液相色谱-串联质谱法检测淡水养殖环境中地西泮及其代谢物

Determination of Diazepam and Its Metabolites in Freshwater Aqua⁃culture Environment by Liquid Chromatography-Tandem Mass Spectrometry

建立了养殖水、植物、沉积物和鲫鱼中地西泮及其代谢物(去甲西泮、奥沙西泮和替马西泮)的液相色谱-串联质谱检测方法。养殖水经0.45µm玻璃纤维膜过滤,用氨水调至pH 8.0后通过反相固相萃取柱(HLB)净化;植物和沉积物经盐析提取后,通过QuEChERS方法净化上样;鲫鱼样品经盐析提取后,通过固相萃取柱(Prime HLB)净化上样。采用Luna C_(18)柱(100 mm×2.1 mm,1.6µm)进行分离,多反应监测(MRM)模式进行测定,外标法定量。结果表明:地西泮及其3种代谢物在0.1~10µg/L质量浓度范围内呈良好的线性关系(r^(2)>0.999)。4种目标物在养殖水体中的检出限为1.0~1.2 ng/L,定量下限为5.0~6.0 ng/L;在植物、沉积物和鲫鱼中的检出限为0.03~0.10µg/kg,定量下限为0.10~0.25µg/kg。在低、中、高3个加标水平下,地西泮及其代谢物的回收率为83.4%~106%,相对标准偏差(RSD,n=6)为1.2%~9.4%。该方法成功应用于养殖水、沉积物、植物和鲫鱼样品中地西泮及其代谢物的检测,能为地西泮污染追查提供检测方法支撑。

A liquid chromatography-tandem mass spectrometric method was developed for the deter⁃mination of diazepam and its metabolites(nordazepam,oxazepam and temazepam)in aquaculture wa⁃ter,plant,sediment and crucian carp.The aquaculture water was filtered through 0.45µm glass fi⁃ber membrane,adjusted to pH 8.0 with ammonia,and then purified by reverse phase solid phase extraction column(HLB).The plants and sediments were extracted by salting out and then cleaned up by QuEChERS method before injection.The crucian carp samples were also extracted by salting out,cleaned up by solid phase extraction column(Prime HLB),and then injected for analysis.The analytes were separated by Luna C_(18) column(100 mm×2.1 mm,1.6µm),determined in multiple reaction monitoring(MRM)mode,and quantified by external standard calibration method.The re⁃sults showed that the linear ranges of diazepam and its three metabolites were 0.1-10µg/L(r^(2)>0.999).The limits of detection and quantitation in aquaculture water were 1.0-1.2 ng/L and 5.0-6.0 ng/L,respectively.The limits of detection and quantitation in plants,sediments and crucian carp were 0.03-0.10µg/kg and 0.10-0.25µg/kg,respectively.The recoveries of diazepam and its metabolites at three spiked levels ranged from 83.4%to 106%,and the relative standard deviations(RSDs,n=6)were 1.2%to 9.4%.The method was successfully applied to the detection of diazepam and its metabolites in aquaculture water,sediments,plants and crucian carp samples.It can pro vide methodological support for tracing diazepam pollution.