Thirty-one congeners of polychlorinated naphthalenes (PCNs) and 21 congeners of polybrominated diphenylethers(PBDEs)in surface sediments at 5 stations and one mussel sample from Qingdao coastal waters were analyzed. T...Thirty-one congeners of polychlorinated naphthalenes (PCNs) and 21 congeners of polybrominated diphenylethers(PBDEs)in surface sediments at 5 stations and one mussel sample from Qingdao coastal waters were analyzed. The maximum contents occur at the station near the Haibo River mouth. The total PCNs contents are in the range of 212-1209 pg/g dw, dominated by tri-Cl CN. The total PBDEs contents are in the range of 117-5510 pg/g dw,dominated by tri- to hexa-BrBDEs. The local sources of PCNs are likely from combustion processes such as incinerations and coal burnings. The sources of PBDEs are molecular diffusion from the materials containing them. Except for the area near the river mouth where is affected by the sewage sludges, an important source of PCNs and PBDEs in this area is believed to be the atmospheric deposition. Mussels enrich PCNs and PBDEs relative to the sediments. The total TEQs of PCNs in mussels are lower than the total TEQs of PCBs.展开更多
以华南某城市生活垃圾焚烧厂一期(WI-A)和二期(WI-B)为研究对象,采集了飞灰和烟气样品,通过GC/MS对其中PCBs和PCNs的全部单体进行了测定,分析了PCBs和PCNs的固气分布(飞灰和烟气中的总量比例)、同系物分布以及毒性当量特征.结果表明,WI-...以华南某城市生活垃圾焚烧厂一期(WI-A)和二期(WI-B)为研究对象,采集了飞灰和烟气样品,通过GC/MS对其中PCBs和PCNs的全部单体进行了测定,分析了PCBs和PCNs的固气分布(飞灰和烟气中的总量比例)、同系物分布以及毒性当量特征.结果表明,WI-A和WI-B焚烧单位垃圾产生的PCBs和PCNs总量分别为0.397 mg·t-1(湿基)和0.363 mg·t-1(湿基).活性炭喷射量对PCBs的固气分布特征和去除率影响较大,对PCNs则不明显.PCBs同系物在烟气中以低氯取代单体为主,在飞灰中以高氯取代单体为主.PCNs同系物在烟气中以五氯单体为主,在飞灰中以四氯、五氯单体为主.WI-A和WI-B排放的烟气总TEQ分别为0.051 ng TEQ·Nm-3和0.096 ng TEQ·Nm-3,WI-A烟气Co-PCBs和Dl-PCNs对总TEQ的贡献率分别为3.2%和0.13%,WI-B烟气Co-PCBs和Dl-PCNs对总TEQ的贡献率分别为5.3%和0.34%,提示垃圾焚烧排放烟气中的Co-PCBs和Dl-PCNs的毒性同样值得关注.展开更多
Chloronaphthalenes （PCNs, polychlorinated naphthalenes） are a group of persistent environmental pollutants. In the present study, geometrical optimization and electrostatic potential calculations have been performed...Chloronaphthalenes （PCNs, polychlorinated naphthalenes） are a group of persistent environmental pollutants. In the present study, geometrical optimization and electrostatic potential calculations have been performed for all 75 PCNs at the HF/6-31G^＊ level of theory. A number of statistic based parameters have been extracted. Linear relationships between gas-chromatographic retention index （RI） of 62 PCNs in a non-polar column （DB-5） and the structural descriptors have been established by stepwise multiple regression technique. The result shows that two quantities derived from electrostatic potential on molecular surface, ∑Vs- and σ＋^2, together with the number of chlorine （ NCl ） and the energy of the highest occupied molecular orbital （EHOMO） can be well used to express the quantitative structure-retention relationship （QSRR） of PCNs. Predictive capability of the model has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient （Rcv^2） of 0.997, and further compared with the results from similar researches published recently. Furthermore, when splitting the 62 PCNs into training and validation sets in the ratio of 2：1, a similar treatment yields an equation of almost equal statistical quality and very similar regression coefficients, validating the robustness and prediction capability of our model. The QSRR model established may provide a new powerful method for predicting chromatographic properties of polychlorinated naphthalenes.展开更多
