Application of multivariate data techniques in photochemical study of polycyclic aromatic hydrocarbons (PAHs) and transformed PAH products in road dust.

Road dust is a key repository for PAHs and transformed PAH products (TPPs) generated from natural and anthropogenic sources in the urban environment. Eventhough PAHs and TPPs are prone to post-emission photochemical processes, very limited studies exist on the subject for road dust. This knowledge gap is of particular concern since some of the resultant TPPs are notably more carcinogenic than their precursor PAHs. This study evaluated the role of 254 nm ultraviolet (UV) photons on the photochemistry of PAHs and TPPs in road dust. The findings show that UV irradiation had varying effects on the fate of analytes, particularly naphthalene (NAP), phenanthrene (PHE), 7, 12-dimethylbenz(a)anthracene (DMBA), 1-hydroxypyrene (HPY), 1-nitropyrene (1NPY), pyrene (PYR) and 5-nitroacenaphthene (5NAC). Photochemical relationship was identified between PYR, 1NPY and HPY, and DMBA and benzo(a)anthracene. Unlike carbonyl-PAHs, parent PAHs, nitro-PAHs and hydroxy-PAHs can originate from photolysis. Photon irradiation durations of 3, 6 and 7.5 h had the most intense influence on the photolytic process with 7.5 h as optimum. The photochemical rate at optimum irradiation duration shows an increasing trend of NAP < PHE < 1NPY < DMBA < 5NAC < HPY with respective estimates of 0.08, 0.11, 0.21, 0.22, 0.43, and 0.59 mg kg hr. Physicochemical properties of analytes such as index of refraction and vapour pressure (in logarithmic form) had an inverse effect on photolysis. The knowledge generated is significant for the in-depth understanding of the fate of PAHs and TPPs on urban road surfaces and contributes to the greater protection of human health and the environment.