Background: Today’s presence of polychlorinated dibenzofurans (PCDFs) in foodstuff, such as milk and milk products, is considered to be the major concern for human health. This study was aimed to determine the concen...Background: Today’s presence of polychlorinated dibenzofurans (PCDFs) in foodstuff, such as milk and milk products, is considered to be the major concern for human health. This study was aimed to determine the concentrations of the most toxic congeners of furans in pasteurized milk samples produced in southwest Iran. Material and method: 15 composite samples of pasteurized milk were collected from 3 major dairy factories in Khuzestan Province (southwest of Iran) in summer, autumn and winter from July 2011 to March 2012. After precipitation of the proteins, fat phase was reduced and extracted with hexane and ether. After dehydration, furans existed in fat percolated with hexane through a column chromatography that contained respectively silica gel/silver nitrate, silica gel, silica gel/sulphuric acid and with percolating output through another column that contained activated charcoal and silica gel and washed the lower column with a mixture of dichloromethane-hexane and toluene, concentrated and dissolved in mobile phase and analyzed using HPLC: 150 mm × 4.6 mm ID, 5 μm cosmosil 5 NPE column equipped with a UV detector at 254 and 235 nm, mobile phase: methanol/water (80:20, v/v) at flow rate of 1 ml/min. Results: All samples were found to be contaminated with furans. The average concentration of 2,3,7,8 TCDF and 2,3,4,7,8 PCDF were 1.91 pg/g and 1.77 pg/g in lipid content ranging from 2% to 3% respectively. The mean total content of furans in milk fat was 0.36 TEQ (Toxic Equivalency) pg/g which was below the recommended EU (European Union) threshold value 3 pg (WHO-PCDFs-TEQ/g fat). Also, result showed that there were statistically significant differences between each factory during 3 seasons.展开更多
Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relation...Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel quantitative structureproperty relationship （QSPR） model for predicting n-octanol/water partition coefficients （lgKow） of PCDFs. The new model of lgKow achieved in this work contains three variables： energy of the highest occupied molecular orbital （EHOMO）, the most negative atomic partial charge （q^-） and average molecular polarizability （a）, of which R^2= 0.9011 and SD = 0,17 with larger t values. In addition, the variation inflation factors （VIF） of variables in the present model are all less than 5.5, suggesting high accuracy of the lgKow model. And the results of cross-validation test （q^2 = 0.8688） and method validation also show this model exhibits optimum stability and better predictive power than semi-empirical method. At the same time, it is found that the aqueous solubility （-lgSw） has high relative correlation with constant volume molar heat capacity （Cv^0）, of which R^2 = 0.9777 and SD = 0.22. Moreover, lgKow and -lgSw values of all PCDF congeners were predicted respectively.展开更多
Based on the identical group as a pseudo atom instead of a typical atom, a novel modified molecular dis-tance-edge (MDE) vector μ was developed in our laboratory to characterize chemical structure of polychlorinated ...Based on the identical group as a pseudo atom instead of a typical atom, a novel modified molecular dis-tance-edge (MDE) vector μ was developed in our laboratory to characterize chemical structure of polychlorinated diben-zofurans (PCDFs) congeners and/or isomers. Quantitative structure-retention relationships (QSRRs) between the new VMDE parameters and gas chromatographic (GC) retention behavior of PCDFs were then generated by multiple linear regression (MLR) method for non-polar, moderately polar, and polar stationary phases. Four excellent models with high correlation coefficients, R=0.984-0.995, were proposed for non-polar columns (DB-5, SE-54, OV-101). For the moder-ately polar columns (OV-1701), the correlation coefficient of the developed good model is only 0.958. For the polar col-umns (SP-2300), the QSRR model is poor with R=0.884. Then cross validation with leave-one out of procedure (CV) is performed in high correlation with the non-polar (Rcv=992-0.974) and weakly polar (Rcv=921) columns and in little cor-relation (Rcv=0.834) with the polar columns. These results show that the new μ vector is suitable for describing the re-tention behaviors of PCDFs on non-polar and moderately polar stationary phases and not for the various gas chroma-tographic retention behaviors of PCDFs on the different po-larity-varying stationary phases.展开更多
Researches on the hydrothermal treatment of municipal solid waste incineration(MSWI)fly ash were conducted to eliminate dioxins and stabilize heavy metals.In order to enhance decomposing polychlorinated dibenzodioxins...Researches on the hydrothermal treatment of municipal solid waste incineration(MSWI)fly ash were conducted to eliminate dioxins and stabilize heavy metals.In order to enhance decomposing polychlorinated dibenzodioxins(PCDDs)and polychlorinated dibenzo-furans(PCDFs)during hydrothermal process,a strong reductant carbohydrazide(CHZ)is introduced.A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature;CHZ was spiked into solution according to specially defined dosage.Experimental results showed that under the temperatures of 518 K and 533 K,the decomposition rates of PCDDs/PCDFs were over 80%and 90%,respectively,by total concentration.However,their toxic equivalent(TEQ)decreased only slightly or even increased due to the rising in concentration of congeners 2,3,7,8-TCDD/TCDF,which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process.Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results.Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.展开更多
