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Graphical methods for representing form and stability of aqueous metal ions

The equilibrium distributions of solute species of aluminum at 25°C and one atmosphere pressure are shown graphically in systems containing fluoride, as functions of the total dissolved aluminum and fluoride. The predominant form of complex and degree of complexing are also shown graphically as functions of pH and fluoride activity. The graphs are based on the simultaneous solution of the equations representing nine complexing equilibria and three stoichiometric summarizations, using a fixed value of ionic strength equal to 0.1. Solubility relationships for aluminum hydroxide and cryolite also are shown graphically, using the same coordinates and additional equilibria. By overlaying an appropriate species distribution graph with a solubility graph a relatively complete summary of chemical relationships in an aqueous aluminum system can be obtained. Although this type of model has important limitations, it can accommodate enough variables simultaneously to have practical value and similar procedures could be used for other elements and systems of interest in low-temperature aqueous geochemistry.

Chemical Geology↗

Surface chemistry associated with the cooling and subaerial weathering of recent basalt flows

The surface chemistry of fresh and weathered historical basalt flows was characterized using surface-sensitive X-ray photoelectron spectroscopy (XPS). Surfaces of unweathered 1987–1990 flows from the Kilauea Volcano, Hawaii, exhibited variable enrichment in Al, Mg, Ca, and F due to the formation of refractory fluoride compounds and pronounced depletion in Si and Fe from the volatilization of SiF 4 and FeF 3 during cooling. These reactions, as predicted from shifts in thermodynamic equilibrium with temperature, are induced by diffusion of HF from the flow interiors to the cooling surface. The lack of Si loss and solid fluoride formation for recent basalts from the Krafla Volcano, Iceland, suggest HF degassing at higher temperatures. Subsequent short-term subaerial weathering reactions are strongly influenced by the initial surface composition of the flow and therefore its cooling history. Successive samples collected from the 1987 Kilauea flow demonstrated that the fluoridated flow surfaces leached to a predominantly SiO 2 composition by natural weathering within one year. These chemically depleted surfaces were also observed on Hawaiian basalt flows dating back to 1801 AD. Solubility and kinetic models, based on thermodynamic and kinetic data for crystalline AlF 3 , MgF 2 , and CaF 2 , support observed elemental depletion rates due to chemical weathering. Additional loss of alkalis from the Hawaiian basalt occurs from incongruent dissolution of the basalt glass substrate during weathering.

Geochimica et Cosmochimica Acta↗

Experimental investigation and modeling of uranium (VI) transport under variable chemical conditions

The transport of adsorbing and complexing metal ions in porous media was investigated with a series of batch and column experiments and with reactive solute transport modeling. Pulses of solutions containing U(VI) were pumped through columns filled with quartz grains, and the breakthrough of U(VI) was studied as a function of variable solution composition ( p H, total U(VI) concentration, total fluoride concentration, and p H-buffering capacity). Decreasing p H and the formation of nonadsorbing aqueous complexes with fluoride increased U(VI) mobility. A transport simulation with surface complexation model (SCM) parameters estimated from batch experiments was able to predict U(VI) retardation in the column experiments within 30%. SCM parameters were also estimated directly from transport data, using the results of three column experiments collected at different p H and U(VI) pulse concentrations. SCM formulations of varying complexity (multiple surface types and reaction stoichiometries) were tested to examine the trade-off between model simplicity and goodness of fit to breakthrough. A two-site model (weak- and strong-binding sites) with three surface complexation reactions fit these transport data well. With this reaction set the model was able to predict (1) the effects of fluoride complexation on U(VI) retardation at two different p H values and (2) the effects of temporal variability of p H on U(VI) transport caused by low p H buffering. The results illustrate the utility of the SCM approach in modeling the transport of adsorbing inorganic solutes under variable chemical conditions.

Water Resources Research↗

A method for the concentration of fine-grained rutile (TiO2) from sediment and sedimentary rocks by chemical leaching

Quaternary marine sediment in the Gulf of Maine basins contains 0.7 to 1.0 wt percent TiO 2 (determined by X-ray fluorescence spectrometry). Most of this TiO 2 exists in the form of silt-size rutile crystals that are visible by using the petrographic microscope with transmitted light (Valentine and Commeau, 1990). The identification of rutile was confirmed by using a scanning electron microscope (SEM) equipped with an energy-dispersive X-ray spectrometer (EDS) system. To quantify the amount of TiO 2 in the sediment contributed by rutile and its polymorphs, anatase and brookite, it was necessary to eliminate as many of the other minerals as possible, especially titanium-bearing minerals such as ilmenite, ilmenomagnetite, biotite, hornblende, oyroxene, and sphene. We accomplished this by developing a method of chemical dissolution that removed the bulk of the raw material and left the TiO 2 minerals intact. Many methods using acids and bases have been developed over the years to dissolve rocks, minerals, and sediments for chemical analysis or to concentrate specific minerals (Dolcater et al., 1970; Church, 1971; Campbell, 1973, and the references cited therein). The method developed by Raman and Jackson (1965) to concentrate rutile and anatase in soils and sediments requires digesting the sample in concentrated hydrofluoric acid (HF) for 24 hours. However, Campbell (1973) found that digestion in HF for more than 2 hours results in a loss of anatase. The method of Dolcater et al. (1970) for concentrating titanium as a free oxide requires the use of hydrofluotitanic acid (H 2 TiF 6 ), which is difficult to find on the commercial market. The acid can be prepared by the reaction of concentrated HF (48%) with an excess of TiO 2 , but the procedure requires 36 hours to complete and should be attempted with caution because it is highly exothermic. Jackson (1979) provides a detailed method for digesting soils, but many of the recommended pretreatment steps employ sodium compounds such as sodium bicarbonate (NaHCO 3 ), sodium citrate (Na 3 C 6 H 5 O 7 -2H 2 O), and sodium dithionate (Na 2 S 2 O 4 ), which are used for the removal of calcium carbonate, iron oxides, and phosphates. In combining the methods of Dolcater and Jackson, sodium compounds must be thoroughly washed from the sample because they form sodium fluotitanate (Na 2 TiF 6 ) in the presence of hydrofluotitanic acid (Fig. 1K). French and Adams (1973) described an inexpensive method for decomposing silicates by HF digestion in polypropylene containers. Their technique was effective for a wide variety of rock types. However, it did not address the problem caused by the precipitation of insoluble fluorides, nor did it outline a procedure to concentrate any residue that remained. As no one method gave the results we required, we modified procedures described in the literature and developed a process that removes 96 to 98 wt percent of the raw sample material. The residue is composed of rutile and minor amounts of micro- and cryptocrystalline TiO 2 (Fig. 1A-J), barite (Fig. 1L), elemental carbon (coal), and insoluble fluorides (Fig. 1J). The fluorides precipitate during the decomposition of siliceous material in hydrofluoric acid (e.g., MgF 2 and MgAlF 5 -2.7H 2 O; Lanmyhr and Kringstad, 1966). Most of the sample analyzed by the method described were marine muds collected from the Gulf of Maine (Valentine and Commeau, 1990). The silt and clay fraction (up to 99 wt% of the sediment) is composed of clay minerals (chiefly illite-mica and chlorite), silt-size quartz and feldspar, and small crystals (2-12 um) of rutile and hematite. The bulk sediment samples contained an average of 2 to 3 wt percent CaCO 3 . Tiher samples analyzed include red and gray Carboniferous and Triassic sandstones and siltstones exposed around the Bay of Fundy region and Paleozoic sandstones, siltstones, and shales from northern Maine and New Brunswick. These rocks are probable sources for the fine-grained rutile found in the Gulf of Maine.

