ORCID Profile
0000-0002-4251-1613
Current Organisation
Colorado State University
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Publisher: American Chemical Society (ACS)
Date: 30-10-2017
Abstract: Biodegradation of the persistent groundwater contaminant 1,4-dioxane is often hindered by the absence of dissolved oxygen and the co-occurrence of inhibiting chlorinated solvents. Using flow-through electrolytic reactors equipped with Ti/IrO
Publisher: Elsevier BV
Date: 06-2020
Publisher: American Chemical Society (ACS)
Date: 10-12-2014
DOI: 10.1021/ES503724K
Abstract: Biocides are critical components of hydraulic fracturing ("fracking") fluids used for unconventional shale gas development. Bacteria may cause bioclogging and inhibit gas extraction, produce toxic hydrogen sulfide, and induce corrosion leading to downhole equipment failure. The use of biocides such as glutaraldehyde and quaternary ammonium compounds has spurred a public concern and debate among regulators regarding the impact of inadvertent releases into the environment on ecosystem and human health. This work provides a critical review of the potential fate and toxicity of biocides used in hydraulic fracturing operations. We identified the following physicochemical and toxicological aspects as well as knowledge gaps that should be considered when selecting biocides: (1) uncharged species will dominate in the aqueous phase and be subject to degradation and transport whereas charged species will sorb to soils and be less bioavailable (2) many biocides are short-lived or degradable through abiotic and biotic processes, but some may transform into more toxic or persistent compounds (3) understanding of biocides' fate under downhole conditions (high pressure, temperature, and salt and organic matter concentrations) is limited (4) several biocidal alternatives exist, but high cost, high energy demands, and/or formation of disinfection byproducts limits their use. This review may serve as a guide for environmental risk assessment and identification of microbial control strategies to help develop a sustainable path for managing hydraulic fracturing fluids.
Publisher: American Chemical Society (ACS)
Date: 16-09-2014
DOI: 10.1021/AC502163K
Abstract: Two series of ethylene oxide (EO) surfactants, polyethylene glycols (PEGs from EO3 to EO33) and linear alkyl ethoxylates (LAEs C-9 to C-15 with EO3-EO28), were identified in hydraulic fracturing flowback and produced water using a new application of the Kendrick mass defect and liquid chromatography/quadrupole-time-of-flight mass spectrometry. The Kendrick mass defect differentiates the proton, ammonium, and sodium adducts in both singly and doubly charged forms. A structural model of adduct formation is presented, and binding constants are calculated, which is based on a spherical cagelike conformation, where the central cation (NH4(+) or Na(+)) is coordinated with ether oxygens. A major purpose of the study was the identification of the ethylene oxide (EO) surfactants and the construction of a database with accurate masses and retention times in order to unravel the mass spectral complexity of surfactant mixtures used in hydraulic fracturing fluids. For ex le, over 500 accurate mass assignments are made in a few seconds of computer time, which then is used as a fingerprint chromatogram of the water s les. This technique is applied to a series of flowback and produced water s les to illustrate the usefulness of ethoxylate "fingerprinting", in a first application to monitor water quality that results from fluids used in hydraulic fracturing.
Publisher: Elsevier BV
Date: 10-2016
DOI: 10.1016/J.CHEMOSPHERE.2016.06.048
Abstract: Irrigation with reclaimed wastewater may result in the ubiquitous presence of pharmaceutical compounds (PCs) and their metabolites in the agroecosystem. In this study, we focused on two highly persistent anticonvulsant drugs, lamotrigine and carbamazepine and two of its metabolites (EP-CBZ and DiOH-CBZ), aiming to elucidate their behavior in agricultural ecosystem using batch and lysimeter experiments. Sorption of the studied compounds by soils was found to be governed mainly by the soil organic matter level. Sorption affinity of compounds to soils followed the order lamotrigine > carbamazepine > EP-CBZ > DiOH-CBZ. Sorption was reversible, and no competition between sorbates in bi-solute systems was observed. The results of the lysimeter studies were in accordance with batch experiment findings, demonstrating accumulation of lamotrigine and carbamazepine in top soil layers enriched with organic matter. Detection of carbamazepine and one of its metabolites in rain-fed wheat previously irrigated with reclaimed wastewater, indicates reversibility of their sorption, resulting in their potential leaching and their availability for plant uptake. This study demonstrates the long-term implication of introduction of PCs to the agroecosystem.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C8EM00336J
Abstract: In the western U.S., produced water from oil and gas wells discharged to surface water augments downstream supplies used for irrigation and livestock watering.
