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Advanced chemical recycling techniques provide new avenues for handling and recycling mixed plastic waste; pyrolysis is a prominent approach involving heating plastic waste in an oxygen-free environment to create pyrolysis oils. Pyrolysis oils must be thoroughly characterized before being refined into fuels and chemical feedstocks. Here, a method based on supercritical fluid chromatography with ultraviolet detection was developed to analyze plastic waste pyrolysis oils. Multiple stationary phases were examined, and 2-ethyl pyridine was chosen as the best stationary phase for resolving pyrolysis oil components. Different standards and different plastic waste pyrolysis oils were compared across the different stationary phases. Up to three columns were serially coupled to increase efficiency and column capacity. It was found that a general method using ethanol as a modifier and two 2-ethyl pyridine columns could effectively resolve plastic waste pyrolysis oils. The potential for differentiating polyethylene and polypropylene feedstocks was demonstrated using principal component analysis., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Jean-Francois Borny reports financial support was provided by The Lummus Technology, LLC. Jean-Francois Borny reports a relationship with Lummus Technology LLC that includes: employment. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

A method for clinical potency determination of psilocybin and psilocin in hallucinogenic mushroom species Psilocybe cubensis was developed using liquid chromatography with tandem mass spectrometry (LC-MS/MS). Five strains of dried, intact mushrooms were obtained and analyzed: Blue Meanie, Creeper, B-Plus, Texas Yellow, and Thai Cubensis. An extraction protocol was developed; this included an evaluation of sample milling technique, extraction solvents, and recovery/stability. Reversed phase chromatography on fused-core particle phases was developed for the determination of the two analytes using internal standard calibration with deuterated isotopologues of each analyte. The separation takes less than 5 min. Matrix effects were investigated by comparing signal response of calibration samples in neat solution and several mushroom matrices; no significant matrix effects were observed. The limit of detection for psilocybin was 1.5 ng/mL (1.5 pg on-column; 300 ng/g mushroom) and for psilocin was 0.15 ng/mL (0.15 pg on-column; 30 ng/g mushroom) using a Shimadzu LCMS-8050 triple quadrupole mass spectrometer. Assessment of the accuracy and precision of the method indicated percent error and RSD were <6 % at all concentration levels. Three whole, intact mushrooms from each strain were analyzed individually to obtain average content differences both between strains and between mushrooms of the same strain. From most to least potent, the study found that the average total psilocybin and psilocin concentrations for the Creeper, Blue Meanie, B+, Texas Yellow, and Thai Cubensis strains were 1.36, 1.221, 1.134, 1.103, and 0.879 % (w/w), respectively. A subset of these mushrooms was also tested in a separate non-affiliated laboratory, and the results were comparable between the two laboratories. Results from the secondary laboratory showed improved precision when multiple mushrooms were homogenized together, prior to extraction., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: JF and SK are employees of Shimadzu Scientific Instruments, the manufacturer of the instrumentation used in this study. SB, ABK, and US are employees of Millipore-Sigma. They performed the secondary potency study and provided chemical standards for this research., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Understanding the thermodynamic interactions between an analyte and the sample phase is of paramount importance when choosing a co-solvent in headspace analysis. A sample phase - gas phase equilibrium partition coefficient (Kp) is used fundamentally to describe the distribution of the analyte between the two phases. Kp determinations by headspace gas chromatography (HS-GC) were acquired by two methods: vapor phase calibration (VPC) and phase ratio variation (PRV). Here, we demonstrated a pressurized - loop headspace system in conjunction with gas chromatography vacuum ultraviolet detection (HS-GC-VUV) to directly calculate the concentration of analytes in the gas phase from room temperature ionic liquids (RTILs) sample phases, using pseudo-absolute quantification (PAQ). PAQ, an attribute of VUV detection, allowed for quick determination of Kp and other thermodynamic properties, such as enthalpy (ΔH) and entropy (ΔS) of the system through the use of van't Hoff plots in the temperature range of 70-110 °C. The Kp determinations by PAQ were comparable to those obtained using the VPC method with percent difference ranging from ≤ 1-33%. Kp determinations were made for analytes (cyclohexane, benzene, octane, toluene, chlorobenzene, ethylbenzene, m-,p-, and o-xylene) at the varying temperatures (70-110 °C) using different RTILs (1-ethyl-3-methylimidazolium ethylsulfate ([EMIM][ESO 4 ]), 1-ethyl-3-methylimidazolium diethylphosphate ([EMIM][DEP]), and tris(2-hydroxyethyl)methylammonium methylsulfate ([MTEOA][MeOSO 3 ])) and (1-ethyl-3-methylimidazolium bis(trisfluoromethanesulfonyl)imide ([EMIM] [NTF 2 ])). The results from the van't Hoff analysis