Ting Tang

Debromination of polybrominated diphenyl ethers (PBDEs) and their conversion to polybrominated dibenzofurans (PBDFs) by UV light: Mechanisms and pathways

Polybrominated diphenyl ethers (PBDEs) are typical flame retardant that have arose widely environmental concerns. Previous studies have found that PBDEs can generate lower BDEs and polybrominated dibenzofuran (PBDFs) under UV exposure, but these two processes were not well understood. In this study, we have investigated them through the case study of three BDE congeners (i.e. BDE-29, BDE-25 and BDE-21), which all have an ortho-, a meta- and a para-bromine substituents. The results shows that the vulnerability rank order of brominated position for these three BDE congeners are totally different, the bromine substituent at each position (ortho-, meta- or para-) can be preferentially removed, indicating it is not scientific to summarize the debromination pathways of PBDEs by comparing the brominated position. The lowest unoccupied molecular orbital (LUMO) of PBDEs in first excited state are well consistent with their actual debromination pathways, suggesting it is a good descriptor to predict the photodebromination pathways of PBDEs. In addition, the PBDEs with an ortho-bromine substituent can generate lower PBDFs, and the first step is to generate lower BDEs with an ortho-carbon radical, followed by ring closure reaction to generate PBDFs.

Rapid debromination of polybrominated diphenyl ethers (PBDEs) by zero valent metal and bimetals: Mechanisms and pathways assisted by density function theory calculation

Polybrominated diphenyl ethers (PBDEs) undergo debromination when they were exposed in zerovalent metal or bimetallic systems. Yet their debromination pathways and mechanisms in these systems were not well understood. Here we reported the debromination pathways of three BDE congeners (BDE-21, 25 and 29) by nano-zerovalent iron (n-ZVI). All these BDE congeners have three bromine substituents that were located in ortho-, meta- and para-positions. Results demonstrated that BDE-21, 25 and 29 preferentially debrominate meta-, ortho- and para-bromines, respectively, suggesting that bromine substituent at each position (i.e. ortho-, meta- or para-) of PBDEs can be preferentially removed. Singly occupied molecular orbitals of BDE anions are well correlated with their actual debromination pathways, which successfully explain why these BDE congeners exhibit certain debromination pathways in n-ZVI system. In addition, microscale zerovalent zinc (m-ZVZ), iron-based bimetals (Fe/Ag and Fe/Pd) were also used to debrominate PBDEs, with BDE-21 as target pollutant. We found that the debromination pathways of BDE-21 in m-ZVZ and Fe/Ag systems are the same to those in n-ZVI system, but were partially different from those in Fe/Pd systems. The debromination of BDE-21 in Pd-H2 system as well as the solvent kinetic isotope effect in single metal and bimetallic systems suggests that H atom transfer is the dominant mechanism in Fe/Pd system, while e-transfer is still the dominant mechanism in Fe/Ag system.

Photodegradation behaviors of polychlorinated biphenyls in methanol by UV-irradiation: Solvent adducts and sigmatropic arrangement

This study has investigated the photolysis of polychlorinated biphenyls (PCBs) in methanol solution under UV irradiation. The results showed that the PCBs containing ortho-chlorine can generate both hydroxylated and methoxylated PCBs (HO-PCBs and MeO-PCBs), while the PCBs with a meta-chlorine but without ortho-chlorine can only generate MeO-PCBs as the only solvent adducts. No solvent adducts were detected during the photochemical reaction of 4-chlorobiphenyl (PCB-3), indicating the para-chlorine cannot be attacked by solvent molecule to form correspondent solvent adducts. The sigmatropic rearrangement was found during the photochemical reaction of ortho-substituted PCBs, but cannot occur in the reaction of PCBs with only meta- or para-chlorine, indicating that ortho-chlorine played a vital role in the sigmatropic rearrangement reaction. In addition, the seteric hindrance can also lead to the generation of sigmatropic rearrangement products. The effect of solvent was investigated in the case of photochemical reaction of 2-chlorobiphenyl (PCB-1), the results showed that sigmatropic rearrangement can occur in different solvents, and corresponding solvent adducts were generated in the photochemical reaction of PCB-1 in different solvents.

Photocatalytic removal of organic phosphate esters by TiO 2 : Effect of inorganic ions and humic acid

In this study, the TiO2-mediated photocatalytic removal of organic phosphate esters (OPEs) under UV irradiation was investigated. In addition, the effects of selected inorganic ions and humic acid (HA) were examined. TCEP, TCPP, and TDCPP hardly undergo degradation via photolysis, and TiO2-mediated photocatalysis was confirmed to be effective for removing OPEs present in a water matrix. Inorganic ions (e.g., PO43-, SO42-, Cl-, and NO3-) and HA inhibited the degradation of OPEs. Among these selected ions, PO43- exhibited the strongest inhibition ability, followed by SO42- and then Cl- and NO3-, and the inhibition effect increased with the ion concentration. The inhibition effect was caused by two main reasons: (1) Inorganic ions or HA served as ·OH scavengers and competed with OPEs for ·OH. (2) On account of the adsorption of inorganic ions and HA on TiO2, the available surface-active sites for OPEs decreased, followed by their oxidation with surface-bound ·OH. The ·OH concentrations were measured by electron spin resonance and the probe method, and it was positively correlated to the degradation rate of OPEs. This study emphasized the importance of inorganic species and HA on the photocatalytic degradation of OPEs and clarified the inhibition mechanism for the degradation of OPEs by the inorganic species or HA.

Experimental and theoretical investigations on debromination pathways of polybrominated biphenyls (PBBs) under ultraviolet light

Polybrominated biphenyls (PBBs) are brominated flame retardants that are widely used in textiles and electronic products. Recently, many researches have been devoted to determining their concentrations in food and in the environment. Yet, their degradation behavior has been less investigated and is not well understood. Here, we have investigated the debromination pathways of PBBs by (UV) light in the case of 2,4,5-tribrominated biphenyl (PBB-29). Our investigation indicates that para-bromine substituent on PBB-29 was preferentially removed. By means of density functional theory (DFT), we found that the energies of the debromination products, the CBr bond length in the excited state (S1), the Mulliken charge of bromine in S1, and the lowest unoccupied molecular orbital (LUMO) in S1 correlated well with the debromination pathways of PBBs. Further, LUMO-based prediction of PBB debromination pathways in S1 suggests that the bromine substituent on all brominated positions (i.e. ortho-, meta- and para-) can be preferentially removed, as the debromination sequence is not based on the brominated position but on the specific brominated arrangement pattern. In addition, reductive debromination preferentially occurs on the benzene ring that has the highest number of bromine substituents. This study provided useful descriptors to predict the debromination pathways of PBBs, and the theoretical result greatly improve our understanding of photolytic debromination of PBBs.