Economic Geology↗

Decadal trends in the quality of groundwater used for public drinking-water supply in California, 2004–2023, California groundwater ambient monitoring and assessment program, priority basin project

This study provides a comprehensive assessment of decadal changes in the quality of groundwater used for public drinking-water supply at 444 monitoring sites across California during 2004–2023. We assessed decadal step trends in groundwater quality for 145 water-quality constituents and geochemical indicators statewide and across geographic and land-use based network groups. We evaluated the statistical significance of directional changes (predominant increase or decrease of constituent concentrations) and the magnitude of those changes across all network groups. Uranium showed the most widespread directional and high-magnitude increases of all constituents with regulatory benchmarks statewide, particularly in the agriculture-dominated Central Valley as well as urban- and desert-dominated regions of Southern California. Fluoride and perchlorate showed the most widespread directional and high-magnitude decreases of all constituents with regulatory benchmarks statewide, which were also most pronounced in Southern California. Although arsenic and nitrate did not often register significant directional changes across network groups, they showed widespread, high-magnitude changes in both directions (increase and decrease) at levels often exceeding 10 percent of respective regulatory benchmarks statewide. Triazine herbicides (atrazine and simazine) and the gasoline oxygenate methyl tert-butyl ether (MTBE) showed significant directional decreases statewide, but not at levels considered to be of high magnitude compared to respective regulatory benchmarks. We observed significant directional and high-magnitude increases of total dissolved solids (TDS) statewide, which were most pronounced in agricultural areas. Analysis of explanatory geochemical indicators indicated that prevalent statewide increases of alkalinity and calcium were the predominant components of the observed statewide increases in TDS by mass. Widespread increases in groundwater alkalinity and calcium across agricultural and urban areas may be related, in part, to warm-season irrigation and other anthropogenic factors that have shifted soil weathering dynamics over the long term. Increasing alkalinity concentrations were related to increasing uranium concentrations, particularly in areas with aquifer materials derived from granitic rocks. Conversely, increasing calcium concentrations were related to decreasing fluoride concentrations, particularly in areas where fluoride occurred naturally at elevated concentrations. Decrease of perchlorate, triazine herbicides, and MTBE are likely related to decreased anthropogenic source inputs over time and natural attenuation in aquifers.

EarthArXiv↗

Quality-assurance data for routine water quality analyses by the U. S. Geological Survey laboratory in Troy, New York; July 1993 through June 1995

A laboratory for analysis of low-ionic strength water has been developed at the U.S. Geological Survey (USGS) office in Troy, N.Y., to analyze samples collected by USGS projects in the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures developed to ensure proper sample collection, processing, and analysis. The quality-assurance/quality-control data are stored in the laboratory's SAS data-management system, which provides efficient review, compilation, and plotting of quality-assurance/quality-control data. This report presents and discusses samples analyzed from July 1993 through June 1995. Quality-control results for 18 analytical procedures were evaluated for bias and precision. Control charts show that data from seven of the analytical procedures were biased throughout the analysis period for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, dissolved inorganic carbon, dissolved organic carbon (soil expulsions), chloride, magnesium, nitrate (colorimetric method), and pH. Three of the analytical procedures were occasionally biased but were within control limits; they were: calcium (high for high-concentration samples for May 1995), dissolved organic carbon (high for highconcentration samples from January through September 1994), and fluoride (high in samples for April and June 1994). No quality-control sample has been developed for the organic monomeric aluminum procedure. Results from the filter-blank and analytical-blank analyses indicate that all analytical procedures in which blanks were run were within control limits, although values for a few blanks were outside the control limits. Blanks were not analyzed for acid-neutralizing capacity, dissolved inorganic carbon, fluoride, nitrate (colorimetric method), or pH. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in 14 of the 18 procedures. Data-quality objectives were met by more than 90 percent of the samples analyzed in all procedures except total monomeric aluminum (85 percent of samples met objectives), total aluminum (70 percent of samples met objectives), and dissolved organic carbon (85 percent of samples met objectives). Triplicate samples were not analyzed for ammonium, fluoride, dissolved inorganic carbon, or nitrate (colorimetric method). Results of the USGS interlaboratory Standard Reference Sample Program indicated high data quality with a median result of 3.6 of a possible 4.0. Environment Canada's LRTAP interlaboratory study results indicated that more than 85 percent of the samples met data-quality objectives in 6 of the 12 analyses; exceptions were calcium, dissolved organic carbon, chloride, pH, potassium, and sodium. Data-quality objectives were not met for calcium samples in one LRTAP study, but 94 percent of samples analyzed were within control limits for the remaining studies. Data-quality objectives were not met by 35 percent of samples analyzed for dissolved organic carbon, but 94 percent of sample values were within 20 percent of the most probable value. Data-quality objectives were not met for 30 percent of samples analyzed for chloride, but 90 percent of sample values were within 20 percent of the most probable value. Measurements of samples with a pH above 6.0 were biased high in 54 percent of the samples, although 85 percent of the samples met data-quality objectives for pH measurements below 6.0. Data-quality objectives for potassium and sodium were not met in one study (only 33 percent of the samples analyzed met the objectives), although 85 percent of the sample values were within control limits for the other studies. Measured sodium values were above the upper control limit in all studies. Results from blind reference-sample analyses indicated that data

Open-File Report↗

Quality-assurance data for routine water analyses by the U.S. Geological Survey laboratory in Troy, New York - July 2003 through June 2005

The laboratory for analysis of low-ionic-strength water at the U.S. Geological Survey (USGS) Water Science Center in Troy, N.Y., analyzes samples collected by USGS projects throughout the Northeast. The laboratory's quality-assurance program is based on internal and interlaboratory quality-assurance samples and quality-control procedures that were developed to ensure proper sample collection, processing, and analysis. The quality-assurance and quality-control data were stored in the laboratory's Lab Master data-management system, which provides efficient review, compilation, and plotting of data. This report presents and discusses results of quality-assurance and quality control samples analyzed from July 2003 through June 2005. Results for the quality-control samples for 20 analytical procedures were evaluated for bias and precision. Control charts indicate that data for five of the analytical procedures were occasionally biased for either high-concentration or low-concentration samples but were within control limits; these procedures were: acid-neutralizing capacity, total monomeric aluminum, pH, silicon, and sodium. Seven of the analytical procedures were biased throughout the analysis period for the high-concentration sample, but were within control limits; these procedures were: dissolved organic carbon, chloride, nitrate (ion chromatograph), nitrite, silicon, sodium, and sulfate. The calcium and magnesium procedures were biased throughout the analysis period for the low-concentration sample, but were within control limits. The total aluminum and specific conductance procedures were biased for the high-concentration and low-concentration samples, but were within control limits. Results from the filter-blank and analytical-blank analyses indicate that the procedures for 17 of 18 analytes were within control limits, although the concentrations for blanks were occasionally outside the control limits. The data-quality objective was not met for dissolved organic carbon. Sampling and analysis precision are evaluated herein in terms of the coefficient of variation obtained for triplicate samples in the procedures for 18 of the 22 analytes. At least 85 percent of the samples met data-quality objectives for all analytes except total monomeric aluminum (82 percent of samples met objectives), total aluminum (77 percent of samples met objectives), chloride (80 percent of samples met objectives), fluoride (76 percent of samples met objectives), and nitrate (ion chromatograph) (79 percent of samples met objectives). The ammonium and total dissolved nitrogen did not meet the data-quality objectives. Results of the USGS interlaboratory Standard Reference Sample (SRS) Project indicated good data quality over the time period, with ratings for each sample in the satisfactory, good, and excellent ranges or less than 10 percent error. The P-sample (low-ionic-strength constituents) analysis had one marginal and two unsatisfactory ratings for the chloride procedure. The T-sample (trace constituents)analysis had two unsatisfactory ratings and one high range percent error for the aluminum procedure. The N-sample (nutrient constituents) analysis had one marginal rating for the nitrate procedure. Results of Environment Canada's National Water Research Institute (NWRI) program indicated that at least 84 percent of the samples met data-quality objectives for 11 of the 14 analytes; the exceptions were ammonium, total aluminum, and acid-neutralizing capacity. The ammonium procedure did not meet data quality objectives in all studies. Data-quality objectives were not met in 23 percent of samples analyzed for total aluminum and 45 percent of samples analyzed acid-neutralizing capacity. Results from blind reference-sample analyses indicated that data-quality objectives were met by at least 86 percent of the samples analyzed for calcium, chloride, fluoride, magnesium, pH, potassium, sodium, and sulfate. Data-quality objectives were not met by samples analyzed for fluoride.

Open-File Report↗

Ground-water resources of the Yucca Valley-Joshua Tree area, San Bernardino County, California

The southeastern part of the Mojave Water Agency area included in this report comprises about 600 square miles. Recharge into the area is almost exclusively from precipitation in the San Bernardino and Little San Bernardino Mountains. About 500 acre-feet per year of recharge enters the western part of the area as underflow through Pipes Wash. Little direct recharge occurs as a result of precipitation directly on the unconsolidated deposits. Presently about 11,000 persons reside in the area and current gross pumpage is about 1,600 acre-feet annually. By the year 2000 the population is estimated to be 62,000 and annual gross pumpage is expected to be nearly 11,000 acre-feet. Although over 1,200,000 acre-feet of ground water are presently in storage, most of the population is centered in the southern part of the area around the towns of Yucca Valley and Joshua Tree. About 70 percent of the population resides in the vicinity of Yucca Valley and is supplied by ground water pumped from the Warren Valley basin. Of the 96,000 acre-feet of ground water in storage in that basin in 1969, about 80,000 acre-feet will be necessary to sustain projected growth there until 2000. Assuming negligible recharge and only about 50 percent recovery of the ground water in storage, if imported water from northern California is not available before about 1990, additional local supplies will have to be developed, possibly in the adjacent Pipes subbasin to the north. Ground water in the southern part of the study area generally contains less than 250 mg/l (milligrams per liter) dissolved solids and 1.0 mg/l fluoride. A general degradation of ground-water quality occurs northward toward the dry lakes where the concentrations of dissolved solids and fluoride approach 2,000 and 5.0 mg/l, respectively. In Reche subbasin some isolated occurrences of fluoride exceeding 1.5 mg/l were noted. The chemical character of ground water in Johnson Valley and Morongo Valley basins differs from well to well and, in general, water from these basins is less desirable for use.

Open-File Report↗

Quality of water in the fractured-bedrock aquifer of New Hampshire

Over the past few decades, New Hampshire has experienced considerable population growth, which is forcing some communities to look for alternative public and private water supplies in the bedrock aquifer. Because the quality of water from the aquifer can vary, the U.S. Geological Survey statistically analyzed well data from 1,353 domestic and 360 public-supply bedrock wells to characterize the ground water. The domestic-well data were from homeowner-collected samples analyzed by the New Hampshire Department of Environmental Services (NHDES) Environmental Laboratory from 1984 to 1994. Bedrock water in New Hampshire often contains high concentrations of iron, manganese, arsenic, and radon gas. Water samples from 21 percent of the domestic bedrock wells contained arsenic above the U.S. Environmental Protection Agency (USEPA) 10 micrograms per liter (?g/L) drinking-water standard for public-water supplies, and 96 percent had radon concentrations greater than the USEPA-proposed 300 picocurie per liter (pCi/L) standard for public-water supplies. Some elevated fluoride concentrations (2 percent of samples) were above the 4 milligrams per liter (mg/L) USEPA drinking-water standard for public-water supplies. Water from the bedrock aquifer also typically is soft to moderately hard, and has a pH greater than 7.0. Variations in bedrock water quality were discernable when the data were compared to lithochemical groupings of the bedrock, indicating that the type of bedrock has an effect on the quality of water in the bedrock aquifer of New Hampshire. Ground-water samples from the metasedimentary lithochemical group have greater concentrations of total iron and total manganese than do the felsic and mafic igneous lithochemical groups. Ground-water samples from the felsic igneous group have higher concentrations of total fluoride than do those from the other lithochemical groups. For arsenic, the calcareous metasedimentary group was identified, using the public-supply database, as having higher concentrations, on average, than the other lithochemical groups. The use of a radon-gas-potential classification of bedrock in the State indicated where high radon concentrations in the air and in water from private and public-supply wells were more likely to occur. In general, samples from the bedrock aquifer tend to have higher pH (are less acidic), greater hardness, much higher concentrations of iron, similar concentrations of manganese, and higher concentrations of fluoride and arsenic than do samples from stratified-drift aquifers in New Hampshire. An understanding of the water-quality conditions of water in bedrock aquifers is important from a public-health perspective because an increasing number of domestic bedrock wells are being drilled and relied upon as a source of drinking water in the State.