revealed that [EMIM] cation-based RTILs exhibit strong solute-solvent interactions with analytes that have π- electrons., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: KAS is a member of the scientific advisory board for VUV Analytics, Inc., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Targeting and quantifying intact proteins from biological samples is still a very challenging research area. Several crucial steps exist in the analytical workflow, including development of a reliable sample preparation method. Here, we developed and applied for the first time a non-immunoaffinity sample preparation method based on a generally widely available micro-elution solid phase extraction (μSPE) strategy for the extraction of multiple lower molecular weight intact proteins (<30 kDa) from various biological matrices. Omission of a time-consuming drying and reconstitution step after extraction resulted in a more simple and rapid sample preparation procedure. A model set of eleven intact proteins (molecular weights: 5.5-29 kDa; isoelectric points: 4.5-11.3) were analyzed in multiple biological fluids using reversed-phase liquid chromatography with a triple quadrupole mass spectrometer operated in multiple reaction monitoring mode. Various sample pre-treatment reagents, sorbent types, and washing and elution solvents were experimentally tested and optimized to obtain the μSPE clean-up condition for a broad mixture of intact proteins having variable physicochemical properties. 1% trifluoroacetic acid and 0.2% Triton 100-X were selected as suitable sample pre-treatment reagents for releasing protein-protein interactions in human serum/plasma and human urine, respectively. Hydrophilic lipophilic balanced μSPE sorbent was selected as a high performing stationary phase. Addition of 1% trifluoroacetic acid to all washing and elution solutions showed the most beneficial effect for the extraction recovery of the proteins. Under the optimized conditions, reproducible extraction recoveries >65% for all targeted proteins (up to 30 kDa) in human urine and >50% for most of the proteins in serum/plasma were achieved. The selected conditions were applied also for the analysis of clinical serum and urine samples to demonstrate the feasibility of the developed method to target intact proteins directly by more affordable μSPE sample preparation and triple quadrupole mass spectrometry, which could be beneficial in many application fields., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Although all beer is brewed using the same four classes of ingredients, contemporary beer styles show wide variation in flavor and color, suggesting differences in their chemical profiles. A selection of 32 beers covering five styles (India pale ale, blonde, stout, wheat, and sour) were investigated to determine chemical features, which discriminate between popular beer styles. The beers were analyzed in an untargeted fashion using liquid chromatography quadrupole time-of-flight mass spectrometry (LC-QTOF-MS). The separation and detection method were tuned to include compounds from important beer components, namely iso-α-acids and phenolic compounds. Due to the sheer number of unknown compounds in beer, multivariate analysis and machine learning techniques were used to pinpoint some of the compounds most influential in distinguishing beer styles. It was determined that while many phenols and iso-α-acids were present in the beers, they were not the compounds most responsible for the variations between styles. However, it was possible to discriminate each beer style using multivariate analysis. Principal component analysis (PCA) was able to separate and cluster the individual beer samples by style. A combination of statistical tools were used to predict formulas for some of the most influential metabolites from each style. Machine learning models accurately classified patterns in the five beer styles, indicating that they can be precisely distinguished by their nonvolatile chemical profile., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Gas well liquification is a problematic process whereby liquids collect in the wellbore and near wellbore reservoir resulting in production impedance in aging gas wells. Removal of these liquids is traditionally performed through human operated blowdown events; however, this practice results in the release of hydrocarbon emissions into the atmosphere. The removal process, called 'deliquification', can also be accomplished through the utilization of various plunger lift technologies. These allow the extraction of retained fluids from the wellbore and near-wellbore reservoir; however, these technologies vary greatly with respect to automation, intelligence, and efficacy. Here we examined the rates of production loss and the frequency of emission events in mature natural gas wells equipped with various automated plunger lift technologies. Overall, 'intelligent' plunger lift systems that base their optimization on reservoir and wellbore conditions, as opposed to standardized or scheduled operations, performed the best exhibiting a 0.13% loss of production gas to atmospheric emissions compared to a 1.37% loss of production observed from wells without a plunger lift system. Additionally, wells equipped with a next generation reservoir optimized plunger lift demonstrated a reduced rate of production decline compared to those wells without a