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Justin T. Kulongoski

Publications and source records attributed to Justin T. Kulongoski.

At least 37 records · Page 2Linked to original sources

A novel method for the extraction, purification and characterization of noble gases in produced fluids

Hydrocarbon systems with declining or viscous oil production are often stimulated using enhanced oil recovery (EOR) techniques, such as the injection of water, steam and CO2, in order to increase oil and gas production. As EOR and other methods of enhancing production such as hydraulic fracturing have become more prevalent, environmental concerns about the impact of both new and historical hydrocarbon production on overlying shallow aquifers have increased. Noble gas isotopes are powerful tracers of subsurface fluid provenance and can be used to understand the impact of EOR on hydrocarbon systems and potentially overlying aquifers. In oil systems, produced fluids can consist of a mixture of oil, water and gas. Noble gases are typically measured in the gas phase; however, it is not always possible to collect gases and therefore produced fluids (which are water, oil and gas mixtures) must be analyzed. We outline a new technique to separate and analyze noble gases in multi-phase hydrocarbon-associated fluid samples. An offline double capillary method has been developed to quantitatively isolate noble gases into a transfer vessel, while effectively removing all water, oil, and less volatile hydrocarbons. The gases are then cleaned and analyzed using standard techniques. Air-saturated water reference materials (n=24) were analyzed and results show a method reproducibility of 2.9% for 4He, 3.8% for 20Ne, 4.5% for 36Ar, 5.3% for 84Kr and 5.7% for 132Xe. This new technique was used to measure the noble gas isotopic compositions in six produced fluid samples from the Fruitvale Oil Field, Bakersfield, California.

Geochemistry, Geophysics, Geosystems↗

Guidelines and standard procedures for high-frequency groundwater-quality monitoring stations—Design, operation, and record computation

High-frequency water-quality monitoring stations measure and transmit data, often in near real-time, from a wide range of aquatic environments to assess the quality of the Nation’s water resources. Common instrumentation for high-frequency water-quality data collection uses a multi-parameter sonde, which typically has sensors that measure and record water temperature, specific conductance, pH, and dissolved oxygen. Nitrate, turbidity, and fluorescent dissolved organic matter can also be monitored at high frequency. High-frequency groundwater-quality monitoring stations provide high-resolution time-series data to improve understanding of the timing of water-quality changes in the subsurface, especially for aquifer systems with short groundwater-residence times. High-frequency time-series data are used to monitor surface-water to groundwater interaction, quantify contaminant transport rates, and study water-quality variability in relation to variability of precipitation and groundwater pumping rates. High-frequency monitoring for contaminants or their surrogates have the added benefit of providing an early warning to protect valuable or sensitive aquifer resources. High-frequency time-series data also reveal short-term trends in groundwater quality, which may not be identifiable from monthly or annual sampling programs which facilitate the interpretation of decadal conditions. Systematic application of water-quality sonde operational procedures and a standard record-computation process are part of the required quality assurance for producing and documenting complete and accurate high-frequency groundwater-quality monitoring records. To collect quality high-frequency groundwater times-series data, water-quality sondes and sensors require careful field operation, cleaning, and calibration, as well as specific procedures for data computation, evaluation, review, and publication of final records. This report provides guidelines for the use of water-quality sondes and sensors for high-frequency groundwater-quality monitoring and updates the guidance pertaining to standardized records computation procedures for a wide range of groundwater environments. This report builds on previous continuous surface-water-quality monitoring guidance documentation for water temperature, specific conductance, pH, dissolved oxygen, and nitrate. The specific groundwater-quality monitoring guidelines presented in this report address station selection, design, installation, and operations; sonde and sensor inspections and cleaning and calibration methods; troubleshooting procedures; data evaluations, data corrections, and record computations; and record review, approval, and auditing procedures for the groundwater environment.

