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Bryant C. Jurgens

Publications and source records attributed to Bryant C. Jurgens.

At least 37 records · Page 2Linked to original sources

Groundwater residence time estimates obscured by anthropogenic carbonate

Groundwater is an important source of drinking and irrigation water. Dating groundwater informs its vulnerability to contamination and aids in calibrating flow models. Here, we report measurements of multiple age tracers ( 14 C, 3 H, 39 Ar, and 85 Kr) and parameters relevant to dissolved inorganic carbon (DIC) from 17 wells in California’s San Joaquin Valley (SJV), an agricultural region that is heavily reliant on groundwater. We find evidence for a major mid-20th century shift in groundwater DIC input from mostly closed- to mostly open-system carbonate dissolution, which we suggest is driven by input of anthropogenic carbonate soil amendments. Crucially, enhanced open-system dissolution, in which DIC equilibrates with soil CO 2 , fundamentally affects the initial 14 C activity of recently recharged groundwater. Conventional 14 C dating of deeper SJV groundwater, assuming an open system, substantially overestimates residence time and thereby underestimates susceptibility to modern contamination. Because carbonate soil amendments are ubiquitous, other groundwater-reliant agricultural regions may be similarly affected.

California↗

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.

California↗

Geochemistry and age of groundwater in the Williston Basin, USA: Assessing potential effects of shale-oil production on groundwater quality

Thirty water wells were sampled in 2018 to understand the geochemistry and age of groundwater in the Williston Basin and assess potential effects of shale-oil production from the Three Forks-Bakken petroleum system (TBPS) on groundwater quality. Two geochemical groups are identified using hierarchical cluster analysis. Group 1 represents the younger (median 4 He = 21.49 × 10 −8 cm 3 STP/g), less chemically evolved water. Group 2 represents the older (median 4 He = 1389 × 10 −8 cm 3 STP/g), more chemically evolved water. At least two samples from each group contain elevated Cl concentrations (>70 mg/L). Br/Cl, B/Cl, and Li/Cl ratios indicate multiple sources account for the elevated Cl concentrations: septic-system leachate/road deicing salt, lignite beds in the aquifers, Pierre Shale beneath the aquifers, and water associated with the TBPS (one sample). 3 H and 14 C data indicate that 10.8, 21.6, and 67.6% of the samples are modern (post-1952), mixed age, and premodern (pre-1953), respectively. Lumped-parameter modeling of 3 H, SF 6 , 3 He, and 14 C concentrations indicates mean ages of the modern and premodern fractions range from ~1 to 30 years and 1300 to >30,000 years, respectively. Group 2 contains the highest CH 4 concentrations (0.0018–32 mg/L). δ 13 C–CH 4 and C 1 /C 2 +C 3 data in groundwater (−91.7 to −70.0‰ and 1280 to 13,600) indicate groundwater CH 4 is biogenic in origin and not from thermogenic shale gas. Four volatile organic compounds (VOCs) were detected in two samples. One mixed-age sample contains chloroform (0.25 μg/L) and dichloromethane (0.05 μg/L), which are probably associated with septic leachate. One premodern sample contains butane (0.082 μg/L) and n-pentane (0.032 μg/L), which are probably associated with thermogenic gas from a nearby oil well. The data indicate hydrocarbon production activities do not currently (2018) widely affect Cl, CH 4 , and VOC concentrations in groundwater. The predominance of premodern recharge in the aquifers indicates the groundwater moves relatively slowly, which could inhibit widespread chemical movement in groundwater overlying the TBPS. Comparison of groundwater-age data from five major unconventional hydrocarbon-production areas indicates aquifer zones used for water supply in the TBPS area have a lower risk of widespread chemical movement in groundwater than similar aquifer zones in the Fayetteville (Arkansas) and Marcellus (Pennsylvania) Shale production areas, but have a higher risk than similar aquifer zones in the Eagle Ford (Texas) and Haynesville (Texas, Louisiana) Shale production areas.

