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The strontium (Sr) concentration and 87Sr/86Sr ratios in leachates extracted from Upper Permian (Wuchiapingian) coals from the Tianjia Mine, Chongqing, southwestern China, were investigated using a selective leaching sequential extraction technique including deionized water, dilute HCl, and a mixture of HF and HNO3. The results show that the Sr concentrations in water-leachates (mean value of 12.9 ppm) and HCl-leachates (78.4 ppm) are lower than HF/HNO3-leachates (131 ppm). The water-leachates had more radiogenic (0.707182–0.707642) 87Sr/86Sr ratios than HCl-leachates (0.707111–0.707609), while the 87Sr/86Sr ratios in the HF/HNO3-leachates had a wide range (0.706972–0.707807), and the highest 87Sr/86Sr ratios. These variations in Sr concentration and 87Sr/86Sr ratios are most likely related to the differential solubility of the different Sr-bearing minerals in the coals, in addition to the Sr associated directly with the organic components of the coals. While the Sr/Ca ratios of the HCl-leachates (median=11.3 mmole/mole) were similar to the ratio of marine carbonate dissolution, the 87Sr/86Sr values in the HCl-leachates were higher than the expected 87Sr/86Sr range of the contemporaneous seawater (0.70700–0.70725) recorded in the Wuchiapingian marine carbonate rocks. This indicates that the carbonate minerals in the coals are not of a syngenetic marine origin, despite the indications that the coal seams were influenced by seawater. The textural properties of the cell and fracture-filling carbonate minerals provide evidence that the carbonate minerals in the Tianjia coals are of late diagenetic or epigenetic origin. The combination of isotopic evolution trends of the coal seam, the petrological characteristics (high vitrinite reflectance and bireflectance) and mineralogical assemblage of NH4-illite-paragonite and kaolinite-paragonite as well as authigenic minerals such as calcite, ferroan dolomite, chamosite, quartz, anatase, and florencite suggests that the Tianjia coals was likely affected by diagenetic processes such as sediment dewatering with increasing burial depth (i.e., upward migration of pore fluids from the mudstones interbedded with the coal seams). These conclusions agree with the regional geological history marked by large-scale uplift and denudation of the crust following regional tectonic evolution (i.e., Dongwu Movement, 258–260.5 Ma).

Elevated concentrations of toxic elements in coal ash pose human and ecological health risks upon release to the environment. Despite wide public concerns about water quality and human health risks from catastrophic coal ash spills and chronic leaking of coal ash ponds, coal ash disposal has only been partially regulated, and its impacts on aquatic sediment quality and ecological health have been overlooked. Here, we present a multiproxy approach of morphologic, magnetic, geochemical, and Sr isotopic analyses, revealing unmonitored coal ash releases over the past 40 to 70 years preserved in the sediment records of five freshwater lakes adjacent to coal-fired power plants across North Carolina. We detected significant sediment contamination and potential chronic ecological risks posed by the occurrence of hundreds of thousands of tons of coal ash solids mainly resulting from high-magnitude stormwater runoff/flooding and direct effluent discharge from coal ash disposal sites. The proximity of hundreds of disposal sites to natural waterways across the U.S. implies that such contamination is likely prevalent nationwide and expected to worsen with climate change.

Coal combustion residuals (CCRs), in particular, coal fly ash, are one of the major industrial solid wastes in the U.S., and due to their high concentrations of toxic elements, they could pose environmental and human health risks. Yet detecting coal fly ash in the environment is challenging given its small particle size. Here, we explore the utility and sensitivity of using geochemical indicators (trace elements, Ra nuclides, and Pb stable isotopes), combined with physical observation by optical point counting, for detecting the presence of trace levels of coal fly ash particles in surface soils near two coal-fired power plants in North Carolina and Tennessee. Through experimental work, mixing models, and field data, we show that trace elements can serve as a first-order detection tool for fly ash presence in surface soils; however, the accuracy and sensitivity of detection is limited for cases with low fly ash proportion (i.e.

Installation of rooftop photovoltaic (PV) solar is expected to change the electricity landscape in the U.S. through reducing greenhouse gas emissions and mitigating global warming, as well as eliminating environmental impacts from fossil fuels utilization. Given the high-water intensity of fossil fuels, nuclear, and hydropower, the transition to solar and wind energy has important implications for also reducing the water footprint of energy production. This study evaluates the reductions in the water footprint from the electricity sector at the statewide and household scales in the contiguous U.S., as well as the expected virtual water footprint of individual homes upon switching to rooftop PV solar. Through integration of the water consumption intensity of the different energy sources that contribute to the current grid electricity, the annual residential electricity consumption, and the number of households, we have established a baseline for the variations of current statewide and household water consumption in the contiguous 48 states. The average nationwide water consumption of the residential sector from the current grid electricity is estimated as 9.84 × 10