plunger lift technology (-0.066%/day and -0.242%/day, respectively). These data have widespread implications for the operational and environmental management of a consistently increasing count of aging natural gas production wells., Competing Interests: Declaration of competing interest The authors attest to there being no conflicts of interest associated with this research. ZLH was commissioned by Avenirre to independently evaluate available emissions data., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Organosilanes are used in a broad range of industrial, cosmetic, and personal care products. They serve as bridges between inorganic or organic substrates and organic/polymeric matrices. They are also versatile intermediates and can be used for a variety of synthetic applications. They do not exist naturally and have to be synthesized. Evaluation of intermediates and products resulting from the synthesis processes of organosilanes can be challenging. In this study, gas chromatography with vacuum ultraviolet spectroscopic detection (VUV) was used to analyze Si-containing compounds that are commercially available or were synthetically prepared. VUV measures full scan absorption in the range of 120-240 nm, a region that provides unique absorption signatures for chemical compounds. VUV absorption spectra of organosilanes showed rich and featured characteristics in this wavelength range. Theoretical computations of VUV absorption spectra based on time-dependent density functional theory were also explored as a complementary tool for identification. In addition, the synthesis process of isomeric benzodioxasiline compounds (ortho-, meta-, and para-) was monitored by GC-VUV. It was demonstrated that GC-VUV can be used for easy and rapid differentiation of organosilanes, including structural isomers., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Despite the same basic ingredients used in brewing, there is a significant variation in beer styles. With the rapid increase in craft brewing, beer styles have become even more numerous and complex in the recent past. A GC-MS/VUV (post-column split for dual detection) instrument with headspace high capacity SPME was used to investigate 21 different beers which represent three beer styles - India pale ales, blondes, and hefeweizens. Since results from untargeted studies can be affected by the sorbent material used, the extraction performances of three high capacity SPME fibers, i.e., polydimethylsiloxane, polydimethylsiloxane/carbon wide range, and polydimethylsiloxane/carbon wide range/divinylbenzene, were evaluated. Good reproducibility (<10% RSD) was obtained for each high capacity fiber using both detectors. The tandem MS/VUV detection coupled with GC separation proved to be particularly valuable for compound identification, especially for isomers and compounds with similar structures. The evaluation of VUV detection for untargeted analysis led to similar performances as MS detection. Both the VUV and the MS were able to effectively differentiate between beer styles using principal component analysis. In addition, the use of 3 different statistical approaches, one-way ANOVA (p-value < 0.05), partial least square discriminant analysis, and random forest, universally identified 12 of the components most influential in distinguishing the three beer styles (e.g., β-myrcene, linalool, isopentyl acetate, 2,4-di-tert-butylphenol). This is the first reported evaluation of VUV detection and the first comparison of simultaneous VUV and MS detection for untargeted classification of complex mixtures using GC., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Coupling supercritical fluid extraction (SFE) on-line with supercritical fluid chromatography (SFC) - tandem mass spectrometry (MS/MS) provides a single platform for efficient extraction, separation, and detection in a chemical analysis. SFE-SFC-MS/MS requires consideration of many extraction and chromatographic variables to not only provide the most efficient extraction, but also to analytically transfer the extracted analytes to the column for separation. There is a fundamental lack of understanding of how the variables in SFE affect those in SFC. Typically, a univariate approach is taken in on-line SFE-SFC-MS/MS method development, but this provides little insight into the relative importance of variables and their potential interactions. Here, a multivariate approach was used to develop a better understanding of the synergistic relationship between the extraction and separation processes by focusing on the optimization of extraction parameters for target analytes with a wide range of physicochemical properties in matrices of variable retentivity. The methodology used a set of optimal on-line SFE-SFC-MS/MS extraction parameters for 18 analytes of variable physicochemical properties in three different silica gel-based sample matrices are presented., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: KT, MN, VC, TO, and WH are employed by Shimadzu Corporation or Shimadzu Scientific Instruments, Inc., the manufacturer of the instrumentation utilized in this work., (Copyright © 2020 Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors attest to there being no conflicts of interest associated with this research. ZLH participated as an expert witness in a number of civil litigations involving multiple sites listed in this study., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Beer is an incredibly complex beverage containing more than 3000 different compounds, including carbohydrates, proteins, ions, microbes, organic acids, and polyphenols, among others. Beer becomes even more complex during storage, for over time it may undergo chemical changes that negatively affect the flavor, aroma, and appearance. Thus, it can be expected that maintaining the quality of beer throughout its lifetime is a difficult task. Since it is such a popular drink throughout the world, being familiar with proper analytical techniques for beer evaluation is useful for researchers and brewers. These techniques include, but are not limited to, gas chromatography, liquid chromatography, matrix assisted laser desorption/ionization, capillary electrophoresis, mass spectrometry, ultraviolet-visible spectroscopy, and flame ionization detection. This review aims to summarize the various ingredients and components of beer, discuss how they affect the finished product, and present some of the analytical methods used for quality control and understanding the formation of chemicals in beer during the brewing process., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Intact proteins are increasingly being recognized as potential biomarkers and biotherapeutic agents for cancer and other serious diseases. Low pH reversed phase plays an important role in both single and multidimensional protein separations for resolving complex protein samples prior to mass spectrometric detection. In this work, we evaluated the use of high pH reversed phase liquid chromatography as an alternative chromatographic separation to gain different selectivity while maintaining the high resolving power and MS compatibility of reversed phase separations. The altered selectivity gained by high pH reversed phase liquid chromatography can further help to separate unresolved protein peaks or to increase peak capacity and resolving power of a multidimensional setup for complex biological samples. Hence, we evaluated the use of different MS-friendly buffers, ion pairing reagents, and stationary phases (silica- and polymer-based) at alkaline pH for intact protein separations. The best chromatographic separation, with complementary selectivity to low pH reversed phase, was achieved using triethylammonium bicarbonate at pH 10 and hybrid silica particles., (Copyright © 2019 Elsevier B.V. All rights reserved.)

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., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Qualitative and quantitative determination of fatty acids in plasma is of extreme importance as these are indicators of metabolic diseases. In this work, a sensitive and rugged method for detecting and quantifying fatty acids (as fatty acid methyl ester derivatives, FAMEs) in blood plasma was developed. The use of large-volume injection (LVI) gas chromatography-vacuum ultraviolet spectroscopy (GC-VUV) for analysis of fatty acids in blood plasma allowed the injection of higher sample volumes to accommodate sufficient analyte on-column for necessary detection ranges with a run time of 45 min. Calibration curves exhibited consistent linearity and reproducibility and were used along with internal standards for the quantification of 11 saturated and 21 unsaturated fatty acids. Intra-day and inter-day (n = 6) CVs had an average of 5 and 6%, respectively, and recoveries an average of 105%. The concentrations of EPA, DHA, and AA, as well as the omega-3 index and omega-6/omega-3 ratio, were calculated and compared with clinically actionable measurement ranges. Due to the use of LVI, the more volatile analyte (C8:0) was lost and therefore impossible to quantify. The volatility cutoff was determined to be the C10:0 analyte with a molecular weight of 186.295 g/mol., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Metabolite profiling can be used as a diagnostic measure for both short and long term co-exposure by individuals to benzene, toluene, ethylbenzene and xylenes (BTEX). A novel one pot derivatization in situ kit (OPDISK) was developed and optimized using a multivariate approach based on central composite design. The OPDISK was designed to simultaneously derivatize, in a urine sample matrix, a series of fourteen carboxylic acid and phenol-bearing urinary metabolites of BTEX to enhance their chromatographic analysis and sensitivity for detection by liquid chromatography - electrospray ionization - tandem mass spectrometry (LC-ESI-MS/MS). Using the reagent kit, the less responsive functional units on the molecules were converted to permanently positively-charged functional units. The kit was composed of three components, 2-fluoro-1-methylpyridinium p-toluenesulfonate (FMP), 3-carbinol-1-methylpyridinium iodide (CMP) and triethylamine (TEA) as a basic catalyst and, only after diluting a urine sample 20 fold with acetonitrile, was applied under mild conditions of room temperature and short reaction time of 20 min. The derivatized biomarkers were then directly analyzed using isotope dilution LC-ESI-MS/MS. The method was sensitive (limit of detection on column ranged from 1.4 pg to 3.1 ng), accurate (mean accuracy from 85% to 114%), and precise (mean coefficient of variation from 1% to 14%). The method results indicated a good linearity (R 2  ≥ 0.990) for all metabolites. ClinChek ® urine control samples were used successfully to