Montana, North Dakota, South Dakota↗

Environmental tracer evidence for connection between shallow and bedrock aquifers and high intrinsic susceptibility to contamination of the conterminous U.S. glacial aquifer

Covering a large portion of the northern conterminous United States (1.87 x 106 km2), the glacial aquifer serves as the primary water supply for 39 million public and domestic water users. Mean groundwater age, groundwater age distribution, and susceptibility to land surface contamination, using a new metric (Susceptibility Index; SI) based on the full age distribution and less prone to bias than estimated mean age, is reported for 168 public and domestic wells across the aquifer. Comparison of groundwater age metrics between well networks of varying spatial scale suggest an extensive sample network of equally spaced, long screened interval wells can be used to characterize aquifer wide groundwater age. Estimated mean age ranges from 1 to 50,000 years and, according to the composite age distribution, approximately 63 percent of all sampled water recharged after 1950 (i.e., modern) and 18 percent of the sampled water was recharged greater than 10,000 years ago. The later finding strongly suggests a connection between the glacial aquifer and underlying bedrock aquifers. Statistical analysis of glacial aquifer hydrogeology and age metrics show groundwater ages are young (less than few 100 years) and more susceptible to land surface contamination (larger SI) in unconfined and shallow portions of the aquifer. Old groundwater (greater than 1000 years) is more often associated with thicker sequences of fine grain sediments and/or shallow bedrock. Calculated SI is shown to be more strongly related to the number of land surface contaminants detected than mean age or fraction modern. Statistical analysis of SI and hydrogeology indicates SI is largely dictated by well depth and confinement. This study demonstrates how sample network design can be used to characterize groundwater age of large aquifers with a limited number of samples and how interpretation of environmental tracers can be used to improve conceptual models of groundwater aquifers and identify groundwater susceptible to contamination.

Glacial aquifer↗

Evaluation of soil zone processes and a novel radiocarbon correction approach for groundwater with mixed sources

Estimates of groundwater age based on 14C is often limited by the uncertainty in geochemical processes that alter the 14C concentration measured in water and the composition (δ13C and 14C) of carbon sources needed to appropriately parametrize 14C adjustment models. Estimated ages for samples that contain a mixture of young and old groundwater will be particularly sensitive to model parametrization as relatively small additions of modern 14C from recent recharge can mask the presence and amount of old groundwater. A novel multi-model approach based on inverse geochemical modeling and lumped parameter modeling of age tracers (3H, 3Hetrit, and SF6) was used to better constrain 14C dilution caused by dissolution of carbonates in the unsaturated zone or shallow parts of the Glacial aquifer, which extends over 2000 miles across the northern contiguous United States. Calibration of 14C inverse geochemical models to LPM computed 14C concentrations in modern water indicated that 14C of soil zone and shallow aquifer carbonates were not 14C-dead (0 pmC), as is typically assumed for 14C correction models. 14C of such carbonates was on average about 53 pmC (ranged 0-110 pmC, n = 72). This information was used to correct 14C concentrations for water recharged entirely before 1950 and water that is a mixture of pre- and post-1950 water. The multi-model approach developed here was compared to an analytical 14C-adjustment model (Revised Fontes and Garnier) that assumed solid carbonates were 14C-dead. 14C corrections using the analytical adjustment model tended to over-correct final 14C concentrations by 21 pmC and underestimates mean ages by 40% for groundwater mixtures. In fact, 14C corrections based on analytical model yielded negative ages (14C > 120 pmC) in nearly 36% of mixed samples. This work presents a new approach to constraining 14C corrections and age estimates of mixtures of young and old groundwater. The new method is applied to three well networks distributed across the spatially expansive Glacial aquifer.

Glacier aquifer system↗

Time scales of arsenic variability and the role of high-frequency monitoring at three water-supply wells in New Hampshire, USA

