Desalting and Concentration of Common Hydraulic Fracturing Fluid Additives and their Metabolites with Solid-Phase Extraction

Kurban A Sitterley; Karl G Linden; Imma Ferrer; E Michael Thurman

doi:10.1016/j.chroma.2020.461094

Desalting and Concentration of Common Hydraulic Fracturing Fluid Additives and their Metabolites with Solid-Phase Extraction

J Chromatogr A. 2020 Jul 5:1622:461094. doi: 10.1016/j.chroma.2020.461094. Epub 2020 Apr 18.

Authors

Kurban A Sitterley¹, Karl G Linden², Imma Ferrer³, E Michael Thurman⁴

Affiliations

¹ Department of Environmental Engineering, University of Colorado, Boulder, CO 80309. Electronic address: kurban.sitterley@colorado.edu.
² Department of Environmental Engineering, University of Colorado, Boulder, CO 80309. Electronic address: karl.linden@colorado.edu.
³ Department of Environmental Engineering, University of Colorado, Boulder, CO 80309. Electronic address: imma.ferrer@colorado.edu.
⁴ Department of Environmental Engineering, University of Colorado, Boulder, CO 80309. Electronic address: michael.thurman@colorado.edu.

PMID: 32362359
DOI: 10.1016/j.chroma.2020.461094

Abstract

This work describes the development of a solid-phase extraction method capable of detecting common fracturing fluid additives in flowback and produced water with mass spectrometry. Dissolved organic carbon (DOC) was used as a bulk measurement to investigate the retentive capacity of seven sorbents and to determine a loading volume. Conductivity was used to determine rinse volume. Based on this, four sorbents (HLB, PPL, Carbon, and C-18) were selected for further investigation of their ability to recover common fluid additives. Enrichment factors were calculated for poly(ethylene) glycols (PEGs), PEG-amines, and their metabolites PEG-carboxylates and PEG-carboxylate-amines, poly(propylene) glycols (PPGs), and linear alkyl ethoxylates (LAEs). The sorbent HLB gave the greatest enrichment for all of these compounds, with an average of 8.0× for PEGs, 11.9× for PEG-amines, 4.9× for PEG-carboxylates, and 21.6× for LAEs, though enrichment was highly dependent on sample composition. The effect was more pronounced for higher molecular weight compounds and enabled detection of some compounds in saltier samples. Then, HLB was used to recover these additives from 1:200 and 1:1000 dilutions in groundwater, illustrating the ability of solid-phase extraction to detect these compounds at low levels (<100 ppb) and highlighting the utility of desalting. This method was used to identify ethoxylated amines in flowback and produced waters from across the country.

Keywords: Fracturing fluid compounds; Hydraulic fracturing; Solid-phase extraction, Desalting.

MeSH terms

Carbon / analysis
Chemistry Techniques, Analytical* / methods
Chemistry Techniques, Analytical* / standards
Groundwater / chemistry
Hydraulic Fracking*
Mass Spectrometry
Solid Phase Extraction*
Wastewater* / chemistry
Water Pollutants, Chemical* / chemistry
Water Pollutants, Chemical* / isolation & purification

Substances

Waste Water
Water Pollutants, Chemical
Carbon