Article(id=1156967528888099771, tenantId=1146029695717560320, journalId=1146119944283992078, issueId=1156967523842347919, 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=1753772154303, onlineDateStr=2025-07-29, pubDate=null, pubDateStr=null, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1753772154303, onlineIssueDateStr=2025-07-29, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1753772154303, creator=13701087609, updateTime=1753772154303, updator=13701087609, issue=Issue{id=1156967523842347919, tenantId=1146029695717560320, journalId=1146119944283992078, year='2024', volume='2', issue='7', pageStart='1', pageEnd='160', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=0, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1753772153100, creator=13701087609, updateTime=1753777984529, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1156991982682854377, tenantId=1146029695717560320, journalId=1146119944283992078, issueId=1156967523842347919, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1156991982682854378, tenantId=1146029695717560320, journalId=1146119944283992078, issueId=1156967523842347919, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=62, endPage=65, ext={EN=ArticleExt(id=1156967530750370775, articleId=1156967528888099771, tenantId=1146029695717560320, journalId=1146119944283992078, language=EN, title=Determination of 5 kinds of heavy metal elements in commom TCM by inductively coupled plasma mass spectrometry, columnId=1156641065621906129, journalTitle=Laboratory Testing, columnName=Innovative Applications, runingTitle=null, highlight=null, articleAbstract=

Objective To establish an inductively coupled plasma massspectrometry (ICP-MS) method for the determination of $\mathrm{{Pb}},\mathrm{{As}},\mathrm{{Hg}},\mathrm{{Cd}},\mathrm{{Hg}}$ in astragali radix, crataegi fructus, lycii fructus, lonicerae japonicaeflos and glycyrrhizae radix et rhizome. Methods After microwavedigestion of forty-five batches of samples, the contents of five heavymetals in commom TCM decoction pieces were determinationed by ICP-MS.The RF power is 1550 W. Kinetic Energy Discrimination mode is used. Thecollisional gas was Helium.The carrier gas was Argon with ${0.8}\mathrm{\;L}/\mathrm{{min}}$ , theplasma gas flow rate was ${14.0}\mathrm{\;L}/\mathrm{{min}}$ . Results Five heavy metal elements showed a good linear relationships $\left({r >{0.999}}\right)$ , whoserecoveries were 84.6%~115.3%, the detection limit was ${0.0001}\sim {0.0140}\mathrm{{mg}}/\mathrm{{kg}}$ .Among the 45 batches of samples, there were individual samples oflonicerae japonicae flos that exceeded the limit. Conclusion This methodis simple, efficient, stable and reliable, which can be used for thequality study of a variety of heavy metals, and provides more basis forits quality control and scientific supervision.

, correspAuthors=Ye LU, authorNote=null, correspAuthorsNote=
*LU Ye, Technician-in-Charge, Inspector, Shanghai Chongming Institute for Food and Drug Control, Shanghai 202150, China. E-mail:
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目的 建立电感耦合等离子体质谱(Inductively Coupled Plasma MassSpectrometry,ICP-MS)法测定黄芪、山楂、枸杞子、金银花、甘草中铅、砷、汞、镉、铜 5种重金属的含量。方法 45 批样品经微波消解后,采用 ICP-MS法同时测定中药材中 5 种重金属含量,射频功率 ${1550}\mathrm{\;W}$ ,采用 KED (KineticEnergy Discrimination) 碰撞模式,碰撞气为氦气,载气为氩气,载气流量 ${0.8}\mathrm{\;L}/\mathrm{{min}}$ ,等离子体气体流量 ${14.0}\mathrm{\;L}/\mathrm{{min}}$结果 5种元素线性关系良好 ( $r>{0.999}$ ),回收率在84.6% 115.3%之间,检出限为0.0001 0.0140mg/kg,45 批次样品中,金银花存在个别样品超标现象。 结论该方法简便高效、稳定可靠,可用于多种重金属的质量研究,并为其质量控制和科学监管提供更多依据。关键词:ICP-MS;中药饮片;重金属