Groundwater geochemistry, redox process classification, high-frequency physicochemical and hydrologic measurements, and climate data were analyzed to identify controls on arsenic (As) concentration changes. Groundwater was monitored in two public-supply wells (one glacial aquifer and one bedrock aquifer), and one bedrock-aquifer domestic well in New Hampshire, USA, from 2014 to 2018 to identify time scales of and controls on As concentration changes. Concentrations of As and other geochemical constituents were measured bimonthly. Specific conductance (SC), pH, dissolved oxygen, and pumping rate/water level were measured at high frequency (every 5 to 15 min). Median (and 95% confidence interval) As concentrations at the three wells were 4.1 (3.7–4.6), 18.9 (17.2–23.6), and 37.5 (30.4–42.9) μg/L. Arsenic variability in each of the three wells, in relative standard deviation, ranged from 9 to 12%. Median quarterly As concentrations were highest in all wells in the spring. The bedrock-aquifer public-supply well As concentration increased over the period of study while pumping rate decreased. In the public-supply wells, As variability was correlated with SC and pH, and As species were related to SC, pH, pumping, precipitation, and changes in redox process. Specific conductance also had a seasonal pattern in the two public-supply wells and was correlated with Na and Cl. Excess Na in water samples suggests possible ion exchange with dissolved Ca, creating more capacity to dissolve CaCO 3 from calcareous rocks, which can increase pH and in turn, As concentrations in wells. High-frequency monitoring data are cost effective to collect, which could be advantageous in other parts of the United States and in the many parts of the world where glacial aquifers are in direct contact with other water supply aquifers or where water from different aquifers have potential to mix.

New Hampshire↗

History and sources of co-occurring pesticides in an abstraction well unravelled by age distributions of depth specific groundwater samples

When groundwater-based drinking water supply becomes contaminated, the timing and source of contamination are obvious questions. However, contaminants often have diffuse sources and different contaminants may have different sources even in a single groundwater well, making these questions complicated to answer. Age dating of groundwater has been used to reconstruct contaminant travel times to wells; however, critics have highlighted that groundwater flow is often complex with mixing of groundwater of different ages. In drinking water wells, where water is typically abstracted from a large depth interval, such mixing is even more problematic. We present a way to overcome some of the obstacles in identifying the source and age of contaminants in drinking water wells by combining depth-specific sampling with age tracer modeling, particle tracking simulations, geological characterization, and contaminant properties. This multitool approach was applied to a drinking water well, where bentazon and dichlorprop contamination was found to have different pollutant sources and release histories, even though both pesticides can be associated with the same land use. Bentazon was derived from recent application to a golf course, while dichlorprop was derived from agricultural use more than 30 years ago. The advantages, limitations, and pitfalls of the proposed course of action are then further discussed.

Environmental Science & Technology↗

Delineation of spatial extent, depth, thickness, and potential volume of aquifers used for domestic and public water-supply in the Central Valley, California

Identification of the groundwater resources used for drinking-water supplies is essential for the design of strategies to manage those resources. In this study, the spatial extent, depths, thicknesses, and volumes of groundwater aquifers used for domestic and public drinking-water supply were estimated from locations and well-construction data from 11,725 domestic-supply wells and 2,376 public-supply wells in the Central Valley, California. The data were compiled as part of the U.S. Geological Survey National Water Quality Assessment Project and California State Water Resources Control Board Groundwater Ambient Monitoring and Assessment Program Priority Basin Project. The spatial distributions of the depth to top and bottom of well screens were interpolated using Empirical Bayesian Kriging across buffer areas surrounding domestic- and public-supply wells. These surfaces provide a measure of the likely maximum horizontal and vertical extent of the aquifer volume accessed for drinking water in the Central Valley during the past century. Well depth generally increased from north to south, and over time from 1905 to 2010. Well-construction depths were generally more consistent in the Sacramento Valley than in the San Joaquin Valley. The total potential aquifer volume accessed for public supply was calculated to be greater than domestic-supply access, even though the estimated spatial extent of domestic-supply wells was 1.5 times larger than the spatial extent of public-supply wells. Public-supply wells commonly have screen lengths greater than 51 meters, whereas domestic-supply wells typically have shorter screen lengths (overall median of 6 meters). Consequently, the accessed thickness and volume of the aquifer is on average 1.8 and 1.4 times greater for public-supply wells than domestic-supply wells, respectively. Results are presented as maps of areal extent, depth, and thickness of zones in the Central Valley aquifer system used for domestic and public drinking-water supplies.

