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Trace elements and radon in groundwater across the United States, 1992-2003

Trace-element concentrations in groundwater were evaluated for samples collected between 1992 and 2003 from aquifers across the United States as part of the U.S. Geological Survey National Water-Quality Assessment Program. This study describes the first comprehensive analysis of those data by assessing occurrence (concentrations above analytical reporting levels) and by comparing concentrations to human-health benchmarks (HHBs). Data from 5,183 monitoring and drinking-water wells representing more than 40 principal and other aquifers in humid and dry regions and in various land-use settings were used in the analysis. Trace elements measured include aluminum (Al), antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), boron (B), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), iron (Fe), lead (Pb), lithium (Li), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), strontium (Sr), thallium (Tl), uranium (U), vanadium (V), and zinc (Zn). Radon (Rn) gas also was measured and is included in the data analysis. Climate influenced the occurrence and distribution of trace elements in groundwater whereby more trace elements occurred and were found at greater concentrations in wells in drier regions of the United States than in humid regions. In particular, the concentrations of As, Ba, B, Cr, Cu, Mo, Ni, Se, Sr, U, V, and Zn were greater in the drier regions, where processes such as chemical evolution, ion complexation, evaporative concentration, and redox (oxidation-reduction) controls act to varying degrees to mobilize these elements. Al, Co, Fe, Pb, and Mn concentrations in groundwater were greater in humid regions of the United States than in dry regions, partly in response to lower groundwater pH and (or) more frequent anoxic conditions. In groundwater from humid regions, concentrations of Cu, Pb, Rn, and Zn were significantly greater in drinking-water wells than in monitoring wells. Samples from drinking-water wells in dry regions had greater concentrations of As, Ba, Pb, Li, Sr, V, and Zn, than samples from monitoring wells. In humid regions, however, concentrations of most trace elements were greater in monitoring wells than in drinking-water wells; the exceptions were Cu, Pb, Zn, and Rn. Cu, Pb, and Zn are common trace elements in pumps and pipes used in the construction of drinking-water wells, and contamination from these sources may have contributed to their concentrations. Al, Sb, Ba, B, Cr, Co, Fe, Mn, Mo, Ni, Se, Sr, and U concentrations were all greater in monitoring wells than in drinking-water wells in humid regions. Groundwater from wells in agricultural settings had greater concentrations of As, Mo, and U than groundwater from wells in urban settings, possibly owing to greater pH in the agricultural wells. Significantly greater concentrations of B, Cr, Se, Ag, Sr, and V also were found in agricultural wells in dry regions. Groundwater from dry-region urban wells had greater concentrations of Co, Fe, Pb, Li, Mn, and specific conductance than groundwater from agricultural wells. The geologic composition of aquifers and aquifer geochemistry are among the major factors affecting trace-element occurrence. Trace-element concentrations in groundwater were characterized in aquifers from eight major groups based on geologic material, including (1) unconsolidated sand and gravel; (2) glacial unconsolidated sand and gravel; (3) semiconsolidated sand; (4) sandstone; (5) sandstone and carbonate rock; (6) carbonate rock; (7) basaltic and other volcanic rock; and (8) crystalline rock. The majority of groundwater samples and the largest percentages of exceedences of HHBs were in the glacial and nonglacial unconsolidated sand and gravel aquifers; in these aquifers, As, Mn, and U are the most common trace elements exceeding HHBs. Overall, 19 percent of wells (962 of 5,097) exceeded an HHB for at least one trace element. The trace elements with HHBs included in this summary were Sb, As, Ba, Be, B, Cd, Cr,

Scientific Investigations Report↗

Capsule- and disk-filter procedure

Capsule and disk filters are disposable, self-contained units composed of a pleated or woven filter medium encased in a polypropylene or other plastic housing that can be connected inline to a sample-delivery system (such as a submersible or peristaltic pump) that generates sufficient pressure (positive or negative) to force water through the filter. Filter media are available in several pore sizes, but 0.45 µm is the pore size used routinely for most studies at this time. Capsule or disk filters (table 5.2.1.A.1) are required routinely for most studies when filtering samples for trace-element analyses and are recommended when filtering samples for major-ion or other inorganic-constituent analyses.

Techniques of Water-Resources Investigations↗

Water-quality trends in the Santa Ana River at MWD Crossing and below Prado Dam, Riverside County, California