, correspAuthors=陆叶, authorNote=null, correspAuthorsNote=
*陆叶,主管技师,检验员,研究方向为食品药品安全检测与质量控制。E-mail:
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陆叶,主管技师,检验员,研究方向为食品药品安全检测与质量控制。

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铜和锌离子对真绸幼鱼组织酶活性的影响[J]. 环境科学, 1998, 9(05): 60-62., articleTitle=铜和锌离子对真绸幼鱼组织酶活性的影响, refAbstract=null), Reference(id=1156967545577234606, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=2002, volume=23, issue=03, pageStart=164, pageEnd=179, url=null, language=null, rfNumber=[9], rfOrder=8, authorNames=李金英, 郭冬发, 姚继军, journalName=质谱学报, refType=null, unstructuredReference=李金英, 郭冬发, 姚继军, 等. 电感耦合等离子体质谱 (ICP-MS) 新进展[J]. 质谱学报, 2002, 23(03): 164-179., articleTitle=电感耦合等离子体质谱 (ICP-MS) 新进展, refAbstract=null), Reference(id=1156967545631760559, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=2002, volume=21, issue=03, pageStart=48, pageEnd=49, url=null, language=null, rfNumber=[10], rfOrder=9, authorNames=张浚清, 刘明生, 符乃光, journalName=中国野生植物资源, refType=null, unstructuredReference=张浚清, 刘明生, 符乃光, 等. 中药材微量元素及重金属研究的意义与方法[J]. 中国野生植物资源, 2002, 21(03): 48-49., articleTitle=中药材微量元素及重金属研究的意义与方法, refAbstract=null), Reference(id=1156967545686286512, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=2023, volume=null, issue=06, pageStart=43, pageEnd=45, url=null, language=null, rfNumber=[11], rfOrder=10, authorNames=马维炜, 寇鹏斌, 王锡龙, journalName=化纤与纺织技术, refType=null, unstructuredReference=马维炜, 寇鹏斌, 王锡龙. 微波消解技术及其在分析化学中的应用[J]. 化纤与纺织技术, 2023(06): 43-45., articleTitle=微波消解技术及其在分析化学中的应用, refAbstract=null), Reference(id=1156967545745006769, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=2016, volume=44, issue=13, pageStart=59, pageEnd=null, url=null, language=null, rfNumber=[12], rfOrder=11, authorNames=倪荣, 张丽, 郭绍芬, journalName=安徽农业科学, refType=null, unstructuredReference=倪荣, 张丽, 郭绍芬, 等. 平邑不同区域金银花各部位及土壤中5种重金属元素含量测定[J]. 安徽农业科学, 2016, 44(13): 59 ., articleTitle=平邑不同区域金银花各部位及土壤中5种重金属元素含量测定, refAbstract=null), Reference(id=1156967545816309938, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=1996, volume=178, issue=01, pageStart=59, pageEnd=66, url=null, language=null, rfNumber=[13], rfOrder=12, authorNames=ZHELJAZKOV VD, NIELSEN N E, journalName=Plant Soil, refType=null, unstructuredReference= ZHELJAZKOV VD , NIELSEN N E . Effect of heavy metals on peppermint and cornmint[J]. Plant Soil, 1996, 178(01): 59-66., articleTitle=Effect of heavy metals on peppermint and cornmint, refAbstract=null), Reference(id=1156967545862447283, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=1986, volume=15, issue=04, pageStart=439, pageEnd=446, url=null, language=null, rfNumber=[14], rfOrder=13, authorNames=SHAW BP, PANIGRAHI AK, journalName=Arch Environ Con Tox, refType=null, unstructuredReference= SHAW BP , PANIGRAHI AK . Uptake and tissue distribution of mercury in some plant species collected from a contaminated area in India: Its ecological implications[J]. Arch Environ Con Tox, 1986, 15(04): 439-446., articleTitle=Uptake and tissue distribution of mercury in some plant species collected from a contaminated area in India: Its ecological implications, refAbstract=null), Reference(id=1156967545916973236, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, doi=null, pmid=null, pmcid=null, year=2023, volume=43, issue=04, pageStart=707, pageEnd=null, url=null, language=null, rfNumber=[15], rfOrder=14, authorNames=左甜甜, 申明睿, 张磊, journalName=药物分析, refType=null, unstructuredReference=左甜甜, 申明睿, 张磊, 等. 