| 119 | 0 | 31 |
| 下载次数 | 被引频次 | 阅读次数 |
镉是我国土壤环境质量管控与国家土壤环境监测网的必测重金属指标。针对常规电感耦合等离子体质谱(ICP-MS)法测定土壤和沉积物中痕量镉时，易受钼、锆相关多原子离子的严重质谱干扰，且存在样品前处理操作繁琐、用酸量大、消解周期长等问题，建立了王水快速密闭消解-电感耦合等离子体串联质谱(ICP-MS/MS)分析方法。通过优化消解条件，确定采用王水体系120℃密闭消解60 min，可在实现镉全量溶出的同时，显著降低干扰元素锆的溶出率；消解液无需赶酸即可直接上机测定，配合一次性带盖具刻度聚丙烯离心管完成全流程前处理，有效降低了交叉污染风险。实验选取111Cd为分析同位素，阐明了氧气反应模式对钼、锆相关多原子离子质谱干扰的消除机理，优化确定氧气的最佳流速为1.2 mL/min；对添加高浓度钼、锆干扰离子的实际样品开展加标回收实验，加标回收率为97.8%～107%，证实干扰消除效果优异。方法学验证结果表明：方法检出限为0.003 mg/kg；测定土壤和沉积物标准物质的相对误差(RE)为-3.4%～5.0%，相对标准偏差(RSD)为1.1%～4.8%，方法正确度与精密度良好；与国家标准方法比对，测定结果无显著性差异(P>0.05)。该方法兼具前处理简便快速、用酸量少、抗干扰能力强、灵敏度高的优势，可高效实现土壤和沉积物中痕量镉的批量精准检测。
Abstract：Cadmium(Cd) is a mandatory pollutant indicator in China's soil environmental quality management and the national soil environmental monitoring network. To address the severe spectral interferences from molybdenum(Mo)-and zirconium(Zr)-related polyatomic ions,as well as the drawbacks of cumbersome sample pretreatment,high acid consumption,and long digestion cycle in the determination of trace cadmium in soil and sediment by conventional inductively coupled plasma mass spectrometry(ICP-MS),an analytical method based on aqua regia rapid closed digestion combined with inductively coupled plasma tandem mass spectrometry(ICP-MS/MS) was established in this study. By optimizing the digestion conditions,closed digestion with an aqua regia system at 120 ℃ for 60 min was determined,which could achieve complete dissolution of cadmium while significantly reducing the dissolution rate of the interfering element zirconium. The digestate could be directly subjected to instrumental analysis without acid evaporation,and the whole pretreatment process was completed in disposable graduated polypropylene centrifuge tubes with lids,which effectively reduced the risk of cross-contamination. In the experiment,111Cd was selected as the analytical isotope. The elimination mechanism of spectral interferences from Mo-and Zr-related polyatomic ions via the oxygen reaction mode was elucidated,and the optimal flow rate of the reaction gas oxygen was optimized and determined to be 1. 2 mL/min. Spike recovery tests were carried out on actual samples spiked with high-concentration Mo and Zr interfering ions,with spike recoveries ranging from 97. 8% to 107%,confirming the excellent interference elimination effect of the method. The methodological validation results showed that the limit of detection of the method was 0. 003 mg/kg. The relative error for the determination of soil and sediment certified reference materials ranged from-3. 4% to 5. 0%,and the relative standard deviation ranged from 1. 1% to 4. 8%,indicating good trueness and precision of the method. Compared with the national standard method,there was no significant difference in the determination results(P>0. 05). This method has the advantages of simple and rapid pretreatment,low acid consumption,strong anti-interference ability and high sensitivity,and can efficiently realize batch and accurate determination of trace cadmium in soil and sediment.
[1]刘莉莉，林岚，殷霄，等.镉毒性研究进展[J].中国职业医学，2012,39(5):445-447.Liu Lili,Lin Lan,Yin Xiao,et al. Research progress on cadmium toxicity[J]. China Occupational Medicine,2012,39(5):445-447.
[2]王凡，刘娟，邓中原.重金属镉的生殖毒性研究进展[J].毒理学杂志，2025,39(5):364-368.Wang Fan,Liu Juan,Deng Zhongyuan. Research progress on reproductive toxicity of heavy metal cadmium[J].Journal of Toxicology,2025,39(5):364-368.
