PFAS Analysis with Ultrahigh Resolution 21T FT-ICR MS: Suspect and Nontargeted Screening with Unrivaled Mass Resolving Power and Accuracy.

Per- and polyfluoroalkyl substances (PFASs) are a large family of thousands of chemicals, many of which have been identified using nontargeted time-of-flight and Orbitrap mass spectrometry methods. Comprehensive characterization of complex PFAS mixtures is critical to assess their environmental transport, transformation, exposure, and uptake. Because 21 tesla (T) Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) offers the highest available mass resolving power and sub-ppm mass errors across a wide molecular weight range, we developed a nontargeted 21 T FT-ICR MS method to screen for PFASs in an aqueous film-forming foam (AFFF) using suspect screening, a targeted formula database (C, H, Cl, F, N, O, P, S; ≤865 Da), isotopologues, and Kendrick-analogous mass difference networks (KAMDNs). False-positive PFAS identifications in a natural organic matter (NOM) sample, which served as the negative control, suggested that a minimum length of 3 should be imposed when annotating CF2-homologous series with positive mass defects. We putatively identified 163 known PFASs during suspect screening, as well as 134 novel PFASs during nontargeted screening, including a suspected polyethoxylated perfluoroalkane sulfonamide series. This study shows that 21 T FT-ICR MS analysis can provide unique insights into complex PFAS composition and expand our understanding of PFAS chemistries in impacted matrices.

Electrochemical Oxidation of Hexafluoropropylene Oxide Dimer Acid (GenX): Mechanistic Insights and Efficient Treatment Train with Nanofiltration.

Hexafluoropropylene oxide dimer acid (HFPO-DA, trade name GenX) is a perfluoroalkyl ether carboxylic acid (PFECA) that has been detected in watersheds around the world. Similar to other per- and polyfluoroalkyl substances (PFASs), few processes are able to break HFPO-DA's persistent carbon-fluorine bonds. This study provides both experimental and computational lines of evidence for HFPO-DA mineralization during electrochemical oxidation at a boron-doped diamond anode with a low potential for the generation of stable organofluorine intermediates. Our density functional theory calculations consider the major operative mechanism, direct electron transfer, throughout the entire pathway. Initial oxidative attack does not break the ether bond, but leads to stepwise mineralization of the acidic side chain. Our mechanistic investigations reveal that hydroxyl radicals are unreactive toward HFPO-DA, while electrochemically activated sulfate facilitates its oxidation. Furthermore, we demonstrate that an NF90 membrane is capable of removing 99.5% of HFPO-DA from contaminated water. Electrochemical treatment of the nanofiltration rejectate is shown to reduce both energy and electrode costs by more than 1 order of magnitude compared to direct electrochemical treatment of the raw water. Overall, a nanofiltration-electrochemical oxidation treatment train is a sustainable destructive approach for the cost-effective elimination of HFPO-DA and other PFASs from contaminated water.

The Mechanism of C-H Bond Oxidation by Aqueous Permanganate.

The permanganate ion (MnO4-) has been widely used as a reagent for water treatment for over a century. It is a strong enough oxidant to activate carbon-hydrogen bonds, one of the most important reactions in biological and chemical systems. Our current textbook understanding of the oxidation mechanism in aqueous solution involves an initial, rate-limiting hydride abstraction by permanganate followed by reaction of the carbocation with bulk water to form an alcohol. This mechanism fits well into the classic oxidation sequence of alkane → alcohol → aldehyde → carboxylate, the central paradigm for both abiotic and biotic alkane oxidation in aqueous environments. In this study, we provide three lines of evidence through (1) a broken-symmetry density functional theory approach, (2) isotope labeling experiments, and (3) kinetic network modeling to demonstrate that aqueous permanganate can circumvent prior alcohol formation and produce aldehydes directly via a reaction path that bifurcates after the initial transition state. In contrast to classic transition state theory, the rate-limiting step is found to not determine product distribution, bearing critical implications for pathway and rate predictions. This complex reaction network provides new insights into the oxidation mechanisms of organic compounds involving transition metal complexes as well as enzyme or metal oxide surface active sites.

