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Article(id=1241034444690215035, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1241034441380917539, articleNumber=null, orderNo=null, doi=10.20043/j.cnki.MPM.202502208, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1739289600000, receivedDateStr=2025-02-12, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1773815268919, onlineDateStr=2026-03-18, pubDate=1749484800000, pubDateStr=2025-06-10, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773815268919, onlineIssueDateStr=2026-03-18, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773815268919, creator=13701087609, updateTime=1773815268919, updator=13701087609, issue=Issue{id=1241034441380917539, tenantId=1146029695717560320, journalId=1227665162245664772, year='2025', volume='52', issue='11', pageStart='1921', pageEnd='2112', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773815268130, creator=13701087609, updateTime=1773815340947, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241034746873049765, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1241034441380917539, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241034746873049766, tenantId=1146029695717560320, journalId=1227665162245664772, issueId=1241034441380917539, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=1963, endPage=1968, ext={EN=ArticleExt(id=1241034445017370756, articleId=1241034444690215035, tenantId=1146029695717560320, journalId=1227665162245664772, language=EN, title=Distribution characteristics and health risk assessment of endocrine disruptors in drinking water in the Henan section of the Yellow River Basin, columnId=1228016570660745413, journalTitle=Modern Preventive Medicine, columnName=Environmental and Occupational Health, runingTitle=null, highlight=null, articleAbstract=
Objective

To investigate the distribution characteristics of three endocrine disruptors (EDCs)—nonylphenol (NP),octyl phenol (OP), and bisphenol A (BPA)—in drinking water in the Henan section of the Yellow River Basin and to conduct a health risk assessment.

Methods

In October 2023, water samples were collected from 32 urban and rural water plants in the Henan section of the Yellow River Basin, with each plant providing one sample each of source water, treated water, and tap water, totaling 96 samples. The concentrations of EDCs were determined using solid-phase extraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS), and potential health risks were assessed using the risk entropy method.

Results

All three EDCs were detected in the drinking water of the Henan section of the Yellow River Basin, with overall concentrations ranging from Not Detected (ND) to 234.00 ng/L. The detection rates for NP and OP were 100%, while BPA had a detection rate of 36.46%. Among the average values of the three EDCs, NP was found to be greater than OP, which was greater than BPA across different water sample types. Specifically, the average concentration of EDCs followed the order: source water > tap water > treated water. EDCs were commonly found in drinking water across various cities, with NP exhibiting the highest average concentration. Compared to relevant domestic and international studies, the level of EDC contamination in drinking water in this region was considered to be moderate to low. The health risk assessment indicated that the non-carcinogenic health risk values for adults and children ranged from 1.07×10-5 to 9.34×10-5, both of which were well below 1, with children’s risks being higher than those for adults.

Conclusion

EDC contamination is prevalent in drinking water in the Henan section of the Yellow River Basin, with low concentration levels and acceptable health risk levels for the population.

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目的

了解黄河流域河南段饮用水中壬基酚、辛基酚和双酚A三种内分泌干扰物(endocrine disrupting chemicals，EDCs)的分布特征，并进行健康风险评估。

方法

2023年10月，选取黄河流域河南段32个城乡水厂进行采样，每个水厂分别采集水源水、出厂水和末梢水各1份，共计96份。采用固相萃取-超高效液相色谱串联质谱法(SPE-UPLC-MS/MS)测定EDCs的含量，并采用风险熵值法评估其对人体的潜在风险。

结果

黄河流域河南段饮用水中三种EDCs均有检出，总体浓度为未检出(not detected，ND)～234.00 ng/L，壬基酚和辛基酚总体检出率为100%，双酚A总体检出率为36.46%。从三种EDCs平均值看，不同水样类型中均为壬基酚>辛基酚>双酚A。从单一EDCs平均值来看，水源水>末梢水>出厂水。不同城市饮用水中EDCs普遍存在，检出浓度平均值最高是壬基酚。与国内外相关研究结果比较，黄河流域河南段饮用水中EDCs处于中低等污染水平。健康风险评估结果显示，成人和儿童非致癌健康风险值为1.07×10-5～9.34×10-5，均远小于1，儿童风险高于成人。

