Prioritization and Risk Ranking of Regulated and Unregulated Chemicals in US Drinking Water.

Drinking water constituents were compared using more than six million measurements (USEPA data) to prioritize and risk-rank regulated and unregulated chemicals and classes of chemicals. Hazard indexes were utilized for hazard- and risk-based chemicals, along with observed (nondetects = 0) and censored (nondetects = method detection limit/2) data methods. Chemicals (n = 139) were risk-ranked based on population exposed, resulting in the highest rankings for inorganic compounds (IOCs) and disinfection byproducts (DBPs), followed by semivolatile organic compounds (SOCs), nonvolatile organic compounds (NVOCs), and volatile organic compounds (VOCs) for observed data. The top 50 risk-ranked chemicals included 15 that were unregulated, with at least one chemical from each chemical class (chromium-6 [#1, IOC], chlorate and NDMA [#11 and 12, DBP], 1,4-dioxane [#25, SOC], PFOS, PFOA, PFHxS [#42, 44, and 49, NVOC], and 1,2,3-trichloropropane [#48, VOC]). These results suggest that numerous unregulated chemicals are of higher exposure risk or hazard in US drinking water than many regulated chemicals. These methods could be applied following each Unregulated Contaminant Monitoring Rule (UCMR) data collection phase and compared to retrospective data that highlight what chemicals potentially pose the highest exposure risk or hazard among US drinking water, which could inform regulators, utilities, and researchers alike.

Aerobic biological degradation of organic matter and fracturing fluid additives in high salinity hydraulic fracturing wastewaters.

Reuse of hydraulic fracturing wastewaters depends on effective tailored treatment to prepare the water for the intended end use. Aerobic biological treatment of hydraulic fracturing produced water was examined to degrade dissolved organic carbon (DOC) and polyethylene glycols (PEGs). Biological treatment experiments of three produced water samples with DOC concentrations ranging from 22 to 420 mg/L and total dissolved solids (TDS) levels ranging from 26 to 157 g/L were conducted in 48-240 h batches. Samples were not pretreated to remove suspended solids and were inoculated with activated sludge and acclimated over several weeks. Results show that between 50% and 80% of DOC was removed in 12-24 h but a sizeable portion, on a mass basis, remained in the samples with higher DOC concentrations. PEGs were also shown to readily biodegrade into singly- and doubly-carboxylated metabolites, but were not shown to degrade past that point, leading to accumulation of PEG-dicarboxylates (PEG-diCs) in the batch reactors. Possible explanations include residence times that were too long, resulting in starved microbial populations (and thus, a stopping of PEG degradation) or the presence of other ethoxylated additives that degraded into PEGs and PEG-diCs and fed this accumulation. This work demonstrates that a well-acclimated microbial culture is capable of degrading a large portion of DOC in hydraulic fracturing wastewaters across a wide spectrum of TDS concentrations, indicating that biological treatment is a viable option for enabling reuse of produced water.

Development of a separation framework for effects-based targeted and non-targeted toxicological screening of water and wastewater.

An environmental water sample fractionation framework was developed based on effects-directed analysis (EDA) to detect known and unknown compounds of concern in different waters. Secondary effluent from a wastewater treatment plant was used to demonstrate the effectiveness of the developed framework for characterizing estrogenic compounds in the effluent. The effluent was spiked with known estrogenic compounds to validate the framework in a targeted approach and an unspiked sample was also investigated in a non-targeted approach. The framework separated compounds based on polarity and adsorption using liquid-liquid extraction followed by solid phase extraction. The targeted and non-targeted effluents generated six fractions each, which were assessed for estrogenic activity using an in vitro bioassay (yeast estrogen screen - YES). Three out of the six fractions in each case, along with the raw effluent, showed estrogen equivalent concentrations (EEQs) ranging between 1.0 and 3.0 µg/L. Directed by the assay results, these estrogenic fractions were further analyzed using liquid- and gas-chromatography coupled with mass spectrometry for compound identification. The developed separation framework coupled with a bioassay aided in identification of both known and unknown compounds producing estrogenic effects in the water sample. The approach of fractionation followed by concentration helped isolate and elevate contaminant levels without necessarily concentrating potential matrix effects that could cause interfering cytotoxicity and inhibition in the bioassay. The targeted analysis showed consistency between predicted and observed results, while the non-targeted analysis revealed the presence of three estrogenic compounds in the unspiked effluent: di-isobutyl phthalate, diethyl phthalate and benzophenone, that were confirmed with standards. The study mainly aimed at development and validation of a simple yet effective EDA framework with low cost techniques for water and wastewater toxicity screening and evaluation, and the results suggested that the developed framework could be used as a screening tool for isolating and identifying unknown compounds in a complex water sample.

