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At least 595 records · Page 33Linked to original sources
USGS2015

Geochemical evolution of groundwater in the Mud Lake area, eastern Idaho, USA

Groundwater with elevated dissolved-solids concentrations—containing large concentrations of chloride, sodium, sulfate, and calcium—is present in the Mud Lake area of Eastern Idaho. The source of these solutes is unknown; however, an understanding of the geochemical sources and processes controlling their presence in groundwater in the Mud Lake area is needed to better understand the geochemical sources and processes controlling the water quality of groundwater at the Idaho National Laboratory. The geochemical sources and processes controlling the water quality of groundwater in the Mud Lake area were determined by investigating the geology, hydrology, land use, and groundwater geochemistry in the Mud Lake area, proposing sources for solutes, and testing the proposed sources through geochemical modeling with PHREEQC. Modeling indicated that sources of water to the eastern Snake River Plain aquifer were groundwater from the Beaverhead Mountains and the Camas Creek drainage basin; surface water from Medicine Lodge and Camas Creeks, Mud Lake, and irrigation water; and upward flow of geothermal water from beneath the aquifer. Mixing of groundwater with surface water or other groundwater occurred throughout the aquifer. Carbonate reactions, silicate weathering, and dissolution of evaporite minerals and fertilizer explain most of the changes in chemistry in the aquifer. Redox reactions, cation exchange, and evaporation were locally important. The source of large concentrations of chloride, sodium, sulfate, and calcium was evaporite deposits in the unsaturated zone associated with Pleistocene Lake Terreton. Large amounts of chloride, sodium, sulfate, and calcium are added to groundwater from irrigation water infiltrating through lake bed sediments containing evaporite deposits and the resultant dissolution of gypsum, halite, sylvite, and bischofite.

Idaho↗
USGS2021

Chemical connectivity and multi-element composition of groundwater in depressional wetlands

Little is known about the element composition of groundwater along flow paths between wetlands. What is known is based on a few major elements, such as Na and Ca. We examined the spatial and temporal variation of elements in a depressional-wetland, groundwater-flow system in the Prairie Pothole Region of North Dakota, USA. Wetlands of the region are characterized by their occurrence in hydrologically connected complexes, where those at higher elevations in the groundwater flow system often recharge groundwater (recharge wetlands), while those at lower elevations receive groundwater (discharge wetlands). The aim of our study was to get a better understanding of factors affecting the distribution of more than 30 elements in groundwater along a flow path between recharge and discharge wetlands. We found that oxidation-reduction potential (ORP) decreased as electrical conductivity (EC) increased along the flow path. As EC increased, so did the concentrations of major ions, such as Na, Ca, and Mg. That was already well known. Less known, however, was that concentrations of Cs, Sn, U and Zr increased along the flow path as well. Not reported before was that concentrations of Sn increased strongly as ORP decreased. The concentrations of most elements in groundwater increased with lower relative elevation in the groundwater flow system, but notable exceptions were Ba and Zn, which both showed opposite patterns. Our results contribute to a better understanding of element cycling in groundwater between wetlands, which in turn is important for our understanding of resultant influences on associated biogeochemistry and ecosystem services.

North Dakota↗
USGS1992

Identification of persistent anionic surfactant-derived chemicals in sewage effluent and groundwater

Preparative isolation and fractionation procedures coupled with spectrometric analyses were used to identify surfactant-derived contaminants in sewage effluent and sewage-contaminated groundwater from a site located on Cape Cod, Massachusetts. Anionic surfactants and their biodegradation intermediates were isolated from field samples by ion exchange and fractionated by solvent extraction and adsorption chromatography. Fractions were analyzed by 13 C nuclear magnetic resonance spectrometry and gas chromatography-mass spectrometry. Carboxylated residues of alkylphenol polyethoxylate surfactants were detected in sewage effluent and contaminated groundwater. Linear alkylbenzenesulfonates (LAS) were identified in sewage effluent and groundwater. Groundwater LAS composition suggested preferential removal of select isomers and homologs due to processes of biodegradation and partitioning. Tetralin and indane sulfonates (DATS), alicyclic analogs of LAS, were also identified in field samples. Although DATS are a minor portion of LAS formulations, equivalent concentrations of LAS and DATS in groundwater suggested persistence of alicyclic contaminant structures over those of linear structure. Sulfophenyl-carboxylated (SPC) LAS biodegradation intermediates were determined in sewage effluent and groundwater. Homolog distributions suggested that SPC containing 3–10 alkyl-chain carbons persist during infiltration and groundwater transport. Surfactant-derived residues detected in well F 300-50 groundwater have a minimum residence time in the range of 2.7–4.6 yr. LAS detected in groundwater at 500 m from infiltration has been stable over an estimated 50–500 half lives.

