Characterizing anecdotal claims of groundwater contamination in shale energy basins.

The increased societal monitoring of unconventional oil and gas development (UD) has brought forth tremendous scrutiny over the environmental stewardship and subsequent public health impacts of surface and sub-surface activities. Concerns over groundwater quality in shale energy basins have prompted concerned citizens into monitoring UD activities for a series of qualitative parameters, and even coordinating sampling efforts for chemical analysis. Here we present a list of analytical parameters, hierarchically structured to guide concerned citizens through an efficient and cost-effective monitoring program. Utilizing this multi-step testing regime, we assessed groundwater quality from 36 private water wells involved in 19 anecdotal claims of alleged UD-related contamination across the Barnett, Eagle Ford, Haynesville, and Marcellus Shale formations in the United States. Our analytical findings aligned with the landowners' accounts of their situation in only 5 of the 36 collected samples, with several cases revealing environmental abnormalities that were unbeknownst to the landowners but likely unrelated to UD activities. These data are some of the first to assess the relationship between landowner perception and analytical determination in a cohort of highly variable anecdotal cases of alleged groundwater contamination, revealing a notable disconnect that is likely attributable to a myriad of societal and environmental factors. The analytical modalities presented here also serve as a step-wise method in a weight of evidence approach to assess the presence or absence of anthropogenic contamination under the most variable hydrogeological conditions.

Comparison of the degree of fouling at various flux rates and modes of operation using forward osmosis for remediation of produced water from unconventional oil and gas development.

Driven by increased energy demands and technological advancements, the energy landscape of the United States has been changed by the expansion of unconventional oil and gas extraction. Unconventional development requires well stimulation, which uses millions of gallons of water per well and generates billions of gallons of wastewater annually. The waste matrix, referred to as produced water, has proven to be challenging to treat due to the complex physical, chemical, and biological composition, which can change over the lifetime of a production well. Here, forward osmosis was used as a remediation technique to extract fresh water from produced water procured from the Permian Basin region of west Texas. These data examine the durability of thin-film hollow-fiber membranes by determining how quickly the membranes irreversibly fouled at various flux rates during two modes of operation: a) active layer in contact with the draw solution (AL-DS); and b) active layer in contact with the feed solution (AL-FS). Membranes used in AL-DS mode fouled faster than their counterparts used in AL-FS mode. Additionally, membranes used with higher flux rates fouled more quickly than those used under low flux conditions. Ultimately, it was determined that produced water will require pretreatment prior to being concentrated using forward osmosis.

Forward osmosis remediation of high salinity Permian Basin produced water from unconventional oil and gas development.

Unconventional oil and gas operations are on the rise, and they are an integral component to meeting the nation's energy needs. Produced water is the primary by-product of oil and gas operations, and it has proven challenging to treat to date. The aim of this study was to evaluate the feasibility of using forward osmosis with thin-film composite hollow fiber membranes as a remediation option for produced water with high total dissolved solids levels from the Permian Basin. Trials consisted of a series of 5 experiments in order to evaluate the performance of the membrane. Three PW samples, each from different locations, were used to conduct the series of experiments and compare the performance of the membranes on samples with TDS levels ranging from 16,000 to 210,000 mg/L. It was concluded that forward osmosis can be used to extract water from high salinity oil field brines and PW. Flux decreased over the course of the trials due to a combination of membrane fouling, concentration polarization, and temperature fluctuations. The flux of the PW was similar to the flux measured for the PW mimic with small difference due to the influence of activity on the osmotic pressure. The flux was also influenced by temperature and the linear velocity of the feed solution and draw solution.

Lab-simulated downhole leaching of formaldehyde from proppants by high performance liquid chromatography (HPLC), headspace gas chromatography-vacuum ultraviolet (HS-GC-VUV) spectroscopy, and headspace gas chromatography-mass spectrometry (HS-GC-MS).

