The water footprint of hydraulic fracturing under different hydroclimate conditions in the Central and Western United States.

The oil and gas (O&G) exploitation via hydraulic fracturing (HF) has augmented both energy production and water demand in the United States. Despite the geographical coincidence of U.S. shale plays with water-scarce areas, the water footprint of HF under drought conditions, as well as its impacts on local water allocation, have not been well understood. In this study, we investigated the water consumption by HF activities under different hydroclimate conditions in eleven O&G-producing states in the central and western U.S. from 2011 to 2020. Our results show that the water consumption under abnormally dry or drought climates accounted for 49.7 % (475.3 billion gallons or 1.8 billion m3) of total water usage of HF, with 9 % (86.1 billion gallons or 325.9 million m3) of water usage occurring under extreme or exceptional drought conditions. The water usage of HF under arid conditions can translate to high densities of water footprint at the local scale, equivalent to >10 % and 50 % of the annual water usage by the irrigation and domestic sectors in 6-29 irrigation-active counties and 11-51 counties (depending on the specific year), respectively. Such water stress imposed by O&G production, however, can be effectively mitigated by the reuse of flowback and produced water. Our findings, for the first time, quantify the water footprint of HF as a function of hydroclimate condition, providing evidence that the water consumption by HF intensifies local water competition and alters water supply threatened by climate variability. This renders wastewater reuse necessary to maintain water sustainability of O&G-producing regions in the context of both a rising O&G industry and a changing climate.

Contrasting Behaviors between Gypsum and Silica Scaling in the Presence of Antiscalants during Membrane Distillation.

Mineral scaling is a major constraint that limits the performance of membrane distillation (MD) for hypersaline wastewater treatment. Although the use of antiscalants is a common industrial practice to mitigate mineral scaling, the effectiveness and underlying mechanisms of antiscalants in inhibiting different mineral scaling types have not been systematically investigated. Herein, we perform a comparative investigation to elucidate the efficiencies of antiscalant candidates with varied functional groups for mitigating gypsum scaling and silica scaling in MD desalination. We show that antiscalants with Ca(II)-complexing moieties (e.g., carboxyl group) are the most effective to inhibit gypsum scaling formed via crystallization, whereas amino-enriched antiscalants possess the best performance to mitigate silica scaling created by polymerization. A set of microscopic and spectroscopic analyses reveal distinct mechanisms of antiscalants required for those two common types of scaling. The mitigating effect of antiscalants on gypsum scaling is attributed to the stabilization of scale precursors and nascent CaSO4 nuclei, which hinders phase transformation of amorphous CaSO4 toward crystalline gypsum. In contrast, antiscalants facilitate the polymerization of silicic acid, immobilizing active silica precursors and retarding the gelation of silica scale layer on the membrane surface. Our study, for the first time, demonstrates that antiscalants with different functionalities are required for the mitigation of gypsum scaling and silica scaling, providing mechanistic insights on the molecular design of antiscalants tailored to MD applications for the treatment of wastewaters containing different scaling types.

On-site treatment capacity of membrane distillation powered by waste heat or natural gas for unconventional oil and gas wastewater in the Denver-Julesburg Basin.

Leveraging waste heat has been considered to have significant potential for promoting the economic feasibility of wastewater treatment in unconventional oil and gas (UOG) production. However, its availability near well sites has not been fully understood and other energy sources may be also feasible. In this work, we quantitatively investigate the viability of using waste heat and well-pad natural gas to power on-site wastewater treatment by membrane distillation (MD) for twenty randomly selected wells located in the Denver-Julesburg (DJ) Basin, U.S. Results show that waste heat produced from on-site electrical loads is insufficient for MD treatment of all the wastewater generated during UOG production (2.2-24.3% of thermal energy required for MD treatment). Waste heat from hydraulic fracturing, which persists only for a short timeframe, is able to meet the full or partial energy requirement during the peak period of wastewater production (17-1005% of thermal energy required for MD treatment within the first two months of production), but this scenario varies among wells and is dependent on the energy efficiency of MD. Compared to waste heat, natural gas is a more consistent energy source. The treatment capacity of MD powered by natural gas at the well pad exceeds full wastewater treatment demands for all the twenty wells, with only two wells requiring short-term wastewater storage. Our work indicates that although waste heat has the potential to reduce the electricity consumption and cost of UOG wastewater treatment, it is unlikely to supply sufficient thermal energy required by MD for long-term treatment. Natural gas can serve as an alternative or complementary energy resource. Further investigations, in particular techno-economic analyses, are needed to identify the best suitable energy source or combination for on-site UOG wastewater treatment.

