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Article(id=1324077681536533179, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1324077560820282023, articleNumber=null, orderNo=null, doi=10.20043/j.cnki.MPM.202509447, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1758729600000, receivedDateStr=2025-09-25, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793614319451, onlineDateStr=2026-11-02, pubDate=1774368000000, pubDateStr=2026-03-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793614319451, onlineIssueDateStr=2026-11-02, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793614319451, creator=13701087609, updateTime=1793614319451, updator=13701087609, issue=Issue{id=1324077560820282023, tenantId=1146029695717560320, journalId=1227665162245664772, year='2026', volume='53', issue='6', pageStart='961', pageEnd='1152', issueExtLink='null', onlineDate='null', pubDate='1774368000000', pubDateStr='2026-03-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1793614290671, creator='13701087609', updateTime=1793614391469, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1324077983656444429, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1324077560820282023, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1324077983660638734, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1324077560820282023, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1106, endPage=1112, ext={EN=ArticleExt(id=1324077681976935100, articleId=1324077681536533179, tenantId=1146029695717560320, journalId=1227665162245664772, language=EN, title=Determination of glyphosate and aminomethylphosphonic acid in human urine by ion chromatography-tandem mass spectrometry, columnId=1228016572065837304, journalTitle=Modern Preventive Medicine, columnName=Experimental Technology and Applications, runingTitle=null, highlight=null, articleAbstract=
Objective

To establish a method for the simultaneous determination of glyphosate and its metabolite aminomethylphosphonic acid in human urine by ion chromatography-tandem mass spectrometry(IC-MS/MS).

Methods

The urine sample was purified using an HLB solid-phase extraction cartridge. After diluted and filtered, the filtrate was used for analysis. Gradient elution was performed using a potassium hydroxide solution as the mobile phase, with separation on an Ionpac AS20 anion exchange column(250 mm×2 mm). Detection was carried out using electrospray ionization in negative ion mode with multiple reaction monitoring, and quantification was achieved via the external standard method.

Results

Glyphosate and aminomethylphosphonic acid showed good linear relationships within the ranges of 0.5-50 μg/L and 4-100 μg/L, respectively, with correlation coefficients greater than 0.999. The method detection limits were 0.8 μg/L and 3.6 μg/L, respectively. The recovery rates of the method were 83.0% to 115.2%. The intra-day and inter-day relative standard deviations(RSDs) ranged from 1.2% to 7.8% and 3.5% to 9.2%, respectively.

Conclusion

This method is reproducible and accurate, and it is suitable for biological monitoring of glyphosate and its metabolite aminomethylphosphonic acid in urine samples of occupational populations.

, authors=Miao HE1, Guang-zhou XU2, Hong-qun ZHANG2, Feng ZHANG3, Hua-liang LIU3, authorsList=Miao HE, Guang-zhou XU, Hong-qun ZHANG, Feng ZHANG, Hua-liang LIU, authorCompany=null, correspAuthors=Hua-liang LIU, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1324077686536143559, articleId=1324077681536533179, tenantId=1146029695717560320, journalId=1227665162245664772, language=CN, title=离子色谱-串联质谱法测定人尿中草甘膦和氨甲基膦酸, columnId=1228016572288135432, journalTitle=现代预防医学, columnName=实验技术及其应用, runingTitle=null, highlight=null, articleAbstract=
目的

建立人尿中草甘膦及其代谢产物氨甲基膦酸的离子色谱-串联质谱（IC-MS/MS）测定方法。

方法

尿样经HLB固相萃取柱净化，稀释后过膜待测，以氢氧化钾溶液为流动相梯度洗脱，经Ionpac AS20阴离子交换柱（250 mm×2 mm）分离，采用电喷雾负离子，多反应监测模式检测，外标法定量。

结果

草甘膦和氨甲基膦酸分别在0.5~50 μg/L和4~100 μg/L范围内线性关系良好，相关系数均大于0.999，方法检出限分别为0.8 μg/L和3.6 μg/L，回收率在83.0%~115.2%之间，日内和日间精密度分别为1.2%~7.8%和3.5%~9.2%。

结论

本法重现性好、准确度高，适用于职业人群尿样中草甘膦及其代谢产物氨甲基膦酸的生物监测。

, authors=何苗1, 徐广洲2, 张宏群2, 张锋3, 刘华良3, authorsList=何苗, 徐广洲, 张宏群, 张锋, 刘华良, authorCompany=null, correspAuthors=刘华良, authorNote=

