Article(id=1157042098550743973, tenantId=1146029695717560320, journalId=1146119944283992078, issueId=1157017136368541764, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=null, receivedDateStr=null, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1753789933096, onlineDateStr=2025-07-29, pubDate=1707321600000, pubDateStr=2024-02-08, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1753789933096, onlineIssueDateStr=2025-07-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1753789933096, creator=13701087609, updateTime=1753789933096, updator=13701087609, issue=Issue{id=1157017136368541764, tenantId=1146029695717560320, journalId=1146119944283992078, year='2024', volume='2', issue='2', pageStart='1', pageEnd='129', issueExtLink='null', onlineDate='null', pubDate='1707321600000', pubDateStr='2024-02-08', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1753783981649, creator='13701087609', updateTime=1784685058336, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1286625645979484234, tenantId=1146029695717560320, journalId=1146119944283992078, issueId=1157017136368541764, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1286625645979484235, tenantId=1146029695717560320, journalId=1146119944283992078, issueId=1157017136368541764, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=18, endPage=22, ext={EN=ArticleExt(id=1157042099372827560, articleId=1157042098550743973, tenantId=1146029695717560320, journalId=1146119944283992078, language=EN, title=Simultaneous determination of four kinds of haloacetic acids and chlorite in drinking water by ion chromatography with large volume injection, columnId=1156641065621906129, journalTitle=Laboratory Testing, columnName=Innovative Applications, runingTitle=null, highlight=null, articleAbstract=

Objective A method for simultaneous determination of MBAA, DBAA, DCAA, TCAA and ${\mathrm{{ClO}}}_{2}{}^{- }$ in drinking water was established by ion chromatography. Methods The water samples were determined by ${0.22\mu}\mathrm{m}$ qeuosystem filter membrane with a volume of ${500\mu }\mathrm{L}$ . The samples were rinsed with $\mathrm{{KOH}}$ solution gradient and separated by IonPac AS19 anion column. The column temperature was set at ${30}^{\circ }\mathrm{C}$ , and the current of the inhibitor was ${75}\mathrm{\;{mA}}$ . Results The results showed that the linearity ranges of ${\mathrm{{ClO}}}_{2}{}^{- }$ , MBAA, DBAA, DCAA and TCAA were found in the range of ${10}\sim {1000\mu}\mathrm{g}/\mathrm{L},\mathrm{r}> {0.9990}$ , with detection limits $\left({3\mathrm{\;S}/\mathrm{N}}\right)$ of ${0.32},{0.76},{1.30},{0.69},{1.58\mu}\mathrm{g}/\mathrm{L}$ . The standard recoveries were ${80}\%\sim {110}\%$ and RSD (n=6) of the determined values were all less than 5.0%. Conclusion The method was simple, sensitive, can meet the detection requirements of four kinds of Haloaeetic Acids and Chlorite in drinking water. The method can be used for the determination of kour kinds of haloaeetic acids and chlorite in drinking water.