结论

黄河流域河南段饮用水普遍存在EDCs污染，浓度水平较低，人群健康风险处于可接受水平。

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卞战强，E-mail:
, copyrightStatement=本刊刊出的所有文章不代表中华预防医学会和本刊编委会的观点，除非特别声明。, copyrightOwner=中华预防医学会和四川大学华西公共卫生学院, extLink=null, articleAbsUrl=null, sourceXml=ii+YR+apqlUhlujt0SLQeQ==, magXml=7+1l66emMzHbzX4e5k8QVA==, pdfUrl=null, pdf=sOwvDXtawyNFfn/WyNFHsg==, pdfFileSize=612611, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=o/vL4k8GZmEafHwsldLHkQ==, mapNumber=null, authorCompany=null, fund=null, authors=

卞战强（1981-），男，硕士，副研究员，研究方向：环境卫生学和分析化学

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Chemosphere, 2009, 77(4): 559-565., articleTitle=Behavior and fate of alkyIphenols in surface water of the Jialu River, Henan Province,China, refAbstract=null)], funds=[Fund(id=1241050840794985462, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, awardId=LHGJ20240621, language=CN, fundingSource=河南省医学科技攻关计划项目(LHGJ20240621), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1241050831248749073, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, xref=1., ext=[AuthorCompanyExt(id=1241050831252943379, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, companyId=1241050831248749073, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Rural Drinking Water Monitoring Office, National Center for Rural Water Supply Technical Guidance, Chinese Center for Disease Control and Prevention, Beijing 102200,China), AuthorCompanyExt(id=1241050831265526293, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, companyId=1241050831248749073, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1.中国疾病预防控制中心农村改水技术指导中心农村饮水监测室，北京 102200)]), AuthorCompany(id=1241050831605264928, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, xref=2., ext=[AuthorCompanyExt(id=1241050831613653539, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, companyId=1241050831605264928, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2.河南省疾病预防控制中心卫生检测检验中心理化室)])], figs=[ArticleFig(id=1241050838190322580, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=EN, label=Table 1, caption=

The BW and IR values of human in Henan Province

, figureFileSmall=null, figureFileBig=null, tableContent=
项目男性女性
儿童成人儿童成人
饮水摄入量 (L/d)0.8541.5350.7841.220
体重 (kg)28.368.425.360.1
), ArticleFig(id=1241050838429397914, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=CN, label=表1, caption=

河南省人群的体重和饮水摄入量取值

, figureFileSmall=null, figureFileBig=null, tableContent=
项目男性女性
儿童成人儿童成人
饮水摄入量 (L/d)0.8541.5350.7841.220
体重 (kg)28.368.425.360.1
), ArticleFig(id=1241050838551032741, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=EN, label=Table 2, caption=

The concentration levels of EDCs in different water sample types

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物水样类型样本数量检出情况[n(%)]检出浓度(ng/L)
平均值最小值中位值最大值
壬基酚水源水3232(100.00)82.638.6282.96234.00
出厂水3232(100.00)65.866.8657.40170.87
末梢水3232(100.00)76.997.7483.76210.00
合计9696(100.00)75.166.8679.52234.00
辛基酚水源水3232(100.00)18.270.5411.5759.20
出厂水3232(100.00)14.621.608.5649.20
末梢水3232(100.00)16.851.2411.9045.20
合计9696(100.00)16.560.5411.2759.20
双酚 A水源水3215(46.88)8.15NDND191.20
出厂水329(28.13)1.07NDND7.52
末梢水3211(34.38)2.06NDND26.40
合计9635(36.46)3.76NDND191.20
), ArticleFig(id=1241050838706222001, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=CN, label=表2, caption=

不同水样类型中EDCs浓度水平

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物水样类型样本数量检出情况[n(%)]检出浓度(ng/L)
平均值最小值中位值最大值
壬基酚水源水3232(100.00)82.638.6282.96234.00
出厂水3232(100.00)65.866.8657.40170.87
末梢水3232(100.00)76.997.7483.76210.00
合计9696(100.00)75.166.8679.52234.00
辛基酚水源水3232(100.00)18.270.5411.5759.20
出厂水3232(100.00)14.621.608.5649.20
末梢水3232(100.00)16.851.2411.9045.20
合计9696(100.00)16.560.5411.2759.20
双酚 A水源水3215(46.88)8.15NDND191.20
出厂水329(28.13)1.07NDND7.52
末梢水3211(34.38)2.06NDND26.40
合计9635(36.46)3.76NDND191.20
), ArticleFig(id=1241050838890771386, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=EN, label=Table 3, caption=