何苗（1989—），女，硕士，讲师，研究方向：预防医学

, correspAuthorsNote=
刘华良，E-mail:
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何苗（1989—），女，硕士，讲师，研究方向：预防医学

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Determination of two perfluorinated compounds in urine by liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Industrial Hygiene and Occupational Diseases, 2024, 42(3): 202-205. 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Development of an ultra-performance liquid chromatography-tandem mass spectrometry for determination of 7 types of food additives in ready-made tea drinks[J]．Jiangsu Journal of Preventive Medicine, 2023, 34(5): 521-523, 621. 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Simultaneous determination of glyphosate,glufosinate,diquat, and paraquat in whole blood and urine by liquid chromatography mass spectrometry[J]. Occupational Health and Emergency Rescue, 2025, 43(1): 106-110. 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Detection of glyphosate and glufosinate in urine using high performance liquid chromatography mass spectrometry combined with mass spectrometry[J]. Chinese Journal of Industrial Medicine, 2024, 37(2): 205-207. 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注：图中每组标注不同字母的数据之间具有显著性差异（P<0.05）。

, figureFileSmall=hLwhUAhDbJnzVTmz3rBIow==, figureFileBig=icCN36zfaEsaG+B2GP2AyQ==, tableContent=null), ArticleFig(id=1324077695465816826, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=EN, label=Fig.4, caption=Effect of dilution on the matrix effect of glyphosate and AMPA in urine samples, figureFileSmall=NsAzAHRXTVmnsb6wzyASFA==, figureFileBig=/4YfN6VtAJptWGUN1+/Wxg==, tableContent=null), ArticleFig(id=1324077695813944059, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=CN, label=图4, caption=稀释对尿样中草甘膦和氨甲基膦酸基质效应的影响, figureFileSmall=NsAzAHRXTVmnsb6wzyASFA==, figureFileBig=/4YfN6VtAJptWGUN1+/Wxg==, tableContent=null), ArticleFig(id=1324077696183042812, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=EN, label=Fig.5, caption=Total ion chromatogram of one typical urine sample, figureFileSmall=ZEkKLozPUgtSuL5Ys5AamQ==, figureFileBig=4/rged3x6Ts8BHLOviZ3Ag==, tableContent=null), ArticleFig(id=1324077696287900413, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=CN, label=图5, caption=某典型尿样的总离子流图, figureFileSmall=ZEkKLozPUgtSuL5Ys5AamQ==, figureFileBig=4/rged3x6Ts8BHLOviZ3Ag==, tableContent=null), ArticleFig(id=1324077697982399230, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=EN, label=Table 1, caption=

Mass parameters

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物母离子（m/z）子离子（m/z）去簇电压（V）碰撞能量（eV）
草甘膦167.963.0a/79.0-30-33/-53
氨甲基膦酸109.963.0a/79.0-30-24/-34
), ArticleFig(id=1324077698095645439, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=CN, label=表1, caption=

质谱参数

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物母离子（m/z）子离子（m/z）去簇电压（V）碰撞能量（eV）
草甘膦167.963.0a/79.0-30-33/-53
氨甲基膦酸109.963.0a/79.0-30-24/-34
), ArticleFig(id=1324077698255028992, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=EN, label=Table 2, caption=

Linearity ranges, linear regression equations, correlation coefficients and detection limits of the method（n=3）

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物线性范围（μg/L）回归方程相关系数（r）检出限（μg/L）方法检出限（μg/L）
草甘膦0.5~50y=1.08×104x + 2.97×1030.999 70.20.8
氨甲基膦酸4~100y=1.82×103x + 1.89×1030.999 20.93.6
), ArticleFig(id=1324077698414412545, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=CN, label=表2, caption=

方法的线性范围、回归方程、相关系数和检出限（n=3）

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物线性范围（μg/L）回归方程相关系数（r）检出限（μg/L）方法检出限（μg/L）
草甘膦0.5~50y=1.08×104x + 2.97×1030.999 70.20.8
氨甲基膦酸4~100y=1.82×103x + 1.89×1030.999 20.93.6
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Precision and recovery of the method（n=6）

