No abstract

No abstract

Chemical additives used for hydraulic fracturing and matrix acidizing of oil reservoirs were reviewed and priority chemicals of concern needing further environmental risk assessment, treatment demonstration, or evaluation of occupational hazards were identified. We evaluated chemical additives used for well stimulation in California, the third largest oil producing state in the USA, by the mass and frequency of use, as well as toxicity. The most frequently used chemical additives in oil development were gelling agents, cross-linkers, breakers, clay control agents, iron and scale control agents, corrosion inhibitors, biocides, and various impurities and product stabilizers used as part of commercial mixtures. Hydrochloric and hydrofluoric acids, used for matrix acidizing and other purposes, were reported infrequently. A large number and mass of solvents and surface active agents were used, including quaternary ammonia compounds (QACs) and nonionic surfactants. Acute toxicity was evaluated and many chemicals with low hazard to mammals were identified as potentially hazardous to aquatic environments. Based on an analysis of quantities used, toxicity, and lack of adequate hazard evaluation, QACs, biocides, and corrosion inhibitors were identified as priority chemicals of concern that deserve further investigation.

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.

About CCSTCCST is a non-profit organization established in 1988 at the request of the California State Government and sponsored by the major public and private postsecondary institutions of California and affiliate federal laboratories in conjunction with leading private-sector firms. CCST's mission is to improve science and technology policy and application in California by proposing programs, conducting analyses, and recommending public policies and initiatives that will maintain California's technological leadership and a vigorous economy. NoteAny opinions, findings, conclusions, or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the views of the organizations or agencies that provided support for the project.