Techniques and Methods↗

Occurrence and sources of radium in groundwater associated with oil fields in the southern San Joaquin Valley, California

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range=0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p<0.001, ρ=0.90, range=145-15,900 mg/L), Mn+Fe concentrations (p<0.001, ρ=0.82, range=<0.005-18.5 mg/L), and pH (p<0.001, ρ=-0.67, range=6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median=3.1) differed from those in oil-field water (median=0.51). PHREEQC mixing calculations and spatial geochemical variations suggest the Ra in oil-field water was removed by co-precipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

California↗

Methane emissions from groundwater pumping in the USA

Atmospheric methane accumulation contributes to climate change, hence quantifying methane emissions is essential to assess and model the impacts. Here we estimate methane emissions from groundwater pumping in the Los Angeles Basin (LAB), north-eastern Pennsylvania, and the Principal aquifers of the USA using the average concentrations of methane in groundwater and annual groundwater pumping volumes. High average methane concentrations, 44.1 mg/L, and extensive groundwater pumping, ~3.1 x 1011 L/a in the LAB, result in the annual emission of ~2.9 x 10-3 Tg of microbial methane. Ethane emissions in the LAB were 3.5 x 10-6 Tg/a. Lower methane emissions estimated for NE Pennsylvania, ~3.0 x 10-8 Tg/a, reflect lower methane concentrations and groundwater pumping, 0.7 mg/L and 4.67 x 107 L/a, respectively. Methane concentrations and groundwater withdrawals, 1.06 x 1014 L, across the USA enabled the estimation of the total emissions of methane from Principal aquifers (92% of total pumping) of 0.044 Tg/a in the year 2000, which represents a small percentage (~0.2%) of the total annual US methane emissions, but a previously unquantified flux in the global methane budget. Globally, groundwater-pumping methane emissions were estimated to be 0.53 Tg/a, 0.2% of global methane emissions, by adopting a global estimate for groundwater extraction, and an average methane concentration in older groundwater of 0.44 mg/L.

Climate and Atmospheric Science↗

Groundwater quality of a public supply aquifer in proximity to oil development, Fruitvale Oil Field, Bakersfield, California

Due to concerns over the effects of oil production activities on groundwater quality in California, chemical, isotopic, dissolved gas and age-dating tracers were analyzed in samples collected from public-supply wells and produced-water sites in the Fruitvale oil field (FVOF). A combination of newly collected and historical data was used to determine whether oil formation fluids have mixed with groundwater used for public supply and what the potential pathways for the migration of oil formation fluids into groundwater may be. Stable isotopes of water (δ 2 H and δ 18 O) and age dating ( 3 H, 3 He trit , SF 6 and 14 C) tracers in groundwater samples were consistent with the Kern River being the main source of recharge to aquifers. The distribution of major ion concentrations and pH with distance from the Kern River indicate that natural processes were the primary controls on groundwater salinity. Two of 14 groundwater samples had δ 13 C-DIC values (−2.4 to +1.9 per mil) consistent with mixtures of <1 to about 9 percent oil-field water. Concentrations of TDS in groundwater samples were generally much lower (129–1,200 milligrams per liter (mg/l), median 216 mg/l) than produced water samples (586–24,930 mg/l, median 2,717 mg/l), suggesting that any mixing of oil-field water with groundwater has not significantly affected groundwater salinity. Trace concentrations of thermogenic methane were detected in three groundwater samples that did not have dissolved inorganic or isotopic indicators consistent with mixing of oil-field water, suggesting that stray gases may have migrated from the subsurface via preferential pathways such as leaky well bores into groundwater aquifers. Low concentrations of petroleum hydrocarbons were detected in samples that also contained anthropogenic VOCs and components of post- and pre-1950s recharge, indicating that petroleum hydrocarbons could have come from subsurface and/or surface sources. Overall, the results of this study indicated that groundwater currently used for public supply in the FVOF was of good quality with little, if any, effects from oil production activities. This may be due in part to the relatively rapid flushing of the aquifer system by recharge from the Kern River.

