The photodegradation of two phthalic acid esters (PAEs), dimethyl phthalate (DMP) and di-n-octyl phthalate (DOP), under simulated sunlight in aqueous or organic phases (n-hexane (HEX) and dichloromethane (DCM)) was investigated. The mean photodegradation rates were ranked by half-lives as follows: DOP in DCM (3.77 hours) < DMP in DCM (9.62 hours) < DOP in H2O (3.99 days) < DMP in H2O (19.2 days) < DOP in HEX (21.0 days) < DMP in HEX (> 30 days). Compound-specific stable isotope analysis (CSIA) combined with intermediate analysis was employed to explore the involved initial photoreaction mechanism. C-O bond cleavage, chlorine radical adduction to the aromatic ring, competing reactions of chlorine radical adduction to the aromatic ring and side chain, and a singlet oxygen-mediated pathway were mainly responsible for initial photodegradation mechanism of PAEs in H2O, DMP in DCM, DOP in DCM, and DOP in HEX, respectively. Furthermore, distinct isotope fractionation patterns of PAEs photodegradation open the possibility of using CSIA to differentiate the involved solvents in the field. More toxic and recalcitrant intermediates were emerged during the photodegradation of DMP in DCM, while the risk to human health was reduced during the photochemical transformation of DOP in organic solvents.
Thirty four sampling sites along an elevation transect in the Tibetan Plateau region were chosen. Soil cores were divided into several layers and a total of 175 horizon soil samples were collected from July to September 2011, for determination of polycyclic aromatic hydrocarbons (PAHs). The measured PAHs concentration in surface soils was 56.26 ± 45.84 ng g−1, and the low molecular weight PAHs (2–3 rings) predominated, accounting for 48% and 35%. We analyzed the spatial (altitudinal and vertical) distribution of PAHs in soil, and explored the influence of related environmental factors. Total organic carbon (TOC) showed a controlling influence on the distribution of PAHs. PAH concentrations declined with soil depth, and the composition patterns of PAHs along soil depth indicated that the heavy PAHs tended to remain in the upper layers (0–10 cm), while the light fractions were transported downward more easily. PAHs inventories (8.77–57.92 mg m−2) for soil cores increased with mean annual precipitation, while the topsoil concentrations decreased with it. This implies that an increase in precipitation could transfer more PAHs from the atmosphere to the soil and further transport PAHs from the topsoil to deeper layers.
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