Synergistic Treatment of Mixed 1,4-Dioxane and Chlorinated Solvent Contaminations by Coupling Electrochemical Oxidation with Aerobic Biodegradation.

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/IrO2-Ta2O5 mesh electrodes, we show that combining electrochemical oxidation with aerobic biodegradation produces an overadditive treatment effect for degrading 1,4-dioxane. In reactors bioaugmented by Pseudonocardia dioxanivorans CB1190 with 3.0 V applied, 1,4-dioxane was oxidized 2.5 times faster than in bioaugmented control reactors without an applied potential, and 12 times faster than by abiotic electrolysis only. Quantitative polymerase chain reaction analyses of CB1190 abundance, oxidation-reduction potential, and dissolved oxygen measurements indicated that microbial growth was promoted by anodic oxygen-generating reactions. At a higher potential of 8.0 V, however, the cell abundance near the anode was diminished, likely due to unfavorable pH and/or redox conditions. When coupled to electrolysis, biodegradation of 1,4-dioxane was sustained even in the presence of the common co-contaminant trichloroethene in the influent. Our findings demonstrate that combining electrolytic treatment with aerobic biodegradation may be a promising synergistic approach for the treatment of mixed contaminants.

Natural Attenuation of Nonionic Surfactants Used in Hydraulic Fracturing Fluids: Degradation Rates, Pathways, and Mechanisms.

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 individual 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.

Watershed-Scale Impacts from Surface Water Disposal of Oil and Gas Wastewater in Western Pennsylvania.

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 samples 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 226Ra/228Ra and 87Sr/86Sr identified that peak concentrations of Ra and Sr were likely sourced from wastewaters that originated from the Marcellus Shale formation.

Advanced Electrochemical Oxidation of 1,4-Dioxane via Dark Catalysis by Novel Titanium Dioxide (TiO2) Pellets.

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.

Spills of Hydraulic Fracturing Chemicals on Agricultural Topsoil: Biodegradation, Sorption, and Co-contaminant Interactions.

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.

Downhole Transformation of the Hydraulic Fracturing Fluid Biocide Glutaraldehyde: Implications for Flowback and Produced Water Quality.

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 (t1/2 < 1 h) autopolymerizes, forming water-soluble dimers and trimers, and eventually precipitates out at high temperatures (∼140 °C) and/or alkaline pH. Interestingly, salinity was found to significantly inhibit GA transformation. Pressure and shale did not affect GA transformation and/or removal from the bulk fluid. On the basis of experimental pseudo-second-order rate constants, a kinetic model for GA downhole half-life predictions for any combination of these conditions within the limits tested was developed. These findings illustrate that the biocidal GA monomer has limited time to control microbial activity in hot and/or alkaline shales, and may return along with its aqueous transformation products to the surface via flowback and produced water in cooler, more acidic, and saline shales.

Biocides in hydraulic fracturing fluids: a critical review of their usage, mobility, degradation, and toxicity.

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.

Analysis of hydraulic fracturing flowback and produced waters using accurate mass: identification of ethoxylated surfactants.

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 example, 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 samples. This technique is applied to a series of flowback and produced water samples to illustrate the usefulness of ethoxylate "fingerprinting", in a first application to monitor water quality that results from fluids used in hydraulic fracturing.

Enhanced removal of per- and polyfluoroalkyl substances in complex matrices by polyDADMAC-coated regenerable granular activated carbon.

Granular activated carbon (GAC) has been used to remove per- and polyfluoroalkyl substances (PFASs) from industrial or AFFF-impacted waters, but its effectiveness can be low because adsorption of short-chained PFASs is ineffective and its sites are exhausted rapidly by co-contaminants. To increase adsorption of anionic PFASs on GAC by electrostatic attractions, we modified GAC's surface with the cationic polymer poly diallyldimethylammonium chloride (polyDADMAC) and tested its capacity in complex water matrices containing dissolved salts and humic acid. Amending with concentrations of polyDADMAC as low as 0.00025% enhanced GAC's adsorption capacity for PFASs, even in the presence of competing ions. This suggests that electrostatic interactions with polyDADMAC's quaternary ammonium functional groups helped bind organic and inorganic ions as well as the headgroup of short-chain PFASs, allowing more overall PFAS removal by GAC. Evaluating the effect of polymer dose is important because excessive addition can block pores and reduce overall PFAS removal rather than increase it. To decrease the waste associated with this adsorption strategy by making the adsorbent viable for more than one saturation cycle, a regeneration method is proposed which uses low-power ultrasound to enhance the desorption of PFASs from the polyDADMAC-GAC with minimum disruption to the adsorbent's structure. Re-modification with the polymer after sonication resulted in a negligible decrease in the sorbent's capacity over four saturation rounds. These results support consideration of polyDADMAC-modified GAC as an effective regenerable adsorbent for ex-situ concentration step of both short and long-chain PFASs from real waters with high concentrations of competing ions and low PFAS loads.

Prediction of contaminant persistence in aqueous phase: a quantum chemical approach.

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.

Release of soil colloids during flow interruption increases the pore-water PFAS concentration in saturated soil.

Groundwater flow through aquifer soils or packed bed systems can fluctuate for various reasons, which could affect the concentration of natural colloids and per- and polyfluoroalkyl substances (PFAS) in the pore water. In such cases, PFAS concentration could either decrease due to matrix diffusion of PFAS or increase by the detachment of colloids carrying PFAS. Yet, the effect of flow fluctuation on PFAS transport or release in porous media has not been examined. To examine the relative importance of either process, we interrupted the flow during an injection of groundwater spiked with perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), and bromide as conservative tracer through clay-rich soil, so that diffusive transport would be prominent during flow interruption. After flow interruption, the PFAS concentration did not decrease indicating an insignificant contribution of matrix diffusion. The concentration increased, potentially due to enhanced release of colloid-associated PFAS. Analysis of samples before and after flow interruption by particle size analysis and SEM confirmed an increase in soil colloid concentration after the flow interruption. XRD analysis of soil and the colloids proved that PFAS were associated with specific sites of the colloids. Due to a higher affinity of PFOA to soil colloids, the total PFOA concentration in the effluent samples increased more than PFBA after the flow interruption process. The results indicate that colloids may have a disproportionally higher role in the transport of PFAS in conditions that release colloids from porous media. Thus, fluctuations in groundwater flow can increase this colloid facilitated mobility of PFAS.

Oil & gas produced water retention ponds as potential passive treatment for radium removal and beneficial reuse.

Oil and gas (O&G) extraction generates large volumes of produced water (PW) in regions that are often water-stressed. In Wyoming, generators are permitted under the National Pollutant Discharge Elimination System (NPDES) program to discharge O&G PW for beneficial use. In one Wyoming study region, downstream of the NPDES facilities exist naturally occurring wetlands referred to herein as produced water retention ponds (PWRPs). Previously, it was found that dissolved radium (Ra) and organic contaminants are removed within 30 km of the discharges and higher-resolution sampling was required to understand contaminant attenuation mechanisms. In this study, we sampled three NPDES discharge facilities, five PWRPs, and a reference background wetland not impacted by O&G PW disposal. Water samples, grab sediments, sediment cores and vegetation were collected. No inorganic PW constituents were abated through the PWRP series but Ra was shown to accumulate within PWRP grab sediments, upwards of 2721 Bq kg-1, compared to downstream sites. Ra mineral association with depth in the sediment profile is likely controlled by the S cycle under varying microbial communities and redox conditions. Under anoxic conditions, common in wetlands, Ra was available as an exchangeable ion, similar to Ca, Ba and Sr, and S was mostly water-soluble. 226Ra concentration ratios in vegetation samples, normalizing vegetation Ra to sediment Ra, indicated that ratios were highest in sediments containing less exchangeable 226Ra. Sequential leaching data paired with redox potentials suggest that oxic conditions are necessary to contain Ra in recalcitrant sediment minerals and prevent mobility and bioavailability.