Occurrence of ß-lactam and polyether ionophore antibiotics in lagoon water and animal manure.

The occurrence of micropollutants in agricultural wastes is an emerging area of interest due to the potential impact of these compounds on the environment. A sensitive and reliable analytical method using liquid chromatography-electrospray tandem mass spectrometry has been developed and validated for the determination of three ß-lactam and three polyether ionophore antibiotics in lagoon water and animal manure matrices. The method was applied to evaluate the occurrence of these compounds from participating farms in northern Colorado. Seven of the 19 lagoon water samples and two of the six animal manures showed detectable. The three targeted ß-lactams (cephapirin, penicillin G, cloxacillin) were found at 0.97-43.31 µg/L in the lagoon water samples. Of the three targeted polyether ionophores, only monensin (94 to 1077 µg/L) was detected in the beef runoff pond water samples. Only cloxacillin was measured in the dairy animal manure samples at levels from 8.09 to 45.20 µg/kg. No cephapirin, penicillin G, cloxacillin, salinomycin, or narasin A were detected in any solid animal manure sample. These results indicate that elevated concentrations of ß-lactam and ionophore compounds might be found in lagoon or runoff pond waters and solid animal manures compared to surface waters, which these compounds are used in veterinary applications.

Colorado Water Watch: real-time groundwater monitoring for possible contamination from oil and gas activities.

Currently, only a few states in the USA (e.g., Colorado and Ohio) require mandatory baseline groundwater sampling from nearby groundwater wells prior to drilling a new oil or gas well. Colorado is the first state to regulate groundwater testing before and after drilling, which requires one pre-drilling sample and two additional post-drilling samples within 6-12 months and 5-6 years of drilling. However, the monitoring method is limited to the state's regulatory agency and to ex situ sampling, which offers only a snapshot in time. To overcome the limitations and increase monitoring performance, a new groundwater monitoring system, Colorado Water Watch (CWW), was introduced as a decision-making tool to support the state's regulatory agency and also to provide real-time groundwater quality data to both the industry and the public. The CWW uses simple in situ water quality sensors based on the surrogate sensing technology that employs an event detection system to screen the incoming data in near real-time.

Concurrence of aqueous and gas phase contamination of groundwater in the Wattenberg oil and gas field of northern Colorado.

The potential impact of rapid development of unconventional oil and natural gas resources using hydraulic fracturing and horizontal drilling on regional groundwater quality has received significant attention. Major concerns are methane or oil/gas related hydrocarbon (such as TPHs, BTEX including benzene, toluene, ethybenzene and xylene) leaks into the aquifer due to the failure of casing and/or stray gas migration. Previously, we investigated the relationship between oil and gas activity and dissolved methane concentration in a drinking water aquifer with the major finding being the presence of thermogenic methane contamination, but did not find detectable concentrations of TPHs or BTEX. To understand if aqueous and gas phases from the producing formation were transported concurrently to drinking water aquifers without the presence of oil/gas related hydrocarbons, the ionic composition of three water groups was studied: (1) uncontaminated deep confined aquifer, (2) suspected contaminated groundwater - deep confined aquifer containing thermogenic methane, and (3) produced water from nearby oil and gas wells that would represent aqueous phase contaminants. On the basis of quantitative and spatial analysis, we identified that the "thermogenic methane contaminated" groundwater did not have similarities to produced water in terms of ionic character (e.g. Cl/TDS ratio), but rather to the "uncontaminated" groundwater. The analysis indicates that aquifer wells with demonstrated gas phase contamination have not been contacted by an aqueous phase from oil and gas operations according to the methodology we use in this study and the current groundwater quality data from COGCC. However, the research does not prove conclusively that this the case. The results may provide insight on contamination mechanisms since improperly sealed well casing may result in stray gas but not aqueous phase transport.

Distribution and origin of groundwater methane in the Wattenberg oil and gas field of northern Colorado.

Public concerns over potential environmental contamination associated with oil and gas well drilling and fracturing in the Wattenberg field in northeast Colorado are increasing. One of the issues of concern is the migration of oil, gas, or produced water to a groundwater aquifer resulting in contamination of drinking water. Since methane is the major component of natural gas and it can be dissolved and transported with groundwater, stray gas in aquifers has elicited attention. The initial step toward understanding the environmental impacts of oil and gas activities, such as well drilling and fracturing, is to determine the occurrence, where it is and where it came from. In this study, groundwater methane data that has been collected in response to a relatively new regulation in Colorado is analyzed. Dissolved methane was detected in 78% of groundwater wells with an average concentration of 4.0 mg/L and a range of 0-37.1 mg/L. Greater than 95% of the methane found in groundwater wells was classified as having a microbial origin, and there was minimal overlap between the C and H isotopic characterization of the produced gas and dissolved methane measured in the aquifer. Neither density of oil/gas wells nor distance to oil/gas wells had a significant impact on methane concentration suggesting other important factors were influencing methane generation and distribution. Thermogenic methane was detected in two aquifer wells indicating a potential contamination pathway from the producing formation, but microbial-origin gas was by far the predominant source of dissolved methane in the Wattenberg field.