California↗

A novel high-frequency groundwater quality monitoring system

High-frequency, long-term monitoring of water quality has revolutionized the study of surface waters in recent years. However, application of these techniques to groundwater has been limited by the ability to remotely pump and analyze groundwater. This paper describes a novel autonomous groundwater quality monitoring system which samples multiple wells to evaluate temporal changes and identify trends in groundwater chemistry. The system, deployed near Fresno, California, USA, collects and transmits high-frequency data, including water temperature, specific conductance, pH, dissolved oxygen, and nitrate, from supply and monitoring wells, in real-time. The system consists of a water quality sonde and optical nitrate sensor, manifold, submersible three-phase pump, variable frequency drive, data collection platform, solar panels, and rechargeable battery bank. The manifold directs water from three wells to a single set of sensors, thereby reducing setup and operation costs associated with multi-sensor networks. Sampling multiple wells at high frequency for several years provided a means of monitoring the vertical distribution and transport of solutes in the aquifer. Initial results show short period variability of nitrate, specific conductivity, and dissolved oxygen in the shallow aquifer, while the deeper portion of the aquifer remains unchanged—observations that may be missed with traditional discrete sampling approaches. In this aquifer system, nitrate and specific conductance are increasing in the shallow aquifer, while invariant changes in deep groundwater chemistry likely reflect relatively slow groundwater flow. In contrast, systems with high groundwater velocity, such as karst aquifers, have been shown to exhibit higher-frequency groundwater chemistry changes. The stability of the deeper aquifer over the monitoring period was leveraged to develop estimates of measurement system uncertainty, which were typically lower than the manufacturer’s stated specifications, enabling the identification of subtle variability in water chemistry that may have otherwise been missed.

California↗

Groundwater-quality and select quality-control data from the National Water-Quality Assessment Project, January through December 2015, and previously unpublished data from 2013 to 2014

Groundwater-quality data were collected from 502 wells as part of the National Water-Quality Assessment Project of the U.S. Geological Survey National Water-Quality Program and are included in this report. Most of the wells (500) were sampled from January through December 2015, and 2 of them were sampled in 2013. The data were collected from five types of well networks: principal aquifer study networks, which are used to assess the quality of groundwater used for public water supply; land-use study networks, which are used to assess land-use effects on shallow groundwater quality; major aquifer study networks, which are used to assess the quality of groundwater used for domestic supply; enhanced trends networks, which are used to evaluate the time scales during which groundwater quality changes; and vertical flow-path study networks, which are used to evaluate changes in groundwater quality from shallow to deeper depths. Groundwater samples were analyzed for a large number of water-quality indicators and constituents, including major ions, nutrients, trace elements, volatile organic compounds, pesticides, radionuclides, and some constituents of special interest (arsenic speciation, chromium [VI], and perchlorate). These groundwater-quality data, along with data from quality-control samples, are tabulated in this report and in an associated data release. Some data from environmental samples collected in 2013 and quality-control samples collected in 2014 also are included in the associated data release; these data are associated with networks described in this report and have not been published previously.

Data Series↗

Origin of methane and sources of high concentrations in Los Angeles groundwater

In 2014, samples from 37 monitoring wells at 17 locations, within or near oil fields, and one site >5 km from oil fields, in the Los Angeles Basin, California, were analyzed for dissolved hydrocarbon gas isotopes and abundances. The wells sample a variety of depths of an aquifer system composed of unconsolidated and semiconsolidated sediments under various conditions of confinement. Concentrations of methane in groundwater samples ranged from 0.002 to 150 mg/L—some of the highest concentrations reported in a densely populated urban area. The δ13C and δ2H of the methane ranged from −80.8 to −45.5 per mil (‰) and −249.8 to −134.9‰, respectively, and, along with oxidation‐reduction processes, helped to identify the origin of methane as microbial methanogenesis and CO2 reduction as its main formation pathway. The distribution of methane concentrations and isotopes is consistent with the high concentrations of methane in Los Angeles Basin groundwater originating from relatively shallow microbial production in anoxic or suboxic conditions. Source of the methane is the aquifer sediments rather than the upward migration or leakage of thermogenic methane associated with oil fields in the basin.

