Strategies to characterize polar organic contamination in wastewater: exploring the capability of high resolution mass spectrometry.

Wastewater effluents contain a multitude of organic contaminants and transformation products, which cannot be captured by target analysis alone. High accuracy, high resolution mass spectrometric data were explored with novel untargeted data processing approaches (enviMass, nontarget, and RMassBank) to complement an extensive target analysis in initial "all in one" measurements. On average 1.2% of the detected peaks from 10 Swiss wastewater treatment plant samples were assigned to target compounds, with 376 reference standards available. Corrosion inhibitors, artificial sweeteners, and pharmaceuticals exhibited the highest concentrations. After blank and noise subtraction, 70% of the peaks remained and were grouped into components; 20% of these components had adduct and/or isotope information available. An intensity-based prioritization revealed that only 4 targets were among the top 30 most intense peaks (negative mode), while 15 of these peaks contained sulfur. Of the 26 nontarget peaks, 7 were tentatively identified via suspect screening for sulfur-containing surfactants and one peak was identified and confirmed as 1,3-benzothiazole-2-sulfonate, an oxidation product of a vulcanization accelerator. High accuracy, high resolution data combined with tailor-made nontarget processing methods (all available online) provided vital information for the identification of a wider range of heteroatom-containing compounds in the environment.

[1]  J. Hollender,et al.  Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water. , 2010, Environmental pollution.

[2]  Beate I. Escher,et al.  Recent advances in environmental risk assessment of transformation products. , 2011, Environmental science & technology.

[3]  A. Marcomini,et al.  Investigation of the fate of linear alkyl benzenesulfonates and coproducts in a laboratory biodegradation test by using liquid chromatography/mass spectrometry , 1999 .

[4]  W. Giger,et al.  Fate of secondary alkane sulfonate surfactants during municipal wastewater treatment , 1995 .

[5]  A. Marinoni,et al.  Characterization of Recalcitrant Intermediates from Biotransformation of the Branched Alkyl Side Chain of Nonylphenol Ethoxylate Surfactants , 1998 .

[6]  Heinz Singer,et al.  Targeting aquatic microcontaminants for monitoring: exposure categorization and application to the Swiss situation , 2010, Environmental science and pollution research international.

[7]  P. Lara-Martín,et al.  Tracking sewage derived contamination in riverine settings by analysis of synthetic surfactants. , 2011, Journal of environmental monitoring : JEM.

[8]  C. Reddy,et al.  Nontargeted comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry method and software for inventorying persistent and bioaccumulative contaminants in marine environments. , 2012, Environmental science & technology.

[9]  P. Lara-Martín,et al.  Seasonal changes in the concentration of anionic surfactants in estuarine sediments from the River Guadalete (Cadiz, Spain) , 2010 .

[10]  Valery Tkachenko,et al.  Identification of “Known Unknowns” Utilizing Accurate Mass Data and ChemSpider , 2011, Journal of The American Society for Mass Spectrometry.

[11]  Christian Zwiener,et al.  Is nontarget screening of emerging contaminants by LC-HRMS successful? A plea for compound libraries and computer tools , 2012, Analytical and Bioanalytical Chemistry.

[12]  René P Schwarzenbach,et al.  Identification of transformation products of organic contaminants in natural waters by computer-aided prediction and high-resolution mass spectrometry. , 2009, Environmental science & technology.

[13]  D. Barceló,et al.  Characterization and quantitative analysis of surfactants in textile wastewater by liquid chromatography/quadrupole-time-of-flight mass spectrometry. , 2008, Rapid communications in mass spectrometry : RCM.

[14]  F. Hernández,et al.  Current use of high-resolution mass spectrometry in the environmental sciences , 2012, Analytical and Bioanalytical Chemistry.

[15]  M. Hirai,et al.  MassBank: a public repository for sharing mass spectral data for life sciences. , 2010, Journal of mass spectrometry : JMS.

[16]  Markus Meringer,et al.  MS/MS Data Improves Automated Determination of Molecular Formulas by Mass Spectrometry , 2011 .

[17]  R. Samperi,et al.  Fate of linear alkyl benzenesulfonates, coproducts, and their metabolites in sewage treatment plants and in receiving river waters , 1999 .

[18]  Stephen Stein,et al.  Mass spectral reference libraries: an ever-expanding resource for chemical identification. , 2012, Analytical chemistry.

[19]  R. Schwarzenbach,et al.  The Challenge of Micropollutants in Aquatic Systems , 2006, Science.

[20]  Oliver Fiehn,et al.  Metabolomic database annotations via query of elemental compositions: Mass accuracy is insufficient even at less than 1 ppm , 2006, BMC Bioinformatics.

[21]  Heinz Singer,et al.  Alleviating the reference standard dilemma using a systematic exact mass suspect screening approach with liquid chromatography-high resolution mass spectrometry. , 2013, Analytical chemistry.

[22]  Martin Krauss,et al.  LC–high resolution MS in environmental analysis: from target screening to the identification of unknowns , 2010, Analytical and bioanalytical chemistry.

[23]  Steffen Neumann,et al.  MetFusion: integration of compound identification strategies. , 2013, Journal of mass spectrometry : JMS.

[24]  Emma L. Schymanski,et al.  CASMI: And the Winner is .. , 2013, Metabolites.

[25]  Félix Hernández,et al.  Strategies for quantification and confirmation of multi-class polar pesticides and transformation products in water by LC–MS2 using triple quadrupole and hybrid quadrupole time-of-flight analyzers , 2005 .

[26]  B. Brownawell,et al.  Multi-residue method for the analysis of synthetic surfactants and their degradation metabolites in aquatic systems by liquid chromatography-time-of-flight-mass spectrometry. , 2011, Journal of chromatography. A.

[27]  Emma L. Schymanski,et al.  Automatic recalibration and processing of tandem mass spectra using formula annotation. , 2013, Journal of mass spectrometry : JMS.

[28]  R. Samperi,et al.  Liquid Chromatography- Electrospray-Mass Spectrometry as a Valuable Tool for Characterizing Biodegradation Intermediates of Branched Alcohol Ethoxylate Surfactants , 1998 .

[29]  J. Fick,et al.  EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents. , 2013, Water research.

[30]  L. Y. Tseng,et al.  Molecular characterization of effluent organic matter identified by ultrahigh resolution mass spectrometry. , 2011, Water research.

[31]  W. Giger,et al.  Determination of secondary alkane sulfonates in sewage wastewaters by solid-phase extraction and injection-port derivatization gas chromatography/mass spectrometry. , 1994, Environmental Science and Technology.

[32]  D. Barceló,et al.  Inter-laboratory comparison of liquid chromatographic techniques and enzyme-linked immunosorbent assay for the determination of surfactants in wastewaters. , 2000, Journal of chromatography. A.

[33]  Emma L. Schymanski,et al.  Small Molecule Identification with MOLGEN and Mass Spectrometry , 2013, Metabolites.

[34]  J. Sanz,et al.  Anaerobic degradation pathway of linear Alkylbenzene sulfonates (LAS) in sulfate-reducing marine sediments. , 2010, Environmental science & technology.

[35]  P. Besse,et al.  Microbial transformations of 2-substituted benzothiazoles , 2001, Applied Microbiology and Biotechnology.