The concentration levels of EDCs in drinking water in different cities

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物城市样本数量检出情况[n(%)]检出浓度(ng/L)
平均值最小值中位值最大值
壬基酚三门峡1212(100.00)116.0884.38117.57144.53
洛阳1212(100.00)48.1312.0628.80210.00
济源1212(100.00)109.5578.43109.84170.87
郑州1212(100.00)95.0676.9396.85112.60
焦作1212(100.00)32.566.8613.4987.20
新乡1212(100.00)70.129.9823.50176.20
开封1212(100.00)41.1714.8229.40102.80
濮阳1212(100.00)88.6019.7682.50234.00
合计9696(100.00)75.166.8679.53234.00
辛基酚三门峡1212(100.00)10.727.6311.2012.06
洛阳1212(100.00)6.460.544.4524.00
济源1212(100.00)33.4824.8030.6059.20
郑州1212(100.00)29.3215.0823.8049.20
焦作1212(100.00)7.193.725.7018.02
新乡1212(100.00)14.911.246.1237.80
开封1212(100.00)11.593.808.9332.80
濮阳1212(100.00)18.991.999.2646.20
合计9696(100.00)16.580.5411.2359.2
双酚 A三门峡124(33.33)1.58NDND7.52
洛阳123(25.00)0.94NDND5.09
济源123(25.00)18.00NDND191.2
郑州12NDNDNDNDND
焦作123(25.00)2.06NDND8.60
新乡125(41.67)0.88NDND2.44
开封128(66.67)2.05ND2.105.66
濮阳129(75.00)4.36ND1.8126.40
合计9635(36.46)3.76NDND191.20
), ArticleFig(id=1241050839243092933, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=CN, label=表3, caption=

不同城市饮用水中EDCs的浓度水平

, figureFileSmall=null, figureFileBig=null, tableContent=
化合物城市样本数量检出情况[n(%)]检出浓度(ng/L)
平均值最小值中位值最大值
壬基酚三门峡1212(100.00)116.0884.38117.57144.53
洛阳1212(100.00)48.1312.0628.80210.00
济源1212(100.00)109.5578.43109.84170.87
郑州1212(100.00)95.0676.9396.85112.60
焦作1212(100.00)32.566.8613.4987.20
新乡1212(100.00)70.129.9823.50176.20
开封1212(100.00)41.1714.8229.40102.80
濮阳1212(100.00)88.6019.7682.50234.00
合计9696(100.00)75.166.8679.53234.00
辛基酚三门峡1212(100.00)10.727.6311.2012.06
洛阳1212(100.00)6.460.544.4524.00
济源1212(100.00)33.4824.8030.6059.20
郑州1212(100.00)29.3215.0823.8049.20
焦作1212(100.00)7.193.725.7018.02
新乡1212(100.00)14.911.246.1237.80
开封1212(100.00)11.593.808.9332.80
濮阳1212(100.00)18.991.999.2646.20
合计9696(100.00)16.580.5411.2359.2
双酚 A三门峡124(33.33)1.58NDND7.52
洛阳123(25.00)0.94NDND5.09
济源123(25.00)18.00NDND191.2
郑州12NDNDNDNDND
焦作123(25.00)2.06NDND8.60
新乡125(41.67)0.88NDND2.44
开封128(66.67)2.05ND2.105.66
濮阳129(75.00)4.36ND1.8126.40
合计9635(36.46)3.76NDND191.20
), ArticleFig(id=1241050839708660680, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=EN, label=Table 4, caption=

