Identifying areas of degrading and improving groundwater-quality conditions in the State of California, USA, 1974-2014.

Areas of improving and degrading groundwater-quality conditions in the State of California were assessed using spatial weighting of a new metric for scoring wells based on constituent concentrations and the direction and magnitude of a trend slope (Sen). Individual well scores were aggregated across 2135 equal-area grid cells covering the entire groundwater resource used for public supply in the state. Spatial weighting allows results to be aggregated locally (well or grid cell), regionally (groundwater basin), provincially, or statewide. Results differentiate degrading (increasing concentration trends) areas with low to moderate concentrations (unimpaired) from degrading areas with moderate to high concentrations (impaired). Results also differentiate improving areas (decreasing concentration trends) in the same manner. Multi-year to decadal groundwater-quality trends were computed from periodic, inorganic water-quality data for 38 constituents collected between 1974 and 2014 for compliance monitoring of nearly 13,000 public-supply wells (PSWs) in the State of California. Mann-Kendall (MK) rank correlations and Sen's slope estimator were used to detect statistically significant trends for the entire period of recorded data (long-term trend), for the period since 2000 (recent trend), for different pumping seasons (seasonal trend), and for reversals of trends. Statewide, the most frequently detected trends since 2000 were for nitrate (36%), gross alpha/uranium (10%), arsenic (14%), total dissolved solids (TDS) (23%), and the major ions that contribute to TDS (19-28%). The Transverse and Selected Peninsular Ranges (TSPR) and the San Joaquin Valley (SJV) hydrogeologic provinces had the largest percentage of areas with moderate to high nitrate concentrations and groundwater quality trends. Improving nitrate concentrations in parts of the TSPR is associated with long-term managed aquifer recharge that has replaced historical, agriculturally affected groundwater with low-nitrate recharge in parts of the TSPR. This example suggests that application of dilute, excess surface water to agricultural fields during the winter could improve groundwater-quality in the SJV over the long term.

Metrics for Assessing the Quality of Groundwater Used for Public Supply, CA, USA: Equivalent-Population and Area.

Data from 11,000 public supply wells in 87 study areas were used to assess the quality of nearly all of the groundwater used for public supply in California. Two metrics were developed for quantifying groundwater quality: area with high concentrations (km(2) or proportion) and equivalent-population relying upon groundwater with high concentrations (number of people or proportion). Concentrations are considered high if they are above a human-health benchmark. When expressed as proportions, the metrics are area-weighted and population-weighted detection frequencies. On a statewide-scale, about 20% of the groundwater used for public supply has high concentrations for one or more constituents (23% by area and 18% by equivalent-population). On the basis of both area and equivalent-population, trace elements are more prevalent at high concentrations than either nitrate or organic compounds at the statewide-scale, in eight of nine hydrogeologic provinces, and in about three-quarters of the study areas. At a statewide-scale, nitrate is more prevalent than organic compounds based on area, but not on the basis of equivalent-population. The approach developed for this paper, unlike many studies, recognizes the importance of appropriately weighting information when changing scales, and is broadly applicable to other areas.

Volatile organic compounds in groundwater used for public supply across the United States: Occurrence, explanatory factors, and human-health context.

This systematic assessment of occurrence for 85 volatile organic compounds (VOCs) in raw (untreated) groundwater used for public supply across the United States (U.S.), which includes 43 compounds not previously monitored by national studies, relates VOC occurrence to explanatory factors and assesses VOC detections in a human-health context. Samples were collected in 2013 through 2019 from 1537 public-supply wells in aquifers representing 78% of the volume pumped for public drinking-water supply. Laboratory detection limits for VOCs generally were less than 0.1 µg/L. Detections were reported for 36% of the sampled principal-aquifer area (38% of sampled wells) and were most common in wells in shallow, unconfined aquifers in urban areas that produce high proportions of modern-age and oxic groundwater. The disinfection by-product trichloromethane (chloroform) was the most commonly detected VOC associated primarily with anthropogenic sources (24% of the sampled area, 25% of sampled wells), followed by the gasoline oxygenate methyl tert-butyl ether (8.4% of area, 11% of wells). Carbon disulfide (12% of area, 14% of wells) was examined separately because of likely substantial contributions from natural sources. Newly monitored VOCs were each detected in <1% of the sampled area. Although detections of 1,4-dioxane in this first national study of its occurrence in raw groundwater were rare, measured concentrations exceeded the most stringent (non-enforceable) human-health benchmark in 0.5% of the sampled area (9 wells). Two wells had exceedances of enforceable benchmarks for tetrachloroethylene and trichloroethylene, and 50 wells total (representing 2.0% of the sampled area, 3.3% of sampled wells) had combined VOC concentrations exceeding 10% of benchmarks of any type. Compared with previous national findings, this study reports lower rates of VOC detection, but confirms widespread anthropogenic influence on groundwater used for public supply, with relatively few concentrations of individual VOCs or mixtures that approach or exceed human-health benchmarks.

Probability of detecting perchlorate under natural conditions in deep groundwater in California and the southwestern United States.

We use data from 1626 groundwater samples collected in California, primarily from public drinking water supply wells, to investigate the distribution of perchlorate in deep groundwater under natural conditions. The wells were sampled for the California Groundwater Ambient Monitoring and Assessment Priority Basin Project. We develop a logistic regression model for predicting probabilities of detecting perchlorate at concentrations greater than multiple threshold concentrations as a function of climate (represented by an aridity index) and potential anthropogenic contributions of perchlorate (quantified as an anthropogenic score, AS). AS is a composite categorical variable including terms for nitrate, pesticides, and volatile organic compounds. Incorporating water-quality parameters in AS permits identification of perturbation of natural occurrence patterns by flushing of natural perchlorate salts from unsaturated zones by irrigation recharge as well as addition of perchlorate from industrial and agricultural sources. The data and model results indicate low concentrations (0.1-0.5 µg/L) of perchlorate occur under natural conditions in groundwater across a wide range of climates, beyond the arid to semiarid climates in which they mostly have been previously reported. The probability of detecting perchlorate at concentrations greater than 0.1 µg/L under natural conditions ranges from 50-70% in semiarid to arid regions of California and the Southwestern United States to 5-15% in the wettest regions sampled (the Northern California coast). The probability of concentrations above 1 µg/L under natural conditions is low (generally <3%).

