Hydraulic fracturing fluids are injected into unconventional oil and gas systems to stimulate hydrocarbon production, returning to the surface in flowback and produced waters containing a complex mixture of xenobiotic additives and geogenic compounds. Nonionic polyethoxylates are commonly added surfactants that act as weatherizers, emulsifiers, wetting agents, and corrosion inhibitors in hydraulic fracturing fluid formulations. Understanding the biodegradability of these ubiquitous additives is critical for produced water pre-treatment prior to reuse and for improving treatment trains for external beneficial reuse. The objective of this study was to determine the effect of produced water total dissolved solids (TDS) from an unconventional natural gas well on the aerobic biodegradation of alkyl ethoxylate and nonylphenol ethoxylate surfactants. Changes in surfactant concentrations, speciation and metabolites, as well as microbial community composition and activity were quantified over a 75-day aerobic incubation period. Alkyl ethoxylates (AEOs) were degraded faster than nonylphenol ethoxylates (NPEOs), and both compound classes and bulk organic carbon biodegraded slower in TDS treatments (10 g L-1, 40 g L-1) as compared to controls. Short-chain ethoxylates were more rapidly biodegraded than longer-chain ethoxylates, and changes in the relative abundance of metabolites including acetone, alcohols, and carboxylate and aldehyde intermediates of alkyl units indicated metabolic pathways may shift in the presence of higher produced water TDS. Our key finding that polyethoxylated alcohol surfactant additives are less labile at high TDS has important implications for produced water management, as these fluids are increasingly recycled for beneficial reuse in hydraulic fracturing fluids and other purposes.
