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 that the Ra in the oil-field water was removed by coprecipitation 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.

Triennial changes in groundwater quality in aquifers used for public supply in California: utility as indicators of temporal trends.

From 2004 to 2011, the U.S. Geological Survey collected samples from 1686 wells across the State of California as part of the California State Water Resources Control Board's Groundwater Ambient Monitoring and Assessment (GAMA) Priority Basin Project (PBP). From 2007 to 2013, 224 of these wells were resampled to assess temporal trends in water quality. The samples were analyzed for 216 water-quality constituents, including inorganic and organic compounds as well as isotopic tracers. The resampled wells were grouped into five hydrogeologic zones. A nonparametric hypothesis test was used to test the differences between initial sampling and resampling results to evaluate possible step trends in water-quality, statewide, and within each hydrogeologic zone. The hypothesis tests were performed on the 79 constituents that were detected in more than 5 % of the samples collected during either sampling period in at least one hydrogeologic zone. Step trends were detected for 17 constituents. Increasing trends were detected for alkalinity, aluminum, beryllium, boron, lithium, orthophosphate, perchlorate, sodium, and specific conductance. Decreasing trends were detected for atrazine, cobalt, dissolved oxygen, lead, nickel, pH, simazine, and tritium. Tritium was expected to decrease due to decreasing values in precipitation, and the detection of decreases indicates that the method is capable of resolving temporal trends.

Geogenic sources of benzene in aquifers used for public supply, California.

Statistical evaluation of two large statewide data sets from the California State Water Board's Groundwater Ambient Monitoring and Assessment Program (1973 wells) and the California Department of Public Health (12,417 wells) reveals that benzene occurs infrequently (1.7%) and at generally low concentrations (median detected concentration of 0.024 µg/L) in groundwater used for public supply in California. When detected, benzene is more often related to geogenic (45% of detections) than anthropogenic sources (27% of detections). Similar relations are evident for the sum of 17 hydrocarbons analyzed. Benzene occurs most frequently and at the highest concentrations in old, brackish, and reducing groundwater; the detection frequency was 13.0% in groundwater with tritium <1 pCi/L, specific conductance >1600 µS/cm, and anoxic conditions. This groundwater is typically deep (>180 m). Benzene occurs somewhat less frequently in recent, shallow, and reducing groundwater; the detection frequency was 2.6% in groundwater with tritium ≥1 pCi/L, depth <30 m, and anoxic conditions. Evidence for geogenic sources of benzene include: higher concentrations and detection frequencies with increasing well depth, groundwater age, and proximity to oil and gas fields; and higher salinity and lower chloride/iodide ratios in old groundwater with detections of benzene, consistent with interactions with oil-field brines.

Geostatistical Mapping of Salinity Conditioned on Borehole Logs, Montebello Oil Field, California.

We present a geostatistics-based stochastic salinity estimation framework for the Montebello Oil Field that capitalizes on available total dissolved solids (TDS) data from groundwater samples as well as electrical resistivity (ER) data from borehole logging. Data from TDS samples (n = 4924) was coded into an indicator framework based on falling below four selected thresholds (500, 1000, 3000, and 10,000 mg/L). Collocated TDS-ER data from the surrounding groundwater basin were then employed to produce a kernel density estimator to establish conditional probabilities for ER data (n = 8 boreholes) falling below the selected TDS thresholds within the Montebello Oil Field area. Directional variograms were estimated from these indicator coded data, and 500 TDS realizations from conditional indicator simulation were generated for the subsurface region above the Montebello Oil Field reservoir. Simulations were summarized as 3D maps of median TDS, most likely salinity class, and probability for exceeding each of the specified TDS thresholds. Results suggested TDS was below 500 mg/L in most of the study area, with a trend toward higher values (500 to 1000 mg/L) to the southwest; consistent with the average regional groundwater flow direction. Discrete localized zones of TDS greater than 1000 mg/L were observed, with one of these zones in the greater than 10,000 mg/L range; however, these areas were not prevalent. The probabilistic approach used here is adaptable and is readily modified to include additional data and types and can be employed in time-lapse salinity modeling through Bayesian updating.

Factors affecting 1,2,3-trichloropropane contamination in groundwater in California.