Comparison of EDCs concentration in water between domestic and abroad

, figureFileSmall=null, figureFileBig=null, tableContent=
采样点 Sampling sites壬基酚辛基酚双酚 A
珠江三角洲河流水源地[3]15.2～2 270ND～1211.19～177
无锡-常州地下水[12]ND～0.29ND～0.400.02～72.09
黄浦江上游水源地[6]ND～19.45ND26.00～64.32
重庆长江流域地表水[21]ND～10 749.691.18～343.3713.10 ～1 134.86
法国水源地[22]100～60517～13025～1 430
马来西亚饮用水[23]NDND～0.440.06～66.4
塞尔维亚饮用水[24]1.2～7.90.4～3.72.5～35.6
黄河流域河南段饮用水6.86～234.000.54～59.2ND～191.20
), ArticleFig(id=1241050840220365783, tenantId=1146029695717560320, journalId=1227665162245664772, articleId=1241034444690215035, language=CN, label=表4, caption=

国内外水中EDCs的浓度比较(ng/L)

, figureFileSmall=null, figureFileBig=null, tableContent=
采样点 Sampling sites壬基酚辛基酚双酚 A
珠江三角洲河流水源地[3]15.2～2 270ND～1211.19～177
无锡-常州地下水[12]ND～0.29ND～0.400.02～72.09
黄浦江上游水源地[6]ND～19.45ND26.00～64.32
重庆长江流域地表水[21]ND～10 749.691.18～343.3713.10 ～1 134.86
法国水源地[22]100～60517～13025～1 430
马来西亚饮用水[23]NDND～0.440.06～66.4
塞尔维亚饮用水[24]1.2～7.90.4～3.72.5～35.6
黄河流域河南段饮用水6.86～234.000.54～59.2ND～191.20
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The non-carcinogenic risk of EDCs in drinking water in Henan section of Yellow River

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人群性别壬基酚辛基酚双酚 A
HQ值HQ值HQ值
儿童男4.22×10-59.09×10-51.59×10-5
女4.34×10-59.34×10-51.64×10-5
成人男3.14×10-56.76×10-51.18×10-5
女2.84×10-56.12×10-51.07×10-5
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黄河流域河南段饮用水中EDCs的非致癌风险

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人群性别壬基酚辛基酚双酚 A
HQ值HQ值HQ值
儿童男4.22×10-59.09×10-51.59×10-5
女4.34×10-59.34×10-51.64×10-5
成人男3.14×10-56.76×10-51.18×10-5
女2.84×10-56.12×10-51.07×10-5
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黄河流域河南段饮用水中内分泌干扰物的分布特征及健康风险评估
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卞战强 1 , 于建 1 , 夏云婷 1 , 苏永恒 2 , 王谢 2 , 马青青 2
现代预防医学 | 环境与职业卫生 2025,52(11): 1963-1968
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现代预防医学 | 环境与职业卫生 2025, 52(11): 1963-1968
黄河流域河南段饮用水中内分泌干扰物的分布特征及健康风险评估
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卞战强1 , 于建1, 夏云婷1, 苏永恒2, 王谢2, 马青青2
作者信息
  • 1.中国疾病预防控制中心农村改水技术指导中心农村饮水监测室，北京 102200
  • 2.河南省疾病预防控制中心卫生检测检验中心理化室

    • 卞战强（1981-），男，硕士，副研究员，研究方向：环境卫生学和分析化学

通讯作者:

卞战强，E-mail:
Distribution characteristics and health risk assessment of endocrine disruptors in drinking water in the Henan section of the Yellow River Basin
Zhan-qiang BIAN1 , Jian YU1, Yun-ting XIA1, Yong-heng SU2, Xie WANG2, Qing-qing MA2
Affiliations
  • Rural Drinking Water Monitoring Office, National Center for Rural Water Supply Technical Guidance, Chinese Center for Disease Control and Prevention, Beijing 102200,China
出版时间: 2025-06-10 doi: 10.20043/j.cnki.MPM.202502208
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摘要
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目的

了解黄河流域河南段饮用水中壬基酚、辛基酚和双酚A三种内分泌干扰物(endocrine disrupting chemicals，EDCs)的分布特征，并进行健康风险评估。

方法

2023年10月，选取黄河流域河南段32个城乡水厂进行采样，每个水厂分别采集水源水、出厂水和末梢水各1份，共计96份。采用固相萃取-超高效液相色谱串联质谱法(SPE-UPLC-MS/MS)测定EDCs的含量，并采用风险熵值法评估其对人体的潜在风险。

