Development of matrix solid-phase dispersion method for the extraction of short-chain chlorinated paraffins in human placenta

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

Long-range atmospheric transport and alpine condensation of short-chain chlorinated paraffins on the southeastern Tibetan Plateau

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.

Validation of a HRGC–ECNI/LRMS method to monitor short-chain chlorinated paraffins in human 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.

The thermal transformation mechanism of chlorinated paraffins:An experimental and density functional theory study

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.

An analytical method for chlorinated paraffins and their determination in soil samples

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.

Predicting Chromatographic Retention Time of C10-Chlorinated Paraffins in Gas Chromatography-Mass Spectrometry Using Quantitative Structure Retention Relationship

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.

Conformation preference and related intramolecular noncovalent interaction of selected short chain chlorinated paraffins

Short chain chlorinated paraffins （SCCPs） are not only research focus of environmental issues but also interesting model mol- ecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions （NCIs）. A systematic study was conducted to reveal the conlk）rmation preference and the related intramolecular NCIs in two C^-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-1etrachlorodecane. The overall conformation profile was deter- mined on the basis of relative energies calculated at the MP2/6-311＋＋G（d,p） level with the geometries optimized by B3LYP/6-31 l＋＋G（d,p） method. Then, quantum theory of atoms in molecules （QTAIM） has been adopted to identify the NCls in the selected conformers of the model molecules at both B31~YP/6-31 l＋＋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 tk）r the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane （tTt） has its three dihedral angles in the T configuration, and there is no intramolecular N（3s found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configmation for the H C C CI axis. Not only inlramolecular H-..CI contacts but also H---H interactions have been identified as driving forces to compensate the instability from steric crowding ot 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.

Short-and medium-chain chlorinated paraffins in imported commercial dry cat and dog food in China:Concentrations,distributions and risk assessment

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.

气相色谱-串联质谱法测定皮革中的短链氯化石蜡

建立了GC-MS/MS测定皮革中短链氯化石蜡(SCCPs)的方法,采用正己烷对样品进行提取,再用GC-MS/MS测定,外标法定量。结果表明:该方法在SCCPs质量浓度为5~50 mg/L范围内线性良好,线性相关系数为0.998,方法检出限为2.58 mg/kg,定量限为8.95 mg/kg,在低、中、高浓度水平的加标试验中,回收率在90.1%~108.9%,精密度为2.29%~6.22%。该方法具有较低的检出限、较好的精密度和准确度,可用于皮革中短链氯化石蜡的检测。

短链氯化石蜡的分析方法研究进展

简要介绍了SCCPs的理化特性、全球生产和使用情况以及环境分布,系统综述了不同环境介质中SCCPs的萃取、净化方法和气相色谱—质谱法、二维气相色谱法、超高效液相色谱质谱法等仪器分析技术,为今后全面的评估SCCPs的生态健康暴露风险,进行污染物防治提供科学依据。

氯化石蜡的环境分析方法研究进展

短链氯化石蜡(SCCPs)具有持久性、生物毒性和生物累积性等,是一种持久性有机污染物,被列入《斯德哥尔摩公约》附件A中,中链氯化石蜡具有SCCPs相似的性质也备受关注。氯化石蜡(chlorinated paraffins,CPs)拥有成千上万种同系物、异构体、对映体,加之环境基质中存在其他有机卤素化合物,CPs分离分析困难,目前我国仍没有环境样品中CPs分析的标准方法。该文对近年来不同环境基质中的CPs分析所采用的样品前处理技术和仪器分析方法两个方面进行综述,提供CPs分析方法最新发展动态,为相关人员对开展此方面的研究提供参考。