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化合物本底值（μg/L）加标水平（μg/L）平均回收率（%）RSD（%）
日内日间
草甘膦未检出5.094.05.48.6
40.0110.84.57.1
160.0115.22.73.5
氨甲基膦酸未检出10.083.07.89.2
80.092.46.17.5
320.098.41.24.0
), ArticleFig(id=1324077698875785987, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=CN, label=表3, caption=

方法的精密度和准确度（n=6）

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物本底值（μg/L）加标水平（μg/L）平均回收率（%）RSD（%）
日内日间
草甘膦未检出5.094.05.48.6
40.0110.84.57.1
160.0115.22.73.5
氨甲基膦酸未检出10.083.07.89.2
80.092.46.17.5
320.098.41.24.0
), ArticleFig(id=1324077698976449284, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=EN, label=Table 4, caption=

Comparison of methods

, figureFileSmall=null, figureFileBig=null, tableContent=
方法参考文献方法检出限（μg/L）
草甘膦氨甲基膦酸
离子色谱-质谱法本试验0.803.60
气相色谱质谱联用法[6]4.661.77
液相色谱-质谱法[23]3.00无
高效液相色谱-质谱法[24]4.00无
), ArticleFig(id=1324077699089695493, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1324077681536533179, language=CN, label=表4, caption=

方法比较

, figureFileSmall=null, figureFileBig=null, tableContent=
方法参考文献方法检出限（μg/L）
草甘膦氨甲基膦酸
离子色谱-质谱法本试验0.803.60
气相色谱质谱联用法[6]4.661.77
液相色谱-质谱法[23]3.00无
高效液相色谱-质谱法[24]4.00无
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离子色谱-串联质谱法测定人尿中草甘膦和氨甲基膦酸
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何苗 1 , 徐广洲 2 , 张宏群 2 , 张锋 3 , 刘华良 3
现代预防医学 | 实验技术及其应用 2026,53(6): 1106-1112
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现代预防医学 |实验技术及其应用 2026 , 53 (6) : 1106 -1112
离子色谱-串联质谱法测定人尿中草甘膦和氨甲基膦酸
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何苗1, 徐广洲2, 张宏群2, 张锋3, 刘华良3
作者信息
  • 1.江苏医药职业学院，江苏 盐城 224005
  • 2.盐城市疾病预防控制中心
  • 3.江苏省疾病预防控制中心
通讯作者:
刘华良，E-mail:
作者简介:

何苗（1989—），女，硕士，讲师，研究方向：预防医学

Determination of glyphosate and aminomethylphosphonic acid in human urine by ion chromatography-tandem mass spectrometry
Miao HE1, Guang-zhou XU2, Hong-qun ZHANG2, Feng ZHANG3, Hua-liang LIU3
Affiliations
  • Jiangsu Medical College, Yancheng, Jiangsu 224005, China
出版时间: 2026-03-25 doi: 10.20043/j.cnki.MPM.202509447
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摘要
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目的

建立人尿中草甘膦及其代谢产物氨甲基膦酸的离子色谱-串联质谱（IC-MS/MS）测定方法。

方法

尿样经HLB固相萃取柱净化，稀释后过膜待测，以氢氧化钾溶液为流动相梯度洗脱，经Ionpac AS20阴离子交换柱（250 mm×2 mm）分离，采用电喷雾负离子，多反应监测模式检测，外标法定量。

结果

草甘膦和氨甲基膦酸分别在0.5~50 μg/L和4~100 μg/L范围内线性关系良好，相关系数均大于0.999，方法检出限分别为0.8 μg/L和3.6 μg/L，回收率在83.0%~115.2%之间，日内和日间精密度分别为1.2%~7.8%和3.5%~9.2%。

结论

本法重现性好、准确度高，适用于职业人群尿样中草甘膦及其代谢产物氨甲基膦酸的生物监测。

草甘膦  /  氨甲基膦酸  /  人尿  /  离子色谱-串联质谱法  /  固相萃取法
Objective

To establish a method for the simultaneous determination of glyphosate and its metabolite aminomethylphosphonic acid in human urine by ion chromatography-tandem mass spectrometry(IC-MS/MS).

Methods

The urine sample was purified using an HLB solid-phase extraction cartridge. After diluted and filtered, the filtrate was used for analysis. Gradient elution was performed using a potassium hydroxide solution as the mobile phase, with separation on an Ionpac AS20 anion exchange column(250 mm×2 mm). Detection was carried out using electrospray ionization in negative ion mode with multiple reaction monitoring, and quantification was achieved via the external standard method.