结果

黄河流域河南段饮用水中三种EDCs均有检出，总体浓度为未检出(not detected，ND)～234.00 ng/L，壬基酚和辛基酚总体检出率为100%，双酚A总体检出率为36.46%。从三种EDCs平均值看，不同水样类型中均为壬基酚>辛基酚>双酚A。从单一EDCs平均值来看，水源水>末梢水>出厂水。不同城市饮用水中EDCs普遍存在，检出浓度平均值最高是壬基酚。与国内外相关研究结果比较，黄河流域河南段饮用水中EDCs处于中低等污染水平。健康风险评估结果显示，成人和儿童非致癌健康风险值为1.07×10-5～9.34×10-5，均远小于1，儿童风险高于成人。

结论

黄河流域河南段饮用水普遍存在EDCs污染，浓度水平较低，人群健康风险处于可接受水平。

内分泌干扰物  /  饮用水  /  分布特征  /  健康风险
Objective

To investigate the distribution characteristics of three endocrine disruptors (EDCs)—nonylphenol (NP),octyl phenol (OP), and bisphenol A (BPA)—in drinking water in the Henan section of the Yellow River Basin and to conduct a health risk assessment.

Methods

In October 2023, water samples were collected from 32 urban and rural water plants in the Henan section of the Yellow River Basin, with each plant providing one sample each of source water, treated water, and tap water, totaling 96 samples. The concentrations of EDCs were determined using solid-phase extraction coupled with ultra-high-performance liquid chromatography-tandem mass spectrometry (SPE-UPLC-MS/MS), and potential health risks were assessed using the risk entropy method.

Results

All three EDCs were detected in the drinking water of the Henan section of the Yellow River Basin, with overall concentrations ranging from Not Detected (ND) to 234.00 ng/L. The detection rates for NP and OP were 100%, while BPA had a detection rate of 36.46%. Among the average values of the three EDCs, NP was found to be greater than OP, which was greater than BPA across different water sample types. Specifically, the average concentration of EDCs followed the order: source water > tap water > treated water. EDCs were commonly found in drinking water across various cities, with NP exhibiting the highest average concentration. Compared to relevant domestic and international studies, the level of EDC contamination in drinking water in this region was considered to be moderate to low. The health risk assessment indicated that the non-carcinogenic health risk values for adults and children ranged from 1.07×10-5 to 9.34×10-5, both of which were well below 1, with children’s risks being higher than those for adults.

Conclusion

EDC contamination is prevalent in drinking water in the Henan section of the Yellow River Basin, with low concentration levels and acceptable health risk levels for the population.