中药中重金属及有害元素限量标准的制定及有关问题的思考[J]. 药物分析, 2023, 43(04): 707 ., articleTitle=中药中重金属及有害元素限量标准的制定及有关问题的思考, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1156967534789484574, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, xref=null, ext=[AuthorCompanyExt(id=1156967534797873183, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, companyId=1156967534789484574, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Shanghai Chongming Institute for Food and Drug Control Shanghai 202150 China), AuthorCompanyExt(id=1156967534806261792, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, companyId=1156967534789484574, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=上海市崇明食品药品检验所 上海 202150)])], figs=[ArticleFig(id=1156967544297971863, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 1, caption=Sample source and batch number, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称 来源 批号 样品名称 来源 批号
黄芪 S1 上海 220702 枸杞子 S1 湖北 220403
黄芪 S2 上海 211011 枸杞子 S2 河北 210702
黄芪 S3 湖南 211005 枸杞子 S3 上海 210510
黄芪 S4 甘肃 210402 枸杞子 S4 上海 211025
黄芪 S5 上海 210714 枸杞子 S5 上海 220702
黄芪 S6 四川 201001 枸杞子 S6 上海 211011
黄芪 S7 甘肃 220816 枸杞子 S7 上海 211005
黄芪 S8 安徽 230803 枸杞子 S8 上海 210402
黄芪 S9 上海 230331 枸杞子 S9 上海 210302
黄芪 S10 湖南 230601 枸杞子 S10 湖北 220710
金银花 S1 河北 221130 甘草 S1 上海 210513
金银花 S2 上海 221217 甘草 S2 上海 211110
金银花 S3 湖北 220801 甘草 S3 上海 210812
金银花 S4 上海 211220 甘草 S4 河北 230112
金银花 S5 上海 220801 甘草 S5 湖南 230101
金银花 S6 上海 220907 甘草 S6 江西 220114
金银花 S7 上海 221201 甘草 S7 上海 230110
金银花 S8 上海 220628 甘草 S8 上海 230201
金银花 S9 上海 230301 甘草 S9 甘肃 230210
金银花 S10 上海 230805 甘草 S10 湖南 231104
山楂 S1 安徽 210302 山楂 S4 江苏 230611
山楂 S2 上海 220710 山楂 S5 安徽 231104
山楂 S3 湖北 221201
), ArticleFig(id=1156967544373469337, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 1, caption=样品来源及批号, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称 来源 批号 样品名称 来源 批号
黄芪 S1 上海 220702 枸杞子 S1 湖北 220403
黄芪 S2 上海 211011 枸杞子 S2 河北 210702
黄芪 S3 湖南 211005 枸杞子 S3 上海 210510
黄芪 S4 甘肃 210402 枸杞子 S4 上海 211025
黄芪 S5 上海 210714 枸杞子 S5 上海 220702
黄芪 S6 四川 201001 枸杞子 S6 上海 211011
黄芪 S7 甘肃 220816 枸杞子 S7 上海 211005
黄芪 S8 安徽 230803 枸杞子 S8 上海 210402
黄芪 S9 上海 230331 枸杞子 S9 上海 210302
黄芪 S10 湖南 230601 枸杞子 S10 湖北 220710
金银花 S1 河北 221130 甘草 S1 上海 210513
金银花 S2 上海 221217 甘草 S2 上海 211110
金银花 S3 湖北 220801 甘草 S3 上海 210812
金银花 S4 上海 211220 甘草 S4 河北 230112
金银花 S5 上海 220801 甘草 S5 湖南 230101
金银花 S6 上海 220907 甘草 S6 江西 220114
金银花 S7 上海 221201 甘草 S7 上海 230110
金银花 S8 上海 220628 甘草 S8 上海 230201
金银花 S9 上海 230301 甘草 S9 甘肃 230210
金银花 S10 上海 230805 甘草 S10 湖南 231104
山楂 S1 安徽 210302 山楂 S4 江苏 230611
山楂 S2 上海 220710 山楂 S5 安徽 231104
山楂 S3 湖北 221201
), ArticleFig(id=1156967544432189594, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 2, caption=Microwave digestion program, figureFileSmall=null, figureFileBig=null, tableContent=
步骤 功率 (W) 温度 $\left({{}^{\circ }\mathrm{C}}\right)$ 升温时间 (min) 恒温时间 (min)
1 1200 120 5 6
2 1200 160 5 10
3 1200 180 5 20
), ArticleFig(id=1156967544486715547, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 2, caption=微波消解程序, figureFileSmall=null, figureFileBig=null, tableContent=
步骤 功率 (W) 温度 $\left({{}^{\circ }\mathrm{C}}\right)$ 升温时间 (min) 恒温时间 (min)
1 1200 120 5 6
2 1200 160 5 10
3 1200 180 5 20
), ArticleFig(id=1156967544537047196, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 3, caption=Linear ranges and detection limits of various elements, figureFileSmall=null, figureFileBig=null, tableContent=