The ability of different methods to analyze formaldehyde and other leachates from proppants was investigated under lab-simulated downhole conditions. These methods include high performance liquid chromatography (HPLC), headspace gas chromatography-vacuum ultraviolet spectroscopy (HS-GC-VUV), and headspace gas chromatography-mass spectrometry (HS-GC-MS). Two different types of resin-coated proppants, phenol-formaldehyde- and polyurethane-based, were examined. Each proppant was tested at different time intervals (1, 4, 15, 20, or 25 hours) to determine the timeframe for chemical dissolution. Analyses were performed at room temperature and heated (93 °C) to examine how temperature affected the concentration of leachates. Multiple matrices were examined to mimic conditions in subsurface environment including deionized water, a solution surrogate to mimic the ionic concentration of produced water, and recovered produced water. The complexity of these samples was further enhanced to simulate downhole conditions by the addition of shale core. The influence of matrix components on the analysis of formaldehyde was greatly correlated to the quantity of formaldehyde measured. Of the three techniques surveyed, HS-GC-MS was found to be better suited for the analysis of formaldehyde leachates in complex samples. It was found that phenol-formaldehyde resin coated proppants leached higher concentrations of formaldehyde than the polyurethane resin coated proppants.

Complex mixture quantification without calibration using gas chromatography and a comprehensive carbon reactor in conjunction with flame ionization detection.

Quantification of complex carbon-containing mixtures is typically a very time-intensive task with regards to the calibration process. A gas chromatograph with a flame ionization detector yields strong responses to organic compounds and provides a wide linear range over many orders of magnitude; however, responses for highly functionalized and heteroatom-containing compounds can be variable. Here, a commercial Polyarc microreactor unit, placed before the flame ionization detector, was investigated as a means of normalizing carbon response across all compounds. The device includes two catalytic reaction chambers, ultimately converting all carbon atoms to methane evenly for flame ionization detection. Three groups of different complex mixtures from n-alkane to terpene and polymer mixtures were analyzed to evaluate the potential for calibration-free quantitation of the new detector arrangement. We have obtained accurate quantification results without time-consuming calibration processes. The quantification of a terpene mixture and a polymer mixture confirms the ability of the detector for analyzing samples that either have complex physical or structural properties or wide concentration range. In summary, compared to other detectors, this methanizer - flame ionization detection system provides a simplified workflow, which can eliminate calibration steps and increase throughput.

Characterizing variable biogeochemical changes during the treatment of produced oilfield waste.

At the forefront of the discussions about climate change and energy independence has been the process of hydraulic fracturing, which utilizes large amounts of water, proppants, and chemical additives to stimulate sequestered hydrocarbons from impermeable subsurface strata. This process also produces large amounts of heterogeneous flowback and formation waters, the subsurface disposal of which has most recently been linked to the induction of anthropogenic earthquakes. As such, the management of these waste streams has provided a newfound impetus to explore recycling alternatives to reduce the reliance on subsurface disposal and fresh water resources. However, the biogeochemical characteristics of produced oilfield waste render its recycling and reutilization for production well stimulation a substantial challenge. Here we present a comprehensive analysis of produced waste from the Eagle Ford shale region before, during, and after treatment through adjustable separation, flocculation, and disinfection technologies. The collection of bulk measurements revealed significant reductions in suspended and dissolved constituents that could otherwise preclude untreated produced water from being utilized for production well stimulation. Additionally, a significant step-wise reduction in pertinent scaling and well-fouling elements was observed, in conjunction with notable fluctuations in the microbiomes of highly variable produced waters. Collectively, these data provide insight into the efficacies of available water treatment modalities within the shale energy sector, which is currently challenged with improving the environmental stewardship of produced water management.

Matrix-effect-free determination of BTEX in variable soil compositions using room temperature ionic liquid co-solvents in static headspace gas chromatography mass spectrometry.

Concerns about the environmental impact of shale energy exploration (i.e., hydraulic fracturing and other well stimulation techniques) have risen due to its rapid expansion in the United States and other countries. Soils in shale basins engaged in unconventional oil and gas development can become contaminated by volatile organic compounds (VOCs), such as benzene, toluene, ethylbenzene, and xylenes (BTEX) through mishandling of chemical additives, products, and/or waste fluids. In this study, room temperature ionic liquids (RTILs) were evaluated as solvents in an effort to increase sensitivity and to reduce and normalize matrix effects associated with varying soil compositions during analysis. Headspace gas chromatography mass spectrometry (HS-GC-MS) experiments demonstrated that hydrophilic RTILs 1-ethyl-3-methylimidazolium ethyl sulfate [EMIM][ESO4], 1-ethyl-3-methylimidazolium diethyl phosphate [EMIM][DEP], and tris(2-hydroxyethyl) methylammonium methylsulfate [MTEOA][MeOSO3] normalized the response for BTEX compounds between 2 different soils, sandy loam and sandy clay loam. Furthermore, the optimization of the HS equilibration time to 30 min resulted in the reduction of matrix effects in certified reference soils of sand, clay, and loam textures. Limits of detection and limits of quantification were in the sub- to mid- pg g-1 level in soil. For determination at 1 g of certified BTEX reference soil, the relative standard deviation was within 10% and percent recoveries were above 80% for toluene, ethylbenzene, and xylenes. This method reduces the need to characterize and matrix-match soil texture for calibration purposes. It also reduces the analysis time and increases precision and accuracy for the quantification of BTEX in variable soil matrices relative to standard methods.

