GCxGC Quantification of Priority and Emerging Nonpolar Halogenated Micropollutants in All Types of Wastewater Matrices: Analysis Methodology, Chemical Occurrence, and Partitioning
We report the development and validation of a method to detect and quantify diverse nonpolar halogenated micropollutants in wastewater treatment plant (WWTP) influent, effluent, primary sludge, and secondary sludge matrices (including both the liquid and particle phases) by comprehensive two-dimensional gas chromatography (GCXGC) coupled to microelectron capture detector (mu ECD). The 59 target analytes included toxaphenes, polychlorinated naphthalenes, organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, and emerging persistent and bioaccumulative chemicals. The method is robust for a wide range of nonpolar halogenated micropollutants in all matrices. For most analytes, recoveries fell between 70% and 130% in all matrix types. GCXGC-mu ECD detections of several target analytes were confirmed qualitatively by further analysis with GCxGC coupled to electron capture negative chemical ionization time-of-flight mass spectrometry (ENCI-TOFMS). We then quantified the concentrations and apparent organic solid water partition coefficients (K-p) of target micropollutants in samples from a municipal WWTP in Switzerland. Several analyzed pollutants exhibited a high frequency of occurrence in WWTP stream samples, including octachloronaphthalene, PCB-44, PCB-52, PCB-153, PCB-180, several organochlorine pesticides, PBDE-10, PBDE-28, PBDE-116, musk tibetene, and pentachloronitrobenzene. Our results suggest that sorption to dissolved organic carbon (DOC) can contribute substantially to the apparent solids-liquid distribution of hydrophobic micropollutants in WWTP streams.