Journal of Contaminant Hydrology↗
USGS2016

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle, USA

This study investigated the potential for the uranium mineral carnotite (K 2 (UO 2 ) 2 (VO 4 ) 2 ·3H 2 O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO 2 . Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO 4 + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO 3 + CO 3 ) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2 m Ca +2 > m HCO 3 − + 2 m CO 3 −2 ) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO 3 + CO 3 ) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2 m Ca +2 < m HCO 3 - + 2 m CO 3 −2 ) carnotite saturation was not achieved. In systems open to CO 2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO 2 ranging from 10 −3.5 to 10 −2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO 2 equal to 10 −2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO 2 .

Texas↗
USGS2003

Helium isotope studies in the Mojave Desert, California: Implications for groundwater chronology and regional seismicity

We report helium isotope and concentration results for groundwaters from the western Mojave River Basin (MRB), 130 km east of Los Angeles, CA. The basin lies adjacent to the NW-SE trending San Andreas Fault (SAF) system. Samples were collected along two groundwater flowpaths that originate in the San Gabriel Mountains and discharge to the Mojave River located ???32 km to the northeast. Additional groundwater samples were collected from Mojave River Deposits underlying the Mojave River. The primary objective of this study is to identify and quantify crustal and mantle helium contributions to the regional groundwater system. A total of 27 groundwaters, sampled previously for chemistry and isotope systematics (including 14C activity) have measured helium concentrations that increase along flowpaths from 9.9??10-8 to 1.0??10-4 cm3 STP g-1 H2O. Concomitantly, 3He/4He ratios decrease from 0.84RA to 0.11RA (RA equals the 3He/4He ratio in air=1.4??10-6). We did not record 3He/4He ratios equivalent to crustal-production values (???0.02RA) in any sample. Dissolved helium concentrations were resolved into components associated with solubility equilibration, air entrainment, mantle-derivation, in-situ production within the aquifer, and extraneous crustal fluxes. All samples contained the first four components, but only older samples had the superimposed effects of helium derived from a crustal flux. The radiogenic He component has chronological significance, and good concordance between 4He and 14C ages for younger groundwaters (<25,000 year) demonstrates the integrity of the 4 He-chronometer in this setting. Helium-rich waters could also be dated with the 4He technique, but only by first isolating the whole crustal flux (3-10??10-6 cm3 STP cm-2 year-1). Mantle-derived 3He (3Hem) is present in all MRB samples irrespective of distance from the SAF. However, regional-aquifer groundwaters near the terminus of the flowpath have a significantly greater content of mantle-derived 3He in comparison with more modern samples. We propose that faults in the basin other than the SAF may be an additional source of mantle-derived helium. The large range in 3He m concentrations may be related to fault activity; however, groundwaters with lower and more constant 3Hem contents may indicate that seismic activity along the SAF has been relatively constant for the past 30,000 years, demonstrating that ancient groundwaters may serve as an archive for paleo-seismic events. ?? 2003 Elsevier B.V. All rights reserved. All rights reserved.

Chemical Geology↗
USGS2007

Isotopic characterization of three groundwater recharge sources and inferences for selected aquifers in the upper Klamath Basin of Oregon and California, USA

