Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/...Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/serum, mainly due to the difficulty of sample preparation and quantitative analysis. A method using high resolution gas chromatography coupled with electron capture negative ionization low resolution mass spectrometry(HRGC–ECNI/LRMS) was developed and validated to measure SCCPs in human plasma. The pretreatment process included protein denaturation and lipid elimination, liquid–liquid extraction with a mixture of n-hexane/dichloromethane(1:1, V/V), and cleanup on a multilayer silica column. The blank controls, including procedural blank, vacuum blood collection tube blank, and instrumental blank, were the most pivotal points for the reliable analysis of SCCPs. The average value of procedural blanks was 9.0 ng/g; and the method detection limit(MDL), calculated as the sum of the average procedural blank value and 3 times of the standard deviation of the procedural blanks, was 12.6 ng/g plasma. The validated method was applied to measure the concentrations of the total SCCPs(∑ SCCPs) in50 plasma samples from a general population. The measured plasma concentrations of ∑SCCPs ranged from <MDL to 203 ng/g wet weight(ww), with an average value of 32.0 ng/g ww.The relative abundance profiles of SCCPs in plasma samples were dominated by C10- and C11-CP congener groups centered on Cl6–7. The developed method can be used for the comprehensive and large-scale investigation of SCCP levels in human plasma.展开更多
The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chl...The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.展开更多
Short chain chlorinated paraffins (SCCPs) are possibly persistent organic pollutants (POPs), and are candidate POPs of the Stockholm Convention. In this study, three quantitative methods for analyzing CPs were compare...Short chain chlorinated paraffins (SCCPs) are possibly persistent organic pollutants (POPs), and are candidate POPs of the Stockholm Convention. In this study, three quantitative methods for analyzing CPs were compared using a gas chromatograph-electron capture detector (GC-ECD), gas chromatograph-electron capture negative ion low resolution mass spectrometry (GC-ECNI-LRMS) and gas chromatograph-electron ionization tandem mass spectrometry (GC-EI-MS2). A quantitative method for the analysis of total CPs in soil samples was established. The environmental levels of CPs in an e-waste dismantling area in China were evaluated.展开更多
Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work...Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work, an efficient, reliable and rapid pretreatment method based on matrix solid-phase dispersion（MSPD） was developed for the analysis of short-chain CPs（SCCPs） in human placenta by gas chromatograph-electron capture negative ion low-resolution mass spectrometry（GC-ECNI-LRMS） and gas chromatography–quadrupole time-of-flight mass spectrometry（GC–QTOF-HRMS）. The MSPD-relevant parameters including dispersing sorbent,sample-to-sorbent mass ratio, and elution solvent were optimized using the orthogonal test.Silica gel was found to be the optimal dispersing sorbent among the selected matrices. Under the optimal conditions, 44% acidic silica gel can be used as the co-sorbent to remove lipid and eluted by the mixture of hexane and dichloromethane（7：3, V/V）. The spiked recoveries of the optimized method were 77.4% and 91.4% for analyzing SCCPs in human placenta by GC-ECNI-LRMS and GC–QTOF-HRMS, and the corresponding relative standard deviations were10.2% and 5.6%, respectively. The method detection limit for the total SCCPs was 36.8 ng/g（dry weight, dw） and 19.2 ng/g（dw） as measured by GC-ECNI-LRMS and GC–QTOF-HRMS,respectively. The concentrations of SCCPs in four human placentas were in the range of展开更多
Pristine alpine regions are ideal regions for investigating the long-range atmospheric transport and cold trapping effects of short chain chlorinated paraffins(SCCPs).The concentrations and alpine condensation of SCCP...Pristine alpine regions are ideal regions for investigating the long-range atmospheric transport and cold trapping effects of short chain chlorinated paraffins(SCCPs).The concentrations and alpine condensation of SCCPs were investigated in lichen samples collected from the southeastern Tibetan Plateau.The concentrations of SCCPs ranged from 3098 to 6999 ng/g lipid weight(lw)and appeared to have an increasing trend with altitude.For congeners,C10 dominated among all the congener groups.The different environmental behavior for different congener groups was closely related to their octanol-air partition coefficient(Koa).C10 congeners showed an increasing trend with altitude,whereas C13 congeners were negatively correlated with altitude.Volumetric bioconcentration factors(BCF)of SCCPs reached 8.71 in lichens,which were higher than other semivolatile organic compounds(SVOCs)such as organochlorine pesticides(OCPs),polybrominated diphenyl ethers(PBDEs),polychlorinated biphenyls(PCBs),and hexabromocyclododecane(HBCD).These results suggested that SCCPs were prone to accumulate in the lichen from the air and provided evidence for the role of lichens as a suitable atmospheric indicator in the Tibetan Plateau.展开更多