, authors=null, authorsList=Yan YOU, Xian-Lin DING, Wei-Xin LI, authorCompany=null, correspAuthors=Yan YOU, authorNote=null, correspAuthorsNote=
*YOU Yan, Master, Chief Technician, Luqiao District Center for Disease Control and Prevention, Taizhou, 318050, China. E-mail:
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目的 建立了离子色谱法同时测定饮用水中一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸和亚氯酸盐的方法。方法 水样经 ${0.22\mu }\mathrm{m}$ 水系微孔滤膜后进样,进样体积为${500\mu}\mathrm{L}$ ,利用 $\mathrm{{KOH}}$ 溶液梯度淋洗, IonPac AS19阴离子色谱柱分离,柱温为 ${30}^{\circ }\mathrm{C}$ ,用电导检测器测定,抑制器电流为 ${75}\mathrm{\;{mA}}$ 。结果 亚氯酸盐、一溴乙酸、 二溴乙酸、二氯乙酸和三氯乙酸在 10-1000μ/L 范围内线性良好, r$>{0.9990}$ ,检出限 $\left({3\mathrm{S}/\mathrm{N}}\right)$ 分别为 0.32,0.76, ${1.30},{0.69},{1.58\mu}\mathrm{g}/\mathrm{L}$ ,加标回收率为 ${80}\%\sim {110}\%$ ,相对标准偏差均 $<{5.0}\%$ 。结论 方法操作简单,灵敏度高,可以满足饮用水中四种卤乙酸和亚氯酸盐的检测要求,本方法可以用于饮用水中四种卤乙酸和亚氯酸盐的检测。

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尤妍,硕士,主管技师,研究方向为检验检测。E-mail: zjyouyan@126.com。

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*尤妍,硕士,主管技师,研究方向为检验检测。E-mail:
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Mutagenesis , 1997 . 12 ( 5 ): 321 - 328 ., articleTitle=Comparative genotoxicity of halogenated acetic acids found in drinking water, refAbstract=null), Reference(id=1157042127160090919, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, doi=null, pmid=null, pmcid=null, year=2005, volume=15, issue=22, pageStart=172, pageEnd=174, url=null, language=null, rfNumber=[15], rfOrder=14, authorNames=郭强, journalName=科技情报开发与经济, refType=null, unstructuredReference=郭强 . 二氧化氯消毒机理及其消毒副产物的控制 [J]. 科技情报开发与经济 , 2005 . 15 ( 22 ): 172 - 174 ., articleTitle=二氧化氯消毒机理及其消毒副产物的控制, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1157042121191596222, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, xref=null, ext=[AuthorCompanyExt(id=1157042121199984831, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, companyId=1157042121191596222, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Luqiao District Center for Disease Control and Prevention Taizhou 318050 China), AuthorCompanyExt(id=1157042121757827276, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, companyId=1157042121191596222, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=台州市路桥区疾病预防控制中心 台州 318050)])], figs=[ArticleFig(id=1157042125360734477, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=EN, label=Fig. 1, caption=Chromatogram of ClO2-, MBAA, DCAA, DBAA, TCAA and common anions, figureFileSmall=18XeVyw7PdkBe8DhlFwgIA==, figureFileBig=PCe9u2TQtqRnU5jVg2WovA==, tableContent=null), ArticleFig(id=1157042125406871822, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=CN, label=图 1, caption=亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸和常见阴离子的色谱图

