in the selected samples. In the samples selected for trace-element analysis, the only trace-element concentration that exceeded an enforceable USEPA drinking-water standard, the Maximum Contaminant Level (MCL), was for arsenic; arsenic concentration exceeded the USEPA MCL of 10 micrograms per liter (μg/L) in 4 percent of the samples. Trace-element concentrations that exceeded the USEPA SDWR or Lifetime Health Advisory level were iron (46 percent of the samples were greater than USEPA SDWR of 300 μg/L), manganese (70 percent of the samples were greater than USEPA SDWR of 50 μg/L), and strontium (4 percent of the samples were greater than USEPA Lifetime Health Advisory level of 4,000 μ/L). The concentration of nitrate plus nitrite as nitrogen (nitrate-N) in the most recent nutrient samples collected from the network wells and from one randomly selected well in the well nests from 1992 to 2009 for most wells (80 percent) ranged from less than 0.06 to 8.55 mg/L, with a median value of 0.12 mg/L. Concentrations of nitrate-N in 13 (7 percent) nutrient samples, 1992 to 2009, were greater than or equal to the USEPA MCL and Nebraska Title-118 standard of 10 mg/L, and concentrations of nitrate-N in 35 (18 percent) nutrient samples, 1992 to 2009, were greater than or equal to 5 mg/L, which is the PMRNRD action level for possible management implementation to reduce nitrate concentrations in groundwater. Of the 61 pesticides or pesticide degradates analyzed from 2007 to 2009, 21 were detected. Three of the 21 pesticides detected (alachlor, atrazine, and metolachlor) have established health-based criteria; all detections of these compounds were at concentrations less than their USEPA standards. From 2007 to 2009, 1 or more pesticide compounds were detected in 16 of the 82 network wells and in 18 of the 26 wells in well nests. From 2007 to 2009, the individual pesticide compounds that were detected most frequently were alachlor ethane sulfonic acid, a degradate of alachlor; deethylcyanazine acid, a degradate of cyanazine; and atrazine. Analytes with concentrations that exceeded 30 percent of the applicable Nebraska Title-118 standard were identified so that the PMRNRD can plan to monitor groundwater in the area and consider possible actions should the analyte concentrations continue to rise. The analytical results from the most recent samples collected in the network wells and all the wells in well nests from 1992 to 2009 indicate that, in at least 1 sample, there was a concentration that exceeded 30 percent of the Nebraska Title-118 standard for at least 1 of 3 major ions (chloride, fluoride, and sulfate), 1 nutrient (nitrate-N), 1 pesticide (atrazine), or 3 trace elements (arsenic, iron, and manganese). In addition, 30 percent of the USEPA MCL or Nebraska Title-118 standard for gross alpha activity likely was exceeded in samples from three wells screened in the Dakota aquifer. Study findings indicate that some alternatives to the current PMRNRD groundwater-sampling approach that could be considered are to collect fewer samples for nutrient analysis and to collect samples periodically for determining concentrations of additional analytes, particularly the analytes with concentrations that were at least 30 percent or more than the Nebraska Title-118 standard.

Nebraska

Assessment of per- and polyfluoroalkyl substances in water resources of New Mexico, 2020–21

Per- and polyfluoroalkyl substances (PFAS) have been detected in public and private drinking-water wells, springs, and surface waters in New Mexico; however, the presence and distribution of PFAS in water resources across the State are not well characterized. From August 2020 to October 2021, the U.S. Geological Survey, in cooperation with the New Mexico Environment Department, collected water-quality samples from groundwater and surface-water sites throughout New Mexico. One hundred and seventeen groundwater wells were sampled from unconfined water-table aquifers for PFAS and a geochemical suite including major ions, trace elements, nutrients, dissolved organic carbon (DOC), stable isotopes of oxygen and hydrogen, tritium, and carbon-14 to provide context for groundwater age and geochemical evolution. Eighteen surface-water samples were analyzed for PFAS, and select samples were analyzed for wastewater tracers, major ions, trace elements, and DOC. Blanks and replicates indicated low bias and variability for PFAS, wastewater tracers, and geochemical compounds. Twenty-seven of the 117 groundwater sites had PFAS concentrations reported above the detection level, and there were no exceedances of the 2016 U.S. Environmental Protection Agency health advisory of 70 nanograms per liter (ng/L) perfluorooctanoic acid plus perfluorooctane sulfonic acid. Twenty-two sites were resampled and showed similar signatures, excluding some springs. Total PFAS concentrations ranged from 0.91 to 80.3 ng/L. The most frequently detected PFAS at groundwater sites were perfluorobutanesulfonic acid (PFBS; 11 sites), perfluoropentanoic acid (10 sites), and perfluorohexanoic acid (9 sites). Correlations were found between certain PFAS compounds that suggest similar sources. PFAS were also correlated with tritium, DOC, and nitrate, which indicated that a presence of anthropogenic compounds could in turn indicate a likelihood of PFAS occurrence. In addition, a cluster analysis showed that varying geochemical processes and sources of anthropogenic compounds likely contribute to the PFAS signature of each groundwater sample. Surface-water samples showed variable total PFAS concentrations ranging from 1.0 to 155.4 ng/L. Sites downstream from urban areas showed numerous PFAS detections. Some undeveloped areas where minimal PFAS detections would be expected had PFAS detections. Correlations between PFAS were found that suggested similar sources. Perfluoropentanoic acid and PFBS were the most frequently detected PFAS, and PFBS had the highest single concentration of 93 ng/L. Results of the study provide an overview of PFAS occurrences in the water resources of New Mexico along with geochemical context and are used to identify areas for further scientific investigations that could further characterize PFAS occurrences in New Mexico.

