Hydrophobic Organic Compounds in Hydraulic Fracturing Flowback Waters: Identification and Source Apportionment

Monday, 15 December 2014
Desiree Plata1, Kathrin Shregglman2, Martin Elsner2, Gordon Getzinger3, Lee Ferguson3, Brian Drollette1, Osman Karatum3, Robert K Nelson4 and Christopher M Reddy4, (1)Yale University, New Haven, CT, United States, (2)Helmholtz Zentrum Munchen, Neuherberg D-85764, Germany, (3)Duke University, Durham, NC, United States, (4)WHOI, Woods Hole, MA, United States
Current hydraulic fracturing technologies rely on organic chemicals to serve multiple critical functions, including corrosion inhibition, in situ gel formation, and friction reduction. While industrial users have disclosed several hundreds of compound and mixture identities, it is unclear which of these are used and where, in what proportion, and with what frequency. Furthermore, while flowback and production waters contain both fracturing additive and geogenic compounds, they may contain potential reaction byproducts as well. Here, we identified several hundred organic compounds present in six hydraulic fracturing flowback waters over the Fayetteville shale. Identifications were made via non-target analysis using two-dimensional gas chromatography with time of flight mass spectrometry for hydrophobic organic compounds and liquid chromatography- orbitrap mass spectrometry. Compound identities were confirmed using purchased standards when available. Using the SkyTruth database and the Waxman list of disclosed compounds, we assigned compounds as either fracturing-fluid-derived or geogenic (or both), or a putative transformation products thereof. Several unreported halogenated compounds were detected, including chlorinated, brominated, and iodated species that have no known natural sources. Control studies indicated that these could not be formed under typical laboratory or field storage conditions, suggesting that halogenation reactions may give rise to novel compounds in the subsurface, presumably via reaction between fracturing fluid additives and shale-derived brines. Further, the six samples were strikingly heterogeneous, reflecting the diversity in fracturing fluid composition and flowback handling procedures at the time of the study.