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3445681 
Journal Article 
Indications of transformation products from hydraulic fracturing additives in shale-gas wastewater 
Hoelzer, K; Sumner, AJ; Karatum, O; Nelson, RK; Drollette, BD; O'Connor, MP; D'Ambro, EL; Getzinger, GJ; Ferguson, PL; Reddy, CM; Elsner, M; Plata, DL 
2016 
1 
Environmental Science & Technology
ISSN: 0013-936X
EISSN: 1520-5851 
AMER CHEMICAL SOC 
WASHINGTON 
50 
15 
8036-8048 
English 
27419914 
WOS:000381063200012 
is supplemented by 3445683 : Supplemental materials
Unconventional natural gas development (UNGD) generates large volumes of wastewater, the detailed composition of which must be known for adequate risk assessment and treatment. In particular, transformation products of geogenic compounds and disclosed additives have not been described. This study investigated six Fayetteville Shale wastewater samples for organic composition using a suite of one- and two-dimensional gas chromatographic techniques to capture a broad distribution of chemical structures. Following the application of strict compound-identification-confidence criteria, we classified compounds according to their putative origin. Samples displayed distinct chemical distributions composed of typical geogenic substances (hydrocarbons and hopane biomarkers), disclosed UNGD additives (e.g., hydrocarbons, phthalates such as diisobutyl phthalate, and radical initiators such as azobis(isobutyronitrile)), and undisclosed compounds (e.g., halogenated hydrocarbons, such as 2-bromohexane or 4-bromoheptane). Undisclosed chloromethyl alkanoates (chloromethyl propanoate, pentanoate, and octanoate) were identified as potential delayed acids (i.e., those that release acidic moieties only after hydrolytic cleavage, the rate of which could be potentially controlled), suggesting they were deliberately introduced to react in the subsurface. In contrast, the identification of halogenated methanes and acetones suggested that those compounds were formed as unintended byproducts. Our study highlights the possibility that UNGD operations generate transformation products and underscores the value of disclosing additives injected into the subsurface. 
Environmental Studies; Natural gas; Risk assessment; Additives; Chromatography; Hydrocarbons 
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