1: $\mathrm{F}\left({{50\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 2: ${\mathrm{{ClO}}}_{2}\left({{100\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 3: $\mathrm{{MBAA}}\left({{100\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 4: $\mathrm{{Cl}}\left({{50\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 5: $\mathrm{{DCAA}}\left({{100\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 6: $\mathrm{{DBAA}}\left({{100\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 7: ${\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }\left({{50\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 8: $\mathrm{{TCAA}}\left({{100\mu }\mathrm{g}/\mathrm{L}}\right)$ ; 9: ${\mathrm{{SO}}}_{4}{}^{2 -}\left({{50\mu }\mathrm{g}/\mathrm{L}}\right)$

, figureFileSmall=18XeVyw7PdkBe8DhlFwgIA==, figureFileBig=PCe9u2TQtqRnU5jVg2WovA==, tableContent=null), ArticleFig(id=1157042125499146511, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=EN, label=Table 1, caption=Program of gradient eluent, figureFileSmall=null, figureFileBig=null, tableContent=
时间(min) 0 5 40 40.1 50
KOH 淋洗液浓度(mmol/L) 4 4 30 4 4
), ArticleFig(id=1157042125549478160, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=CN, label=表 1, caption=梯度淋洗程序, figureFileSmall=null, figureFileBig=null, tableContent=
时间(min) 0 5 40 40.1 50
KOH 淋洗液浓度(mmol/L) 4 4 30 4 4
), ArticleFig(id=1157042125599809809, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=EN, label=Table 2, caption=Results of retention time and resolution of ${\mathrm{{ClO}}}_{2}{}^{- }$ , MBAA, DCAA, DBAA, TCAA and common anions, figureFileSmall=null, figureFileBig=null, tableContent=
阴离子 ${\mathrm{F}}^{- }$ ${\mathrm{{ClO}}}_{2}$ MBAA Cl- DCAA DBAA ${\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }$ TCAA ${\mathrm{{SO}}}_{4}{}^{2 -}$
保留时间(min) 9.097 12.314 13.160 14.204 16.110 17.717 20.277 23.840 26.694
分离度(EP) 3.51 2.93 3.63 5.80 3.74 5.79 7.04 2.23 5.71
), ArticleFig(id=1157042125666918674, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=CN, label=表 2, caption=亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸和水中常见阴离子的和常见阴离子的保留时间和分离度, figureFileSmall=null, figureFileBig=null, tableContent=
阴离子 ${\mathrm{F}}^{- }$ ${\mathrm{{ClO}}}_{2}$ MBAA Cl- DCAA DBAA ${\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }$ TCAA ${\mathrm{{SO}}}_{4}{}^{2 -}$
保留时间(min) 9.097 12.314 13.160 14.204 16.110 17.717 20.277 23.840 26.694
分离度(EP) 3.51 2.93 3.63 5.80 3.74 5.79 7.04 2.23 5.71
