Determination of low-density polyethylene-water partition coefficients for novel halogenated flame retardants with...

The partition coefficient (K_pew) of an analyte between low-density polyethylene (LDPE) film and water is a critical parameter for measuring freely dissolved concentrations of the analyte with PE passive sampling devices. Measuring log K_pew for super hydrophobic organic chemicals (HOCs) have been proven extremely difficult. The present study developed a large volume model for measuring log K_pew of super HOCs, i.e., novel halogenated flame retardants (NHFRs). Results showed that the measured log K_pew values of selected PAHs and PCBs obtained by the large volume model were in line with those from the co-solvent model and the literature data within less 0.3 log units of difference, while those of NHFRs (6.27-7.34) except for hexachlorocyclopentadienyldibromocyclooctane (HCDBCO) and Decabromodiphenyl ethane (DBDPE) were significantly lower than those (6.51-8.89) from the co-solvent model. A curvilinear relationship was observed between log K_pew and log K_ow of all target compounds, with the turning point at log K_ow = ∼8.0 in the large volume model, but that was not found for the co-solvent model. These can be attributed to the large molecular volumes (> 450 Å³) for NHFRs, which require high Gibbs free energy to penetrate into the inside structures of LDPE in the large volume model. However, the solvent swelling effects in the co-solvent model needs to be investigated. Therefore, the large volume model is robust to determine the K_pew values of super HOCs for facilitating the application of aquatic passive sampling techniques.