Endocrine disruptors  /  Drinking water  /  Distribution characteristics  /  Health risk
卞战强, 于建, 夏云婷, 苏永恒, 王谢, 马青青. 黄河流域河南段饮用水中内分泌干扰物的分布特征及健康风险评估. 现代预防医学, 2025 , 52 (11) : 1963 -1968 . DOI: 10.20043/j.cnki.MPM.202502208
Zhan-qiang BIAN, Jian YU, Yun-ting XIA, Yong-heng SU, Xie WANG, Qing-qing MA. Distribution characteristics and health risk assessment of endocrine disruptors in drinking water in the Henan section of the Yellow River Basin[J]. Modern Preventive Medicine, 2025 , 52 (11) : 1963 -1968 . DOI: 10.20043/j.cnki.MPM.202502208
正文
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内分泌干扰物(endocrine disrupting chemicals，EDCs)是指由于人类的生产、生活而释放到环境中的，影响人体和动物体内正常激素水平的外源性化学物质[1-2]。EEDs主要通过污水处理厂的出水、生活污水以及工业废水等途径直接排放进入到水环境中，对水生生态系统和人类健康构成了严重的威胁[3-4]。近年来，EDCs在国内外一些饮用水源地和自来水厂中均有检出的报道，含量一般在ng/L水平[5-7]。双酚A、壬基酚和辛基酚是内分泌干扰物中的典型代表[8]，它们不仅具有内分泌干扰性，还具有生物毒性。壬基酚和辛基酚已被联合国环境规划署列入持久性有毒污染物清单[9]，双酚A被我国生态环境部列入《第一批化学物质环境风险优先评估计划》[10]，因此，开展饮用水中三种EDCs的分布特征及健康风险评估研究具有积极的现实意义。
黄河作为我国第二大河流，不仅是主要的农业、工业用水来源，也是众多城市生活用水的重要水源，其河南段流经三门峡、洛阳、济源、郑州、焦作、新乡、开封和濮阳等地区，为这些城市提供了重要的水资源。随着城市的发展，环境污染问题日益凸显，特别是对饮用水的潜在污染[11]。为探究该流域河南段饮用水中EDCs的污染特征和健康风险，本研究选择该流域河南段城乡水厂为研究对象，采集水源水、出厂水及末梢水，检测饮用水中三种EDCs的含量，并评估其对人体健康的潜在风险，以期为黄河流域河南段EDCs的管理和防控提供科学依据和参考。
1　对象与方法
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1.1　仪器和试剂
超高效液相色谱串联质谱(美国Waters公司，ACQUITY UPLC TM BEH)；色谱柱(C18柱，100 mm × 2.1 mm，1.7 μm)；固相萃取柱(Agilent公司，HLB，500 mg，6 ml)；三种内分泌干扰物标准物质(德国Dr.Ehrenstorfer GmbH公司)；甲醇(美国Fisher公司，色谱纯)；抗坏血酸(国药集团上海化学试剂有限公司，分析纯)。
1.2　样品采集
2023年10月选取黄河流域河南段城乡水厂进行采样，三门峡、洛阳、济源、焦作、开封，每市选择2个以黄河流域为水源的水厂，再选择2个该流域附近以地下水为水源的水厂；郑州、新乡和濮阳由于缺少以黄河流域为水源的水厂，故每市选择4个在该流域附近以地下水为水源的水厂，共选取32个水厂，每个水厂分别采集水源水、出厂水和末梢水各1份，共计96份。水样采集于1 L螺口棕色玻璃瓶中，每升水样加入50 mg抗坏血酸，4 ℃下避光保存，并尽快进行前处理。
1.3　样品前处理和样品分析
取500 ml水样，用6 mol/L盐酸调节pH至3.0，加入内标物充分混匀；采用固相萃取装置配合HLB固相萃取柱进行萃取，用甲醇洗脱，收集洗脱液，40 ℃氮气吹至近干，用1ml 40%甲醇/水(v/v)溶液溶解定容；采用BEH C18色谱柱(100 mm × 2.1 mm，1.7 μm)对化合物进行分离，甲醇-水梯度洗脱，超高效液相色谱串联质谱(UPLC-MS/MS)法测定，内标法定性定量分析。该分析方法灵敏度较高，三种EDCs标准曲线相关系数≥0.995。分析过程中通过方法空白、样品平行和加标回收对实验进行质量控制，三种EDCs的方法检出限(LOQ)为0.19～0.57 ng/L；平行样品测定结果的相对标准差(relative stardard deviation，RSD)≤10%；抽取不少于10%的样品进行加标回收测定，平均加标回收率为97.0%～120.1%，RSD为2.51%～8.82%。