Scientific Investigations Report↗

Status and understanding of groundwater quality in the two southern San Joaquin Valley study units, 2005-2006 - California GAMA Priority Basin Project

Groundwater quality in the southern San Joaquin Valley was investigated from October 2005 through March 2006 as part of the Priority Basin Project of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA Priority Basin Project is conducted by the U.S. Geological Survey (USGS) in collaboration with the California State Water Resources Control Board and the Lawrence Livermore National Laboratory. There are two study units located in the southern San Joaquin Valley: the Southeast San Joaquin Valley (SESJ) study unit and the Kern County Subbasin (KERN) study unit. The GAMA Priority Basin Project in the SESJ and KERN study units was designed to provide a statistically unbiased, spatially distributed assessment of untreated groundwater quality within the primary aquifers. The status assessment is based on water-quality and ancillary data collected in 2005 and 2006 by the USGS from 130 wells on a spatially distributed grid, and water-quality data from the California Department of Public Health (CDPH) database. Data was collected from an additional 19 wells for the understanding assessment. The 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 CDPH database for the SESJ and KERN study units. The status assessment of groundwater quality used data from samples analyzed for anthropogenic constituents such as volatile organic compounds (VOCs) and pesticides, as well as naturally occurring inorganic constituents such as major ions and trace elements. The status assessment is intended to characterize the quality of untreated groundwater resources within the primary aquifers in the SESJ and KERN study units, not the quality of drinking water delivered to consumers. Although the status assessment applies to untreated groundwater, Federal and California regulatory and non-regulatory water-quality benchmarks that apply to drinking water are used to provide context for the results. Relative-concentrations (sample concentration divided by benchmark concentration) were used for evaluating groundwater. A relative-concentration greater than 1.0 indicates a concentration greater than the benchmark and is classified as high. The relative-concentration threshold for classifying inorganic constituents as moderate or low was 0.5; for organic constituents the threshold between moderate and low was 0.1. Aquifer-scale proportion was used as the primary metric for assessing the quality of untreated groundwater for the study units. High aquifer-scale proportion is defined as the areal percentage of the primary aquifers with a high relative-concentration for a particular constituent or class of constituents. Moderate and low aquifer-scale proportions were defined as the areal percentage of the primary aquifers with moderate and low relative-concentrations, respectively. Two statistical approaches—grid-based and spatially weighted—were used to evaluate aquifer-scale proportions for individual constituents and classes of constituents. Grid-based and spatially weighted estimates were comparable for the two study units in the southern San Joaquin Valley (within 90 percent confidence intervals). The status assessment showed that inorganic constituents were more prevalent than organic constituents and that relative-concentrations were higher for inorganic constituents than for organic constituents. For inorganic constituents with human-health benchmarks, the relative-concentration of at least one constituent in the SESJ study unit was high in 30 percent of the primary aquifers. In the KERN study unit, the relative-concentration of at least one constituent was high in 23 percent of the primary aquifers. In the SESJ and KERN study units, the inorganic constituents with human-health benchmarks detected at high relative-concentrations in more than 2 percent of the primary aquifers were arsenic, boron, vanadium, nitrate, uranium, and gross alpha radioactivity. Additional constituents with human-health benchmarks—antimony, radium, and fluoride—were detected at high relative-concentrations in the KERN study unit. For inorganic constituents with aesthetic benchmarks (secondary maximum contaminant levels, SMCLs), the relative-concentration of at least one constituent in the SESJ study unit was high in 6.6 percent of the primary aquifers. In the KERN study unit, the relative-concentration of at least one constituent was high in 22 percent of the primary aquifers. Inorganic constituents with aesthetic benchmarks detected at high relative-concentrations in the primary aquifers in the SESJ and KERN study units were iron and manganese. Additional constituents with aesthetic benchmarks—total dissolved solids (TDS), sulfate, and chloride—were detected at high relative-concentrations in the KERN study unit. In contrast, the status assessment for organic constituents with human-health benchmarks showed that relative-concentrations were high in 4.8 percent and 2.1 percent of the primary aquifers in the SESJ and KERN study units, respectively. The special-interest constituent, perchlorate, was detected at high relative-concentrations in 1.2 percent of the primary aquifers in the SESJ study unit. Twenty-eight of the 78 VOCs (not including fumigants) analyzed were detected. Of these 28 VOCs, benzene had high relative-concentrations in the SESJ study unit, and relative-concentrations for the other 27 VOCs were moderate and low. Five of the 10 fumigants were detected; 1,2-dibromo-3-chloropropane (DBCP) was the only fumigant with high relative-concentrations in the SESJ and KERN study units. Of the 136 pesticides and pesticide degradates analyzed, 33 were detected. Human-health benchmarks were established for eighteen of the detected pesticides. Dieldrin was detected at moderate relative-concentrations in the SESJ and KERN study units. All other pesticides detected with human-health benchmarks were present at low relative-concentrations. The detection frequencies for two of these pesticides—simazine and atrazine—were greater than or equal to 10 percent in the SESJ and KERN study units. The understanding assessment of groundwater quality included an analysis of correlations of selected water-quality constituents or classes of constituents with potential explanatory factors. The understanding assessment indicated that the concentrations of many trace elements and major ions were correlated to well depth, groundwater age, and/or geochemical conditions. Many trace elements were positively correlated with depth. Arsenic, boron, vanadium, fluoride, manganese, and iron concentrations increased with well depth or depth to top-of-perforations. The concentrations for these trace elements also were higher in older (pre-modern) groundwater. In contrast, uranium concentrations decreased with increasing depth and groundwater age. Most trace elements were correlated to geochemical conditions. Arsenic, antimony, boron, fluoride, manganese, and iron concentrations generally were higher wherever the pH of the groundwater was greater than 7.6. Concentrations for these constituents generally were higher at low concentrations of dissolved oxygen (DO). Uranium was the exception; uranium concentrations generally were lower at high pH and at high concentrations of DO. Nitrate concentrations generally were lower in deeper wells. Nitrate concentrations also were higher in groundwater with higher DO. Total dissolved solids, sulfate, and chloride concentrations were higher in the KERN study unit than in the SESJ study unit. Total dissolved solids were negatively correlated with pH in the KERN study unit. Total dissolved solids and sulfate were higher in areas with more agricultural land use. Chloride concentrations increased with depth to top-of-perforations in the KERN study unit. Organic constituents and constituents of special interest, like many inorganic constituents, were correlated with well depth, groundwater age, and DO. Unlike most trace elements, however, solvent and pesticide detections, and total trihalomethanes (THM), DBCP, and perchlorate concentrations decreased with increasing well depth. Volatile organic compound, solvent, and pesticide detections, and THM concentrations also were lower in older (pre-modern) groundwater than in modern-age groundwater. Solvent detections and total THM, DBCP, and perchlorate concentrations increased with increasing DO concentrations.

California↗

Overview of groundwater quality in the Piceance Basin, western Colorado, 1946--2009