The Santa Ana River, located in an extensively urbanized basin, drains about 2,670 square miles near Los Angeles, California. Almost all flow in the river, about 200,000 acre-feet annually, is diverted to ponds where it infiltrates and recharges underlying aquifers. About 2 million people are dependent on these aquifers for water supply. In recent years, base flow in the river has increased as a result of increased discharge of treated municipal wastewater, and high flows have increased as a result of increase precipitation and urbanization. Trends in water quality were calculated for two sites?at the Metropolitan Water District (MWD) Crossing (an upstream site) and below Prado Dam (a downstream site)?using the computer program ESTREND. Water-quality data for these sites were collected by the U.S. Geological Survey from 1969 to 1995. At MWD Crossing, flow-adjusted downward trends of -1.1 microsiemens per centimeter (iS/cm) per year and -1.6 milligrams per liter (mg/L) per year were calculated for specific conductance and dissolved solids, respectively. In contrast, a flow-adjusted upward trends of 2.2 iS/cm per year for dissolved solids was calculated for the Santa Ana River below Prado Dam. Specific conductance and dissolved solids in the Santa Ana River below Prado Dam had downward unadjusted trends (not adjusted for streamflow) of -8.3 iS/cm per year and -6.0 mg/L per year, respectively. For the Santa Ana River below Prado Dam, downward unadjusted trends were calculated for ammonia (-0.04 mg/L per year) and total organic carbon (0.19 mg/L per year); flow-adjusted upward trends were calculated for nitrite plus nitrate (0.15 mg/L per year), total dissolved nitrogen (0.39 mg/L per year), and orthophosphate (0.03 mg/L per year). Statistically significant unadjusted and flow-adjusted trends were not obtained for organic nitrogen, phosphorus, and dissolved organic carbon. Data for selected trace elements and organic compounds collected between 1970-94 also are summarized in this report.

Water-Resources Investigations Report↗

Stability of dilute solutions of uranium, lead, and thorium ions

Standard solutions and samples containing a few micrograms of metallic ions per milliliter are frequently used in determination of trace elements. It is important to know whether the concentrations of such solutions remain constant from day to day. The stability of dilute solutions of three metallic ions-uranium, lead, and thorium-has been investigated. Solutions containing concentrations of metallic ions, ranging from 1000 to 0.1 γ per milliliter, were allowed to stand for approximately 2.5 months, and then the metallic ion content of those solutions that had lost strength was determined. Both adsorption and hydrolysis variously influenced the solute loss, but the minimum pH at which loss of concentration of lead and uranium occurred seemed to coincide with the pH at which the hydrolyzed metal ions began to precipitate. No increase in the stability of the solutions was obtained by substituting polyethylene containers for borosilicate glass. The solutions that lost strength could not be restored promptly to the original concentration by manual means, such as shaking them vigorously for several minutes.

Analytical Chemistry↗

Reconnaissance investigation of water quality, bottom sediment, and biota associated with irrigation drainage in the Kendrick Reclamation Project Area, Wyoming, 1986-87

A reconnaissance investigation of the Kendrick Reclamation Project in central Wyoming was conducted during 1986-87 to determine if irrigation drainage has caused or has the potential to cause harmful effects on human health, fish, and wildlife, or other water uses. The investigation of the Kendrick Reclamation Project is one of nine similar investigations being conducted in the western conterminous United States as part of the Department of the Interior 's Irrigation Drainage Program. Samples of surface water were collected at 10 sites and ground water at 5 sites. Surface-water analyses included trace elements, radiochemicals, and pesticides. Concentrations in the water generally were less than national standards for public water supplies, with the exception of selenium. The median concentration of dissolved selenium was 7.5 microgm/L in 24 samples of surface and groundwater. Of the 11 samples that contained dissolved- selenium concentrations greater than the national standard for public water supplies of 10 microgm/L, 10 of the samples were collected at sites on streams that are not used for public water supplies; the eleventh sample was collected from a shallow well. Dissolved-selenium concentrations ranged from less than 1 to 300 microgm/L. Concentrations of dissolved selenium in the North Platte River, which supplies drinking water for several municipalities, ranged from less than 1 to 4 microgm/L. The dissolved-selenium concentration and selenium discharge in the North Platte River increased in the downstream direction. The four principal tributaries that receive drainage from the Kendrick Reclamation Project contributed substantially to the increase in selenium concentration and discharge in the North Platte River. Bottom-sediment samples from the North Platte River contained selenium contents of 1.2 microgm/g or less. (Author 's abstract)

Water-Resources Investigations Report↗

Groundwater quality data for the Tahoe-Martis study unit, 2007: Results from the California GAMA Program

