悬浮固化-分散液液微萃取-液相色谱-串联质谱测定纺织废水中磷系阻燃剂

建立了悬浮固化-分散液液微萃取结合液相色谱-串联质谱测定纺织废水中5种痕量磷系阻燃剂的方法。通过对萃取过程中萃取剂、分散剂的种类与体积、盐浓度、溶液pH值等对萃取效率的影响因素优化，确立了最佳萃取条件。采用了密度小于水的十一烷醇（400 μL）为萃取剂，甲醇（300 μL）为分散剂，控制溶液pH值在6~9之间，NaCl添加量为2 g，萃取时间为涡旋2 min。在优化的萃取条件下，该方法在2~100 μg/L均有良好的线性关系，相关系数大于0.995，除二（2，3-二溴丙基）磷酸酯（BIS）的检出限为5 μg/L外，三（2-氯乙基）磷酸酯（TCEP）、三（1，3-二氯-异丙基）磷酸酯（TDCP）、三（1-氮丙啶基）氧化膦（TEPA）和三（2，3-二溴丙基）磷酸酯（TRIS）的检出限均为2 μg/L。后整理、染色和印花等实际废水样品加标试验表明，方法的平均回收率为71.6%~114.5%，RSD为2.7%~11.2%（n=6）。对11个样品进行检测，其中3个废水样品检出TCEP与TDCP化合物，含量为2.6~3.4 μg/L。本方法简单，快速，灵敏度好且环保绿色，能够对纺织废水中的5种痕量磷系阻燃剂进行准确的定性与定量检测。

Determination of organophosphorus flame retardants in textile wastewater by dispersive liquid-liquid microextraction based on solidification of floating organic drop followed by ultra-high performance liquid chromatography-tandem mass spectrometry

A rapid method for the determination of five organophosphorus flame retardants (OPFRs) in textile wastewater was established by dispersive liquid-liquid microextraction (DLLME) based on solidification of floating organic drop (SFO) coupled with ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The analytes were extracted from the water samples by SFO-DLLME, which was performed using a mixture of an extraction solvent that was less dense than water, 1-undecanol, and a dispersive solvent, methanol. The influences of the SFO-DLLME parameters on the extraction efficiencies were studied. 1-Undecanol (extraction solvent, 400 μL) and methanol (dispersive solvent, 300 μL) were added to textile wastewater (containing 2 g NaCl) with pH between 6 and 9, and the solution was shaken for 2 min. Under optimum conditions, the linear ranges of the proposed method were from 2 μg/L to 100 μg/L with correlation coefficients (R²) above 0.99 for all the analytes. The limits of detection (S/N=3) ranged from 2 μg/L to 5 μg/L. The precision of the method was evaluated in terms of repeatability; the relative standard deviations varied from 2.7% to 11.2% (n=6). The relative recoveries ranged from 71.6% to 117.6% for all analytes. Only 3 of the 11 selected samples were tested positive for OPFRs, and the total concentrations of OPFRs in them were in the range of 2.6-3.4 μg/L. Hence, this method is accurate, environmentally friendly, fast, and convenient for the routine analysis of OPFRs in textile wastewater.