Chlorinated paraffins（CPs） are potential persistent organic pollutants（POPs）, which threat the safety of environment and organisms. However, the analysis of CPs is a difficult task due to their complex composition...Chlorinated paraffins（CPs） are potential persistent organic pollutants（POPs）, which threat the safety of environment and organisms. However, the analysis of CPs is a difficult task due to their complex composition containing thousands of congeners. In the present work, quantitative structure retention relationship（QSRR） of CPs was studied. A total of 470 molecular descriptors were generated, for describing the structures of 28 CPs and 12 descriptors relevant to retention time of the CPs were selected by stepwise regression. Then, QSRR models between retention time on the one hand and the selected descriptors on the other hand were established by multiple linear regres- sion（MLR）, partial least squares（PLS） and least square support vector regression（LS-SVR）. The result shows that PLS model is better than MLR and LS-SVR, obtaining a squared correlation coefficient（r2） of 0.9996 and a root mean squared error（RMSE） of 0.015. The PLS model was then used to predict the retention time of 49 C10-CPs. Three of them were investigated by gas chromatography coupled with mass spectrometry（GC-MS）. A well-defined correlation was found between the measured retention time and the predicted value.展开更多
Short chain chlorinated paraffins(SCCPs) are not only research focus of environmental issues but also interesting model molecules for organic chemistry which exhibit diverse conformation preference and intramolecular ...Short chain chlorinated paraffins(SCCPs) are not only research focus of environmental issues but also interesting model molecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions(NCIs). A systematic study was conducted to reveal the conformation preference and the related intramolecular NCIs in two C_(10)-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-tetrachlorodecane. The overall conformation profile was determined on the basis of relative energies calculated at the MP2/6-311++G(d,p) level with the geometries optimized by B3LYP/6-311++G(d,p) method. Then, quantum theory of atoms in molecules(QTAIM) has been adopted to identify the NCIs in the selected conformers of the model molecules at both B3LYP/6-311++G(d,p) and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed for the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane(t Tt) has its three dihedral angles in the T configuration, and there is no intramolecular NCIs found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configuration for the H–C–C–Cl axis. Not only intramolecular H···Cl contacts but also H···H interactions have been identified as driving forces to compensate the instability from steric crowding of the gauche configuration. The gggg and g′g′g′g′ conformers are the most popular ones, while the populations of tggg and tg′g′g′ conformer are second to those of the gggg and g′g′g′g′ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.展开更多
Chlorinated paraffins(CPs)are produced in large amounts and used worldwide.Dietary intake is the primary pathway for the exposure of pets to CPs,but limited information is available concerning the potential contaminat...Chlorinated paraffins(CPs)are produced in large amounts and used worldwide.Dietary intake is the primary pathway for the exposure of pets to CPs,but limited information is available concerning the potential contamination of pet food by CPs.In the present study,the concentrations and congener group profiles of short-chain CPs(SCCPs)and medium-chain CPs(MCCPs)were assessed in 35 imported commercial dry cat and dog foods collected in China,and the estimated daily intakes of SCCPs and MCCPs for cats and dogs through the consumption of such foods was calculated.The concentrations of SCCPs and MCCPs in the cat and dog foods were determined to be in the ranges of 108e45,300 ng/g(median:1340 ng/g)and 3.8e52,700 ng/g(median:11 ng/g),respectively.The predominant congener groups were C10Cl6 for SCCPs and C14Cl7-8 for MCCPs.The high levels of CPs found in certain pet foods suggest the potential for adverse health effects.展开更多
基金supported by the National Natural Science Foundation of China (No.21337002)the National Basic Research Program (973) of China (No.2015CB453100)
文摘Short-chain chlorinated paraffins(SCCPs) are produced in high volume and have the high potential to pose a threat to human health. However, little information is available for SCCP contamination in human blood/plasma/serum, mainly due to the difficulty of sample preparation and quantitative analysis. A method using high resolution gas chromatography coupled with electron capture negative ionization low resolution mass spectrometry(HRGC–ECNI/LRMS) was developed and validated to measure SCCPs in human plasma. The pretreatment process included protein denaturation and lipid elimination, liquid–liquid extraction with a mixture of n-hexane/dichloromethane(1:1, V/V), and cleanup on a multilayer silica column. The blank controls, including procedural blank, vacuum blood collection tube blank, and instrumental blank, were the most pivotal points for the reliable analysis of SCCPs. The average value of procedural blanks was 9.0 ng/g; and the method detection limit(MDL), calculated as the sum of the average procedural blank value and 3 times of the standard deviation of the procedural blanks, was 12.6 ng/g plasma. The validated method was applied to measure the concentrations of the total SCCPs(∑ SCCPs) in50 plasma samples from a general population. The measured plasma concentrations of ∑SCCPs ranged from <MDL to 203 ng/g wet weight(ww), with an average value of 32.0 ng/g ww.The relative abundance profiles of SCCPs in plasma samples were dominated by C10- and C11-CP congener groups centered on Cl6–7. The developed method can be used for the comprehensive and large-scale investigation of SCCP levels in human plasma.