Groundwater-quality data from public and private sources for the period 1946 to 2009 were compiled and put into a common data repository for the Piceance Basin. The data repository is available on the web at http://rmgsc.cr.usgs.gov/cwqdr/Piceance/index.shtml. A subset of groundwater-quality data from the repository was compiled, reviewed, and checked for quality assurance for this report. The resulting dataset consists of the most recently collected sample from 1,545 wells, 1,007 (65 percent) of which were domestic wells. From those samples, the following constituents were selected for presentation in this report: dissolved oxygen, dissolved solids, pH, major ions (chloride, sulfate, fluoride), trace elements (arsenic, barium, iron, manganese, selenium), nitrate, benzene, toluene, ethylbenzene, xylene, methane, and the stable isotopic compositions of water and methane. Some portion of recharge to most of the wells for which data were available was derived from precipitation (most likely snowmelt), as indicated by δ2H [H2O] and δ18O[H2O] values that plot along the Global Meteoric Water Line and near the values for snow samples collected in the study area. Ninety-three percent of the samples were oxic, on the basis of concentrations of dissolved oxygen that were greater than or equal to 0.5 milligrams per liter. Concentration data were compared with primary and secondary drinking-water standards established by the U.S. Environmental Protection Agency. Constituents that exceeded the primary standards were arsenic (13 percent), selenium (9.2 percent), fluoride (8.4 percent), barium (4.1 percent), nitrate (1.6 percent), and benzene (0.6 percent). Concentrations of toluene, xylenes, and ethylbenzene did not exceed standards in any samples. Constituents that exceeded the secondary standard were dissolved solids (72 percent), sulfate (37 percent), manganese (21 percent), iron (16 percent), and chloride (10 percent). Drinking-water standards have not been established for methane, which was detected in 24 percent of samples. Methane concentrations were greater than or equal to 1 milligram per liter in 8.5 percent of samples. Methane isotopic data for samples collected primarily from domestic wells in Garfield County indicate that methane in samples with relative high methane concentrations were derived from both biogenic and thermogenic sources. Many of the constituents that exceeded standards, such as arsenic, fluoride, iron, and manganese, were derived from rock and sediment in aquifers. Elevated nitrate concentrations were most likely derived from human sources such as fertilizer and human or animal waste. Information about the geologic unit or aquifer in which a well was completed generally was not provided by data sources. However, limited data indicate that Quaternary deposits in Garfield and Mesa Counties, the Wasatch Formation in Garfield County, and the Green River Formation in Rio Blanco County had some of the highest median concentrations of selected constituents. Variations in concentration with depth could not be evaluated because of the general lack of well-depth and water-level data. Concentrations of several important constituents, such as arsenic, manganese, methane, and nitrate, were related to concentrations of dissolved oxygen. Concentrations of arsenic, manganese, and methane were significantly higher in groundwater with low dissolved-oxygen concentrations than in groundwater with high dissolved-oxygen concentrations. In contrast, concentrations of nitrate were significantly higher in groundwater with high dissolved-oxygen concentrations than in groundwater with low dissolved-oxygen concentrations. These results indicate that measurements of dissolved oxygen may be a useful indicator of groundwater vulnerability to some human-derived contaminants and enrichment from some natural constituents. Assessing such a large and diverse dataset as the one available through the repository poses unique challenges for reporting on groundwater quality in the study area. The repository contains data from several studies that differed widely in purpose and scope. In addition to this variability in available data, gaps exist spatially, temporally, and analytically in the repository. For example, groundwater-quality data in the repository were not evenly distributed throughout the study area. Several key water-quality constituents or indicators, such as dissolved oxygen, were underrepresented in the repository. Ancillary information, such as well depth, depth to water, and the geologic unit or aquifer in which a well was completed, was missing for more than 50 percent of samples. Future monitoring could avoid several limitations of the repository by making relatively minor changes to sample- collection and data-reporting protocols. Field measurements for dissolved oxygen could be added to sampling protocols, for example. Information on well construction and the geologic unit or aquifer in which a well was completed should be part of the water-quality dataset. Such changes would increase the comparability of data from different monitoring programs and also add value to each program individually and to that of the regional dataset as a whole. Other changes to monitoring programs could require greater resources, such as sampling for a basic set of constituents that is relevant to major water-quality issues in the regional study area. Creation of such a dataset for the regional study area would help to provide the kinds of information needed to characterize background conditions and the spatial and temporal variability in constituent concentrations associated with those conditions. Without such information, it is difficult to identify departures from background that might be associated with human activities.

Colorado↗

Water quality of groundwater and stream base flow in the Marcellus Shale Gas Field of the Monongahela River Basin, West Virginia, 2011-12

The Marcellus Shale gas field underlies portions of New York, Pennsylvania, Ohio, Virginia, Maryland, Tennessee, and West Virginia. Development of hydraulic fracturing and horizontal drilling technology led to extensive development of gas from the Marcellus Shale beginning about 2007. The need to identify and monitor changes in water-quality conditions related to development of the Marcellus Shale gas field prompted the U.S. Geological Survey, in cooperation with the West Virginia Department of Environmental Protection, Division of Water and Waste Management, to document water quality for comparison with water quality in samples collected at a future date. The identification of change in water-quality conditions over time is more difficult if baseline water-quality conditions have not been documented. U.S. Geological Survey personnel sampled groundwater and surface water in West Virginia’s Monongahela River Basin during 2011–12. A groundwater survey, in which 39 wells and 2 springs were sampled, was conducted during June through September 2011. A base-flow survey was conducted during July through October 2012; 50 stream sites were sampled under base-flow conditions in this survey. Because additives to hydraulic fracturing fluids are variable and decrease in flowback water over a relatively short time, water-quality analyses for this study focused on documenting the water-quality characteristics typical of water from shallow aquifers; water derived from contact with the Marcellus Shale (flowback from hydraulic fracturing or formation water); and water with constituents from conventional oil and gas development, sewage effluent, and coal-mine drainage. All samples were analyzed for field properties (water temperature, pH, specific conductance, dissolved oxygen, and turbidity), major ions, trace elements, naturally occurring radioactive materials, and stable isotopes. In addition to documenting baseline water-quality conditions for an area of shale-gas development, these data were examined for patterns in water quality. Groundwater and base-flow survey data were compared to historical data from the Monongahela River Basin in West Virginia. Additionally, groundwater- and base-flow survey samples were grouped by Marcellus Shale gas production in the subbasin in which that sampling site was located. The comparisons of data collected as part of this study with historical data identified few differences. No significant difference was found in a comparison of groundwater survey data and historical data. Base-flow survey samples differed significantly from historical data for pH, chloride, and strontium, all of which had higher concentrations in the base-flow survey samples. Differences in pH are likely related to changes in mining regulation beginning in 1977. Concentrations of chloride and strontium elevated above background concentrations may be related to saline groundwater; saline water is within 300 feet of the land surface in parts of the study area. In the comparison of base-flow survey samples grouped by shale-gas-production setting, significant differences were found for fluoride and barium. Concentrations of fluoride and barium were higher in stream subbasins with active Marcellus Shale production than in subbasins not near active Marcellus Shale production. Elevated fluoride and barium are associated with deep brines. Generally, naturally occurring radioactive materials were not found in elevated concentrations in either groundwater or base-flow samples. Only 3 samples, 2 from the groundwater survey and one from the base-flow survey, exceeded the U.S. Environmental Protection Agency maximum contaminant level for radium isotopes of 5.0 picocurie per liter for either a single isotope or a combined value of radium-226 and radium-228. Stable isotope composition indicates broad similarity among surface water, shallow groundwater, and precipitation in the region. Neither shallow groundwater nor surface water showed a marked similarity with the deep brines associated with shale gas. In most of the groundwater survey samples, 38 of 41 samples, dissolved gas profiles were similar to those previously found in samples from shallow, domestic wells in the region. This study provides a baseline of water-quality conditions in the Monongahela River Basin in West Virginia during the early phases of development of the Marcellus Shale gas field. Although not all inclusive, the results of this study provide a set of reliable water-quality data against which future data sets can be compared and the effects of shale-gas development may be determined.

