The impact of using low-saline oilfield produced water for irrigation on water and soil quality in California.

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.

Occurrence and distribution of hexavalent chromium in groundwater from North Carolina, USA.

Hexavalent chromium (Cr(VI)) is a groundwater contaminant that is potentially harmful to human health. Understanding the occurrence of Cr(VI) in groundwater resources is critical for evaluating its risks to human health. Here we report a large dataset (n = 1362) of Cr(VI) and total chromium (CrT) concentrations in public, private, and monitoring wells from different aquifers across North Carolina. These water quality data come from new and previous measurements conducted at Duke University, as well as data reported by the U.S. Environmental Protection Agency, the N.C. Department of Environmental Quality, and the U.S. Geological Survey. The data confirm that Cr(VI) is the predominant species of dissolved Cr and that groundwater from aquifers in the Piedmont region contain significantly higher concentrations than groundwater from the coastal plain. Though there is only one exceedance of the U.S. EPA Maximum Contaminant Level (100 µg/L for CrT) in the dataset, over half of all wells measured for Cr(VI) (470 out of 865) in the dataset exceeded the N.C. Health Advisory Level of 0.07 µg/L. Using information from this dataset, we explore three different approaches to predicting Cr(VI) in groundwater: (1) CrT concentrations as a proxy for Cr(VI); (2) Exceedance probabilities of health goals for groundwater from aquifers located in specific geologic areas; and (3) Censored linear regression using commonly measured field parameters (pH, electrical conductivity, dissolved oxygen) with relationships to Cr(VI) as regressors. Combining these approaches, we have identified several areas in the Piedmont region where Cr(VI) in drinking water wells is expected to be higher than the advisory level, which coincide with large population groundwater reliant populations. While this study focuses on N.C., the wide-spread occurrence of Cr(VI) in groundwater at concentrations above health guidelines in aquifers of the Piedmont region could pose high human health risks to large populations in the eastern U.S.

Occurrence and Sources of Radium in Groundwater Associated with Oil Fields in the Southern San Joaquin Valley, California.

Geochemical data from 40 water wells were used to examine the occurrence and sources of radium (Ra) in groundwater associated with three oil fields in California (Fruitvale, Lost Hills, South Belridge). 226Ra+228Ra activities (range = 0.010-0.51 Bq/L) exceeded the 0.185 Bq/L drinking-water standard in 18% of the wells (not drinking-water wells). Radium activities were correlated with TDS concentrations (p < 0.001, ρ = 0.90, range = 145-15,900 mg/L), Mn + Fe concentrations (p < 0.001, ρ = 0.82, range = <0.005-18.5 mg/L), and pH (p < 0.001, ρ = -0.67, range = 6.2-9.2), indicating Ra in groundwater was influenced by salinity, redox, and pH. Ra-rich groundwater was mixed with up to 45% oil-field water at some locations, primarily infiltrating through unlined disposal ponds, based on Cl, Li, noble-gas, and other data. Yet 228Ra/226Ra ratios in pond-impacted groundwater (median = 3.1) differed from those in oil-field water (median = 0.51). PHREEQC mixing calculations and spatial geochemical variations suggest that the Ra in the oil-field water was removed by coprecipitation with secondary barite and adsorption on Mn-Fe precipitates in the near-pond environment. The saline, organic-rich oil-field water subsequently mobilized Ra from downgradient aquifer sediments via Ra-desorption and Mn/Fe-reduction processes. This study demonstrates that infiltration of oil-field water may leach Ra into groundwater by changing salinity and redox conditions in the subsurface rather than by mixing with a high-Ra source.

Evidence for unmonitored coal ash spills in Sutton Lake, North Carolina: Implications for contamination of lake ecosystems.

Coal combustion residuals (CCRs, also known as "coal ash") contain high concentrations of toxic and carcinogenic elements that can pose ecological and human health risks upon their release into the environment. About half of the CCRs that are generated annually in the U.S. are stored in coal ash impoundments and landfills, in most cases adjacent to coal plants and waterways. Leaking of coal ash ponds and CCR spills are major environmental concerns. One factor which may impact the safety of CCRs stored in impoundments and landfills is the storage area's predisposition to flooding. The southeastern U.S., in particular, has a large number of coal ash impoundments located in areas that are vulnerable to flooding. In order to test for the possible presence of CCR solids in lake sediments following Hurricane Florence, we analyzed the magnetic susceptibility, microscopic screening, trace element composition, and strontium isotope ratios of bottom sediments collected in 2015 and in 2018 from Sutton Lake in eastern North Carolina and compared them to a reference lake. The results suggest multiple, apparently previously unmonitored, CCR spills into Sutton Lake from adjacent CCR storage sites. The enrichment of metals in Sutton Lake sediments, particularly those with known ecological impact such as As, Se, Cu, Sb, Ni, Cd, V, and Tl, was similar to or even higher than those in stream sediments impacted by the Tennessee Valley Authority (TVA) in Kingston, Tennessee, and the Dan River, North Carolina coal ash spills, and exceeded ecological screening standards for sediments. High levels of contaminants were also found in leachates extracted from Sutton Lake sediments and co-occurring pore water, reflecting their mobilization to the ambient environment. These findings highlight the risks of large-scale unmonitored spills of coal ash solids from storage facilities following major storm events and contamination of nearby water resources throughout the southeastern U.S.