California↗

Hydrogeologic controls and geochemical indicators of groundwater movement in the Niles Cone and southern East Bay Plain groundwater subbasins, Alameda County, California

Beginning in the 1970s, Alameda County Water District began infiltrating imported water through ponds in repurposed gravel quarries at the Quarry Lakes Regional Park, in the Niles Cone groundwater subbasin, to recharge groundwater and to minimize intrusion of saline, San Francisco Bay water into freshwater aquifers. Hydraulic connection between distinct aquifers underlying Quarry Lakes allows water to recharge the upper aquifer system to depths of 400 feet below land surface, and the Deep aquifer to depths of more than 650 feet. Previous studies of the Niles Cone and southern East Bay Plain groundwater subbasins suggested that these two subbasins may be hydraulically connected. Characterization of storage capacities and hydraulic properties of the complex aquifers and the structural and stratigraphic controls on groundwater movement aids in optimal storage and recovery of recharged water and provides information on the ability of aquifers shared by different water management agencies to fulfill competing storage and extraction demands. The movement of recharge water through the Niles Cone groundwater subbasin from Quarry Lakes and the possible hydraulic connection between the Niles Cone and the southern East Bay Plain groundwater subbasins were investigated using interferometric synthetic aperture radar (InSAR), water-chemistry, and isotopic data, including tritium/helium-3, helium-4, and carbon-14 age-dating techniques. InSAR data collected during refilling of the Quarry Lakes recharge ponds show corresponding ground-surface displacement. Maximum uplift was about 0.8 inches, reasonable for elastic expansion of sedimentary materials experiencing an increase in hydraulic head that resulted from pond refilling. Sodium concentrations increase while calcium and magnesium concentrations in groundwater decrease along groundwater flowpaths from the Niles Cone groundwater subbasin through the Deep aquifer to the northwest toward the southern East Bay Plain groundwater subbasin. Residual effects of pre-1970s intrusion of saline water from San Francisco Bay, including high chloride concentrations in groundwater, are evident in parts of the Niles Cone subbasin. Noble gas recharge temperatures indicate two primary recharge sources (Quarry Lakes and Alameda Creek) in the Niles Cone groundwater subbasin. Although recharge at Quarry Lakes affects hydraulic heads as far as the transition zone between the Niles Cone and East Bay Plain groundwater subbasins (about 5 miles), the effect of recharged water on water quality is only apparent in wells near (less than 2 miles) recharge sources. Groundwater chemistry from upper aquifer system wells near Quarry Lakes showed an evaporated signal (less negative oxygen and hydrogen isotopic values) relative to surrounding groundwater and a tritium concentration (2 tritium units) consistent with recently recharged water from a surface-water impoundment. Uncorrected carbon-14 activities measured in water sampled from wells in the Niles Cone groundwater subbasin range from 16 to 100 percent modern carbon (pmC). The geochemical reaction modeling software NETPATH was used to interpret carbon-14 ages along a flowpath from Quarry Lakes toward the East Bay Plain groundwater subbasin. Model results indicate that changes in groundwater chemistry are controlled by cation exchange on clay minerals and weathering of primary silicate minerals. Old groundwater (lower carbon-14 activities) is characterized by high dissolved silica and pH. Interpreted carbon-14 ages ranged from 830 to more than 7,000 years before present and are less than helium-4 ages that range from 2,000 to greater than 11,000 years before present. The average horizontal groundwater velocity along the studied flowpath, as calculated using interpreted carbon-14 ages, through the Deep aquifer of the Niles Cone groundwater subbasin is between 3 and 12 feet per year. The groundwater velocity decreases near the boundary of the transition zone to the southern East Bay Plain groundwater subbasin to about 0.5 feet per year. These changes may result from water recharged from different sources converging in flowpaths north of the transition zone, or a boundary to flow between the Niles Cone and southern East Bay Plain groundwater subbasins, likely owing to changes in lithology caused by depositional patterns.