West Virginia↗

Evaluation of background concentrations of selected chemical and radiochemical constituents in water from the eastern Snake River Plain aquifer at and near the Idaho National Laboratory, Idaho

The U.S. Geological Survey and Idaho Department of Environmental Quality Idaho National Laboratory (INL) Oversight Program in cooperation with the U.S. Department of Energy determined background concentrations of selected chemical and radiochemical constituents in the eastern Snake River Plain aquifer to aid with ongoing cleanup efforts at the INL. Chemical and radiochemical constituents including calcium, magnesium, sodium, potassium, silica, chloride, sulfate, fluoride, bicarbonate, chromium, nitrate, tritium, strontium-90, chlorine-36, iodine-129, plutonium-238, plutonium-239, -240 (undivided), americium-241, technetium-99, uranium-234, uranium-235, and uranium-238 were selected for the background study because they were either not analyzed in earlier studies or new data became available to give a more recent determination of background concentrations. Samples of water collected from wells and springs at and near the INL that were not believed to be influenced by wastewater disposal were used to identify background concentrations. Groundwater in the eastern Snake River Plain aquifer at and near the INL was divided into two major water types (western tributary and eastern regional) based on concentrations of lithium less than and greater than 5 micrograms per liter (&mu;g/L). Median concentrations for each constituent were used to define the upper limit of background. The upper limit of background concentrations for inorganic chemicals for western tributary water was 40.7 milligrams per liter (mg/L) for calcium, 15.3 mg/L for magnesium, 8.30 mg/L for sodium, 2.32 mg/L for potassium, 23.1 mg/L for silica, 11.8 mg/L for chloride, 21.4 mg/L for sulfate, 0.20 mg/L for fluoride, 176 mg/L for bicarbonate, 4.00 &mu;g/L for chromium, and 0.655 mg/L for nitrate. The upper limit of background concentrations for inorganic chemicals for eastern regional water was 34.05 mg/L for calcium, 13.85 mg/L for magnesium, 14.85 mg/L for sodium, 3.22 mg/L for potassium, 31.0 mg/L for silica, 14.15 mg/L for chloride, 20.2 mg/L for sulfate, 0.4675 mg/L for fluoride, 165 mg/L for bicarbonate, 3.00 &mu;g/L for chromium, and 0.995 mg/L for nitrate. The upper limit of background concentrations for radiochemical constituents for western tributary water was 34.15 &plusmn;2.35 picocuries per liter (pCi/L) for tritium, 0.00098 &plusmn;0.00006 pCi/L for chlorine-36, 0.000011 &plusmn;0.000005 pCi/L for iodine-129, <0.0000054 pCi/L for technetium-99, 0 pCi/L for strontium-90, plutonium-238, plutonium-239, -240 (undivided), and americium-241, 1.36 pCi/L with undetermined uncertainty for uranium-234, 0.025 &plusmn;0.001 pCi/L for uranium-235, and 0.541 &plusmn;0.001 pCi/L for uranium-238. The upper limit of background concentrations for radiochemical constituents for eastern regional water was 5.43 &plusmn;0.574 pCi/L for tritium, 0.0002048 &plusmn;0.0000054 pCi/L for chlorine-36, 0.000000865 &plusmn;0.000000015 pCi/L for iodine-129, <0.0000054 pCi/L for technetium-99, 0 pCi/L for strontium-90, plutonium-238, plutonium-239, -240 (undivided), and americium-241, 1.32 &plusmn;0.77 pCi/L for uranium-234, 0.016 &plusmn;0.012 pCi/L for uranium-235, and 0.477 &plusmn;0.044 pCi/L for uranium-238.

Idaho↗

Status and understanding of groundwater quality in the Bear Valley and Lake Arrowhead Watershed Study Unit, 2010: California GAMA Priority Basin Project

Groundwater quality in the 112-square-mile Bear Valley and Lake Arrowhead Watershed (BEAR) study unit was investigated as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The study unit comprises two study areas (Bear Valley and Lake Arrowhead Watershed) in southern California in San Bernardino County. The GAMA-PBP is conducted by the California State Water Resources Control Board (SWRCB) in cooperation with the U.S. Geological Survey (USGS) and the Lawrence Livermore National Laboratory. The GAMA BEAR study was designed to provide a spatially balanced, robust assessment of the quality of untreated (raw) groundwater from the primary aquifer systems in the two study areas of the BEAR study unit. The assessment is based on water-quality collected by the USGS from 38 sites (27 grid and 11 understanding) during 2010 and on water-quality data from the SWRCB-Division of Drinking Water (DDW) database. The primary aquifer system is defined by springs and the perforation intervals of wells listed in the SWRCB-DDW water-quality database for the BEAR study unit. This study included two types of assessments: (1) a status assessment , which characterized the status of the quality of the groundwater resource as of 2010 by using data from samples analyzed for volatile organic compounds, pesticides, and naturally present inorganic constituents, such as major ions and trace elements, and (2) an understanding assessment , which evaluated the natural and human factors potentially affecting the groundwater quality. The assessments were intended to characterize the quality of groundwater resources in the primary aquifer system of the BEAR study unit, not the treated drinking water delivered to consumers. Bear Valley study area and the Lake Arrowhead Watershed study area were also compared statistically on the basis of water-quality results and factors potentially affecting the groundwater quality. Relative concentrations (RCs), which are sample concentration of a particular constituent divided by its associated health- or aesthetic-based benchmark concentrations, were used for evaluating the groundwater quality for those constituents that have Federal or California regulatory or non-regulatory benchmarks for drinking-water quality. An RC greater than 1.0 indicates a concentration greater than a benchmark. Organic (volatile organic compounds and pesticides) and special-interest (perchlorate) constituent RCs were classified as “high” (RC greater than 1.0), “moderate” (RC less than or equal to 1.0 and greater than 0.1), or “low” (RC less than or equal to 0.1). For inorganic (radioactive, trace element, major ion, and nutrient) constituents, the boundary between low and moderate RCs was set at 0.5. Aquifer-scale proportion was used as the primary metric in the status assessment for evaluating groundwater quality at the study-unit scale or for its component areas. High aquifer-scale proportion was defined as the percentage of the area of the primary aquifer system with a RC greater than 1.0 for a particular constituent or class of constituents; the percentage is based on area rather than volume. Moderate and low aquifer-scale proportions were defined as the percentage of the primary aquifer system with moderate and low RCs, respectively. A spatially weighted statistical approach was used to evaluate aquifer-scale proportions for individual constituents and classes of constituents. The status assessment for the Bear Valley study area found that inorganic constituents with health-based benchmarks were detected at high RCs in 9.0 percent of the primary aquifer system and at moderate RCs in 13 percent. The high RCs of inorganic constituents primarily reflected high aquifer-scale proportions of fluoride (in 5.4 percent of the primary aquifer system) and arsenic (3.6 percent). The RCs of organic constituents with health-based benchmarks were high in 1.0 percent of the primary aquifer system, moderate in 8.1 percent, and low in 70 percent. Organic constituents were detected in 79 percent of the primary aquifer system. Two groups of organic constituents and two individual organic constituents were detected at frequencies greater than 10 percent of samples from the USGS grid sites: trihalomethanes (THMs), solvents, methyl tert -butyl ether (MTBE), and simazine. The special-interest constituent perchlorate was detected in 93 percent of the primary aquifer system; it was detected at moderate RCs in 7.1 percent and at low RCs in 86 percent. The status assessment in the Lake Arrowhead Watershed study area showed that inorganic constituents with human-health benchmarks were detected at high RCs in 25 percent of the primary aquifer system and at moderate RCs in 41 percent. The high aquifer-scale proportion of inorganic constituents primarily reflected high aquifer-scale proportions of radon‑222 (in 62 percent of the primary aquifer system) and uranium (26 percent). RCs of organic constituents with health-based benchmarks were moderate in 7.7 percent of the primary aquifer system and low in 46 percent. Organic constituents were detected in 54 percent of the primary aquifer system. The only organic constituents that were detected at frequencies greater than 10 percent of samples from the USGS grid sites were THMs. Perchlorate was detected in 62 percent of the primary aquifer system at uniformly low RCs. The second component of this study, the understanding assessment , identified the natural and human factors that could have affected the groundwater quality in the BEAR study unit by evaluating statistical correlations between water-quality constituents and potential explanatory factors. The potential explanatory factors evaluated were land use (including density of septic tanks and leaking or formerly leaking underground fuel tanks), site type, aquifer lithology, well construction (well depth and depth to the top-of-perforated interval), elevation, aridity index, groundwater-age distribution, and oxidation-reduction condition (including pH and dissolved oxygen concentration). Results of the statistical evaluations were used to explain the distribution of constituents in groundwater of the BEAR study unit. In the Bear Valley study area, high and moderate RCs of fluoride were found in sites known to be influenced by hydrothermic conditions or that had high concentrations of fluoride historically. The high RC of arsenic can likely be attributed to desorption of arsenic from aquifer sediments saturated in old groundwater with high pH under reducing conditions. The THMs were detected more frequently at USGS grid sites that were wells, part of a large urban water system, and surrounded by urban land use. Solvents, MTBE, and simazine were all detected more frequently at USGS grid sites that were wells with a greater urban percentage of surrounding land use and that accessed older groundwater than other USGS grid sites. Comparison between the observed and predicted detection frequencies of perchlorate at USGS grid sites indicated that anthropogenic sources could have contributed to low levels of perchlorate in the groundwater of the Bear Valley study area. In the Lake Arrowhead Watershed study area, high and moderate RCs of radon-222 and uranium can be attributed to older groundwater from the granitic fractured-rock primary aquifer system. Low RCs of THMs were detected at USGS grid sites that were wells and part of small water systems. The similarities between the observed and predicted detection frequencies of perchlorate in samples from USGS grid sites indicated that the source and distribution of perchlorate were most likely attributable to precipitation (rain and snow), with minimal, if any, contribution from anthropogenic sources.