基金supported by the National Natural Science Foundation of China (Nos.21625702,21337002,21621064)the National Basic Research Program of China (No.2015CB453102)the Strategic Priority Research Program of the Chinese Academy of Sciences (No.XDB14010400)
文摘The increasing production and usage of chlorinated paraffins(CPs) correspondently increase the amount of CPs that experience thermal processes. Our previous study revealed that a significant amount of medium-chain chlorinated paraffins(MCCPs), short-chain chlorinated paraffins(SCCPs) as well as aromatic and chlorinated polycyclic aromatic hydrocarbons(Cl-PAHs) were formed synergistically during the thermal decomposition of CP-52(a class of CP products).However, the transformation mechanisms of CP-52 to these compounds are still not very clear.This article presents a mechanistic analysis on the decomposition of CP-52 experimentally and theoretically. It was found that CP-52 initially undergoes dehydrochlorination and carbon chain cleavage and it transformed into chlorinated and unsaturated hydrocarbons. Cyclization and aromatization were the most accessible pathways at low temperatures(200–400°C), both of which produce mostly aromatic hydrocarbons. As the temperature exceeds 400°C, the hydrocarbons could decompose into small molecules, and the subsequent radical-induced reactions become the predominant pathways, leading to the formation of Cl-PAHs. The decomposition of CP-52 was investigated by using density functional theory and calculations demonstrating the feasibility and rationality of PCB and PCN formation from chlorobenzene. The results improve the understanding of the transformation processes from CP-52 to SCCPs and Cl-PAHs as well as provide data for reducing their emissions during thermal-related processes.
基金supported by the National Basic Research Program of China (2009CB421605)the National Natural Science Foundation (20897010, 20737003)+1 种基金the Knowledge Innovation Program of the Chinese Academy of Sciences (RCEES-QN-200703)the Special Funds for Young Scholars of RCEES, CAS
文摘Short chain chlorinated paraffins (SCCPs) are possibly persistent organic pollutants (POPs), and are candidate POPs of the Stockholm Convention. In this study, three quantitative methods for analyzing CPs were compared using a gas chromatograph-electron capture detector (GC-ECD), gas chromatograph-electron capture negative ion low resolution mass spectrometry (GC-ECNI-LRMS) and gas chromatograph-electron ionization tandem mass spectrometry (GC-EI-MS2). A quantitative method for the analysis of total CPs in soil samples was established. The environmental levels of CPs in an e-waste dismantling area in China were evaluated.
基金supported by the National Natural Science Foundation of China(Nos.21625702,21337002,21621064)the National Basic Research Program of China(No.2015CB453102)the Strategic Priority Research Program of the Chinese Academy of Science(No.XDB14010400)for the joint financial support
文摘Chlorinated paraffins（SCCPs） are widely used worldwide, and they can be released into the environment during their production, transport, usage and disposal, which pose potential risks for human health. In this work, an efficient, reliable and rapid pretreatment method based on matrix solid-phase dispersion（MSPD） was developed for the analysis of short-chain CPs（SCCPs） in human placenta by gas chromatograph-electron capture negative ion low-resolution mass spectrometry（GC-ECNI-LRMS） and gas chromatography–quadrupole time-of-flight mass spectrometry（GC–QTOF-HRMS）. The MSPD-relevant parameters including dispersing sorbent,sample-to-sorbent mass ratio, and elution solvent were optimized using the orthogonal test.Silica gel was found to be the optimal dispersing sorbent among the selected matrices. Under the optimal conditions, 44% acidic silica gel can be used as the co-sorbent to remove lipid and eluted by the mixture of hexane and dichloromethane（7：3, V/V）. The spiked recoveries of the optimized method were 77.4% and 91.4% for analyzing SCCPs in human placenta by GC-ECNI-LRMS and GC–QTOF-HRMS, and the corresponding relative standard deviations were10.2% and 5.6%, respectively. The method detection limit for the total SCCPs was 36.8 ng/g（dry weight, dw） and 19.2 ng/g（dw） as measured by GC-ECNI-LRMS and GC–QTOF-HRMS,respectively. The concentrations of SCCPs in four human placentas were in the range of
基金the Strategic Priority Research Program of the Chinese Academy of Sciencesthe Pan-Third Pole Environment Study for a Green Silk Road(Pan-TPE)(No.XDA2004050203)+3 种基金the Second Tibetan Plateau Scientific Expedition and Research Program(No.2019QZKK0605)the National Natural Science Foundation of China(No.21906096)the Youth Science Funds of Shandong Academy of Sciences(No.2019QN008)the Youth Innovation Promotion Association of CAS(No.2018052)。
文摘Pristine alpine regions are ideal regions for investigating the long-range atmospheric transport and cold trapping effects of short chain chlorinated paraffins(SCCPs).The concentrations and alpine condensation of SCCPs were investigated in lichen samples collected from the southeastern Tibetan Plateau.The concentrations of SCCPs ranged from 3098 to 6999 ng/g lipid weight(lw)and appeared to have an increasing trend with altitude.For congeners,C10 dominated among all the congener groups.The different environmental behavior for different congener groups was closely related to their octanol-air partition coefficient(Koa).C10 congeners showed an increasing trend with altitude,whereas C13 congeners were negatively correlated with altitude.Volumetric bioconcentration factors(BCF)of SCCPs reached 8.71 in lichens,which were higher than other semivolatile organic compounds(SVOCs)such as organochlorine pesticides(OCPs),polybrominated diphenyl ethers(PBDEs),polychlorinated biphenyls(PCBs),and hexabromocyclododecane(HBCD).These results suggested that SCCPs were prone to accumulate in the lichen from the air and provided evidence for the role of lichens as a suitable atmospheric indicator in the Tibetan Plateau.
