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

Many transformation products (TPs) from organic micropollutants are not included in routine environmental monitoring programs due to limited knowledge of their occurrence and fate. An efficient method to identify and prioritize critical compounds in terms of environmental relevance is needed. In this study, we applied a strategic screening approach based on a case-control concept to identify TPs formed along wastewater-impacted rivers. Time-integrated samples were collected over one week at both ends of a river stretch downstream of a wastewater treatment plant (WWTP) outfall and were analyzed by ultrahigh performance liquid chromatography interfaced with quadrupole time-of-flight mass spectrometry (UHPLC-QToF-MS/MS). The screening procedure of the high-resolution MS (HRMS) datasets consisted of three major steps: (i) screening for parent compounds (PCs) attenuated along the stretch; (ii) prediction of potential TPs from these PCs; and (iii) screening for TPs from this list with an increasing trend along the stretch. In total, 32 PCs decreased along the investigated river stretches. From these PCs, eight TPs had increasing concentrations along the studied stretches and could be tentatively identified. The identification of one TP (benzamide) was confirmed by its corresponding reference standard, while no standards were available for the remaining TPs.

[1]  Matthias Müller-Hannemann,et al.  In silico fragmentation for computer assisted identification of metabolite mass spectra , 2010, BMC Bioinformatics.

[2]  Heinz Singer,et al.  Assessing exposure to transformation products of soil-applied organic contaminants in surface water: comparison of model predictions and field data. , 2011, Environmental science & technology.

[3]  M. Loos,et al.  Quantitative target and systematic non-target analysis of polar organic micro-pollutants along the river Rhine using high-resolution mass-spectrometry--Identification of unknown sources and compounds. , 2015, Water research.

[4]  M. Radke,et al.  Screening for pharmaceutical transformation products formed in river sediment by combining ultrahigh performance liquid chromatography/high resolution mass spectrometry with a rapid data-processing method. , 2014, Analytica chimica acta.

[5]  Philip H Howard,et al.  Identifying new persistent and bioaccumulative organics among chemicals in commerce II: pharmaceuticals. , 2011, Environmental science & technology.

[6]  S. Snyder,et al.  Critical assessment of the ubiquitous occurrence and fate of the insect repellent N,N-diethyl-m-toluamide in water. , 2016, Environment international.

[7]  B. Kasprzyk-Hordern,et al.  A review on emerging contaminants in wastewaters and the environment: current knowledge, understudied areas and recommendations for future monitoring. , 2015, Water research.

[8]  Sobek Anna,et al.  The dilemma in prioritizing chemicals for environmental analysis: known versus unknown hazards. , 2016, Environmental science. Processes & impacts.

[9]  T. Poiger,et al.  Ubiquitous occurrence of the artificial sweetener acesulfame in the aquatic environment: an ideal chemical marker of domestic wastewater in groundwater. , 2009, Environmental science & technology.

[10]  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.

[11]  Heinz Singer,et al.  A tiered procedure for assessing the formation of biotransformation products of pharmaceuticals and biocides during activated sludge treatment. , 2010, Journal of environmental monitoring : JEM.

[12]  Edward P. Kolodziej,et al.  Attenuation of wastewater-derived contaminants in an effluent-dominated river. , 2006, Environmental science & technology.

[13]  A. Lin,et al.  Phototransformation of cephalosporin antibiotics in an aqueous environment results in higher toxicity. , 2012, Environmental science & technology.

[14]  M. Junghans,et al.  How a complete pesticide screening changes the assessment of surface water quality. , 2014, Environmental science & technology.

[15]  H. Ngo,et al.  A review on the occurrence of micropollutants in the aquatic environment and their fate and removal during wastewater treatment. , 2014, The Science of the total environment.

[16]  Nikolaos S. Thomaidis,et al.  Targeted and non-targeted liquid chromatography-mass spectrometric workflows for identification of transformation products of emerging pollutants in the aquatic environment , 2015 .

[17]  Lynda B. M. Ellis,et al.  The University of Minnesota Biocatalysis/Biodegradation Database: improving public access , 2009, Nucleic Acids Res..

[18]  Emma L. Schymanski,et al.  Identifying small molecules via high resolution mass spectrometry: communicating confidence. , 2014, Environmental science & technology.

[19]  G. Massmann,et al.  Occurrence and distribution of psychoactive compounds and their metabolites in the urban water cycle of Berlin (Germany). , 2012, Water research.

[20]  Kyungho Choi,et al.  Pharmaceuticals and Personal Care Products in the Environment: What Are the Big Questions? , 2012, Environmental health perspectives.

[21]  Thomas Letzel,et al.  Non-target screening with high-resolution mass spectrometry: critical review using a collaborative trial on water analysis , 2015, Analytical and Bioanalytical Chemistry.

[22]  Anna Kärrman,et al.  Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of-flight tandem mass spectrometry and a case-control approach. , 2015, Environmental science & technology.

[23]  M. Mezcua,et al.  Rapid automated screening, identification and quantification of organic micro-contaminants and their main transformation products in wastewater and river waters using liquid chromatography-quadrupole-time-of-flight mass spectrometry with an accurate-mass database. , 2010, Journal of chromatography. A.

[24]  M. Radke,et al.  Using chemical benchmarking to determine the persistence of chemicals in a Swedish lake. , 2015, Environmental science & technology.

[25]  D. Barceló,et al.  Transformation products of emerging contaminants in the environment and high-resolution mass spectrometry: a new horizon , 2015, Analytical and Bioanalytical Chemistry.

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

[27]  M. Radke,et al.  Fate of Pharmaceuticals and Their Transformation Products in Four Small European Rivers Receiving Treated Wastewater. , 2016, Environmental science & technology.

[28]  A. Fernández-Alba,et al.  Use of an accurate-mass database for the systematic identification of transformation products of organic contaminants in wastewater effluents. , 2011, Journal of chromatography. A.

[29]  Martin Krauss,et al.  Identification of novel micropollutants in wastewater by a combination of suspect and nontarget screening. , 2014, Environmental pollution.

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

[31]  Diana S Aga,et al.  Pharmaceutical metabolites in the environment: Analytical challenges and ecological risks , 2009, Environmental toxicology and chemistry.

[32]  K. Kümmerer,et al.  Identification of phototransformation products of the antiepileptic drug gabapentin: Biodegradability and initial assessment of toxicity. , 2015, Water research.

[33]  D. Barceló,et al.  LC-HRMS suspect screening for detection-based prioritization of iodinated contrast media photodegradates in surface waters. , 2015, Environmental science & technology.

[34]  Reza Aalizadeh,et al.  Extended Suspect and Non-Target Strategies to Characterize Emerging Polar Organic Contaminants in Raw Wastewater with LC-HRMS/MS. , 2015, Environmental science & technology.

[35]  P. Howard,et al.  Identifying new persistent and bioaccumulative organics among chemicals in commerce. , 2010, Environmental science & technology.

[36]  A. Fernández-Alba,et al.  Post-acquisition data processing for the screening of transformation products of different organic contaminants. Two-year monitoring of river water using LC-ESI-QTOF-MS and GCxGC-EI-TOF-MS , 2014, Environmental Science and Pollution Research.

[37]  Heinz Singer,et al.  High-throughput identification of microbial transformation products of organic micropollutants. , 2010, Environmental science & technology.

[38]  K. Demeestere,et al.  Balancing the false negative and positive rates in suspect screening with high-resolution Orbitrap mass spectrometry using multivariate statistics. , 2015, Analytical chemistry.