Shale gas wastewater (SGW) disposal is a major challenge in the areas in central China due to its increasing volume associated with intensification of shale gas exploration and its high levels of contaminants. In the Fuling shale gas field of Sichuan Basin, a small amount of SGW originated from the flowback and produced water (FPW) is treated and then discharged to a local stream. This study investigated the inorganic water geochemistry and Sr isotopic composition of the FPW in Fuling shale gas field, the SGW effluent that is generated in the treatment facility, and the quality of a local river after the disposal of treated SGW. The data generated in this study reveals that FPW generate after several years of shale gas operation maintain the original geochemical fingerprints detected in early stages of FPW generation, and consistent with the FPW composition detected in other shale gas fields in Sichuan Basin. We show that reuse of saline FPW for hydraulic fracturing can generate an inverse salinity trend, where the salinity of FPW decreases with time, reflecting the increase of the contribution of formation water with lower salinity. The treatment of the FPW results in ~40 % reduction of the salts by dilution with freshwater and selective (80-90 %) removal of some of the inorganic contaminants. The original geochemical fingerprints of the FPW from Fuling shale gas field was not modified during FPW treatment, reinforcing the applicability of these tracers for detecting SGW in the environment. Discharge of treated SGW effluent to a local river causes a major 200-fold dilution and reduction of all contaminants levels below drinking water and ecological standards. Overall, this study emphasizes the importance of water quality monitoring of treated SGW and the overall measures needed to protect public health and the environment in areas of shale gas development.

Reuse of oilfield‐produced water (OPW) for crop irrigation has the potential to make a critical difference in the water budgets of highly productive but drought‐stressed agricultural watersheds. This is the first peer‐reviewed study to evaluate how trace metals in OPW used to irrigate California crops may affect human health. We modeled and quantified risks associated with consuming foods irrigated with OPW using available concentration data. The probabilistic risk assessment simulated OPW metal concentrations, crop uptake, human exposures, and potential noncancer and carcinogenic health effects. Overall, our findings indicate that there is a low risk of ingesting toxic amounts of metals from the consumption of tree nuts, citrus, grapes, and root vegetables irrigated with low‐saline OPW. Results show increased arsenic cancer risk (at 10−6) for adult vegetarians, assuming higher consumption of multiple foods irrigated with OPW that contain high arsenic concentrations. All other cancer risks are below levels of concern and all noncancer hazards are far below levels of concern. Arsenic risk concerns could be mitigated by practices such as blending high‐arsenic OPW. Future risk assessment research should model the risks of organic compounds in OPW, as our study focused on inorganic compounds. Nevertheless, our findings indicate that low‐saline OPW may provide a safe and sustainable alternative irrigation water source if water quality is adequately monitored and blended as needed prior to irrigation.

Hexavalent chromium (Cr(VI)) is known to occur naturally in shallow oxic groundwater, typically from aquifers associated with mafic and ultramafic formations, but information on the occurrence of Cr(VI) in deep groundwater from large sedimentary basins is limited. This study shows that groundwater from the Baiyangdian Lake Basin (BYB), home to the future second capital city of China, had high Cr concentration (10 μg/L, up to 86 μg/L) in the deep aquifer (150 m), while shallow groundwater had lower Cr concentration (10 μg/L). Chromium occurred predominantly as Cr(VI) (95%). Shallow groundwater was characterized by higher Mn and Fe concentrations relative to deep groundwater, likely indicating more reducing conditions. Sequential extraction experiments from aquifer sediments suggest that Cr(VI) may derive from silicate weathering and that Mn oxides in the aquifer play a major role in the formation of Cr(VI) in groundwater. Inverse correlations between Mn and Cr(VI) suggest that reductive dissolution of Mn oxides constrains Cr(VI) mobilization in the shallow groundwater, while oxic-suboxic conditions in the deep aquifer limit Mn solubility, which enhances oxidation of Cr(III) to Cr(VI) and promotes desorption of Cr(VI) under alkaline conditions. This study demonstrates the potential geogenic occurrence of high Cr(VI) concentration in deep groundwater from a nonmafic, large sedimentary basin containing Mn oxides in the aquifer sediments.