1,2,3-Trichloropropane (1,2,3-TCP) is a volatile organic chemical of eminent concern due to its carcinogenic, mutagenic, and reproductive effects, and its frequent occurrence at concentrations of concern worldwide. In California, 1,2,3-TCP was detected in 6.5% of 1237 wells sampled by the U. S. Geological Survey (USGS). About 8% of domestic wells had a detection of 1,2,3-TCP, compared to 5% of public-supply wells. 1,2,3-TCP was detected in 5.5% of most recent samples from 7787 public-supply well sources of the California State Water Resources Control Board Division of Drinking Water (DDW). Concentrations ranged from <0.005 to 2.7 µg/L. The California maximum contaminant level (MCL) is 0.005 µg/L. Most of the detections occurred in the San Joaquin Valley, where 1,2,3-TCP was detected above the MCL in 16% of USGS sampled wells and 18% of DDW wells. 1,2,3-TCP occurrence and concentrations are related to legacy fumigant use and hydrogeologic factors. Understanding factors affecting 1,2,3-TCP will aid in determining vulnerability and long term persistence in the San Joaquin Valley, which can help focus efforts to manage drinking water resources on the most vulnerable areas and also inform efforts in other areas of the state and worldwide. Widespread occurrence of 1,2,3-TCP is related to nonpoint source agricultural contaminant inputs. High concentrations of 1,2,3-TCP are in young, shallow, oxic groundwater beneath primarily orchard/vineyard crops. These areas are in coarse-grained sediments that promote rapid recharge, related to proximal alluvial fan sediments deposited by large streams that drain glaciated watersheds of the Sierra Nevada. 1,2,3-TCP co-occurs with 1,2-dibromo-3-chloropropane (DBCP) and 1,2-dichloropropane (1,2-DCP) throughout modern age groundwater, indicating its long term persistence with little degradation. The highest concentrations of 1,2,3-TCP were observed at point source cleanup sites in urban areas; depending on the age and source of groundwater to nearby public-supply wells, these areas may see increasing concentrations of 1,2,3-TCP.

Effects of surface run-off on the transport of agricultural chemicals to ground water in a sandplain setting.

An experiment was conducted at a depressional (lowland) and an upland site in sandy soils to evaluate the effects of surface run-off on the transport of agricultural chemicals to ground water. Approximately 16.5 cm of water was applied to both sites during the experiment, representing a natural precipitation event with a recurrence interval of approximately 100 years. Run-off was quantified at the lowland site and was not detected at the upland site during the experiment. Run-off of water to the lowland site was the most important factor affecting differences in the concentrations and fluxes of the agricultural chemicals between the two sites. Run-off of water to the lowland site ppears to have played a dual role by diluting chemical concentrations in the unsaturated zone as well as increasing the concentrations at the water table, compared to the upland site. Concentrations of chloride, nitrate and atrazine plus metabolites were noticeably greater at the water table than in the unsaturated zone at both sites. The estimated mass flux of chloride and nitrate to the water table during the test were 5-2 times greater, respectively, at the lowland site compared to the upland site, whereas the flux of sulfate and atrazine plus metabolites was slightly greater at the upland site. Results indicate that matrix flow of water and chemicals was the primary process causing the observed differences between the two sites. Results of the experiment illustrate the effects of heterogeneity and the complexity of evaluating chemical transport through the unsaturated zone.

Trends in concentrations of nitrate and total dissolved solids in public supply wells of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins, San Bernardino County, California: influence of legacy land use.

Concentrations and temporal changes in concentrations of nitrate and total dissolved solids (TDS) in groundwater of the Bunker Hill, Lytle, Rialto, and Colton groundwater subbasins of the Upper Santa Ana Valley Groundwater Basin were evaluated to identify trends and factors that may be affecting trends. One hundred, thirty-one public-supply wells were selected for analysis based on the availability of data spanning at least 11 years between the late 1980s and the 2000s. Forty-one of the 131 wells (31%) had a significant (p<0.10) increase in nitrate and 14 wells (11%) had a significant decrease in nitrate. For TDS, 46 wells (35%) had a significant increase and 8 wells (6%) had a significant decrease. Slopes for the observed significant trends ranged from -0.44 to 0.91 mg/L/yr for nitrate (as N) and -8 to 13 mg/L/yr for TDS. Increasing nitrate trends were associated with greater well depth, higher percentage of agricultural land use, and being closer to the distal end of the flow system. Decreasing nitrate trends were associated with the occurrence of volatile organic compounds (VOCs); VOC occurrence decreases with increasing depth. The relations of nitrate trends to depth, lateral position, and VOCs imply that increasing nitrate concentrations are associated with nitrate loading from historical agricultural land use and that more recent urban land use is generally associated with lower nitrate concentrations and greater VOC occurrence. Increasing TDS trends were associated with relatively greater current nitrate concentrations and relatively greater amounts of urban land. Decreasing TDS trends were associated with relatively greater amounts of natural land use. Trends in TDS concentrations were not related to depth, lateral position, or VOC occurrence, reflecting more complex factors affecting TDS than nitrate in the study area.

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.