), ArticleFig(id=1157042125729833235, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=EN, label=Table 3, caption=Linearity parameters, detection limits and lower limits of determination for ${\mathrm{{ClO}}}_{2}{}^{- }$ , MBAA, DBAA, DCAA and TCAA, figureFileSmall=null, figureFileBig=null, tableContent=
消毒副产物 线性回归方程 相关系数 检出限(μg/L) 定量限(μg/L)
${\mathrm{{ClO}}}_{2}$ y=0.0027x-0.1063 0.9991 0.32 1.07
MBAA y=0.0013x-0.0139 0.9994 0.76 2.54
DBAA y=0.0010x+0.0025 0.9997 1.30 4.33
DCAA y=0.0016x-0.0014 0.9998 0.69 2.30
TCAA y=0.0011x-0.0074 0.9999 1.58 5.26
), ArticleFig(id=1157042125801136404, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=CN, label=表 3, caption=亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸线性参数、检出限和定量限, figureFileSmall=null, figureFileBig=null, tableContent=
消毒副产物 线性回归方程 相关系数 检出限(μg/L) 定量限(μg/L)
${\mathrm{{ClO}}}_{2}$ y=0.0027x-0.1063 0.9991 0.32 1.07
MBAA y=0.0013x-0.0139 0.9994 0.76 2.54
DBAA y=0.0010x+0.0025 0.9997 1.30 4.33
DCAA y=0.0016x-0.0014 0.9998 0.69 2.30
TCAA y=0.0011x-0.0074 0.9999 1.58 5.26
), ArticleFig(id=1157042125872439573, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=EN, label=Table 4, caption=Results of tests for percision and recovery $\left({\mathrm{n}= 6}\right)$, figureFileSmall=null, figureFileBig=null, tableContent=
消毒副产物 本底值(μg/L) 加标量 $\left({\mu \mathrm{g}/\mathrm{L}}\right)$ 测定均值(μg/L) 平均回收率(%) RSD(%)
50 51.0 102.0 1.54
${\mathrm{{ClO}}}_{2}$- N.D. 500 496.5 99.3 1.21
900 909.0 101.0 1.11
50 52.5 105.0 3.88
MBAA N.D. 500 508.5 101.7 3.63
900 838.8 93.2 2.12
50 50.7 101.4 1.51
DBAA N.D. 500 455.0 91.0 1.07
900 838.8 93.2 1.21
50 46.0 92.0 3.21
DCAA N.D. 500 475.5 95.1 1.05
900 820.8 91.2 1.45
50 47.5 95.0 3.04
TCAA N.D. 500 451.0 90.2 0.99
900 882.9 98.1 0.65
), ArticleFig(id=1157042125960519958, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=CN, label=表 4, caption=精密度和回收率试验结果(n=6), figureFileSmall=null, figureFileBig=null, tableContent=
消毒副产物 本底值(μg/L) 加标量 $\left({\mu \mathrm{g}/\mathrm{L}}\right)$ 测定均值(μg/L) 平均回收率(%) RSD(%)
50 51.0 102.0 1.54
${\mathrm{{ClO}}}_{2}$- N.D. 500 496.5 99.3 1.21
900 909.0 101.0 1.11
50 52.5 105.0 3.88
MBAA N.D. 500 508.5 101.7 3.63
900 838.8 93.2 2.12
50 50.7 101.4 1.51
DBAA N.D. 500 455.0 91.0 1.07
900 838.8 93.2 1.21
50 46.0 92.0 3.21
DCAA N.D. 500 475.5 95.1 1.05
900 820.8 91.2 1.45
50 47.5 95.0 3.04
TCAA N.D. 500 451.0 90.2 0.99
900 882.9 98.1 0.65
), ArticleFig(id=1157042126044406039, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=EN, label=Table 5, caption=Effects of different concentrations of common anions on recoveries of ${\mathrm{{ClO}}}_{2}$ , MBAA, DBAA, DCAA and TCAA, figureFileSmall=null, figureFileBig=null, tableContent=