High concentrations of metal(loid)s in phosphate rocks and wastewater associated with phosphate mining and fertilizer production operations pose potential contamination risks to water resources. Here, we propose using Sr isotopes as a tracer to determine possible water quality impacts induced from phosphate mining and fertilizers production. We utilized a regional case study in the northeastern Negev in Israel, where salinization of groundwater and a spring have been attributed to historic leaking and contamination from an upstream phosphate mining wastewater. This study presents a comprehensive dataset of major and trace elements, combined with Sr isotope analyses of the Rotem phosphate rocks, local aquifer carbonate rocks, wastewater from phosphate operation in Mishor Rotem Industries, saline groundwater suspected to be impacted by Rotem mining activities, and two types of background groundwater from the local Judea Group aquifer. The results of this study indicate that trace elements that are enriched in phosphate wastewater were ubiquitously present in the regional and non-contaminated groundwater at the same levels as detected in the impacted waters, and thus cannot be explicitly linked to the phosphate wastewater. The

Anthropogenic lead (Pb) in soils poses risks to human health, particularly to the neuropsychological development of exposed children. Delineating the sources and potential bioavailability of soil Pb, as well as its relationship with other contaminants is critical in mitigating potential human exposure. Here, we present an integrative geochemical analysis of total elemental concentrations, radionuclides of 137Cs and 210Pb, Pb isotopic compositions, and in vitro bioaccessibility of Pb in surface soils sampled from different locations near Durham, North Carolina. Elevated Pb (>400 mg/kg) was commonly observed in soils from urban areas (i.e., near residential house foundation and along urban streets), which co-occurred with other potentially toxic metal(loids) such as Zn, Cd, and Sb. In contrast, soils from city parks and suburban areas had systematically lower concentrations of metal(loids) that were comparable to geological background. The activities of 137Cs and excess 210Pb, coupled with their correlations with Pb and co-occurring metal(loids) were used to indicate the persistence and remobilization of historical atmospherically deposited contaminants. Coupled with total Pb concentrations, the soil Pb isotopic compositions further indicated that house foundation soils had significant input of legacy lead-based paint (mean = 1.1895 and 2.0618 for 206Pb/207Pb and 208Pb/206Pb, respectively), whereas urban streetside soils exhibited a clear mixed origin, dominantly of legacy leaded gasoline (1.2034 and 2.0416) and atmospheric deposition (1.2004–1.2055 and 2.0484–2.0525). The in vitro bioaccessibility of Pb in contaminated urban soils furthermore revealed that more than half of Pb in the contaminated soils was potentially bioavailable, whose Pb isotope ratios were identical to that of bulk soils, demonstrating the utility of using Pb isotopes for tracking human exposure to anthropogenic Pb in soils and house dust. Overall, this study demonstrated a holistic assessment for comprehensively understanding anthropogenic Pb in urban soils, including its co-occurrence with other toxic contaminants, dominant sources, and potential bioavailability upon human exposure.

Lead (Pb) isotopes have been widely used to delineate Pb pollutants in the environment. Here, we present, for the first time, a systematic analysis of Pb isotopes in coal fly ash derived from coals...

Northwest India suffers from severe water scarcity issues due to a combination of over-exploitation and climate effects. Along with concerns over water availability, endemic water quality issues are critical and affect the usability of available water and potential human health risks. Here we present data from 243 groundwater wells, representing nine aquifer lithologies in 4 climate regions that were collected from the Northwestern Indian state of Rajasthan. Rajasthan is India's largest state by area, and has a significant groundwater reliant population due to a general lack of surface water accessibility. We show that the groundwater, including water that is used for drinking without any treatment, contains multiple inorganic contaminants in levels that exceed both Indian and World Health Organization (WHO) drinking water guidelines. The most egregious of these violations were for fluoride, nitrate, and uranium; 76% of all water samples in this study had contaminants levels that exceed the WHO guidelines for at least one of these species. In addition, we show that much of the groundwater contains high concentrations of dissolved organic carbon (DOC) and halides, both of which are risk factors for the formation of disinfectant byproducts in waters that are treated with chemical disinfectants such as chlorine. By using geochemical and isotopic (oxygen, hydrogen, carbon, strontium, and boron isotopes) data, we show that the water quality issues derive from both geogenic (evapotranspiration, water-rock interactions) and anthropogenic (agriculture, domestic sewage) sources, though in some cases anthropogenic activities, such as infiltration of organic- and nitrate-rich water, may contribute to the persistence and enhanced mobilization of geogenic contaminants. The processes affecting Rajasthan's groundwater quality are common in many other worldwide arid areas, and the lessons learned from evaluation of the mechanisms that affect the groundwater quality are universal and should be applied for other parts of the world.

This critical review presents the key factors that control the occurrence of natural elements from the uranium- and thorium decay series, also known as naturally occurring radioactive materials (NORM), including uranium, radium, radon, lead, polonium, and their isotopes in groundwater resources. Given their toxicity and radiation, elevated levels of these nuclides in drinking water pose human health risks, and therefore understanding the occurrence, sources, and factors that control the mobilization of these nuclides from aquifer rocks is critical for better groundwater management and human health protection. The concentrations of these nuclides in groundwater are a function of the groundwater residence time relative to the decay rates of the nuclides, as well as the net balance between nuclide mobilization (dissolution, desorption, recoil) and retention (adsorption, precipitation). This paper explores the factors that control this balance, including the relationships between nuclide chemistry (e.g., solubility and speciation), lithological and hydrogeological factors, groundwater geochemistry (e.g., redox state, pH, ionic strength, ion-pairs availability), and their combined effects and interactions. The various chemical properties of each of the nuclides results in different likelihoods for co-occurrence. For example, the primordial 238U, 222Rn, and, in cases of high colloid concentrations also 210Po, are all more likely to be found in oxic groundwater. In contrast, in reducing aquifers, Ra nuclides, 210Pb, and in absence of high colloid concentrations, 210Po, are more mobile and frequently occur in groundwater. In highly permeable sandstone aquifers that lack sufficient adsorption sites, Ra is often enriched, even in low salinity and oxic groundwater. This paper also highlights the isotope distributions, including those of relatively long-lived nuclides (238U/235U) with abundances that depend on geochemical conditions (e.g., fractionation induced from redox processes), as well as shorter-lived nuclides (234U/238U, 228Ra/226Ra, 224Ra/228Ra, 210Pb/222Rn, 210Po/210Pb) that are strongly influenced by decay-related (recoil), lithological, and geochemical factors. Special attention is paid in evaluating the ability to use these isotope variations to elucidate the sources of these nuclides in groundwater, mechanisms of their mobilization from the rock matrix (e.g., recoil, ion-exchange), and retention into secondary mineral phases and ion-exchange sites.

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The rise of hydraulic fracturing and unconventional oil and gas (UOG) exploration in the United States has increased public concerns for water contamination induced from hydraulic fracturing fluids and associated wastewater spills. Herein, we collected surface and groundwater samples across Garfield County, Colorado, a drilling-dense region, and measured endocrine bioactivities, geochemical tracers of UOG wastewater, UOG-related organic contaminants in surface water, and evaluated UOG drilling production (weighted well scores, nearby well count, reported spills) surrounding sites. Elevated antagonist activities for the estrogen, androgen, progesterone, and glucocorticoid receptors were detected in surface water and associated with nearby shale gas well counts and density. The elevated endocrine activities were observed in surface water associated with medium and high UOG production (weighted UOG well score-based groups). These bioactivities were generally not associated with reported spills nearby, and often did not exhibit geochemical profiles associated with UOG wastewater from this region. Our results suggest the potential for releases of low-saline hydraulic fracturing fluids or chemicals used in other aspects of UOG production, similar to the chemistry of the local water, and dissimilar from defined spills of post-injection wastewater. Notably, water collected from certain medium and high UOG production sites exhibited bioactivities well above the levels known to impact the health of aquatic organisms, suggesting that further research to assess potential endocrine activities of UOG operations is warranted.

Accurate and precise analyses of oil and gas (O&G) wastewaters and solids (e.g., sediments and sludge) are important for the regulatory monitoring of O&G development and tracing potential O&G contamination in the environment. In this study, 15 laboratories participated in an inter-laboratory comparison on the chemical characterization of three O&G wastewaters from the Appalachian Basin and four solids impacted by O&G development, with the goal of evaluating the quality of data and the accuracy of measurements for various analytes of concern. Using a variety of different methods, analytes in the wastewaters with high concentrations (i.e., >5 mg L−1) were easily detectable with relatively high accuracy, often within ±10% of the most probable value (MPV). In contrast, often less than 7 of the 15 labs were able to report detectable trace metal(loid) concentrations (i.e., Cr, Ni, Cu, Zn, As, and Pb) with accuracies of approximately ±40%. Despite most labs using inductively coupled plasma mass spectrometry (ICP-MS) with low instrument detection capabilities for trace metal analyses, large dilution factors during sample preparation and low trace metal concentrations in the wastewaters limited the number of quantifiable determinations and likely influenced analytical accuracy. In contrast, all the labs measuring Ra in the wastewaters were able to report detectable concentrations using a variety of methods including gamma spectroscopy and wet chemical approaches following Environmental Protection Agency (EPA) standard methods. However, the reported radium activities were often greater than ±30% different to the MPV possibly due to calibration inconsistencies among labs, radon leakage, or failing to correct for self-attenuation. Reported radium activities in solid materials had less variability (±20% from MPV) but accuracy could likely be improved by using certified radium standards and accounting for self-attenuation that results from matrix interferences or a density difference between the calibration standard and the unknown sample. This inter-laboratory comparison illustrates that numerous methods can be used to measure major cation, minor cation, and anion concentrations in O&G wastewaters with relatively high accuracy while trace metal(loid) and radioactivity analyses in liquids may often be over ±20% different from the MPV.