Groundwater quality in the approximately 460-square-mile Tahoe–Martis study unit was investigated in June through September 2007 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). The study was designed to provide a spatially unbiased assessment of the quality of raw groundwater used for public water supplies within the Tahoe–Martis study unit (Tahoe–Martis) and to facilitate statistically consistent comparisons of groundwater quality throughout California. Samples were collected from 52 wells in El Dorado, Placer, and Nevada Counties. Forty-one of the wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the study area (grid wells), and 11 were selected to aid in evaluation of specific water-quality issues (understanding wells). The groundwater samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOC], pesticides and pesticide degradates, and pharmaceutical compounds), constituents of special interest (perchlorate and N -nitrosodimethylamine [NDMA]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), radioactive constituents, and microbial indicators. Naturally occurring isotopes (tritium, carbon-14, strontium isotope ratio, and stable isotopes of hydrogen and oxygen of water), and dissolved noble gases also were measured to help identify the sources and ages of the sampled groundwater. In total, 240 constituents and water-quality indicators were investigated. Three types of quality-control samples (blanks, replicates, and samples for matrix spikes) each were collected at 12 percent of the wells, and the results obtained from 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 data for the groundwater samples were not compromised by possible contamination during sample collection, handling or analysis. Differences between replicate samples were within acceptable ranges. 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, raw water 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 raw groundwater. However, to provide some context for the results, concentrations of constituents measured in the raw groundwater were compared with regulatory and nonregulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH), and with aesthetic and technical thresholds established by CDPH. Comparisons between data collected for this study and drinking-water thresholds are for illustrative purposes only and do not indicate of compliance or noncompliance with regulatory thresholds. The concentrations of most constituents detected in groundwater samples from the Tahoe–Martis wells were below drinking-water thresholds. Organic compounds (VOCs and pesticides) were detected in about 40 percent of the samples from grid wells, and most concentrations were less than 1/100th of regulatory and nonregulatory health-based thresholds, although the conentration of perchloroethene in one sample was above the USEPA maximum contaminant level (MCL-US). Concentrations of all trace elements and nutrients in samples from grid wells were below regulatory and nonregulatory health-based thresholds, with five exceptions. Concentrations of arsenic were above the MCL-US in 20 percent of the samples from grid wells. Gross alpha particle activity (MCL-US), boron (CDPH notification level, NL-CA), and molybdenum (USEPA lifetime health advisory, HAL-US) were each detected above thresholds in two of the samples from grid wells, and radon (proposed alternative MCL-US) was detected above the threshold in one sample from a grid well. Most of the samples from Tahoe–Martis grid wells had concentrations of major elements, total dissolved solids, and trace elements below the CDPH secondary maximum contaminant levels, nonenforceable thresholds set for aesthetic and technical concerns. Fifteen percent of the samples from grid wells contained iron, manganese, or total dissolved solids at concentrations above these levels.

California, Nevada↗

Groundwater-quality data in the Colorado River study unit, 2007: Results from the California GAMA Program

Groundwater quality in the 188-square-mile Colorado River Study unit (COLOR) was investigated October through December 2007 as part of the Priority Basin Project of the California State Water Resources Control Board (SWRCB) 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 the U.S. Geological Survey (USGS) is the technical project lead. The Colorado River study was designed to provide a spatially unbiased assessment of the quality of raw groundwater used for public water supplies within COLOR, and to facilitate statistically consistent comparisons of groundwater quality throughout California. Samples were collected from 28 wells in three study areas in San Bernardino, Riverside, and Imperial Counties. Twenty wells were selected using a spatially distributed, randomized grid-based method to provide statistical representation of the Study unit; these wells are termed ‘grid wells’. Eight additional wells were selected to evaluate specific water-quality issues in the study area; these wells are termed ‘understanding wells.’ The groundwater samples were analyzed for organic constituents (volatile organic compounds [VOC], gasoline oxygenates and degradates, pesticides and pesticide degradates, pharmaceutical compounds), constituents of special interest (perchlorate, 1,4-dioxane, and 1,2,3-trichlorpropane [1,2,3-TCP]), naturally occurring inorganic constituents (nutrients, major and minor ions, and trace elements), and radioactive constituents. Concentrations of naturally occurring isotopes (tritium, carbon-14, and stable isotopes of hydrogen and oxygen in water), and dissolved noble gases also were measured to help identify the sources and ages of the sampled groundwater. In total, approximately 220 constituents and water-quality indicators were investigated. Quality-control samples (blanks, replicates, and matrix spikes) were collected at approximately 30 percent of the wells, and the results were used to evaluate the quality of the data obtained from 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. Differences between replicate samples were within acceptable ranges and 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, raw groundwater typically is treated, disinfected, or blended with other waters to maintain acceptable water quality. Regulatory thresholds apply to water that is served to the consumer, not to raw groundwater. However, to provide some context for the results, concentrations of constituents measured in the raw groundwater were compared to regulatory and nonregulatory health-based thresholds established by the U.S. Environmental Protection Agency (USEPA) and the California Department of Public Health (CDPH) and to thresholds established for aesthetic concerns by CDPH. Comparisons between data collected for this study and drinking-water thresholds are for illustrative purposes only and do not indicate compliance or noncompliance with those thresholds. The concentrations of most constituents detected in groundwater samples were below drinking-water thresholds. Volatile organic compounds (VOC) were detected in approximately 35 percent of grid well samples; all concentrations were below health-based thresholds. Pesticides and pesticide degradates were detected in about 20 percent of all samples; detections were below health-based thresholds. No concentrations of constituents of special interest or nutrients were detected above health-based thresholds. Most of the major and minor ion constituents sampled do not have health-based thresholds; the exception is chloride. Concentrations of chloride, sulfate, and total dissolved solids detected in some of the well samples were above the nonenforceable thresholds for aesthetic concerns. Concentrations of fluoride were detected in 5 samples (from 4 grid wells and 1 understanding well) above the maximum contaminant level for California (MCL-CA). Concentrations of most of the trace elements in samples from the COLOR study were below health-based thresholds; exceptions included arsenic above the MCL-US, boron above the notification level for California (NL-CA), iron and manganese above the secondary maximum contaminant level for California (SMCL-CA), and molybdenum and strontium above the lifetime health advisory level (HAL-US) threshold. Most detections of radioactive constituents were below health-based thresholds; exceptions were alpha, uranium, and radon radioactivity. Alpha radioactivity with 72 hour count detections occurred in four grid wells and one understanding well, and 30-day count detections in two grid wells above the MCL-US. Uranium was detected twice in grid wells above the MCL-US threshold. Also, radon-222 was detected at concentrations above the proposed MCL-US in 19 samples (14 grid and 5 understanding wells). No radon-222 was detected above the proposed MCL-US upper threshold.