Degradation of polyethylene glycols and polypropylene glycols in microcosms simulating a spill of produced water in shallow groundwater.

Polyethylene glycols (PEGs) and polypropylene glycols (PPGs) are frequently used in hydraulic fracturing fluids and have been detected in water returning to the surface from hydraulically fractured oil and gas wells in multiple basins. We identified degradation pathways and kinetics for PEGs and PPGs under conditions simulating a spill of produced water to shallow groundwater. Sediment-groundwater microcosm experiments were conducted using four produced water samples from two Denver-Julesburg Basin wells at early and late production. High-resolution mass spectrometry was used to identify the formation of mono- and di-carboxylated PEGs and mono-carboxylated PPGs, which are products of PEG and PPG biodegradation, respectively. Under oxic conditions, first-order half-lives were more rapid for PEGs (<0.4-1.1 d) compared to PPGs (2.5-14 d). PEG and PPG degradation corresponded to increased relative abundance of primary alcohol dehydrogenase genes predicted from metagenome analysis of the 16S rRNA gene. Further degradation was not observed under anoxic conditions. Our results provide insight into the differences between the degradation rates and pathways of PEGs and PPGs, which may be utilized to better characterize shallow groundwater contamination following a release of produced water.

Succession of toxicity and microbiota in hydraulic fracturing flowback and produced water in the Denver-Julesburg Basin.

Hydraulic fracturing flowback and produced water (FPW) samples were analyzed for toxicity and microbiome characterization over 220 days for a horizontally drilled well in the Denver-Julesberg (DJ) Basin in Colorado. Cytotoxicity, mutagenicity, and estrogenicity of FPW were measured via the BioLuminescence Inhibition Assay (BLIA), Ames II mutagenicity assay (AMES), and Yeast Estrogen Screen (YES). Raw FPW stimulated bacteria in BLIA, but were cytotoxic to yeast in YES. Filtered FPW stimulated cell growth in both BLIA and YES. Concentrating 25× by solid phase extraction (SPE) revealed significant toxicity throughout well production by BLIA, toxicity during the first 55 days of flowback by YES, and mutagenicity by AMES. The selective pressures of fracturing conditions (including toxicity) affected bacterial and archaeal communities, which were characterized by 16S rRNA gene V4V5 region sequencing. Conditions selected for thermophilic, anaerobic, halophilic bacteria and methanogenic archaea from the groundwater used for fracturing fluid, and from the native shale community. Trends in toxicity echoed the microbial community, which indicated distinct stages of early flowback water, a transition stage, and produced water. Biota in another sampled DJ Basin horizontal well resembled similarly aged samples from this well. However, microbial signatures were unique compared to samples from DJ Basin vertical wells, and wells from other basins. These data can inform treatability, reuse, and management decisions specific to the DJ Basin to minimize adverse environmental health and well production outcomes.

Assessment of temperature and ultraviolet radiation effects on sunburn incidence at an inland U.S. Beach: A cohort study.

BACKGROUND: Increases in outdoor temperature may lead to increases in sunburn, outdoor exposure, and skin cancer in human populations. OBJECTIVE: This study aimed to quantify sunburn incidence and risk for Ohio beachgoers exposed to varying outdoor conditions. METHODS: Sunburn incidence data were obtained through a prospective cohort study at East Fork Lake (Cincinnati, Ohio, USA). Recruitment occurred over 26 weekend days. Beach interviews and follow-up telephone interviews obtained exposure and health information. New sunburns were self-reported 8-9 days post-enrollment. Survey data were paired with ultraviolet radiation (UVR) index and temperature data for statistical analysis. RESULTS: Among 947 beachgoers, new sunburns were reported in 18% of swimmers. Sunburn incidence was associated with temperature (odds ratio = 1.2; 95% CI: 1.1 - 1.4) and UVR index (odds ratio = 1.6; 95% CI: 1.0 - 2.5) in models adjusted for water exposure, arrival time, and beach visit frequency. Some evidence of a temperature+UVR interaction was observed. LIMITATIONS: Exposure and sunburn data were self-reported without clinical diagnosis and date of onset. The follow-up period enabled sunburns to be reported from a variety of days rather than only the beach visit day thereby limiting interpretation. Sun protection behaviors were not evaluated. CONCLUSIONS: Temperature and UVR influence sunburn frequency. Temperature, however was more strongly associated with sunburn in beachgoers than the nearest measured UVR index, suggesting future investigations are needed to better understand how temperature effects sunburn development. Interventions for decreasing sunburn are needed.

