Halogens are common in industrial thermal processes and can induce formation of toxic organic pollutants.Currently,the specific effects of coexisting halogens on toxic pollutant formation are unclear.In this study,we ...Halogens are common in industrial thermal processes and can induce formation of toxic organic pollutants.Currently,the specific effects of coexisting halogens on toxic pollutant formation are unclear.In this study,we found the boosting effects of halogens on organic pollutants formation during thermal processes.In situ electron paramagnetic resonance spectroscopy was used to distinguish the organic free radical intermediates of organic pollutants during thermal processes.The pure chlorine-containing reaction system dominantly induce the formation of highly chlorinated phenoxy radicals,whereas the pure bromine-containing reaction system induce the formation of semiquinone radicals.The results provide clear evidence for the molecular mechanisms by which halogen coexistence boosts pollutants formation.Coexisting halogens made the reactions much more complex.Bromine atom radicals(Br·)can enhance the level of active chlorine atoms radicals(Cl·),then(1)facilitating highly chlorinated organic radicals and toxic pollutants formation,(2)activating polycyclic aromatic hydrocarbons molecules for subsequent ring growth and(3)accelerating oxidation reactions.Combining the identification of organic free radical intermediates and characteristics of products,detailed mechanisms of halogens on the formations of organic pollutants during thermal-related processes were clarified,which can be helpful for their efficient control in the widespread bromines and chlorines co-existence reaction system.展开更多
A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, w...A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).展开更多
In this paper,a series of GdOF-based green phosphors doped with Ho^(3+) and Yb^(3+) ions was prepared by a simple co-precipitation method.The crystal structure s and optical prope rties were investigated in detail.The...In this paper,a series of GdOF-based green phosphors doped with Ho^(3+) and Yb^(3+) ions was prepared by a simple co-precipitation method.The crystal structure s and optical prope rties were investigated in detail.The intensity of the emission of GdOF:Yb^(3+),Ho^(3+) phosphors is enhanced by the effective energy transfer from Yb^(3+) to Ho^(3+),and the optimal luminescence is achieved with the Ho^(3+)doping amount of 0.1 mol%as well as Yb^(3+) doping amount of 5 mol%.Tunable UC emission of samples is achieved by adjusting the doping concentration of Ho^(3+) or Yb^(3+).The purity of the green UC emission is further improved by enhancing the excitation pumping power.In addition,logarithmic functions of green,red and nearinfrared radiation intensities were calculated versus logarithmic function of pump power for further study.A possible UC luminescence mechanism between Yb^(3+) and Ho^(3+) is discussed based on powerdependent UC luminescence spectrum and decay lifetimes.These results suggest that GdOF:Yb^(3+),Ho^(3+)phosphors with bright and high-purity green UC emission have potential applications in the fields of bioimaging,display and illumination.展开更多
Incineration has been the globally controversial and concerned method of solid waste disposal.Energy recovery and volume reduction are the benefits from waste incineration,but risk due to release of persistent organic...Incineration has been the globally controversial and concerned method of solid waste disposal.Energy recovery and volume reduction are the benefits from waste incineration,but risk due to release of persistent organic pollutants is the major public concern in the world.In this study,the emission of organic pollutants including dioxins and polychlorinated naphthalenes from solid waste incineration in China was comprehensively evaluated,and a relationship between energy benefit and pollutant emission was firstly established.The results show that production of medical and industrial waste was smaller than that of municipal waste but yielded comparable or even higher emission of dioxins.The energy benefit-to-emission index for organic pollutants(EBEIOP)for evaluation of solid waste management on a local or regional scale was proposed.Significant correlations between net energy benefit and pollutant emission for provinces with higher EBEIOP values were found.Furthermore,higher EBEIOP values were associated with economic factors while lower values were influenced by emission from incineration of medical and industrial waste.We suggest that an EBEIOP value of R60 can serve as a reference for“profitable”solid waste management,assisting decision making during energy benefit and environmental risk assessment.展开更多
基金supported by the National Key Research and Development Program of China(No.2023YFC3707004)the National Natural Science Foundation of China(Nos.22376204,22076201 and 92143201)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Nos.XDB0750400,XDB0750100 and XDB0750000)the Second Tibetan Plateau Scientific Expedition and Research Program(STEP)(No.2019 QZKK0605).