California↗

Occurrence and distribution of trace elements in snow, streams, and streambed sediments, Cape Krusenstern National Monument, Alaska, 2002-2003

Cape Krusenstern National Monument is located in Northwest Alaska. In 1985, an exchange of lands and interests in lands between the Northwest Alaska Native Association and the United States resulted in a 100-year transportation system easement for 19,747 acres in the monument. A road was then constructed along the easement from the Red Dog Mine, a large zinc concentrate producer and located northeast of the monument, through the monument to the coast and a port facility. Each year approximately 1.3 million tonnes of zinc and lead concentrate are transported from the Red Dog Mine via this access road. Concern about the possible deposition of cadmium, lead, zinc and other trace elements in the monument was the basis of a cooperative project with the National Park Service. Concentrations of dissolved cadmium, dissolved lead, and dissolved zinc from 28 snow samples from a 28 mile by 16 mile grid were below drinking water standards. In the particulate phase, approximately 25 percent of the samples analyzed for these trace elements were higher than the typical range found in Alaska soils. Boxplots of concentrations of these trace elements, both in the dissolved and particulate phase, indicate higher concentrations north of the access road, most likely due to the prevailing southeast wind. The waters of four streams sampled in Cape Krusenstern National Monument are classified as calcium bicarbonate. Trace-element concentrations from these streams were below drinking water standards. Median concentrations of 39 trace elements from streambed sediments collected from 29 sites are similar to the median concentrations of trace elements from the U.S. Geological Survey?s National Water-Quality Assessment database. Statistical differences were noted between trace-element concentrations of cadmium, lead, and zinc at sites along the access road and sites north and south of the access road; concentrations along the access road being higher than north or south of the road. When normalized to 1 percent organic carbon, the concentrations of these trace elements are not expected to be toxic to aquatic life when compared to criteria established by the Canadian government and other recent research.

Scientific Investigations Report↗

Origin and characteristics of discharge at San Marcos Springs based on hydrologic and geochemical data (2008-10), Bexar, Comal, and Hays Counties, Texas

The Edwards aquifer in south-central Texas is a productive and important water resource. Several large springs issuing from the aquifer are major discharge points, popular locations for recreational activities, and habitat for threatened and endangered species. Discharges from Comal and San Marcos Springs, the first and second largest spring complexes in Texas, are used as thresholds in groundwater management strategies for the Edwards aquifer. Comal Springs is generally understood to be supplied by predominantly regional groundwater flow paths; the hydrologic connection of San Marcos Springs with the regional flow system, however, is less understood. During November 2008–December 2010, a hydrologic and geochemical investigation of San Marcos Springs was conducted by the U.S. Geological Survey (USGS) in cooperation with the San Antonio Water System. The primary objective of this study was to define and characterize sources of discharge from San Marcos Springs. During this study, hydrologic conditions transitioned from exceptional drought (the dry period, November 1, 2008 to September 8, 2009) to wetter than normal (the wet period, September 9, 2009 to December 31, 2010), which provided the opportunity to investigate the hydrogeology of San Marcos Springs under a wide range of hydrologic conditions. Water samples were collected from streams, groundwater wells, and springs at and in the vicinity of San Marcos Springs, including periodic (routine) sampling (every 3–7 weeks) and sampling in response to storms. Samples were analyzed for major ions, trace elements, nutrients, and selected stable and radiogenic isotopes (deuterium, oxygen, carbon, strontium). Additionally, selected physicochemical properties were measured continuously at several sites, and hydrologic data were compiled from other USGS efforts (stream and spring discharge). Potential aquifer recharge was evaluated from local streams, and daily recharge or gain/loss estimates were computed for several local streams. Local rainfall and recharge events were compared with physicochemical properties and geochemical variability at San Marcos Springs, with little evidence for dilution by local recharge.