On-line supercritical fluid extraction-supercritical fluid chromatography-mass spectrometry of polycyclic aromatic hydrocarbons in soil.

On-line supercritical fluid extraction - supercritical fluid chromatography - mass spectrometry (SFE-SFC-MS) has been applied for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil. The purpose of this study was to develop and validate the first on-line SFE-SFC-MS method for the quantification of PAHs in various types of soil. By coupling the sample extraction on-line with chromatography and detection, sample preparation is minimized, diminishing sample loss and contamination, and significantly decreasing the required extraction time. Parameters for on-line extraction coupled to chromatographic analysis were optimized. The method was validated for concentrations of 10-1500 ng of PAHs per gram of soil in Certified Reference Material (CRM) sediment, clay, and sand with R2 ≥ 0.99. Limits of detection (LOD) were found in the range of 0.001-5 ng/g, and limits of quantification (LOQ) in the range of 5-15 ng/g. The method developed in this study can be effectively applied to the study of PAHs in the environment, and may lay the foundation for further applications of on-line SFE-SFC-MS.

Characterization of bacterial diversity in contaminated groundwater using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Groundwater is a major source for drinking water in the United States, and therefore, its quality and quantity is of extreme importance. One major concern that has emerged is the possible contamination of groundwater due to the unconventional oil and gas extraction activities. As such, the impacts of exogenous contaminants on microbial ecology is an area to be explored to understand what are the chemical and physical conditions that allow the proliferation of pathogenic bacteria and to find alternatives for water treatment by identifying organic-degrading bacteria. In this work, we assess the interplay between groundwater quality and the microbiome in contaminated groundwaters rich in hydrocarbon gases, volatile organic and inorganic compounds, and various metals. Opportunistic pathogenic bacteria, such as Aeromonas hydrophila, Bacillus cereus, Pseudomonas aeruginosa, and Stenotrophomonas maltophilia, were identified, increasing the risk for consumption of and exposure to these contaminated groundwaters. Additionally, antimicrobial tests revealed that many of the identified bacteria were resistant to different antibiotics. The MALDI-TOF MS results were successfully confirmed with 16S rRNA gene sequencing, proving the accuracy of this high-throughput method. Collectively, these data provide a seminal understanding of the microbial populations in contaminated groundwater overlying anthropogenic activities like unconventional oil and gas development.

Exploring the links between groundwater quality and bacterial communities near oil and gas extraction activities.

Bacterial communities in groundwater are very important as they maintain a balanced biogeochemical environment. When subjected to stressful environments, for example, due to anthropogenic contamination, bacterial communities and their dynamics change. Studying the responses of the groundwater microbiome in the face of environmental changes can add to our growing knowledge of microbial ecology, which can be utilized for the development of novel bioremediation strategies. High-throughput and simpler techniques that allow the real-time study of different microbiomes and their dynamics are necessary, especially when examining larger data sets. Matrix-assisted laser desorption-ionization (MALDI) time-of-flight mass spectrometry (TOF-MS) is a workhorse for the high-throughput identification of bacteria. In this work, groundwater samples were collected from a rural area in southern Texas, where agricultural activities and unconventional oil and gas development are the most prevalent anthropogenic activities. Bacterial communities were assessed using MALDI-TOF MS, with bacterial diversity and abundance being analyzed with the contexts of numerous organic and inorganic groundwater constituents. Mainly denitrifying and heterotrophic bacteria from the Phylum Proteobacteria were isolated. These microorganisms are able to either transform nitrate into gaseous forms of nitrogen or degrade organic compounds such as hydrocarbons. Overall, the bacterial communities varied significantly with respect to the compositional differences that were observed from the collected groundwater samples. Collectively, these data provide a baseline measurement of bacterial diversity in groundwater located near anthropogenic surface and subsurface activities.

MALDI-TOF MS for the Identification of Cultivable Organic-Degrading Bacteria in Contaminated Groundwater near Unconventional Natural Gas Extraction Sites.