元素 回归方程 相关系数 $r$ 线性范围 $\left({\mu \mathrm{g}/\mathrm{L}}\right)$ 检出限 (mg/kg)
Pb $Y ={128950.4883X}+ {67590.8059}$ 0.9991 1~20 0.0022
As $Y ={2154.1207X}+ {127.3198}$ 0.9997 1~20 0.0015
$\mathrm{{Hg}}$ $Y ={15837.2807X}+ {402.4289}$ 0.9992 0.25~5 0.0069
Cd $Y ={10288.5788X}+ {212.5113}$ 0.9998 0.5~10 0.0001
Cu Y=28146.4779X+82636.3525 0.9999 25~500 0.0140
), ArticleFig(id=1156967544591573149, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 3, caption=各元素的线性范围和检出限, figureFileSmall=null, figureFileBig=null, tableContent=
元素 回归方程 相关系数 $r$ 线性范围 $\left({\mu \mathrm{g}/\mathrm{L}}\right)$ 检出限 (mg/kg)
Pb $Y ={128950.4883X}+ {67590.8059}$ 0.9991 1~20 0.0022
As $Y ={2154.1207X}+ {127.3198}$ 0.9997 1~20 0.0015
$\mathrm{{Hg}}$ $Y ={15837.2807X}+ {402.4289}$ 0.9992 0.25~5 0.0069
Cd $Y ={10288.5788X}+ {212.5113}$ 0.9998 0.5~10 0.0001
Cu Y=28146.4779X+82636.3525 0.9999 25~500 0.0140
), ArticleFig(id=1156967544658682014, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 4, caption=Results of precision repeatability and stability, figureFileSmall=null, figureFileBig=null, tableContent=
元素名称 精密度 RSD (%) 重复性 RSD (%) 稳定性 RSD (%)
Pb 0.27 1.38 2.86
As 0.46 3.55 4.13
$\mathrm{{Hg}}$ 1.75 4.68 2.97
Cd 0.25 0.84 1.66
Cu 1.36 3.87 3.72
), ArticleFig(id=1156967544709013663, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 4, caption=各元素精密度、重复性和稳定性, figureFileSmall=null, figureFileBig=null, tableContent=
元素名称 精密度 RSD (%) 重复性 RSD (%) 稳定性 RSD (%)
Pb 0.27 1.38 2.86
As 0.46 3.55 4.13
$\mathrm{{Hg}}$ 1.75 4.68 2.97
Cd 0.25 0.84 1.66
Cu 1.36 3.87 3.72
), ArticleFig(id=1156967544750956704, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 5, caption=Results of recovery tests, figureFileSmall=null, figureFileBig=null, tableContent=
元素名称 加标量 $\left({\mu \mathrm{g}}\right)$ 回收率 (%)
Pb 0.05/2.5/3.75 97.1/107.1/115.3
As ${0.05}/{1.0}/{1.5}$ 90.8/107.8/101.7
$\mathrm{{Hg}}$ 0.05/0.1/0.15 102.5/101.6/84.6
Cd 0.025/0.5/0.75 103.5/104.8/97.0
Cu ${1.25}/{10}/{15}$ 85.9/98.6/87.8
), ArticleFig(id=1156967544805482657, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 5, caption=各元素加标回收率, figureFileSmall=null, figureFileBig=null, tableContent=
元素名称 加标量 $\left({\mu \mathrm{g}}\right)$ 回收率 (%)
Pb 0.05/2.5/3.75 97.1/107.1/115.3
As ${0.05}/{1.0}/{1.5}$ 90.8/107.8/101.7
$\mathrm{{Hg}}$ 0.05/0.1/0.15 102.5/101.6/84.6
Cd 0.025/0.5/0.75 103.5/104.8/97.0
Cu ${1.25}/{10}/{15}$ 85.9/98.6/87.8
), ArticleFig(id=1156967544851620002, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 6, caption=Five heavy metals determination and pollution assessment in TCMs (mg/kg), figureFileSmall=null, figureFileBig=null, tableContent=
饮片名称 Pb As $\mathrm{{Hg}}$ Cd Cu 综合指数
黄芪(10 批) 0.01~0.93 0.005~0.10 0~0.095 0~0.05 3.2~9.1 0.213
甘草(10 批) 0.01~0.29 0.003 ~0.18 0~0.067 0~0.045 2.2~7.7 0.219
枸杞子(10 批) 0~0.62 0.004~0.05 0~0.084 0~0.12 5.4~7.9 0.26
山楂(5 批) 0.01~0.31 0~0.22 0~0.10 0~0.05 3.1~13.1 0.229
金银花 (10 批) 0.3~3.7 0.07~0.23 0~0.32 0~0.34 6.7~10.6 0.576
), ArticleFig(id=1156967544910340259, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 6, caption=5 种中药饮片重金属含量及污染评价 $\left({\mathrm{{mg}}/\mathrm{{kg}}}\right)$, figureFileSmall=null, figureFileBig=null, tableContent=
饮片名称 Pb As $\mathrm{{Hg}}$ Cd Cu 综合指数
黄芪(10 批) 0.01~0.93 0.005~0.10 0~0.095 0~0.05 3.2~9.1 0.213
甘草(10 批) 0.01~0.29 0.003 ~0.18 0~0.067 0~0.045 2.2~7.7 0.219
枸杞子(10 批) 0~0.62 0.004~0.05 0~0.084 0~0.12 5.4~7.9 0.26
山楂(5 批) 0.01~0.31 0~0.22 0~0.10 0~0.05 3.1~13.1 0.229
金银花 (10 批) 0.3~3.7 0.07~0.23 0~0.32 0~0.34 6.7~10.6 0.576
