液液提取-固相萃取-LC-MS/MS测定人体尿液中有机磷系阻燃剂及其二酯类代谢物
Determination of organophosphate flame retardants and their diesters in urine by liquid-liquid extraction and solid-phase extraction coupled with LC-MS/MS
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摘要: 本研究基于液液提取和固相萃取技术建立了检测人体尿液中有机磷系阻燃剂（OPFRs）及其二酯类代谢产物（diesters）的前处理方法，采用液相色谱串联三重四极杆质谱（LC-MS/MS）进行定性定量分析.根据OPFRs与diesters理化性质的差异，尿液酶解后采用甲基叔丁基醚（MTBE）与二氯甲烷：正己烷（4∶1，V/V）混合液提取，有机相经Florisil固相萃取柱净化，乙酸乙酯洗脱后，测定OPFRs含量；水相过Strata-X-AW柱萃取，5%三乙胺/乙腈（V/V）洗脱后，测定diesters含量.在优化的实验条件下，OPFRs和diesters在相应浓度范围内呈良好线性关系，相关系数r介于0.9978—0.9997之间；尿液样品中OPFRs加标回收率平均值在72.4%—125%之间，RSD为0.62%—4.40%；6种diesters平均加标回收率为79.7%—126%，RSD介于2.20%—9.75%之间.本方法所需样品量少且能对OPFRs和diesters同时进行检测，方法的平行性好、结果可靠.使用该方法对15例尿液样品中的OPFRs与diesters含量进行分析发现，尿液中OPFRs检出率较低，7种OPFRs检出率均小于50%；6种diesters中仅双（丁氧乙基）磷酸酯（BBOEP）未在任何样品检出，其余5种diesters检出率介于33.3%—93.3%之间，其中磷酸二苯酯（DPHP）和双（1，3-二氯-2-丙基）磷酸酯（BDCIPP）检出率分别达93.3%和86.7%，是检出最高的两种化合物.Abstract: An effective method was established for the analysis of organophosphate flame retardants and their diesters in urine by liquid-liquid extraction and solid-phase extraction, followed by triple quadrupole liquid chromatography-tandem mass spectrometry (LC-MS/MS) for quantification. After enzymolysis by β-glucuronidase deconjugation enzyme, urine samples were extracted by a mixture of MTBE and DCM:HEX (4:1,V/V). The organic phase (containing OPFRs) was cleaned-up by Florisil cartridges, and OPFRs were eluted with ethyl acetate, then analyzed by LC-MS/MS. The aqueous phase (containing diesters) was loaded onto Strata-X-AW cartridges for extraction and further clean-up, and the target compounds were eluted by 5% triethylamine in acetonitrile (V/V), then the analysis of diesters was performed using LC-MS/MS. Under the optimized conditions, good linearities for both OPFRs and diesters were achieved as the analytes in the corresponding concentration range and the correlation coefficients (r) are 0.9978-0.9997. The average recoveries of OPFRs and diesters in urine ranged from 72.4% to 125% with RSD values of 0.62%-4.40% and from 79.7% to 126% with RSD values of 2.20%-9.75%, respectively. The developed method was stable and reliable, and OPFRs and diesters were analysed with a small volume of urine sample. The method was applied for the determination of OPFRs and diesters in urine samples from 15 e-waste dismantling workers. A low detection frequency (<50%) was found for all OPFRs. As for diesters, the detection frequencies were between 33.3% and 93.3%, except for bis (butoxyethyl) phosphate (BBOEP), which was not detected in any samples. Diphenyl phosphate (DPHP) and bis (1,3-dichloro-2-propyl) phosphate (BDCIPP) were the most ubiquitous compounds with detection frequencies of 93.3% and 86.7%, respectively.
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