California↗

Regional patterns in the geochemistry of oil-field water, southern San Joaquin Valley, California, USA

Chemical and isotopic data for water co-extracted with hydrocarbons in oil and gas fields are commonly used to examine the source of the formation water and possible impacts on groundwater in areas of oil and gas development. Understanding the geochemical variability of oil-field water could help to evaluate its origin and delineate possible contamination of shallow aquifers in cases where oil-field water is released to the environment. Here we report geochemical and multiple isotope (H, C, O, Sr, Ra) data from 22 oil wells, three sources of produced water that are disposed of in injection wells, and two surface disposal ponds in four oil fields in the southern San Joaquin Valley, California (Fruitvale, Lost Hills, North and South Belridge). Correlations between Cl and δ 18 O, as well as other ions, and gradual increases in salinity with depth, indicate dilution of one or more saline end-members by meteoric water. The saline end-members, represented by deep samples (610 m–2621 m) in three oil-bearing zones, are characterized by Na Cl composition, near-seawater Cl concentrations (median 20,000 mg/L), enriched δ 18 O H 2 O (median 3.4‰), high ammonium(up to 460 mg-N/L), and relatively high radium activity ( 226 Ra+ 228 Ra = 12.3 Bq/L). The deepest sample has low Na/Cl (0.74), high Ca/Mg (5.0), and low 87 Sr/ 86 Sr (0.7063), whereas the shallower samples have higher Na/Cl (0.86–1.2), Ca/Mg near 1, and higher 87 Sr/ 86 Sr (∼0.7083). The data are consistent with an original seawater source being modified by various depth and lithology dependent diagenetic processes. Dilution by meteoric water occurs naturally on the east side of the valley, and in association with water-injectionactivities on the west side. Meteoric-water flushing, particularly on the east side, results in lower solute concentrations (minimum total dissolved solids 2730 mg/L) and total radium (minimum 0.27 Bq/L) in oil-field water, and promotes biodegradation of dissolved organic carbon and hydrocarbon gases like propane. Acetate concentrations and δ 13 C of dissolved inorganic carbon indicate biogenic methane production occurs in some shallow oil zones. Natural and human processes produce substantial variability in the geochemistry of oil-field water that should be considered when evaluating mixing between oil-field waters and groundwater. The variability could result in uncertainty as to detecting the potential source and impact of oil-field water on groundwater.

California↗

Tracing enhanced oil recovery signatures in casing gases from the Lost Hills oil field using noble gases

Enhanced oil recovery (EOR) and hydraulic fracturing practices are commonly used methods to improve hydrocarbon extraction efficiency; however the environmental impacts of such practices remain poorly understood. EOR is particularly prevalent in oil fields throughout California where water resources are in high demand and disposal of high volumes of produced water may affect groundwater quality. Consequently, it is essential to better understand the fate of injected (EOR) fluids in California and other subsurface petroleum systems, as well as any potential effect on nearby aquifer systems. Noble gases can be used as tracers to understand hydrocarbon generation, migration, and storage conditions, as well as the relative proportions of oil and water present in the subsurface. In addition, a noble gas signature diagnostic of injected (EOR) fluids can be readily identified. We report noble gas isotope and concentration data in casing gases from oil production wells in the Lost Hills oil field, northwest of Bakersfield, California, and injectate gas data from the Fruitvale oil field, located within the city of Bakersfield. Casing and injectate gas data are used to: 1) establish pristine hydrocarbon noble-gas signatures and the processes controlling noble gas distributions, 2) characterize the noble gas signature of injectate fluids, 3) trace injectate fluids in the subsurface, and 4) construct a model to estimate EOR efficiency. Noble gas results range from pristine to significantly modified by EOR, and can be best explained using a solubility exchange model between oil and connate/formation fluids, followed by gas exsolution upon production. This model is sensitive to oil-water interaction during hydrocarbon expulsion, migration, and storage at reservoir conditions, as well as any subsequent modification by EOR.