The concentrations and distribution of polychlorinated naphthalenes（PCNs） in the whole blood of eight typical terrestrial meat animals（chicken, duck, rabbit, pig, cattle, sheep,horse and donkey） consumed daily in ...The concentrations and distribution of polychlorinated naphthalenes（PCNs） in the whole blood of eight typical terrestrial meat animals（chicken, duck, rabbit, pig, cattle, sheep,horse and donkey） consumed daily in our life were investigated. The total concentrations（on a liquid volume basis） of PCNs were in a range from 305 to 987 pg/L. Donkey blood contained the highest PCN concentrations. Mono-CNs were the dominant homolog group,accounting for 38%–71% PCNs. Apart from the mono-CNs and tri-CNs homolog groups, two hepta-CNs（mean： 9.5%） contributed most, followed by tetra-CNs（mean： 6.5%）. The congeners CN1, 5/7, 24/14, 27/30, 52/60, 66/67, and 73 were the most abundant congeners or congener groups. The highest toxicity equivalencies（TEQs） were observed in cattle blood（117.4 fg TEQ/L） then chicken blood（117.1 fg TEQ/L）. CN73 contributed 65% to total TEQs,followed by CN70（20%） and CN66/67（14%）. The dietary intakes of PCNs were also estimated.Chicken meat, which forms the second largest component of meat product consumption in China, contributed most to the total TEQs（61%）, followed by beef（27%） and pork（5.9%）. The consumption of chicken might pose the highest risk from exposure to PCNs than other types of meat to populations who prefer to eat chicken meat.展开更多
The concentrations and congener profiles of poly- chlorinated naphthalenes （PCNs） in surface sediment samples collected from the Yangtze and Yellow River Estuaries were inves- tigated. PCN congeners （from MoCNs to ...The concentrations and congener profiles of poly- chlorinated naphthalenes （PCNs） in surface sediment samples collected from the Yangtze and Yellow River Estuaries were inves- tigated. PCN congeners （from MoCNs to OCN） were determined by isotope dilution/high-resolution gas chromatography/high- resolution mass spectrometry （HRGC-HRMS）. The total concen- trations of PCNs were 34.3-303.0 pg/g （dry weight, dw） in the Yangtze Estuary samples and 6.2-408.0 pg/g （dw） in the Yellow River Estuary samples, which were lower compared with that in other sediments reported by previous studies. In addition, the re- markably different homologue or congener profiles of PCNs have been obtained in this study. Samples dominated with MoCNs to TrCNs might be attributed to atmospheric deposition and global fractionation, while in other samples taken from the surrounding industrial areas the enrichment of higher chlorinated homologues suggested that the industrial and human activities should be the main potential sources.展开更多
C3 hydrocarbons(HCs),especially propylene and propane,are high‐volume products of the chemical industry as they are utilized for the production of fuels,polymers,and chemical commodities.Demand for C3 HCs as chemical...C3 hydrocarbons(HCs),especially propylene and propane,are high‐volume products of the chemical industry as they are utilized for the production of fuels,polymers,and chemical commodities.Demand for C3 HCs as chemical building blocks is increasing but obtaining them in sufficient purity(>99.95%)for polymer and chemical processes requires economically and energetically costly methods such as cryogenic distillation.Adsorptive separations using porous coordination networks(PCNs)could offer an energy‐efficient alternative to current technolo-gies for C3 HC purification because of the lower energy footprint of sorbent separations for recycling versus alternatives such as distillation,solvent extraction,and chemical transformation.In this review,we address how the structural modularity of porous PCNs makes them amenable to crystal engineering that in turn enables control over pore size,shape,and chemistry.We detail how control over pore structure has enabled PCN sorbents to offer benchmark performance for C3 separations thanks to several distinct mechanisms,each of which is highlighted.We also discuss the major challenges and opportunities that remain to be addressed before the commercial development of PCNs as advanced sorbents for C3 separation becomes viable.