Publisher: Elsevier BV
Date: 03-2021
Publisher: Elsevier BV
Date: 09-2011
DOI: 10.1016/J.CHROMA.2011.07.020
Abstract: The widely used solvent hexamethylphosphoramide (HMPA) and its biological (metabolic) and chemical (abiotic) phosphoramide-based oxidation products may cause adverse health effects through occupational exposure and intake of contaminated groundwater. However, no current methods exist for the separation and the detection of the many polar HMPA oxidation products. Thus, we developed a new RPLC/ESI-TOF-MS method and further investigated the chromatographic performances of two columns (i.e., XTerra Phenyl and XBridge Phenyl). In addition, the impact of (forced) acid hydrolysis for optimized chromatographic performance of the XTerra Phenyl column is investigated. The XTerra Phenyl column showed the best separation of the less polar major metabolic oxidation products pentamethylphosphoramide and hydroxymethyl-pentamethylphosphoramide, however, only after treating the column with formic acid (acid-treated). The XTerra column separated most of the investigated HMPA oxidation products (11 of 16 compounds) in a single chromatographic run. In contrast, the XBridge Phenyl column requires one method for the less polar and another method for the more polar oxidation products. However, this results in an overall better separation performance of the XBridge Phenyl column, especially for the less polar major abiotic oxidation products hydroxymethyl-pentamethylphosphoramide and formyl-pentamethylphosphoramide, as well as for 11 highly polar oxidation products (R(S)>1.5). The RPLC/ESI-TOF-MS method presented and validated in this study is the first analytical method that can be used to separate and detect HMPA (LOD 0.10 μM without preconcentration) and all of its oxidation products.
Publisher: Royal Society of Chemistry (RSC)
Date: 2019
DOI: 10.1039/C9EM00153K
Abstract: Chemical changes to hydraulic fracturing fluids within fractured unconventional reservoirs may affect hydrocarbon recovery and, in turn, the environmental impact of unconventional oil and gas development.
Publisher: Elsevier BV
Date: 03-2018
Publisher: American Chemical Society (ACS)
Date: 08-08-2018
Abstract: The permanganate ion (MnO
Publisher: American Chemical Society (ACS)
Date: 29-07-2016
Abstract: 1,4-dioxane is an emerging groundwater contaminant with significant regulatory implications. Because it is resistant to traditional groundwater treatments, remediation of 1,4-dioxane is often limited to costly ex situ UV-based advanced oxidation. By varying applied voltage, electrical conductivity, seepage velocity, and influent contaminant concentration in flow-through reactors, we show that electrochemical oxidation is a viable technology for in situ and ex situ treatment of 1,4-dioxane under a wide range of environmental conditions. Using novel titanium dioxide (TiO2) pellets, we demonstrate for the first time that this prominent catalyst can be activated in the dark even when electrically insulated from the electrodes. TiO2-catalyzed reactors achieved efficiencies of greater than 97% degradation of 1,4-dioxane, up to 4.6 times higher than noncatalyzed electrolytic reactors. However, the greatest catalytic enhancement (70% degradation versus no degradation without catalysis) was observed in low-ionic-strength water, where conventional electrochemical approaches notoriously fail. The TiO2 pellet's dark-catalytic oxidation activity was confirmed on the pharmaceutical lamotrigine and the industrial solvent chlorobenzene, signifying that electrocatalytic treatment has tremendous potential as a transformative remediation technology for persistent organic pollutants in groundwater and other aqueous environments.
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D0EM00413H
Abstract: Oil and gas extraction generates large volumes of produced water (PW) in regions that are water-stressed. PW can be passively treated in retention ponds prior to beneficial use. Oxic conditions lead to sequestration and lower bioavailability of Ra.