${\mathrm{F}}^{- }\text{、}{\mathrm{{Cl}}}^{- }\text{、}{\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }\text{、}{\mathrm{{SO}}}_{4}{}^{2 -}$ 浓度(μg/L) ${\mathrm{{ClO}}}_{2}{}^{- }$ MBAA DBAA DCAA TCAA
测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%)
50 89.5 89.5 107.5 107.5 102.0 102.0 80.5 80.5 99.5 99.5
250 88.7 88.7 106.1 106.1 103.2 103.2 81.8 81.8 98.1 98.1
500 93.7 93.7 102.9 102.9 94.5 94.5 83.1 83.1 89.9 89.9
1000 91.1 91.1 86.2 86.2 94.2 94.2 80.2 80.2 90.5 90.5
), ArticleFig(id=1157042126107320600, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1157042098550743973, language=CN, label=表 5, caption=不同浓度常见阴离子对亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸回收率的影响, figureFileSmall=null, figureFileBig=null, tableContent=
${\mathrm{F}}^{- }\text{、}{\mathrm{{Cl}}}^{- }\text{、}{\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }\text{、}{\mathrm{{SO}}}_{4}{}^{2 -}$ 浓度(μg/L) ${\mathrm{{ClO}}}_{2}{}^{- }$ MBAA DBAA DCAA TCAA
测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%) 测定值 (μg/L) 回收率 (%)
50 89.5 89.5 107.5 107.5 102.0 102.0 80.5 80.5 99.5 99.5
250 88.7 88.7 106.1 106.1 103.2 103.2 81.8 81.8 98.1 98.1
500 93.7 93.7 102.9 102.9 94.5 94.5 83.1 83.1 89.9 89.9
1000 91.1 91.1 86.2 86.2 94.2 94.2 80.2 80.2 90.5 90.5
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大体积进样-离子色谱法同时测定饮用水中4种卤乙酸和亚氯酸盐含量
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尤妍 * , 丁仙林 , 李炜鑫
实验室检测 | 创新应用 2024,2(2): 18-22
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实验室检测 |创新应用 2024 , 2 (2) : 18 -22
大体积进样-离子色谱法同时测定饮用水中4种卤乙酸和亚氯酸盐含量
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尤妍* , 丁仙林, 李炜鑫
作者信息
  • 台州市路桥区疾病预防控制中心 台州 318050
通讯作者:
*尤妍,硕士,主管技师,研究方向为检验检测。E-mail:
Simultaneous determination of four kinds of haloacetic acids and chlorite in drinking water by ion chromatography with large volume injection
Yan YOU* , Xian-Lin DING, Wei-Xin LI
Affiliations
  • Luqiao District Center for Disease Control and Prevention Taizhou 318050 China
  • Corresponding Author:
    *YOU Yan, Master, Chief Technician, Luqiao District Center for Disease Control and Prevention, Taizhou, 318050, China. E-mail:
出版时间: 2024-02-08
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目的 建立了离子色谱法同时测定饮用水中一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸和亚氯酸盐的方法。方法 水样经 ${0.22\mu }\mathrm{m}$ 水系微孔滤膜后进样,进样体积为${500\mu}\mathrm{L}$ ,利用 $\mathrm{{KOH}}$ 溶液梯度淋洗, IonPac AS19阴离子色谱柱分离,柱温为 ${30}^{\circ }\mathrm{C}$ ,用电导检测器测定,抑制器电流为 ${75}\mathrm{\;{mA}}$ 。结果 亚氯酸盐、一溴乙酸、 二溴乙酸、二氯乙酸和三氯乙酸在 10-1000μ/L 范围内线性良好, r$>{0.9990}$ ,检出限 $\left({3\mathrm{S}/\mathrm{N}}\right)$ 分别为 0.32,0.76, ${1.30},{0.69},{1.58\mu}\mathrm{g}/\mathrm{L}$ ,加标回收率为 ${80}\%\sim {110}\%$ ,相对标准偏差均 $<{5.0}\%$ 。结论 方法操作简单,灵敏度高,可以满足饮用水中四种卤乙酸和亚氯酸盐的检测要求,本方法可以用于饮用水中四种卤乙酸和亚氯酸盐的检测。

