Quantitative structure–property relationships on direct photolysis of PCDD/Fs on surfaces of fly ash

Abstract

Fly ash samples containing polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were generated by combustion of polyvinyl chloride, wood, high-density polyethylene and styrene. By partial least-squares (PLS) regression, quantitative structure–property relationship (QSPR) models were developed for photolysis half-lives (t 1/2) of PCDD/Fs adsorbed on fly ash surfaces and irradiated by UV-B of simulated sunlight. Quantum chemical descriptors computed by PM3 hamiltonian were used as predictor variables. The cross validated value for the optimal QSPR model was 0.678, indicating robustness and good predictive abilities of the model. The QSPR results showed that the stability of the PCDD/F molecules increased with the increase of chlorine atoms in the parent molecules. Increasing the energy of the highest occupied molecular orbital (E HOMO), the energy of the lowest unoccupied molecular orbital (E LUMO), E LUMO+E HOMO and E LUMO-E HOMO values of the PCDD/Fs led to decrease of log t 1/2 values. Increasing the most negative atomic charge on the oxygen atom of PCDD/Fs led to elevated log t 1/2 values. The log t 1/2 values of PCDD/Fs increased with the decrease of the largest negative atomic charge on a carbon atom.