色谱2025，Vol.43Issue(2)：155-163,9.DOI:10.3724/SP.J.1123.2024.03008
通过式固相萃取-超高效液相色谱-串联质谱法测定沉积物中草铵膦、草甘膦及其代谢物
Determination of glufosinate,glyphosate and their metabolites in sediment by ultra-high performance liquid chromatography-tandem mass spectrometry with pass-through solid-phase extraction
摘要
Abstract
Glufosinate(GLUF)and glyphosate(GLY)are nonselective phosphorus-containing amino acid herbicides that are widely used in agricultural gardens and noncultivated areas.These herbicides give rise to a number of key metabolites,with 3-methyl phosphinicopropionic acid(MPPA),N-acetyl glufosinate(N-acetyl GLUF),aminomethyl phosphonic acid(AMPA),N-acetyl aminomethyl phosphonic acid(N-acetyl AMPA),N-acetyl glyphosate(N-acetyl GLY),N-methyl glyphosate(N-methyl GLY)as the major metabolites obtained from GLUF and GLY.Extensive use of these herbicides may lead to their increased presence in the environ-ment,especially aquatic ecosystems.An increasing number of research studies into the toxici-ties of GLUF,GLY,and their metabolites have shown that these herbicides are potentially toxic to aquatic biota.GLUF and GLY,as well as their metabolites,are extremely polar and water-soluble,and they lack chromogenic and fluorescent groups;therefore,their concentrations are difficult to determine using conventional methods.Most analytical methods used to date have largely depended on derivatization procedures,leading to overall determination processes that are tedious and time-consuming.Therefore,establishing a quick and sensitive method that does not require derivatives for determining GLUF,GLY,and their metabolites in water environ-ments,including surface water,sediments,and aquatic organisms,is an important endeavor. In this study,a new approach was developed based on pass-through solid-phase extraction coupled with ultra-high performance liquid chromatography-tandem mass spectrometry(UH-PLC-MS/MS)to determine GLUF,GLY,and their metabolites,including MPPA,N-acetyl GLUF,AMPA,N-acetyl AMPA,N-acetyl GLY,and N-methyl GLY,in sediments.Samples were extracted with 4％(v/v)ammonia water and purified using PRiME HLB pass-through solid-phase extraction columns.The extracts were filtered through a polyethersulfone microfiltration membrane and analyzed by UHPLC-MS/MS.Compounds were separated on a Metrosep A Supp 5 column(150 mmx4.0 mm,5 μm)using gradient elution with water and 200 mmol/L ammo-nium hydrogen carbonate solution containing 0.05％(v/v)ammonia water as the mobile pha-ses.Analytes were detected using MS/MS with a negative electrospray ionization(ESI-)source in the multiple reaction monitoring(MRM)mode.A matrix-matched external-standard ap-proach was used for quantitative analysis.GLUF,GLY,and their metabolites were detected within 15 min with good peak shapes and high responses.Calibration curves were linear in the range of 2.0-200 μg/L,with correlation coefficients exceeding 0.995.This method delivered limits of detection(LODs)and limits of quantification(LOQs)of 5 μg/kg and 20 μg/kg,re-spectively,for GLUF,MPPA,N-acetyl-GLUF,N-acetyl AMPA,N-acetyl GLY,and N-methyl GLY,and 10 μg/kg and 30 μg/kg,for GLY and AMPA,respectively.Average spiked recoveries at three levels(LOQ,5LOQ,10LOQ)in sediment with low organic matter content were in the range of 78.5％-107％,and the relative standard deviations(RSDs)were in the range of 1.32％-14.7％(n=6).Average spiked recoveries of 76.4％-113％were determined for three levels(LOQ,5LOQ,and 10LOQ)in sediments with high organic matter contents,with RSDs of 2.60％-11.2％(n=6).The developed method was used to analyze GLUF,GLY,and their me-tabolites in ponds,lakes,reservoirs,and river sediments.No target compounds were detected in any sediment sample obtained from a lake,reservoir,or river;however,GLY and AMPA were detected in one pond-sediment sample at levels of 31.7 and 52.3 μg/kg,respectively.The developed approach is simple,fast,and green;moreover,it offers advantages,including high accuracies,high sensitivities,and good reproducibilities.Accordingly,the developed method is suitable for determining GLUF,GLY,and their metabolites in sediments and can provide tech-nical support for studying residue characteristics and environmental behavior in sediments.关键词
超高效液相色谱-串联质谱/通过式固相萃取/草铵膦/草甘膦/代谢物/沉积物/非衍生化Key words
ultra-high performance liquid chromatography-tandem mass spectrometry(UH-PLC-MS/MS)/pass-through solid-phase extraction/glufosinate/glyphosate/metabolites/sedi-ment/non-derivatization分类
化学化工引用本文复制引用
杨霄,谢仲桂,李小玲,索纹纹,陈相艺,万译文..通过式固相萃取-超高效液相色谱-串联质谱法测定沉积物中草铵膦、草甘膦及其代谢物[J].色谱,2025,43(2):155-163,9.基金项目
湖南省科技创新计划项目(2023NK4168) （2023NK4168）
国家现代农业产业技术体系建设项目(CARS-48-39).Science and Technology Innovation Program of Hunan Province(No.2023NK4168) （CARS-48-39）
Earmarked Fund for China Agriculture Research System(No.CARS-48-39). （No.CARS-48-39）