1.4　统计分析
采用Excel 2016进行数据整理，采用SPSS 23.0进行统计分析。当待测物质未检出时，以方法检出限的1/2进行统计计算。由于数据为非正态分布，采用Kruskal-Wallis H检验，检验水准α=0.05。
1.5　健康风险评估
本研究重点考虑饮用水摄入三种EDCs所导致的非致癌风险，采用美国环境保护署（EPA）推荐的非致癌评价风险模型[12-14]，以儿童和成人为受体人群，对研究区三种EDCs的健康风险进行评价。计算公式如下：
式中，HQ为非致癌风险值，当HQ≥1时认为会对人体产生健康危害，当HQ<1时表示风险较小；CDI为长期单位体重日摄入量［mg/(kg·d)］；RfD为目标物的非致癌参考剂量［mg/(kg·d)］。双酚A的RfD值为0.05，从美国EPA综合风险信息系统(IRIS)中查询[15]；壬基酚和辛基酚的ADI值分别为0.15、0.015，从澳大利亚水循环利用指南中查询[16]。
水中化学物质经口摄入途径的暴露量，使用公式（2）计算：
式中：C为饮用水中EDCs的浓度(mg/L)；IR为饮水摄入量(L/d)；EF为暴露频率(d/a)；ED为暴露持续时间(a)；BW是体重(kg)；AT是平均暴露时间(d)。EF、ED和AT取值参照文献[17-18]，EF取值为365 d/a，成人ED取30 a，AT取10 950 d；儿童ED取6 a，AT取2 190 d。河南省人群BW和IR采用《中国人群暴露参数手册》(成人卷和儿童卷)推荐值[19-20]。见表1。
2　结果
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2.1　EDCs在不同水样类型中检出情况
所采集的水样，pH值在6.82～8.4l之间，水温在16.0 ℃～26.0 ℃之间。三种EDCs在不同水样类型中的检出率和浓度见表2。黄河流域河南段饮用水中EDCs均有检出，壬基酚和辛基酚总体检出率为100%，双酚A总体检出率为36.46%；总体浓度为ND～234.00 ng/L。在水源水中，壬基酚检出率为100%，检出浓度为8.62～234.00 ng/L；辛基酚检出率为100%，检出浓度为0.54～59.20 ng/L；双酚A检出率为46.88%，检出浓度为ND～191.20 ng/L。在出厂水中，壬基酚检出率为100%，检出浓度为6.86～170.87 ng/L；辛基酚检出率为100%，检出浓度为14.62～49.20 ng/L；双酚A检出率为28.13，检出浓度为ND～7.52 ng/L。在末梢水中，壬基酚检出率为100%，检出浓度为7.74～210.00 ng/L；辛基酚检出率为100%，检出浓度为1.24～45.20 ng/L；双酚A检出率为34.38%，检出浓度为ND～26.40 ng/L。从壬基酚和辛基酚的检出率来看，这两种EDCs普遍存在于黄河流域河南段城市饮用水中。从三种EDCs平均值看，不同水样类型中均为壬基酚>辛基酚>双酚A。从单一EDCs平均值看，水源水>末梢水>出厂水。通过Kruskal-Wallis H 检验，三种EDCs在同水样类型中的浓度，差异有统计学意义(P<0.05)。单种EDC在不同水样类型中的浓度，差异无统计学意义(P>0.05)。
2.2　EDCs在不同城市中检出情况
黄河流域河南段不同城市饮用水中均有EDCs的检出，结果见表3。不同城市饮用水中壬基酚和辛基酚检出率均为100%，双酚A检出率为ND～75.00%；壬基酚检出浓度为6.86～234.00 ng/L，辛基酚检出浓度为0.54～59.2 ng/L，双酚A检出浓度为ND～191.20 ng/L，检出浓度平均值最高是的壬基酚，其次为辛基酚，双酚A最低。壬基酚浓度平均值最高点在三门峡，依次是济源和郑州，最大值在濮阳。辛基酚浓度平均值最高点在济源，依次是郑州和濮阳，最大值在济源；双酚A浓度平均值最高点在济源，依次是濮阳和焦作，最大值在济源。通过Kruskal-Wallis H检验，三种EDCs在不同城市饮用水中的浓度，差异有统计学意义(P<0.05)。
2.3　与国内外水体中EDCs的污染水平的对比
表4对比了国内外水体中三种EDCs的污染水平情况。从中可以看出，与国内外水体相比，本研究中壬基酚的浓度水平与法国水源地处于同一水平，低于我国珠江三角洲河流水源地及重庆长江流域地表水，高于马来西亚饮用水、塞尔维亚饮用水和我国无锡-常州地下水及黄浦江上游水源；辛基酚的浓度水平与法国水源地和我国珠江三角洲河流水源地及重庆长江流域地表水处于同一水平，高于马来西亚饮用水、塞尔维亚饮用水和我国无锡-常州地下水及黄浦江上游水源；双酚A的浓度水平与马来西亚饮用水、塞尔维亚饮用水和我国无锡-常州地下水、珠江三角洲河流水源地及黄浦江上游水源地处于同一水平，低于法国水源地和我国重庆长江流域地表水。总之，与国内外水体相比，本研究中三种EDCs的污染处于较低至中等水平。
2.4　健康风险评估