), ArticleFig(id=1156967544981643428, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=EN, label=Table 7, caption=Element in Barrenwort, figureFileSmall=null, figureFileBig=null, tableContent=
元素 标准参考值 (μg/g) 实测值 $\left({\mu \mathrm{g}/\mathrm{g}}\right)$
Pb ${3.61}\pm {0.15}$ 3.67
As ${0.363}\pm {0.014}$ 0.344
$\mathrm{{Hg}}$ ${0.060}\pm {0.004}$ 0.064
Cd ${0.339}\pm {0.021}$ 0.322
Cu ${7.5}\pm {0.3}$ 7.34
), ArticleFig(id=1156967545027780773, tenantId=1146029695717560320, journalId=1146119944283992078, articleId=1156967528888099771, language=CN, label=表 7, caption=淫羊藿无机成分分析标准物质, figureFileSmall=null, figureFileBig=null, tableContent=
元素 标准参考值 (μg/g) 实测值 $\left({\mu \mathrm{g}/\mathrm{g}}\right)$
Pb ${3.61}\pm {0.15}$ 3.67
As ${0.363}\pm {0.014}$ 0.344
$\mathrm{{Hg}}$ ${0.060}\pm {0.004}$ 0.064
Cd ${0.339}\pm {0.021}$ 0.322
Cu ${7.5}\pm {0.3}$ 7.34
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电感耦合等离子体质谱法测定常见中药饮片中5种重金属含量
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陆叶 * , 邹丹凤 , 张学博 , 郁爱萍 , 陈云忠
实验室检测 | 创新应用 2024,2(7): 62-65
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实验室检测 | 创新应用 2024, 2(7): 62-65
电感耦合等离子体质谱法测定常见中药饮片中5种重金属含量
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陆叶* , 邹丹凤, 张学博, 郁爱萍, 陈云忠
作者信息
  • 上海市崇明食品药品检验所 上海 202150
  • 陆叶,主管技师,检验员,研究方向为食品药品安全检测与质量控制。

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*陆叶,主管技师,检验员,研究方向为食品药品安全检测与质量控制。E-mail:
Determination of 5 kinds of heavy metal elements in commom TCM by inductively coupled plasma mass spectrometry
Ye LU* , Dan-Feng ZOU, Xue-Bo ZHANG, Ai-Ping YU, Yun-Zhong CHEN
Affiliations
  • Shanghai Chongming Institute for Food and Drug Control Shanghai 202150 China
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目的 建立电感耦合等离子体质谱(Inductively Coupled Plasma MassSpectrometry,ICP-MS)法测定黄芪、山楂、枸杞子、金银花、甘草中铅、砷、汞、镉、铜 5种重金属的含量。方法 45 批样品经微波消解后,采用 ICP-MS法同时测定中药材中 5 种重金属含量,射频功率 ${1550}\mathrm{\;W}$ ,采用 KED (KineticEnergy Discrimination) 碰撞模式,碰撞气为氦气,载气为氩气,载气流量 ${0.8}\mathrm{\;L}/\mathrm{{min}}$ ,等离子体气体流量 ${14.0}\mathrm{\;L}/\mathrm{{min}}$结果 5种元素线性关系良好 ( $r>{0.999}$ ),回收率在84.6% 115.3%之间,检出限为0.0001 0.0140mg/kg,45 批次样品中,金银花存在个别样品超标现象。 结论该方法简便高效、稳定可靠,可用于多种重金属的质量研究,并为其质量控制和科学监管提供更多依据。关键词:ICP-MS;中药饮片;重金属

ICP-MS  /  中药饮片  /  重金属

Objective To establish an inductively coupled plasma massspectrometry (ICP-MS) method for the determination of $\mathrm{{Pb}},\mathrm{{As}},\mathrm{{Hg}},\mathrm{{Cd}},\mathrm{{Hg}}$ in astragali radix, crataegi fructus, lycii fructus, lonicerae japonicaeflos and glycyrrhizae radix et rhizome. Methods After microwavedigestion of forty-five batches of samples, the contents of five heavymetals in commom TCM decoction pieces were determinationed by ICP-MS.The RF power is 1550 W. Kinetic Energy Discrimination mode is used. Thecollisional gas was Helium.The carrier gas was Argon with ${0.8}\mathrm{\;L}/\mathrm{{min}}$ , theplasma gas flow rate was ${14.0}\mathrm{\;L}/\mathrm{{min}}$ . Results Five heavy metal elements showed a good linear relationships $\left({r >{0.999}}\right)$ , whoserecoveries were 84.6%~115.3%, the detection limit was ${0.0001}\sim {0.0140}\mathrm{{mg}}/\mathrm{{kg}}$ .Among the 45 batches of samples, there were individual samples oflonicerae japonicae flos that exceeded the limit. Conclusion This methodis simple, efficient, stable and reliable, which can be used for thequality study of a variety of heavy metals, and provides more basis forits quality control and scientific supervision.