离子色谱  /  四种卤乙酸  /  亚氯酸盐  /  饮用水

Objective A method for simultaneous determination of MBAA, DBAA, DCAA, TCAA and ${\mathrm{{ClO}}}_{2}{}^{- }$ in drinking water was established by ion chromatography. Methods The water samples were determined by ${0.22\mu}\mathrm{m}$ qeuosystem filter membrane with a volume of ${500\mu }\mathrm{L}$ . The samples were rinsed with $\mathrm{{KOH}}$ solution gradient and separated by IonPac AS19 anion column. The column temperature was set at ${30}^{\circ }\mathrm{C}$ , and the current of the inhibitor was ${75}\mathrm{\;{mA}}$ . Results The results showed that the linearity ranges of ${\mathrm{{ClO}}}_{2}{}^{- }$ , MBAA, DBAA, DCAA and TCAA were found in the range of ${10}\sim {1000\mu}\mathrm{g}/\mathrm{L},\mathrm{r}> {0.9990}$ , with detection limits $\left({3\mathrm{\;S}/\mathrm{N}}\right)$ of ${0.32},{0.76},{1.30},{0.69},{1.58\mu}\mathrm{g}/\mathrm{L}$ . The standard recoveries were ${80}\%\sim {110}\%$ and RSD (n=6) of the determined values were all less than 5.0%. Conclusion The method was simple, sensitive, can meet the detection requirements of four kinds of Haloaeetic Acids and Chlorite in drinking water. The method can be used for the determination of kour kinds of haloaeetic acids and chlorite in drinking water.

ion chromatography  /  four kinds of haloaeetic acids  /  chlorite  /  drinking water
尤妍, 丁仙林, 李炜鑫. 大体积进样-离子色谱法同时测定饮用水中4种卤乙酸和亚氯酸盐含量. 实验室检测, 2024 , 2 (2) : 18 -22 .
Yan YOU, Xian-Lin DING, Wei-Xin LI. Simultaneous determination of four kinds of haloacetic acids and chlorite in drinking water by ion chromatography with large volume injection[J]. Laboratory Testing, 2024 , 2 (2) : 18 -22 .
水是生命的源泉, 饮用水的好坏与人体健康息息相关。 含氯和溴的消毒剂与水中的有机物发生反应, 产生包括四种卤乙酸和亚氯酸盐的消毒副产物, 他们在水中普遍存在 [ 1 - 3 ] 。卤乙酸具有明显的致癌性和致突变性,具有胚胎毒性, 可造成免疫器官损伤 [ 1 - 12 ] 。研究表明卤乙酸的致癌风险占消毒副产物致癌风险的 91.9%以上[ 13 ]。几种典型卤乙酸的细胞毒性大小依次为一溴乙酸>二溴乙酸>二氯乙酸>三氯乙酸 [ 14 ] 。通过对成年雄性大鼠口服毒性研究,发现一溴乙酸口服毒性是二溴乙酸的 10 倍, 可致精子变异、退化, 是一种精子毒剂。亚氯酸盐能引起高铁血红蛋白症、溶血性贫血和变性血红蛋白血癌,有较强的致突变性,可能会抑制血清甲状腺素的作用,引起胎儿小脑重量下降、神经行为作用迟缓或细胞数下降[ 15 ]。随着生活水平的提高,大家很关注饮用水的安全问题,消毒副产物逐渐被人们所重视, GB 5749-2022 生活饮用水卫生标准将消毒副产物二氯乙酸和三氯乙酸从水质非常规指标移入常规检测指标, 限值分别为 ${50\mu }\mathrm{g}/\mathrm{L}$ 和 ${100\mu }\mathrm{g}/\mathrm{L}$ 。亚氯酸盐一直都是生活饮用水的常规监测指标,限值为 ${700\mu }\mathrm{g}/\mathrm{L}$ 。美国环保局将一溴乙酸、二溴乙酸纳入水质评估监测目录。
卤乙酸和亚氯酸盐的检测方法主要有气相色谱法、离子色谱法和离子色谱-质谱法(IC-MS/MS)。气相色谱法使用的有机溶剂易挥发, 方法重现性差, 萃取试剂和衍生试剂对人体健康和环境有害, 虽然仪器检测的灵敏度较高, 但是样品检测时会有杂峰干扰检测。IC-MS/MS 仪器定性和定量的准确性都很高, 但是成本高, 目前较难推广。离子色谱使用纯水为流动相,对人体无害,对环境不产生污染且方法的准确性和重复性较好, 目前各检测机构和科研院所对该仪器的配备率较高。本研究采用离子色谱仪测定饮用水中四种卤乙酸和亚氯酸盐。
卤乙酸和亚氯酸盐均为消毒副产物, 在水中不稳定, 需要尽快检测, 分开测定耗时长且不准确。本试验旨在建立一种同时测定四种卤乙酸和亚氯酸盐的方法, 通过优化离子色谱条件,以 $\mathrm{{KOH}}$ 为淋洗液,梯度洗脱,同时测定饮用水中亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸,并探索水样的保存条件,为更好监测饮用水中消毒副产物提供依据。
