Evaluation of GC-EI&CI-TOFMS for Nontarget Analysis of Industrial Wastewater Using Hydrophilic-Lipophilic-Balanced SPME

The evaluation of nontarget analysis (NTA) techniques for the monitoring of wastewater is important as wastewater is an anthropogenic pollution source for aquatic ecosystems and a threat to human and environmental health. This study presents the proof-of-concept NTA of industrial wastewater samples. A prototype hydrophilic-lipophilic-balanced (HLB) SPME and gas chromatography interfaced with time-of-flight high-resolution mass spectrometry (GC-TOFMS) with electron ionization (EI) and chemical ionization (CI) in parallel are employed. The HLB-SPME consists of a poly(divinylbenzene-co-N-vinylpyrrolidone) structure, allowing the extraction of hydrophilic as well as lipophilic substances. As the combination of parallel CI and EI data provides a comprehensive data set as a unique feature, this study is strongly focused on the compound identification procedure and confidence reporting of exemplary substances. Furthermore, the use of three different CI reagent ions, including [N2H](+)/[N4H](+), [H3O](+), and [NH4](+), enables a broad range of analytes to be ionized in terms of selectivity and softness. The complementary information provided by EI and CI data allows a level 3 identification or higher in 69% of cases. The polarity coverage based on the physicochemical properties of the analytes (such as volatility, water solubility, hydrophilicity, and lipophilicity) was visualized by using Henry's law and octanol-water partitioning constants. In conclusion, the presented approach is shown to be valuable for wat