Groundwater quality in the Western San Joaquin Valley study unit, 2010: California GAMA Priority Basin Project

Abstract

Water quality in groundwater resources used for public drinking-water supply in the Western San Joaquin Valley (WSJV) was investigated by the USGS in cooperation with the California State Water Resources Control Board (SWRCB) as part of its Groundwater Ambient Monitoring and Assessment (GAMA) Program Priority Basin Project. The WSJV includes two study areas: the Delta–Mendota and Westside subbasins of the San Joaquin Valley groundwater basin. Study objectives for the WSJV study unit included two assessment types: (1) a status assessment yielding quantitative estimates of the current (2010) status of groundwater quality in the groundwater resources used for public drinking water, and (2) an evaluation of natural and anthropogenic factors that could be affecting the groundwater quality. The assessments characterized the quality of untreated groundwater, not the quality of treated drinking water delivered to consumers by water distributors. The status assessment was based on data collected from 43 wells sampled by the U.S. Geological Survey for the GAMA Priority Basin Project (USGS-GAMA) in 2010 and data compiled in the SWRCB Division of Drinking Water (SWRCB-DDW) database for 74 additional public-supply wells sampled for regulatory compliance purposes between 2007 and 2010. To provide context, concentrations of constituents measured in groundwater were compared to U.S. Environmental Protection Agency (EPA) and SWRCB-DDW regulatory and non-regulatory benchmarks for drinking-water quality. The status assessment used a spatially weighted, grid-based method to estimate the proportion of the groundwater resources used for public drinking water that has concentrations for particular constituents or class of constituents approaching or above benchmark concentrations. This method provides statistically unbiased results at the study-area scale within the WSJV study unit, and permits comparison of the two study areas to other areas assessed by the GAMA Priority Basin Project statewide. Groundwater resources used for public drinking water in the WSJV study unit are among the most saline and most affected by high concentrations of inorganic constituents of all groundwater resources used for public drinking water that have been assessed by the GAMA Priority Basin Project statewide. Among the 82 GAMA Priority Basin Project study areas statewide, the Delta–Mendota study area ranked above the 90th percentile for aquifer-scale proportions of groundwater resources having concentrations of total dissolved solids (TDS), sulfate, chloride, manganese, boron, chromium(VI), selenium, and strontium above benchmarks, and the Westside study area ranked above the 90th percentile for TDS, sulfate, manganese, and boron. In the WSJV study unit as a whole, one or more inorganic constituents with regulatory or non-regulatory, health-based benchmarks were present at concentrations above benchmarks in about 53 percent of the groundwater resources used for public drinking water, and one or more organic constituents with regulatory health-based benchmarks were detected at concentrations above benchmarks in about 3 percent of the resource. Individual constituents present at concentrations greater than health-based benchmarks in greater than 2 percent of groundwater resources used for public drinking water included: boron (51 percent, SWRCB-DDW notification level), chromium(VI) (25 percent, SWRCB-DDW maximum contaminant level (MCL)), arsenic (10 percent, EPA MCL), strontium (5.1 percent, EPA Lifetime health advisory level (HAL)), nitrate (3.9 percent, EPA MCL), molybdenum (3.8 percent, EPA HAL), selenium (2.6 percent, EPA MCL), and benzene (2.6 percent, SWRCB-DDW MCL). In addition, 50 percent of the resource had TDS concentrations greater than non-regulatory, aesthetic-based SWRCB-DDW upper secondary maximum contaminant level (SMCL), and 44 percent had manganese concentrations greater than the SWRCB-DDW SMCL. 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, inferences from geochemical and age-dating tracer results, and by considering the water-quality results in the context of the hydrogeologic setting of the WSJV study unit. Natural factors, particularly the lithologies of the source areas for groundwater recharge and of the aquifers, were the dominant factors affecting groundwater quality in most of the WSJV study unit. However, where groundwater resources used for public supply included groundwater recharged in the modern era, mobilization of constituents by recharge of water used for irrigation also affected groundwater quality. Public-supply wells in the Westside study area had a median depth of 305 m and primarily tapped groundwater recharged hundreds to thousands of years ago, whereas public-supply wells in the Delta–Mendota study area had a median depth of 85 m and primarily tapped either groundwater recharged within the last 60 years or groundwater consisting of mixtures of this modern recharge and older recharge. Public-supply wells in the WSJV study unit are screened in the Tulare Formation and zones above and below the Corcoran Clay Member are used. The Tulare Formation primarily