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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.

The effective treatment of unconventional oil and gas (UOG) wastewater is a promising and potentially necessary strategy of wastewater management in the UOG industry. While tremendous efforts have ...

Unconventional oil and gas (UOG) production requires intensive freshwater consumption, but whether hydroclimate variation, which alters regional water availability, affects its activity and water f...

The oil and gas (OG) 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 OG-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 m

Projected climate change impacts on the hydrological regime and corresponding flood risks were examined for the years 2030 (near-term) and 2050 (long-term), under representative concentration pathways (RCP) 4.5 (moderate) and 8.5 (high) emission scenarios. The United States Army Corps of Engineers' (USACE) Hydrologic Engineering Center's Hydrologic Modeling System was used to simulate the complete hydrologic processes of the various dendritic watershed systems and USACEs' Hydrologic Engineering Center's River Analysis System hydraulic model was used for the two-dimensional unsteady flow flood calculations. Climate projections are based on recent global climate model simulations developed for the International Panel on Climate Change, Coupled Model Inter-comparison Project Phase 5. Hydrographs for frequent (high-recurrence interval) storms were derived from 30-year historical daily precipitation data and decadal projections for both time frames and RCP scenarios. Since the climate projections for each scenario only represented ten years of data, 100-year or 500-year storms cannot be derived. Hence, this novel approach of identifying frequent storms is used as an indicator to compare across the various time frames and climate scenarios. Hydrographs were used to generate inundation maps and results are used to identify vulnerabilities and formulate adaptation strategies to flooding at 43 locations worldwide.

The occurrence and fate of veterinary antibiotics in lagoon water and animal manure are an emerging area of interest due to the potential impact of these compounds on the aquatic environment. The objective of this study was to evaluate the degradation of oxytetracycline (OTC), sulfamethoxazole (SMX), tylosin (TYL), and monensin (MON) in dairy lagoon waters under aerobic and anaerobic conditions. Biodegradation of OTC, SMX, TYL and MON occurred at both 20 °C and 4 °C under aerobic and anaerobic conditions. More than 88% of all antibiotics were degraded at 20 °C under aerobic treatment. Concentrations decreased at 4 °C, but none of these compounds completely biodegraded in either treatment within 242 days at 4 °C. Calculated first-order degradation half-lives of OTC, SMX, TYL and MON at 20 °C were 12, 6.5, 16, and 9.2 days, respectively, under aerobic treatment and 17, 59, 19, and 71 days, respectively, under anaerobic treatment. At 4 °C, half-lives were 80, 204, 46, and 128 days, respectively, under aerobic treatment and 110, >242, 103, and 193 days, respectively, under anaerobic treatment. Therefore, these results show that degradation of antibiotics, in general, is faster under aerobic conditions, compared to anaerobic conditions. It was found that lower temperature (4 °C) reduced the biodegradation rate of antibiotics.

We developed an integrated treatment train that enables effective treatment of shale oil and gas produced water generated from the Wattenberg field in northeast Colorado. Membrane distillation (MD) was performed in tandem with simple and inexpensive pretreatment steps, namely precipitative softening (PS) and walnut shell filtration (WSF). PS removed various particulate, organic, and inorganic foulants, thereby mitigating fouling and scaling potential of the produced water. WSF displayed exceptional efficiencies (≥95%) in eliminating volatile toxic compounds including benzene, ethylbenzene, toluene, and xylenes (BTEX) along with additional gasoline and diesel range organic compounds. With pretreatment, the water vapor flux of MD decreased by only 10% at a total water recovery of 82.5%, with boron and total BTEX concentrations in the MD distillate meeting the regulatory requirements for irrigation and typical discharge limits, respectively. The use of pretreatment also led to robust membrane reusability within three consecutive treatment cycles, with MD water flux fully restored after physical membrane cleaning. Our results highlight the necessity of pretreatment prior to MD treatment of produced water and demonstrate the potential of our treatment train to achieve a cost-effective and on-site wastewater treatment system that improves the sustainability of the shale oil and gas industry.

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.