Stable isotope (??D and ??18O) signatures of three principal groundwater recharge areas in the 21,000-km2 upper Klamath Basin are used to infer recharge sources for aquifers in the interior parts of the basin. Two of the principal recharge areas, the Cascade Range on the western and southern margin of the basin and uplands along the eastern margin, are defined by mean annual precipitation that exceeds approximately 60 cm. A third recharge area coincides with the extensive irrigation canal system in the south central part of the basin. The stable isotope signature for Cascade Range groundwater falls near the global meteoric water line (GMWL). The stable isotope signature for the groundwater of the eastern basin uplands also falls near the GMWL, but is depleted in heavy isotopes relative to the Cascade Range groundwater. The stable isotope signature for water from the irrigation canal system deviates from the GMWL in a manner indicative of fractionation by evaporation. Groundwater provenance was previously unknown for two aquifers of interest: that supplying deep (225-792 m), large-capacity irrigation wells along the Oregon-California border, and that of the geothermal system near Klamath Falls. Groundwater produced by the deep irrigation wells along the Oregon-California border appears to be a mixture of eastern-basin groundwater and water with an evaporative isotopic signature. The component with an evaporative isotopic signature appears in some places to consist of infiltrated irrigation water. Chloride data suggest that much of the component with the evaporative isotopic signature may be coming from an adjacent subbasin. After accounting for the 18O shift common in geothermal waters, isotope data suggest that the geothermal groundwater in the upper Klamath Basin may emanate from the eastern basin uplands. Findings demonstrate that stable isotope and chloride data can illuminate certain details of a regional groundwater flow system in a complex geologic setting where other hydrologic data are ambiguous. ?? 2007 Elsevier B.V. All rights reserved.

Journal of Hydrology↗
USGS2011

Groundwater chemistry near an impoundment for produced water, Powder River Basin, Wyoming, USA

The Powder River Basin is one of the largest producers of coal-bed natural gas (CBNG) in the United States. An important environmental concern in the Basin is the fate of the large amounts of groundwater extracted during CBNG production. Most of this produced water is disposed of in unlined surface impoundments. A 6-year study of groundwater flow and water chemistry at one impoundment, Skewed Reservoir, has produced the most detailed data set for any impoundment in the Basin. Data were collected from a network of 21 observation wells and three suction lysimeters. A groundwater mound formed atop bedrock within initially unsaturated, unconsolidated deposits underlying the reservoir. Heterogeneity in physical and chemical properties of sediments resulted in complex groundwater flow paths and highly variable groundwater chemistry. Sulfate, bicarbonate, sodium, and magnesium were the dominant ions in all areas, but substantial variability existed in relative concentrations; pH varied from less than 3 to more than 9, and total dissolved solids concentrations ranged from less than 5000 to greater than 100,000 mg/L. Selenium was a useful tracer of reservoir water; selenium concentrations exceeded 300 μg/L in samples obtained from 18 of the 24 sampling points. Groundwater travel time from the reservoir to a nearby alluvial aquifer (a linear distance of 177 m) was calculated at 474 days on the basis of selenium concentrations. The produced water is not the primary source of solutes in the groundwater. Naturally occurring salts and minerals within the unsaturated zone, dissolved and mobilized by infiltrating impoundment water, account for most of the solute mass in groundwater. Gypsum dissolution, cation-exchange, and pyrite oxidation appear to be important reactions. The complex geochemistry and groundwater flow paths at the study site underscore the difficulty in assessing effects of surface impoundments on water resources within the Powder River Basin.

Wyoming↗
USGS2023

Thirty years of regional groundwater-quality trend studies in the United States: Major findings and lessons learned

Changes in groundwater quality have been evaluated for more than 2,200 wells in 25 Principal Aquifers in the United States based on repeated decadal sampling (once every 10 years) from 1988 to 2021. The purpose of this study is to identify contaminants with changing concentrations, the locations and magnitude of those changes, the factors driving those changes, the obstacles to interpreting the changes, and approaches to ameliorate those obstacles. Sampling was conducted in 89 networks of 20–30 wells each that represent various geographic regions, aquifer types and land use types. Each network, and the wells that comprise them, are sampled on a rotating basis once every 10 years. Of the 28 constituents evaluated for trends, concentrations of Na, Cl, dissolved solids, SO 4 , and NO 3 exhibited statistically significant increases at the network level more frequently than other constituents. Factors affecting trends in Cl and NO 3 are emphasized in this study. Regional patterns show large increases of Cl in urban areas in the Northeast and Midcontinent, where road-deicing salt application rates are 10 to 100 times greater than in other regions of the country, and in semiarid and arid regions of the western United States, where evaporation concentrates solutes in recharge. The largest increases in NO 3 were in agricultural areas of the semiarid west, arid west and Pacific regions which are characterized by oxic groundwater, long-term increases in nitrogen fertilizer usage, and high rates of irrigation. However, finding a direct relation between increasing contaminant sources and corresponding groundwater quality response, particularly when sampling once every 10 years, can be complicated by factors such as uncertainty in the timing, mass, and location of contaminant sources, groundwater residence time (recharge date), geochemical conditions in the aquifer that affect contaminant transport, and variability in water quality due to climatic factors such as seasonality and hydrologic conditions. Understanding groundwater residence time allows the changes in groundwater quality to be evaluated in the context of recharge date rather than the sample date. Likewise, information on geochemical characteristics of the aquifer can be helpful for understanding relations between contaminant source inputs and groundwater concentrations. For example, oxic geochemical conditions in the aquifer may allow for conservative transport and accumulation of NO 3 in groundwater, whereas reducing environments could favor NO 3 degradation. Differences in hydrologic conditions (wetter or drier than average) on the date of sampling could impact the statistical results of sampling at decadal intervals and obscure long-term patterns. Samples collected under substantially different hydrologic conditions can be identified, and high-frequency sampling can improve interpretation of measured results in these cases. Although decadal sampling and associated water-quality interpretations have limitations, repeated, scheduled sampling of thousands of wells over multiple decades has great value for identifying and understanding long-term, regional groundwater-quality trends. Despite these limitations, the concepts presented herein provide options that could be used to interpret trends or changes when sampling over longer timespans, which is less common than trend networks with higher frequency sampling intervals.