New Mexico

Groundwater-quality data in 12 GAMA study units: Results from the 2006–10 initial sampling period and the 2008–13 trend sampling period, California GAMA Priority Basin Project

The Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) program was developed in response to the Groundwater Quality Monitoring Act of 2001 and is being conducted by the U.S. Geological Survey in cooperation with the California State Water Resources Control Board. From 2004 through 2012, the GAMA-PBP collected samples and assessed the quality of groundwater resources that supply public drinking water in 35 study units across the State. Selected sites in each study unit were sampled again approximately 3 years after initial sampling as part of an assessment of temporal trends in water quality by the GAMA-PBP. Twelve of the study units, initially sampled during 2006–11 (initial sampling period) and sampled a second time during 2008–13 (trend sampling period) to assess temporal trends, are the subject of this report. The initial sampling was designed to provide a spatially unbiased assessment of the quality of untreated groundwater used for public water supplies in the 12 study units. In these study units, 550 sampling sites were selected by using a spatially distributed, randomized, grid-based method to provide spatially unbiased representation of the areas assessed (grid sites, also called “status sites”). After the initial sampling period, 76 of the previously sampled status sites (approximately 10 percent in each study unit) were randomly selected for trend sampling (“trend sites”). The 12 study units sampled both during the initial sampling and during the trend sampling period were distributed among 6 hydrogeologic provinces: Coastal (Northern and Southern), Transverse Ranges and Selected Peninsular Ranges, Klamath, Modoc Plateau and Cascades, and Sierra Nevada Hydrogeologic Provinces. For the purposes of this trend report, the six hydrogeologic provinces were grouped into two hydrogeologic regions based on location: Coastal and Mountain. The groundwater samples were analyzed for a number of synthetic organic constituents (volatile organic compounds, pesticides, and pesticide degradates), constituents of special interest (perchlorate and 1,2,3-trichloropropane), and natural inorganic constituents (nutrients, major and minor ions, and trace elements). Isotopic tracers (tritium, carbon-14, and stable isotopes of hydrogen and oxygen in water) also were measured to help identify processes affecting groundwater quality and the sources and ages of the sampled groundwater. More than 200 constituents and water-quality indicators were measured during the trend sampling period. Quality-control samples (blanks, replicates, matrix-spikes, and surrogate compounds) were collected at about one-third of the trend sites, and the results for these samples were used to evaluate the quality of the data for the groundwater samples. On the basis of detections in laboratory and field blank samples collected by GAMA-PBP study units, including the 12 study units presented here, reporting levels for some groundwater results were adjusted in this report. Differences between replicate samples were mostly within acceptable ranges, indicating low variability in analytical results. Matrix-spike recoveries were largely within the acceptable range (70 to 130 percent). This study did not attempt to evaluate the quality of water delivered to consumers. After withdrawal, groundwater used for drinking water typically is treated, disinfected, and blended with other waters to achieve acceptable water quality. The comparison benchmarks used in this report apply to treated water that is served to the consumer, not to untreated groundwater. To provide some context for the results, however, concentrations of constituents measured in these groundwater samples were compared with benchmarks established by the U.S. Environmental Protection Agency and the State of California. Comparisons between data collected for this study and benchmarks for drinking water are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. Most organic constituents that were detected in groundwater samples from the trend sites were found at concentrations less than health-based benchmarks. One volatile organic compound—perchloroethene—was detected at a concentration greater than the health-based benchmark in samples from one trend site during the initial and trend sampling periods. Chloroform was detected in at least 10 percent of the samples at trend sites in both sampling periods. Methyl tert -butyl ether was detected in samples from more than 10 percent of the trend sites during the initial sampling period. No pesticide or pesticide degradate was detected in greater than 10 percent of the samples from trend sites or at concentrations greater than their health-based benchmarks during either sampling period. Nutrients were not detected at concentrations greater than their health-based benchmarks during either sampling period. Most detections of major ions and trace elements in samples from trend sites were less than health-based benchmarks during both sampling periods. Arsenic and boron each were detected at concentrations greater than the health-based benchmark in samples from four trend sites during the initial and trend sampling periods. Molybdenum was detected in samples from four trend sites at concentrations greater than the health-based benchmark during both sampling periods. Samples from two of these trend sites had similar molybdenum concentrations, and two had substantially different concentrations during the initial and trend sampling periods. Uranium was detected at a concentration greater than the health-based benchmark only at two trend sites.