The production of chlorine by the chlor-alkali process using graphite electrodes was one of the largest sources of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/PCDFs)in history with estimates in the kg TEQ...The production of chlorine by the chlor-alkali process using graphite electrodes was one of the largest sources of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/PCDFs)in history with estimates in the kg TEQ range for individual factories.In addition,the chlorine production predecessor processes in the former Leblanc soda factories generated large amounts of PCDD/PCDFs,also in kg TEQ range for individual sites.In both processes coal tar,used as pitch binder for electrodes in the chlor-alkali process or tars for sealing chlorine chambers,was the major source for PCDD/PCDFs formation.The complex PAH mixture in the tars which were chlorinated in the processes contained approx.1%dibenzofuran.Therefore in this study we screened the full range of chlorinated aromatic and heteroaromatic compounds in contaminated soils from former chlor-alkali plants in Germany and Japan as well as from a German Leblanc factory,using high resolution time-of-flight mass spectrometry GC-HR-TOF-MS.At all three sites the full range of unintentionally produced persistent organic pollutants(POPs)listed in the Stockholm Convention(PCDFs,PCDDs,PCBs,PCNs,HCB,HCBD and PeCBz)were present at high ppb levels and TEQ was up to several 100,000 ng/kg soil in hot spot areas.Additionally,a wide range of other polychlorinated(PC-)PAHs(PC-phenanthrene/anthracene,PC-pyrene/fluoranthene,PC-benzo(a)anthracene/chrysene)were detected.Some of these compound classes were present in one to two order of magnitude higher concentrations compared to PCDFs.Furthermore,polychlorinated methyldibenzofurans,polychlorinated dimethyl-/ethyl-dibenzofurans,and polychlorinated carbazoles e the N-analogue of dibenzofuran-were detected at levels comparable to PCDFs at all three sites.Polychlorinated benzonitriles were detected in addition to chlorobenzenes as monoaromatic pollutant.Since all three factories have stopped production 50e120 years ago,all detected chlorinated aromatics can be regarded as very persistent.The technologies have been used in several hundred locations globally.These(former)chlorine production sites should be assessed for contamination and their contemporary threat to humans and the environment should be evaluated.The toxicity of most of these polychlorinated PAHs and hetero-PAHs is unknown but due to their related structures,similar toxicity profiles can be expected and need to be investigated.Furthermore,all processes where chlorine and complex organic material are present should be screened for the entire resulting chlorinated pollutant mixture,the detailed fingerprints should be documented,and the overall toxicological risk assessed for individual processes to inform policy making.展开更多
Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information fo...Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil （ASKAREL Nr 1740） in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry （HRGC/HRMS）. The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners （i.e., # 153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181） account for more than 50% of the total PCB concentrations. Total concentration ofPCDDs, PCDFs and dioxin-like PCBs （DL-PCBs） was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF 〉 HxCDFs 〉 HpCDFs 〉 PeCDFs 〉 TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners （i.e., #118, #156, #157） accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.展开更多
文摘Background: Today’s presence of polychlorinated dibenzofurans (PCDFs) in foodstuff, such as milk and milk products, is considered to be the major concern for human health. This study was aimed to determine the concentrations of the most toxic congeners of furans in pasteurized milk samples produced in southwest Iran. Material and method: 15 composite samples of pasteurized milk were collected from 3 major dairy factories in Khuzestan Province (southwest of Iran) in summer, autumn and winter from July 2011 to March 2012. After precipitation of the proteins, fat phase was reduced and extracted with hexane and ether. After dehydration, furans existed in fat percolated with hexane through a column chromatography that contained respectively silica gel/silver nitrate, silica gel, silica gel/sulphuric acid and with percolating output through another column that contained activated charcoal and silica gel and washed the lower column with a mixture of dichloromethane-hexane and toluene, concentrated and dissolved in mobile phase and analyzed using HPLC: 150 mm × 4.6 mm ID, 5 μm cosmosil 5 NPE column equipped with a UV detector at 254 and 235 nm, mobile phase: methanol/water (80:20, v/v) at flow rate of 1 ml/min. Results: All samples were found to be contaminated with furans. The average concentration of 2,3,7,8 TCDF and 2,3,4,7,8 PCDF were 1.91 pg/g and 1.77 pg/g in lipid content ranging from 2% to 3% respectively. The mean total content of furans in milk fat was 0.36 TEQ (Toxic Equivalency) pg/g which was below the recommended EU (European Union) threshold value 3 pg (WHO-PCDFs-TEQ/g fat). Also, result showed that there were statistically significant differences between each factory during 3 seasons.
