Geochemical Conditions and the Occurrence of Selected Trace Elements in Groundwater Basins Used for Public Drinking-Water Supply, Desert and Basin and Range Hydrogeologic Provinces, 2006–11: California GAMA Priority Basin Project

Abstract

The geochemical conditions, occurrence of selected trace elements, and processes controlling the occurrence of selected trace elements in groundwater were investigated in groundwater basins of the Desert and Basin and Range (DBR) hydrogeologic provinces in southeastern California as part of the Priority Basin Project (PBP) of the Groundwater Ambient Monitoring and Assessment (GAMA) Program. The GAMA PBP is designed to provide an assessment of the quality of untreated (raw) groundwater in the aquifer systems that are used for public drinking-water supply. The GAMA PBP is being conducted by the California State Water Resources Control Board in collaboration with the U.S. Geological Survey and the Lawrence Livermore National Laboratory.

The DBR hydrogeologic provinces consist of 141 defined groundwater basins separated by mountain ranges, faults, and other features. This report presents analyses of data collected from nine study areas within the DBR hydrogeologic provinces: Antelope Valley, Borrego Valley, the Central Desert area, Coachella Valley, Colorado River, Indian Wells Valley, Low-Use Basins of the Mojave and Sonoran Deserts, the Mojave, and Owens Valley. Collectively, these nine study areas are referred to as the DBR study unit. The study unit covers approximately 7,000 square miles and includes the 63 groundwater basins in the DBR hydrogeologic provinces in which groundwater is used for public drinking-water supply. The vast majority of the 223 wells sampled for this study were long-screened production wells used primarily for public supply.

Uncorrected carbon-14 (¹⁴C) groundwater ages for samples collected in the DBR study unit ranged from less than (<) 100 to 33,700 years before present (BP). Sixty-six percent of sample ages were greater than (>) 100 years BP, and 40 percent were >3,800 years BP. Samples collected from wells located adjacent to mountain-front recharge areas or major surface-water features generally had younger groundwater ages than did samples collected from wells located away from mountain fronts or towards the distal ends of basin groundwater flow paths. Most groundwater sampled in the DBR study unit had alkaline pH: 89 percent of sample pH values ranged from 7.1 to 9.8, with 37 percent greater than or equal to (≥) 7.9. Groundwater age was significantly correlated (positively) with pH, likely because silicate weathering is a primary control on groundwater pH and is a slow process. The oxidation-reduction (redox) condition of the groundwater sampled in the DBR study unit was predominantly oxic (71 percent), except in the Colorado River study area where organic-rich fluvial aquifers provide the electron donors necessary to support iron-reducing (anoxic-Fe) redox processes. The cation type of 78 percent of the samples was either sodium- or mixed-type, and the anion type of 83 percent of the samples was either bicarbonate- or mixed-type. Sodium-type groundwaters generally were older and more alkaline than calcium-type groundwaters, consistent with the change in water chemistry expected from cation exchange between groundwater and aquifer sediments over long periods of time. Because of the correlation with young groundwater, calcium-type groundwater was predominantly from wells located adjacent to mountain-front recharge areas.

Arsenic (As), boron (B), fluoride (F), molybdenum (Mo), strontium (Sr), uranium (U), and vanadium (V) were selected for assessment in this study because they occurred at concentrations greater than California Department of Public Health or U.S. Environmental Protection Agency regulatory or non-regulatory drinking-water-quality benchmarks in more than 2 percent of the 223 samples collected in the DBR study unit. As and F were detected most commonly (18 and 13 percent, respectively) at concentrations above associated water-quality benchmarks and Sr and V least frequently (both at 3 percent). Given that ¹⁴C groundwater ages are predominantly >100 years BP, land use in the study unit is primarily undeveloped, and chemicals derived from anthropogenic sources, such as volatile organic compounds, were infrequently detected, high concentrations of these trace elements in groundwater were most likely the result of natural factors and not anthropogenic factors.

As, F, Mo, and V concentrations showed significant positive correlations to groundwater age and to pH. This relation is partly due to the sources of trace elements likely being the weathering of primary minerals, such as silicate minerals, which is a slow process that takes place over hundreds to thousands of years. This relation also reflects the positive correlation between groundwater age and pH. Geochemical modeling predicted that the dominant species of As, Mo, and V in solution were oxyanions (HAsO₄^2–, MoO₄^2–, and H₂VO^4–), which are likely to be mobile in alkaline groundwater because mineral surfaces composing aquifer matrices have a predominantly negative surface charge under alkaline conditions. F also exists predominantly as a negatively charged ion (F^–). At pH values >7.5, saturation indices generated by the geochemical modeling program PHREEQC indicated that F solubility may be somewhat limited by the precipitation of the mineral fluorapatite [Ca₅(PO₄)₃F]. Speciation modeling of As in anoxic-Fe groundwater (iron-reducing conditions) showed that samples were supersaturated with orpiment (As₂S₃), indicating that mineral precipitation may be responsible for low As concentrations observed in reducing groundwater.

In contrast, U concentrations showed significant negative correlations to groundwater age and to pH. Higher U concentrations generally occurred in samples for which geochemical modeling indicated that the uncharged ternary complex Ca₂UO₂(CO₃)₃ was the dominant aqueous U species. This uncharged complex is not attracted to the charged surfaces of minerals and thus increases U solubility. Formation of Ca₂UO₂(CO₃)₃ was greater in younger groundwaters because calcium and uranium concentrations generally were lower in older groundwaters, likely due to cation-exchange processes and precipitation of the mineral calcite as groundwater pH increased. Co-precipitation of U with the calcite (CaCO₃) may remove U from the aqueous phase. Saturation indices indicated that the anoxic-Fe groundwaters from the Colorado River study area were supersaturated with the mineral uraninite (UO₂), suggesting that UO₂ precipitation may be responsible for the low concentrations of U observed in these samples.

Concentrations of strontium, which exists primarily in a cationic form (Sr²⁺), were not significantly correlated with either groundwater age or pH. Strontium concentrations showed a strong positive correlation with total dissolved solids (TDS). Dissolved constituents, such as Sr, that interact with mineral surfaces through outer-sphere complexation become increasingly soluble with increasing TDS concentrations of groundwater. Boron concentrations also showed a significant positive correlation with TDS, indicating the B may interact to a large degree with mineral surfaces through outer-sphere complexation.

First posted January 30, 2015