ICP-MS  /  TCM decoction pieces  /  heavy metals
陆叶, 邹丹凤, 张学博, 郁爱萍, 陈云忠. 电感耦合等离子体质谱法测定常见中药饮片中5种重金属含量. 实验室检测, 2024 , 2 (7) : 62 -65 .
Ye LU, Dan-Feng ZOU, Xue-Bo ZHANG, Ai-Ping YU, Yun-Zhong CHEN. Determination of 5 kinds of heavy metal elements in commom TCM by inductively coupled plasma mass spectrometry[J]. Laboratory Testing, 2024 , 2 (7) : 62 -65 .
中药是中医用来预防和治疗疾病的药物。传统中药主要包括中药材、中药饮片和中成药。中药材和中药饮片没有绝对的界限。中药饮片是指在中医药理论的指导下, 可直接用于调配或制剂的中药材及其中药材的加工炮制品,在中医临床上被广泛使用 [ 1 - 4 ] 。随着中药现代化的发展,重金属残留问题受到国内外高度关注 [ 5 ] 。重金属元素能与体内的酶蛋白结合使蛋白质结构发生不可逆的改变,从而透过细胞影响细胞组织功能 [ 6 - 8 ] 。中药饮片中重金属超标不仅直接影响中药质量、降低临床疗效, 甚至还会危害人体健康。
电感耦合等离子体质谱法 (ICP-MS) 具有灵敏度高、准确性好、多元素同时测定等优点, 在中药重金属检测中具有独特的优势 [ 9 - 10 ] 。本文采用微波消解联合 ICP-MS 对黄芪、山楂、枸杞子、金银花、甘草 5 种饮片进行铅、砷、汞、镉、铜 5 种重金属含量测定, 进一步补充完善大宗中药饮片品种的重金属及有害元素污染监测数据,为其质量安全和科学监管提供了技术支撑。
iCAP RQ 型电感耦合等离子体质谱仪 ( 美国 Thermo 公司 ); MARS6 型微波消解仪 (美国 CEM 公司); AL204-IC 型天平 (万分之一,瑞士 Mettler 公司)。
铅 (Pb)、镉 (Cd)、汞 (Hg)、砷 (As)、铜 (Cu) 单元素标准溶液质量浓度均为 (中国计量科学研究院,批号分别为。
锗(Ge)、铟(In)、铋(Bi)、金(Au)元素标准溶液质量浓度均为 (国家有色金属及电子材料分析测试中心,批号分别为。
ICP-MS 调谐溶液 ( ${1\mu }\mathrm{g}/\mathrm{L},\mathrm{{Ba}}$$\mathrm{{Bi}}$$\mathrm{{Ce}}$$\mathrm{{Co}}$$\mathrm{{In}}$$\mathrm{{Li}}$$\mathrm{U}$ , Alfa Aesar )。
硝酸(优级纯,德国Merck公司);超纯水(电阻率 $\geq {18.2}\mathrm{M}\Omega \cdot \mathrm{{cm}}$ ,德国 Merck 公司); 载气为 99.999% 高纯氩气。
黄芪、枸杞子、金银花、甘草各 10 批,山楂 5 批,见 表 1 , 由药品经营单位购得, 常温下置塑料袋中保存。
仪器经调谐成功后, 通过在线加入内标消除基体效应, KED 模式消除多原子分子干扰,射频功率 ${1550}\mathrm{W}$ ,冷却水流量 ${0.6}\mathrm{\;L}/\mathrm{{min}}$ ,冷却气流量 ${14.0}\mathrm{\;L}/\mathrm{{min}}$ ,载气气流量 ${0.8}\mathrm{\;L}/\mathrm{{min}}$ ,雾化器气体流量 1.0 L/min,碰撞气 (氦气) 流量 ${4.0}\mathrm{\;{mL}}/\mathrm{{min}}$ ,雾化室温度 ${2.7}^{\circ }\mathrm{C}$ ,进样泵泵速度 ${40}\mathrm{r}/\mathrm{{min}}$ ,采样深度 ${15}\mathrm{\;{mm}}$ ,重复读数 3 次,积分时间 ${0.03}\mathrm{\;s}$