California↗

Status and understanding of groundwater quality in the North San Francisco Bay Shallow Aquifer study unit, 2012; California GAMA Priority Basin Project (ver. 1.1, February 2018)

Groundwater quality in the North San Francisco Bay Shallow Aquifer study unit (NSF-SA) was investigated as part of the Priority Basin Project of the California Groundwater Ambient Monitoring and Assessment (GAMA) Program. The study unit is in Marin, Mendocino, Napa, Solano, and Sonoma Counties and included two physiographic study areas: the Valleys and Plains area and the surrounding Highlands area. The NSF-SA focused on groundwater resources used for domestic drinking water supply, which generally correspond to shallower parts of aquifer systems than that of groundwater resources used for public drinking water supply in the same area. The assessments characterized the quality of untreated groundwater, not the quality of drinking water. This study included three components: (1) a status assessment , which characterized the status of the quality of the groundwater resources used for domestic supply for 2012; (2) an understanding assessment , which evaluated the natural and human factors potentially affecting water quality in those resources; and (3) a comparison between the groundwater resources used for domestic supply and those used for public supply. The status assessment was based on data collected from 71 sites sampled by the U.S. Geological Survey for the GAMA Priority Basin Project in 2012. To provide context, concentrations of constituents measured in groundwater were compared to U.S. Environmental Protection Agency (EPA) and California State Water Resources Control Board Division of Drinking Water regulatory and non-regulatory benchmarks for drinking-water quality. The status assessment used a grid-based method to estimate the proportion of the groundwater resources that has concentrations of water-quality constituents approaching or above benchmark concentrations. This method provides statistically unbiased results at the study-area scale and permits comparisons to other GAMA Priority Basin Project study areas. In the NSF-SA study unit as a whole, inorganic constituents with human-health benchmarks were detected at high relative concentrations (RCs) in 27 percent of the shallow aquifer system, and inorganic constituents with secondary maximum contaminant levels (SMCL) were detected at high RCs in 24 percent of the system. The inorganic constituents detected at high RCs were arsenic, boron, fluoride, manganese, nitrate, iron, sulfate, and total dissolved solids (TDS). Organic constituents with human-health benchmarks were detected at high RCs in 1 percent of the shallow aquifer system. Of the 148 organic constituents analyzed, 30 constituents were detected, although only 1, chloroform, had a detection frequency greater than 10 percent. Natural and anthropogenic factors that could affect the groundwater quality were evaluated by using results from statistical testing of associations between constituent concentrations and values of potential explanatory factors. Groundwater age class (modern, mixed, or pre-modern), redox class (oxic or anoxic), aquifer lithology class (metamorphic, sedimentary, or volcanic), and dissolved oxygen concentrations were the explanatory factors that explained distribution patterns of most of the inorganic constituents best. Groundwater classified primarily as pre-modern or mixed in age was associated with higher concentrations of arsenic and fluoride than waters classified as modern. Anoxic or mixed redox conditions were associated with higher concentrations of boron, fluoride, and manganese. Similar patterns of association with explanatory variables were seen for inorganic constituents with aesthetic-based benchmarks detected at high concentrations. Nitrate and perchlorate had higher concentrations in oxic than in the anoxic redox class and were positively correlated with urban land use. The NSF-SA water-quality results were compared to those of the GAMA North San Francisco Bay Public-Supply Aquifer study unit (NSF-PA). The NSF-PA was sampled in 2004 and covers much of the same area as the NSF-SA, but focused on the deeper public-supply aquifer system. The comparison of the NSF-PA to the NSF-SA showed that there were more differences between the Valleys and Plains study areas of the two study units than between the Highlands study areas of the two study units. As expected from the shallower depth of wells, the NSF-SA Valleys and Plains study area had a lesser proportion of pre-modern age groundwater and greater proportion of modern age groundwater than the NSF-PA Valleys and Plains study area. In contrast, well depths and groundwater ages were not significantly different between the two Highlands study areas. Arsenic, manganese, and nitrate were present at high RCs, and perchlorate was detected in greater proportions of the NSF-SA Valleys and Plains study area than the NSF-PA Valleys and Plains study area.