California

Assessment of shallow ground-water quality in recently urbanized areas of Sacramento, California, 1998

Evidence for anthropogenic impact on shallow ground-water quality beneath recently developed urban areas of Sacramento, California, has been observed in the sampling results from 19 monitoring wells in 1998. Eight volatile organic compounds (VOCs), four pesticides, and one pesticide transformation product were detected in low concentrations, and nitrate, as nitrogen, was detected in elevated concentrations; all of these concentrations were below National and State primary and secondary maximum contaminant levels. VOC results from this study are more consistent with the results from urban areas nationwide than from agricultural areas in the Central Valley, indicating that shallow ground-water quality has been impacted by urbanization. VOCs detected may be attributed to either the chlorination of drinking water, such as trichloromethane (chloroform) detected in 16 samples, or to the use of gasoline additives, such as methyl tert-butyl ether (MTBE), detected in 2 samples. Pesticides detected may be attributed to use on household lawns and gardens and rights-of-way, such as atrazine detected in three samples, or to past agricultural practices, and potentially to ground-water/surface-water interactions, such as bentazon detected in one sample from a well adjacent to the Sacramento River and downstream from where bentazon historically was used on rice. Concentrations of nitrate may be attributed to natural sources, animal waste, old septic tanks, and fertilizers used on lawns and gardens or previously used on agricultural crops. Seven sample concentrations of nitrate, as nitrogen, exceeded 3.0 milligrams per liter, a level that may indicate impact from human activities. Ground-water recharge from rainfall or surface-water runoff also may contribute to the concentrations of VOCs and pesticides observed in ground water. Most VOCs and pesticides detected in ground-water samples also were detected in air and surface-water samples collected at sites within or adjacent to the recently developed urban areas. Five arsenic sample concentrations exceeded the U.S. Environmental Protection Agency (USEPA) primary maximum contaminant level (MCL) of 10 milligrams per liter adopted in 2001. Measurements that exceeded USEPA or California Department of Health Services recommended secondary maximum contaminant levels include manganese, iron, chloride, total dissolved solids, and specific conductance. These exceedances are probably a result of natural processes. Variations in stable isotope ratios of hydrogen (2H/1H) and oxygen (18O/16O) may indicate different sources or a mixing of recharge waters to the urban ground water. These variations also may indicate recharge directly from surface water in one well adjacent to the Sacramento River. Tritium concentrations indicate that most shallow ground water has been recharged since the mid-1950s, and tritium/helium-3 age dates suggest that recharge has occurred in the last 2 to 30 years in some areas. In areas where water table depths exceed 20 meters and wells are deeper, ground-water recharge may have occurred prior to 1950, but low concentrations of pesticides and VOCs detected in these deeper wells indicate a mixing of younger and older waters. Overall, the recently urbanized areas can be divided into two groups. One group contains wells where few VOCs and pesticides were detected, nitrate mostly was not detected, and National and State maximum contaminant levels, including the USEPA MCL for arsenic, were exceeded; these wells are adjacent to rivers and generally are characterized by younger water, shallow (1 to 4 meters) water table, chemically reducing conditions, finer grained sediments, and higher organics in the soils. In contrast, the other group contains wells where more VOCs, pesticides, and elevated nitrate concentrations were detected; these wells are farther from rivers and are generally characterized by a mixture of young and old waters, intermediate to deep (7 to 35 meters) wate

Scientific Investigations Report

Hydrogeologic and geochemical characterization and evaluation of two arroyos for managed aquifer recharge by surface infiltration in the Pojoaque River Basin, Santa Fe County, New Mexico, 2014–15

In order to provide long-term storage of diverted surface water from the Rio Grande as part of the Aamodt water rights settlement, managed aquifer recharge by surface infiltration in Pojoaque River Basin arroyos was proposed as an option. The initial hydrogeologic and geochemical characterization of two arroyos located within the Pojoaque River Basin was performed in 2014 and 2015 in cooperation with the Bureau of Reclamation to evaluate the potential suitability of these two arroyos as sites for managed aquifer recharge through surface infiltration. The selected reaches were high-gradient (average 3.0–3.5 percent) braided channels filled with unconsolidated sand and gravel-sized deposits that were generally 30–50 feet thick. Saturation was not observed in the unconsolidated channel sands in four subsurface borings but was found at 7–60 feet below the contact between the unconsolidated channel sands and the bedrock. The poorly to well-cemented alluvial deposits that make up the bedrock underlying the unconsolidated channel material is the Tesuque Formation. The individual beds of the Tesuque Formation are reported to be highly heterogeneous and anisotropic, and the bedrock at the site was observed to have variable moisture and large changes in lithology. Surface electrical-resistivity geophysical survey methods showed a sharp contrast between the electrically resistive unconsolidated channel sands and the highly conductive bedrock; however, because of the high conductivity, the resistivity methods were not able to image the water table or preferential flow paths (if they existed) in the bedrock. Infiltration rates measured by double-ring and bulk infiltration tests on a variety of channel morphologies in the study reaches were extremely large (9.7–94.5 feet per day), indicating that the channels could potentially accommodate as much as 6.6 cubic feet per second of applied water without generating surface runoff out of the reach; however, the small volume available for storage in the unconsolidated channel sands (about 410 acre-feet in the east arroyo and about 190 acre-feet in the west arroyo) and the potential for the infiltrating water to preferentially flow over the bedrock contact and out of the reach present a challenge for storing water. Although a detailed assessment of the infiltration rate of the Tesuque Formation is beyond the scope of this investigation, one double-ring infiltrometer test was conducted on an outcrop, resulting in an estimated infiltration rate of about 4 feet per day. The shallow groundwater observed in this investigation was determined to be recharged locally on the basis of groundwater elevations and geochemical and isotopic signatures. The channel sands and shallow bedrock were observed to be weathered, indicating contact with oxic groundwater following deposition. This observation was supported by whole-rock elemental analysis and mineralogy of several core samples. The downward groundwater gradient between the shallow wells and those wells screened at greater depths suggests that the shallow groundwater is recharged by local precipitation and has the potential to migrate to the deeper aquifer units. The two age-dating tracers measured in this investigation, however, demonstrate that the shallow groundwater flow paths are very slow and that the deeper flow paths are likely part of a larger regional system. The composition of the shallow, native groundwater suggests that storing water diverted from the Rio Grande is not likely to leach constituents of concern that would cause the stored water to exceed health-based U.S. Environmental Protection Agency Maximum Contaminant Levels.