Groundwater quality and quantity is of extreme importance as it is a source of drinking water in the United States. One major concern has emerged due to the possible contamination of groundwater from unconventional oil and natural gas extraction activities. Recent studies have been performed to understand if these activities are causing groundwater contamination, particularly with respect to exogenous hydrocarbons and volatile organic compounds. The impact of contaminants on microbial ecology is an area to be explored as alternatives for water treatment are necessary. In this work, we identified cultivable organic-degrading bacteria in groundwater in close proximity to unconventional natural gas extraction. Pseudomonas stutzeri and Acinetobacter haemolyticus were identified using matrix-assisted laser desorption/ionization-time-of-flight-mass spectrometry (MALDI-TOF MS), which proved to be a simple, fast, and reliable method. Additionally, the potential use of the identified bacteria in water and/or wastewater bioremediation was studied by determining the ability of these microorganisms to degrade toluene and chloroform. In fact, these bacteria can be potentially applied for in situ bioremediation of contaminated water and wastewater treatment, as they were able to degrade both compounds.

Characterization of methane plumes downwind of natural gas compressor stations in Pennsylvania and New York.

The extraction of unconventional oil and natural gas from shale energy reservoirs has raised concerns regarding upstream and midstream activities and their potential impacts on air quality. Here we present in situ measurements of ambient methane concentrations near multiple natural gas compressor stations in New York and Pennsylvania using cavity ring-down laser spectrometry coupled with global positioning system technology. These data reveal discernible methane plumes located proximally to compressor stations, which exhibit high variability in their methane emissions depending on the weather conditions and on-site activities. During atmospheric temperature inversions, when near-ground mixing of the atmosphere is limited or does not occur, residents and properties located within 1 mile of a compressor station can be exposed to rogue methane from these point sources. These data provide important insight into the characterization and potential for optimization of natural gas compressor station operations.

A reconnaissance analysis of groundwater quality in the Eagle Ford shale region reveals two distinct bromide/chloride populations.

The extraction of oil and natural gas from unconventional shale formations has prompted a series of investigations to examine the quality of the groundwater in the overlying aquifers. Here we present a reconnaissance analysis of groundwater quality in the Eagle Ford region of southern Texas. These data reveal two distinct sample populations that are differentiable by bromide/chloride ratios. Elevated levels of fluoride, nitrate, sulfate, various metal ions, and the detection of exotic volatile organic compounds highlight a high bromide group of samples, which is geographically clustered, while encompassing multiple hydrogeological strata. Samples with bromide/chloride ratios representative of connate water displayed elevated levels of total organic carbon, while revealing the detection of alcohols and chlorinated compounds. These findings suggest that groundwater quality in the Western Gulf Basin is, for the most part, controlled by a series of natural processes; however, there is also evidence of episodic contamination events potentially attributed to unconventional oil and gas development or other anthropogenic activities. Collectively, this characterization of natural groundwater constituents and exogenous compounds will guide targeted remediation efforts and provides insight for agricultural entities, industrial operators, and rural communities that rely on groundwater in southern Texas.

Point source attribution of ambient contamination events near unconventional oil and gas development.

We present an analysis of ambient benzene, toluene, and xylene isomers in the Eagle Ford shale region of southern Texas. In situ air quality measurements using membrane inlet mobile mass spectrometry revealed ambient benzene and toluene concentrations as high as 1000 and 5000 parts-per-billion, respectively, originating from specific sub-processes on unconventional oil and gas well pad sites. The detection of highly variant contamination events attributable to natural gas flaring units, condensate tanks, compressor units, and hydrogen sulfide scavengers indicates that mechanical inefficiencies, and not necessarily the inherent nature of the extraction process as a whole, result in the release of these compounds into the environment. This awareness of ongoing contamination events contributes to an enhanced knowledge of ambient volatile organic compounds on a regional scale. While these reconnaissance measurements on their own do not fully characterize the fluctuations of ambient BTEX concentrations that likely exist in the atmosphere of the Eagle Ford Shale region, they do suggest that contamination events from unconventional oil and gas development can be monitored, controlled, and reduced.

Temporal variation in groundwater quality in the Permian Basin of Texas, a region of increasing unconventional oil and gas development.

