Kinetics of PCDD/Fs Formation from Non-Wood Pulp Bleaching with Chlorine

Chlorine bleaching is still practiced by most of nonwood pulp and paper mills, resulting in a considerable amount of polychlorinated dibenzo-<i>p</i>-dioxins and polychlorinated dibenzofurans (PCDD/Fs) formation and emission. In this study, the effects of primary chlorination conditions on the formation of PCDD/Fs from nonwood pulp bleaching with elemental chlorine were investigated. It was found that low-chlorinated PCDD/Fs were usually formed and then underwent further chlorination to form highly chlorinated PCDD/Fs with increasing chlorination time. Higher available chlorine dosages and lower system pH values greatly accelerated dioxin formation, and pH 3 was the threshold for the formation of tetra- to octa-CDD/Fs. Higher temperatures promoted the formation of lower-chlorinated PCDD/Fs, while caused significant reduction of tetra- to hepta-CDDs and penta- to octa-OCDFs. PCDFs were formed much faster than PCDDs. A first-order kinetic model showed a good fit to the data for tetra- to oct-CDFs formation under different chlorination conditions, indicating that chlorine substitution was the rate determining step for their formation. Finally, the optimum chlorination conditions for minimizing and eliminating the formation of 2,3,7,8-TCDD/TCDF in nonwood pulp bleaching with elemental chlorine were established

Hazy Weather-Induced Variation in Environmental Behavior of PCDD/Fs and PBDEs in Winter Atmosphere of A North China Megacity

Haze is a serious pollution problem during the wintertime in North China. In this study, we investigated how the periodic cycle of winter haze events affect the environmental behaviors of two typical persistent organic pollutants, namely, polychlorinated dibenzo-<i>p</i>-dioxins and dibenzofurans (PCDD/Fs) and polybrominated diphenyl ethers (PBDEs), in the atmosphere of a typical megacity, Beijing. The average atmospheric concentrations of the total di- to octa-CDD/Fs (∑PCDD/Fs: 378.0 pg/m³) and the total mono- to nona-BDEs (∑_9hPBDEs: 166.5 pg/m³) during haze episodes increased by 3.6-fold and 1.9-fold compared with those during the nonhaze periods, respectively; and their concentrations both linearly increased with PM_2.5 levels and decreased as a power function of the atmospheric boundary layer height. The elevated concentrations could be clearly attributed to the vertically sinking motion of airflow in the midlower troposphere. When a haze event occurred, the partitioning rate of PCDD/Fs and PBDEs into particles was reduced; the largest fraction of the particle-bound ∑PCDD/Fs was shifted from ultrafine particles to accumulation mode particles; and a steady-state model (Li-Ma-Yang model) satisfactorily described the gas-particle partitioning of the PCDD/F and PBDE homologues. The inhalation exposure risk evaluation indicated that special attention should be paid to the increased cancer risk induced by the elevated inhalation intake of PCDD/Fs during haze episodes