California↗

Tritium as an indicator of modern, mixed, and premodern groundwater age

Categorical classification of groundwater age is often used for the assessment and understanding of groundwater resources. This report presents a tritium-based age classification system for the conterminous United States based on tritium ( 3 H) thresholds that vary in space and time: modern (recharged in 1953 or later), if the measured value is larger than an upper threshold; premodern (recharged prior to 1953) if the measured value is smaller than a lower threshold; or mixed if the measured value is between the two thresholds. Inclusion of spatially varying thresholds, rather than a single threshold, accounts for the observed systematic variation in 3 H deposition across the United States. Inclusion of time-varying thresholds, rather than a single threshold, accounts for the date of sampling given the radioactive decay of 3 H. The efficacy of the tritium-based age classification system was evaluated at national and regional scales. The system was evaluated at a national scale by classifying samples from 1,788 public-supply wells distributed across 19 principal aquifers and comparing those results with expectations based on hydrogeologic principles. The regional-scale data are from five paired networks of shallow and deep wells (287 wells). As expected, modern groundwater is more prevalent in shallow wells than in deeper wells, in fractured-rock and carbonate aquifers as compared to clastic aquifers, in unconfined areas as compared to confined areas, and in humid climates as compared to arid climates. The results from a tritium-based age classification system compared favorably with the results of 14 previous studies of groundwater ages that used different age tracers and analytical methods. The wells and samples from the Cambrian-Ordovician aquifer that had been analyzed using a more complex multi-tracer analysis were also analyzed using the tritium-based age classification system, and there was a close match between the two methods. The results from these various studies suggest that the tritium-based age classification system may be informative as a screening tool prior to selecting more expensive and complex age-dating tracers and methods, or to provide an explanatory variable for other water-quality data where more complex methods or tracers are not available. This work improves on previous groundwater age classification using 3 H by developing methods that (1) determine 3 H thresholds for groundwater recharged in 1953 or later that minimize the misclassification of modern samples as mixed; (2) determine a pre-1953 threshold to estimate premodern background concentrations; and (3) add a mixed category to classify samples that are clearly neither entirely modern nor entirely premodern. As with any tritium-based approach, it can fail when the 3 H record in precipitation does not accurately reflect the record of 3 H in recharge

Conterminous United States↗

Hydrocarbons in upland groundwater, Marcellus Shale Region, Northeastern Pennsylvania and Southern New York, USA

Water samples from 50 domestic wells located <1 km (proximal) and >1 km (distal) from shale-gas wells in upland areas of the Marcellus Shale region were analyzed for chemical, isotopic, and groundwater-age tracers. Uplands were targeted because natural mixing with brine and hydrocarbons from deep formations is less common in those areas compared to valleys. CH 4 -isotope, predrill CH 4 -concentration, and other data indicate that one proximal sample (5% of proximal samples) contains thermogenic CH 4 (2.6 mg/L) from a relatively shallow source (Catskill/Lock Haven Formations) that appears to have been mobilized by shale-gas production activities. Another proximal sample contains five other volatile hydrocarbons (0.03–0.4 μg/L), including benzene, more hydrocarbons than in any other sample. Modeled groundwater-age distributions, calibrated to 3 H, SF 6 , and 14 C concentrations, indicate that water in that sample recharged prior to shale-gas development, suggesting that land-surface releases associated with shale-gas production were not the source of those hydrocarbons, although subsurface leakage from a nearby gas well directly into the groundwater cannot be ruled out. Age distributions in the samples span ∼20 to >10000 years and have implications for relating occurrences of hydrocarbons in groundwater to land-surface releases associated with recent shale-gas production and for the time required to flush contaminants from the system.

New York, Pennsylvania↗

Assessing the lead solubility potential of untreated groundwater of the United States

In the U.S., about 44 million people rely on self-supplied groundwater for drinking water. Because most self-supplied homeowners do not treat their water to control corrosion, drinking water can be susceptible to lead (Pb) contamination from metal plumbing. To assess the types and locations of susceptible groundwater, a geochemical reaction model that included pure Pb minerals and solid solutions of calcite (Ca x Pb 1– x CO 3 ) and apatite [Ca x Pb 5-x (PO 4 ) 3 (OH; Cl; F)] was developed to estimate the lead solubility potential (LSP) for over 8300 untreated groundwater samples collected from domestic and public-supply sites between 2000 and 2016 in the U.S. The LSP is the calculated amount of Pb metal that could dissolve at 25 °C before a Pb-bearing mineral precipitates. About 33% of untreated groundwater samples had LSP greater than 15 μg/L—the USEPA action level for dissolved plus particulate forms of Pb. Five percent of samples had high LSP (above 300 μg/L) and tended to occur in the eastern and southeastern U.S. Measured Pb concentrations above 15 μg/L were rarely detected (<1%) but always coincided with high LSP values. Future work will provide a better understanding of the relation between water chemistry, Pb-mineral formation, and dissolved Pb concentrations in tap water.