Relative phosphorus load inputs from wastewater treatment plants in a northern colorado watershed.

Excess nutrients are among the leading sources of water quality impairment in the Unites States, and the USEPA has been working with state regulatory agencies to develop nutrient criteria for wastewater treatment plants (WWTPs). The Colorado Department of Public Health and Environment is scheduled to establish nutrient regulations in 2013, and stream total P (TP) concentration standards of 0.16 mg L in warm water and 0.11 mg L in cold water have been proposed for the rivers in the state. The objectives of this study were to monitor TP concentrations and loads along the Cache La Poudre River as it flows from the pristine upstream area through urban regions and finally through a mixture of agricultural and urban land uses. The study attempts to evaluate the sources and influences of TP under different hydrologic conditions. Twelve sampling events were completed from April 2010 to August 2011 to assess the influence of various flow and precipitation conditions on aqueous TP concentrations. During midrange flows and dry conditions, WWTPs were the major sources of TP, but other sources were more significant under high-flow and wet conditions according to a load analysis. The analysis indicates that reducing the TP load from WWTPs will only marginally affect the TP load in the river, and therefore it appears that other sources (e.g., stormwater and agricultural runoff) need to be addressed before the aquatic life-based stream standard can be achieved.

Will stringent total nitrogen wastewater treatment plant discharge regulations achieve stream water quality goals?

The Colorado Department of Public Health and Environment (CDPHE) proposed the in-stream numeric nutrient criteria as 2 mg TN per L and 0.16 mg TP per L for warm surface waters and 0.40 mg TN per L and 0.11 mg TP per L for cold surface waters. Consequently the department presented the nutrient limits for the municipal wastewater treatment plants (WWTPs) as annual averages of 0.7 mg TP per L and 5.7 mg TIN per L and quarterly averages of 1.0 mg TP per L and 9.0 mg TIN per L. Implementing stringent nutrient reduction at point sources is unlikely to result in improvements to the environment without non-point source controls. In this study, total nitrogen (TN) load inputs from known point source, WWTPs, and other non-point sources at six sub-basins of the Cache La Poudre (CLP) River Basin were estimated and compared under various hydrologic conditions. Significant loading exceedance from the proposed limits was observed during lower flow conditions and other sources dominated during events when the exceedance was observed except for one point. The point receives direct TN inputs from a WWTP which has the highest TN concentration in its effluent among all WWTPs in the study area; however, TN loads entered the point from other sources were significant during higher flow conditions. TN loads in the CLP River were simulated to determine whether the loads meet the proposed in-stream limits in a case in which all WWTPs comply with the proposed regulations for WWTPs. From this study, it was observed that reducing TN concentrations only at WWTPs merely impacts total TN loads in the river.

Response of antibiotics and resistance genes to high-intensity and low-intensity manure management.

The purpose of this study was to determine the response of antibiotics and antibiotic resistance genes (ARG) to manure management. A pilot field study was conducted using horse manure containing no antibiotics, into which chlortetracycline (CTC), tylosin (TYL), and monensin (MON) were spiked and compared to unspiked controls. Subsequently, a large-scale field study was conducted comparing manure from a dairy with minimal use of antibiotics and a feedlot with regular subtherapeutic use of antibiotics. The manures were subjected to high-intensity management (HIM) (amending, watering, and turning) and low-intensity management (LIM) (no amending, watering, or turning) and were monitored for antibiotic concentrations and levels of tetracycline ARG [tet(W) and tet(O)] using quantitative real-time polymerase chain reaction. All three antibiotics in the pilot study dissipated more rapidly in HIM manure, with half-lives ranging from 4 to 15 d, compared to LIM manure, with half-lives ranging from 8 to 30 d. Levels of tet(W) were significantly higher after 141 d of treatment, but levels of tet(O) were significantly lower in all treatments. In the large-scale study, the feedlot manure had higher initial concentrations than the dairy manure of tetracycline (TC), oxytetracycline (OTC), and CTC as well as tet(W) and tet(O). Tetracycline and OTC dissipated more rapidly in HIM manure, with half-lives ranging from 6 to 15 d, compared to LIM manure, with half-lives ranging from 7 to 31 d. After 6 mo of treatment, tet(W) and tet(O) decreased significantly in feedlot manure, whereas dairy manure required only 4 mo of treatment for similar results.