consists of alluvial sediments derived from the Coast Ranges to the west, except along the valley trough at the eastern margin of the WSJV study unit where the Tulare Formation consists of fluvial sands derived from the Sierra Nevada to the east. Groundwater from wells screened in the Sierra Nevada sands had manganese-reducing or manganese- and iron-reducing oxidation-reduction (redox) conditions. These redox conditions commonly were associated with elevated arsenic or molybdenum concentrations, and the dominance of arsenic(III) in the dissolved arsenic supports reductive dissolution of iron and manganese oxyhydroxides as the mechanism. In addition, groundwater from many wells screened in Sierra Nevada sands contained low concentrations of nitrite or ammonium, indicating reduction of nitrate by denitrification or dissimilatory processes, respectively. Geology of the Coast Ranges westward of the study unit strongly affects groundwater quality in the WSJV. Elevated concentrations of TDS, sulfate, boron, selenium and strontium in groundwater were primarily associated with aquifer sediments and recharge derived from areas of the Coast Ranges dominated by Cretaceous-to-Miocene age, organic-rich, reduced marine shales, known as the source of selenium in WSJV soils, surface water, and groundwater. Low sulfur-isotopic values (δ34S) of dissolved sulfate indicate that the sulfate was largely derived from oxidation of biogenic pyrite from the shales, and correlations with trace element concentrations, geologic setting, and groundwater geochemical modeling indicated that distributions of sulfate, strontium, and selenium in groundwater were controlled by dissolution of secondary sulfate minerals in soils and sediments. Elevated concentrations of chromium(VI) were primarily associated with aquifer sediments and recharge derived from areas of the Coast Ranges dominated by the Franciscan Complex and ultramafic rocks. The Franciscan Complex also has boron-rich, sodium-chloride dominated hydrothermal fluids that contribute to elevated concentrations of boron and TDS. Groundwater from wells screened in Coast Ranges alluvium was primarily oxic and relatively alkaline (median pH value of 7.55) in the Delta–Mendota study area, and primarily nitrate-reducing or suboxic and alkaline (median pH value of 8.4) in the Westside study area. Many groundwater samples from those wells have elevated concentrations of arsenic(V), molybdenum, selenium, or chromium(VI), consistent with desorption of metal oxyanions from mineral surfaces under those geochemical conditions. High concentrations of benzene were associated with deep wells located in the vicinity of petroleum deposits at the southern end of the Westside study area. Groundwater from these wells had premodern age and anoxic geochemical conditions, and the ratios among concentrations of hydrocarbon constituents were different from ratios found in fuels and combustion products, which is consistent with a geogenic source for the benzene rather than contamination from anthropogenic sources. Water stable-isotope compositions, groundwater recharge temperatures, and groundwater ages were used to infer four types of groundwater: (1) groundwater derived from natural recharge of water from major rivers draining the Sierra Nevada; (2) groundwater primarily derived from natural recharge of water from Coast Ranges runoff; (3) groundwater derived from recharge of pumped groundwater applied to the land surface for irrigation; and (4) groundwater derived from recharge during a period of much cooler paleoclimate. Water previously used for irrigation was found both above and below the Corcoran Clay, supporting earlier inferences that this clay member is no longer a robust confining unit. Recharge of water used for irrigation has direct and indirect effects on groundwater quality. Elevated nitrate concentrations and detections of herbicides and fumigants in the Delta–Mendota study area generally were associated with greater agricultural land use near the well and with water recharged during the last 60 years. However, the extent of the groundwater resource affected by agricultural sources of nitrate was limited by groundwater redox conditions sufficient to reduce nitrate. The detection frequency of perchlorate in Delta–Mendota groundwater was greater than expected for natural conditions. Perchlorate, nitrate, selenium, and strontium concentrations were correlated with one another and were greater in groundwater inferred to be recharge of previously pumped groundwater used for irrigation. The source of the perchlorate, selenium, and strontium appears to be salts deposited in the soils and sediments of the arid WSJV that are dissolved and flushed into groundwater by the increased amount of recharge caused by irrigation. In the Delta–Mendota study area, the groundwater with elevated concentrations of selenium was found deeper in the aquifer system than it was reported by a previous study 25 years earlier, suggesting that this transient front of groundwater with elevated concentrations of constituents derived from dissolution of soil salts by irrigation recharge is moving down through the aquifer system and is now reaching the depth zone used for public drinking water supply.