Environmental Science & Technology↗

Arsenic variability and groundwater age in three water supply wells in southeast New Hampshire

Three wells in New Hampshire were sampled bimonthly over three years to evaluate the temporal variability of arsenic concentrations and groundwater age. All samples had measurable concentrations of arsenic throughout the entire sampling period and concentrations in individual wells varied, on average, by more than 7 µg/L. High arsenic concentrations (>10 µg/L) were measured in bedrock wells KFW-87 and SGW-93, consistent with the high pH and low dissolved oxygen typically found in fractured crystalline bedrock aquifers in New Hampshire. Lower arsenic concentrations (<10 µg/L) at well SGW-65 were consistent with lower pH typical of glacial aquifers in New Hampshire.

New Hampshire↗

Tritium deposition in precipitation in the United States, 1953–2012

Tritium is a radioactive isotope of hydrogen (half-life is equal to 12.32 years). Since it is part of the water molecule, tritium can be used to track and date groundwater and surface water when the history of tritium in precipitation and recharge is known. To facilitate that effort, tritium concentrations in precipitation were reconstructed from measurements and correlations for 10 precipitation stations in the continental United States. Using these data, and other data sets and correlations, estimates of tritium concentrations in precipitation from 1953 through 2012 and total tritium deposition from 1953 through 1983 were derived for 2 degrees latitude by 5 degrees longitude quadrangles of the continental United States. For August 1953 through December 1987 correlations were derived from the data of the Ottawa, Canada, station; for estimates after 1987, the Vienna, Austria, station was used. For quadrangles where no precipitation station records are available from measurements or correlations, concentrations were interpolated. The International Atomic Energy Agency has proposed that a correlation with the Vienna, Austria, station, which has been in operation since 1960, be used instead of the Ottawa, Canada, station for the period after 1987. Linear correlations calculated for all stations with the Vienna data are reported. Correlations also have been calculated for each latitude-longitude quadrangle using the estimated concentrations and the measured Vienna data for 1960–87. Because the Vienna, Austria, station is on a different continent, and not subject to the same seasonal weather patterns that affect North American stations, a correlation was obtained for each month individually. This reflects the fact that the North American stations were strongly affected by the input of low-tritium moisture from the south during the summer. The correlated station values were then used with measured Vienna data to obtain estimates of tritium concentrations in precipitation for the period 1988–2012 at each precipitation station and latitude-longitude quadrangles. This approach has two major advantages: (1) it blends the Ottawa correlation with the Vienna correlation to cover the period 1953 to present, and (2) it yields correlation coefficients for each quadrangle that can be used in future years when more data become available from the Vienna, Austria, station. The data, the estimated tritium concentrations derived from the correlations, and the correlation coefficients are provided as spreadsheets and associated comma delimited files in a data release that accompanies this report.

Scientific Investigations Report↗

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 variability of nitrate fluxes in the unsaturated zone and groundwater, Wisconsin, USA

Process-based modeling of regional NO3− fluxes to groundwater is critical for understanding and managing water quality, but the complexity of NO3− reactive transport processes make implementation a challenge. This study introduces a regional vertical flux method (VFM) for efficient estimation of reactive transport of NO3− in the vadose zone and groundwater. The regional VFM was applied to 443 well samples in central-eastern Wisconsin. Chemical measurements included O2, NO3−, N2 from denitrification, and atmospheric tracers of groundwater age including carbon-14, chlorofluorocarbons, tritium, and tritiogenic helium. VFM results were consistent with observed chemistry, and calibrated parameters were in-line with estimates from previous studies. Results indicated that (1) unsaturated zone travel times were a substantial portion of the transit time to wells and streams (2) since 1945 fractions of applied N leached to groundwater have increased for manure-N, possibly due to increased injection of liquid manure, and decreased for fertilizer-N, and (3) under current practices and conditions, approximately 60% of the shallow aquifer will eventually be affected by downward migration of NO3−, with denitrification protecting the remaining 40%. Recharge variability strongly affected the unsaturated zone lag times and the eventual depth of the NO3− front. Principal components regression demonstrated that VFM parameters and predictions were significantly correlated with hydrogeochemical landscape features. The diverse and sometimes conflicting aspects of N management (e.g. limiting N volatilization versus limiting N losses to groundwater) warrant continued development of large-scale holistic strategies to manage water quality and quantity.