The consecutive occurrence of drought and reduction in natural water availability over the past several decades requires searching for alternative water sources for the agriculture sector in California. One alternative source to supplement natural waters is oilfield produced water (OPW) generated from oilfields adjacent to agricultural areas. For over 25 years, OPW has been blended with surface water and used for irrigation in the Cawelo Water District of Kern County, as permitted by California Water Board policy. This study aims to evaluate the potential environmental impact, soil quality, and crop health risks of this policy. We examined a large spectrum of salts, metals, radionuclides (226Ra and 228Ra), and dissolved organic carbon (DOC) in OPW, blended OPW used for irrigation, groundwater, and soils irrigated by the three different water sources. We found that all studied water quality parameters in the blended OPW were below current California irrigation quality guidelines. Yet, soils irrigated by blended OPW showed higher salts and boron relative to soils irrigated by groundwater, implying long-term salts and boron accumulation. We did not, however, find systematic differences in 226Ra and 228Ra activities and DOC in soils irrigated by blended or unblended OPW relative to groundwater-irrigated soils. Based on a comparison of measured parameters, we conclude that the blended low-saline OPW used in the Cawelo Water District of California is of comparable quality to the local groundwater in the region. Nonetheless, the salt and boron soil accumulation can pose long-term risks to soil sodification, groundwater salinization, and plant health; as such, the use of low-saline OPW for irrigation use in California will require continual blending with fresh water and planting of boron-tolerant crops to avoid boron toxicity.

The co-occurrence of contaminants in drinking water may pose enhanced risks to health beyond the effects of single contaminants. Here, we investigated the co-occurrence of four health-relevant redox-sensitive elements (U, As, V, and Cr) in 1494 groundwater wells across North Carolina. The highest concentrations of these elements were measured mostly in groundwater from fractured igneous and metamorphic formations throughout the Piedmont region. Arsenic occurred most frequently in suboxic to mixed redox character groundwater, whereas U, V, and Cr occurred mostly in oxic groundwater. Occurrences of As, and to a lesser extent U, increased with pH, likely reflecting desorption, while higher Cr and V levels were measured in near-neutral pH and oxic groundwater, reflecting greater sensitivity to redox conditions. Due to similar geochemistry, V and Cr co-occurred most frequently. Concentrations of V and Cr(VI) co-exceeded health recommendations from the NC Department of Health and Human Services in up to 84% of wells from the King's Mountain Belt and the Charlotte and Milton Belts of the Piedmont region. This study highlights the large gap between health recommendations and enforceable regulations and demonstrates a degree of co-occurrence between redox-sensitive elements, which may pose additional risks to groundwater-reliant individuals.

Permitted and accidental releases of contaminants from coal combustion residual (CCR) storage facilities pose environmental and ecological risks for associated freshwater ecosystems around the worl...

Chemical and isotopic data for water co-extracted with hydrocarbons in oil and gas fields are commonly used to examine the source of the formation water and possible impacts on groundwater in areas of oil and gas development. Understanding the geochemical variability of oil-field water could help to evaluate its origin and delineate possible contamination of shallow aquifers in cases where oil-field water is released to the environment. Here we report geochemical and multiple isotope (H, C, O, Sr, Ra) data from 22 oil wells, three sources of produced water that are disposed of in injection wells, and two surface disposal ponds in four oil fields in the southern San Joaquin Valley, California (Fruitvale, Lost Hills, North and South Belridge). Correlations between Cl and δ18O, as well as other ions, and gradual increases in salinity with depth, indicate dilution of one or more saline end-members by meteoric water. The saline end-members, represented by deep samples (610 m–2621 m) in three oil-bearing zones, are characterized by Na Cl composition, near-seawater Cl concentrations (median 20,000 mg/L), enriched δ18O H2O (median 3.4‰), high ammonium (up to 460 mg-N/L), and relatively high radium activity (226Ra+228Ra = 12.3 Bq/L). The deepest sample has low Na/Cl (0.74), high Ca/Mg (5.0), and low 87Sr/86Sr (0.7063), whereas the shallower samples have higher Na/Cl (0.86–1.2), Ca/Mg near 1, and higher 87Sr/86Sr (∼0.7083). The data are consistent with an original seawater source being modified by various depth and lithology dependent diagenetic processes. Dilution by meteoric water occurs naturally on the east side of the valley, and in association with water-injection activities on the west side. Meteoric-water flushing, particularly on the east side, results in lower solute concentrations (minimum total dissolved solids 2730 mg/L) and total radium (minimum 0.27 Bq/L) in oil-field water, and promotes biodegradation of dissolved organic carbon and hydrocarbon gases like propane. Acetate concentrations and δ13C of dissolved inorganic carbon indicate biogenic methane production occurs in some shallow oil zones. Natural and human processes produce substantial variability in the geochemistry of oil-field water that should be considered when evaluating mixing between oil-field waters and groundwater. The variability could result in uncertainty as to detecting the potential source and impact of oil-field water on groundwater.