California↗

Groundwater-quality data from the National Water-Quality Assessment Project, January through December 2014 and select quality-control data from May 2012 through December 2014

Groundwater-quality data were collected from 559 wells as part of the National Water-Quality Assessment Project of the U.S. Geological Survey National Water-Quality Program from January through December 2014. The data were collected from four types of well networks: principal aquifer study networks, which are used to assess the quality of groundwater used for public water supply; land-use study networks, which are used to assess land-use effects on shallow groundwater quality; major aquifer study networks, which are used to assess the quality of groundwater used for domestic supply; and enhanced trends networks, which are used to evaluate the time scales during which groundwater quality changes. Groundwater samples were analyzed for a large number of water-quality indicators and constituents, including major ions, nutrients, trace elements, volatile organic compounds, pesticides, radionuclides, and some constituents of special interest (arsenic speciation, chromium [VI] and perchlorate). These groundwater-quality data, along with data from quality-control samples, are tabulated in this report and in an associated data release.

Data Series↗

Data from exploratory sampling of groundwater in selected oil and gas areas of coastal Los Angeles County and Kern and Kings Counties in southern San Joaquin Valley, 2014–15: California oil, gas, and groundwater project

Exploratory sampling of groundwater in coastal Los Angeles County and Kern and Kings Counties of the southern San Joaquin Valley was done by the U.S. Geological Survey from September 2014 through January 2015 as part of the California State Water Resources Control Board’s Water Quality in Areas of Oil and Gas Production Regional Groundwater Monitoring Program. The Regional Groundwater Monitoring Program was established in response to the California Senate Bill 4 of 2013 mandating that the California State Water Resources Control Board design and implement a groundwater-monitoring program to assess potential effects of well-stimulation treatments on groundwater resources in California. The U.S. Geological Survey is in cooperation with the California State Water Resources Control Board to collaboratively implement the Regional Groundwater Monitoring Program through the California Oil, Gas, and Groundwater Project. Many researchers have documented the utility of different suites of chemical tracers for evaluating the effects of oil and gas development on groundwater quality. The purpose of this exploratory sampling effort was to determine whether tracers reported in the literature could be used effectively in California. This reconnaissance effort was not designed to assess the effects of oil and gas on groundwater quality in the sampled areas. A suite of water-quality indicators and geochemical tracers were sampled at groundwater sites in selected areas that have extensive oil and gas development. Groundwater samples were collected from a total of 51 wells, including 37 monitoring wells at 17 multiple-well monitoring sites in coastal Los Angeles County and 5 monitoring wells and 9 water-production wells in southern San Joaquin Valley, primarily in Kern and Kings Counties. Groundwater samples were analyzed for field waterquality indicators; organic constituents, including volatile and semi-volatile organic compounds and dissolved organic carbon indicators; naturally present inorganic constituents, including trace elements, nutrients, major and minor ions, and iron species; naturally present stable and radioactive isotopes; dissolved noble gases; dissolved standard and hydrocarbon gases, δ13C of methane, ethane, and δ2 H of methane. In total, 249 constituents and water-quality indicators were measured. Four types of quality-control samples (blanks, replicates, matrix spikes, and surrogates spiked in environmental and blank samples) were collected at approximately 10 percent of the wells. The quality-control data were used to determine whether the groundwater-sample data were of sufficient quality for the measured analytes to be used as potential indicators of oil and gas effects. The data from the 51 groundwater samples and from the quality-control samples are presented in this report.