[3]卢天一，艾艳梅，汪洋，等.镉污染土壤中水稻的镉富集特征和生长响应[J].草业学报，2025,34(8):66-78.Lu Tianyi,Ai Yanmei,Wang Yang,et al. Cadmium enrichment characteristics and growth response of rice under excess cadmium stress in soil[J]. Acta Prataculturae Sinica,2025,34(8):66-78.
[4]杨娇，葛文静，闫怡新，等.基于文献计量分析的农田土壤镉污染研究热点与进展[J].环境工程学报，2025,19(6):1517-1530.Yang Jiao,Ge Wenjing,Yan Yixin,et al. Research hotspots and progress of farmland soil cadmium pollution based on bibliometric analysis[J]. Chinese Journal of Environmental Engineering,2025,19(6):1517-1530.
[5]邓杰帆，吴翠玉，卢瑛，等.东莞某工业镇农用地土壤镉污染及生态风险评价[J].广东农业科学，2019,46(3):78-84.Deng Jiefan,Wu Cuiyu,Lu Ying,et al. Soil cadmium pollution and ecological risk assessment of agricultural land in an industrial town of Dongguan[J]. Guangdong Agricultural Sciences,2019,46(3):78-84.
[6]GB/T 17141—1997土壤质量铅、镉的测定石墨炉原子吸收分光光度法[S].GB/T 17141—1997 Soil quality:determination of lead,cadmium-Graphite furnace atomic absorption spectrophotometry[S].
[7]曹静，汪浩，袁金华.土壤中镉的分步消解-石墨炉原子吸收光谱测定法[J].环境与健康杂志，2023,40(3):270-272.Cao Jing,Wang Hao,Yuan Jinhua. Determination of cadmium in soil by step digestion-Graphite furnace atomic absorption spectrometry[J]. Journal of Environment and Health,2023,40(3):270-272.
[8]王要才，杨小林，熊静，等.纳米钯基体改进剂-石墨炉原子吸收光谱法测定土壤和沉积物中镉的含量[J].理化检验-化学分册，2022,58(12):1401-1406.Wang Yaocai,Yang Xiaolin,Xiong Jing,et al.Determination of cadmium in soil and sediment by graphite furnace atomic absorption spectrometry with nanopalladium matrix modifier[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2022,58(12):1401-1406.
[9]杜桂月，哈莹，张时佳，等.电感耦合等离子体原子发射光谱法测定土壤有效态镉的不确定度评定[J].化学分析计量，2025,34(11):140-144.Du Guiyue,Ha Ying,Zhang Shijia,et al. Evaluation of uncertainty in determination of available cadmium in soil by inductively coupled plasma atomic emission spectrometry[J]. Chemical Analysis and Meterage,2025,34(11):140-144.
[10]刘文艳，颜忠国. ICP-OES测定矿山尾矿库外沿土壤样品中铜、铅、镉、砷等四种重金属元素[J].世界有色金属，2025(8):189-191.Liu Wenyan,Yan Zhongguo. ICP-OES determination of four heavy metal elements,including copper,lead,cadmium,and arsenic,in soil samples along the outer edge of mine tailings ponds[J]. World Nonferrous Metals,2025(8):189-191.
[11]何恬叶，张颖红，胡子文.微波消解ICP-OES法测定土壤样品中22种元素[J].分析试验室，2018,37(1):84-87.He Tianye,Zhang Yinghong,Hu Ziwen. Determination of 22 elements in soil by ICP-OES with microwave digestion[J]. Chinese Journal of Analysis Laboratory,2018,37(1):84-87.
[12]中华人民共和国环境保护部.土壤和沉积物12种金属元素的测定王水提取-电感耦合等离子体质谱法：HJ803—2016[S].北京：中国环境科学出版社，2016.Ministry of Environmental Protection of the People's Republic of China. Soil and sediment:determination of aqua regia extracts of 12 metal elements-Inductively coupled plasma mass spectrometry:HJ 803—2016[S].Beijing:China Environmental Science Press,2016.
[13]中华人民共和国生态环境部.土壤和沉积物19种金属元素总量的测定电感耦合等离子体质谱法：HJ 1315—2023[S].北京：中国环境科学出版社，2023.Ministry of Environmental Protection of the People's Republic of China. Soil and sediment:determination of total contents of 19 metal elements by inductively coupled plasma mass spectrometry:HJ 1315—2023[S]. Beijing:China Environmental Science Press,2023.