Extensive efforts have been made to tailor membrane surface wettability in order to mitigate fouling and wetting in membrane distillation (MD), but the developed membranes have rarely been challenged with real industrial wastewater. This study compared three membranes – a hydrophobic PVDF membrane, a superhydrophobic PVDF membrane, and a composite PVDF membrane with hydrophilic coating – in MD desalination of shale oil and gas produced water from the Wattenberg field in northeast Colorado. Two produced water samples with varied chemical compositions were collected and used as the feedwater. In a single treatment cycle, the composite membrane showed the best fouling resistance for the first sample, while all the tested membranes experienced similar flux decline with the second sample. Thus, the relationship between membrane surface wettability and fouling propensity in MD treatment of real produced water was influenced by feedwater composition. This effect was reflected by distinct features of fouling layers resulting from the two produced water samples, revealed by detailed microscopic and spectroscopic characterization. In three treatment cycles with physical membrane cleaning, the hydrophobic and composite membranes suffered from accelerated membrane fouling after each cycle, whereas a decelerated flux decline was observed for the superhydrophobic membrane. The better reusability of the superhydrophobic membrane, however, was achieved at the expense of initial water vapor flux. Our study suggests that one should comprehensively consider fouling/wetting resistance, water productivity, and reusability in the design and selection of appropriate membranes for MD treatment, and that long-term testing with multiple treatment cycles should be performed to assess MD membrane performance more accurately.

Unconventional oil and gas (UOG) production requires a vast quantity of freshwater while generating substantial volumes of wastewater. Although numerous studies have focused on technology development, other aspects beyond treatment technology, including regulations, economics, system logistics, and public perception, play equally or more important roles collectively in the selection and deployment of UOG wastewater management practices. In this article, we begin with a critical analysis of the motivations that drive UOG wastewater management towards treatment and reuse. Then we examine four main barriers against such a paradigm shift, pertaining to treatment technology, regulatory compliance, economic feasibility, and social acceptance. Despite the need of further improving technology efficiency for UOG wastewater treatment, the lack of established regulatory framework, the uncertainties of economic viability, as well as public resistance, hinder practical implementation of treatment technologies. We highlight the importance of knowledge and collaborative efforts from engineers, regulators, policy makers, economists, and social scientists to address those barriers, and emphasize that future research efforts should be directed at domains well beyond treatment technology. A systems approach and broader collaboration across multiple disciplines is needed to translate technology innovation into solutions that truly improve water sustainability in the context of rising UOG production.

High volumes of flowback and produced water are generated everyday as a byproduct of hydraulic fracturing operations and shale gas developments across the United States. Since most shale gas developments are located in semi-arid to arid U.S. regions close to agricultural production, there are many opportunities for reusing these waters as potential alternatives or supplements to fresh water resources for irrigation activities. However, the impacts of high salinity and total organic content of these types of water on crop physiological parameters and plant growth needs to be investigated to determine their utility and feasibility. The aim of the present study was to evaluate the response of switchgrass and rapeseed to treated produced water as an irrigation water source. In this greenhouse study, the influence of produced water at four total organic carbon (TOC) concentrations [1.22, 38.3, 232.2 and 1352.4 mg/l] and three total dissolved solids (TDS) levels [400,3,500, and 21,000 mg/l] on rapeseed (Brassica napus L.) and switchgrass (Panicum virgatum L.), two relatively salt-tolerant, non-food, biofuel crops, was studied. Seedling emergence, biomass yield, plant height, leaf electrolyte leakage, and plant uptake were evaluated. Irrigation water with the highest salinity and TOC concentration resulted in significantly lower growth health and physiological characteristics of both crop species. The organic content of the produced water had a negative impact on biomass yield and physiological parameters of both species. The results of this study could be valuable for regulators and stakeholders in development of treatment standards in which organic matter should be removed to less than 50 mg/l to keep leaf EL (cell damage) to less than 50% and a TOC concentration of less than 5 mg/l required to keep a sustainable biomass production rate.

Shale oil and gas exploitation not only consumes substantial amounts of freshwater but also generates large quantities of hazardous wastewater. Tremendous research efforts have been invested in developing membrane-based technologies for the treatment of shale oil and gas wastewater. Despite their success at the laboratory scale, membrane processes have not been implemented at full scale in the oil and gas fields. In this article, we analyze the growing demands of wastewater treatment in shale oil and gas production, and then critically review the current stage of membrane technologies applied to the treatment of shale oil and gas wastewater. We focus on the unique niche of those technologies due to their advantages and limitations, and use mechanical vapor compression as the benchmark for comparison. We also highlight the importance of pretreatment as a key component of integrated treatment trains, in order to improve the performance of downstream membrane processes and water product quality. We emphasize the lack of sufficient efforts to scale up existing membrane technologies, and suggest that a stronger collaboration between academia and industry is of paramount importance to translate membrane technologies developed in the laboratory to the practical applications by the shale oil and gas industry.

Currently, only a few states in the U.S. (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, requiring one pre-drilling sample and two additional post-drilling samples within 6 - 12 months and 5 - 6 years of drilling, respectively. However, the monitoring method is limited to ex-situ sampling, which offers only a snapshot in time. To overcome the limitations and increase monitoring effectiveness, 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 industry and the public. The CWW uses simple in-situ water quality sensors based on surrogate sensing technology that employs an event detection system to screen the incoming data in near real-time. This objective of this study was to improve the understanding of groundwater quality in Wattenberg field and assess event detection methods. The data obtained from 5 sites (the earliest monitoring sites in the CWW network) for 3 years of the regional monitoring network in Wattenberg field is used to illustrate the background information about groundwater quality and its changing trend, and make comparisons between two outlier detection methods, CANARY and simple moving median.

