Organophosphite Antioxidants and Novel Organophosphate Esters in Dust from China: Large-Scale Distribution and Heterogeneous Phototransformation

A large-scale survey was conducted by measuring five organophosphite antioxidants (OPAs) and three novel organophosphate esters (NOPEs) in 139 dust samples across China. The median summed concentrations of OPAs and NOPEs in outdoor dust were 33.8 ng/g (range: 0.12–53,400 ng/g) and 7990 ng/g (2390–27,600 ng/g), respectively. The dust concentrations of OPAs associated with the increasing economic development and population density from western to eastern China, whereas the NOPE concentration in Northeast China (median, 11,900 ng/g; range, 4360–16,400 ng/g) was the highest. Geographically, the distribution of NOPEs was significantly associated with annual sunshine duration and precipitation at each sampling site. Results of laboratory experiments further revealed that the simulated sunlight irradiation promoted the heterogeneous phototransformation of OPAs in dust, and this process was accelerated with the existence of reactive oxygen species and enhanced relative humidity. Importantly, during this phototransformation, the hydroxylated, hydrolyzed, dealkylated, and methylated products, e.g., bis(2,4-di-tert-butylphenyl) methyl phosphate, were identified by nontargeted analysis, part of which were estimated to be more toxic than their parent compounds. The heterogeneous phototransformation pathway of OPAs was suggested accordingly. For the first time, the large-scale distribution of OPAs and NOPEs and the phototransformation of these "new chemicals" in dust were revealed.