文摘Halogens are common in industrial thermal processes and can induce formation of toxic organic pollutants.Currently,the specific effects of coexisting halogens on toxic pollutant formation are unclear.In this study,we found the boosting effects of halogens on organic pollutants formation during thermal processes.In situ electron paramagnetic resonance spectroscopy was used to distinguish the organic free radical intermediates of organic pollutants during thermal processes.The pure chlorine-containing reaction system dominantly induce the formation of highly chlorinated phenoxy radicals,whereas the pure bromine-containing reaction system induce the formation of semiquinone radicals.The results provide clear evidence for the molecular mechanisms by which halogen coexistence boosts pollutants formation.Coexisting halogens made the reactions much more complex.Bromine atom radicals(Br·)can enhance the level of active chlorine atoms radicals(Cl·),then(1)facilitating highly chlorinated organic radicals and toxic pollutants formation,(2)activating polycyclic aromatic hydrocarbons molecules for subsequent ring growth and(3)accelerating oxidation reactions.Combining the identification of organic free radical intermediates and characteristics of products,detailed mechanisms of halogens on the formations of organic pollutants during thermal-related processes were clarified,which can be helpful for their efficient control in the widespread bromines and chlorines co-existence reaction system.
基金supported by the National Natural Science Foundation of China(No.21777172)the Collaborative Project supported by Chinese Academy of Sciences and Hebei Academy of Sciences(No.181602)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2016038)
文摘A field study and theoretical calculations were performed to clarify the levels, profiles, and distributions of polybrominated dibenzo-p-dioxins and dibenzofurans(PBDD/Fs) in a cement kiln co-processing solid waste, with a focus on the PBDF formation mechanism.The raw materials contributed greatly to input of PBDD/Fs into the cement kiln. The PBDD/F concentrations in the raw materials were much higher than those in particle samples from different process stages in the cement kiln. The PBDD/F concentrations in the clinkers were1.40% of the concentrations in the raw materials, which indicated that the high destruction efficiencies for PBDD/Fs by cement kiln. PBDD/F distribution patterns in particle samples collected from different process stages indicated the cement kiln backend was a major site for PBDD/F formation. PBDFs with high levels of halogenation, such as heptabrominated furans(Hp BDF), were the dominant contributors to the total PBDD/F concentrations and accounted for 42%–73% of the total PBDD/F concentrations in the particle samples. Our results showed that co-processing of municipal solid waste in a cement kiln may influence the congener profile of PBDD/Fs, especially for the higher halogenated PBDD fraction. In addition, there were significant correlations between the decabromodiphenyl ether and heptabrominated furan concentrations, which is an indicator of transformation from polybrominated diphenyl ethers to PBDD/Fs. Theoretical calculations were performed and demonstrated that elimination of HBr and Br_2 from polybrominated diphenyl ethers were the dominant formation pathways for PBDD/Fs. These pathways differed from that for polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs).
基金Project supported by the National Natural Science Foundation of China(51202111)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘In this paper,a series of GdOF-based green phosphors doped with Ho^(3+) and Yb^(3+) ions was prepared by a simple co-precipitation method.The crystal structure s and optical prope rties were investigated in detail.The intensity of the emission of GdOF:Yb^(3+),Ho^(3+) phosphors is enhanced by the effective energy transfer from Yb^(3+) to Ho^(3+),and the optimal luminescence is achieved with the Ho^(3+)doping amount of 0.1 mol%as well as Yb^(3+) doping amount of 5 mol%.Tunable UC emission of samples is achieved by adjusting the doping concentration of Ho^(3+) or Yb^(3+).The purity of the green UC emission is further improved by enhancing the excitation pumping power.In addition,logarithmic functions of green,red and nearinfrared radiation intensities were calculated versus logarithmic function of pump power for further study.A possible UC luminescence mechanism between Yb^(3+) and Ho^(3+) is discussed based on powerdependent UC luminescence spectrum and decay lifetimes.These results suggest that GdOF:Yb^(3+),Ho^(3+)phosphors with bright and high-purity green UC emission have potential applications in the fields of bioimaging,display and illumination.
基金This work was supported by the National Natural Science Foundation of China(grants 21936007,21777172,and 91843301)CAS Interdisciplinary Innovation Team(JCTD-2019-03)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(grant 2016038).
文摘Incineration has been the globally controversial and concerned method of solid waste disposal.Energy recovery and volume reduction are the benefits from waste incineration,but risk due to release of persistent organic pollutants is the major public concern in the world.In this study,the emission of organic pollutants including dioxins and polychlorinated naphthalenes from solid waste incineration in China was comprehensively evaluated,and a relationship between energy benefit and pollutant emission was firstly established.The results show that production of medical and industrial waste was smaller than that of municipal waste but yielded comparable or even higher emission of dioxins.The energy benefit-to-emission index for organic pollutants(EBEIOP)for evaluation of solid waste management on a local or regional scale was proposed.Significant correlations between net energy benefit and pollutant emission for provinces with higher EBEIOP values were found.Furthermore,higher EBEIOP values were associated with economic factors while lower values were influenced by emission from incineration of medical and industrial waste.We suggest that an EBEIOP value of R60 can serve as a reference for“profitable”solid waste management,assisting decision making during energy benefit and environmental risk assessment.