demonstrate the accuracy of the method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Unconventional oil and gas development is achieved through a series of sub-processes, which utilize large amounts of water, proppant, and chemical additives to retrieve sequestered hydrocarbons from low permeability petroliferous strata. As a result, a large amount of wastewater is produced, which is traditionally disposed of via subsurface injection into non-productive stratum throughout the country. However, this method of waste management has been linked to the induction of seismic events in a number of regions across North America, calling into question the environmental stewardship and sustainability of subsurface waste disposal. Advancements in water treatment technologies have improved the efficacy and financial viability of produced water recycling for beneficial reuse in the oil and gas sector. This review will cover the various treatment options that are currently being utilized in shale energy basins to remove organic, inorganic, and biological constituents, as well as some emerging technologies that are designed to remove pertinent contaminants that would otherwise preclude the reuse of produced water for production well stimulation., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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][ESO 4 ], 1-ethyl-3-methylimidazolium diethyl phosphate [EMIM][DEP], and tris(2-hydroxyethyl) methylammonium methylsulfate [MTEOA][MeOSO 3 ] 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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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 R 2  ≥ 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., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The identification of microorganisms is very important in different fields and alternative methods are necessary for a rapid and simple identification. The use of fatty acids for bacterial identification is gaining attention as phenotypic characteristics are reflective of the genotype and are more easily analyzed. In this work, gas chromatography-vacuum ultraviolet spectroscopy (GC-VUV) was used to determine bacteria fatty acid methyl esters (FAMEs), to identify and discriminate different environmental bacteria based on their fatty acid profile. Microorganisms were grown in agar and their fatty acids extracted, saponified, and esterified before analysis. Unique FAME profiles were obtained for each microorganism mainly composed of branched, cyclopropane, hydroxy, saturated, and unsaturated fatty acid methyl esters. S. maltophilia showed a higher diversity of fatty acids while Bacillus species showed higher complexity in terms of branched-chain FAMEs, with several iso and anteiso forms. 12 different bacteria genera and 15 species were successfully differentiated based on their fatty acid profiles after performing PCA and cluster analysis. Some difficult to differentiate species, such as Bacillus sp., which are genetically very similar, were differentiated with the developed method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

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., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Stable-isotopically-labeled internal standards are commonly incorporated in methods for trace analysis that utilize mass spectrometric detection. They closely mimic the physicochemical properties of the analyte, but their signal is easily differentiable based on a change in molecular mass. To investigate the potential to transfer methods incorporating such internal standards for analysis by vacuum ultraviolet detection, a study was conducted to compare the spectral shape (from 125 to 240nm) of stable-isotopically-labeled compounds with their non-labeled counterparts. Gas chromatography - vacuum ultraviolet spectroscopic analysis was performed for a series of benzene isotopologues, as well as for clinically- and environmentally-relevant standard compounds and their deuterated counterparts. The absorption characteristics of the benzene isotopologues were evaluated based on similarity (normalized spectra), as well as on their magnitude of absorption. In general, very minor differences in absorption spectra were observed; however, increasing degree of deuteration did generally increase the spectral difference between labeled and non-labeled analytes. Sum of squared residuals were used as quantitative measures to assess spectral similarity (and dissimilarity). Theoretical computation of absorption spectra for benzene using time-dependent density functional theory was also examined; though, further work is needed in this area to extend the analysis to isotopologue analysis., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The knowledge of metabolic pathways and biotransformation of xenobiotics, artificial substances foreign to the entire biological system, is crucial for elucidation of degradation routes of potentially toxic substances. Nowadays, there are many methods to simulate xenobiotic metabolism in the human body in vitro. In this review, the metabolism of various substances in the human body is described, followed by a summary of methods used for prediction of metabolic pathways and biotransformation. Above all, focus is placed on the coupling of electrochemistry to mass spectrometry, which is still a relatively new technique. This promising tool can mimic