Utility of benzothiazoles as markers of tire-derived inputs to estuarine waters assessed by polyethylene sheets

Tire-derived particles and polyethylene (PE) debris co-exist in estuaries and potentially deteriorate water quality. Chemicals can be emitted from tire-derived particles and resorb to PE debris. However, there was lack of information about the interaction (e.g., sorption and desorption) between tire-derived chemicals and PE debris. By combining batch sorption and desorption experiments along with in situ field deployment of PE sheets, we examined the utility of benzothiazoles (BTZs) sorbed in PE as suitable markers of tire-derived inputs. The sorptive characteristics and PE-water partition coefficients (often designated as Kₚₑw) of selected tire-derived marker candidates, i.e., polycyclic aromatic hydrocarbons (PAHs), benzothiophenes (BTPs) and BTZs, were measured. Moderately polar BTPs and BTZs (except for 2-(4-morpholinyl) benzothiazole) reached equilibrium within 2–8 days, compared to 20 days for nonpolar PAHs. The measure Kₚₑw values and octanol-water partition coefficients of PAHs and BTZs were linearly correlated with each other (r² > 0.80; p < 0.05). The desorption potentiality of PAHs and BTZs from tire particles is consistent with the hydrophilic properties of the target chemicals, while desorption ratios of BTZs and PAHs are 25–87% and <20%, respectively. Samplers with PE sheets as the sorbent phase were deployed in Hailing Bay, an urbanized estuary in South China, to measure concentrations of PAHs, BTPs and BTZs. Benzothiazoles sorbed in PE samples were associated with the massive utilization of automobile tires, while PAHs were linked to the boat maintenance facilities and BTPs were not detected in any tire particle and field PE samples. Therefore sorbed BTZs in PE can potentially serve as chemical markers of tire-derived inputs to estuaries.