展开更多
文摘Thirty-one congeners of polychlorinated naphthalenes (PCNs) and 21 congeners of polybrominated diphenylethers(PBDEs)in surface sediments at 5 stations and one mussel sample from Qingdao coastal waters were analyzed. The maximum contents occur at the station near the Haibo River mouth. The total PCNs contents are in the range of 212-1209 pg/g dw, dominated by tri-Cl CN. The total PBDEs contents are in the range of 117-5510 pg/g dw,dominated by tri- to hexa-BrBDEs. The local sources of PCNs are likely from combustion processes such as incinerations and coal burnings. The sources of PBDEs are molecular diffusion from the materials containing them. Except for the area near the river mouth where is affected by the sewage sludges, an important source of PCNs and PBDEs in this area is believed to be the atmospheric deposition. Mussels enrich PCNs and PBDEs relative to the sediments. The total TEQs of PCNs in mussels are lower than the total TEQs of PCBs.
文摘以华南某城市生活垃圾焚烧厂一期(WI-A)和二期(WI-B)为研究对象,采集了飞灰和烟气样品,通过GC/MS对其中PCBs和PCNs的全部单体进行了测定,分析了PCBs和PCNs的固气分布(飞灰和烟气中的总量比例)、同系物分布以及毒性当量特征.结果表明,WI-A和WI-B焚烧单位垃圾产生的PCBs和PCNs总量分别为0.397 mg·t-1(湿基)和0.363 mg·t-1(湿基).活性炭喷射量对PCBs的固气分布特征和去除率影响较大,对PCNs则不明显.PCBs同系物在烟气中以低氯取代单体为主,在飞灰中以高氯取代单体为主.PCNs同系物在烟气中以五氯单体为主,在飞灰中以四氯、五氯单体为主.WI-A和WI-B排放的烟气总TEQ分别为0.051 ng TEQ·Nm-3和0.096 ng TEQ·Nm-3,WI-A烟气Co-PCBs和Dl-PCNs对总TEQ的贡献率分别为3.2%和0.13%,WI-B烟气Co-PCBs和Dl-PCNs对总TEQ的贡献率分别为5.3%和0.34%,提示垃圾焚烧排放烟气中的Co-PCBs和Dl-PCNs的毒性同样值得关注.
基金Supported by the Analysis and Measurement Planning Project of Zhejiang Province (2007F70053)
文摘Chloronaphthalenes （PCNs, polychlorinated naphthalenes） are a group of persistent environmental pollutants. In the present study, geometrical optimization and electrostatic potential calculations have been performed for all 75 PCNs at the HF/6-31G^＊ level of theory. A number of statistic based parameters have been extracted. Linear relationships between gas-chromatographic retention index （RI） of 62 PCNs in a non-polar column （DB-5） and the structural descriptors have been established by stepwise multiple regression technique. The result shows that two quantities derived from electrostatic potential on molecular surface, ∑Vs- and σ＋^2, together with the number of chlorine （ NCl ） and the energy of the highest occupied molecular orbital （EHOMO） can be well used to express the quantitative structure-retention relationship （QSRR） of PCNs. Predictive capability of the model has been demonstrated by leave-one-out cross-validation with the cross-validated correlation coefficient （Rcv^2） of 0.997, and further compared with the results from similar researches published recently. Furthermore, when splitting the 62 PCNs into training and validation sets in the ratio of 2：1, a similar treatment yields an equation of almost equal statistical quality and very similar regression coefficients, validating the robustness and prediction capability of our model. The QSRR model established may provide a new powerful method for predicting chromatographic properties of polychlorinated naphthalenes.