New Mexico

Insights into mercury source identification and bioaccumulation using stable isotope approaches in the Hannibal Pool of the Ohio River

Mercury contamination in river systems due to historic and current Hg releases is a persistent concern for both wildlife and human health. In larger rivers, like the Ohio River, USA, it is difficult to directly link Hg discharges to bioaccumulation due to the existence of multiple industrial Hg sources as well as the varied dietary and migratory habits of biota. To better understand how industrial effluent influences the cycling and bioaccumulation of Hg within the Ohio River, Hg stable isotope analysis was applied to various nonbiological and biological media. High Hg concentrations in suspended particulate matter suggest this vector was the largest contributor of Hg to the water column, and distinct Hg source signatures were observed in effluent particulates from different industrial processes, such as chlor‐alkali activity (δ 202 Hg = −0.52‰) and coal power plant discharge (δ 202 Hg = −1.39‰). Despite this distinction, average sediments (δ 202 Hg = −1.00 ± 0.23‰) showed intermediate isotopic signatures that suggest the accumulation of a mixed Hg source driven by multiple industrial discharges. Biota in the system were shown to have a conserved range of δ 202 Hg and estimation approaches related these signatures back to particulate matter within Hannibal Pool. Mussels were found to conserve Hg isotopes signatures independently of food web drivers and served as ideal water column indicators of bioaccumulated Hg sources. This study highlights the complexity of Hg cycling within an industrialized river and shows that an isotope tracer approach can provide insight to water column sources of Hg. Integr Environ Assess Manag 2021;17:233−242. Published 2020. This article is a US Government work and is in the public domain in the USA.

Ohio

Groundwater-quality data in the Monterey–Salinas shallow aquifer study unit, 2013: Results from the California GAMA Program

