Physical-chemical evaluation of hydraulic fracturing chemicals in the context of produced water treatment.

Produced water is a significant waste stream that can be treated and reused; however, the removal of production chemicals-such as those added in hydraulic fracturing-must be addressed. One motivation for treating and reusing produced water is that current disposal methods-typically consisting of deep well injection and percolation in infiltration pits-are being limited. Furthermore, oil and gas production often occurs in arid regions where there is demand for new water sources. In this paper, hydraulic fracturing chemical additive data from California are used as a case study where physical-chemical and biodegradation data are summarized and used to screen for appropriate produced water treatment technologies. The data indicate that hydraulic fracturing chemicals are largely treatable; however, data are missing for 24 of the 193 chemical additives identified. More than one-third of organic chemicals have data indicating biodegradability, suggesting biological treatment would be effective. Adsorption-based methods and partitioning of chemicals into oil for subsequent separation is expected to be effective for approximately one-third of chemicals. Volatilization-based treatment methods (e.g. air stripping) will only be effective for approximately 10% of chemicals. Reverse osmosis is a good catch-all with over 70% of organic chemicals expected to be removed efficiently. Other technologies such as electrocoagulation and advanced oxidation are promising but lack demonstration. Chemicals of most concern due to prevalence, toxicity, and lack of data include propargyl alcohol, 2-mercaptoethyl alcohol, tetrakis hydroxymethyl-phosphonium sulfate, thioglycolic acid, 2-bromo-3-nitrilopropionamide, formaldehyde polymers, polymers of acrylic acid, quaternary ammonium compounds, and surfactants (e.g. ethoxylated alcohols). Future studies should examine the fate of hydraulic fracturing chemicals in produced water treatment trains to demonstrate removal and clarify interactions between upstream and downstream processes.