Groundwater overexploitation has caused massive groundwater depletion and raised concerns for water and food security in India. Groundwater in India also suffers from multiple water quality issues such as arsenic and fluoride contamination that pose human health risks. Here we report new data showing that the occurrence in uranium in Indian groundwater is an emerging and widespread phenomenon. We present compiled data on groundwater uranium from 16 Indian states and new data from 324 wells in the states of Rajasthan and Gujarat that show a high prevalence of uranium concentrations above the World Health Organization provisional guideline value of 30 μg/L across India. Using geochemical and uranium isotope data, we suggest factors that may drive high uranium concentrations in groundwater, including uranium content in aquifer rocks, oxidation state, and groundwater chemistry that promotes the formation of soluble uranyl carbonate complexes. While the primary source of uranium is geogenic, anthropogenic fact...

Radium isotopes and water-rock interaction were evaluated in an aquifer storage and recovery (ASR) pilot study conducted in 2010–2011 in Minnesota (USA) in order to identify mechanisms governing Ra activities when low-Ra water is recharged into a sandstone aquifer. Groundwater in the aquifer selected for the study, the Cambrian Mt. Simon Sandstone, contains naturally occurring radium that in many areas exceeds United States drinking water standards (185 mBq/L or 5 pCi/L combined 226Ra+228Ra), highlighting the need to identify the rates and mechanisms by which stored water acquires Ra isotopes. Major element concentrations of recovered water largely resembled recharged water, while Ra activities exceeded the Ra activities of the recharged water. 224Ra reached ∼100 mBq/L during the first 8 h of recovery (overall range 15.5–133 mBq/L). 226Ra and 228Ra also increased during the 47-day recovery period (23.7–82.5 mBq/L and 33.7–85.5 mBq/L, respectively). Ra isotope ratios indicate the relative contribution of alpha recoil vs. chemical processes (e.g. adsorption/desorption). During recovery, the 224Ra/228Ra and 228Ra/226Ra ratios declined, approaching their expected limiting values near unity. Collectively, the rates of Ra activity change with time, trends in Ra isotope ratios, barium concentrations, and manganese concentrations suggest that Ra was governed by chemical processes and alpha recoil, in which the half-lives of each Ra isotope determined the primary mechanism(s) controlling radionuclide mobilization from the aquifer solids. Radium-mobilizing processes during storage may include: (1) recharge of low-Ra water into an aquifer containing high-Ra groundwater induced adsorption/desorption disequilibrium and caused net Ra desorption; (2) chemical conditions during storage (e.g. the Ba content of the recharge water or the reducing conditions in the aquifer) could have further released Ra from the aquifer solids or reduced the effectiveness of Ra adsorption; and/or (3) mobilization from radioactive decay of solid-phase thorium parents (alpha recoil) contributed Ra isotopes into the low-Ra recharge water. The short-lived 224Ra was released dominantly by alpha recoil while the longer-lived 226Ra was dominantly released by chemical mechanisms such as desorption. Radium-228, of intermediate half-life, also appears to have been released predominantly by alpha recoil, although significant chemical release of 228Ra cannot be ruled out. Accordingly, at near-neutral pH, groundwater geochemical conditions (such as redox state and/or shifts in Ra activities or Ba concentrations) can influence observed Ra activities in recovered water, which in proportional terms impart the largest effect on the longer-lived 226Ra. Given the roles for both alpha recoil and chemical reactions, the duration of storage could influence radium activities in recovered water from ASR wells.