Conterminous United States↗
USGS2016

Controls on selenium distribution and mobilization in an irrigated shallow groundwater system underlain by Mancos Shale, Uncompahgre River Basin, Colorado, USA

Elevated selenium (Se) concentrations in surface water and groundwater have become a concern in areas of the Western United States due to the deleterious effects of Se on aquatic ecosystems. Elevated Se concentrations are most prevalent in irrigated alluvial valleys underlain by Se-bearing marine shales where Se can be leached from geologic materials into the shallow groundwater and surface water systems. This study presents groundwater chemistry and solid-phase geochemical data from the Uncompahgre River Basin in Western Colorado, an irrigated alluvial landscape underlain by Se-rich Cretaceous marine shale. We analyzed Se species, major and trace elements, and stable nitrogen and oxygen isotopes of nitrate in groundwater and aquifer sediments to examine processes governing selenium release and transport in the shallow groundwater system. Groundwater Se concentrations ranged from below detection limit (< 0.5 μg L − 1 ) to 4070 μg L − 1 , and primarily are controlled by high groundwater nitrate concentrations that maintain oxidizing conditions in the aquifer despite low dissolved oxygen concentrations. High nitrate concentrations in non-irrigated soils and nitrate isotopes indicate nitrate is largely derived from natural sources in the Mancos Shale and alluvial material. Thus, in contrast to areas that receive substantial NO 3 inputs through inorganic fertilizer application, Se mitigation efforts that involve limiting NO 3 application might have little impact on groundwater Se concentrations in the study area. Soluble salts are the primary source of Se to the groundwater system in the study area at-present, but they constitute a small percentage of the total Se content of core material. Sequential extraction results indicate insoluble Se is likely composed of reduced Se in recalcitrant organic matter or discrete selenide phases. Oxidation of reduced Se species that constitute the majority of the Se pool in the study area could be a potential source of Se in the future as soluble salts are progressively depleted.

Colorado↗
USGS2016

Pre/post-closure assessment of groundwater pharmaceutical fate in a wastewater‑facility-impacted stream reach

Pharmaceutical contamination of contiguous groundwater is a substantial concern in wastewater-impacted streams, due to ubiquity in effluent, high aqueous mobility, designed bioactivity, and to effluent-driven hydraulic gradients. Wastewater treatment facility (WWTF) closures are rare environmental remediation events; offering unique insights into contaminant persistence, long-term wastewater impacts, and ecosystem recovery processes. The USGS conducted a combined pre/post-closure groundwater assessment adjacent to an effluent-impacted reach of Fourmile Creek, Ankeny, Iowa, USA. Higher surface-water concentrations, consistent surface-water to groundwater concentration gradients, and sustained groundwater detections tens of meters from the stream bank demonstrated the importance of WWTF effluent as the source of groundwater pharmaceuticals as well as the persistence of these contaminants under effluent-driven, pre-closure conditions. The number of analytes (110 total) detected in surface water decreased from 69 prior to closure down to 8 in the first post-closure sampling event approximately 30 d later, with a corresponding 2 order of magnitude decrease in the cumulative concentration of detected analytes. Post-closure cumulative concentrations of detected analytes were approximately 5 times higher in proximal groundwater than in surface water. About 40% of the 21 contaminants detected in a downstream groundwater transect immediately before WWTF closure exhibited rapid attenuation with estimated half-lives on the order of a few days; however, a comparable number exhibited no consistent attenuation during the year-long post-closure assessment. The results demonstrate the potential for effluent-impacted shallow groundwater systems to accumulate pharmaceutical contaminants and serve as long-term residual sources, further increasing the risk of adverse ecological effects in groundwater and the near-stream ecosystem.

