化工样品中六氯丁二烯的气相色谱-质谱分析方法

Analytical method for hexachlorobutadiene in chemical manufacturing samples by gas chromatography-mass spectrometrometry

六氯丁二烯(hexachlorobutadiene,HCBD)已于2017年被增列入斯德哥尔摩公约管控名单,是一类新持久性有机污染物(POPs).氯碱等化工生产过程能够无意产生HCBD副产物,是目前HCBD的主要来源,然而目前对于化工生产过程样品和化工产品中HCBD的研究较少,尚无完善的HCBD分析方法.本研究建立了氯乙烯、氯苯等典型化工产品生产过程样品中HCBD的气相色谱-质谱(GC-MS)分析方法,优化了进样口温度、升温程序、载气流速等色谱参数,标准曲线线性范围为0—500 ng·mL^(−1),方法加标回收率为77.8%—102%,相对标准偏差为3.6%—6.0%,标准曲线相关系数R^(2)为0.9998,方法检出限为0.049 ng·mL^(−1),定量限为0.16 ng·mL^(−1),能够满足化工样品中HCBD的准确定性和定量要求.将建立的GC-MS分析方法应用于我国典型氯乙烯、氯苯等化工生产过程样品中HCBD的检测分析,发现三、四氯乙烯生产过程中HCBD浓度远高于氯苯,浓度范围为0.003—243000μg·mL^(−1).本方法的建立能够为化工生产过程中HCBD的排放研究提供技术支撑,为化工行业HCBD的源识别和管控提供重要信息.

Hexachlorobutadiene(HCBD)has been listed in Stockholm Convention in 2017,as a kind of emerging persistent organic pollutants(POPs).Chemical manufacturing processes such as chlor-alkali production can unintentionally produce HCBD as byproducts,which is considered as the main source of HCBD at present.Current HCBD related studies mainly focused on environmental samples such as soil and atmosphere surrounding chemical production plants.However,few studies has been conducted on HCBD occurrences in chemical products or chemical residues during the chemical manufacturing processes.This study established a gas chromatography-mass spectrometry(GC-MS)method for the analysis of HCBD in chemical manufacturing samples such as chloroethylene and chlorobenzene.The chromatographic parameters containing inlet temperature,heating procedure and carrier gas flow rate were optimized.The linear range of the standard curve is 0-500 ng·mL^(−1).The recoveries of the method were 77.8%-102%,and the relative standard deviations were 3.6%-6.0%.The correlation coefficient R^(2) of the standard curve was 0.9998.The detection limit was 0.049 ng·mL^(−1),and the limit of quantification was 0.16 ng·mL^(−1),which could meet the accurate qualitative and quantitative requirements of HCBD in chemical samples.The established GC-MS analysis method was then applied to the analysis of HCBD in practical chemical samples from typical chloroethylene and chlorobenzene manufacturing processes in China.It was found that the concentration of HCBD in the production of trichloroethylene and tetrachloroethylene(0.003-243000μg·mL^(−1))was much higher than that of chlorobenzene.The method can provide technical support for the study of HCBD emission in the chemical production process,and provide important information for their source identification and emission control.