Origin of Flowback and Produced Waters from Sichuan Basin, China.

Shale gas extraction through hydraulic fracturing and horizontal drilling is increasing in China, particularly in Sichuan Basin. Production of unconventional shale gas with minimal environmental effects requires adequate management of wastewater from flowback and produced water (FP water) that is coextracted with natural gas. Here we present, for the first time, inorganic chemistry and multiple isotope (oxygen, hydrogen, boron, strontium, radium) data for FP water from 13 shale gas wells from the Lower Silurian Longmaxi Formation in the Weiyuan gas field, as well as produced waters from 35 conventional gas wells from underlying (Sinian, Cambrian) and overlying (Permian, Triassic) formations in Sichuan Basin. The chemical and isotope data indicate that the formation waters in Sichuan Basin originated from relics of different stages of evaporated seawater modified by water-rock interactions. The FP water from shale gas wells derives from blending of injected hydraulic fracturing water and entrapped saline (Cl ∼ 50,000 mg/L) formation water. Variations in the chemistry, δ18O, δ11B, and 87Sr/86Sr of FP water over time indicate that the mixing between the two sources varies with time, with a contribution of 75% (first 6 months) to 20% (>year) of the injected hydraulic fracturing water in the blend that compose the FP water. Mass-balance calculation suggests that the returned hydraulic fracturing water consisted of 28-49% of the volume of the injected hydraulic fracturing water, about a year after the initial hydraulic fracturing. We show differential mobilization of Na, B, Sr, and Li from the shale rocks during early stages of operation, which resulted in higher Na/Cl, B/Cl, Li/Cl, and 87Sr/86Sr and lower δ11B of the FP water during early stages of FP water formation relative to the original saline formation water recorded in late stages FP water. This study provides a geochemical framework for characterization of formation waters from different geological strata, and thus the ability to distinguish between different sources of oil and gas wastewater in Sichuan Basin.

The intensification of the water footprint of hydraulic fracturing.

Unconventional oil and gas exploration in the United States has experienced a period of rapid growth, followed by several years of limited production due to falling and low natural gas and oil prices. Throughout this transition, the water use for hydraulic fracturing and wastewater production in major shale gas and oil production regions has increased; from 2011 to 2016, the water use per well increased up to 770%, while flowback and produced water volumes generated within the first year of production increased up to 1440%. The water-use intensity (that is, normalized to the energy production) increased ubiquitously in all U.S. shale basins during this transition period. The steady increase of the water footprint of hydraulic fracturing with time implies that future unconventional oil and gas operations will require larger volumes of water for hydraulic fracturing, which will result in larger produced oil and gas wastewater volumes.

Quantity of flowback and produced waters from unconventional oil and gas exploration.

The management and disposal of flowback and produced waters (FP water) is one of the greatest challenges associated with unconventional oil and gas development. The development and production of unconventional natural gas and oil is projected to increase in the coming years, and a better understanding of the volume and quality of FP water is crucial for the safe management of the associated wastewater. We analyzed production data using multiple statistical methods to estimate the total FP water generated per well from six of the major unconventional oil and gas formations in the United States. The estimated median volume ranges from 1.7 to 14.3millionL (0.5 to 3.8milliongal) of FP per well over the first 5-10years of production. Using temporal volume production and water quality data, we show a rapid increase of the salinity associated with a decrease of FP production rates during the first months of unconventional oil and gas production. Based on mass-balance calculations, we estimate that only 4-8% of FP water is composed of returned hydraulic fracturing fluids, while the remaining 92-96% of FP water is derived from naturally occurring formation brines that is extracted together with oil and gas. The salinity and chemical composition of the formation brines are therefore the main limiting factors for beneficial reuse of unconventional oil and gas wastewater.

Radium and barium removal through blending hydraulic fracturing fluids with acid mine drainage.

Wastewaters generated during hydraulic fracturing of the Marcellus Shale typically contain high concentrations of salts, naturally occurring radioactive material (NORM), and metals, such as barium, that pose environmental and public health risks upon inadequate treatment and disposal. In addition, fresh water scarcity in dry regions or during periods of drought could limit shale gas development. This paper explores the possibility of using alternative water sources and their impact on NORM levels through blending acid mine drainage (AMD) effluent with recycled hydraulic fracturing flowback fluids (HFFFs). We conducted a series of laboratory experiments in which the chemistry and NORM of different mix proportions of AMD and HFFF were examined after reacting for 48 h. The experimental data combined with geochemical modeling and X-ray diffraction analysis suggest that several ions, including sulfate, iron, barium, strontium, and a large portion of radium (60-100%), precipitated into newly formed solids composed mainly of Sr barite within the first ∼ 10 h of mixing. The results imply that blending AMD and HFFF could be an effective management practice for both remediation of the high NORM in the Marcellus HFFF wastewater and beneficial utilization of AMD that is currently contaminating waterways in northeastern U.S.A.