Nontarget profiling of organic compounds in a temporal series of hydraulic fracturing flowback and produced waters.

Hydraulic fracturing (HF) flowback and produced water (FPW) can be toxic to aquatic life but its chemical content is largely unknown, variable and complex. Seven FPW samples were collected from a HF operation in the Duvernay Formation (Alberta, Canada) over 30 days of flowback and characterized by a nontarget workflow based on high performance liquid chromatography - high resolution mass spectrometry (HRMS). A modified Kendrick mass defect plot and MS/MS spectral interpretation revealed seven series of homologues composed of ethylene oxide (i.e. -CH2CH2O-), among which a series of aldehydes was proposed as degradation products of polyethylene glycols, and two series of alkyl ethoxylate carboxylates could be proprietary HF additives. Many other ions were confidently assigned a formula by accurate mass measurement and were subsequently prioritized for identification by matching to records in ChemSpider and the US EPA's CompTox Chemistry Dashboard. Quaternary ammonium compounds, amine oxides, organophosphorous compounds, phthalate diesters and hydroxyquinoline were identified with high confidence by MS/MS spectra (Level 3), matching to reference spectra in MassBank (Level 2) or to authentic standards (Level 1). Temporal trends showed that most of the compounds declined in abundance over the first nine days of flowback, except for phthalate diesters and hydroxyquinoline that were still observed on Day 30 and had disappearance half-lives of 61 and 91 days, respectively. All the compounds followed first-order disappearance kinetics in flowback, except for polyoxygenated acids which followed second-order kinetics. This analysis and the workflow, based largely on public on-line databases, enabled profiling of complex organic compounds in HF-FPW, and will likely be useful for further understanding the toxicity and chemical fate of HF-FPW.

Chemical and toxicological characterizations of hydraulic fracturing flowback and produced water.

Hydraulic fracturing (HF) has emerged as a major method of unconventional oil and gas recovery. The toxicity of hydraulic fracturing flowback and produced water (HF-FPW) has not been previously reported and is complicated by the combined complexity of organic and inorganic constituents in HF fluids and deep formation water. In this study, we characterized the solids, salts, and organic signatures in an HF-FPW sample from the Duvernay Formation, Alberta, Canada. Untargeted HPLC-Orbitrap revealed numerous unknown dissolved polar organics. Among the most prominent peaks, a substituted tri-phenyl phosphate was identified which is likely an oxidation product of a common polymer antioxidant. Acute toxicity of zebrafish embryo was attributable to high salinity and organic contaminants in HF-FPW with LC50 values ranging from 0.6% to 3.9%, depending on the HF-FPW fractions and embryo developmental stages. Induction of ethoxyresorufin-O-deethylase (EROD) activity was detected, due in part to polycyclic aromatic hydrocarbons (PAHs), and suspended solids might have a synergistic effect on EROD induction. This study demonstrates that toxicological profiling of real HF-FPW sample presents great challenges for assessing the potential risks and impacts posed by HF-FPW spills.