各精密量取 ${1000\mu }\mathrm{g}/\mathrm{{mL}}\mathrm{{Pb}}$ 、As、Cd、Cu、Hg 单元素标准溶液适量, 5% 硝酸稀释制成质量浓度均分别含 Pb、As 1、2、 $4\text{、}8\text{、}{16}\text{、}{20}\mathrm{{ng}}/\mathrm{{mL}},\mathrm{{Cd}}{0.5}\text{、}1\text{、}2\text{、}4\text{、}8\text{、}{10}\mathrm{{ng}}/\mathrm{{mL}},\mathrm{{Cu}}{25}$${50}\text{、}{100}\text{、}{200}\text{、}{400}\text{、}{500}\mathrm{{ng}}/\mathrm{{mL}},\mathrm{{Hg}}$ (与金标 $1 :{20}$ 配制) 0.25、 ${0.5}\text{、}1\text{、}2\text{、}4\text{、}5\mathrm{{ng}}/\mathrm{{mL}}$ 的系列浓度混合溶液,随行试剂为空白。
各精密量取 ${1000\mu }\mathrm{g}/\mathrm{{mL}}\mathrm{{Ge}}$$\mathrm{{In}}$$\mathrm{{Bi}}$ 元素标准溶液适量, $5\%$ 硝酸稀释制成质量浓度均为 $5\mathrm{{ng}}/\mathrm{{mL}}$ 的混合内标溶液。以 ${}^{72}\mathrm{{Ge}}$ 为内标测定 ${}^{63}\mathrm{{Cu}}$${}^{75}\mathrm{{As}}$ ; 以 ${}^{209}\mathrm{{Bi}}$ 为内标测定 ${}^{202}\mathrm{{Hg}}$${}^{208}\mathrm{{Pb}}$ ; 以 ${}^{115}\mathrm{{In}}$ 为内标测定 ${}^{114}\mathrm{{Cd}}$
45 批样品烘干粉碎过 2 号筛,精密称取 ${0.5}\mathrm{\;g}$ ,置 ${50}\mathrm{\;{mL}}$ 聚四氟乙烯消解管中,加硝酸 $7\mathrm{\;{mL}}$ 混匀,盖上内盖, ${110}^{\circ }\mathrm{C}$ 加热预消解 ${30}\mathrm{\;{min}}$ ,取出,冷却至室温,旋紧外盖,置微波消解仪中消解,程序见 表 2 ,消解完全后,冷却至 ${60}^{\circ }\mathrm{C}$ 以下,取出消解罐,将消解液转移至 ${50}\mathrm{\;{mL}}$ 量瓶中,超纯水少量多次洗涤, 洗液一并转入,用水定容至刻度,摇匀,用 ${0.22\mu }\mathrm{m}$ 微孔滤膜过滤, 即得。同法制备样品加标和试剂空白溶液。
取“2.2.1”项下混合标准溶液,在“2.1”项条件下进样测定,“2.2.2” 项下内标溶液校正, 仪器分析过程中, 内标管始终插入内标溶液中,以各元素的质量浓度为横坐标(X),离子强度为纵坐标(Y)进行回归 (扣除空白干扰),结果见 表 3 ,各元素相关系数 $r >{0.999}$ ,说明各元素在各自范围内线性关系良好。
取“2.2.1”项下混合标准溶液,在“2.1”项条件下进样测定 6 次, 结果见 表 4 , 可知仪器精密度良好。
精密称取 ${0.5}\mathrm{\;g}$ 样品 (黄芪 $\mathrm{S}1$ ) 粉末,按 “2.2.3” 项下方法平行制备 6 份供试品溶液, 在 “2.1” 项条件下进样测定, 结果见 表 4 , 可知该方法重复性良好。
精密称取 ${0.5}\mathrm{\;g}$ 样品 (黄芪 $\mathrm{S}1$ ) 粉末,按 “2.2.3项下方法制备供试品溶液,于 $0\text{、}4\text{、}8\text{、}{12}\text{、}{16}\text{、}{24}\mathrm{\;h}$ 在2.1项条件下进样测定,结果见 表 4 ,可知溶液在 ${24}\mathrm{\;h}$ 内稳定性良好。