Hydraulic fracturing uses a large volume a water to extract the oil and gas deposited in shale gas and oil formations. Many oil and gas developments are located in semiarid to arid areas in the United States (US), where freshwater resources are scarce. Using lower quality waters, such as brackish water during hydraulic fracturing, could be a good alternative to freshwater resources, reducing the competition on these sources and easing the public concerns with water shortages. This article examines using brackish water with total dissolved solids (TDS) of 2500 mg/L, optimization of carboxylmethyl cellulose (CMC) based fracturing fluid at different pH ranges and polymer concentrations. Five three dimensional (3D) contour maps were generated for peak viscosity at a polymer loading of 25–45 pounds per thousand gallons (ppt) of water. These viscosity maps are the first of their kind and help demonstrate that using poor quality water can be managed by optimizing the chemical composition of the fracturing fluid.

Flowback/produced water reuse cannot be optimized without a thorough understanding of the quality of the water that needs to be treated for reuse, including the temporal variability. Samples for flowback/produced water were collected over a 200-day period (day 0 refers to when flowback began) from two wells. One of the frac fluids had an initial pH greater than 10 and used a guar-based gel and the second fluid contained a non-guar polysaccharide based polymer with an initial pH of less than 6. Total dissolved solids (TDS) and total organic carbon (TOC) were used as macro-indicators and key ions (barium, calcium, chloride, magnesium, sodium, strontium, boron and iron) were compared to TDS with the different frac fluids and there were significant positive correlations observed between the key ions and TDS with relatively high values of the coefficient of determinant (over 0.85). The concentrations of calcium, chloride, sodium and strontium are statistically equivalent between the two fluids. A mass balance approach was applied to evaluate the quantity of mass of injected additives that was recovered over the 200-day period. Recoveries of zirconium, potassium and aluminum ranged from 3% to 33% after 200 days, and notable differences were observed between frac fluids.

Summary It has been common practice to use a freshwater source (either ground water or surface water) as the base fluid for hydraulic fracturing with crosslinked-gel fluids. Currently, oil and gas operators are beginning to reuse and recycle the main byproduct of oil extraction, which is produced water. However, because of the high variability of produced-water quality (temporal and spatial), and the high content of total dissolved solids (TDS), the viscosity targets for the fluid can be difficult to achieve. The research described in this paper examines the sensitivity of higher-salinity waters to several variables related to the gel-formation process. The polymer used for the gel fluid was a carboxymethyl cellulose (CMC) derivative, and zirconium (Zr) was used as the crosslinking metal. Rheology experiments were conducted at different pH values, polymer loading, and crosslinker concentrations. The outcome of this research is presented in 3D contour-peak-viscosity maps that can be used by oil and gas operators and service companies to optimize the chemicals that are applied, thus reducing costs.

Summary Recycling oilfield wastewater for hydraulic fracturing requires a good understanding of the water chemical characteristics and how these interact with the fracturing fluid. The viscosity and rheological properties of fracturing fluids affect proppant placement, length and width of fractures, fracture conductivity, and, consequently, the success of the treatment. The objective of the research described here was to understand if dissolved organic matter (DOM) at high concentrations influences subsequent fracturing with a gelled fluid. Experimental studies were conducted on four types of water: (1) model water with low DOM, (2) recycled water from an industrial-treatment facility (medium DOM), (3) untreated early-time flowback (ETFB) water (high DOM), and (4) untreated produced water (high DOM). A low-pH, zirconium-crosslinker-gelled fluid at 200°F was examined in the study. All three water samples that had significant levels of organic matter [total organic content (TOC) > 1000 mg/L] exhibited lower peak viscosities and more-rapid viscosity decay than the model water without organic matter. The destabilizing influence of organic matter on carboxyl methyl cellulose (CMC) gelled fracturing-fluid viscosity is thought to be caused by secondary crosslinking of the short-chain polymer residuals in the flowback, resulting in lower initial viscosity and stability.

Wastewater from shale oil and gas wells contains high levels of organic and inorganic compounds, and the beneficial reuse of produced water requires some level of treatment to remove emulsified oil and grease, suspended solids, and multivalent ions. It is important to identify the quantity and makeup of solids in produced water, so that an optimized reuse or treatment approach can be achieved. This study provides a qualitative and quantitative characterization of solids in frac flowback and produced water from five horizontal wells at two separate sites in the Wattenberg field of Northern Colorado. Difference in solids from wells fractured with fresh water and recycled water is compared in this study, and their distribution and characterization are identified by particle size distribution measurement and X-ray photoelectron spectroscopy (XPS). Results show that particle sizes were smaller and more uniform in produced water samples collected during the first week of production from the wells fractured with recycled water, suggesting that the recycled water was more compatible with the shale formation and wells fractured with recycled water tend to clean out faster.

