Assessment of environmental forensic indicator for anthropogenic groundwater contamination via Target/Suspect/Nontarget analysis using HRMS techniques

This study compared target/suspect/nontarget analysis via liquid chromatography-high-resolution mass spectrometry (LC-HRMS) with traditional environmental forensic methods, specifically nitrate and its stable N isotope, in assessing groundwater pollution from livestock manure and agriculture. Using an in-house database of 1471 target and suspects, 35 contaminants (pesticides, veterinary drugs, surfactants) were identified, some uniquely linked to specific pollution sources, such as sulfamethazine and 4-formylaminoantipyrine in manure-affected areas. Pesticides were widespread, typically showing higher intensity in agricultural zones. On the other hand, the results of stable N isotope analysis (δ15N-NO3: 4.8 to 16.4‰) indicated the influence of human activities such as fertilizers, sewage, and manure in all sampling sites, including the control site far from the pollution sources and cannot differentiate the specific sources. The study underscores LC-HRMS's efficacy in different pollution sources, surpassing the limitations of stable N isotope analysis, and provides valuable insights for polluted groundwater source tracking strategies.