Organic Chemical Characterization and Mass Balance of a Hydraulically Fractured Well: From Fracturing Fluid to Produced Water over 405 Days.

A long-term field study (405 days) of a hydraulically fractured well from the Niobrara Formation in the Denver-Julesburg Basin was completed. Characterization of organic chemicals used in hydraulic fracturing and their changes through time, from the preinjected fracturing fluid to the produced water, was conducted. The characterization consisted of a mass balance by dissolved organic carbon (DOC), volatile organic analysis by gas chromatography/mass spectrometry, and nonvolatile organic analysis by liquid chromatography/mass spectrometry. DOC decreased from 1500 mg/L in initial flowback to 200 mg/L in the final produced water. Only ∼11% of the injected DOC returned by the end of the study, with this 11% representing a maximum fraction returned since the formation itself contributes DOC. Furthermore, the majority of returning DOC was of the hydrophilic fraction (60-85%). Volatile organic compound analysis revealed substantial concentrations of individual BTEX compounds (0.1-11 mg/L) over the 405-day study. Nonvolatile organic compounds identified were polyethylene glycols (PEGs), polypropylene glycols (PPG), linear alkyl-ethoxylates, and triisopropanolamine (TIPA). The distribution of PEGs, PPGs, and TIPA and their ubiquitous presence in our samples and the literature illustrate their potential as organic tracers for treatment operations or in the event of an environmental spill.

Temporal characterization of flowback and produced water quality from a hydraulically fractured oil and gas well.

This study examined water quality, naturally-occurring radioactive materials (NORM), major ions, trace metals, and well flow data for water used and produced from start-up to operation of an oil and gas producing hydraulically-fractured well (horizontal) in the Denver-Julesburg (DJ) Basin in northeastern Colorado. Analysis was conducted on the groundwater used to make the fracturing fluid, the fracturing fluid itself, and nine flowback/produced water samples over 220days of operation. The chemical oxygen demand of the wastewater produced during operation decreased from 8200 to 2500mg/L, while the total dissolved solids (TDS) increased in this same period from 14,200 to roughly 19,000mg/L. NORM, trace metals, and major ion levels were generally correlated with TDS, and were lower than other shale basins (e.g. Marcellus and Bakken). Although at lower levels, the salinity and its origin appear to be the result of a similar mechanism to that of other shale basins when comparing Cl/Br, Na/Br, and Mg/Br ratios. Volumes of returned wastewater were low, with only 3% of the volume injected (11millionliters) returning as flowback by day 15 and 30% returning by day 220. Low levels of TDS indicate a potentially treatment-amenable wastewater, but low volumes of flowback could limit onsite reuse in the DJ Basin. These results offer insight into the temporal water quality changes in the days and months following flowback, along with considerations and implications for water reuse in future hydraulic fracturing or for environmental discharge.

Identification of polypropylene glycols and polyethylene glycol carboxylates in flowback and produced water from hydraulic fracturing.