Groundwater quality in the 3,016-square-mile Monterey–Salinas Shallow Aquifer study unit was investigated by the U.S. Geological Survey (USGS) from October 2012 to May 2013 as part of the California State Water Resources Control Board Groundwater Ambient Monitoring and Assessment (GAMA) Program’s Priority Basin Project. The GAMA Monterey–Salinas Shallow Aquifer study was designed to provide a spatially unbiased assessment of untreated-groundwater quality in the shallow-aquifer systems in parts of Monterey and San Luis Obispo Counties and to facilitate statistically consistent comparisons of untreated-groundwater quality throughout California. The shallow-aquifer system in the Monterey–Salinas Shallow Aquifer study unit was defined as those parts of the aquifer system shallower than the perforated depth intervals of public-supply wells, which generally corresponds to the part of the aquifer system used by domestic wells. Groundwater quality in the shallow aquifers can differ from the quality in the deeper water-bearing zones; shallow groundwater can be more vulnerable to surficial contamination. Samples were collected from 170 sites that were selected by using a spatially distributed, randomized grid-based method. The study unit was divided into 4 study areas, each study area was divided into grid cells, and 1 well was sampled in each of the 100 grid cells (grid wells). The grid wells were domestic wells or wells with screen depths similar to those in nearby domestic wells. A greater spatial density of data was achieved in 2 of the study areas by dividing grid cells in those study areas into subcells, and in 70 subcells, samples were collected from exterior faucets at sites where there were domestic wells or wells with screen depths similar to those in nearby domestic wells (shallow-well tap sites). Field water-quality indicators (dissolved oxygen, water temperature, pH, and specific conductance) were measured, and samples for analysis of inorganic constituents (trace elements, nutrients, major and minor ions, silica, total dissolved solids, and alkalinity) were collected at all 170 sites. In addition to these constituents, the samples from grid wells were analyzed for organic constituents (volatile organic compounds, pesticides and pesticide degradates), constituents of special interest (perchlorate and N -nitrosodimethylamine, or NDMA), radioactive constituents (radon-222 and gross-alpha and gross-beta radioactivity), and geochemical and age-dating tracers (stable isotopes of carbon in dissolved inorganic carbon, carbon-14 abundances, stable isotopes of hydrogen and oxygen in water, and tritium activities). Three types of quality-control samples (blanks, replicates, and matrix spikes) were collected at up to 11 percent of the wells in the Monterey–Salinas Shallow Aquifer study unit, and the results for these samples were used to evaluate the quality of the data from the groundwater samples. With the exception of trace elements, blanks rarely contained detectable concentrations of any constituent, indicating that contamination from sample-collection procedures was not a significant source of bias in the data for the groundwater samples. Low concentrations of some trace elements were detected in blanks; therefore, the data were re-censored at higher reporting levels. Replicate samples generally were within the limits of acceptable analytical reproducibility. The median values of matrix-spike recoveries were within the acceptable range (70 to 130 percent) for the volatile organic compounds (VOCs) and N -nitrosodimethylamine (NDMA), but were only approximately 64 percent for pesticides and pesticide degradates. The sample-collection protocols used in this study were designed to obtain representative samples of groundwater. The quality of groundwater can differ from the quality of drinking water because water chemistry can change as a result of contact with plumbing systems or the atmosphere; because of treatment, disinfection, or blending with water from other sources; or some combination of these. Water quality in domestic wells is not regulated in California, however, to provide context for the water-quality data presented in this report, results were compared to benchmarks established for drinking-water quality. The primary comparison benchmarks were maximum contaminant levels established by the U.S. Environmental Protection Agency and the State of California (MCL-US and MCL-CA, respectively). Non-regulatory benchmarks were used for constituents without maximum contaminant levels (MCLs), including Health Based Screening Levels (HBSLs) developed by the USGS and State of California secondary maximum contaminant levels (SMCL-CA) and notification levels. Most constituents detected in samples from the Monterey–Salinas Shallow Aquifer study unit had concentrations less than their respective benchmarks. Of the 148 organic constituents analyzed in the 100 grid-well samples, 38 were detected, and all concentrations were less than the benchmarks. Volatile organic compounds were detected in 26 of the grid wells, and pesticides and pesticide degradates were detected in 28 grid wells. The special-interest constituent NDMA was detected above the HBSL in three samples, one of which also had a perchlorate concentration greater than the MCL-CA. Of the inorganic constituents, 6 were detected at concentrations above their respective MCL benchmarks in grid-well samples: arsenic (5 grid wells above the MCL of 10 micrograms per liter, μg/L), selenium (3 grid wells, MCL of 50 μg/L), uranium (4 grid wells, MCL of 30 μg/L), nitrate (16 grid wells, MCL of 10 milligrams per liter, mg/L), adjusted gross alpha particle activity (10 grid wells, MCL of 15 picocuries per liter, pCi/L), and gross beta particle activity (1 grid well, MCL of 50 pCi/L). An additional 4 inorganic constituents were detected at concentrations above their respective HBSL benchmarks in grid-well samples: boron (1 grid well above the HBSL of 6,000 μg/L), manganese (8 grid wells, HBSL of 300 μg/L), molybdenum (6 grid wells, HBSL of 40 μg/L), and strontium (6 grid wells, HBSL of 4,000 μg/L). Of the inorganic constituents, 4 were detected at concentrations above their non-health based SMCL benchmarks in grid-well samples: iron (9 grid wells above the SMCL of 300 μg/L), chloride (7 grid wells, SMCL of 500 mg/L), sulfate (14 grid wells, SMCL of 500 mg/L), and total dissolved solids (27 grid wells, SMCL of 1,000 mg/L). Of the inorganic constituents analyzed in the 70 shallow-well tap sites, 10 were detected at concentrations above the benchmarks. Of the inorganic constituents, 3 were detected at concentrations above their respective MCL benchmarks in shallow-well tap sites: arsenic (2 shallow-well tap sites above the MCL of 10 μg/L), uranium (2 shallow-well tap sites, MCL of 30 μg/L), and nitrate (24 shallow-well tap sites, MCL of 10 mg/L). An additional 3 inorganic constituents were detected above their respective HBSL benchmarks in shallow-well tap sites: manganese (4 shallow-well tap sites above the HBSL of 300 μg/L), molybdenum (4 shallow-well tap sites, HBSL of 40 μg/L), and zinc (2 shallow-well tap sites, HBSL of 2,000 μg/L). Of the inorganic constituents, 4 were detected at concentrations above their non-health based SMCL benchmarks in shallow-well tap sites: iron (6 shallow-well tap sites above the SMCL of 300 μg/L), chloride (1 shallow-well tap site, SMCL of 500 mg/L), sulfate (9 shallow-well tap sites, SMCL of 500 mg/L), and total dissolved solids (15 shallow-well tap sites, SMCL of 1,000 mg/L).

California

Investigating the temporal effects of metal-based coagulants to remove mercury from solution in the presence of dissolved organic matter

The presence of mercury (Hg), particularly methylmercury (MeHg), is a concern for both human and ecological health as MeHg is a neurotoxin and can bioaccumulate to lethal levels in upper trophic level organisms. Recent research has demonstrated that coagulation with metal-based salts can effectively remove both inorganic mercury (IHg) and MeHg from solution through association with dissolved organic matter (DOM) and subsequent flocculation and precipitation. In this study, we sought to further examine interactions between Hg and DOM and the resulting organo-metallic precipitate (floc) to assess if (1) newly added IHg could be removed to the same extent as ambient IHg or whether the association between IHg and DOM requires time, and (2) once formed, if the floc has the capacity to remove additional Hg from solution. Agricultural drainage water samples containing ambient concentrations of both DOM and IHg were spiked with a traceable amount of isotopically enriched IHg and dosed with ferric sulfate after 0, 1, 5, and 30 days. Both ambient and newly added IHg were removed within hours, with 69–79 % removed. To a separate sample set, isotopically enriched IHg was added to solution after floc had formed. Under those conditions, 81–95 % of newly added Hg was removed even at Hg concentrations 1000-fold higher than ambient levels. Results of this study indicate coagulation with ferric sulfate effectively removes both ambient and newly added IHg entering a system and suggests rapid association between IHg and DOM. This work also provides new information regarding the ability of floc to remove additional Hg from solution even after it has formed.