Texas↗

Groundwater quality data in 15 GAMA study units: results from the 2006–10 Initial sampling and the 2009–13 resampling of wells, 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 (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). From May 2004 to March 2012, the GAMA-PBP collected samples from more than 2,300 wells in 35 study units across the State. Selected wells 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. This triennial (every 3 years) trend sampling of GAMA-PBP study units concluded in December 2013. Fifteen of the study units, initially sampled between January 2006 and June 2010 and sampled a second time between April 2009 and April 2013 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 15 study units. In these study units, 730 wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the areas assessed (grid wells, also called “status wells”). Approximately 3 years after the initial sampling, 93 of the previously sampled status wells (approximately 10 percent in each study unit) were randomly selected for trend sampling (“trend wells”). The 15 study units sampled for trends were distributed among 4 hydrogeologic provinces: Central Valley, Basin and Range, Desert, and Transverse and selected Peninsular Ranges. The total number of status wells sampled, along with those sampled again for trends, varied by study unit. In the Central Valley hydrogeologic province, the numbers of status wells and trend wells in each study unit were as follows: Kern County subbasin study unit—47 status wells, 5 trend wells Central Eastside San Joaquin Basin study unit—58 status wells, 6 trend wells Middle Sacramento Valley study unit—71 status wells, 8 trend wells Northern Sacramento Valley study unit—43 status wells, 4 trend wells Madera–Chowchilla study unit—30 status wells, 4 trend wells Western San Joaquin Valley study unit—39 status wells, 4 trend wells. The Basin and Range hydrogeologic province had only one study unit: Owens and Indian Wells Valleys study unit—53 status wells, 6 trend wells. In the Desert hydrogeologic province, the numbers of wells were as follows: Coachella Valley study unit—19 status wells 4 trend wells Colorado River study unit—20 status wells, 3 trend wells Antelope Valley study unit—56 status wells, 6 trend wells Mojave study unit—52 status wells, 7 trend wells Borrego Valley, Central Desert and Low-Use Basins of the Mojave and Sonoran Deserts study unit—49 status wells, 6 trend wells. In the Transverse and Selected Peninsular Ranges hydrogeologic province, the numbers of wells were as follows: Coastal Los Angeles Basin study unit—61 status wells, 8 trend wells Upper Santa Ana Watershed study unit—90 status wells, 16 trend wells Santa Clara River Valley study unit—42 status wells, 6 trend wells. The groundwater samples were analyzed for a number of synthetic organic constituents (volatile organic compounds, 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 (nutrients, major and minor ions, and trace elements). Naturally occurring isotopes (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 investigated. Quality-control samples (blanks, replicates, or samples for matrix spikes) were collected at 34 percent of the trend wells, 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 blanks in samples from GAMA-PBP study units, including the study units presented here, some groundwater results were adjusted in this report. Differences between replicate samples were mostly within acceptable ranges, indicating acceptably low variability in analytical results. Median matrix-spike recoveries were within the acceptable range (70 to 130 percent) for 189 of the 224 compounds for which matrix spikes were analyzed (84 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 attain acceptable water quality. The 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 California Department of Public Health. Comparisons between data collected for this study and benchmarks for drinking-water quality are for illustrative purposes only and are not indicative of compliance or non-compliance with those benchmarks. Most constituents that were detected in groundwater samples from the trend wells were found at concentrations less than drinking-water benchmarks. Two volatile organic compounds (VOCs)—tetrachloroethene and trichloroethene—were detected in samples from one or more wells at concentrations greater than their health-based benchmarks, and three VOCs—chloroform, tetrachloroethene, and trichloroethene—were detected in at least 10 percent of the trend-well samples from the initial sampling period and the later trend sampling period. No pesticides were detected at concentrations near or greater than their health-based benchmarks. Three pesticide constituents—atrazine, deethylatrazine, and simazine—were detected in more than 10 percent of the trend-well samples in both sampling periods. Perchlorate, a constituent of special interest, was detected at a concentration greater than its health-based benchmark in samples from one trend well in the initial sampling and trend sampling periods, and in an additional trend well sample only in the trend sampling period. Most detections of nutrients, major and minor ions, and trace elements in samples from trend wells were less than health-based benchmarks in both sampling periods. Exceptions included nitrate, fluoride, arsenic, boron, molybdenum, strontium, and uranium; these were all detected at concentrations greater than their health-based benchmarks in at least one well sample in both sampling periods. Lead and vanadium were detected above their health-based benchmarks in one sample each collected in the initial sampling period only. The isotopic ratios of oxygen and hydrogen in water and the activities of tritium and carbon-14 generally changed little between sampling periods.

California↗

Water-quality assessment of part of the upper Mississippi River basin, Minnesota and Wisconsin — Design and implementation of water-quality studies, 1995-98

From 1995 through 1998, water-quality and aquatic-biological samples were collected, processed, and analyzed for the U.S. Geological Survey's National Water-Quality Assessment Program in the Upper Mississippi River Basin in Minnesota and Wisconsin. Sites were selected and samples collected for integrated studies designed to provide a comprehensive description of water-quality conditions, to identify trends, and to determine the factors that affect existing conditions. This report describes the design, site-selection, and implementation of the study. Methods used to collect, process, and analyze samples; characterize sites; and assess habitat are described. A comprehensive list of sample sites is provided. Sample analyses for water-quality studies included chlorophyll a , major inorganic constituents, nutrients, trace elements, tritium, radon, environmental isotopes, organic carbon, pesticides, volatile organic compounds, and other synthetic and naturallyoccurring organic compounds. Aquatic-biological samples included fish, benthic macroinvertebrates, and algal enumeration and identification, as well as synthetic-organic compounds and trace elements in fish tissue.