California↗

Status of groundwater quality in the Santa Barbara Study Unit, 2011: California GAMA Priority Basin Project

Groundwater quality in the 48-square-mile Santa Barbara study unit was investigated in 2011 as part of the California State Water Resources Control Board’s Groundwater Ambient Monitoring and Assessment (GAMA) Program Priority Basin Project. The study unit is mostly in Santa Barbara County and is in the Transverse and Selected Peninsular Ranges hydrogeologic province. The GAMA Priority Basin Project is carried out by the U.S. Geological Survey in collaboration with the California State Water Resources Control Board and Lawrence Livermore National Laboratory. The GAMA Priority Basin Project was designed to provide a statistically unbiased, spatially distributed assessment of the quality of untreated groundwater in the primary aquifer system of California. The primary aquifer system is defined as that part of the aquifer corresponding to the perforation interval of wells listed in the California Department of Public Health database for the Santa Barbara study unit. This status assessment is intended to characterize the quality of groundwater resources in the primary aquifer system of the Santa Barbara study unit, not the treated drinking water delivered to consumers by water purveyors. The status assessment for the Santa Barbara study unit was based on water-quality and ancillary data collected in 2011 by the U.S. Geological Survey from 23 sites and on water-quality data from the California Department of Public Health database for January 24, 2008–January 23, 2011. The data used for the assessment included volatile organic compounds; pesticides; pharmaceutical compounds; two constituents of special interest, perchlorate and N -nitrosodimethylamine (NDMA); and naturally present inorganic constituents, such as major ions and trace elements. Relative-concentrations (sample concentration divided by the health- or aesthetic-based benchmark concentration) were used to evaluate groundwater quality for those constituents that have federal or California regulatory and non-regulatory benchmarks for drinking-water quality. For inorganic, organic, and special-interest constituents, a relative-concentration greater than 1.0 indicates a concentration greater than the benchmark and is classified as high. Inorganic constituents are classified as moderate if relative-concentrations are greater than 0.5 and less than or equal to 1.0 and are classified as low if relative-concentrations are less than or equal to 0.5. For organic and special-interest constituents, the boundary between moderate and low relative-concentrations was set at 0.1. Aquifer-scale proportion was used as the primary metric for evaluating regional-scale groundwater quality. High aquifer-scale proportion is defined as the areal percentage of the primary aquifer system with a relative-concentration greater than 1.0 for a particular constituent or class of constituents. Moderate and low aquifer-scale proportions were defined as the areal percentage of the primary aquifer system that had moderate and low relative-concentrations, respectively. Two statistical approaches—grid based and spatially weighted—were used to calculate aquifer-scale proportions for individual constituents and constituent classes. Grid-based and spatially weighted estimates were comparable in this the study (within 90-percent confidence intervals). Grid-based results were selected for use in the status assessment unless, as was observed in a few cases, a grid-based result was zero and the spatially weighted result was not zero, in which case, the spatially weighted result was used. Inorganic constituents that have human-health benchmarks were present at high relative-concentrations in 5.3 percent of the primary aquifer system and at moderate concentrations in 32 percent. High aquifer-scale proportions of inorganic constituents primarily were a result of high aquifer-scale proportions of boron (5.3 percent) and fluoride (5.3 percent). Inorganic constituents that have aesthetic-based benchmarks, referred to as secondary maximum contaminant levels, were present at high relative-concentrations in 58 percent of the primary aquifer system and at moderate concentrations in 37 percent. Iron, manganese, sulfate, and total dissolved solids were the inorganic constituents with secondary maximum contaminant levels present at high relative-concentrations. In contrast, organic and special-interest constituents that have health-based benchmarks were not detected at high relative-concentrations in the primary aquifer system. Of the 218 organic constituents analyzed, 10 were detected—9 that had human-health benchmarks. Organic constituents were present at moderate relative-concentrations in 11 percent of the primary aquifer system. The moderate aquifer-scale proportions were a result of moderate relative-concentrations of the volatile organic compounds methyl tert- butyl ether (MTBE, 11 percent) and 1,2-dichloroethane (5.6 percent). The volatile organic compounds 1,1,1-trichloroethane, 1,1-dichloroethane, bromodichloromethane, chloroform, MTBE, and perchloroethene (PCE); the pesticide simazine; and the special-interest constituent perchlorate were detected at more than 10 percent of the sites in the Santa Barbara study unit. Perchlorate was present at moderate relative-concentrations in 50 percent of the primary aquifer system. Pharmaceutical compounds and NDMA were not detected in the Santa Barbara study unit.