Iowa↗
USGS2020

Poultry litter as potential source of pathogens and other contaminants in groundwater and surface water proximal to large-scale confined poultry feeding operations

Manure from livestock production has been associated with the contamination of water resources. To date, research has primarily focused on runoff of these contaminants from animal operations into surface water, and the introduction of poultry-derived pathogenic zoonoses and other contaminants into groundwater is under-investigated. We characterized pathogens and other microbial and chemical contaminants in poultry litter, groundwater, and surface water near confined poultry feeding operations (chicken layer, turkey) at 9 locations in Iowa and one in Wisconsin from May and June 2016. Results indicate that poultry litter from large-scale poultry confined feeding operations is a likely source of environmental contamination and that groundwater is also susceptible to such poultry-derived contamination. Poultry litter, groundwater, and surface water samples had detections of viable bacteria growth (Salmonella spp., enterococci, staphylococci, lactobacilli), multi-drug resistant Salmonella DT104 flost and int genes, F+ RNA coliphage (group I and IV), antibiotic resistance genes (ARGs; blaDHA, blaOXA-48, blaTEM, blaCMY-2, tetM), phytoestrogens (biochanin A, daidzein, formononetin), and a progestin (progesterone). In addition, mcr-1 (a colistin ARG), was detected in a groundwater sample and in another groundwater sample, antibiotic resistant isolates were positive for Brevibacterium spp., a potential signature of poultry in the environment. Detectable estrogenicity was not measured in poultry litter, but was observed in 67% of the surface water samples and 22% were above the U.S. Environmental Protection Agency trigger level of 1 ng/L. The transport of microbial pathogens to groundwater was significantly greater (p < 0.001) than the transport of trace organic contaminants to groundwater in this study. In addition to viable pathogens, several clinically important ARGs were detected in litter, groundwater, and surface water, highlighting the need for additional research on sources of these contaminants in livestock dominated areas.

Iowa, Wisconsin↗
USGS2005

An evaluation of effects of groundwater exchange on nearshore habitats and water quality of western Lake Erie

Historically, the high potentiometric surface of groundwater in the Silurian/Devonian carbonate aquifer in Monroe County, MI resulted in discharge of highly mineralized, SO 4 -rich groundwater to the Lake Erie shoreline near both Erie State Game Area (ESGA) and Pointe Mouillee State Game Area (PMSGA). Recently, regional groundwater levels near PMSGA have been drawn down as much as 45 m below lake level in apparent response to quarry dewatering. From August to November of 2003, we conducted preliminary studies of groundwater flow dynamics and chemistry, shallow lake water chemistry, and fish and invertebrate communities at both sites. Consistent with regional observations, groundwater flow direction in the nearshore at ESGA was upward, or toward Lake Erie, and shallow nearshore groundwater chemistry was influenced by regional groundwater chemistry. In contrast, at PMSGA, the groundwater flow potential was downward and lake water, influenced by quarry discharge seeping downward into nearshore sediments, produced a different lake and shallow groundwater chemistry than at ESGA. Although the invertebrate and young fish community was similar at the two sites, taxonomic groups tolerant of degraded water quality were more prevalent at PMSGA. Sensitive taxa were more prevalent at ESGA. We propose a conceptual model, based on well-described models of groundwater/seawater interaction along coastal margins, to describe the interconnection among geologic, hydrologic, chemical, and biological processes in the different nearshore habitats of Lake Erie, and we identify processes that warrant further detailed study in the Great Lakes.