The recent expansion of natural gas and oil extraction using unconventional oil and gas development (UD) practices such as horizontal drilling and hydraulic fracturing has raised questions about the potential for environmental impacts. Prior research has focused on evaluations of air and water quality in particular regions without explicitly considering temporal variation; thus, little is known about the potential effects of UD activity on the environment over longer periods of time. Here, we present an assessment of private well water quality in an area of increasing UD activity over a period of 13months. We analyzed samples from 42 private water wells located in three contiguous counties on the Eastern Shelf of the Permian Basin in Texas. This area has experienced a rise in UD activity in the last few years, and we analyzed samples in four separate time points to assess variation in groundwater quality over time as UD activities increased. We monitored general water quality parameters as well as several compounds used in UD activities. We found that some constituents remained stable over time, but others experienced significant variation over the period of study. Notable findings include significant changes in total organic carbon and pH along with ephemeral detections of ethanol, bromide, and dichloromethane after the initial sampling phase. These data provide insight into the potentially transient nature of compounds associated with groundwater contamination in areas experiencing UD activity.

Elucidating hydraulic fracturing impacts on groundwater quality using a regional geospatial statistical modeling approach.

Hydraulic fracturing operations have been viewed as the cause of certain environmental issues including groundwater contamination. The potential for hydraulic fracturing to induce contaminant pathways in groundwater is not well understood since gas wells are completed while isolating the water table and the gas-bearing reservoirs lay thousands of feet below the water table. Recent studies have attributed ground water contamination to poor well construction and leaks in the wellbore annulus due to ruptured wellbore casings. In this paper, a geospatial model of the Barnett Shale region was created using ArcGIS. The model was used for spatial analysis of groundwater quality data in order to determine if regional variations in groundwater quality, as indicated by various groundwater constituent concentrations, may be associated with the presence of hydraulically fractured gas wells in the region. The Barnett Shale reservoir pressure, completions data, and fracture treatment data were evaluated as predictors of groundwater quality change. Results indicated that elevated concentrations of certain groundwater constituents are likely related to natural gas production in the study area and that beryllium, in this formation, could be used as an indicator variable for evaluating fracturing impacts on regional groundwater quality. Results also indicated that gas well density and formation pressures correlate to change in regional water quality whereas proximity to gas wells, by itself, does not. The results also provided indirect evidence supporting the possibility that micro annular fissures serve as a pathway transporting fluids and chemicals from the fractured wellbore to the overlying groundwater aquifers.

A Comprehensive Analysis of Groundwater Quality in The Barnett Shale Region.

The exploration of unconventional shale energy reserves and the extensive use of hydraulic fracturing during well stimulation have raised concerns about the potential effects of unconventional oil and gas extraction (UOG) on the environment. Most accounts of groundwater contamination have focused primarily on the compositional analysis of dissolved gases to address whether UOG activities have had deleterious effects on overlying aquifers. Here, we present an analysis of 550 groundwater samples collected from private and public supply water wells drawing from aquifers overlying the Barnett shale formation of Texas. We detected multiple volatile organic carbon compounds throughout the region, including various alcohols, the BTEX family of compounds, and several chlorinated compounds. These data do not necessarily identify UOG activities as the source of contamination; however, they do provide a strong impetus for further monitoring and analysis of groundwater quality in this region as many of the compounds we detected are known to be associated with UOG techniques.

Vacuum ultraviolet detector for gas chromatography.

Analytical performance characteristics of a new vacuum ultraviolet (VUV) detector for gas chromatography (GC) are reported. GC-VUV was applied to hydrocarbons, fixed gases, polyaromatic hydrocarbons, fatty acids, pesticides, drugs, and estrogens. Applications were chosen to feature the sensitivity and universal detection capabilities of the VUV detector, especially for cases where mass spectrometry performance has been limited. Virtually all chemical species absorb and have unique gas phase absorption cross sections in the approximately 120-240 nm wavelength range monitored. Spectra are presented, along with the ability to use software for deconvolution of overlapping signals. Some comparisons with experimental synchrotron data and computed theoretical spectra show good agreement, although more work is needed on appropriate computational methods to match the simultaneous broadband electronic and vibronic excitation initiated by the deuterium lamp. Quantitative analysis is governed by Beer-Lambert Law relationships. Mass on-column detection limits reported for representatives of different classes of analytes ranged from 15 (benzene) to 246 pg (water). Linear range measured at peak absorption for benzene was 3-4 orders of magnitude. Importantly, where absorption cross sections are known for analytes, the VUV detector is capable of absolute determination (without calibration) of the number of molecules present in the flow cell in the absence of chemical interferences. This study sets the stage for application of GC-VUV technology across a wide breadth of research areas.