both oxidative phase I and conjugative phase II metabolism. Different experimental arrangements, with or without a separation step, and various applications of this technique are illustrated and critically reviewed., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Lipid mediators (LMs) are a class of bioactive metabolites of the essential polyunsaturated fatty acids (PUFA), which are involved in many physiological processes. Their quantification in biological samples is critical for understanding their functions in lifestyle and chronic diseases, such as diabetes, as well allergies, cancers, and in aging processes. We developed a rapid, and sensitive LC-MS/MS method to quantify the concentrations of 14 lipid mediators of interest in mouse skeletal muscle tissue without time-consuming liquid-liquid or solid-phase extractions. A restricted-access media (RAM) based trap was used prior to LC-MS as cleanup process to prevent the analytical column from clogging and deterioration. The system enabled automatic removal of residual proteins and other biological interferences presented in the tissue extracts; the target analytes were retained in the trap and then eluted to an analytical column for separation. Matrix evaluation tests demonstrated that the use of the combined RAM trap and chromatographic separation efficiently eliminated the biological or chemical matrix interferences typically encountered in bioanalytical analysis. Using 14 LM standards and 12 corresponding deuterated compounds as internal standards, the five-point calibration curves, established over the concentration range of 0.031-320 ng mL -1 , demonstrated good linearity of r 2  > 0.9903 (0.9903-0.9983). The lower detection limits obtained were 0.016, 0.031, 0.062, and 0.31 ng mL -1 (0.5, 1, 2, and 10 pg on column), respectively, depending on the specific compounds. Good accuracy (87.1-114.5%) and precision (<13.4%) of the method were observed for low, medium, and high concentration quality control samples. The method was applied to measure the amount of 14 target LMs in mouse skeletal muscle tissues. All 14 analytes in this study were successfully detected and quantified in the gastrocnemius muscle samples, which provided crucial information for both age and gender-related aspects of LMs signaling in skeletal muscles previously unknown. This method could be applied to advance the understanding of skeletal muscle pathophysiology to study the role of LMs in health and disease. Furthermore, we will expand the application of this methodology to humans and other tissues/matrices in the near future., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Methodology for qualitative and quantitative determination of carbohydrates with gas chromatography coupled to vacuum ultraviolet detection (GC-VUV) is presented. Saccharides have been intently studied and are commonly analyzed by gas chromatography-mass spectrometry (GC-MS), but not always effectively. This can be attributed to their high degree of structural complexity: α/β anomers from their axial/equatorial hydroxyl group positioning at the C1-OH and flexible ring structures that lead to the open chain, five-membered ring furanose, and six-membered ring pyranose configurations. This complexity can result in convoluted chromatograms, ambiguous fragmentation patterns and, ultimately, analyte misidentification. In this study, mono-, di, and tri-saccharides were derivatized by two different methods-permethylation and oximation/pertrimethylsilylation-and analyzed by GC-VUV. These two derivatization methods were then compared for their efficiency, ease of use, and robustness. Permethylation proved to be a useful technique for the analysis of ketopentoses and pharmaceuticals soluble in dimethyl sulfoxide (DMSO), while the oximation/pertrimethylsilylation method prevailed as the more promising, overall, derivatization method. VUV spectra have been shown to be distinct and allow for efficient differentiation of isomeric species such as ketopentoses and reducing versus non-reducing sugars. In addition to identification, pharmaceutical samples containing several compounds were derivatized and analyzed for their sugar content with the GC-VUV technique to provide data for qualitative analysis., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Silica hydride, or Type C silica, has been developed as an alternative chromatographic support material for liquid chromatography. There are various bonded phases available with this new support. For four such phases (Cholesterol, Bidentate C18, Diamond Hydride, and Diol), retention and selectivity behavior were investigated using liquid chromatography coupled with triple quadrupole mass spectrometry. A set of small molecules from several chemical classes of interest, and varying in their physicochemical properties, were chromatographed under both reversed-phase and aqueous normal phase modes. To screen the columns, column switching was performed using an automated platform controlled by associated software and an additional valve. A typical scouting gradient was implemented. The separation conditions were not further optimized since the goal was simply to evaluate the variable retention behavior of the phases and selectivity under generic conditions. Further, retention of the analytes were evaluated under isocratic conditions with varying percentages of organic phase to visualize the potential for