Lake Erie↗
USGS2023

Uptake of per- and polyfluoroalkyl substances by fish, mussel, and passive samplers in mobile laboratory exposures using groundwater from a contamination plume at a historical fire training area, Cape Cod, Massachusetts

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L –1 in reference groundwater and 6100 to 15,000 ng L –1 in contaminated groundwater. Biotic concentration factors (CF b ) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg –1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CF b generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CF b between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CF b = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CF b , and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Massachusetts↗
USGS2012

Assessing California groundwater susceptibility using trace concentrations of halogenated volatile organic compounds

Twenty-four halogenated volatile organic compounds (hVOCs) and SF 6 were measured in groundwater samples collected from 312 wells across California at concentrations as low as 10 –12 grams per kilogram groundwater. The hVOCs detected are predominately anthropogenic (i.e., “ahVOCs”) and as such their distribution delineates where groundwaters are impacted and susceptible to human activity. ahVOC detections were broadly consistent with air-saturated water concentrations in equilibrium with a combination of industrial-era global and regional hVOC atmospheric abundances. However, detection of ahVOCs in nearly all of the samples collected, including ancient groundwaters, suggests the presence of a sampling or analytical artifact that confounds interpretation of the very-low concentration ahVOC data. To increase our confidence in ahVOC detections we establish screening levels based on ahVOC concentrations in deep wells drawing ancient groundwater in Owens Valley. Concentrations of ahVOCs below the Owens Valley screening levels account for a large number of the detections in prenuclear groundwater across California without significant loss of ahVOC detections in shallow, recently recharged groundwaters. Over 80% of the groundwaters in this study contain at least one ahVOC after screening, indicating that the footprint of human industry is nearly ubiquitous and that most California groundwaters are vulnerable to contamination from land-surface activities.

California↗
USGS1997

The urban atmosphere as a non-point source for the transport of MTBE and other volatile organic compounds (VOCS) to shallow groundwater

Infiltration and dispersion (including molecular diffusion) can transport volatile organic compounds (VOCs) from urban air into shallow groundwater. The gasoline additive methyl- tert -butyl ether (MTBE) is of special interest because of its (1) current levels in some urban air, (2) strong partitioning from air into water, (3) resistance to degradation, (4) use as an octane-booster since the 1970s, (5) rapidly increasing use in the 1990s to reduce CO and O 3 in urban air, and (6) its frequent detection at low microgram per liter levels in shallow urban groundwater in Denver, New England, and elsewhere. Numerical simulations were conducted using a 1-D model domain set in medium sand (depth to water table = 5 m) to provide a test of whether MTBE and other atmospheric VOCs could move to shallow groundwater within the 10−15 y time frame over which MTBE has now been used in large amounts. Degradation and sorption were assumed negligible. In case 1 (no infiltration, steady atmospheric source), 10 y was not long enough to permit significant VOC movement by diffusion into shallow groundwater. Case 2 considered a steady atmospheric source plus 36 cm/y of net infiltration; groundwater at 2 m below the water table became nearly saturated with atmospheric levels of VOC within 5 y. Case 3 was similar to case 2, but considered the source to be seasonal, being “on” for only 5 of 12 months each year, as with the use of MTBE during the winter fuel-oxygenate season; groundwater at 2 m below the water table became equilibrated with 5 / 12 of the “source-on” concentration within 5 y. Cases 4 and 5 added an evapotranspiration (ET) loss of 36 cm/y, resulting in no net recharge. Case 4 took the ET from the surface, and case 5 took the ET from the capillary fringe at a depth of 3.5 m. Net VOC mass transfer to shallow groundwater after 5 y was less for both cases 4 and 5 than for case 3. However, it was significantly greater for cases 4 and 5 than for case 1, even though cases 1, 4, and 5 were all no-net recharge cases. The mechanism responsible for this effect was the dispersion acting on each downward infiltration event, and also on the ET-induced flow. The ability of MTBE to reach groundwater in cases 2−5 is taken as evidence of the potential importance of urban air as a non-point source for VOCs in shallow urban groundwater. Two subcases were run for both case 4 and case 5: subcase a (water and VOCs move with ET) and subcase b (water only moves with ET).

