反相超高效液相色谱-高分辨质谱法测定自来水消毒副产物卤代乙酸

Determination of Haloacetic Acids,Disinfection Byproducts,in Tap Water with Reversed-Phase Ultra-Performance Liquid Chromatography-High Resolution Mass Spectrometry

目的建立一种检测自来水中消毒副产物卤代乙酸的反相超高效液相色谱-四极杆-轨道阱质谱法。方法水样加入0.70 g/L抗坏血酸作脱氯剂,过滤后进样分析。采用1.0 mm内径的五氟苯基(PFP)色谱柱,以比窄径柱常规流速更高的线流速和更低的体积流速洗脱,电喷雾电离源负离子模式下电离,一级质谱全扫描和数据依赖的二级质谱全扫描采集数据。为校正基质效应,采用基质匹配校准曲线法对9种卤代乙酸(一氯乙酸、一溴乙酸、二氯乙酸、一溴一氯乙酸、二溴乙酸、三氯乙酸、一溴二氯乙酸、二溴一氯乙酸和三溴乙酸)进行定量分析。结果9种卤代乙酸在各自的线性范围内线性关系良好,方法检出限和定量限分别为0.020~1.0μg/L和0.060~3.0μg/L,回收率为69.8%~119%。结论所建方法分离快速、定性准确,无需复杂的前处理步骤,可满足自来水样的分析要求。

Objective To establish a method for quantitative analysis of haloacetic acids(HAAs),disinfection byproducts,in tap water with reversed-phase ultra-performance liquid chromatography-quadrupole-orbitrap high resolution mass spectrometry.Methods Tap water samples were collected and 0.70 g/L ascorbic acid was added to eliminate residual chlorine.Then,the water samples were directly injected into the instrument for analysis after filtration.After separation on a pentafluorobenzene(PFP)column with an inner diameter of 1.0 mm at a higher linear velocity and a lower volume flow rate compared with those of a narrow-bore column,nine HAAs,namely,monochloroacetic acid(MCAA),monobromoacetic acid(MBAA),dichloroacetic acid(DCAA),bromochloroacetic acid(BCAA),dibromoacetic acid(DBAA),trichloroacetic acid(TCAA),bromodichloroacetic acid(BDCAA),chlorodibromoacetic acid(CDBAA)and tribromoacetic acid(TBAA),were examined by negative electrospray ionization and full MS/dd-MS2 acquisition mode.In order to adjust for the matrix effect,matrix matching calibration curves were used to quantitate the nine HAAs.Results Good linearity was obtained for each of the nine HAAs within their respective linear ranges.The detection limits and quantification limits of the method were 0.020-1.0μg/L and 0.060-3.0μg/L.The recoveries were 69.8%-119%.Conclusion The proposed method showed strengths in separation speed and qualitative accuracy.It did not require for complicated pretreatment procedures and can meet the need of tap water sample analysis.