海水中兽药多残留分析时,基质效应会对测定准确度产生较大影响.以反渗透水为空白对照,液相色谱-串联质谱联用(lIQuId CHrOMATOgrAPHy-TAndEM MASS SPECTrOMETry,lC-MS/MS)检测,在500倍浓缩条件下,评价了3种常用亲水-亲油平衡(HydrOPHIlE-lyOPHIlE bAlAnCE,Hlb)固相萃取柱(WATErS、SuPElCO和安谱)对海水中35种兽药的基质效应和保留效果.研究发现:反渗透水实验中3种Hlb柱表现出柱填料的外源性基质效应,喹诺酮类和四环素类兽药呈现基质正效应,雌激素类等呈现基质负效应,磺胺类和氯霉素类兽药基质效应不显著.海水基质实验中由于外源性杂质与内源性杂质共同作用,大部分喹诺酮类和四环素类兽药呈现基质正效应,氯霉素类和雌激素类呈现基质负效应,磺胺类兽药基质效应不显著.与外标法相比较,基质匹配标准校正法可有效消除基质效应.在50和200ng/l两个加标质量浓度下,3种Hlb柱对海水中35种目标兽药校正后的回收率分别为26.8%~147.8%(WATErS)、60.4%~159.3%(SuPElCO)和52.0%~112.1%(安谱);两个加标浓度的相对标准偏差(rSd)(n=4)在0.1%~11.1%.结果表明,相同实验条件下,3种Hlb柱的基质效应不容忽视,采用基质匹配标准校正法可以有效克服基质效应,为海水样品中兽药多残留分析方法准确度的改善提供了参考数据.Matrix effect frequently influences determination accuracy of trace veterinary drugs in different matrices.In this paper,the evaluation and improvement method of matrix effect on determination accuracy of 35veterinary drugs spiked in seawater were studied using reverse osmosis(RO)water as control matrix.LC-MS/MS was used for detection and HLB cartridges of three brands(Waters,Supelco and Anpel)for concentration under 500folds concentration.In RO water only exogenous matrix effects were observed.Sulfonamides and chloramphenicols were found not significantly affected by matrix effect.Quinolones and tetracyclines showed positive matrix effects while estrogens showed negative matrix effects.In sea water,due to the co-existed exogenous and endogenous interfering substances,most quinolones and tetracyclines also showed positive matrix effects.Chloramphenicols and estrogens showed negative matrix effects,only sulfonamides were not significantly affected.Matrix matched calibration method effectively overcame matrix effects with better quantization results than external calibration method.Recoveries of 35target veterinary drugs spiked in seawater at 50ng/L and 200ng/L levels were in the ranges of 26.8%-147.8%(Waters),60.4%-159.3%(Supelco),and 52.0%-112.1%(Anpel)with RSDs(n=4)0.1%-11.1%.Research indicated that matrix effect could not be ignored and matrix matched calibration method would provide better results when using different HLB cartridges for trace veterinary drug determination in waters.福建省自然科学基金项目(2012J01048); 中国科学院城市环境研究所开放基金(KLUEH201009