Environmental Science & Technology↗
USGS2000

Carbonate ions and arsenic dissolution by groundwater

Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.Samples of Marshall Sandstone, a major source of groundwater with elevated arsenic levels in southeast Michigan, were exposed to bicarbonate ion under controlled chemical conditions. In particular, effects of pH and redox conditions on arsenic release were evaluated. The release of arsenic from the aquifer rock was strongly related to the bicarbonate concentration in the leaching solution. The results obtained suggest that the carbonation of arsenic sulfide minerals, including orpiment (As2S3) and realgar (As2S2), is an important process in leaching arsenic into groundwater under anaerobic conditions. The arseno-carbonate complexes formed, believed to be As(CO3)2-, As(CO3)(OH)2-, and AsCO3+, are stable in groundwater. The reaction of ferrous ion with the thioarsenite from carbonation process can result in the formation of arsenopyrite which is a common mineral in arsenic-rich aquifers.The role of bicarbonate in leaching arsenic into groundwater was investigated by conducting batch experiments using core samples of Marshall Sandstone from southeast Michigan and different bicarbonate solutions. The effects of pH and redox conditions on As dissolution were examined. Results showed that As was not leached significantly out of the Marshall Sandstone samples after 3 d using either deionized water or groundwater, but As was leached efficiently by sodium bicarbonate, potassium bicarbonate, and ferric chloride solutions. The leaching rate with sodium bicarbonate was about 25% higher than that with potassium bicarbonate. The data indicated that bicarbonate ion was involved primarily in As dissolution and that hydroxyl radical ion did not affect As dissolution to any significant degree. The amount of As leached was dependent upon the sodium bicarbonate concentration, increasing with reaction time for each concentration. Significant As leaching was found in the extreme pH ranges of <1.9 and 8.0-10.4. The resulting arseno-carbonate complexes formed were stable in groundwater.

Environmental Science & Technology↗
USGS2000

Mechanism and rate of denitrification in an agricultural watershed: Electron and mass balance along groundwater flow paths

The rate and mechanism of nitrate removal along and between groundwater flow paths were investigated using a series of well nests screened in an unconfined sand and gravel aquifer. Intensive agricultural activity in this area has resulted in nitrate concentrations in groundwater often exceeding drinking water standards. Both the extent and rate of denitrification varied depending on the groundwater flow path. While little or no denitrification occurred in much of the upland portions of the aquifer, a gradual redox gradient is observed as aerobic upland groundwater moves deeper in the aquifer. In contrast, a sharp shallow redox gradient is observed adjacent to a third‐order stream as aerobic groundwater enters reduced sediments. An essentially complete loss of nitrate concurrent with increases in excess N 2 provide evidence that denitrification occurs as groundwater enters this zone. Electron and mass balance calculations suggest that iron sulfide (e.g., pyrite) oxidation is the primary source of electrons for denitrification. Denitrification rate estimates were based on mass balance calculations using nitrate and excess N 2 coupled with groundwater travel times. Travel times were determined using a groundwater flow model and were constrained by chlorofluorocarbon‐based age dates. Denitrification rates were found to vary considerably between the two areas where denitrification occurs. Denitrification rates in the deep, upland portions of the aquifer were found to range from <0.01 to 0.14 m M of N per year; rates at the redoxcline along the shallow flow path range from 1.0 to 2.7 m M of N per year. Potential denitrification rates in groundwater adjacent to the stream may be much faster, with rates up to 140 m M per year based on an in situ experiment conducted in this zone.

Water Resources Research↗
USGS2010

Emergency use of groundwater as a backup supply: Quantifying hydraulic impacts and economic benefits

Groundwater can play an important role in water‐supply emergency planning. A framework is presented for assessing the hydraulic impacts and associated costs of using groundwater as a backup supply when imported‐water deliveries are disrupted, and for quantifying the emergency benefits of groundwater management strategies that enable better response to such disruptions. Response functions are derived, which relate additional groundwater pumpage during water‐supply emergencies to impacts such as increased pumping costs, subsidence, and seawater intrusion. Monte Carlo analysis is employed to estimate the incremental costs of using groundwater as a backup supply. The emergency benefits of alternative groundwater management strategies are computed for different expected durations of imported water disruption, percentages of imported water replaced by groundwater, and threshold drawdowns for subsidence impacts. The methodology is applied to the coastal Los Angeles Basin. For this case study, emergency benefits of artificial recharge strategies are dominated by reduction of potential subsidence costs. The variance of the results also is primarily due to subsidence effects. Incorporation of probability distributions reflecting a larger expected use of groundwater during the imported‐water disruption results in higher estimated emergency benefits of artificial recharge strategies. The framework presented for quantifying incremental costs and economic benefits of using groundwater as a backup supply could be applied to a broad range of water emergency planning decisions.

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