Results

Glyphosate and aminomethylphosphonic acid showed good linear relationships within the ranges of 0.5-50 μg/L and 4-100 μg/L, respectively, with correlation coefficients greater than 0.999. The method detection limits were 0.8 μg/L and 3.6 μg/L, respectively. The recovery rates of the method were 83.0% to 115.2%. The intra-day and inter-day relative standard deviations(RSDs) ranged from 1.2% to 7.8% and 3.5% to 9.2%, respectively.

Conclusion

This method is reproducible and accurate, and it is suitable for biological monitoring of glyphosate and its metabolite aminomethylphosphonic acid in urine samples of occupational populations.

Glyphosate  /  Aminomethylphosphonic acid  /  Human urine  /  Ion chromatography tandem mass spectrometry  /  Solid-phase extraction
何苗, 徐广洲, 张宏群, 张锋, 刘华良. 离子色谱-串联质谱法测定人尿中草甘膦和氨甲基膦酸. 现代预防医学, 2026 , 53 (6) : 1106 -1112 . DOI: 10.20043/j.cnki.MPM.202509447
Miao HE, Guang-zhou XU, Hong-qun ZHANG, Feng ZHANG, Hua-liang LIU. Determination of glyphosate and aminomethylphosphonic acid in human urine by ion chromatography-tandem mass spectrometry[J]. Modern Preventive Medicine, 2026 , 53 (6) : 1106 -1112 . DOI: 10.20043/j.cnki.MPM.202509447
正文
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草甘膦 [glyphosate，N-（膦羧甲基）甘氨酸]，是全球使用最广、产量最大的非选择性有机磷除草剂。氨甲基膦酸（aminomethylphosphonic acid，AMPA）是草甘膦的主要降解产物，是其持续污染的体现[1]。由于大量、长期使用，草甘膦及其代谢产物在土壤、水体及植物中普遍残留，可通过膳食暴露和职业暴露等途径进入人体[2]。2015年，世界卫生组织国际癌症研究机构（IARC）经过评估，将草甘膦划为2A类致癌物，即“Probably carcinogenic to humans”[3]，引发全球对其健康风险的广泛关注和深入研究[1,2,4]。国内已制定草甘膦的生物监测指标（尿液）和职业接触生物限值（0.6 mg/L）[5]，但尚未有标准检验检测方法。我国为农业大国，也是全球最大的草甘膦生产国和供应国，工业和农业职业因素接触草甘膦的人群数量十分庞大[6]。因此，建立一种简单高效、稳定准确的人尿中草甘膦和氨甲基膦酸的检测方法，对于开展职业人群生物监测和流行病学研究至关重要。