California↗

Geochemical assessment of groundwater in the Big Chino subbasin, Arizona, 2011–18

A geochemical characterization of groundwater in the Big Chino subbasin of Arizona was conducted by the U.S. Geological Survey, in cooperation with the City of Prescott, the Town of Prescott Valley, and the Salt River Project, to understand groundwater evolution through the study area and the source of water to springs along the gaining reach of the Verde River just downstream from its confluence with Granite Creek. Samples were collected between 2011 and 2018 in groundwater wells completed in basin-fill and carbonate aquifers and at selected springs, including two discrete springs discharging along the aforementioned stretch of the Verde River. Five newly installed monitoring wells completed in the carbonate aquifer were sampled in 2018. Water-quality results obtained from these samples include the first known geochemical data for carbonate groundwater beneath the basin-fill in the Big Chino subbasin downgradient from Walnut Creek near Paulden, Arizona, as well as other parts of the study area without previous data. Groundwater samples were collected and analyzed for major ions, arsenic, nutrients, stable isotopes of oxygen and hydrogen (δ 18 O and δ 2 H), strontium isotopes ( 87 Sr/ 86 Sr), carbon-14, isotopes of carbon (δ 13 C), and noble gases. Significant differences in groundwater geochemistry between the basin-fill and carbonate aquifers were driven primarily by higher pH, tritium, and δ 18 O and δ 2 H in the basin-fill aquifer samples and higher specific conductance and higher concentrations of calcium, sodium, bicarbonate, fluoride, and arsenic in the carbonate aquifer samples. All but one sample from the carbonate aquifer and two samples from the basin-fill aquifer exceeded the U.S. Environmental Protection Agency (EPA) drinking water standard for arsenic of 10 micrograms per liter. One basin-fill aquifer sample exceeded the EPA drinking water standard for fluoride of 4 milligrams per liter, and one carbonate aquifer sample exceeded the EPA secondary drinking water standard for fluoride of 2 milligrams per liter. A component of modern groundwater recharged following aboveground nuclear testing beginning in the mid-1950s is present in some basin-fill and spring groundwater from this study. Groundwater that can be dated using radiocarbon decay is also present in the study area, with four groundwater samples indicating possible recharge during the Pleistocene with groundwater ages ranging from approximately 34,600 to 13,300 years before present. Other groundwater sampled during this study that can dated using radiocarbon decay ranged in age from about 7,500 to 1,100 years before present, indicating possible recharge during the Holocene. The gaining reach of the Verde River downstream from the confluence with Granite Creek shows areal changes in temperature, pH, and specific conductance, indicating multiple zones of groundwater input. Surface-water samples for analyses of δ 18 O and δ 2 H have been collected at the Verde River near Paulden, Ariz. streamgage (09503700) during discharge measurements since 2009, and a trend analysis of the δ 18 O and δ 2 H data indicated no significant trend exists for the 10-year period of record. Additional groundwater samples from the carbonate aquifer beneath the basin-fill upgradient and downgradient from Walnut Creek would provide valuable information to understand groundwater evolution along the Big Chino subbasin.

Arizona↗

Decadal trends in the quality of groundwater used for public drinking-water supply in California, 2004–23, California Groundwater Ambient Monitoring and Assessment Program, Priority Basin Project

This study provides a comprehensive assessment of decadal changes in the quality of groundwater used for public drinking-water supply at 444 monitoring sites across California during 2004–23. We assessed decadal step trends in groundwater quality for 145 water-quality constituents and geochemical indicators statewide and across geographic and land-use based network groups. We evaluated the statistical significance of directional changes (predominant increase or decrease of constituent concentrations) and the magnitude of those changes across all network groups. Uranium showed the most widespread directional and high-magnitude increases of all constituents with regulatory benchmarks statewide, particularly in the agriculture-dominated Central Valley as well as urban-and desert-dominated regions of Southern California. Fluoride and perchlorate showed the most widespread directional and high-magnitude decreases of all constituents with regulatory benchmarks statewide, which were also most pronounced in Southern California. Although arsenic and nitrate did not often register significant directional changes across network groups, they showed widespread, high-magnitude changes in both directions (increase and decrease) at levels often exceeding 10 percent of respective regulatory benchmarks statewide. Triazine herbicides (atrazine and simazine) and the gasoline oxygenate methyl tert -butyl ether showed significant directional decreases statewide, but not at levels considered to be of high magnitude compared to respective regulatory benchmarks. We observed significant directional and high-magnitude increases of total dissolved solids statewide, which were most pronounced in agricultural areas. Analysis of explanatory geochemical indicators indicated that prevalent statewide increases of alkalinity and calcium were the predominant components of the observed statewide increases in total dissolved solids by mass. Widespread increases in groundwater alkalinity and calcium across agricultural and urban areas may be related, in part, to warm-season irrigation and other anthropogenic factors that have shifted soil weathering dynamics over the long term. Increasing alkalinity concentrations were related to increasing uranium concentrations, particularly in areas with aquifer materials derived from granitic rocks. Conversely, increasing calcium concentrations were related to decreasing fluoride concentrations, particularly in areas where fluoride occurred naturally at elevated concentrations. Decrease of perchlorate, triazine herbicides, and methyl tert -butyl ether are likely related to decreased anthropogenic source inputs over time and natural attenuation in aquifers.

California↗

Geohydrology and ground-water quality at selected sites in Meade County, Kentucky, 1987-88

Meade County in north-central Kentucky is about 305 sq mi in size, and is underlain by thick beds of limestone and dolomite which are the principal sources of drinking water for about 8 ,500 residents. About half the area contains mature, karst terrain with abundant sinkholes, springs, and caves. Because of this karst terrain, groundwater is susceptible to rapid changes in water quality and contamination from human sources. Thirty-seven wells and 12 springs were selected as sampling points to characterize groundwater quality in the area. Water was analyzed for major anions and cations, nitrates, trace elements, and organic compounds. Water from selected sites was also analyzed for fecal species of coliform streptococci bacteria and total coliform content. Except for fluoride and lead, the water quality was within the range expected for carbonate aquifers.The fluoride content was significantly higher in water from wells than in water from springs. Concentrations of detectable lead ranged from 10 to 50 micrograms/L and had a median value of 7.5 microg/L. Dissolved solids ranged from 100 to 2,200 mg/L and the median value was 512 mg/L. Hardness ranged from 20 to 1,100 mg/L and the median value was 290 mg/L. Organic compounds detected by the gas chromatographic/flame ionization detection scans, did not indicate evidence of concentrations in excess of the current Federal drinking water standards. Analysis for specific organic compounds indicated that the presence of these compounds was associated with agricultural chemicals, usually pesticides. Total coliform content exceeded drinking water standards in water from all 12 springs and in 18 wells. Statistical analysis of the groundwater quality data indicates that the variance of the concentrations of fluoride and chloride may be attributed to the site type. There was strong correlation between hardness and dissolved solids, hardness and sulfate, and sulfate and dissolved solids. No apparent relations were detected between water quality and the geographic location of sampling sites. However, seasonal variations were detected in the concentrations of dissolved solids, hardness, and iron. (Lantz-PTT)

Water-Resources Investigations Report↗