In an effort to determine impacts of the increased use of treated produced water in new fracs, the rheology of two fracturing fluids was observed for varying water qualities. Specific ions of interest were spiked at varying concentrations into tap water that was used as a base for the fluids. Apparent viscosities were measured using a Chandler 5500 viscometer once fluids were formulated. Empirically, it was determined that at the chosen concentrations for this study, aluminum, iron, phosphorous, potassium, and sodium all have negative impacts on fracturing fluid stability. Calcium and magnesium improved fluid stability until a critical concentration was reached, resulting in lowered viscosities and a less stable fluid. The carboxymethyl cellulose (CMC) fluid was more resilient to aluminum, potassium, and sodium, and other ions that negatively impacted stability than the guar based fluid. The guar based fluid also benefited from divalent cations more than the CMC fluid. The effect of using concentrated gel hydrated with fresh water and then diluted with concentrated ion solutions was also evaluated and did not show any improvement in fluid stability. It appears that specific cations compete for crosslink sites on the gel polymer either through shielding or complexing with active sites that the crosslinker metal would normally complex with. This results in less crosslink sites available for the quatrovalent metal and a less stable fluid. In addition to crosslinked sites that an added crosslinker would complex with, hydrogen bonds can also make a weak crosslink. In the case of calcium and magnesium, the added cations displace hydrogen bonds and form a slightly stronger crosslink. However, this crosslink is not as strong as the ones made by the added crosslinker, and when a critical concentration of calcium or magnesium is reached, the cation competes with the added crosslinker as well, reducing fluid stability.

With the increased development of oil and gas activities in northern Colorado, public concerns over the environmental impacts associated with well drilling and hydraulic fracturing have continued to rise. Issues such as leakages of “toxic” products from oil and gas operations to the subsurface environment (such as groundwater contamination) have led to community action and state regulations related to the establishment of groundwater quality monitoring sites in oil and gas activity areas, particularly those adjacent to urban development. Colorado Water Watch was a groundwater quality monitoring network comprised of seven monitoring wells in northern Colorado to monitor groundwater quality near oil and gas wells and give early warnings of contamination. Our study is aimed at developing a quantitative methodology to find ideal monitoring locations as well as evaluate them. We utilized hydraulic and geological data to select the most preferred sites to monitor groundwater quality, understand the temporal trends and identify unique anomaly signals in the oil and gas active area (Wattenberg field, northern Colorado). In addition to the site selection methodology, water quality data from Colorado Water Watch over 2 years is used to do evaluate the performance using entropy information and Principal Component Analysis. The analysis indicates that the earliest functional monitoring site (CHILL) is the most informative monitoring well, and the most recently installed monitoring sites (Gilcrest and LaSalle) are the least informative and least important stations due to their low data efficiency.

Liquid chromatography quadrupole time-of-flight mass spectrometry was performed to understand how frac fluid with recycled water (RWA) and frac fluid with fresh water (FWA) compare when subjected to downhole temperature and oxidation conditions. Ethylene oxide and propylated glycol functional units were quantified from both RWA and FWA. Qualitative analysis was performed using Agilent qualitative analysis software B.06.00 based on the exact mass of the chemical compound. Ac e tone, aldol, alkoxylated phenol formaldehyde resin, diethylbenzene, dipropylene glycol, d-Limonene, ether salt, ethylbenzene, n-dodecyl-2-pyrrolidone, dodecylbenzenesulfonate isopropanolamine, polyethylene glycol, and triethylene glycol were detected in FWA and RWA samples. In the van Krevelen diagram, FWA and RWA show a low degree of oxidation and highly saturated organic compounds. Kendrick mass defect (KMD) analysis was applied using ethylene oxide and propylated glycol units. KMD analysis based on ethylene oxide was scattered between 0 and 0.1, while some KMD analyses based on the propylated glycol are close to 1. FWA had an average carbon number of 32.3 and double bond equivalent (DBE) of 9.8 while RWA had average carbon number of 31.5 and DBE of 9.5. RWA contained predominantly C21-C40 compounds, while FWA had a higher concentration in the over C41 range.

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.

