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Analysis of hydraulic fracturing additives by LC/Q-TOF-MS

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Abstract

The chemical additives used in fracturing fluids can be used as tracers of water contamination caused by hydraulic fracturing operations. For this purpose, a complete chemical characterization is necessary using advanced analytical techniques. Liquid chromatography coupled with quadrupole time-of-flight mass spectrometry (LC/Q-TOF-MS) was used to identify chemical additives present in flowback and produced waters. Accurate mass measurements of main ions and fragments were used to characterize the major components of fracking fluids. Sodium adducts turned out to be the main molecular adduct ions detected for some additives due to oxygen-rich structures. Among the classes of chemical components analyzed by mass spectrometry include gels (guar gum), biocides (glutaraldehyde and alkyl dimethyl benzyl ammonium chloride), and surfactants (cocamidopropyl dimethylamines, cocamidopropyl hydroxysultaines, and cocamidopropyl derivatives). The capabilities of accurate mass and MS-MS fragmentation are explored for the unequivocal identification of these compounds. A special emphasis is given to the mass spectrometry elucidation approaches used to identify a major class of hydraulic fracturing compounds, surfactants.

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Acknowledgments

We would like to thank Dr. James Rosenblum and Dr. Yaal Lester for providing the flowback and produced water samples shown in Figs. 3 and 6, respectively. The samples were obtained through the AirWaterGas Sustainability Research Network, funded by the National Science Foundation under Grant No. CBET-1240584. We also thank Agilent Technologies for instrument support.

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  1. Center for Environmental Mass Spectrometry, University of Colorado, 1111 Engineering Drive, ECOT 441, 428 UC, Boulder, CO, 80309, USA

    Imma Ferrer & E. Michael Thurman

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  1. Imma Ferrer
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  2. E. Michael Thurman
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Correspondence to Imma Ferrer.

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Any opinion, findings, and conclusions or recommendations expressed in this paper are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

Published in the topical collection High-Resolution Mass Spectrometry in Food and Environmental Analysis with guest editor Aldo Laganà.

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Ferrer, I., Thurman, E.M. Analysis of hydraulic fracturing additives by LC/Q-TOF-MS. Anal Bioanal Chem 407, 6417–6428 (2015). https://doi.org/10.1007/s00216-015-8780-5

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