Publisher: American Chemical Society (ACS)
Date: 28-09-2016
Abstract: Hydraulic fracturing fluid (HFF) additives are used to enhance oil and gas extraction from unconventional shale formations. Several kilometers downhole, these organic chemicals are exposed to temperatures up to 200 °C, pressures above 10 MPa, high salinities, and a pH range from 5-8. Despite this, very little is known about the fate of HFF additives under these extreme conditions. Here, stainless steel reactors are used to simulate the downhole chemistry of the commonly used HFF biocide glutaraldehyde (GA). The results show that GA rapidly (t
Publisher: American Chemical Society (ACS)
Date: 19-05-2016
Abstract: Hydraulic fracturing frequently occurs on agricultural land. Yet the extent of sorption, transformation, and interactions among the numerous organic frac fluid and oil and gas wastewater constituents upon environmental release is hardly known. Thus, this study aims to advance our current understanding of processes that control the environmental fate and toxicity of commonly used hydraulic fracturing chemicals. Poly(ethylene glycol) surfactants were completely biodegraded in agricultural topsoil within 42-71 days, but their transformation was impeded in the presence of the biocide glutaraldehyde and was completely inhibited by salt at concentrations typical for oil and gas wastewater. At the same time, aqueous glutaraldehyde concentrations decreased due to sorption to soil and were completely biodegraded within 33-57 days. While no aqueous removal of polyacrylamide friction reducer was observed over a period of 6 months, it cross-linked with glutaraldehyde, further lowering the biocide's aqueous concentration. These findings highlight the necessity to consider co-contaminant effects when we evaluate the risk of frac fluid additives and oil and gas wastewater constituents in agricultural soils in order to fully understand their human health impacts, likelihood for crop uptake, and potential for groundwater contamination.
Publisher: Wiley
Date: 07-09-2022
DOI: 10.1002/SAE2.12029
Abstract: Citrus greening (aka Huanglongbing, HLB) caused primarily by the bacterial pathogen Candidatus Liberibacter asiaticus ( C Las) has devastating effects on the global citrus industry. Agricultural management‐induced changes in microbial communities are hypothesised to contribute toward HLB resistance by reducing pathogen titre and increasing root and soil health. However, we have a limited understanding of the impacts of management practices on the soil microbiome, making the extent of HLB management uncertain. Here we investigated the effect of agricultural management practices on reducing C Las titer via changes in rhizosphere‐associated bacterial communities. Rhizosphere and root s les were collected from two sites in Florida where different management practices (e.g., metalized reflective mulch ground covers, compost application and microbial inoculations) are currently being implemented to prevent HLB. Management‐induced changes in the rhizosphere bacterial community were assessed using licon sequencing. qPCR assays were used to quantify the titer of the pathogen C Las in roots. In addition, we measured soil properties and the activities of microbial enzymes involved in soil nutrient cycling. Our results indicated that certain management practices lead to shifts in the community structure of rhizosphere bacterial communities that negatively interact with the HLB pathogen. Management practices improved soil quality and reduced C Las titer. Additionally, we found that Actinobacteria were frequently enriched in the successful treatment sites, suggesting that Actinobacteria taxa could be indicators for HLB suppression properties in the soil. Our results suggest that microbiome manipulation, either through changes in the management practices or microbial amendment, can increase the suppressive potential of soils, resulting in the reduction in C Las titer and potentially leading to HLB suppression in citrus groves.
Publisher: American Chemical Society (ACS)
Date: 07-07-2010
DOI: 10.1021/ES1006675
Abstract: Models used to predict the fate of aqueous phase contaminants are often limited by their inability to address the widely varying redox conditions in natural and engineered systems. Here, we present a novel approach based on quantum chemical calculations that identifies the thermodynamic conditions necessary for redox-promoted degradation and predicts potential degradation pathways. Hexamethylphosphoramide (HMPA), a widely used solvent and potential groundwater contaminant, is used as a test case. Its oxidation is estimated to require at least iron-reducing conditions at low to neutral pH and nitrate-reducing conditions at high pH. Furthermore, the transformation of HMPA by permanganate is predicted to proceed through sequential N-demethylation. Experimental validation based on LC/TOF-MS analysis confirms the predicted pathways of HMPA oxidation by permanganate to phosphoramide via the formation of less methylated as well as singly and multiply oxygenated reaction intermediates. Pathways predicted to be thermodynamically or kinetically unfavorable are similarly absent in the experimental studies. Our newly developed methodology will enable scientists and engineers to estimate the favorability of contaminant degradation at a specific field site, suitable approaches to enhance degradation, and the persistence of a contaminant and its reaction intermediates.