短链氯化石蜡对人体正常肝细胞的代谢干扰

短链氯化石蜡(SCCPs)是一类新兴的持久性有机污染物,广泛存在于环境基质和人体样本中。SCCPs具有环境持久性以及远距离迁移能力,能够在生物体内积累并具有广泛的生物毒性效应,威胁着人类健康。本研究采用代谢组学方法评估了低剂量组(1μg/L)、中剂量组(10μg/L)以及高剂量组(100μg/L)的SCCPs暴露对人体正常肝细胞L02的代谢干扰。主成分分析(PCA)与代谢扰乱水平指数(MELI)计算结果表明3个剂量组的SCCPs均能够引起L02细胞代谢活动的紊乱。在3个暴露组中,72个差异代谢物经二级质谱图信息定性或标准品验证。其中,1μg/L SCCPs暴露组与10μg/L SCCPs暴露组、100μg/L SCCPs暴露组分别有33个、36个相同的差异代谢物。10μg/L SCCPs暴露组与100μg/L SCCPs暴露组有46个相同的差异代谢物。3个暴露组有33个相同的差异代谢物。在72个经二级质谱图信息定性或标准品验证的差异代谢物中,参与氨基酸代谢、核苷酸代谢和脂质代谢通路的差异代谢物分别有9、9以及45个。富集通路分析结果表明:SCCPs对L02细胞的代谢干扰主要表现在脂质代谢、脂肪酸β氧化以及核苷酸代谢通路上,且中、高剂量的SCCPs暴露引起更广泛的代谢通路的紊乱。SCCPs暴露干扰了甘油磷脂以及鞘脂类的代谢通路,其中,磷脂酰胆碱、磷脂酰乙醇胺以及鞘磷脂丰度的显著变化表明SCCPs暴露对细胞的生物膜有一定的损伤。同时,SCCPs暴露通过降低短链和中链酰基肉碱的含量抑制L02细胞中脂肪酸β氧化,提示细胞通过氧化脂肪酸供能减少。值得注意的是,与中剂量和低剂量SCCPs相比,高剂量的SCCPs暴露对脂肪酸β氧化的抑制作用更强。此外,SCCPs暴露诱导了核苷酸代谢通路的紊乱。次黄嘌呤水平显著升高提示SCCPs暴露可能诱导了L02细胞的缺氧、活性氧增多或者致癌等相关不良效应。

山东省南四湖表层水和沉积物中SCCPs赋存特征及风险评价

短链氯化石蜡(SCCPs)具有良好的化学稳定性和热稳定性,被我国广泛用作金属加工中的润滑剂、密封剂,纺织品中的阻燃剂以及塑料中的增塑剂。但SCCPs的持久性、高毒性、长距离迁移特性和生物蓄积性会对生物体的肝脏、新陈代谢以及发育产生影响,对人类的健康具有潜在危害。目前SCCPs已广泛存在于环境中,然而对其在湖泊淡水环境中的赋存特征及风险评价仍缺乏系统的研究。本文采用GC-MS分析了南四湖表层水和表层沉积物中SCCPs的含量水平、组成特征,探讨了污染物的主要来源及潜在风险。结果表明:①表层水中SCCPs总浓度为53.9~1287.7 ng/L,沉积物中SCCPs总含量为609.9~113761.7 ng/g(以干质量计,下同)。南四湖表层水中SCCPs浓度的空间分布呈现北部较高、南部较低的特征,沉积物中SCCPs含量的空间分布呈现两端高、中间较低的特征。结合南四湖周边环境因素分析,这可能与周边码头船只使用的燃料排放、湖泊水动力、大坝工程以及工业农业生产有关。②C_(10)SCCPs和C_(13)SCCPs是南四湖表层水和沉积物中主要的碳链基团,表层水中Cl_(6)SCCPs、Cl7SCCPs和Cl_(9)SCCPs是主要氯同类物,沉积物中Cl_(6)SCCPs是主要氯同类物。③主成分分析结果表明,南四湖表层水和沉积物中SCCPs的来源关联性较弱,可能与环境条件、人类活动及周边地区生产使用不同种类的氯化石蜡产品等多种因素有关。④熵值法初步风险评估表明,南四湖表层水大部分取样点处于中风险,部分取样点处于高风险,RQ平均值为0.85,整体处于中风险等级。沉积物取样点大部分处于高风险,部分取样点处于中风险,RQ平均值为21.07,整体处于高风险等级。研究显示,南四湖SCCPs污染日益加重,表层水中SCCPs浓度处于中风险等级,沉积物中SCCPs含量总体上已处于高风险等级,需要引起特别的关注。