California↗

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

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

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Preliminary results from exploratory sampling of wells for the California oil, gas, and groundwater program, 2014–15

Introduction In 2014 and 2015, the U.S. Geological Survey (USGS) sampled water wells in the Los Angeles Basin and southern San Joaquin Valley, California, and oil wells in the San Joaquin Valley for analysis of multiple chemical, isotopic, and groundwater-age tracers. The purpose of this reconnaissance sampling was to evaluate the utility of tracers for assessing the effects of oil and gas production activities on groundwater quality in California. The study was done in cooperation with the California State Water Resources Control Board. Results of the study are intended to help design a regional groundwater-monitoring program to be implemented as part of California Senate Bill 4 (SB 4 statutes of 2013). The regional monitoring program plans to assess the effects of oil and gas production activities on groundwater quality and to provide a regional context for local monitoring of the groundwater-quality effects from well-stimulation treatments, which are techniques used to improve oil and gas production by increasing their rate of flow to the well. California SB 4 mandates that this local monitoring is to be done by oil-well operators in accordance with monitoring criteria established by the State Water Board. This report evaluates the utility of the chemical, isotopic, and groundwater-age tracers for assessing sources of salinity, methane, and petroleum hydrocarbons in groundwater overlying or near several California oil fields. Tracers of dissolved organic carbon in oil-field-formation water are also discussed. Tracer data for samples collected from 51 water wells and 4 oil wells are examined.

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Groundwater quality data from the National Water-Quality Assessment Project, May 2012 through December 2013

Groundwater-quality data were collected from 748 wells as part of the National Water-Quality Assessment Project of the U.S. Geological Survey National Water-Quality Program from May 2012 through December 2013. The data were collected from four types of well networks: principal aquifer study networks, which assess the quality of groundwater used for public water supply; land-use study networks, which assess land-use effects on shallow groundwater quality; major aquifer study networks, which assess the quality of groundwater used for domestic supply; and enhanced trends networks, which evaluate the time scales during which groundwater quality changes. Groundwater samples were analyzed for a large number of water-quality indicators and constituents, including major ions, nutrients, trace elements, volatile organic compounds, pesticides, and radionuclides. These groundwater quality data are tabulated in this report. Quality-control samples also were collected; data from blank and replicate quality-control samples are included in this report.

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Geostatistical analysis of tritium, groundwater age and other noble gas derived parameters in California

Key characteristics of California groundwater systems related to aquifer vulnerability, sustainability, recharge locations and mechanisms, and anthropogenic impact on recharge are revealed in a spatial geostatistical analysis of a unique data set of tritium, noble gases and other isotopic analyses unprecedented in size at nearly 4000 samples. The correlation length of key groundwater residence time parameters varies between tens of kilometers ( 3 H; age) to the order of a hundred kilometers ( 4 He ter ; 14 C; 3 He trit ). The correlation length of parameters related to climate, topography and atmospheric processes is on the order of several hundred kilometers (recharge temperature; δ 18 O). Young groundwater ages that highlight regional recharge areas are located in the eastern San Joaquin Valley, in the southern Santa Clara Valley Basin, in the upper LA basin and along unlined canals carrying Colorado River water, showing that much of the recent recharge in central and southern California is dominated by river recharge and managed aquifer recharge. Modern groundwater is found in wells with the top open intervals below 60 m depth in the southeastern San Joaquin Valley, Santa Clara Valley and Los Angeles basin, as the result of intensive pumping and/or managed aquifer recharge operations.

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