基金Supported by the National Natural Science Foundation of China（No.21175074）.
文摘Chlorinated paraffins（CPs） are potential persistent organic pollutants（POPs）, which threat the safety of environment and organisms. However, the analysis of CPs is a difficult task due to their complex composition containing thousands of congeners. In the present work, quantitative structure retention relationship（QSRR） of CPs was studied. A total of 470 molecular descriptors were generated, for describing the structures of 28 CPs and 12 descriptors relevant to retention time of the CPs were selected by stepwise regression. Then, QSRR models between retention time on the one hand and the selected descriptors on the other hand were established by multiple linear regres- sion（MLR）, partial least squares（PLS） and least square support vector regression（LS-SVR）. The result shows that PLS model is better than MLR and LS-SVR, obtaining a squared correlation coefficient（r2） of 0.9996 and a root mean squared error（RMSE） of 0.015. The PLS model was then used to predict the retention time of 49 C10-CPs. Three of them were investigated by gas chromatography coupled with mass spectrometry（GC-MS）. A well-defined correlation was found between the measured retention time and the predicted value.
基金the Chinese Academy of Sciences (KZCX2-YW-BR-25, XDB14030500, YSW2013B01)the National High Technology Research and Development Program of China (2013AA065201)
文摘Short chain chlorinated paraffins(SCCPs) are not only research focus of environmental issues but also interesting model molecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions(NCIs). A systematic study was conducted to reveal the conformation preference and the related intramolecular NCIs in two C_(10)-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-tetrachlorodecane. The overall conformation profile was determined on the basis of relative energies calculated at the MP2/6-311++G(d,p) level with the geometries optimized by B3LYP/6-311++G(d,p) method. Then, quantum theory of atoms in molecules(QTAIM) has been adopted to identify the NCIs in the selected conformers of the model molecules at both B3LYP/6-311++G(d,p) and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed for the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane(t Tt) has its three dihedral angles in the T configuration, and there is no intramolecular NCIs found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configuration for the H–C–C–Cl axis. Not only intramolecular H···Cl contacts but also H···H interactions have been identified as driving forces to compensate the instability from steric crowding of the gauche configuration. The gggg and g′g′g′g′ conformers are the most popular ones, while the populations of tggg and tg′g′g′ conformer are second to those of the gggg and g′g′g′g′ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.
基金the National Natural Science Foundation of China(grant nos.21707164 and 3187131629)the Central Public Interest Scientific Institution Basal Research Fund of the Chinese Academy of Agricultural Sciences(grant no.Y2020PT38).
文摘Chlorinated paraffins(CPs)are produced in large amounts and used worldwide.Dietary intake is the primary pathway for the exposure of pets to CPs,but limited information is available concerning the potential contamination of pet food by CPs.In the present study,the concentrations and congener group profiles of short-chain CPs(SCCPs)and medium-chain CPs(MCCPs)were assessed in 35 imported commercial dry cat and dog foods collected in China,and the estimated daily intakes of SCCPs and MCCPs for cats and dogs through the consumption of such foods was calculated.The concentrations of SCCPs and MCCPs in the cat and dog foods were determined to be in the ranges of 108e45,300 ng/g(median:1340 ng/g)and 3.8e52,700 ng/g(median:11 ng/g),respectively.The predominant congener groups were C10Cl6 for SCCPs and C14Cl7-8 for MCCPs.The high levels of CPs found in certain pet foods suggest the potential for adverse health effects.