Oil sands operations in Alberta, Canada generate large volumes (>840 × 106 m3) of oil sands process-affected water (OSPW) that contains contaminants that are toxic to aquatic life. OSPW is stored in open tailings ponds and leakage from the ponds presents a potential long-term environmental risk. However, the presence of naturally occurring saline water in the oil sands region in Alberta presents a challenge for delineating the impact of OSPW in cases where OSPW is leaked to the environment. Here, we characterize the inorganic chemistry and isotopic variations of boron (δ11B), lithium (δ7Li), and strontium ( e S r S W ) of OSPW from tailings ponds in order to evaluate the source of salinity in OSPW and the potential utilization of these isotope ratios as forensic tracers of OSPW migration in the environment. In addition to generating new data, we compiled published data to build a comprehensive dataset of the geochemical composition of different water sources in the oil sands region of Alberta. OSPW is brackish (TDS ∼ 1800 mgL−1), with elevated chloride (392 ± 184 mg L−1), boron (2.2 ± 0.4 mg L−1), and lithium (0.12 ± 0.11 mg L−1) concentrations relative to the Athabasca River that is used for bitumen extraction. OSPW is characterized by narrow ranges of δ11B (23.7 ± 1.8‰), δ7Li (16.3 ± 1.7‰), and 87Sr/86Sr ratios ( e S r S W =-3.9 ± 19.2). The geochemical and isotope ratios in OSPW reflect mixing of residual, saline formation water from Lower Cretaceous units with fresh surface water that has been modified by interactions with the solid oil sands. The elevated boron and lithium concentrations and δ11B, δ7Li and e S r S W variations we observed are distinct from the compositions of a shallow freshwater aquifer in the area (8.1 ± 5.0‰, 11.3 ± 0.9‰ and 9.7 ± 5.6, respectively) and the local rivers (15.6 ± 4.7‰, 15.1 ± 1.4‰ and 30.3 ± 16.0). However, groundwater and saline springs in the region presents a wider range of geochemical and isotopic values that are not always distinguishable from OSPW. The integration of boron, lithium, and strontium isotopes provides a potential monitoring tool for tracing OSPW release to local freshwater sources.

Environmental concerns regarding the potential for drinking water contamination in shallow aquifers have accompanied unconventional energy development in the northern Appalachian Basin. These activities have also raised several critical questions about the hydrogeological parameters that control the naturally occurring presence and migration of hydrocarbon gases in shallow aquifers within petroliferous basins. To interrogate these factors, we analyzed the noble gas, dissolved ion, and hydrocarbon gas (molecular and isotopic composition) geochemistry of 98 groundwater samples from south-central New York. All samples were collected ≫1km from unconventional drilling activities and sample locations were intentionally targeted based on their proximity to various types of documented fault systems. In agreement with studies from other petroliferous basins, our results show significant correlations between elevated levels of radiogenic [4 He], thermogenic [CH4 ], and dissolved ions (e.g., Cl, Br, Sr, Ba). In combination, our data suggest that faults have facilitated the transport of exogenous hydrocarbon-rich brines from Devonian source rocks into overlying Upper Devonian aquifer lithologies over geologic time. These data conflict with previous reports, which conclude that hydrodynamic focusing regulates the occurrence of methane and salt in shallow aquifers and leads to elevated levels of these species in restricted flow zones within valley bottoms. Instead, our data suggest that faults in Paleozoic rocks play a fundamental role in gas and brine transport from depth, regulate the distribution of their occurrence in shallow aquifers, and influence the geochemistry of shallow groundwater in this petroliferous basin.

Enhanced production of unconventional hydrocarbons in the United States has driven interest in natural gas development globally, but simultaneously raised concerns regarding water quantity and quality impacts associated with hydrocarbon extraction. We conducted a pre-development assessment of groundwater geochemistry in the critically water-restricted Karoo Basin, South Africa. Twenty-two springs and groundwater samples were analyzed for major dissolved ions, trace elements, water stable isotopes, strontium and boron isotopes, hydrocarbons and helium composition. The data revealed three end-members: a deep, saline groundwater with a sodium-chloride composition, an old, deep freshwater with a sodium-bicarbonate-chloride composition and a shallow, calcium-bicarbonate freshwater. In a few cases, we identified direct mixing of the deep saline water and shallow groundwater. Stable water isotopes indicate that the shallow groundwater was controlled by evaporation in arid conditions, while the saline waters were diluted by apparently fossil meteoric water originated under wetter climatic conditions. These geochemical and isotopic data, in combination with elevated helium levels, suggest that exogenous fluids are the source of the saline groundwater and originated from remnant seawater prior to dilution by old meteoric water combined with further modification by water-rock interactions. Samples with elevated methane concentrations (>14 ccSTP/kg) were strongly associated with the sodium-chloride water located near dolerite intrusions, which likely provide a preferential pathway for vertical migration of deeply sourced hydrocarbon-rich saline waters to the surface. This pre-drill evaluation indicates that the natural migration of methane- and salt-rich waters provides a source of geogenic contamination to shallow aquifers prior to shale gas development in the Karoo Basin.