固废墨泥对非极性三元乙丙橡胶和极性丁腈/氯化聚乙烯橡胶的协效增塑效果

将不同用量墨泥与不同牌号石蜡油和氯化聚乙烯进行配合,重点研究墨泥作为协效增塑剂对三元乙丙橡胶和丁腈/氯化聚乙烯橡胶增塑效果的影响。结果表明,非极性三元乙丙橡胶和极性丁腈/氯化聚乙烯橡胶的物理机械性能和硫化性能随着墨泥用量的增加有一定程度的提高,说明墨泥有软化增塑的作用且增塑效果较好。

东海典型海岛城市居民常食用的贝类中氯化石蜡的含量及膳食风险评估

氯化石蜡(CPs)是一种产量较高的持久性有毒工业化学品,并普遍存在于各种环境基质中.本研究对东海典型海岛城市玉环市常见的8种贝类进行了短链和中链氯化石蜡的定量分析.短链氯化石蜡(SCCPs)的浓度为101-535 ng·g^(−1)dw;中链氯化石蜡(MCCPs)的浓度为100-740 ng·g^(−1)dw.8种贝类的主要CPs为碳链长度为C_(10)的SCCPs和碳链长度为C14的MCCPs.风险评估结果表明,通过贝类摄入CPs对人类健康造成影响可以忽略.

微生物去除氯化石蜡的研究进展

氯化石蜡在很多方面具有应用价值,目前还没有好的替代品,同时短链氯化石蜡还具有一定毒性。如何去除氯化石蜡和对氯化石蜡进行绿色降解,减少其对生态环境的污染已成为研究的重要课题。目前,去除环境中有机污染物的方法包括生物吸附或生物降解。本文主要综述了现阶段降解氯化石蜡的微生物(主要是细菌)的降解模式和参与的酶类,对自然环境中有机污染物的治理具有较大的理论意义。

基于生态风险的土壤短链氯化石蜡环境基准研究

短链氯化石蜡(Short Chain Chlorinated Paraffins,SCCPs)是一种持久性有机污染物,广泛应用于电缆、人造革等工业生产中,具有很强的生物毒性,并可以通过多种途径进入土壤环境,威胁着土壤生态环境安全。针对新污染物之一的SCCPs,已经有相关研究做出了基于淡水环境的基准,而目前关于SCCPs的土壤生态环境基准和风险的研究仍旧缺乏。鉴于此,本研究分别采用物种敏感度分布法和分配系数法推导了土壤中SCCPs的生态环境基准阈值,并对我国典型土壤中的生态风险进行了评价。结果表明:采用物种敏感度分布法得出土壤的无效应浓度为71.46mg/kg;采用分配系数法得到土壤的无效应浓度为10.1mg/kg。经过与相关研究对比,最终选择利用分配系数法得到的基准值作为SCCPs的土壤生态环境基准值。由于物种选择和研究方法的差异性等,本研究获得的SCCPs土壤生态环境基准与其他国家存在一定差异。另外,运用风险商值法对土壤中的SCCPs环境风险进行评价,结果表明,目前我国主要地区的不同土壤类型中SCCPs的HQ值为7.23×10^(-5)~0.5017,为低风险。本研究的结果可为土壤SCCPs环境质量标准的制定与环境风险管理提供参考依据。

一种复配型氯化石蜡抗剥落性能的研究

对一种复配型氯化石蜡产品的抗剥落性能展开研究,并与同一系列非胺类抗剥落剂、消石灰等常规抗剥落产品进行对比试验得出数据,将这些数据进行系统分析。为了说明两者之间的差异,采取红外谱图比对分析的方法,尝试从结构变化方面详细解释非胺类抗剥落剂在应用过程中的作用机理。

氯化石蜡对钢丝绳芯阻燃输送带芯胶性能的影响研究

对比了不同含量氯化石蜡对钢丝绳芯阻燃输送带芯胶性能的影响,确定了25份氯化石蜡含量为综合性能最佳,芯胶性能既能满足标准要求也能满足生产要求。