草甘膦和氨甲基膦酸由于极性强、缺乏发色团等原因，对其的检测面临挑战。传统方法存在方法前处理繁琐复杂、稳定性差等问题[6-11]，气相色谱或质谱法须先衍生化降低极性后才能测定[6]；常规反相液相色谱分析几乎无保留，需使用柱前衍生法降低极性提高保留同时增加发色团[8]；液相色谱质谱法既要解决保留问题，又要考虑高浓度缓冲盐水相对质谱耐受性的影响，分离保留效果较差，且易受干扰[9-11]。离子色谱（ion chromatography, IC）是分析无机阴离子和小分子极性有机阴离子的首选方法[12]，是生活饮用水中草甘膦和氨甲基膦酸的标准检验检测方法[7]，然而在面对如食品、尿液等复杂基质样品时，离子色谱常用的电导和安培检测器存在灵敏度不足、抗干扰能力差等问题。分析小分子极性和离子型化合物时，离子色谱与质谱检测器的串联使用，可充分发挥离子色谱的分离和质谱检测器特异性强、高灵敏度的优势，实现复杂样本中目标物的准确定量[13-16]。本试验建立了一种基于离子色谱-串联质谱（IC-MS/MS）的分析方法，同时测定人尿中的草甘膦和氨甲基膦酸，并应用于职业接触人群尿样的分析。
1　材料与方法
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1.1　仪器、试剂和材料
AQUIONRFIC离子色谱仪（带淋洗液自动发生器EGC），ASRS 2 mm阴离子抑制器，AS-DV自动进样器（外接水模式），Ionpac AS20型阴离子分析柱（250 mm×2 mm），Ionpac AG20保护柱（50 mm×2 mm），ST 16R高速冷冻离心机，均为美国赛默飞公司生产；AB-SCIEX API 3200MD三重四级杆质谱仪（AB SCIEX，美国）；Milli-Q 7000纯水仪（Millipore，美国）；固相萃取装置（12位，SUPELCO，美国）；Vortex-Genie 2涡旋振荡器（SI，美国）。
草甘膦、氨甲基膦酸，浓度均为100 mg/L（坛墨质检，中国常州）；HLB固相萃取柱、C18固相萃取柱（60 mg/3cc，Waters，美国）、草甘膦专用柱（3 ml，逗点生物，中国深圳）；微孔滤膜：尼龙（Nylon）、聚四氟乙烯（PTFE）、聚醚砜（PES）滤膜均为13 mm×0.22 μm（津腾，中国天津）。纯水满足实验用水要求，待测物草甘膦和氨甲基膦酸检测结果低于方法检出限[17]。
1.2　方法
1.2.1　样品采集和保存
样本来自于某草甘膦生产工厂职业人群。参考GBZ2.1—2019《工作场所有害因素职业接触限值 第1部分：化学有害因素》中生物监测指标及采样时间要求[5]，收集接触人群工作班末的中段尿液（≥50 ml）[17]，冷链运输，-80 ℃保存。
1.2.2　色谱条件
氢氧化钾淋洗溶液由EGC自动在线产生，流速0.25 ml/min，柱温30 ℃，池温35 ℃，抑制器电流25 mA；进样量25 μl。梯度淋洗程序：氢氧化钾溶液初始浓度5 mmol/L保持24 min，24~25 min逐渐升至30 mmol/L，保持9 min，34 min返回初始浓度，保持1 min。
1.2.3　质谱条件
电喷雾离子源负离子模式（ESI-）；多反应监测（MRM）模式；离子源温度600 ℃；喷雾电压 -4500 V；气帘气压力207 kPa，雾化气压力（Gas 1）414 kPa，辅助气压力（Gas 2）414 kPa，离子对、去簇电压（DP）和碰撞能量（CE）等参数见表1。
1.2.4　样品的预处理
尿样于4 ℃解冻后平衡至室温，涡旋混匀。HLB小柱先后用甲醇3 ml和水3 ml活化，取3 ml尿样过柱净化，收集全部流出液，稀释4倍后，过0.22 μm PTFE膜后测定。
1.2.5　标准溶液的配制
准确吸取500 μl草甘膦和1 000 μl氨甲基膦酸的标准溶液（100 mg/L）于10 ml聚四氟乙烯容量瓶中，用纯水稀释至刻度，配制成草甘膦（5.00 mg/L）和氨甲基膦酸（10.0 mg/L）的混合标准液，4 ℃保存7天。
1.2.6　基质匹配标准溶液的配制
空白尿样同样品预处理后，为基质空白溶液，待用。准确吸取500 μl草甘膦和1 000 μl氨甲基膦酸的标准溶液（100 mg/L）于10 ml聚四氟乙烯容量瓶中，用基质空白溶液稀释至刻度，配制成草甘膦（5.00 mg/L）和氨甲基膦酸（10.0 mg/L）的基质混合标准液，4 ℃保存7天。
1.2.7　质控措施
参考GBZ/T 295—2017《职业人群生物监测方法 总则》，制定检测质量控制程序[17]。每批次样品进行空白、加标和10%平行试验。每进行20个样品的检测后，进行加标检测，加标回收率不超出70%~120%；否则应重新测定上一批次加标样后的尿样。
2　结果与讨论
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2.1　质谱条件的优化
