Extended Suspect and Non-Target Strategies to Characterize Emerging Polar Organic Contaminants in Raw Wastewater with LC-HRMS/MS

Abstract

An integrated workflow based on liquid chromatography coupled to a quadrupole-time-of-flight mass spectrometer (LC-QTOF-MS) was developed and applied to detect and identify suspect and unknown contaminants in Greek wastewater. Tentative identifications were initially based on mass accuracy, isotopic pattern, plausibility of the chromatographic retention time and MS/MS spectral interpretation (comparison with spectral libraries, in silico fragmentation). Moreover, new specific strategies for the identification of metabolites were applied to obtain extra confidence including the comparison of diurnal and/or weekly concentration trends of the metabolite and parent compounds and the complementary use of HILIC. Thirteen of 284 predicted and literature metabolites of selected pharmaceuticals and nicotine were tentatively identified in influent samples from Athens and seven were finally confirmed with reference standards. Thirty four nontarget compounds were tentatively identified, four were also confirmed. The sulfonated surfactant diglycol ether sulfate was identified along with others in the homologous series (SO4C2H4(OC2H4)xOH), which have not been previously reported in wastewater. As many surfactants were originally found as nontargets, these compounds were studied in detail through retrospective analysis.

A strategic screening approach to identify transformation products of organic micropollutants formed in natural waters

“…[16][17][18][19][20][21] These techniques are enabled by high-resolution mass spectrometry (HRMS). Most studies are initially based on laboratory experiments at elevated concentrations to facilitate the identication of TPs, [22][23][24] which are then searched for in environmental samples.…”

“…Most studies are initially based on laboratory experiments at elevated concentrations to facilitate the identication of TPs, [22][23][24] which are then searched for in environmental samples. 16,25,26 Strategies have also been developed to assist and simplify the detection of TPs directly in natural waters and wastewater, based on the use of characteristic fragmentation 27,28 or mass defect ltering. 29 Such applications mostly contribute with information on the occurrence of TPs 18,25 likely formed under the conditions during conventional wastewater treatment processes and emitted directly from the WWTPs.…”

Facilitating high resolution mass spectrometry data processing for screening of environmental water samples: An evaluation of two deconvolution tools

“…In the literature, three different approaches are described for the detection and/or identification of compounds: target, suspect/post-target and non-target (Aceña et al, 2015;Bletsou et al, 2015;Gago-Ferrero et al, 2015;Hernández et al, 2015b, Hernández et al, 2014, Hernández et al, 2005Krauss et al, 2010;Leendert et al, 2015). Target methods are limited to a restricted number of compounds, for all of which reference standards must be obtained and, therefore, information on the occurrence of other unknown, relevant micropollutants may be missed.…”

Advanced analytical tools for the investigation of licit and illicit drug residues in water

“…target, suspect/post-target and non-target (Aceña et al, 2015;Gago-Ferrero et al, 2015;Hernández et al, 2015bHernández et al, , 2014Leendert et al, 2015). Target methods are limited to a restricted number of compounds, for all of which reference standards must be obtained and, therefore, information on the occurrence of other unknown, relevant micropollutants may be missed.…”