Perfluoroalkyl acids on suspended particles: Significant transport pathways in surface runoff, surface waters, and subsurface soils.

Eroded particles from the source zone could transport a high concentration of perfluoroalkyl acids (PFAAs) to sediments and water bodies. Yet, the contribution of suspended particles has not been systematically reviewed. Analyzing reported studies, we quantitatively demonstrate that suspended particles in surface water can contain significantly higher concentrations of PFAAs than the sediment below, indicating the source of suspended particles are not the sediment but particles eroded and carried from the source zone upstream. The affinity of PFAAs to particles depends on the particle composition, including organic carbon fraction and iron or aluminum oxide content. In soils, most PFAAs are retained within the top 5 m below the ground surface. The distribution of PFAAs in the subsurface varies based on site properties and local weather conditions. The depth corresponding to the maximum concentration of PFAA in soil decreases with an increase in soil organic carbon or rainfall amount received in the catchment areas. We attribute a greater accumulation of PFAAs near the upper layer of the subsurface to an increase in the accumulation of particles eroded from source zones upstream receiving heavy rainfall. Precursor transformation in the aerobic zone is significantly higher than in the anaerobic zone, thereby making the aerobic subsurface zone serve as a long-term source of groundwater pollution. Collectively, these results suggest that suspended particles, often an overlooked vector for PFAAs, can be a dominant pathway for the transport of PFAAs in environments.

Constructed wetlands for polishing oil and gas produced water releases.

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. In some areas in Wyoming, constructed wetlands (CWs) are used to polish PW downstream of National Pollutant Discharge Elimination System (NPDES) PW release points. In recent years, there has been increased interest in finding lower cost options, such as CWs, for PW treatment. The goal of this study was to understand the efficacy of removal and environmental fate of O&G organic chemical additives in CW systems used to treat PW released for agricultural beneficial reuse. To achieve this goal, we analyzed water and sediment samples for organic O&G chemical additives and conducted 16S rRNA gene sequencing for microbial community characterization on three such systems in Wyoming, USA. Three surfactants (polyethylene glycols, polypropylene glycols, and nonylphenol ethoxylates) and one biocide (alkyldimethylammonium chloride) were detected in all three PW discharges and >94% removal of all species from PW was achieved after treatment in two CWs in series. These O&G extraction additives were detected in all sediment samples collected downstream of PW discharges. Chemical and microbial analyses indicated that sorption and biodegradation were the main attenuation mechanisms for these species. Additionally, all three discharges showed a trend of increasingly diverse, but similar, microbial communities with greater distance from NPDES PW discharge points. Results of this study can be used to inform design and management of constructed wetlands for produced water treatment.

Fate and transport of per- and polyfluoroalkyl substances (PFASs) in the vadose zone.

Per- and polyfluoroalkyl substances (PFASs) are a heterogeneous group of persistent organic pollutants that have been detected in various environmental compartments around the globe. Emerging research has revealed the preferential accumulation of PFASs in shallow soil horizons, particularly at sites impacted by firefighting activities, agricultural applications, and atmospheric deposition. Once in the vadose zone, PFASs can sorb to soil, accumulate at interfaces, become volatilized, be taken up in biota, or leach to the underlying aquifer. At the same time, polyfluorinated precursor species may transform into highly recalcitrant perfluoroalkyl acids, changing their chemical identity and thus transport behavior along the way. In this review, we critically discuss the current state of the knowledge and aim to interconnect the complex processes that control the fate and transport of PFASs in the vadose zone. Furthermore, we identify key challenges and future research needs. Consequently, this review may serve as an interdisciplinary guide for the risk assessment and management of PFAS-contaminated sites.