基金This work was supported by the China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel quantitative structureproperty relationship （QSPR） model for predicting n-octanol/water partition coefficients （lgKow） of PCDFs. The new model of lgKow achieved in this work contains three variables： energy of the highest occupied molecular orbital （EHOMO）, the most negative atomic partial charge （q^-） and average molecular polarizability （a）, of which R^2= 0.9011 and SD = 0,17 with larger t values. In addition, the variation inflation factors （VIF） of variables in the present model are all less than 5.5, suggesting high accuracy of the lgKow model. And the results of cross-validation test （q^2 = 0.8688） and method validation also show this model exhibits optimum stability and better predictive power than semi-empirical method. At the same time, it is found that the aqueous solubility （-lgSw） has high relative correlation with constant volume molar heat capacity （Cv^0）, of which R^2 = 0.9777 and SD = 0.22. Moreover, lgKow and -lgSw values of all PCDF congeners were predicted respectively.
基金This work was supported by the Chunhui Project Fund of the Ministry of Education(Grant No.SCPF99-4-4+37)Fok Ying-Tung Educational Foundation(Grant No.FYTF98-7-6)+1 种基金Chongqing Applied Science Fund(Grant No,CASF01-3-6)Chongqing University ZYXT Innovation Fund(Grant No.CUIF03-5-6+04-10-10).
文摘Based on the identical group as a pseudo atom instead of a typical atom, a novel modified molecular dis-tance-edge (MDE) vector μ was developed in our laboratory to characterize chemical structure of polychlorinated diben-zofurans (PCDFs) congeners and/or isomers. Quantitative structure-retention relationships (QSRRs) between the new VMDE parameters and gas chromatographic (GC) retention behavior of PCDFs were then generated by multiple linear regression (MLR) method for non-polar, moderately polar, and polar stationary phases. Four excellent models with high correlation coefficients, R=0.984-0.995, were proposed for non-polar columns (DB-5, SE-54, OV-101). For the moder-ately polar columns (OV-1701), the correlation coefficient of the developed good model is only 0.958. For the polar col-umns (SP-2300), the QSRR model is poor with R=0.884. Then cross validation with leave-one out of procedure (CV) is performed in high correlation with the non-polar (Rcv=992-0.974) and weakly polar (Rcv=921) columns and in little cor-relation (Rcv=0.834) with the polar columns. These results show that the new μ vector is suitable for describing the re-tention behaviors of PCDFs on non-polar and moderately polar stationary phases and not for the various gas chroma-tographic retention behaviors of PCDFs on the different po-larity-varying stationary phases.
基金the National High-Tech Research and Development(863)Program of China(Grant No.2008AA06Z340)the National Natural Science Foundation of China(Grant No.50708068).
文摘Researches on the hydrothermal treatment of municipal solid waste incineration(MSWI)fly ash were conducted to eliminate dioxins and stabilize heavy metals.In order to enhance decomposing polychlorinated dibenzodioxins(PCDDs)and polychlorinated dibenzo-furans(PCDFs)during hydrothermal process,a strong reductant carbohydrazide(CHZ)is introduced.A hydrothermal reactor was set up by mixing raw MSWI fly ash or the pre-treated fly ash with water and then heated to a pre-set temperature;CHZ was spiked into solution according to specially defined dosage.Experimental results showed that under the temperatures of 518 K and 533 K,the decomposition rates of PCDDs/PCDFs were over 80%and 90%,respectively,by total concentration.However,their toxic equivalent(TEQ)decreased only slightly or even increased due to the rising in concentration of congeners 2,3,7,8-TCDD/TCDF,which might be resulted from the highly chlorinated congeners losing their chlorine atoms and being degraded during the hydrothermal process.Better results of TEQ reduction were also obtained under the higher tested temperature of 533 K and reactor with addition of 0.1%wt CHZ was corresponded to the best results.Good stabilization of heavy metals was also obtained in the same hydrothermal process especially when ferrous sulphate was added as auxiliary agent.
