Relook on the Linear Free Energy Relationships Describing the Partitioning Behavior of Diverse Chemicals for Polyethylene Water Passive Samplers

Over the past 3 decades, low-density polyethylene (PE) passive sampling devices have been widely used to scout organic chemicals in air, water, sediments, and biotic phases. Experimental partition coefficient data, required to calculate the concentrations in environmental compartments, are not widely available. In this study, we developed and rigorously evaluated linear free energy relationships (LFERs) to predict the partition coefficient between the PE and the water phase (log Kpe-w). Poly-parameter (pp) LFERs based on Abraham solute parameters performed better (root-mean-square error, rmse = 0.333-0.350 log unit) in predicting log Kpe-w compared to the two one-parameter (op) LFERs built on n-hexadecane-water and octanol-water partition coefficients (rmse = 0.41-0.42 log unit), indicating that one parameter is not able to account for all types of interactions experienced by a chemical during PE-water exchange. Dimensionality analyses show that the calibration dataset used to train pp-LFERs fulfills all the requirements to obtain a robust model for log Kpe-w. Van der Waals interactions of the molecule tend to favor the PE phase, and polar interactions of the molecule favor the water phase. The PE phase is the most sensitive to polarizable chemicals compared to other commonly used passive sampling polymeric phases such as polydimethylsiloxane, polyoxymethylene, and polyacrylate. For op-LFERs, the PE phase is better represented by the hexadecane phase than by the octanol phase. A computational method based on the conductor-like screening model for real solvents theory did good job in estimating log Kpe-w for chemicals that were neither very hydrophobic nor very hydrophilic in nature. Our models can be used to reliably predict the log Kpe-w values of simple neutral organic chemicals. This study provides insights into the partitioning behavior of PE samplers compared to other commonly used passive samplers.

Automated summary

Over the past 30 years, low-density polyethylene (PE) has been widely used as passive sampling devices to detect organic chemicals in various environmental compartments. This study developed and evaluated linear free energy relationships (LFERs) to predict the partition coefficient between PE and water. The findings suggest that the calibration dataset used to train the poly-parameter LFERs fulfills the requirements for obtaining a robust model for predicting log Kpe-w. Furthermore, the computational method based on the conductor-like screening model for real solvents theory performed well in estimating log Kpe-w for chemicals that were moderately hydrophobic or hydrophilic.