Environmental Management

Effects of land use and hydrogeology on the water quality of alluvial aquifers in eastern Iowa and southern Minnesota, 1997

Ground-water samples were collected from monitoring wells at 31 agricultural and 30 urban sites in the Eastern Iowa Basins study unit during June–August 1997 to evaluate the effects of land use and hydrogeology on the water quality of alluvial aquifers. Ground-water samples were analyzed for common ions, nutrients, dissolved organic carbon, tritium, radon-222, pesticides and pesticide metabolites, volatile organic compounds, and environmental isotopes. Calcium, magnesium, and bicarbonate were the dominant ions in most samples and were likely derived from solution of carbonate minerals (calcite and dolomite) present in alluvial detrital deposits. Chloride and nitrate were dominant anions in samples from several wells. Sodium and chloride concentrations were significantly higher in samples from urban areas, where roads are more numerous and road salts may be more frequently applied, than in agricultural areas. Nitrate was detected in 94 percent of samples from agricultural areas and 77 percent of samples from urban areas. Nitrate concentrations were significantly higher in agricultural areas than in urban areas and exceeded the U.S. Environmental Protection Agency maximum ontaminant level for drinking water (10 milligrams per liter as N) in 39 percent of samples from agricultural areas. Nitrate concentrations in samples from urban areas did not exceed the maximum contaminant level. Greater use of fertilizers in agricultural areas most likely contributes to higher nitrate concentrations in samples from those areas. Tritium-based ages indicate ground water was most likely recharged after the 1950’s at all but one sampling site. Agricultural and urban land-use areas have remained relatively stable in the study area since the 1950’s; therefore, the effects of current land use should be reflected in ground water sampled during this study. Radon-222 was detected in all samples and exceeded the U.S. Environmental Protection Agency’s previously proposed maximum contaminant level for drinking water (300 picocuries per liter) in 71 percent of samples. Pesticides were detected in 84 percent of samples from agricultural areas and 70 percent from urban areas. Atrazine and metolachlor were the most frequently detected pesticides in samples from agricultural areas; atrazine and prometon were the most frequently detected pesticides in samples from urban areas. None of the pesticide oncentrations exceeded U.S. Environmental Protection Agency maximum contaminant levels or lifetime health advisories for drinking water. Pesticide metabolites were detected in 94 percent of samples from agricultural areas and 53 percent from urban areas. Metolachlor ethane sulfonic acid and deethylatrazine were the most frequently detected metabolites in samples from agricultural areas; metolachlor ethane sulfonic acid and alachlor ethane sulfonic acid were the most frequently detected metabolites in samples from urban areas. Total metabolite concentrations were significantly higher in samples from agricultural areas than in samples from urban areas. Total pesticide concentrations (parent compounds) tended to be higher in samples from agricultural areas; however, this difference was not statistically significant. Metabolites constituted the major portion of the total residue concentration in the alluvial aquifer. Volatile organic compounds were detected in 40 percent of samples from urban areas and 10 percent from agricultural areas. Methyl tertbutyl ether was the most commonly detected volatile organic compound and was present in 23 percent of samples from urban areas. Elevated concentrations (greater than 30 micrograms per liter) of methyl tert-butyl ether and BTEX compounds (benzene, toluene, ethylbenzene, and xylene) in two samples from urban areas suggest the possible presence of point-source gasoline leaks or spills. Factors other than land use may contribute to observed differences in water quality between and within agricultural and urban areas. Nitrate, atrazine, deethylatrazine, and deisopropylatrazine concentrations were significantly higher in shallow wells with sample intervals nearer the water table and in wells with thinner cumulative clay thickness above the sample intervals. These relations suggest that longer flow paths allow for greater residence time and increase opportunities for sorption, degradation, and dispersion, which may contribute to decreases in nutrient and pesticide concentrations with depth. Nitrogen speciation was influenced by redox conditions. Nitrate concentrations were significantly higher in ground water with dissolved-oxygen concentrations in excess of 0.5 milligram per liter. Ammonia concentrations were higher in ground water with dissolved-oxygen concentrations of 0.5 milligram per liter or less; however, this relation was not statistically significant. The amount of available organic matter may limit denitrification rates. Elevated nitrate concentrations (greater than 2.0 mg/L) were significantly related to lower dissolved organic carbon concentrations in water samples from both agricultural and urban areas. A similar relation between nitrate concentrations (in water) and organic carbon concentrations (in aquifer material) also was observed but was not statistically significant.