为了能够更好地评估黄河流域河南段饮用水中EDCs的人体健康风险水平，且考虑到末梢水会对人体健康产生直接影响，因此，选取了末梢水中三种EDCs最大值来评估人群的健康风险。由表5可知，三种EDCs对于成人和儿童的非致癌风险值HQ处于1.07×10-5～9.34×10-5之间，均远小于1，表明在研究区内饮用水中三种EDCs所致人体健康风险处于较低水平。儿童段女性HQ值高于男性，成人段男性HQ值高于女性，不同EDCs对人群的HQ值为辛基酚>壬基酚>双酚A，从整体看，儿童所受的非致癌风险高于成人。
3　讨论
收起
黄河流域河南段饮用水中EDCs均有检出，壬基酚和辛基酚总体检出率为100%，双酚A总体检出率为36.46%；壬基酚总体浓度为6.86～234.00 ng/L，辛基酚总体浓度为0.54～59.20 ng/L，双酚A总体浓度为ND～191.20 ng/L；饮用水双酚A最大值未超过《生活饮用水卫生标准》(GB 5749-2022)中规定限值0.01 mg/L的要求；壬基酚最大值未超过深圳城市生活饮用水卫生标准(DB4403/T 60-2020)中规定限值0.03 mg/L和美国EPA推荐淡水中壬基酚限值6.6 μg/L的要求。末梢水中三种EDCs平均值均高于出厂水，这可能是饮用水在输送的过程，所使用的塑料水管在和水长期接触过程中会从管材中逐渐溶出造成的[25-26]。
不同城市饮用水中壬基酚和辛基酚检出率均为100%，双酚A检出率为ND～75.00%；检出浓度平均值最高的是壬基酚，其次为辛基酚，双酚A最低。壬基酚最大值为濮阳某集体自建井的水源水，附近存在生活垃圾堆放现象。辛基酚和双酚A最大值均为济源某一水厂的水源水，该水厂周围存在多家工业园区和风景游览区，这可能是沿岸工业废水或生活污水经处理后排放到水环境中造成的[27]。
与国内外研究相比较，黄河流域河南段城市饮用水中三种EDCs处于中低等污染水平，健康风险评估结果显示，成人和儿童通过饮水途径引起的非致癌风险值都远低于规定值1，表明黄河流域河南段饮用水中三种EDCs的暴露水平目前处于可接受范围内。但长期持续低剂量暴露，也可能会在人体内逐渐蓄积，对人体健康造成潜在危害，需引起持续关注。
本研究存在一定的局限性。第一，监测数据是从具有代表性水厂收集的，只采集一次水样，缺乏连续监测结果，可能无法完全反映EDCs浓度的真实变化趋势，使得代表性存在局限，除此之外，暴露参数(暴露周期、性别等)、检测技术灵敏程度等，也可能会使健康风险评估结果具有不确定性。第二，本研究分析了三种EDCs，且只计算了单种EDCs的健康风险，而未考虑EDCs之间的联合作用以及在人体内的累积效应，存在低估健康风险的可能。第三，本研究仅从饮水途径分析了EDCs对人体的健康危害，未评估其他摄入途径的健康风险，如经皮肤暴露途径、经食物摄入途径等，可能低估了健康风险。
基金
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  • 河南省医学科技攻关计划项目(LHGJ20240621)
文献
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2025年第52卷第11期
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doi: 10.20043/j.cnki.MPM.202502208
  • 接收时间：2025-02-12
  • 首发时间：2026-03-18
  • 出版时间：2025-06-10
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  • 收稿日期：2025-02-12
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河南省医学科技攻关计划项目(LHGJ20240621)
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    1.中国疾病预防控制中心农村改水技术指导中心农村饮水监测室，北京 102200
    2.河南省疾病预防控制中心卫生检测检验中心理化室

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卞战强，E-mail:
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https://castjournals.cast.org.cn/joweb/xdyfyx/CN/10.20043/j.cnki.MPM.202502208
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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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