1 mg/L草甘膦和氨甲基膦酸的标准溶液分别进样，在ESI-模式下Q1全扫描出[M-H]-离子，确定母离子，并对母离子进行二级质谱碎片离子扫描，得到子离子，根据特异性强、响应高和基线噪声小等原则，选取2个相对丰度强且稳定的子离子，确定草甘膦和氨甲基膦酸的定量离子对和定性离子对。MRM模式下，优化选定离子对的DP电压和CE电压，确定试验的最优质谱条件（表1）。
2.2　色谱条件的优化
离子色谱柱的分离效能取决于其固定相的键合相结构、柱容量以及亲水特性[12]。草甘膦在常见阴离子色谱柱上强保留[18]，试验选择高容量、弱保留的Ionpac AS20阴离子分析柱。本试验条件下淋洗液为氢氧化钾溶液，在保持仪器默认参数（流速0.25 ml/min，柱温30 ℃，池温35 ℃）不变情况下等度淋洗60 min，考察不同浓度氢氧化钾淋洗液（5、6、8、10、12、16、20、30、40 mmol/L）对标准溶液（草甘膦25 μg/L，氨甲基膦酸50 μg/L）中草甘膦和氨甲基膦酸的影响。结果显示，氨甲基膦酸随着淋洗液浓度变大，保留时间逐渐变小，峰面积变化不大。当氢氧化钾浓度低于12 mmol/L时，草甘膦在60 min内未出峰，在AS20阴离子色谱柱上保留；当氢氧化钾浓度高于16 mmol/L，随着淋洗液浓度的增加，草甘膦保留时间逐渐变短，峰形更加尖锐但峰面积变化不大（图1）。
为兼顾方法简便、分析效率和分离度，试验16 mmol/L氢氧化钾溶液等度淋洗空白加标尿样（草甘膦25 μg/L，氨甲基膦酸50 μg/L），结果检出草甘膦，氨甲基膦酸几乎无响应。又考察了不同浓度（5、6、8、10、12、16 mmol/L氢氧化钾溶液）淋洗液对空白加标尿样（氨甲基膦酸50 μg/L）中目标化合物出峰的影响（图2）。随着淋洗液浓度增加，氨甲基膦酸保留时间变短，与尿液中内源性盐类分离不完全，基质效应抑制了氨甲基膦酸的响应[19]。氢氧化钾淋洗液浓度较低时草甘膦在色谱柱上强保留，氢氧化钾淋洗液浓度高时又会导致尿液中氨甲基膦酸的响应低。试验采用梯度洗脱，可以实现尿液中草甘膦和氨甲基膦酸有效分离和分析。
2.3　样品前处理条件优化
尿液基质复杂，含有多种无机盐类、蛋白质等，蛋白质等大分子易造成离子色谱系统堵塞[20]，内源性盐类会引起基质效应[19]。
2.3.1　固相萃取小柱的选择
草甘膦和氨甲基膦酸的极性强，非极性吸附剂（如C18，HLB）的固相萃取小柱对目标物基本不吸附[21]，空白尿样加标（草甘膦25 μg/L，氨甲基膦酸50 μg/L），分别经C18、草甘膦专用柱和HLB固相萃取柱净化，C18、草甘膦专用柱过柱净化方法与HLB一致。结果发现，尿液净化前为淡黄色，离心后有沉渣，经三种固相萃取小柱净化后，尿样均透明澄清，离心无沉渣。比较过柱前后目标物的响应（图3），草甘膦的峰面积，过柱前与过HLB和C18柱后的峰面积统计学无显著性差异；氨甲基膦酸的峰面积，过3种固相萃取柱后统计学无显著性差异，比过柱前增加，说明过柱降低了基质效应。草甘膦和氨甲基膦酸在这3种小柱上几乎不保留。考虑到尿液pH波动范围大，试验选择HLB这种pH稳定性更广（pH 0-14）、使用更加方便和通用的固相萃取小柱。
2.3.2　稀释倍数的优化
尿液经HLB固相萃取柱净化后，草甘膦和氨甲基膦酸响应依然较标准溶液中低很多，由于HLB基本不保留草甘膦和氨甲基膦酸，考虑方法存在基质干扰。直接稀释法是生物样本中常见的消除基质干扰方法，取不同稀释倍数的空白基质加标，同时配制相同浓度的纯水标准溶液，比较两者在质谱中的响应（图4），评价基质效应（ME）。ME=（A/B-1）×100%（n=3），A为空白基质的加标溶液的响应值，B为相同浓度标准溶液的响应，ME>0为基质增强，ME<0为基质抑制，|ME|≤20%可认为基质效应不显著[22]。实验结果显示，试验方法中尿液基质会抑制草甘膦和氨甲基膦酸的响应，稀释可以降低尿液基质对目标物响应的抑制作用，当稀释倍数大于3，草甘膦和氨甲基膦酸|ME|≤20%。由于稀释倍数越大，方法的灵敏度越低，本试验综合考虑采用4倍稀释。
2.3.3　滤膜的选择
试验比较了PES、PTFE、Nylon滤膜对草甘膦和氨甲基膦酸的吸附情况。结果显示，3种滤膜均不吸附草甘膦和氨甲基膦酸，与参考文献一致[18]，试验选择常用的PTFE滤膜。
2.4　标准曲线和检出限