Quantifying anthropogenic contributions to century-scale groundwater salinity changes, San Joaquin Valley, California, USA.

Total dissolved solids (TDS) concentrations in groundwater tapped for beneficial uses (drinking water, irrigation, freshwater industrial) have increased on average by about 100 mg/L over the last 100 years in the San Joaquin Valley, California (SJV). During this period land use in the SJV changed from natural vegetation and dryland agriculture to dominantly irrigated agriculture with growing urban areas. Century-scale salinity trends were evaluated by comparing TDS concentrations and major ion compositions of groundwater from wells sampled in 1910 (Historic) to data from wells sampled in 1993-2015 (Modern). TDS concentrations in subregions of the SJV, the southern (SSJV), western (WSJV), northeastern (NESJV), and southeastern (SESJV) were calculated using a cell-declustering method. TDS concentrations increased in all regions, with the greatest increases found in the SSJV and SESJV. Evaluation of the Modern data from the NESJV and SESJV found higher TDS concentrations in recently recharged (post-1950) groundwater from shallow (<50 m) wells surrounded predominantly by agricultural land uses, while premodern (pre-1950) groundwater from deeper wells, and recently recharged groundwater from wells surrounded by mainly urban, natural, and mixed land uses had lower TDS concentrations, approaching the TDS concentrations in the Historic groundwater. For the NESJV and SESJV, inverse geochemical modeling with PHREEQC indicated that weathering of primary silicate minerals accounted for the majority of the increase in TDS concentrations, contributing more than nitrate from fertilizers and sulfate from soil amendments combined. Bicarbonate showed the greatest increase among major ions, resulting from enhanced silicate weathering due to recharge of irrigation water enriched in CO2 during the growing season. The results of this study demonstrate that large anthropogenic changes to the hydrologic regime, like massive development of irrigated agriculture in semi-arid areas like the SJV, can cause large changes in groundwater quality on a regional scale.

Occurrence and concentrations of pharmaceutical compounds in groundwater used for public drinking-water supply in California.

Pharmaceutical compounds were detected at low concentrations in 2.3% of 1231 samples of groundwater (median depth to top of screened interval in wells=61 m) used for public drinking-water supply in California. Samples were collected statewide for the California State Water Resources Control Board's Groundwater Ambient Monitoring and Assessment (GAMA) Program. Of 14 pharmaceutical compounds analyzed, 7 were detected at concentrations greater than or equal to method detection limits: acetaminophen (used as an analgesic, detection frequency 0.32%, maximum concentration 1.89 µg/L), caffeine (stimulant, 0.24%, 0.29 µg/L), carbamazepine (mood stabilizer, 1.5%, 0.42 µg/L), codeine (opioid analgesic, 0.16%, 0.214 µg/L), p-xanthine (caffeine metabolite, 0.08%, 0.12 µg/L), sulfamethoxazole (antibiotic, 0.41%, 0.17 µg/L), and trimethoprim (antibiotic, 0.08%, 0.018 µg/L). Detection frequencies of pesticides (33%), volatile organic compounds not including trihalomethanes (23%), and trihalomethanes (28%) in the same 1231 samples were significantly higher. Median detected concentration of pharmaceutical compounds was similar to those of volatile organic compounds, and higher than that of pesticides. Pharmaceutical compounds were detected in 3.3% of the 855 samples containing modern groundwater (tritium activity>0.2 TU). Pharmaceutical detections were significantly positively correlated with detections of urban-use herbicides and insecticides, detections of volatile organic compounds, and percentage of urban land use around wells. Groundwater from the Los Angeles metropolitan area had higher detection frequencies of pharmaceuticals and other anthropogenic compounds than groundwater from other areas of the state with similar proportions of urban land use. The higher detection frequencies may reflect that groundwater flow systems in Los Angeles area basins are dominated by engineered recharge and intensive groundwater pumping.

Effects of groundwater development on uranium: Central Valley, California, USA.

Uranium (U) concentrations in groundwater in several parts of the eastern San Joaquin Valley, California, have exceeded federal and state drinking water standards during the last 20 years. The San Joaquin Valley is located within the Central Valley of California and is one of the most productive agricultural areas in the world. Increased irrigation and pumping associated with agricultural and urban development during the last 100 years have changed the chemistry and magnitude of groundwater recharge, and increased the rate of downward groundwater movement. Strong correlations between U and bicarbonate suggest that U is leached from shallow sediments by high bicarbonate water, consistent with findings of previous work in Modesto, California. Summer irrigation of crops in agricultural areas and, to lesser extent, of landscape plants and grasses in urban areas, has increased Pco(2) concentrations in the soil zone and caused higher temperature and salinity of groundwater recharge. Coupled with groundwater pumping, this process, as evidenced by increasing bicarbonate concentrations in groundwater over the last 100 years, has caused shallow, young groundwater with high U concentrations to migrate to deeper parts of the groundwater system that are tapped by public-supply wells. Continued downward migration of U-affected groundwater and expansion of urban centers into agricultural areas will likely be associated with increased U concentrations in public-supply wells. The results from this study illustrate the potential long-term effects of groundwater development and irrigation-supported agriculture on water quality in arid and semiarid regions around the world.

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon.

Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.