dual retention modes on the same column for certain analytes. Four analytes (fentanyl, hydrocodone, hydromorphone, and matrine) showed dual mode retention behavior with all four phases. Especially, fentanyl exhibited dramatic "U-shaped" retention profiles on Cholesterol and Bidentate C18 phases. Overall, changes in the retention order between reversed phase and aqueous normal phases emphasized the potential for altered selectivity. Results showed that the Cholesterol phase provided the highest retention for most analytes compared to the other phases. The more polar Diol phase still provided good retention in reversed phase mode. Retention and selectivity were all highly reproducible., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Distinguishing isomeric representatives of "bath salts", "plant food", "spice", or "legal high" remains a challenge for analytical chemistry. In this work, we used vacuum ultraviolet spectroscopy combined with gas chromatography to address this issue on a set of forty-three designer drugs. All compounds, including many isomers, returned differentiable vacuum ultraviolet/ultraviolet spectra. The pair of 3- and 4-fluoromethcathinones (m/z 181.0903), as well as the methoxetamine/meperidine/ethylphenidate (m/z 247.1572) triad, provided very distinctive vacuum ultraviolet spectral features. On the contrary, spectra of 4-methylethcathinone, 4-ethylmethcathinone, 3,4-dimethylmethcathinone triad (m/z 191.1310) displayed much higher similarities. Their resolution was possible only if pure standards were probed. A similar situation occurred with the ethylone and butylone pair (m/z 221.1052). On the other hand, majority of forty-three drugs was successfully separated by gas chromatography. The detection limits for all the drug standards were in the 2-4 ng range (on-column amount), which is sufficient for determinations of seized drugs during forensics analysis. Further, state-of-the-art time-dependent density functional theory was evaluated for computation of theoretical absorption spectra in the 125-240 nm range as a complementary tool., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The present paper is focused on the use of a vacuum ultraviolet absorption spectrometer (VUV) for gas chromatography (GC), within the context of flow modulated comprehensive two-dimensional gas chromatography (FM GC×GC). The features of the VUV detector were evaluated through the analysis of petrochemical and fatty acids samples. Besides responding in a predictable fashion via Beer's law principles, the detector provides additional spectroscopic information for qualitative analysis. Virtually all chemical species absorb and have unique gas phase absorption features in the 120-240nm wavelength range monitored. The VUV detector can acquire up to 90 full range absorption spectra per second, allowing its coupling with comprehensive two-dimensional gas chromatography. This recent form of detection can address specific limitations related to mass spectrometry (e.g., identification of isobaric and isomeric species with very similar mass spectra or labile chemical compounds), and it is also able to deconvolute co-eluting peaks. Moreover, it is possible to exploit a pseudo-absolute quantitation of analytes based on pre-recorded absorption cross-sections for target analytes, without the need for traditional calibration. Using this and the other features of the detector, particular attention was devoted to the suitability of the FM GC×GC-VUV system toward qualitative and quantitative analysis of bio-diesel fuel and different kinds of fatty acids. Satisfactory results were obtained in terms of tailing factor (1.1), asymmetry factor (1.1), and similarity (average value 97%), for the FAMEs mixtures analysis., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Polychlorinated biphenyls (PCBs) are a group of synthetic chlorinated compounds that have been widely used as dielectric fluids in capacitors and transformers. Due to their toxicity, persistence, and bioaccumulation in the food chain, PCBs are an environmental concern and among the most analyzed compounds in environmental analysis. The most common analytical methods for analysis of PCBs are based on gas chromatography-electron capture detection (GC-ECD) and gas chromatography-mass spectrometry (GC-MS). However, the number of possible congeners (209), similarities of physical and chemical properties, and complexity of sample matrices make it difficult to distinguish and accurately speciate PCB congeners using existing methods. This study presents a new method using gas chromatography with vacuum ultraviolet detection (GC-VUV), which offers absorption detection in the range of 120-240nm, where all chemical species have absorption. The VUV absorption spectra for all 209 PCB congeners were collected and shown to be differentiable. The capability of VUV data analysis software for deconvolution of co-eluting signals was also demonstrated. An automated time interval deconvolution (TID) procedure was applied to rapidly speciate individual PCBs, as well as classify commercial Aroclor mixtures based on their degree of chlorination. The data showed excellent agreement between the stated nominal and determined degrees of chlorination (less than 1% deviation for highly chlorinated mixtures). GC-VUV was verified to provide excellent specificity, high sensitivity (100-150pg limit of detection), and fast