基金supported by the Chinese Academy of Sciences“Strategic Leading Science and Technology Projects”(No.XDB14020000)the National Natural Science Foundation of China(Nos.21677169,21477150,21621064,and 21577148)
文摘The concentrations and distribution of polychlorinated naphthalenes（PCNs） in the whole blood of eight typical terrestrial meat animals（chicken, duck, rabbit, pig, cattle, sheep,horse and donkey） consumed daily in our life were investigated. The total concentrations（on a liquid volume basis） of PCNs were in a range from 305 to 987 pg/L. Donkey blood contained the highest PCN concentrations. Mono-CNs were the dominant homolog group,accounting for 38%–71% PCNs. Apart from the mono-CNs and tri-CNs homolog groups, two hepta-CNs（mean： 9.5%） contributed most, followed by tetra-CNs（mean： 6.5%）. The congeners CN1, 5/7, 24/14, 27/30, 52/60, 66/67, and 73 were the most abundant congeners or congener groups. The highest toxicity equivalencies（TEQs） were observed in cattle blood（117.4 fg TEQ/L） then chicken blood（117.1 fg TEQ/L）. CN73 contributed 65% to total TEQs,followed by CN70（20%） and CN66/67（14%）. The dietary intakes of PCNs were also estimated.Chicken meat, which forms the second largest component of meat product consumption in China, contributed most to the total TEQs（61%）, followed by beef（27%） and pork（5.9%）. The consumption of chicken might pose the highest risk from exposure to PCNs than other types of meat to populations who prefer to eat chicken meat.
基金Supported by the National Natural Science Foundation of China(20677070, 20621703)
文摘The concentrations and congener profiles of poly- chlorinated naphthalenes （PCNs） in surface sediment samples collected from the Yangtze and Yellow River Estuaries were inves- tigated. PCN congeners （from MoCNs to OCN） were determined by isotope dilution/high-resolution gas chromatography/high- resolution mass spectrometry （HRGC-HRMS）. The total concen- trations of PCNs were 34.3-303.0 pg/g （dry weight, dw） in the Yangtze Estuary samples and 6.2-408.0 pg/g （dw） in the Yellow River Estuary samples, which were lower compared with that in other sediments reported by previous studies. In addition, the re- markably different homologue or congener profiles of PCNs have been obtained in this study. Samples dominated with MoCNs to TrCNs might be attributed to atmospheric deposition and global fractionation, while in other samples taken from the surrounding industrial areas the enrichment of higher chlorinated homologues suggested that the industrial and human activities should be the main potential sources.
基金Science Foundation Ireland,Grant/Award Numbers:13/RP/B2549,16/IA/4624H2020 European Research Council,Grant/Award Number:ADG 885695Irish Research Council,Grant/Award Number:IRCLA/2019/167。
文摘C3 hydrocarbons(HCs),especially propylene and propane,are high‐volume products of the chemical industry as they are utilized for the production of fuels,polymers,and chemical commodities.Demand for C3 HCs as chemical building blocks is increasing but obtaining them in sufficient purity(>99.95%)for polymer and chemical processes requires economically and energetically costly methods such as cryogenic distillation.Adsorptive separations using porous coordination networks(PCNs)could offer an energy‐efficient alternative to current technolo-gies for C3 HC purification because of the lower energy footprint of sorbent separations for recycling versus alternatives such as distillation,solvent extraction,and chemical transformation.In this review,we address how the structural modularity of porous PCNs makes them amenable to crystal engineering that in turn enables control over pore size,shape,and chemistry.We detail how control over pore structure has enabled PCN sorbents to offer benchmark performance for C3 separations thanks to several distinct mechanisms,each of which is highlighted.We also discuss the major challenges and opportunities that remain to be addressed before the commercial development of PCNs as advanced sorbents for C3 separation becomes viable.