Publisher: American Chemical Society (ACS)
Date: 13-11-2017
Abstract: Hydraulic fracturing fluids are injected into shales to extend fracture networks that enhance oil and natural gas production from unconventional reservoirs. Here we evaluated the biodegradability of three widely used nonionic polyglycol ether surfactants (alkyl ethoxylates (AEOs), nonylphenol ethoxylates (NPEOs), and polypropylene glycols (PPGs)) that function as weatherizers, emulsifiers, wetting agents, and corrosion inhibitors in injected fluids. Under anaerobic conditions, we observed complete removal of AEOs and NPEOs from solution within 3 weeks regardless of whether surfactants were part of a chemical mixture or amended as in idual additives. Microbial enzymatic chain shortening was responsible for a shift in ethoxymer molecular weight distributions and the accumulation of the metabolite acetate. PPGs bioattenuated the slowest, producing sizable concentrations of acetone, an isomer of propionaldehyde. Surfactant chain shortening was coupled to an increased abundance of the diol dehydratase gene cluster (pduCDE) in Firmicutes metagenomes predicted from the 16S rRNA gene. The pduCDE enzymes are responsible for cleaving ethoxylate chain units into aldehydes before their fermentation into alcohols and carboxylic acids. These data provide new mechanistic insight into the environmental fate of hydraulic fracturing surfactants after accidental release through chain shortening and biotransformation, emphasizing the importance of compound structure disclosure for predicting biodegradation products.
Publisher: Elsevier BV
Date: 04-2020
DOI: 10.1016/J.SCITOTENV.2020.136607
Abstract: Produced water (PW) is the largest waste stream associated with oil and gas extraction and contains organics, salts, metals and radioactive materials. In the United States, west of the 98th meridian, the National Pollutant Discharge Elimination System exemption allows for release of PW to surface waters for agricultural beneficial reuse if it is "of good enough quality". Due to the complex and variable composition of PW, the downstream impacts of these releases are not fully understood. In this study, a detailed chemical analysis was conducted on a stream composed of PW released for agricultural beneficial reuse. Over 50 geogenic and anthropogenic organic chemicals not specified in the effluent limits were detected at the discharge including hydrocarbons, halogenated compounds, and surfactants. Most were removed within 15 km of the discharge due to volatilization, biodegradation, and sorption to sediment. Inorganics detected at the discharge were within regulatory effluent limits. While some inorganic species (i.e., strontium, barium and radium) decreased in concentration downstream due to co-precipitation, concentrations of many inorganic species including sodium, sulfate and boron increased due to water evaporation. Consequently, downstream water quality changes need to be considered to adequately evaluate the potential impact of discharged PW. Regulatory health thresholds for humans, livestock, and aquatic species for most chemical species present at the discharge are still lacking. As a result, toxicity tests are necessary to determine the potential health impacts to downstream users.
Publisher: American Chemical Society (ACS)
Date: 06-10-2021
Publisher: Elsevier BV
Date: 11-2014
DOI: 10.1016/J.CHEMOSPHERE.2014.03.109
Abstract: Polychlorinated biphenyls (PCBs) are well-known for being hydrophobic and persistent in the environment. Although many treatment approaches have been demonstrated to result in degradation of PCBs in water or water/cosolvent systems, few ex les exist where such approaches have been applied successfully for PCB degradation in soil-water systems. A possible explanation for the limited treatment of PCBs in soil-water systems is that reactants that are capable of degrading PCBs in the aqueous phase are unlikely to persist long enough to achieve meaningful treatment of slowly-desorbing PCBs associated with the soil phase. To investigate this explanation, laboratory studies were conducted to evaluate chemical reductants, including zero valent metals, palladium (Pd) catalyst, and emulsified zero valent iron (EZVI), for dechlorination of PCBs in the presence and absence of soil. In the absence of soil, Pd-catalyzed treatments (Pd with electrolytic ZVI or iron/aluminum alloy) achieved rapid destruction of a model PCB congener, 2-chlorobiphenyl, with half-lives ranging from 43 to 110 min. For treatment of soils containing Aroclor 1248 at an initial concentration of approximately 1,500 mg kg(-1), Pd-catalyzed treatments achieved no measurable enhancement over the background PCB depletion rate (i.e., that measured in the untreated control) of 5.3 mg kg(-1)week(-1). In the presence of soils, EZVI was the only approach evaluated that resulted in a clear enhancement in PCB dechlorination rates. EZVI achieved PCB concentration reductions of greater than 50% at an average rate of 19 mg kg(-1)week(-1). The results suggest that slow PCB desorption limits treatment effectiveness in soils.