选取黄芪基质进行加标回收试验,精密称取 ${0.5}\mathrm{\;g}$ 样品(黄芪 S1)粉末平行 12 份,按 “2.2.3” 项下方法制备供试品溶液, 测定其中 3 份来计算各元素本底含量, 剩余 9 份按低、中、高 3 个浓度梯度加入 “2.3.1” 项下标准溶液适量, 在 “2.1” 项条件下进样测定, 计算回收率。结果表 5 , 各元素加样回收率在 84.6%~115.3% 范围内。
取 45 批样品,按 “2.2.3” 项下方法制备供试品溶液,在 “2.1” 项条件下进样测定,其中金银花中有 1 批汞含量为 ${0.32}\mathrm{{mg}}/\mathrm{{kg}}$ , 超限度 $\left({{0.2}\mathrm{{mg}}/\mathrm{{kg}}}\right){160}\%$ ,根据内梅罗综合指数法对 5 种饮片金属污染情况进行综合评价,综合指数越高表明重金属污染状况越严重,结果见 表 6
精密称取 ${0.5}\mathrm{\;g}$ 质控样粉末 (淫羊藿无机成分分析标准物质 GBW08589 批号:1206 中国计量科学研究院),按 “2.2.3” 项下方法制备, 结果见 表 7 , 由该方法所测得的数据均在标准参考值范围内,表明该方法准确可靠。
本实验研究对象为中医临床上应用十分广泛的大宗中药品种, 在低温加热和微波消解的双重前处理作用下, 样品消解的更加均匀彻底,操作较为简便、安全性更高,密闭式微波消解进一步减少了 $\mathrm{{Hg}}$$\mathrm{{As}}$ 元素的挥发损失,是较为理想的样品前处理方法 [ 11 ]
现行《中国药典》2020 年版重金属限量标准规定:铅≤5 mg/kg; 砷 $\leq 2\mathrm{{mg}}/\mathrm{{kg}}$ ;汞 $\leq {0.2}\mathrm{{mg}}/\mathrm{{kg}}$ ;镉 $\leq 1\mathrm{{mg}}/\mathrm{{kg}}$ ;铜 $\leq {20}\mathrm{{mg}}/\mathrm{{kg}}$ 。根据实验结果, 从不同的药用部位分析 5 种饮片的重金属污染情况, 花类 (金银花) 最高,其次是果实和种子类 (枸杞子和山楂), 根和根茎类 (黄芪和甘草) 最低, 由结果可知, 金银花中仍存在部分样品重金属超标的现象, 初步推测可能有以下几种原因, 首先有研究表明, 植物体不同部位对重金属的富集能力不同, 倪蓉 [ 12 ] 等研究发现忍冬科花部位(金银花为忍冬科忍冬属)中 $\mathrm{{Hg}}$$\mathrm{{As}}$ 的含量显著高于忍冬其他部位 (茎、叶、根),因此相比原药材,经净制处理后的金银花饮片中 $\mathrm{{Hg}}$$\mathrm{{As}}$ 的含量随药用部位比例的提高也相对提高, 第二, 植物在生长和加工过程中若使用了含汞农药或加工设备也可能导致汞超标。此外在暴露于污染的环境中时, 金银花植物进行光合作用吸入含汞的工业废气,或含汞粉尘附着于植物表面造成污染 [ 13 - 14 ]
本实验为重金属及有害元素污染和拟定限量标准提供了一定的数据基础,但研究仍存在不足,在标准限量制定时,应充分考虑不同重金属的毒性大小和中毒机理,以及临床用药方式、 剂量、疗程等各方面的影响。综合分析并在风险评估的基础上制定限量标准 [ 15 ] 。因此在未来有必要加强中药中重金属污染的研究, 针对不同种类的中药材及饮片制定出更加合理准确的限量标准。
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2024年第2卷第7期
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    上海市崇明食品药品检验所 上海 202150

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*陆叶,主管技师,检验员,研究方向为食品药品安全检测与质量控制。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

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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