高效液相色谱串联质谱法测定环境水体中的全氟磺酸替代物

Determination of polyfluoroalkyl sulfonates and emerging alternatives in riverine water by high performance liquid chromatography coupled with mass spectrometry

建立了高效液相色谱串联质谱同时分析环境水体中4种全氟磺酸污染物及4种替代物(3种全氟调聚磺酸及1种氯代多氟醚基磺酸)的分析方法.优化样品p H值、洗脱液用量等固相萃取(SPE)条件,并对萃取柱柱容进行了评估.采用亲水疏水平衡(HLB)固相萃取柱,在p H值为10的条件下对样品进行萃取,萃取柱干燥之后使用9 m L甲醇作为洗脱液分3次对萃取柱进行洗脱.方法在0.1—50.0 ng·m L-1范围内呈现良好的线性关系(r>0.998),方法检出限(S/N>3)为1.0—62 pg·L-1,加标回收率53.2%—134.1%.测定了来自4个不同地区的河水样品中全氟磺酸及替代物的残留水平.调聚磺酸类污染物中仅发现6∶2 FTS的存在(0.2—0.6 ng·L-1),而氯代多氟醚基磺酸在样品中都有检出(3.7—57.0 ng·L-1).该方法简单、高效,可满足水体中全氟磺酸类污染物及其替代物的检测.

A method was developed for the simultaneous analysis of four polyfluoroalkyl sulfonates and four alternatives （ three fluorotelomer sulfonates and one chlorinated polyfluoroalkyl ether sulfonate ） by high performance liquid chromatography coupled with triple quadrupole mass spectrometry （ HPLC-MS/MS） . Solid phase extraction （ SPE） was selected for sample pretreatment and the influential factors including pH value and eluent volume were evaluated. With the cartridge adsorption capacity assessed, hydrophilic-lipophilic balance （ HLB） cartridges was selected, and the pH value of 10 was optimized for the water samples during the SPE procedure. Nine milliliter methanol was used to elute the cartridges for three times. Satisfactory method validation results were obtained in linearity （ r〉0.998, 0.1—50.0 ng·mL^-1 ） , and low method detection limits in the range of 1.0—62 ng·L^-1 , and spiked recoveries for all analytes were 53. 2%—134. 1%. The established method was applied for the trace analysis of the polyfluoalkyl sulfonates in several riverine samples. 6∶2 FTS presented as the only fluorotelomer sulfonate analogues （ 0. 2—0. 6 ng·L^-1 ） , while 6∶2 Cl-PFAES were found in all samples with the concentration in the range of 3.7—57.0 ng·L^-1. The method was simple and efficient, which could be used for the analysis of polufluoroalkyl sulfonates and the alternative pollutants in riverine samples.