Wastewater from shale oil and gas wells is an issue that has received significant attention although limited research has been conducted on the variability of water production from hydraulically fractured wells. In this paper, sources of variability in flowback and produced water volumes from horizontal oil and gas wells were examined and correlations established. Horizontal wells in the Denver-Julesburg basin operated by Noble Energy were studied and results show that water production varies with time, location and wellbore length as expected. Additionally, production volume variation with fracturing fluid type and water source (fresh versus recycled) was explored. Results indicate that both of these variables should also be considered when developing a general model for water production. A guar based frac fluid resulted in greater water production when compared to a cellulose-derivative based fluid. Finally, wells fraced with a fresh water based fluid had significantly greater produced water volume than geospatially-paired wells with a 1/7-recycled/fresh blend based fluid.

The occurrence and fate of antibiotic compounds in the aquatic environment has been recognized as an emerging area of interest in environmental chemistry. An analytical method was developed and validated for determining β-lactam and polyether ionophore antibiotics in surface water, urban wastewater, and sediment based on solid-phase extraction (SPE) and liquid chromatography–ion trap tandem mass spectrometry (LC-MS-MS). The average recovery of β-lactams and polyether ionophores from all the fortified samples was generally higher than 80% (except for amoxicillin and ampicillin). A total of 400 actual water and sediment samples were analysed using SPE-LC-MS-MS to evaluate the occurrence and fate of these antibiotic compounds in a river and a wastewater treatment plant in northern Colorado. Most samples were found to be negative for β-lactam compounds. In those samples with positive results, β-lactam compounds were found at 15–17 ng/L in influent wastewater samples, 9–11 ng/L in surface water samples, and 0....

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.

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 β-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 β-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 β-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.

The combination of advances in hydraulic-fracturing and horizontal-drilling technologies has led to a resurgence in oil and gas activity in multiple regions across the United States. To minimize the impact of the increased water use, many oil and gas companies are pursuing fracture-flowback-water and produced-water recycling for subsequent drilling and fracturing operations. Common processes in a recycling strategy include metal precipitation to minimize scaling potential and electrocoagulation for removing solids that may foul a well when water is reused. In this study, precipitation of calcium, magnesium, barium, and strontium were examined experimentally by adding target ligands followed by solids separation with electrocoagulation. In addition, removal efficacy was modeled using commercially available chemical-equilibrium software (OLI Systems). The experimental results were compared with the predicted data at pH values of 9.5 and 10.2. The differences between the modeled data and the experimental data indicated a deficiency in the solid/liquid-separation process in the laboratory. Results also showed that the pH value did not affect the treatment efficiency, except in the case of magnesium; however, sequencing of softening relative to coagulation was important. An additional finding was that, on the basis of the target metal, either sulfate or carbonate needs to be greater than a threshold concentration to achieve precipitation goals. Chemical consumption at pH values of 9.5 and 10.2 was significantly different. Chemical-equilibrium modeling predicts that the average base usage was 30% lower at a pH of 9.5 compared with a pH of 10.2 and 34% lower for acid usage. The reduction in use experimentally was 27% for base and 43% for acid.

The objectives of this study were to monitor total phosphorus concentrations and loads along the Cache la Poudre River in Northern Colorado as it flows from a pristine area through urban regions and, finally, through mixed land uses. The study attempted to evaluate the sources and influences of total phosphorus under different hydrologic conditions. Nine sampling events were completed from April 2010 to May 2011 to assess the influence of various hydrologic conditions on aqueous and riverbed sediment total phosphorus concentrations. Total phosphorus concentrations and loads exceeded the in-stream limits proposed by the Colorado Department of Public Health and Environment in all observed hydrologic conditions, and nonpoint sources were significant in high-flow conditions. Reducing nutrients only at water resource recovery facilities (WRRFs) could not achieve the in-stream limits without substantial reduction of non-point-source loads. The study exposed a need for flexibility in WRRF discharge limits based on the overall total phosphorus load in the river from other sources.

Public concerns related to the fast-growing shale oil and gas industry have increased during recent years. The major concern regarding shale gas production is the potential of fracturing fluids being injected into the well or produced fluids flowing out of the well to contaminate drinking water resources such as surface water and groundwater. Fracturing fluids contain high total dissolved solids (TDS); thus, changes in TDS concentrations in groundwater might indicate influences of fracturing fluids. An increase of methane concentrations in groundwater could also potentially be due to hydraulic fracturing activities. To understand the possible contamination of groundwater by fracturing activities, real-time groundwater monitoring is being implemented in the Denver-Julesburg basin of northeast Colorado. A strategy of monitoring of surrogate parameters was chosen instead of measuring potential contaminants directly, an approach that is not cost effective or operationally practical. Contaminant surrogates of TDS and dissolved methane were proposed in this study, and were tested for correlation and data distribution with laboratory experiments. Correlations between TDS and electrical conductivity (EC), and between methane contamination and oxidation–reduction potential (ORP) were strong at low concentrations of contaminants (1 mg/L TDS and 0.3 mg/L CH4). Dissolved oxygen (DO) was only an effective surrogate at higher methane concentrations (≥2.5 mg/L). The results indicated that EC and ORP are effective surrogates for detecting concentration changes of TDS and methane, respectively, and that a strategy of monitoring for easy to measure parameters can be effective detecting real-time, anomalous behavior relative to a predetermined baseline.