亚氯酸盐 ${1000}\mathrm{{mg}}/\mathrm{L}$ (农业部环境保护科研监测所)、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸标溶液均为 1000 $\mathrm{{mg}}/\mathrm{L}$ (坛墨质检科技股份有限公司)。 $\mathrm{{Ba}}/\mathrm{{Ag}}/\mathrm{H}$ 柱、钠柱(美国 Thermo Fisher); 氢氧化钠(分析纯,国药集团化学试剂有限公司)。
水样: 路桥区各乡镇街道。
ICS-1100 离子色谱仪配淋洗液在线循环装置、淋洗液自动发生装置 RFC-30、全自动电解抑制器、控温电导池(美国 Thermo Fisher); 不同量程数字单道可调量程移液器(德国 Eppendorf); 实验室水纯化系统(上海和泰)。
水样经 ${0.22\mu }\mathrm{m}$ 水系微孔滤膜后进行离子色谱仪分析。如遇Cl ${}^{- }$ 和 ${\mathrm{{SO}}}_{4}{}^{2 -}$ 含量高的试样,可将水样依次通过 $\mathrm{{Ba}}/\mathrm{{Ag}}/\mathrm{H}$ 柱和 ${0.22\mu }\mathrm{m}$ 微孔滤膜过滤。具体步骤为: 先注入 ${15}\mathrm{\;{mL}}$ 纯水活化 $\mathrm{{Ba}}/\mathrm{{Ag}}/\mathrm{H}$ 柱,放置 ${0.5}\mathrm{\;h}$ 后使用。将水样以 $2\mathrm{\;{mL}}/\mathrm{{min}}$ 的速度依次通过 $\mathrm{{Ba}}/\mathrm{{Ag}}/\mathrm{H}$ 柱和 ${0.2\mu }\mathrm{m}$ 微孔滤膜过滤器,前 $6\mathrm{\;{mL}}$ 滤液弃掉后,取 $5 \sim {10}\mathrm{\;{mL}}$ 的滤液进行离子色谱仪分析。如遇重金属含量高的水样(井水),水样依次通过钠柱和 ${0.22\mu }\mathrm{m}$ 微孔滤膜过滤。具体步骤为: 先注入 ${15}\mathrm{\;{mL}}$ 甲醇活化钠柱,放置 ${0.5}\mathrm{\;h}$ 后用 ${10}\mathrm{\;{mL}}$ 超纯水洗去甲醇后备用。将水样以 $2\mathrm{\;{mL}}/\mathrm{{min}}$ 的速度依次通过钠柱和 ${0.2\mu }\mathrm{m}$ 微孔滤膜过滤器,前 $6\mathrm{{mL}}$ 滤液弃掉后,取 $5 \sim {10}$ $\mathrm{{mL}}$ 的滤液进行离子色谱仪分析。
混合标准储备液:分别移取上述四种卤乙酸和亚氯酸盐各 $1\mathrm{\;{mL}}$ 于 ${100}\mathrm{\;{mL}}$ 容量瓶中,用超纯水定容至刻度,即得 ${10}\mathrm{{mg}}/\mathrm{L}$ 的混合标准储备液。
混合标准溶液系列: 分别移取亚氯酸盐、一溴乙酸、 二溴乙酸、二氯乙酸、三氯乙酸混合标准储备液各 0,0.20, ${0.50},{1.00},{2.00},{5.00},{10.00}\mathrm{\;{mL}}$ 于7个 ${100}\mathrm{\;{mL}}$ 容量瓶中,用水稀释,配制成质量浓度分别为0,20,50,100, 200,500,1000 $\mu \mathrm{g}/\mathrm{L}$ 的混合标准溶液,现配现用。
IonPac AS19 阴离子交换柱 $\left({{250}\mathrm{\;{mm}}\times 4\mathrm{\;{mm}}}\right)$ ; IonPac AS19 保护柱 $\left({{50}\mathrm{\;{mm}}\times 4\mathrm{\;{mm}}}\right)$ ;抑制器电流 ${75}\mathrm{\;{mA}}$ ;柱温 ${30}^{\circ }\mathrm{C}$ ; 流速 ${1.0}\mathrm{\;{mL}}/\mathrm{{min}}$ ; 进样体积 ${500\mu }\mathrm{L}$ 。以 $\mathrm{{KOH}}$ 溶液为淋洗液, 梯度淋洗程序见 表 1 。按照仪器工作条件测定其中的四种卤乙酸和亚氯酸盐。待基线平稳后, 取相应体积处理后的样品滤液进行色谱分析, 记录四种卤乙酸和亚氯酸盐的峰面积。
$\mathrm{{KOH}}$ 淋洗体系被抑制后产物为水,背景电导值较低, 水负峰不明显, 信噪比高, 可以通过大体积进样提高仪器灵敏度,选择进样体积 ${500\mu }\mathrm{L}$ 。通过考察不同流速对分析效果和时间的影响,最后选择 ${1.0}\mathrm{\;{mL}}/\mathrm{{min}}$ 为淋洗液流速。
$\mathrm{{KOH}}$ 淋洗液浓度的选择是影响阴离子分离效果的关键。亚氯酸盐和一溴乙酸的保留时间比较接近, 其他几种卤乙酸分离效果较好。分别选择 $4\text{、}6\text{、}8\text{、}{10}\mathrm{{mmol}}/\mathrm{L}\mathrm{{KOH}}$ 初始浓度考察亚氯酸盐和一溴乙酸的分离度。结果发现分离度随着 $\mathrm{{KOH}}$ 初始浓度的增加而降低。在 $4\mathrm{{mmol}}/\mathrm{L}$ 时, 四种卤乙酸、亚氯酸盐及常见 4 种阴离子分离度均>1.5, 达到了分离效果。在 $5 \sim {40}\mathrm{\;{min}}$ 内,将淋洗液浓度缓慢升至 ${30}\mathrm{{mmol}}/\mathrm{L}$ ,可以降低因淋洗液浓度变化带来的基线漂移, 各离子能有效分离。在优化的仪器工作条件下, 四种卤乙酸、亚氯酸盐和常见 4 种阴离子的保留时间和分离度见 表 2 , 色谱图如 图 1 。