[14]熊丽萍，赵一敏，王瑶，等.全自动石墨消解-电感耦合等离子体质谱法测定土壤中7种重金属元素的含量[J].理化检验-化学分册，2025,61(4):463-468.Xiong Liping,Zhao Yimin,Wang Yao,et al.Determination of 7 heavy metal elements in soil by inductively coupled plasma mass spectrometry with automatic graphite digestion[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2025,61(4):463-468.
[15]王妃，王德淑，汤德能.浅析锡对电感耦合等离子体质谱法测定镉的干扰[J].中国无机分析化学，2015,5(2):12-18.Wang Fei,Wang Deshu,Tang Deneng. Study on interference of tin in the determination of cadmium by inductively coupled plasma mass spectrometry[J].Chinese Journal of Inorganic Analytical Chemistry,2015,5(2):12-18.
[16]黄勤，凤海元，吴忠忠.电感耦合等离子体质谱法测定环境评价性土壤中铬铜镉铅[J].化学研究与应用，2017,29(9):1444-1448.Huang Qin,Feng Haiyuan,Wu Zhongzhong.Determination of Cr,Cu,Cd and Pb in environmental evaluation soils by inductively coupled plasma-mass spectrometry[J]. Chemical Research and Application,2017,29(9):1444-1448.
[17]迟清华，鄢明才.应用地球化学元素丰度数据手册[M].北京：地质出版社，2007:140-142.Chi Qinghua,Yan Mingcai. Handbook of elemental abundance for applied geochemistry[M]. Beijing:Geological Publishing House,2007:140-142.
[18]徐义邦，赖新云，高明，等.氨气反应模式-电感耦合等离子体串联质谱法测定水体中微量钛[J].化学研究与应用，2025(6):1679-1684.Xu Yibang,Lai Xinyun,Gao Ming,et al. Determination of trace titanium in water by ICP-MS/MS at ammonia reaction mode[J]. Chemical Research and Application,2025(6):1679-1684.
[19]刘跃，王记鲁，林冬，等.氨气模式-电感耦合等离子体串联质谱法测定土壤中镉的质谱干扰消除研究[J].中国测试，2023,49(10):90-96.Liu Yue,Wang Jilu,Lin Dong,et al. Study on the interference elimination of cadmium in soil samples by ICP-MS/MS using ammonia mode[J]. China Measurement&Test,2023,49(10):90-96.
[20]赵志飞，任小荣，李策，等.氧气反应模式-电感耦合等离子体串联质谱法测定土壤中的镉[J].岩矿测试，2021,40(1):95-102.Zhao Zhifei,Ren Xiaorong,Li Ce,et al. Determination of cadmium in soil samples by ICP-MS/MS using oxygen reaction mode[J]. Rock and Mineral Analysis,2021,40(1):95-102.
[21]刘跃，王记鲁，李静，等.氧气反应模式-电感耦合等离子体串联质谱法测定土壤中砷和硒[J].冶金分析，2022,42(10):30-37.Liu Yue,Wang Jilu,LI Jing,et al. Determination of arsenic and selenium in soil by inductively coupled plasma tandem mass spectrometry at oxygen reaction mode[J].Metallurgical Analysis,2022,42(10):30-37.
[22]蔡松韬，黄莹秀，袁亮，等.基于氧反应模式的ICP-MS/MS高灵敏测定食品中痕量镍[J].分析试验室，2023,42(9):1179-1185.Cai Songtao,Huang Yingxiu,Yuan Liang,et al.Highly sensitive determination of trace nickel in food by inductively coupled plasma tandem mass spectrometry based on oxygen reaction mode[J]. Chinese Journal of Analysis Laboratory,2023,42(9):1179-1185.
[23]汤少展，任小荣，李策，等.电感耦合等离子体串联质谱法同时测定土壤和水系沉积物中关键矿产稀散元素镓铟锗硒碲[J].岩矿测试，2025,44(6):1203-1212.Tang Shaozhan,Ren Xiaorong,Li Ce,et al. Simultaneous quantification of critical mineral elements gallium,indium,germanium,selenium,and tellurium in soils and stream sediments by inductively coupled plasma-tandem mass spectrometry[J]. Rock and Mineral Analysis,2025,44(6):1203-1212.
[24]Bolea-Fernandez E,Balcaen L,Resano M,et al.Interference-free determination of ultra-trace concentrations of arsenic and selenium using methyl fluoride as a reaction gas in ICP-MS/MS[J]. Analytical and Bioanalytical Chemistry,2015,407(3):919-929.
