混合模式吸附剂固相萃取-气相色谱-质谱法测定皮革中的磷酸三(2-氯乙基)酯  

Determination of tris( 2-chloroethyl) phosphate in leather by gas chromatography-mass spectrometry coupled with mixed-mode sorbent solid phase extraction

作　　者：张伟亚[1] 朱玉玲 王成云[1] 李丽霞[1] 张珺清 邢钧[2] 

机构地区：[1]深圳出入境检验检疫局工业品检测技术中心,广东深圳518067 [2]生物医学分析化学教育部重点实验室武汉大学化学与分子科学学院,湖北武汉430072

出　　处：《色谱》2014年第10期1157-1162,共6页Chinese Journal of Chromatography

基　　金：国家质检总局科研项目(2011IK105)

摘　　要：磷酸三（2-氯乙基）酯（TCEP）是一种皮革生产中常用的加工助剂，其具有致癌、神经毒性和生殖毒性，被欧洲化学品管理局列入禁用的第二批授权物质清单。由于皮革产品基质复杂，采用常用的固相萃取（ SPE）方法提取对TCEP的回收率不高。Silica-WCX是一种自制的含有羧基与烷基的新型混合模式吸附剂。研究表明，通过在酸性条件下使其羧基保持质子化状态，能有效增强 Silica-WCX 对极性化合物 TCEP 的萃取性能，使 TCEP 的回收率得到明显提高。本文以 Silica-WCX为 SPE材料，建立了测定皮革中 TCEP的 SPE-GC-MS方法。该方法的线性范围为0.10-100.0μg/L，定量限（ S/N＝10）为44.46 ng/kg，不同添加水平下 TCEP的平均回收率在91.45％-99.98％之间，相对标准偏差（ RSD）在4.33％~5.97％之间。该方法简便快捷，灵敏度高，定量限低于欧盟《化学品的注册、评估、授权和限制》（ registration，evaluation，authorization and restriction of chemicals，REACH）法规的限量要求，适用于皮革及其制品中 TCEP的测定。Leather is one of the important exporting products to European Union（ EU ）,and tris（2-chloroethyl）phosphate（TCEP）is a commonly used flame retardant in leather and leath-er products. Recently,TCEP has been classified as a kind of substance of very high concern （SVHC）by EU for its carcinogenicity and reproductive toxicity. But to date,there is not a rec-ognized method for the determination of TCEP in leather and leather products due to the seri-ous matrix interferences and relatively low recovery of TCEP. In this work,a home-made mixed-mode sorbent（ Silica-WCX）with carboxyl and alkyl groups was tested as the sorbent of solid phase extraction（ SPE ） to extract TECP from leather. The results demonstrated that, making the carboxyl groups protonized under acidic condition,Silica-WCX exhibited better ex-traction performance towards TCEP over some frequently used commercial sorbents tested. Af-ter the optimization of the SPE conditions based on Silica-WCX,a method of gas chromatogra-phy/mass spectrometry（ GC-MS）was established for the determination of TCEP in leather samples. The linear range for TCEP ranged from 0. 10 to 100. 0 μg/L and the limit of quantifica-tion（LOQ,S/N=10）was 44. 46 ng/kg. The recoveries of TCEP spiked in samples at variedevels were in the range of 91. 45%-99. 98% with the relative standard deviations（ RSDs ） of 4. 33%-5. 97%. The method is simple,sensitive and reliable for the analysis of TCEP in leather and leather products.

关 键 词：混合模式吸附剂 固相萃取 气相色谱-质谱法 磷酸三(2-氯乙基)酯 皮革 

分 类 号：O658[理学—分析化学]