data acquisition for this application., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Novel citric acid based photoluminescent dyes and biodegradable polymers are synthesized via a facile "one-pot" reaction. A comprehensive understanding of the fluorescence mechanisms of the resulting citric acid-based fluorophores is reported. Two distinct types of fluorophores are identified: a thiozolopyridine family with high quantum yield, long lifetime, and exceptional photostability, and a dioxopyridine family with relatively lower quantum yield, multiple lifetimes, and solvent-dependent band shifting behavior. Applications in molecular labeling and cell imaging were demonstrated. The above discoveries contribute to the field of fluorescence chemistry and have laid a solid foundation for further development of new fluorophores and materials that show promise in a diversity of fluorescence-based applications., Statement of Significance: Photoluminescent materials are pivotal for fluorescence based imaging, labeling and sensing applications. Understanding their fluorescence mechanism is challenging and imperative. We develop a new class of citric acid-derived fluorescent materials in forms of polymers and small molecular dyes by a one-step solvent free reaction. We discovered two different classes of citric acid-derived fluorophores. A two-ring thiozolopyridine structure demonstrates strong fluorescence and exceptional resistance to photo-bleaching. A one-ring dioxopyridine exhibits relative weak fluorescence but with intriguing excitation and solvent-dependent emission wavelength shifting. Our methodology of synthesizing citric acid-derived fluorophores and the understanding on their luminescence are instrumental to the design and production of a large number of new photoluminescent materials for biological and biomedical applications., (Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The vacuum ultraviolet detector (VUV) is a new non-destructive mass sensitive detector for gas chromatography that continuously and rapidly collects full wavelength range absorption between 120 and 240 nm. In addition to conventional methods of quantification (internal and external standard), gas chromatography - vacuum ultraviolet spectroscopy has the potential for pseudo-absolute quantification of analytes based on pre-recorded cross sections (well-defined absorptivity across the 120-240 nm wavelength range recorded by the detector) without the need for traditional calibration. The pseudo-absolute method was used in this research to experimentally evaluate the sources of sample loss and gain associated with sample introduction into a typical gas chromatograph. Standard samples of benzene and natural gas were used to assess precision and accuracy for the analysis of liquid and gaseous samples, respectively, based on the amount of analyte loaded on-column. Results indicate that injection volume, split ratio, and sampling times for splitless analysis can all contribute to inaccurate, yet precise sample introduction. For instance, an autosampler can very reproducibly inject a designated volume, but there are significant systematic errors (here, a consistently larger volume than that designated) in the actual volume introduced. The pseudo-absolute quantification capability of the vacuum ultraviolet detector provides a new means for carrying out system performance checks and potentially for solving challenging quantitative analytical problems. For practical purposes, an internal standardized approach to normalize systematic errors can be used to perform quantitative analysis with the pseudo-absolute method., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

An issue with most gas chromatographic detectors is their inability to deconvolve coeluting isomers. Dimethylnaphthalenes are a class of compounds that can be particularly difficult to speciate by gas chromatography - mass spectrometry analysis, because of their significant coelution and similar mass spectra. As an alternative, a vacuum ultraviolet spectroscopic detector paired with gas chromatography was used to study the systematic deconvolution of mixtures of coeluting isomers of dimethylnaphthalenes. Various ratio combinations of 75:25; 50:50; 25:75; 20:80; 10:90; 5:95; and 1:99 were prepared to test the accuracy, precision, and sensitivity of the detector for distinguishing overlapping isomers that had distinct, but very similar absorption spectra. It was found that, under reasonable injection conditions, all of the pairwise overlapping isomers tested could be deconvoluted up to nearly two orders of magnitude (up to 99:1) in relative abundance. These experimental deconvolution values were in agreement with theoretical covariance calculations performed for two of the dimethylnaphthalene isomers. Covariance calculations estimated high picogram detection limits for a minor isomer coeluting with low to mid-nanogram quantity of a more abundant isomer. Further characterization of the analytes was performed using density functional theory computations to compare theory with experimental measurements. Additionally, gas chromatography - vacuum ultraviolet spectroscopy was shown to be able to speciate dimethylnaphthalenes in jet and diesel fuel samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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., (Copyright © 2015 Elsevier B.V. All rights reserved.)