Extensive development of horizontal drilling and hydraulic fracturing enhanced energy production but raised concerns about drinking-water quality in areas of shale-gas development. One particularly controversial case that has received significant public and scientific attention involves possible contamination of groundwater in the Trinity Aquifer in Parker County, Texas. Despite extensive work, the origin of natural gas in the Trinity Aquifer within this study area is an ongoing debate. Here, we present a comprehensive geochemical dataset collected across three sampling campaigns along with integration of previously published data. Data include major and trace ions, molecular gas compositions, compound-specific stable isotopes of hydrocarbons (δ13C-CH4, δ13C-C2H6, δ2H-CH4), dissolved inorganic carbon (δ13C-DIC), nitrogen (δ15N-N2), water (δ18O, δ2H, 3H), and noble gases (He, Ne, Ar), boron (δ11B) and strontium (87Sr/86Sr) isotopic compositions of water samples from 20 drinking-water wells from the Trinity Aquifer. The compendium of data confirms mixing between a deep, naturally occurring salt- (Cl >250 mg/L) and hydrocarbon-rich groundwater with a low-salinity, shallower, and younger groundwater. Hydrocarbon gases display strong evidence for sulfate reduction-paired oxidation, in some cases followed by secondary methanogenesis. A subset of drinking-water wells contains elevated levels of hydrocarbons and depleted atmospherically-derived gas tracers, which is consistent with the introduction of fugitive thermogenic gas. We suggest that gas originating from the intermediate-depth Strawn Group (“Strawn”) is flowing along the annulus of a Barnett Shale gas well, and is subsequently entering the shallow aquifer system. This interpretation is supported by the expansion in the number of affected drinking-water wells during our study period and the persistence of hydrocarbon levels over time. Our data suggest post-genetic secondary water quality changes occur following fugitive gas contamination, including sulfate reduction paired with hydrocarbon oxidation and secondary methanogenesis. Importantly, no evidence for upward migration of brine or natural gas associated with the Barnett Shale was identified.

Molybdenum (Mo) is an essential trace nutrient but has negative health effects at high concentrations. Groundwater typically has low Mo (

The extraction of unconventional oil and gas—from shale rocks, tight sand, and coalbed formations—is shifting the geographies of fossil fuel production, with complex consequences. Following Jackson et al.’s ( 1 ) natural science survey of the environmental consequences of hydraulic fracturing, this review examines social science literature on unconventional energy. After an overview of the rise of unconventional energy, the review examines energy economics and geopolitics, community mobilization, and state and private regulatory responses. Unconventional energy requires different frames of analysis than conventional energy because of three characteristics: increased drilling density, low-carbon and “clean” energy narratives of natural gas, and distinct ownership and royalty structures. This review points to the need for an interdisciplinary approach to analyzing the resulting dynamic, multilevel web of relationships that implicates land, water, food, and climate. Furthermore, the review highlights how scholarship on unconventional energy informs the broader energy landscape and contested energy futures.

The geochemical and isotopic (strontium, boron, radium, oxygen, hydrogen) variations of geothermal waters from five different regions in Morocco were investigated in order to evaluate the sources of solutes and the mechanisms of water-rock interaction. During 2008 to 2010, twenty-two geothermal water samples were collected from the southern, central, and northern parts of Morocco. The water samples were analyzed for major and trace elements, stable isotopes (δ 18 O, δ 2 H) naturally occurring radionuclides ( 226 Ra, 228 Ra, 224 Ra), and isotopes of dissolved strontium ( 87 Sr/ 86 Sr) and boron (δ 11 B). The Moroccan geothermal waters exhibited a wide range of salinity, ranging from 590 to 25,000 mg/L with predominance of chloride, sodium, sulfate, calcium, and bicarbonate ions. Integration of the geochemical and isotope data suggests that the geothermal waters in Morocco originate from recharge of meteoric water and water-rock interactions. The predominance of chloride and sodium and the relatively low Br/Cl ratios ( −3 ), combined with Ca/SO 4 ratios ∼1 suggest that halite and sulfate (gypsum/anhydrite) minerals are the major rock sources for mineralization of the geothermal waters. The variations of 87 Sr/ 86 Sr ratios (0.7076–0.7122) and δ 11 B (5.3‰–29.3‰) were used to distinguish two rock sources (1) dissolution of marine sulfate/carbonate rocks with Sr isotope composition that correspond to the expected ratios in seawater during time of deposition; and (2) non-marine sources with higher 87 Sr/ 86 Sr and δ 11 B, presumably from interactions with clay minerals and shale rocks. The variations of radium isotopes indicate that the alpha-recoil of the parent nuclides on the host rocks caused mobilization of the short-lived 224 Ra and 228 Ra to the geochemical waters. The low 228 Ra/ 226 Ra ratios (activity ratios of 0.04–0.14) measured in the geothermal waters mimic the Th/U ratios in the source rocks, which indicate predominance of uranium over thorium. Our data show that some of the geothermal waters in Morocco are characterized by high salinity, and in some systems also by elevated radioactivity above international drinking water standards, which limits their utilization for agricultural and domestic applications. Adequate treatment is therefore required to use geothermal waters in Morocco as an alternative or additional water source. Other geothermal waters with low mineralization can be utilized as alternative resource for the agricultural and domestic sectors without any restrictions.

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