[Identification of vibration characteristics in infrared spectrum of polybrominated diphenyl ethers congeners based on Br substituents].

Structure optimization and frequency calculations of 209 kinds of PBDEs homologues were carried out at the B3LYP/6-31G(d) level based on density functional theory, the known experimental parameters of 4 PBDEs congeners were compared with the calculated values, and the average analog coefficient was 0. 989. The main vibration of DE and BDE-209 which contained only H atoms or Br substituent in the benzene ring was assigned due to their less interference for various infrared spectrum vibrations. C-Br bond vibration which was often coupled with other forms of vibration was not easy to distinguish between PBDEs congeners. With the characteristics of universality, strong vibration and identifiable, triangular breathing vibration of the benzene rings in the infrared spectrum was selected as a characteristic vibration among different PBDEs homologues, the analysis results showed that the ortho-substituted and para-substituted Br could significantly improve the vibration frequency of triangular breathing vibration, while the meta-substituted Br played the opposite role; For the low bromide, the more the substituents in ortho position, the higher the frequency, while for the high bromide homologues, simultaneous existence in ortho-position and para-position would have a higher frequency; With the same substituted location, the more the substituent in the same benzene ring, the higher the vibration frequency. SVM regression model was used to verify the relative relationship between Br substituent and triangle breathing vibration frequency of the benzene rings, and the simulation efficiency coefficient of model was 0. 956. The study provided a theoretical basis and guidance for actually testing and identifying PBDEs homologues in the environment.

A dynamic multimedia fuzzy-stochastic integrated environmental risk assessment approach for contaminated sites management.

A dynamic multimedia fuzzy-stochastic integrated environmental risk assessment approach was developed for contaminated sites management. The contaminant concentrations were simulated by a validated interval dynamic multimedia fugacity model, and different guideline values for the same contaminant were represented as a fuzzy environmental guideline. Then, the probability of violating environmental guideline (Pv) can be determined by comparison between the modeled concentrations and the fuzzy environmental guideline, and the constructed relationship between the Pvs and environmental risk levels was used to assess the environmental risk level. The developed approach was applied to assess the integrated environmental risk at a case study site in China, simulated from 1985 to 2020. Four scenarios were analyzed, including "residential land" and "industrial land" environmental guidelines under "strict" and "loose" strictness. It was found that PAH concentrations will increase steadily over time, with soil found to be the dominant sink. Source emission in soil was the leading input and atmospheric sedimentation was the dominant transfer process. The integrated environmental risks primarily resulted from petroleum spills and coke ovens, while the soil environmental risks came from coal combustion. The developed approach offers an effective tool for quantifying variability and uncertainty in the dynamic multimedia integrated environmental risk assessment and the contaminated site management.