Iowa, Minnesota

Baseline groundwater quality from 34 wells in Wayne County, Pennsylvania, 2011 and 2013

Wayne County, Pennsylvania, is underlain by the Marcellus Shale, which currently (2014) is being developed elsewhere in Pennsylvania for natural gas. All residents of largely rural Wayne County rely on groundwater for water supply, primarily from bedrock aquifers (shales and sandstones). This study, conducted by the U.S. Geological Survey in cooperation with the Pennsylvania Department of Conservation and Natural Resources, Bureau of Topographic and Geologic Survey (Pennsylvania Geological Survey), provides a groundwater-quality baseline for Wayne County prior to development of the natural gas resource in the Marcellus Shale. Selected wells completed in the Devonian-age Catskill Formation, undifferentiated; the Poplar Gap and Packerton Members of the Catskill Formation, undivided; and the Long Run and Walcksville Members of the Catskill Formation, undivided, were sampled. Water samples were collected once from 34 domestic wells during August 2011 and August and September 2013 and analyzed to characterize their physical and chemical quality. Samples were analyzed for 45 constituents and properties, including nutrients, major ions, metals and trace elements, radioactivity, and dissolved gases, including methane and radon-222. The quality of the sampled groundwater was generally within U.S. Environmental Protection Agency (USEPA) drinking-water standards, although in some samples, the concentrations of a few constituents exceeded USEPA drinking-water standards and health advisories. The pH of water samples ranged from 5.5 to 9.3 with a median of 7.0. The pH was outside the USEPA secondary maximum contaminant level (SMCL) range of 6.5 to 8.5 in water samples from 14 of the 34 wells (41 percent). Eleven samples had a pH less than 6.5, and three samples had a pH greater than 8.5. Dissolved oxygen concentrations ranged from 0.2 to 11.5 milligrams per liter (mg/L) with a median of 4.7 mg/L. The dissolved oxygen concentration was less than 1 mg/L in water samples from 6 wells; 5 of these 6 water samples had a pH greater than 7.7. Concentrations of dissolved methane ranged from less than 0.00006 to 3.3 mg/L. Methane was detectable in 22 of the 34 wells sampled (65 percent). Methane concentrations were greatest in the 5 samples with pH of 7.8 or higher, ranging from 0.040 to 3.3 mg/L. These samples also had among the lowest concentrations of dissolved oxygen. Three water samples, which had sufficient dissolved methane concentrations (greater than 0.9 mg/L), were analyzed for isotopes of carbon and hydrogen in the methane. The isotopic ratio values fell within (two samples) or close to (one sample) the range for a thermogenic natural gas source. The total dissolved solids concentration ranged from 33 to 346 mg/L; the median concentration was 126 mg/L. Sodium concentrations ranged from 1.07 to 116 mg/L; the median concentration was 9.42 mg/L. The sodium concentration exceeded the USEPA health advisory for sodium of 20 mg/L in water samples from 7 of the 34 wells (21 percent). Concentrations of dissolved arsenic ranged from less than 0.06 to 21.8 micrograms per liter (µg/L); the median concentration was 0.59 µg/L. Water samples from 2 of the 34 wells (6 percent) exceeded the USEPA maximum contaminant level (MCL) of 10 µg/L for arsenic. Concentrations of dissolved manganese ranged from less than 0.15 to 61.5 µg/L; the median concentration was 0.42 µg/L. A water sample from 1 of the 34 wells (3 percent) exceeded the USEPA SMCL of 50 µg/L for manganese; the concentration was less than the USEPA lifetime health advisory of 300 µg/L for manganese. Activities of radon-222 in water from the 34 sampled wells ranged from 110 to 7,180 picocuries per liter (pCi/L); the median activity was 2,105 pCi/L. Water samples from 33 of the 34 wells (97 percent) exceeded the proposed USEPA MCL of 300 pCi/L, and 4 water samples (12 percent) exceeded the USEPA proposed alternative MCL of 4,000 pCi/L for radon-222. Differences in groundwater chemistry were related to pH. Water with a pH greater than 7.6 generally had low dissolved oxygen concentrations, indicating reducing conditions in the aquifer. These high pH waters also had relatively elevated concentrations of methane, arsenic, boron, bromide, fluoride, lithium, and sodium but low concentrations of copper, nickel, and zinc. Water samples with a pH greater than 7.8 had methane concentrations equal to or greater than 0.04 mg/L.

Pennsylvania

Trophodynamics of per- and polyfluoroalkyl substances in the food web of a large Atlantic slope river

Per- and polyfluoroalkyl substances (PFASs) have attracted scientific and regulatory attention due to their persistence, bioaccumulative potential, toxicity, and global distribution. We determined the accumulation and trophic transfer of 14 PFASs (5 short-chain and 9 long-chain) within the food web of the Yadkin-Pee Dee River of North Carolina and South Carolina, US. Food web components and pathways were determined by stable isotope analyses of producers, consumers, and organic matter. Analyses of water, sediment, organic matter, and aquatic biota revealed that PFASs were prevalent in all food web compartments. Biofilm, an aggregation of bacteria, fungi, algae, and protozoans and a basal resource for the aquatic food web, showed high PFAS accumulation (in 10 of 14 compounds), particularly for perfluorooctanoic acid, with the greatest mean concentration of 463.73 ng/g. The food web compartment with the most detections and greatest concentrations of PFASs was aquatic insects; all 14 PFASs were detected in individual aquatic insect samples (range of <limit of detection [<LOD] to 1670.10 ng/g of wet weight [WW]). These findings may suggest a trophic link between biofilm PFASs and aquatic insect PFASs. Individual fish tissue samples ranged from <LOD to 797.00 ng/g of WW, where perfluorooctanesulfonate (PFOS) was the dominant PFAS among all samples (64%). The ova of an imperiled fish, the robust redhorse ( Moxostoma robustum ), had concentrations of 10 PFASs (range of <LOD to 482.88 ng/g of WW) and the highest PFOS concentration (482.88 ng/g of WW), indicating a likely maternal transfer. The trophic magnification factors (TMFs) calculated in this study showed that various taxa accumulated PFAS compounds differently. PFBS, a short-chain PFAS compound that would presumably exhibit lesser TMFs, had nine values among our compartments and organisms >1.0 (range of 0.57 to 2.33); it is possible that an unmeasured PFBS precursor may be accumulating in biota and metabolizing to PFBS, leading to a higher than expected TMFs for this compound. Our findings demonstrate the prevalence of PFASs in a freshwater food web with potential implications for ecological and human health.