Response of antibiotic resistance genes (ARG) to biological treatment in dairy lagoon water.

To explore the response of antibiotic resistance genes (ARG) to biological treatment, dairy lagoon water was incubated anaerobically or aerobically at 20 degrees C or 4 degrees C. Three conditions were compared: Antibiotic (Ab) Spiked, Ab Spiked and Killed, and Background (unamended). For Ab Spiked conditions, oxytetracycline, sulfamethoxazole, tylosin, and monensin were each added at 20 mg/L. Antibiotics and ARG were monitored using high-performance liquid chromatography/tandem mass spectrometry and quantitative real-time polymerase chain reaction, respectively. Biological degradation of antibiotics in all treatments and varied responses of different ARG was observed. Aerobic versus anaerobic treatment had no effect on tet(W), with an overall pattern of increase in the presence of antibiotics followed by decrease to initial levels. tet(O) responded differently under aerobic versus anaerobic treatment, increasing to highest levels at 4 degrees C under aerobic treatment and at 20 degrees C under anaerobic treatment before returning to initial levels. sul(I) and sul (II) showed similar patterns and increased in all Ab Spiked conditions, failing to return to initial levels at 4 degrees C and in some of the 20 degrees C treatments. ere(A) and msr(A) were lower than the other two ARG classes and remained constant in all treatments.

Antibiotic resistance genes as emerging contaminants: studies in northern Colorado.

This study explores antibiotic resistance genes (ARGs) as emerging environmental contaminants. The purpose of this study was to investigate the occurrence of ARGs in various environmental compartments in northern Colorado, including Cache La Poudre (Poudre) River sediments, irrigation ditches, dairy lagoons, and the effluents of wastewater recycling and drinking water treatment plants. Additionally, ARG concentrations in the Poudre River sediments were analyzed at three time points at five sites with varying levels of urban/agricultural impact and compared with two previously published time points. It was expected that ARG concentrations would be significantly higher in environments directly impacted by urban/agricultural activity than in pristine and lesser-impacted environments. Polymerase chain reaction (PCR) detection assays were applied to detect the presence/absence of several tetracycline and sulfonamide ARGs. Quantitative real-time PCR was used to further quantify two tetracycline ARGs (tet(W) and tet(O)) and two sulfonamide ARGs (sul(I) and sul(II)). The following trend was observed with respect to ARG concentrations (normalized to eubacterial 16S rRNA genes): dairy lagoon water > irrigation ditch water > urban/agriculturally impacted river sediments (p < 0.0001), except for sul(II), which was absent in ditch water. It was noted that tet(W) and tet(O) were also present in treated drinking water and recycled wastewater, suggesting that these are potential pathways for the spread of ARGs to and from humans. On the basis of this study, there is a need for environmental scientists and engineers to help address the issue of the spread of ARGs in the environment.

Effect of river landscape on the sediment concentrations of antibiotics and corresponding antibiotic resistance genes (ARG).

The purpose of this study was to quantify antibiotic resistance genes (ARG) in the sediments of the mixed-landscape Cache La Poudre River, which has previously been studied and shown to have high concentrations of antibiotics related to urban and agricultural activities. River sediments were sampled during two events (high-flow and low-flow) from five sites with varying urban and agricultural impact levels. Polymerase-chain-reaction (PCR) detection assays were conducted for four sulfonamide resistance gene families, using newly designed primers, and five tetracycline resistance gene families, using previously published primers. Sul(I), sul(II), tet(W), and tet(O) gene families were further quantified by real-time quantitative polymerase chain reaction (Q-PCR). Resistance to four classes of antibiotics (tetracyclines, sulfonamides, ionophores, and macrolides) was also investigated using a culture-based approach. The quantities of resistance genes normalized to the 16S gene copy number were significantly different between the sites, with higher resistance gene concentrations at the impacted sites than at the pristine site. Total resistant CFUs were over an order of magnitude lower at the pristine site, but differences were less apparent when normalized to the total CFUs. Six tetracyclines and six sulfonamides were also quantified in the sediments and were found to be highest at sites impacted by urban and agricultural activity, with no antibiotics detected at the pristine sit. To the knowledge of the authors, this study is the first to demonstrate a relationship between urban and agricultural activity and microbial resistance in river sediments using quantitative molecular tools.