Combining Experimental Sorption Parameters with QSAR to Predict Neonicotinoid and Transformation Product Sorption to...

We recently discovered that transformation of the neonicotinoid insecticidal pharmacophore alters sorption propensity to activated carbon, with products adsorbing less than parent compounds. To assess the environmental fate of novel transformation products that lack commercially available standards, researchers must rely on predictive approaches. In this study, we combined computationally derived quantitative structure-activity relationship (QSAR) parameters for neonicotinoids and neonicotinoid transformation products with experimentally determined Freundlich partition constants (log K _F for sorption to carbon nanotubes [CNTs] and granular activated carbon [GAC]) to model neonicotinoid and transformation product sorption. QSAR models based on neonicotinoid sorption to functionalized/nonfunctionalized CNTs (used to generalize/simplify neonicotinoid-GAC interactions) were iteratively generated to obtain a multiple linear regression that could accurately predict neonicotinoid sorption to CNTs using internal and external validation (within 0.5 log units of the experimentally determined value). The log K _F,CNT values were subsequently related to log K _F,GAC where neonicotinoid sorption to GAC was predicted within 0.3 log-units of experimentally determined values. We applied our neonicotinoid-specific model to predict log K _F,GAC for a suite of novel neonicotinoid transformation products (i.e., formed via hydrolysis, biotransformation, and chlorination) that do not have commercially available standards. We present this modeling approach as an innovative yet relatively simple technique to predict fate of highly specialized/unique polar emerging contaminants and/or transformation products that cannot be accurately predicted via traditional methods (e.g., pp-LFER), and highlights molecular properties that drive interactions of emerging contaminants.