Development and application of retention time prediction models in the suspect and non-target screening of emerging...

Hydrophilic interaction liquid chromatography (HILIC) and reversed phase LC (RPLC) coupled to high resolution mass spectrometry (HRMS) are widely used for the identification of suspects and unknown compounds in the environment. For the identification of unknowns, apart from mass accuracy and isotopic fitting, retention time (t_R) and MS/MS spectra evaluation is required. In this context, a novel comprehensive workflow was developed to study the t_R behavior of large groups of emerging contaminants using Quantitative Structure-Retention Relationships (QSRR). 682 compounds were analyzed by HILIC-HRMS in positive Electrospray Ionization mode (ESI). Moreover, an extensive dataset was built for RPLC-HRMS including 1830 and 308 compounds for positive and negative ESI, respectively. Support Vector Machines (SVM) was used to model the t_R data. The applicability domains of the models were studied by Monte Carlo Sampling (MCS) methods. The MCS method was also used to calculate the acceptable error windows for the predicted t_R from various LC conditions. This paper provides validated models for predicting t_R in HILIC/RPLC-HRMS platforms to facilitate identification of new emerging contaminants by suspect and non-target HRMS screening, and were applied for the identification of transformation products (TPs) of emerging contaminants and biocides in wastewater and sludge.