Minnesota, Wisconsin↗

Groundwater-quality data in seven GAMA study units: results from initial sampling, 2004-2005, and resampling, 2007-2008, of wells: California GAMA Program 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 (USGS) in cooperation with the California State Water Resources Control Board (SWRCB). The GAMA-PBP began sampling, primarily public supply wells in May 2004. By the end of February 2006, seven (of what would eventually be 35) study units had been sampled over a wide area of the State. Selected wells in these first seven study units were resampled for water quality from August 2007 to November 2008 as part of an assessment of temporal trends in water quality by the GAMA-PBP. The initial sampling was designed to provide a spatially unbiased assessment of the quality of raw groundwater used for public water supplies within the seven study units. In the 7 study units, 462 wells were selected by using a spatially distributed, randomized grid-based method to provide statistical representation of the study area. Wells selected this way are referred to as grid wells or status wells. Approximately 3 years after the initial sampling, 55 of these previously sampled status wells (approximately 10 percent in each study unit) were randomly selected for resampling. The seven resampled study units, the total number of status wells sampled for each study unit, and the number of these wells resampled for trends are as follows, in chronological order of sampling: San Diego Drainages (53 status wells, 7 trend wells), North San Francisco Bay (84, 10), Northern San Joaquin Basin (51, 5), Southern Sacramento Valley (67, 7), San Fernando–San Gabriel (35, 6), Monterey Bay and Salinas Valley Basins (91, 11), and Southeast San Joaquin Valley (83, 9). The groundwater samples were analyzed for a large number of synthetic organic constituents (volatile organic compounds [VOCs], 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 (nutrients, major and minor ions, and trace elements). Naturally-occurring isotopes (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. Nearly 300 constituents and water-quality indicators were investigated. Quality-control samples (blanks, replicates, and samples for matrix spikes) were collected at 24 percent of the 55 status wells resampled for trends, 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 noticeable source of bias in the data for the groundwater samples. Differences between replicate samples were mostly within acceptable ranges, indicating acceptably low variability in analytical results. Matrix-spike recoveries were within the acceptable range (70 to 130 percent) for 75 percent of the compounds for which matrix spikes were collected. This study did not attempt to evaluate the quality of water delivered to consumers. After withdrawal, groundwater typically is treated, disinfected, and blended with other waters to maintain acceptable water quality. The 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 (USEPA) and California Department of Public Health (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 constituents that were detected in groundwater samples from the trend wells were found at concentrations less than drinking-water benchmarks. Four VOCs—trichloroethene, tetrachloroethene, 1,2-dibromo-3-chloropropane, and methyl tert-butyl ether—were detected in one or more wells at concentrations greater than their health-based benchmarks, and six VOCs were detected in at least 10 percent of the samples during initial sampling or resampling of the trend wells. No pesticides were detected at concentrations near or greater than their health-based benchmarks. Three pesticide constituents—atrazine, deethylatrazine, and simazine—were detected in more than 10 percent of the trend-well samples during both sampling periods. Perchlorate, a constituent of special interest, was detected more frequently, and at greater concentrations during resampling than during initial sampling, but this may be due to a change in analytical method between the sampling periods, rather than to a change in groundwater quality. Another constituent of special interest, 1,2,3-TCP, was also detected more frequently during resampling than during initial sampling, but this pattern also may not reflect a change in groundwater quality. Samples from several of the wells where 1,2,3-TCP was detected by low-concentration-level analysis during resampling were not analyzed for 1,2,3-TCP using a low-level method during initial sampling. Most detections of nutrients and trace elements in samples from trend wells were less than health-based benchmarks during both sampling periods. Exceptions include nitrate, arsenic, boron, and vanadium, all detected at concentrations greater than their health-based benchmarks in at least one well during both sampling periods, and molybdenum, detected at concentrations greater than its health-based benchmark during resampling only. The isotopic ratios of oxygen and hydrogen in water and tritium and carbon-14 activities generally changed little between sampling periods, suggesting that the predominant sources and ages of groundwater in most trend wells were consistent between the sampling periods.

