灰尘中有机磷系阻燃剂及其降解产物检测方法的建立

Establishment of detection method for organic phosphorus flame retardants and their degradation products in dust

本研究建立了QuEChERS与液相色谱串联质谱(LC-MS/MS)联用方法,同时提取、净化灰尘样品中6种有机磷系阻燃剂(磷酸三苯酯(TPhP)、磷酸三丁酯(TnBP)、磷酸三(2-丁氧乙基)酯(TBOEP)、磷酸三(2-氯乙基)酯(TCEP)、磷酸三(2-氯丙基)酯(TCPP)、三(1,3-二氯-2-丙基)磷酸酯(TDCPP)及其降解产物(磷酸二苯酯(DPP)、磷酸二丁酯(DBP)、双(丁氧乙基)磷酸酯(BBOEP)、双(2-氯乙基)磷酸酯(BCEP)、双(1-氯-2-丙基)磷酸酯(BCPP)、双(1,3-二氯-2-丙基)磷酸酯(BDCPP)),上机检测.50 mg灰尘样品用3 mol·L^-1乙酸铵水溶液:乙腈(1∶1,V/V)混合溶液提取,加75 mg硫酸镁(MgSO4)、25 mg N-丙基乙二胺(PSA)、25 mg碳18(C18)、25 mg石墨化碳黑(GCB)和75μL三乙胺进行净化,定容至1 mL后使用LC-MS/MS进行分析.色谱的流动相为甲醇和0.01 mol·L^-1乙酸铵水溶液,梯度洗脱,用多反应通道监测(MRM)模式进行定性和定量分析.该检测方法在2.0-1000.0 ng·mL-1的范围内线性关系良好(R2>0.996). OPFRs的加标回收率范围在92%-128%,相对标准偏差(RSDs)介于6.5%-9.5%.OPFRs降解产物的加标回收率范围在93%-129%,RSDs介于7.8%-14.9%.使用本文建立的方法对13例灰尘样品中OPFRs及其降解产物进行定量分析,TPhP、TnBP、TBOEP、TCEP、TCPP、TDCPP的平均浓度介于347.61-2197.58 ng·g^-1,TPhP检出率最高,为100%,而TBOEP和TDCCP的检出率最低,为8%.DPP、DBP、BBOEP、BCEP、BCPP、BDCPP的平均浓度介于nd-1411.18 ng·g^-1,DPP和BCEP检出率最高,为100%,而BBOEP的检出率最低,未被检出.

A method of simultaneously extracting and purifying six organophosphorus flame retardants(OPFRs including TPhP, TnBP, TBOEP, TCEP, TCPP, and TDCPP) and their degradation products(DPP, DBP, BBOEP, BCEP, BCPP, and BDCPP) in dust samples was established using QuEChERS and liquid chromatography-tandem mass spectrometry(LC-MS/MS). The dust samples were extracted with mixed 3 mol·L^-1 ammonium acetate: acetonitrile(1∶1, V/V) and purified by adding 75 mg MgSO4, 25 mg PSA, 25 mg C18, 25 mg GCB and 75 μL triethylamine. After being concentrated to 1 mL, the extracts were analyzed by LC-MS/MS. The mobile phases were methanol and 0.01 mol·L^-1 ammonium acetate aqueous solution. Multi-reaction channel monitoring(MRM) mode was used for qualitative and quantitative analysis. The standard curve(in range of 2.0-1000 ng·mL-1) had a good linearity(R2> 0.996). The recoveries of OPFRs ranged from 92% to 128%, with relative standard deviations(RSDs) of 6.5%-9.5%. The recoveries of OPFR degradation products ranged from 93% to 129%, with RSDs of 7.8%-14.9%. The method was applied for OPFRs and their degradation products in 13 dust samples. The average concentrations of TPhP, TnBP, TBOEP, TCEP, TCPPs and TDCPP in 13 dust samples were between 347.61 and 2197.58 ng·g^-1. The detection frequencies ranged from 8%(for TBOEP and TDCPP) and 100%(for TPhP). The average concentrations of DPP, DBP, BBOEP, BCEP, BCPP and BDCPP were between non-detectable and 1411.18 ng·g^-1). DPP and BCEP were found in all the samples, but BBOEP was not found in the samples.