Issue 2, 2019

Exploring matrix effects and quantifying organic additives in hydraulic fracturing associated fluids using liquid chromatography electrospray ionization mass spectrometry

Abstract

Hydraulic fracturing (HF) operations utilize millions of gallons of water amended with chemical additives including biocides, corrosion inhibitors, and surfactants. Fluids injected into the subsurface return to the surface as wastewaters, which contain a complex mixture of additives, transformation products, and geogenic chemical constituents. Quantitative analytical methods are needed to evaluate wastewater disposal alternatives or to conduct adequate exposure assessments. However, our narrow understanding of how matrix effects change the ionization efficiency of target analytes limits the quantitative analysis of polar to semi-polar HF additives by means of liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS). To address this limitation, we explored the ways in which matrix chemistry influences the ionization of seventeen priority HF additives with a modified standard addition approach. We then used the data to quantify HF additives in HF-associated fluids. Our results demonstrate that HF additives generally exhibit suppressed ionization in HF-associated fluids, though HF additives that predominantly form sodiated adducts exhibit significantly enhanced ionization in produced water samples, which is largely the result of adduct shifting. In a preliminary screening, we identified glutaraldehyde and 2-butoxyethanol along with homologues of benzalkonium chloride (ADBAC), polyethylene glycol (PEG), and polypropylene glycol (PPG) in HF-associated fluids. We then used matrix recovery factors to provide the first quantitative measurements of individual homologues of ADBAC, PEG, and PPG in HF-associated fluids ranging from mg L−1 levels in hydraulic fracturing fluid to low μg L−1 levels in PW samples. Our approach is generalizable across sample types and shale formations and yields important data to evaluate wastewater disposal alternatives or implement exposure assessments.

Graphical abstract: Exploring matrix effects and quantifying organic additives in hydraulic fracturing associated fluids using liquid chromatography electrospray ionization mass spectrometry

Supplementary files

Article information

Article type
Paper
Submitted
24 Бер 2018
Accepted
15 Тра 2018
First published
17 Тра 2018

Environ. Sci.: Processes Impacts, 2019,21, 195-205

Author version available

Exploring matrix effects and quantifying organic additives in hydraulic fracturing associated fluids using liquid chromatography electrospray ionization mass spectrometry

M. Nell and D. E. Helbling, Environ. Sci.: Processes Impacts, 2019, 21, 195 DOI: 10.1039/C8EM00135A

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements