In the present work, a very sensitive and fully automated direct immersion PAL SPME Arrow procedure, coupled with GC–MS, has been developed and validated for determination of nine phosphorus flame retardants in different types of water samples (river, drinking and rainwater). PDMS/DVB was selected among three commercially available SPME Arrows (PDMS/DVB, DVB/PDMS/CWR and PDMS/CWR), since it resulted in the best sensitivity. The important experimental parameters were optimized via a central composite design response surface methodology and as result, extraction time of 65 min, extraction temperature of 80 °C and added salt concentration of 19% (w/v), were selected as the optimum values. The optimized method showed linear response over the calibration range (2 – 500 ng L⁻¹), with R²-values higher than 0.9937. The precision (RSD%) measured by replicate analyses (n = 7) was estimated at 2 and 100 ng L⁻¹ and was less than 29% and 21%, respectively. The LOQ of PAL SPME Arrow, calculated as S/N = 10, was between 0.2 and 1.2 ng L⁻¹ (for triphenyl phosphate and tris-(1‑chloro‑2-propyl) phosphate, respectively) with extraction efficiencies between 5.9 and 31% (for tris-(1,3-dichloro-2-propyl) phosphate and tri-n‑butyl phosphate, respectively). To assess the performance of the developed technique for real samples, two river water samples, tap water from two regions and a rainwater sample were analyzed. Most of the target analytes were observed in the river samples with concentrations of 1.0 – 250 ng L⁻¹ and the obtained recoveries at 50 ng L⁻¹ ranged between 60 and 107%. Considering the figures of merit of the optimized method, PAL SPME Arrow-GC–MS showed to be the most sensitive analytical approach for determination of phosphorus flame retardants in water, with satisfying precision and accuracy, compared with conventional SPME-NPD, LLE-GC–MS and SPE-LC-MS/MS.

在目前的工作中，已经开发出一种非常灵敏的，全自动的直接浸入式PAL SPME Arrow方法，并结合了GC-MS，可用于测定不同类型的水样（河流，饮用水和雨水）中的九种磷阻燃剂。PDMS / DVB从三个市售SPME箭头（PDMS / DVB，DVB / PDMS / CWR和PDMS / CWR）中选择，因为它具有最佳的灵敏度。通过中央复合设计响应面方法对重要的实验参数进行了优化，结果选择了65分钟的提取时间，80°C的提取温度和19％（w / v）的添加盐浓度作为最佳值。经过优化的方法在R ²的校准范围内（2- 500 ng L ^-1）表现出线性响应。值高于0.9937。通过重复分析（n  = 7 ）测得的精密度（RSD％）估计为2和100 ng L ^-1，分别小于29％和21％。以S / N  = 10计算的PAL SPME Arrow的LOQ在0.2到1.2 ng L ^-1之间（分别对于磷酸三苯酯和磷酸三（1-氯-2-丙基）酯），萃取效率在5.9到1.5 ng之间。 31％（对于三- （1,3-二氯-2-丙基）酯和磷酸三ñ分别为磷酸正丁酯）。为了评估所开发技术对真实样品的性能，分析了两个河水样品，两个地区的自来水和雨水样品。在河流样品中观察到大多数目标分析物的浓度为1.0 – 250 ng L ^-1，在50 ng L ^-1时获得的回收率在60％至107％之间。考虑到优化方法的优点，与传统的SPME-NPD，LLE-GC相比，PAL SPME Arrow-GC-MS是测定水中磷阻燃剂的最灵敏的分析方法，具有满意的精密度和准确度。 –MS和SPE-LC-MS / MS。