混合型离子交换反相吸附固相萃取-超高效液相色谱-三重四极杆质谱法测定水中23种非甾体抗炎药的残留

Determination of 23 non-steriodal antiinflammatory drugs residues in water using mixed ion exchange reversed phase adsorption solid phase extraction by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry

非甾体抗炎药(NSAIDs)作为一种新型有机污染物,在环境水体中普遍检出,对生态系统及人体健康造成潜在的威胁,开发准确、可靠的测定水中痕量非甾体抗炎药的检测方法至为重要.本文采用Oasis MCX固相萃取柱对水样进行富集,建立测定水中23种非甾体抗炎药的超高效液相色谱-三重四极杆质谱分析方法.采用酸性条件(pH=4)萃取水样,上样的流速为2 mL·min^(−1),用4 mL甲醇-4 mL5%氨水甲醇进行洗脱,浓缩定容后用ACQUITY UPLCTM BEH C18柱(2.1 mm×100 mm,1.7μm),以2 mmol·L^(−1)乙酸铵+0.05%(V/V)甲酸水溶液-乙腈作为流动相进行梯度洗脱,多反应选择离子监测(MRM)模式进行检测,内标法定量.23种NSAIDs在相关线性范围内线性良好(r=0.9951—0.9992),回收率为80.2%—120%,相对标准偏差为0.4%—12.5%,方法检出限为0.20—4.84 ng·L^(−1).将该方法应用于10份地表水的检测,结果显示有10种NSAIDs检出,质量浓度在ND—83.5 ng·L^(−1)之间.该方法简单、灵敏、高效,可应用于环境水体中NSAIDs的检测.

Non-steroidal anti-inflammatory drugs(NSAIDs)are emerging contaminants that have recently attracted attention.They have been frequently detected in environmental water.They have been considered as a potential threat to the aquatic ecosystem and human health.It is important to develop accurate and reliable methods for the determination of trace amounts of NSAIDs in water.An analytical method was developed for the determination of 23 NSAIDs in water by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry.Filtered water samples were adjusted to pH of 4 and extracted by SPE with Oasis MCX cartridges(500 mg and 6 mL)at a flow rate of 2 mL·min^(−1).Then NSAIDs retained on the cartridges were eluted with 4 mL of 5%(V/V)ammoniated methanol and 4 mL of methanol.The eluates were finally evaporated to near dryness and redissolved in 1 mL of methanol.The target analytes were separated on ACQUITY UPLCTM BEH C18 column(2.1 mm×100 mm,1.7μm)using acetonitrile and aqueous solution mixture containing 0.05%(V/V)formic acid and 2 mmol·L^(−1) ammonium acetate as mobile phase.The analysis was performed under multiple reaction monitoring(MRM)mode,quantified with internal standard method.Good linearity was observed for all the tested NSAIDs,with a correlation coefficient(r)greater than 0.995.The method detection limits(MDLs)ranged from 0.20—4.84 ng·L^(−1).The average recoveries ranged from 80.2%to 120%,while the relative standard deviations(RSDs)were ranged from 0.4%to 12.5%.The method was successfully applied to the determination of 10 surface water samples.Ten NSAIDs,viz.salicylic acid,sulindac,etodolac,diclofenac,mefenamic acid,piroxicam,parecoxib,antipyrine,nabumetone and acetaminophen,were detected in the 10 water samples.The total NSAIDs content in each sample ranged from not detected to 83.5 ng·L^(−1).The developed method is simple,rapid,and efficient,and it shows promise for the simultaneous determination of trace levels of the 23 NSAIDs in environmental water.