[25]刘宏伟，陈雪峰，黎树春，等.电感耦合等离子体串联质谱测定高纯稀土及稀土氧化物中超痕量铁[J].分析化学，2023,51(9):1518-1525.Liu Hongwei,Chen Xuefeng,Li Shuchun,et al.Determination of ultra-trace iron in high purity rare earth and rare earth oxide by inductively coupled plasmatandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2023,51(9):1518-1525.
[26]Pinheiro F C,Amaral C D B,Schiavo D,et al.Determination of arsenic in fruit juices using inductively coupled plasma tandem mass spectrometry(ICP-MS/MS)[J]. Food Analytical Methods,2017,10(4):992-998.
[27]D'Ilio S,Violante N,Majorani C,et al. Dynamic reaction cell ICP-MS for determination of total As,Cr,Se and V in complex matrices:still a challenge A review[J].Analytica Chimica Acta,2011,698(1/2):6-13.
[28]赵志南，陈观宇，杨仁康.土壤样品快速消解与ICP-MS测定条件的优化[J].环境化学，2017,36(6):1428-1431.Zhao Zhinan,Chen Guanyu,Yang Renkang. The optimization of soil digestion and ICP-MS testing conditions[J]. Environmental Chemistry,2017,36(6):1428-1431.
[29]邓彬彬，刘秋辛，林君铿，等.基于快速消解的海洋沉积物重金属ICP-MS测定条件优化[J].中国环境监测，2024,40(3):12-18.Deng Binbin,Liu Qiuxin,Lin Junkeng,et al.Optimization of conditions for the determination of heavy metals in marine sediments by ICP-MS based on rapid digestion[J]. Environmental Monitoring in China,2024,40(3):12-18.
[30]黄赛.快速消解ICP-MS法测定土壤中痕量镉及其干扰消除[J].现代农业科技，2019(7):173-174.Huang Sai. Determination of trace amounts of cadmium in soil by ICP-MS with rapid digestion and its interference elimination[J]. XianDai NongYe KeJi,2019(7):173-174.
[31]张吴，徐义邦，熊鹏翔，等.快速密闭消解-基体匹配法测定土壤中镉含量[J].化学工程师，2020,34(8):31-34.Zhang Wu,Xu Yibang,Xiong Pengxiang,et al.Determination of cadmium in soil by the rapid closed digestion and the matched matrix method[J]. Chemical Engineer,2020,34(8):31-34.
[32]孙孟华，李晓敬，王文娟，等.过氧化钠碱熔-电感耦合等离子体质谱法测定地质样品中锆铌铪钽锂铍钒磷铀锰[J].冶金分析，2022,42(1):78-84.Sun Menghua,Li Xiaojing,Wang Wenjuan,et al.Determination of zirconium,niobium,hafnium,tantalum,lithium,beryllium,vanadium,phosphorus,uranium and manganese in geological samples by inductively coupled plasma mass spectrometry with sodium peroxide alkali fusion[J]. Metallurgical Analysis,2022,42(1):78-84.
[33]何袖辉，段文，王银剑，等.王水水浴消解-电感耦合等离子体质谱（ICP-MS）法测定地质样品中镉、硒和银[J].中国无机分析化学，2025,15(5):683-689.He Xiuhui,Duan Wen,Wang Yinjian,et al. Determination of cadmium,selenium and silver in geological samples by inductively coupled plasma mass spectrometry(ICP-MS)with aqua regia bath digestion[J]. Chinese Journal of Inorganic Analytical Chemistry,2025,15(5):683-689.
基本信息:
DOI：10.20236/j.CJIAC.2026.07.003
中图分类号:O657.63;X830
引用信息:
[1]徐义邦,张吴,邓维,等.王水快速密闭消解-电感耦合等离子体串联质谱（ICP-MS/MS）法测定土壤和沉积物中镉[J].中国无机分析化学,2026,16(07):1186-1195.DOI:10.20236/j.CJIAC.2026.07.003.
基金信息:
国家自然科学基金资助项目(22264001); 江西省科技厅青年基金资助项目(20232BAB213089); 生态环境部重金属污染监测重点实验室开放基金资助项目(KLMHM202533,SKLMHM202317)~~
2026-03-30
2026-03-30
2026-03-30