North Carolina, South Carolina

Occurrence and distribution of organic chemicals and nutrients and comparison of water-quality data from public drinking-water supplies in the Columbia aquifer in Delaware, 2000-08

The U.S. Geological Survey, in cooperation with the Delaware Department of Natural Resources and Environmental Control and the Delaware Geological Survey, conducted a groundwater-quality investigation to (a) describe the occurrence and distribution of selected contaminants, and (b) document any changes in groundwater quality in the Columbia aquifer public water-supply wells in the Coastal Plain in Delaware between 2000 and 2008. Thirty public water-supply wells located throughout the Columbia aquifer of the Delaware Coastal Plain were sampled from August through November of 2008. Twenty-two of the wells in the sampling network for this project were previously sampled in 2000. Eight new wells were selected to replace wells no longer in use. Groundwater collected from the wells was analyzed for the occurrence and distribution of selected pesticides, pesticide degradates, volatile organic compounds, nutrients, and major inorganic ions. Nine of the wells were analyzed for radioactive elements (radium-226, radium-228, and radon). Groundwater-quality data were compared for sites sampled in both 2000 and 2008 to document any changes in water quality. One or more pesticides were detected in samples from 29 of the 30 wells. There were no significant differences in pesticide and pesticide degradate concentrations and similar compounds were detected when comparing sampling results from 2000 and 2008. Pesticide and pesticide degradate concentrations were generally less than 1 microgram per liter. Twenty-four compounds, 14 pesticides, and 10 pesticide degradates were detected in at least one sample; the pesticide degradates, metolachlor ethanesulfonic acid, deethylatrazine, and alachlor ethanesulfonic acid were the most frequently detected compounds, each found in more than 50 percent of samples. Almost 80 percent of the detected pesticides were agricultural herbicides, which reflects the prevalence and wide distribution of agriculture in sampled areas, as well the dominance of agricultural pesticides among the target analytes for this study. No concentration of a pesticide or pesticide degradate exceeded any regulatory standard. Dieldrin, an insecticide that has been banned for several decades, was detected at a concentration that exceeded a non-regulatory health-based screening level of 0.002 micrograms per liter at nine sites. Volatile organic compounds (VOCs) were generally detected at concentrations of less than 1 microgram per liter, although 7 of the 31 detected VOCs had concentrations greater than 1 microgram per liter. There were no significant differences in VOC concentrations from 2000 to 2008; however, among the resampled wells, the mean number of VOCs detected per well was significantly different over the 8-year period. The number of VOCs detected per well decreased in 73 percent of the resampled wells; the decrease ranged from one to eight fewer detections in 2008 than in 2000. Chloroform and methyl tert-butyl ether were the most frequently detected VOCs, at 90 percent and 63 percent, respectively, among the 30 wells. Solvents were the most frequently detected class of VOCs. All measured concentrations of VOCs in groundwater were below established standards for drinking water and below other health-based guidelines. There were no significant differences in nutrient or major-ion concentrations between 2000 and 2008, however, the medians of two field measurements, pH and dissolved oxygen, were significantly higher in 2008 than in 2000 in the resampled wells. Although pH and dissolved oxygen were higher, water was still acidic and predominantly oxic. Nitrate was the predominant nutrient species in the Columbia aquifer, with a 90-percent detection frequency. The median nitrate concentration in groundwater was 4.88 milligrams per liter, which was slightly lower than, but not significantly different from, the median of 5.23 milligrams per liter for the 2000 samples. Concentrations of nitrate exceeded the U.S. Environmental Protection Agency's Maximum Contaminant Level or Federal drinking-water standard of 10 milligrams per liter as nitrogen in samples from two wells. Eight of the 30 wells sampled had iron or manganese concentrations that exceeded the U.S. Environmental Protection Agency's Secondary Maximum Contaminant Level; nine samples exceeded the Health Advisory Limit set by the Delaware Division of Public Health of 20 milligrams per liter for sodium in drinking water. Two radiochemical isotopes, radium-226 and radon-222, were detected in all nine groundwater samples analyzed; five samples had detectable levels of radium-228 activity. None of the samples exceeded the U.S Environmental Protection Agency's Maximum Contaminant Level for radium or radon in drinking water. Although radioactive elements were more frequently detected in 2008 than in 2000, this increased detection frequency is more likely due to lower detection levels in 2008 than 2000. The average age of groundwater entering the screens of the production wells sampled in 2008 ranged from 6 to 35 years, with a median groundwater age of 22 years. Groundwater age was positively correlated with well depth and negatively correlated with dissolved oxygen. Data from the 22 resampled wells indicate a significant positive difference in the average modeled groundwater-sample-age results. The average groundwater age from samples collected in 2008 was generally 7 years older than the average groundwater age from samples collected in 2000.

Delaware