The objective of this study was to develop models that could be used to predict frac flowback and produced water volumes considering the unique decline rates that exist for different types of oil and gas wells. Specifically, water production data from the Colorado Oil and Gas Conservation Commission (COGCC) and Noble Energy Inc. were used to develop models for water production for vertical and horizontal wells, a distinction made largely due to the different amounts of water used for each. If centralized water treatment and handling facilities are going to be designed and constructed, it is important to have a reliable estimate of the water that will be produced in the future as wells are completed and brought on line. An Excel-based tool was developed utilizing the horizontal and vertical well models for predicting total volume of water production by current and future wells in Wattenberg Field. Two case studies have been conducted including one with all of the Noble wells in Wattenberg Field and one with a subset assuming a regional treatment center might be established. Uncertainty of the predictions was determined using standard error calculations on the two modeling parameters for water flow decline rates. An interactive Excel-based spreadsheet has been developed to allow predictions of water production based on the number of horizontal and vertical wells drilled in the future.

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.

Instant and accurate detection of chemical contamination in a water distribution system is significant in protecting public health and water resource. Using water quality surrogates to signal a contamination occurrence offers the advantage of detecting a large number of chemicals. This article describes how the indigenous biofilm in a contaminated drinking water system may provide an effective indirect surrogate response with either turbidity or ultraviolet changes (UV254). Rotating annular bioreactors (RAB) and pipe loops were used to quantify biofilm along with turbidity and UV254 measurements. The number of biofilm cells on the polyvinyl chloride (PVC) analytical coupons was also enumerated, using automated fluorescence microscopy. Measuring the biosensing capacity, the analytical coupons were submersed into beakers with potential chemical contaminants such as aldicarb, cyanide, cycloheximide, nicotine, sodium arsenate, and sodium fluoroacetate. Resulting data indicated that turbidity was a useful surr...

The development of unconventional resources in tight shales has stimulated considerable growth of oil and gas production in Northeastern Colorado, but has led to concerns about added demands on the region’s strained water resources. Northeastern Colorado’s semi-arid environment, population growth, competing water demands and uncertainty about drilling and hydraulic fracturing water requirements have resulted in scrutiny and conflict surrounding water use for tight shales. This study collects water use data from wells in Northeastern Colorado to improve water estimates and to better understand important contributing factors. Most water resource studies use estimates for the number of future wells to predict water demands. This study shows that the number of hydraulic fracturing stages is a better measure of the future water demands for horizontal wells. Vertical wells use significantly less water than horizontal wells and will be less prevalent in the future.

Summary Reusing waste water from the oil field for hydraulic fracturing has become an important topic in the oil and gas industry, and it requires a thorough understanding of both the quality and quantity of the waste water. In this paper, water production from horizontal shale wells in five sections of the Wattenberg field in northeastern Colorado was analyzed. Models were developed for these wells for future water-production prediction. A spatial analysis was also conducted by comparing water production from each section with the gas/oil-ratio (GOR) value for each well. Results indicate that the GOR value of wells has a significant impact on water production in the first year of operation. Wells with low GOR value tend to have higher fracturing-flowback volume and, furthermore, water-recovery rate. Results from this study also provide valuable information for estimating water production from unconventional shale fields, which is critical for the design of wastewater collection and treatment facilities in the field.

Two typical animal waste management practices, composting and stockpiling, were evaluated for their effect on the degradation of three veterinary antibiotics (VAs), chlortetracycline (CTC), tylosin (TYL), and monensin (MNS). The VAs were applied to horse manure plots subject to composting or stockpiling, and core samples were collected over a period of time. Selected buffer solutions were used to extract the VAs and analysis for concentration was conducted with solid phase extraction (SPE) followed by high performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS) technique. The VAs demonstrated rapid dissipation within ten days followed by a gradual decrease in concentration until the end of the experimental period (141 days). All three VAs degraded more rapidly in the composting samples than in the stockpiling samples, particularly between 20 and 60 days of the observation period. Degradation of the three VAs generally followed a first-order kinetic model, and a fitted model with a calculated rate constant was determined for each treatment. TYL in composting showed the fastest degradation, with a calculated rate constant of 0.91 day -1 ; the slowest degradation was exhibited by MNS in stockpiling, with rate constant of 0.17 day -1 . Calculated correlation coefficients ranged from 0.89 to 0.96, indicating a strong correlation between measured concentrations and fitted values in this study. Although concentration of TYL in composting treatment showed below detection limit during the test period, this study suggests that composting can reduce animal waste contaminants prior to field application as fertilizer.