以 ${200\mu }\mathrm{g}/\mathrm{L}$ 亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸混合标准溶液为样液,分别设置 ${30}^{\circ }\mathrm{C}\text{、}{35}^{\circ }\mathrm{C}$ 、 ${40}^{\circ }\mathrm{C}$ 、 ${45}^{\circ }\mathrm{C}$ 柱温,考察柱温对以上各离子的保留时间、峰面积和分离度的影响。发现一溴乙酸和二溴乙酸色谱峰的分离度随温度的升高而降低,当柱温为 ${45}^{\circ }\mathrm{C}$ 时,一溴乙酸色谱峰的分离度仅为 1.48 ,无法有效分离。柱温对其他各阴离子保留时间的影响不大, 峰面积随着柱温的升高而降低,当柱温为 ${45}^{\circ }\mathrm{C}$ 时,一溴乙酸、二氯乙酸、二溴乙酸峰面积分别下降了 49.8%、10.7%、38.4%,可能是由于消毒副产物不稳定,高温会让其快速分解。故选择 ${30}^{\circ }\mathrm{C}$ 作为检测的柱温。
$\mathrm{{KOH}}$ 淋洗液浓度为 ${30}\mathrm{{mmol}}/\mathrm{L}$ 时,推荐的抑制器电流为 ${87}\mathrm{\;{mA}}$ ,抑制器在持续高电流状态下运行会影响寿命, 增加检测成本。以 ${200\mu }\mathrm{g}/\mathrm{L}$ 亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸混合标准溶液为样液,比较抑制器电流在 ${60}\sim {87}\mathrm{\;{mA}}$ 对各离子保留时间、峰面积和分离度的影响。发现随着抑制器电流的降低, 各阴离子的保留时间几乎不影响, 峰面积逐渐下降, 基线逐渐上升, 分离度呈下降趋势。当抑制器电流为 ${75}\mathrm{\;{mA}}$ 时,峰面积和分离度下降不明显。故选择 75 mA 作为抑制器电流。
按照仪器最优工作条件测定混合标准溶液系列, 以质量浓度为横坐标, 峰面积为纵坐标绘制标准曲线。结果表明:亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸在 ${10}- {1000\mu }\mathrm{g}/\mathrm{L}$ 范围内线性良好, $\mathrm{r}> {0.9990}$ 。以 3 倍和 10 倍信噪比(S/N)分别计算检出限(3 S/N)和定量限(10 $\mathrm{S}/\mathrm{N})$ ,结果见 表 3 ,检出限和定量限均符合要求。
对水样进行低、中、高 3 浓度水平的加标回收试验, 每个浓度水平平行测定 6 次, 计算回收率和测定值的相对标准偏差(RSD%),结果见 表 4 。RSD%均<5%,平均回收率为 90.2%~105.0%,满足检测要求。
自来水中氟化物、氯化物、硝酸盐氮、硫酸盐 4 种阴离子较常见,配制 ${100\mu }\mathrm{g}/\mathrm{L}$ 亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸混合标准溶液,分别加入 50、250、 ${500}\text{、}{1000\mu }\mathrm{g}/\mathrm{L}{\mathrm{F}}^{- }\text{、}{\mathrm{{Cl}}}^{- }\text{、}{\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }\text{、}{\mathrm{{SO}}}_{4}{}^{2 -}4$ 种不同浓度的干扰物混合标准溶液, 测定四种卤乙酸和亚氯酸盐的加标回收率,加标回收率为 80.5%~107.5%,能满足日常检查的需求。结果见 表 5 。
取 ${1000}\mathrm{{mg}}/\mathrm{L}$ 亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸标准溶液,用纯水配制成 ${10}\mathrm{{mg}}/\mathrm{L}$ 的混合标准溶液,不加任何保护剂,分别放入 ${50}\mathrm{\;{mL}}$ 透明玻璃瓶和棕色玻璃瓶中,与 ${4}^{\circ }\mathrm{C}$ 冷藏和常温保存。另取 ${1000}\mathrm{{mg}}/\mathrm{L}$ 亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸、三氯乙酸标准溶液,用 $5\mathrm{{mmol}}/\mathrm{L}$ 氢氧化钠溶液配制成 ${10}\mathrm{{mg}}/\mathrm{L}$ 的混合标准溶液,分别放入 ${50}\mathrm{\;{mL}}$ 透明玻璃瓶和棕色玻璃瓶中, 常温保存。在第 1 天和第 14 天分别对样品进行分析。结果表明, 14 天后在棕色玻璃瓶内保存的四种卤乙酸和亚氯酸盐的稳定性优于透明玻璃瓶;不加保护剂的样品 ${4}^{\circ }\mathrm{C}$ 冷藏保存条件下四种卤乙酸和亚氯酸盐的稳定性优于常温保存。用氢氧化钠溶液保存的样品中四种卤乙酸和亚氯酸盐的稳定性较好,与 ${4}^{\circ }\mathrm{C}$ 冷藏保存条件下四种卤乙酸和亚氯酸盐的稳定性差异不大。在日常样品检测过程中, 可以选用氢氧化钠溶液作为水样的保存剂。
按照试验方法测定 46 份管网末梢水和二次供水中四种卤乙酸和亚氯酸盐。本地区目前水质较好,样品中均未检出以上消毒副产物,Cl ${}^{- }\text{、}{\mathrm{{NO}}}_{3}- {\mathrm{N}}^{- }\text{、}{\mathrm{{SO}}}_{4}{}^{2 -}$ 的存在不影响测定。亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸的加标回收率为 80%~110%。
本研究建立了离子色谱法同时测定饮用水中亚氯酸盐、一溴乙酸、二溴乙酸、二氯乙酸和三氯乙酸的方法, 通过优化淋洗液浓度, 选择合适的柱温和抑制器电流, 优化检测参数, 实现了各阴离子的有效分离。本方法准确性、 重现性好, 灵敏度高, 可用于饮用水中四种卤乙酸和亚氯酸盐的测定。低浓度的氢氧化钠溶液可有效延长水样中消毒副产物的保存期限。本研究为更好监测饮用水中消毒副产物提供依据。

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*尤妍,硕士,主管技师,研究方向为检验检测。E-mail:
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