Publisher: American Chemical Society (ACS)
Date: 20-02-2011
DOI: 10.1021/ES1028662
Abstract: At contaminated field sites where active remediation measures are not feasible, monitored natural attenuation is sometimes the only alternative for surface water or groundwater decontamination. However, due to slow degradation rates of some contaminants under natural conditions, attenuation processes and their performance assessment can take several years to decades to complete. Here, we apply quantum chemical calculations to predict contaminant persistence in the aqueous phase. For the test compound hexamethylphosphoramide (HMPA), P-N bond hydrolysis is the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. Through calculation of aqueous Gibbs free energies of activation for all potential reaction mechanisms, it is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. At pH 0, where the hydrolysis reaction is rapid enough to enable measurement, the experimentally determined rate constant and half-life are in excellent agreement with the predicted values. Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable.
Publisher: Elsevier BV
Date: 05-2020
Publisher: Royal Society of Chemistry (RSC)
Date: 2021
DOI: 10.1039/D1EM00311A
Abstract: Produced water (PW) is the largest waste stream associated with oil and gas (O& G) operations and contains petroleum hydrocarbons, heavy metals, salts, naturally occurring radioactive materials and any remaining chemical additives.
Publisher: American Chemical Society (ACS)
Date: 12-07-2017
Abstract: Combining horizontal drilling with high volume hydraulic fracturing has increased extraction of hydrocarbons from low-permeability oil and gas (O&G) formations across the United States accompanied by increased wastewater production. Surface water discharges of O&G wastewater by centralized waste treatment (CWT) plants pose risks to aquatic and human health. We evaluated the impact of surface water disposal of O&G wastewater from CWT plants upstream of the Conemaugh River Lake (dam controlled reservoir) in western Pennsylvania. Regulatory compliance data were collected to calculate annual contaminant loads (Ba, Cl, total dissolved solids (TDS)) to document historical industrial activity. In this study, two CWT plants 10 and 19 km upstream of a reservoir left geochemical signatures in sediments and porewaters corresponding to peak industrial activity that occurred 5 to 10 years earlier. Sediment cores were sectioned for the collection of paired s les of sediment and porewater, and analyzed for analytes to identify unconventional O&G wastewater disposal. Sediment layers corresponding to the years of maximum O&G wastewater disposal contained higher concentrations of salts, alkaline earth metals, and organic chemicals. Isotopic ratios of
Publisher: Elsevier BV
Date: 03-2022
Publisher: Elsevier BV
Date: 04-2018
DOI: 10.1016/J.SCITOTENV.2017.11.078
Abstract: Hydraulic fracturing (HF) has allowed for the utilization of previously unattainable shale oil and gas (O&G) resources. After HF is complete, the waters used to increase the facies' permeability return uphole as wastewaters. When these waters return to the surface, they are characterized by complex organic and inorganic chemistry, and can pose a health risk if not handled correctly. Therefore, these waters must be treated or disposed of properly. However, the variability of these waters' chemical composition over time is poorly understood and likely limits the applicability of their reuse. This study examines the water chemistry of a hydraulically fractured site in the Niobrara formation throughout the flowback period. S les were collected every other day for the first 18days, then on a regular basis for three months. We identified HF fluid additives, including benzalkonium chlorides (BACs), alkyl ethoxylates (AEOs), and polyethylene glycols (PEGs), as well as geogenic components present in flowback and produced waters, their overall temporal pattern, and variables affecting the reuse of these waters. Observations indicate that alkalinity and iron may limit the reuse of these waters in HF, while chloride and alkalinity may limit the use of these waters for well-casing cement. The presence of numerous surfactant homologs, including biocides, was also observed, with the highest levels at the beginning of the flowback period. Principal component analysis identified three unique groupings in the chemical data that correspond to different stages in the flowback period: (1) the flowback stage (days 1-2) (2) the transition stage (days 6-21) and (3) the produced water stage (days 21-87). Results from this study will be important when designing decision frameworks for assessing water treatment options, particularly if onsite treatment is attempted. Successful reclamation of these waters may alleviate stress on water resources that continues to negatively impact the U. S.
No related grants have been discovered for Thomas Borch.