The purpose of the study was to separate and identify the unknown surfactants present in flowback and produced water from oil and gas wells in the Denver-Julesburg Basin (Niobrara Formation) in Weld County, Colorado, USA. Weld County has been drilled extensively during the last five years for oil and gas between 7000-8000 feet below land-surface. Polypropylene glycols (PPGs) and polyethylene glycols carboxylates (PEG-Cs) were found for the first time in these flowback and produced water samples. These ethoxylated surfactants may be used as friction reducers, clay stabilizers, and surfactants. Ultrahigh-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry (UHPLC/QTOF-MS) was used to separate and identify the different classes of PPGs, PEG-Cs, and their isomers. The Kendrick mass scale was applied along with mass spectrometry/mass spectrometry (MS-MS) with accurate mass for rapid and unequivocal identification. The PPGs and their isomers occur at the ppm concentration range and may be useful as "fingerprints" of hydraulic-fracturing. Comparing these detections to the compounds used in the fracturing process from FracFocus 3.0 (https://fracfocus.org), it appears that both PPGs and polyethylene glycols (PEGs) are commonly named as additives, but the PEG-Cs have not been reported. The PEG-Cs may be trace impurities or degradation products of PEGs.

Evaluating UV-C LED disinfection performance and investigating potential dual-wavelength synergy.

A dual-wavelength UV-C LED unit, emitting at peaks of 260 nm, 280 nm, and the combination of 260|280 nm together was evaluated for its inactivation efficacy and energy efficiency at disinfecting Escherichia coli, MS2 coliphage, human adenovirus type 2 (HAdV2), and Bacillus pumilus spores, compared to conventional low-pressure and medium-pressure UV mercury vapor lamps. The dual-wavelength unit was also used to measure potential synergistic effects of multiple wavelengths on bacterial and viral inactivation and DNA and RNA damage. All five UV sources demonstrated similar inactivation of E. coli. For MS2, the 260 nm LED was most effective. For HAdV2 and B. pumilus, the MP UV lamp was most effective. When measuring electrical energy per order of reduction, the LP UV lamp was most efficient for inactivating E. coli and MS2; the LP UV and MP UV mercury lamps were equally efficient for HAdV2 and B. pumilus spores. Among the UV-C LEDs, there was no statistical difference in electrical efficiency for inactivating MS2, HAdV2, and B. pumilus spores. The 260 nm and 260|280 nm LEDs had a statistical energy advantage for E. coli inactivation. For UV-C LEDs to match the electrical efficiency per order of log reduction of conventional LP UV sources, they must reach efficiencies of 25-39% or be improved on by smart reactor design. No dual wavelength synergies were detected for bacterial and viral inactivation nor for DNA and RNA damage.

Low-energy hydraulic fracturing wastewater treatment via AC powered electrocoagulation with biochar.

Produced and flowback waters are the largest byproducts associated with unconventional oil and gas exploration and production. Sustainable and low cost technologies are needed to treat and reuse this wastewater to avoid the environmental problems associated with current management practices (i.e., deep well injection). This study presents a new process to integrate AC-powered electrocoagulation (EC) with granular biochar to dramatically reduce energy use and electrode passivation while achieving high treatment efficiency. Results show achieving a 99% turbidity and TSS removal for the AC-EC-biochar system only used 0.079 kWh/m(3) or 0.15 kWh/kg TSS, which is 70% lower than traditional DC-EC systems and orders of magnitude lower than previous studies. The amount of biochar added positively correlates with energy saving, and further studies are needed to improve organic carbon and salt removal through system integration.

Influence of seasonal fluctuation and loading rates on microbial and chemical indicators during semi-continuous anaerobic digestion.

Minimal attention is paid towards the performance of the 40 million small-scale digesters which frequently operate at psychrophilic temperatures. Understanding the levels of microbial and chemical indicators at various loading rates and temperatures is useful for improving treatment efficiency and management strategies for small-scale digesters. In this study, semi-continuous anaerobic digesters were operated in replicate at four different loading rates (control, 0.3, 0.8 and 1.3 kg VS/m(3)/day) and housed in an environment that simulated seasonal change (27.5°C,10°C and 27.5°C). The results illustrate that class B quality biosolids were generated for all treatments as per guidelines from the United States Environmental Protection Agency (USEPA). The simulated seasonal change did not influence Escherichia coli or faecal coliform levels, while it did appear to have an effect upon levels of Enterococci. Reduced loading rates led to a more stable environment (in terms of pH, levels of volatile fatty acids (VFAs) and total inorganic carbonate (TIC)) as well as lower levels of indicator bacteria, but generated slightly lower biogas volumes (high--53.23 L vs. low--53.19 L) over the course of the study. The results provide important data to improve the performance of small-scale psychrophilic digesters, specifically by reducing loading rates to prevent souring during winter months.