Influence of photolysis on source characterization and health risk of polycyclic aromatic hydrocarbons (PAHs), and carbonyl-, nitro-, hydroxy- PAHs in urban road dust

In this study, PAHs and their transformed PAH products (TPPs) in road dust were subjected to UV driven photolysis, and then extracted using simultaneous pressurized fluid extraction, and analysed using Shimadzu Triple Quadrupole GC/MS. The results of the analysis were used to investigate the robustness and reliability of 14 existing diagnostic ratios (DRs) and two newly proposed molecular DRs that are relevant for characterizing the sources of PAHs and TPPs. The influence of photolysis on the carcinogenic health risk posed to humans by these hazardous pollutants was then assessed. The findings indicated that the DRs segregated into stable, moderately stable and non-stable classes of source characteristics under the influence of photolysis. Only two of the existing DRs, namely, benzo(a)pyrene/benzo(ghi)perylene (BaP/BghiP) and total index exhibited consistent stability to photolysis, whilst fluoranthene/(fluoranthene + pyrene) (FRT/(FRT+PYR)) showed moderate stability. The two newly proposed DRs, naphthalene/1-nitronaphthalene (NAP/NNAP) and pyrene/(1-nitropyrene + 1-hydroxypyrene) (PYR/(1NPY+HPY)) were found to be highly reliable in post-emission source characterization. The cross-plots of the most stable DRs showed that traffic emissions is the primary source of PAHs, whilst post-emission photolysis is the secondary source of nitro-PAH (NPAH) TPPs. The percent resonance energy thermodynamic stability of the PAH pollutants does not exert any direct influence on the source characteristics of the DRs. Adults are more vulnerable to potential carcinogenic risks as a result of PAH and TPPs photolysis whereas negligible risk exist for children. This study contributes to a more reliable diagnosis of PAH and TPP sources and thus, to the regulatory mitigation of these hazardous pollutants thereby, promoting enhanced protection of human health and the environment.