A reactive stream stabilization (RS2) system based on aluminum as the adsorbent and garden mulch as the organic matter source was designed to minimize release of agricultural nonpoint source pollutants and installed along the bank of the Little Bogue Creek, MS in 2008. The scope of this research was to design, install and assess the performance of a field scale RS2 structure based on results from previous lab scale studies. Concentrations of alum and total organic carbon (TOC) in the RS2 test barrier and surrounding area were measured to evaluate design parameters of RS2 and the removal effectiveness was examined from soils and monitoring wells that were sampled in 2009. The mean concentration of Al from the reactive barrier was 2.1 mg/g and organic matter from the monitoring wells was 4.7 mg/L, values significantly greater than the surrounding area (p < 0.05). Soil Mehlich-3 P and total phosphorus (TP) were decreased by 55% and 30%, and 40% of the TN and 51% of the nitrate in the ground water were removed through the RS2. The design objectives have been satisfied with the installed RS2 system and the initial sampling data shows effective nutrient removal.

Veterinary antibiotics, leached from contaminated manure that is applied as fertilizer, could be transported to surface water as runoff or infiltrated to groundwater after a significant rainfall. The main objective of this study was to evaluate the transport behaviour of ten antibiotics belonging to four different groups in soil through the column leaching study under biotic and abiotic conditions. Among compared antibiotic groups, tetracyclines (TCs) were found to have no residual in the leachate and mainly remained sorbed to the fixed column soil ranging 34~81% of initially applied mass. In contrast, sulfamethazine(SMTs), one of the sulfonamides (SAs) group, was mostly recovered in the leachate at the ranges of 74~83% of the total mass applied. Also, colloidal-facilitated transport of antibiotics was observed. Depending on the antibiotics, recovered mass of colloidal-facilitated transport was 0.4~22.7% for biotic and 0.2~62.5% for abiotic treatment as compared to total mass applied in soil. In general, a less mass was recovered in biotic leachate and soil columns indicating that microorganism activity might be a minor attenuation mechanism. Results indicated that phase partitioning of antibiotics would be a major factor to be assessed in evaluation of fate and transport of antibiotics in soil.

Occurrence of human and veterinary antibiotics has been reported in various environmental compartments. Yet, there is a lack of information verifying the transport mechanisms from source to environment, particularly the transport of veterinary antibiotics as a non-point source pollutant. A rainfall simulation study was conducted to address surface runoff as a possible transport mechanism of veterinary antibiotics introduced in the field and mass balance was calculated with supplementary surface and depth soil measurement. Seven veterinary antibiotics that are the most abundantly used in agriculture for therapeutic and non-therapeutic (growth-promotion) purposes were examined in this study, including tetracycline (TC), chlortetracycline (CTC), sulfathiazole (STZ), sulfamethazine (SMZ), erythromycin (ETM), tylosin (TYL), and monensin (MNS). Runoff in aqueous and sediment phases was collected every 5 min for 1h with varied rainfall intensity and additional surface (0-2 cm) and depth (2-30 cm) soil samples were collected after rainfall simulation for mass balance analysis. Quantification of antibiotic concentration in all collected samples was based on solid phase extraction (SPE) followed by measurement with high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). MNS showed the highest concentration in runoff aqueous samples (0.22 mg plot(-1)), while ETM showed the highest concentration in runoff sediment samples (0.08 mg plot(-1)). The highest concentration of each applied antibiotic in surface soil samples occurred at different locations. This result might indicate the mobility of these compounds in surface soil varies due to different physicochemical properties among the antibiotics. Further, the analysis results showed that all of the subject antibiotics had penetrated into the subsurface; yet, no residuals were found for STZ, suggesting this compound might have penetrated even deeper into the soil. These results indicate that aqueous or sediment erosion control might reduce the transport of veterinary antibiotics in the environment.

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.

The occurrence of 15 antibiotics belonging to three different groups, tetracyclines (TCs), sulfonamides (SAs), and macrolides (MLs), mainly used to prevent or treat illness for humans and also to control disease or to promote the growth for animals was studied in aqueous and sediment matrices. The result of spatial and temporal statistical analysis revealed that measured concentrations of individual antibiotics were significantly different depending on sampling location and time periods for aqueous and sediment samples. High concentrations of human-used antibiotics were detected downstream of a wastewater treatment plant, and animal-used antibiotics were mainly found in a region with significant agricultural activity. Generally, the highest concentrations of antibiotics for both water and sediment samples were measured in winter indicating that low flow conditions and cold-water temperatures might enhance the persistence of these compounds. Furthermore, a pseudo-partitioning coefficient (P-PC) was introdu...