虽然尿液经净化稀释等前处理，降低了基质效应，试验中草甘膦在尿液和标准溶液中保留时间一致，但氨甲基膦酸在尿液中的保留时间仍然比标准溶液中短，推测尿液中高浓度基体离子的存在影响了氨甲基膦酸的保留[12]，因此本方法采用基质曲线外标法定量。配制成草甘膦（0.20、0.50、1.00、2.00、5.00、10.0、20.0、50.0、100.0 μg/L）和氨甲基膦酸（0.40、1.00、2.00、4.00、10.0、20.0、40.0、100.0、200.0 μg/L）的基质混合标准溶液，按本法依次分别测定3次，得到不同浓度草甘膦和氨甲基膦酸的离子流图。以质量浓度为横坐标，定量离子峰面积的平均值为纵坐标，绘制基质标准曲线。以最低浓度点相对偏差的绝对值不大于30%为标准，确定标准曲线最低点，由于高浓度草甘膦（100.0 μg/L）、氨甲基膦酸（200.0 μg/L）响应出现下降趋势，确定方法线性范围见表2。
参照GBZ/T 295—2017《职业人群生物监测方法 总则》[17]，以接近空白尿液样本，按本法连续测定8次，以测定值3倍标准偏差计算检出限，两种化合物的检出限乘以稀释倍数得到方法检出限，结果见表2。
2.5　精密度和回收试验
对空白尿样进行低、中、高3个不同浓度水平的加标回收试验，各测定6次，结果见表3。草甘膦和氨甲基膦酸的平均回收率在83.0%~115.2%之间。对上述尿液样本进行日内精密度和日间精密度的考察[16]，日内精密度为1.2%~7.8%，日间精密度为3.5%~9.2%。方法的最低检测浓度小于0.1倍的草甘膦职业接触限值0.6 mg/L[5]，相关系数大于0.995 0，回收率在75%～125%范围内，精密度（RSD）≤10%，说明方法的灵敏度、准确性和稳定性能满足职业人群生物监测方法要求[17]。
2.6　样品分析
按本法对某草甘膦生产工厂职业人群90份尿样进行测定。草甘膦的职业接触生物限值为0.6 mg/L，氨甲基膦酸尚未有职业接触生物限值[5]。结果表明，草甘膦检出率为65.6%，超标率为5.6%，检出值范围为1.20~816 μg/L；氨甲基膦酸检出率为3.3%，检出值范围4.60~48.0 μg/L，说明草甘膦的职业人群暴露是广泛存在的，且存在一定的健康风险。图5为某一典型尿样的总离子流图。
2.7　方法比较
将本试验与已报道的文献方法进行比较，结果如表4所示，2种目标物的方法检出限处于较优或相当水平。与此同时，本试验仅在前处理过程使用少量甲醇，离子色谱以水为溶剂，淋洗液自动在线产生，产生的废液为清洁水，对实验人员健康危害小、环境污染低[18]。
3　结论
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本法基于IC-MS/MS，前处理快捷简单，仅需过HLB固相萃取柱和稀释，可实现快速分析尿液中草甘膦及其代谢产物氨甲基膦酸，同时具备较高的灵敏度、准确度和精密度。试验发现高浓度淋洗液会抑制尿液中氨甲基膦酸的响应，样品基质和稀释倍数也会影响氨甲基膦酸测定的保留时间和响应。方法满足生物监测的需求，可为科学评估草甘膦的人体暴露水平及其健康风险提供可靠的技术支撑。

文献
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参考文献 引证文献
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2026年第53卷第6期
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doi: 10.20043/j.cnki.MPM.202509447
  • 接收时间：2025-09-25
  • 首发时间：2026-11-02
  • 出版时间：2026-03-25
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  • 收稿日期：2025-09-25
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    1.江苏医药职业学院，江苏 盐城 224005
    2.盐城市疾病预防控制中心
    3.江苏省疾病预防控制中心

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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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