Wisconsin↗

Radium mobility and the age of groundwater in public-drinking-water supplies from the Cambrian-Ordovician aquifer system, north-central USA

High radium (Ra) concentrations in potable portions of the Cambrian-Ordovician (C-O) aquifer system were investigated using water-quality data and environmental tracers ( 3 H, 3 He trit , SF 6 , 14 C and 4 He rad ) of groundwater age from 80 public-supply wells (PSWs). Groundwater ages were estimated by calibration of tracers to lumped parameter models and ranged from modern (<50 yr) in upgradient, regionally unconfined areas to ancient (>1 Myr) in the most downgradient, confined portions of the potable system. More than 80 and 40 percent of mean groundwater ages were older than 1000 and 50,000 yr, respectively. Anoxic, Fe-reducing conditions and increased mineralization develop with time in the aquifer system and mobilize Ra into solution resulting in the frequent occurrence of combined Ra (Ra c = 226 Ra + 228 Ra) at concentrations exceeding the USEPA MCL of 185 mBq/L (5 pCi/L). The distribution of the three Ra isotopes comprising total Ra (Ra t = 224 Ra + 226 Ra + 228 Ra) differed across the aquifer system. The concentrations of 224 Ra and 228 Ra were strongly correlated and comprised a larger proportion of the Ra t concentration in samples from the regionally unconfined area, where arkosic sandstones provide an enhanced source for progeny from the 232 Th decay series. 226 Ra comprised a larger proportion of the Ra t concentration in samples from downgradient confined regions. Concentrations of Ra t were significantly greater in samples from the regionally confined area of the aquifer system because of the increase in 226 Ra concentrations there as compared to the regionally unconfined area. 226 Ra distribution coefficients decreased substantially with anoxic conditions and increasing ionic strength of groundwater (mineralization), indicating that Ra is mobilized to solution from solid phases of the aquifer as adsorption capacity is diminished. The amount of 226 Ra released from solid phases by alpha-recoil mechanisms and retained in solution increases relative to the amount of Ra sequestered by adsorption processes or co-precipitation with barite as adsorption capacity and the concentration of Ba decreases. Although 226 Ra occurred at concentrations greater than 224 Ra or 228 Ra, the ingestion exposure risk was greater for 228 Ra owing to its greater toxicity. In addition, 224 Ra added substantial alpha-particle radioactivity to potable samples from the C-O aquifer system. Thus, monitoring for Ra isotopes and gross-alpha-activity (GAA) is important in upgradient, regionally unconfined areas as downgradient, and GAA measurements made within 72 h of sample collection would best capture alpha-particle radiation from the short-lived 224 Ra.

Applied Geochemistry↗

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.

California↗

Methane and benzene in drinking-water wells overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas

Water wells ( n = 116) overlying the Eagle Ford, Fayetteville, and Haynesville Shale hydrocarbon production areas were sampled for chemical, isotopic, and groundwater-age tracers to investigate the occurrence and sources of selected hydrocarbons in groundwater. Methane isotopes and hydrocarbon gas compositions indicate most of the methane in the wells was biogenic and produced by the CO 2 reduction pathway, not from thermogenic shale gas. Two samples contained methane from the fermentation pathway that could be associated with hydrocarbon degradation based on their co-occurrence with hydrocarbons such as ethylbenzene and butane. Benzene was detected at low concentrations (<0.15 μg/L), but relatively high frequencies (2.4–13.3% of samples), in the study areas. Eight of nine samples containing benzene had groundwater ages >2500 years, indicating the benzene was from subsurface sources such as natural hydrocarbon migration or leaking hydrocarbon wells. One sample contained benzene that could be from a surface release associated with hydrocarbon production activities based on its age (10 ± 2.4 years) and proximity to hydrocarbon wells. Groundwater travel times inferred from the age-data indicate decades or longer may be needed to fully assess the effects of potential subsurface and surface releases of hydrocarbons on the wells.

Environmental Science & Technology↗