Sample preparation optimization by central composite design for multi class determination of 172 emerging contaminants in wastewaters and tap water using liquid chromatography high-resolution mass spectrometry

Anna Ofrydopoulou; Christina Nannou; Eleni Evgenidou; Dimitra Lambropoulou

doi:10.1016/j.chroma.2021.462369

Sample preparation optimization by central composite design for multi class determination of 172 emerging contaminants in wastewaters and tap water using liquid chromatography high-resolution mass spectrometry

J Chromatogr A. 2021 Aug 30:1652:462369. doi: 10.1016/j.chroma.2021.462369. Epub 2021 Jun 29.

Authors

Anna Ofrydopoulou¹, Christina Nannou¹, Eleni Evgenidou¹, Dimitra Lambropoulou²

Affiliations

¹ Department of Chemistry, Aristotle University of Thessaloniki, GR 54124, Thessaloniki, Greece; Centre for Interdisciplinary Research and Innovation (CIRI-AUTH), Balkan Center, 10th km Thessaloniki-Thermi Rd, GR 57001, Thessaloniki, Greece.
² Department of Chemistry, Aristotle University of Thessaloniki, GR 54124, Thessaloniki, Greece; Centre for Interdisciplinary Research and Innovation (CIRI-AUTH), Balkan Center, 10th km Thessaloniki-Thermi Rd, GR 57001, Thessaloniki, Greece. Electronic address: dlambro@chem.auth.gr.

PMID: 34246959
DOI: 10.1016/j.chroma.2021.462369

Abstract

Multi-residue analysis is highly desirable for water quality control. To this end, a comprehensive workflow for the quantitative analysis of 172 anthropogenic organic compounds belonging to emerging contaminants (pharmaceuticals and personal care products, illicit drugs, organophosphate flame retardants and perfluoroalkyl substances) has been developed for application to wastewater and tap water, based on solid phase extraction (SPE) and Orbitrap high resolution mass spectrometry (HRMS). Due to the large number of analytes with various physicochemical characteristics that should be efficiently extracted, the response surface methodology (RSM) employing a central composite design (CCD) and desirability function (DF) approach was exploited to optimize the sample preparation process, instead of the conventional single-factor analysis. The factors included in the design of experiments (DoE) were sample pH, eluent solvents composition and volume. Statistical analysis (ANOVA) proved the adequacy of the proposed model (2- factor interaction) as p-value < 0.05 followed by different diagnostic tests confirmed the good fitting. The best values to acquire DF close to 1 were pH 3.5, methanol/ethyl acetate ratio 87:13 and eluent volume 6 mL. The streamlined method was validated in terms of accuracy, linearity, method limits, reproducibility, and matrix effect. The proposed workflow combines sensitivity and robustness, with recoveries over 70%, method quantification limits <1 ng/L, and relative standard deviations <20% for most of the compounds. Slight matrix effect (ME) was observed for most of PPCPs, IDs and PFAs, in contrast with most of the OPFRs, for which strong ME was calculated. Method applicability was tested over wastewater collected from a municipal wastewater treatment plant in Thessaloniki (Greece), revealing the presence of 69 and 40 compounds in influents and effluents, respectively, at varying concentrations.

Keywords: OPFRs; Orbitrap High Resolution Mass Spectrometry; PFAs; PPCPs; Response Surface Methodology; Water.

MeSH terms

Chemistry Techniques, Analytical* / methods
Chromatography, High Pressure Liquid
Chromatography, Liquid*
Drinking Water* / chemistry
Reproducibility of Results
Solid Phase Extraction
Tandem Mass Spectrometry*
Wastewater* / analysis
Water Pollutants, Chemical* / analysis

Substances

Drinking Water
Waste Water
Water Pollutants, Chemical