California↗

Transient changes in shallow groundwater chemistry during the MSU ZERT CO2 injection experiment

Food-grade CO 2 was injected into a shallow aquifer through a perforated pipe placed horizontally 1–2 m below the water table at the Montana State University Zero Emission Research and Technology (MSU-ZERT) field site at Bozeman, Montana. The possible impact of elevated CO 2 levels on groundwater quality was investigated by analyzing 80 water samples taken before, during, and following CO 2 injection. Field determinations and laboratory analyses showed rapid and systematic changes in pH, alkalinity, and conductance, as well as increases in the aqueous concentrations of trace element species. The geochemical data were first evaluated using principal component analysis (PCA) in order to identify correlations between aqueous species. The PCA findings were then used in formulating a geochemical model to simulate the processes likely to be responsible for the observed increases in the concentrations of dissolved constituents. Modeling was conducted taking into account aqueous and surface complexation, cation exchange, and mineral precipitation and dissolution. Reasonable matches between measured data and model results suggest that: (1) CO 2 dissolution in the groundwater causes calcite to dissolve. (2) Observed increases in the concentration of dissolved trace metals result likely from Ca +2 -driven ion exchange with clays (smectites) and sorption/desorption reactions likely involving Fe (hydr)oxides. (3) Bicarbonate from CO 2 dissolution appears to compete for sorption with anionic species such as HAsO 4 −2 , potentially increasing dissolved As levels in groundwater.

Conference Paper↗

Water-quality assessment of the Kentucky River Basin, Kentucky: Results of investigations of surface-water quality, 1987-90

The U.S. Geological Survey investigated the water quality of the Kentucky River Basin in Kentucky as part of the National Water-Quality Assessment program. Data collected during 1987-90 were used to describe the spatial and temporal variability of water-quality constituents including metals and trace elements, nutrients, sediments, pesticides, dissolved oxygen, and fecal-coliform bacteria. Oil-production activities were the source of barium, bromide, chloride, magnesium, and sodium in several watersheds. High concentrations of aluminum, iron, and zinc were related to surface mining in the Eastern Coal Field Region. High concentrations of lead and zinc occurred in streambed sediments in urban areas, whereas concentrations of arsenic, strontium, and uranium were associated with natural geologic sources. Concentrations of phosphorus were significantly correlated with urban and agricultural land use. The high phosphorus content of Bluegrass Region soils was an important source of phosphorus in streams. At many sites in urban areas, most of the stream nitrogen load was attributable to wastewater-treatment-plant effluent. Average suspended-sediment concentrations were positively correlated with discharge. There was a downward trend in suspended-sediment concentrations downstream in the Kentucky River main stem during the study. The most frequently detected herbicides in water samples were atrazine, 2,4-D, alachlor, metolachlor, and dicamba. Diazinon, malathion, and parathion were the most frequently detected organophosphate insecticides in water samples. Detectable concentrations of aldrin, chlordane, DDT, DDE, dieldrin, endrin, endosulfan, heptachlor, and lindane were found in streambed-sediment samples. Dissolved-oxygen concentrations were sometimes below the minimum concentration needed to sustain aquatic life. At some sites, high concentrations of fecal-indicator bacteria were found and water samples did not meet sanitary water-quality criteria.

Kentucky↗

The weathering of a sulfide orebody: Speciation and fate of some potential contaminants

Various potentially toxic trace elements such as As, Cu, Pb and Zn have been remobilized by the weathering of a sulfide orebody that was only partially mined at Leona Heights, California. As a result, this body has both natural and anthropogeni- cally modified weathering profiles only 500 m apart. The orebody is located in a heavily urbanized area in suburban Oakland, and directly affects water quality in at least one stream by producing acidic conditions and relatively high concentrations of dissolved elements (e.g., ??500 ??g/L Cu, ??3700 ??g/L Zn). Micrometric-scale mineralogical investigations were performed on the authigenic metal-bearing phases (less than 10 ??m in size) using electron-probe micro-analysis (EPMA), micro-Raman, micro X-ray absorption spectroscopy (??XAS), scanning X-ray diffraction ((??SXRD) and scanning X-ray fluorescence (??-SXRF) mapping techniques. Those measurements were coupled with classical mineralogical laboratory techniques, X-ray diffraction (XRD) and scanning electron microscopy (SEM). Authigenic metal-bearing phases identified are mainly sulfates (jarosite, epsomite, schwertmannite), Fe (oxy-)hydroxides (goethite, hematite and poorly crystalline Fe products) and poorly crystalline Mn (hydr-)oxides. Sulfates and Fe (oxy-)hydroxides are the two main secondary products at both sites, whereas Mn (hydr-) oxides were only observed in the samples from the non-mining site. In these samples, the various trace elements show different affinities for Fe or Mn compounds. Lead is preferentially associated with Mn (hydr-)oxides and As with Fe (oxy-)hydroxides or sulfates. Copper association with Mn and Fe phases is questionable, and the results obtained rather indicate that Cu is present as individual Cu-rich grains (Cu hydroxides). Some ochreous precipitates were found at both sites and correspond to a mixture of schwertmannite, goethite and jarosite containing some potentially toxic trace elements such as Cu, Pb and Zn. According to the trace element distribution and relative abundance of the unweathered sulfides, this orebody still represents a significant reservoir of potential contaminants for the watershed, especially at the non-mining site, as a much greater proportion of sulfides is left to react and because of the lower porosity at this site.

Canadian Mineralogist↗

Quality of Water from Shallow Wells in Urban Residential and Light Commercial Areas in Lafayette Parish, Louisiana, 2001 through 2002

In 2001-02, the U.S. Geological Survey installed and sampled 28 shallow wells in urban residential and light commercial areas in Lafayette Parish, Louisiana, for a land-use study in the Acadian-Pontchartrain Study Unit of the National Water-Quality Assessment (NAWQA) Program. The wells were installed in the Chicot aquifer system, the primary source of water for irrigation and public-water supplies in southwestern Louisiana. The purpose of this report is to describe the quality of water from the 28 shallow wells and to relate that water quality to natural factors and to human activities. Ground-water samples were analyzed for general ground-water properties and about 240 water-quality contituents, including dissolved solids, major inorganic ions, trace elements, nutrients, dissolved organic carbon (DOC), radon, chlorofluorocarbons, selected stable isotopes, pesticides, pesticide degradation products, and volatile organic compounds (VOC's).

Water-Resources Investigations Report↗

Quality of shallow ground water in alluvial aquifers of the Willamette Basin, Oregon, 1993-95

The current (1993?95) quality of shallow ground water (generally, <25 meters below land surface) in Willamette Basin alluvium is described using results from two studies. A Study-Unit Survey, or regional assessment of shallow groundwater quality in alluvium, was done from June through August 1993. During the Study-Unit Survey, data were collected from 70 domestic wells chosen using a random-selection process and located mostly in areas of agricultural land use. An urban Land-Use Study, which was a reconnaissance of shallow urban ground-water quality from 10 monitoring wells installed in areas of residential land use, was done in July 1995. Concentrations of nitrite plus nitrate (henceforth, nitrate, because nitrite concentrations were low) ranged from <0.05 to 26 mg N/L (milligrams nitrogen per liter) in ground water from 70 Study-Unit-Survey wells; concentrations exceeded the U.S. Environmental Protection Agency (USEPA) Maximum Contaminant Level (MCL) of 10 mg N/L in 9 percent of Study-Unit-Survey samples. Relationships were observed between nitrate concentrations and dissolved-oxygen concentrations, the amount of clay present within and overlying aquifers, overlying geology, and upgradient land use. Tritium (3H) data indicate that 21 percent of Study-Unit-Survey samples represented water recharged prior to 1953. Nitrogen-fertilizer application rates in the basin have increased greatly over the past several decades. Thus, some observed nitrate concentrations may reflect nitrogen loading rates that were smaller than those presently applied in the basin. Concentrations of phosphorus ranged from <0.01 to 2.2 mg/L in 70 Study-Unit-Survey wells and exceeded 0.10 mg/L in 60 percent of the samples. Phosphorus and nitrate concentrations were inversely correlated. From 1 to 5 pesticides and pesticide degradation products (henceforth, pesticides) were detected in ground water from each of 23 Study-Unit-Survey wells (33 percent of 69 wells sampled for pesticides) for a total of 51 pesticide detections. Thirteen different pesticides were detected; atrazine was the most frequently encountered pesticide. Although detections were widespread, concentrations were low (generally <1,000 ng/L [nanograms per liter]). (One ng/L is equal to 0.001 mg/L [micrograms per liter].) One detection (dinoseb, at 7,900 ng/L) exceeded a USEPA MCL. Relationships were observed between the occurrence of pesticides and the amount of clay present within and overlying aquifers, overlying geology, and land use. Between 1 and 5 volatile organic compounds (VOCs) were detected at each of 7 Study-Unit-Survey sites (11 percent of 65 sites evaluated), for a total of 14 VOC detections. One detection (tetrachloroethylene, at 29 mg/L) exceeded a USEPA MCL. Other detections were at low concentrations (0.2 to 2.0 mg/L). VOC detections generally were from sites associated with urban land use. Concentrations of arsenic ranged from <1 to 13 mg/L in 70 Study-Unit-Survey wells. Concentrations in 16 percent of samples exceeded the USEPA Risk-Specific-Dose Health Advisory of 2 mg/L. Radon concentrations ranged from 200 to 1,200 pCi/L (picocuries per liter) in 51 Study-Unit-Survey wells. All samples exceeded the USEPA Risk-Specific-Dose Health Advisory of 150 pCi/L. All urban Land-Use-Study samples were well oxygenated; thus, nitrate reduction probably did not affect these samples. Urban Land-Use-Study nitrate concentrations were similar to those of the well oxygenated, agricultural subset of Study-Unit-Survey samples. Pesticides were detected in samples from three urban Land-Use-Study sites, but concentrations were low (1 to 5 ng/L). In contrast, VOCs were detected in ground water from 80 percent of urban Land-Use-Study wells; concentrations ranged up to 7.6 mg/L. Trace-element concentrations in the urban Land-Use Study samples were low. Median concentrations consistently were <10 mg/L and frequently were <1 mg/L

Water-Resources Investigations Report↗