文摘The production of chlorine by the chlor-alkali process using graphite electrodes was one of the largest sources of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/PCDFs)in history with estimates in the kg TEQ range for individual factories.In addition,the chlorine production predecessor processes in the former Leblanc soda factories generated large amounts of PCDD/PCDFs,also in kg TEQ range for individual sites.In both processes coal tar,used as pitch binder for electrodes in the chlor-alkali process or tars for sealing chlorine chambers,was the major source for PCDD/PCDFs formation.The complex PAH mixture in the tars which were chlorinated in the processes contained approx.1%dibenzofuran.Therefore in this study we screened the full range of chlorinated aromatic and heteroaromatic compounds in contaminated soils from former chlor-alkali plants in Germany and Japan as well as from a German Leblanc factory,using high resolution time-of-flight mass spectrometry GC-HR-TOF-MS.At all three sites the full range of unintentionally produced persistent organic pollutants(POPs)listed in the Stockholm Convention(PCDFs,PCDDs,PCBs,PCNs,HCB,HCBD and PeCBz)were present at high ppb levels and TEQ was up to several 100,000 ng/kg soil in hot spot areas.Additionally,a wide range of other polychlorinated(PC-)PAHs(PC-phenanthrene/anthracene,PC-pyrene/fluoranthene,PC-benzo(a)anthracene/chrysene)were detected.Some of these compound classes were present in one to two order of magnitude higher concentrations compared to PCDFs.Furthermore,polychlorinated methyldibenzofurans,polychlorinated dimethyl-/ethyl-dibenzofurans,and polychlorinated carbazoles e the N-analogue of dibenzofuran-were detected at levels comparable to PCDFs at all three sites.Polychlorinated benzonitriles were detected in addition to chlorobenzenes as monoaromatic pollutant.Since all three factories have stopped production 50e120 years ago,all detected chlorinated aromatics can be regarded as very persistent.The technologies have been used in several hundred locations globally.These(former)chlorine production sites should be assessed for contamination and their contemporary threat to humans and the environment should be evaluated.The toxicity of most of these polychlorinated PAHs and hetero-PAHs is unknown but due to their related structures,similar toxicity profiles can be expected and need to be investigated.Furthermore,all processes where chlorine and complex organic material are present should be screened for the entire resulting chlorinated pollutant mixture,the detailed fingerprints should be documented,and the overall toxicological risk assessed for individual processes to inform policy making.
文摘Homolog and congener profiles of polychlori- nated biphenyls （PCBs）, polychlorinated dibenzo-p- dioxins （PCDDs） and polychlorinated dibenzofurans （PCDFs） in commercial PCBs formulations are useful information for the source appointment of PCBs contam- ination as well as the risk assessment caused by potential exposure. Dielectric oil （ASKAREL Nr 1740） in an imported transformer found in China was sampled and analyzed by isotope dilution technology using high resolution gas chromatography-high resolution mass spectrometry （HRGC/HRMS）. The detailed homolog and congener profiles of PCBs obtained were compared with those of known Aroclor formulations. High similarity in the homolog profile between the oil sample and Aroclor 1260was found, with the hexachlorinated and hepta- chlorinated biphenyls accounting for more than 80.2% of the total PCBs concentration. Severn indicator PCBs contribute about 30%, while 12 PCB congeners （i.e., # 153, #143, #168, #180, #149, #165, #138, #170, #190, #187, #174, #181） account for more than 50% of the total PCB concentrations. Total concentration ofPCDDs, PCDFs and dioxin-like PCBs （DL-PCBs） was found to be 740 ng TEQ/g, of which 620 ng TEQ/g came from DL-PCBs. The contribution of PCDDs to the total TEQ was neglectable. The concentration of PCDFs homologs follows the order of OCDF 〉 HxCDFs 〉 HpCDFs 〉 PeCDFs 〉 TeCDFs, which is in consistence with the previous study on Aroclor 1260. Three DL-PCBs congeners （i.e., #118, #156, #157） accounted for 77% of the total concentration of DL-PCBs, also they contribute 72% in the TEQ caused by DL-PCBs.