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 waterirrigation ditch waterurban/agriculturally impacted river sediments (p0.0001), 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.

An analytical method was developed and tested for four different groups of veterinary antibiotics in both river water and sediment matrices. Solid phase extraction (SPE) was used to enrich and to clean up the aqueous sample. Also, Mcllvaine and ammonium hydroxide buffer solutions were used to extract the compounds from the sediment matrix. High performance liquid chromatography (HPLC) equipped with tandem mass spectrometry (MS/MS) was used to separate and quantify the samples. The range of recoveries (in percent) for tetracyclines (TCs), sulfonamides (SAs), macrolides (MLs), and ionophore polyethers (IPs) in the water matrix were 102.2-124.8, 76.6-124.3, 89.5-114.7, 82.7-117.5 with 1-13 (%) of relative standard deviation respectively with three different concentrations. For sediment, the percent recovery ranges were 32.8-114.8, 62.4-108.9, 53.4-128.4 and 51.3-105.4 for TCs, SAs, MLs and IPs, respectively. The relative standard deviation ranged from 16 - 27 (%) over three different concentrations. The limit of quantification (LOQ) was determined by two different methods and calculated to be in the range of 0.01-0.04 microg/l and 0.3-2.5 microg/kg for TCs, SAs, and MLs in water and sediment, respectively. For IPs, the LOQ was 0.001-0.003 microg/l in river water and 0.4-3.6 microg/kg for sediment. The sediment concentration measured in an agriculture-influenced river was much higher than in the overlying water matrix, indicating a high degree of sediment partitioning for these compounds.

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.

Analytical methods for quantifying three ionophore antibiotics, monensin, salinomycin, and narasin, were developed for water and sediment matrices. Sample preparation was based on solid-phase extraction (SPE) and high-performance liquid chromatography (HPLC) tandem mass spectrometry (MS/MS) was used to separate and detect the compounds. Recoveries ranged from 83% to 117% for water and from 51% to 105% for sediment in three different concentrations with less than 10% of relative standard deviation. The statistical detection limit was 0.001-0.003 microg/L for water and 0.4-3.6 microg/kg for sediment. Ionophore antibiotics are only used to treat coccidiostats for broilers or turkeys, and to increase growth and feed efficiency for beef and dairy cattle. Since they are not used for human purposes, these compounds can act as markers for the transport of animal pharmaceuticals to the watershed. The occurrence of three ionophore compounds was determined at five sampling sites along the Cache la Poudre River in Northern Colorado representing pristine, urban, and agriculture landscapes. Statistical analysis demonstrates that the measured concentration was significantly different among sampling sites in different sampling events for both water and sediment. In addition, significant differences were observed among different sampling times at each sampling site. Furthermore, all three ionophores were found in the sediments at much higher concentrations than in water indicating the importance of this matrix when determining environmental impacts.

Two wastewater treatment plants (WWTPs) of northern Colorado were monitored for anhydroerythromycin and tylosin. An analytical method has been developed and validated for the trace determination and confirmation of these compounds in the raw influent and final effluent water matrices. This method was used to evaluate the occurrence and fate of these compounds in WWTPs. The method uses solid-phase extraction and liquid chromatography-tandem mass spectrometry with positive electrospray ionization. Detection and quantification was performed using selected reaction monitoring, and a method detection limit of between 0.01 and 0.06 microg/L was obtained. Unequivocal confirmation analysis of analyte identity according to the criteria (based on the use of identification points) of the 2002/657/EC European Commission Decision was possible with satisfactory results. Average recoveries for the two compounds ranged from 89.2+/-9.7% for raw influent to 93.7+/-6.9% for effluent wastewaters. The within-run precision of the assay was found to be always less than 14.1% for the two analytes. The overall precision was always less than 13.7%. The relative uncertainty of the present assay was also evaluated and the combined relative uncertainty ranged from 6.4 to 15.5% over three days of the validation study. These compounds were partially removed in the WWTPs with a removal efficiency of >50%. The measured concentrations in raw influents and effluents ranged from 0.09-0.35 and 0.04-0.12 microg/L for anhydroerythromycin to 0.06-0.18 and ND-0.06 microg/L for tylosin, respectively. The results indicate that WWTP effluents are relevant point sources for residues of these compounds in the aquatic environment. These occurrence results were compared with those in WWTP wastewaters of other countries.

This four-page summary provides a general overview of the complete text of this article, which is available online in e-JOURNAL AWWA at www.awwa.org/communications/journal/2005/july.