利用微波等离子体炬四极杆质谱在线测定稀土矿样中的多种稀土元素

初晨; 张瑛; 王尚贤; 周润芝; 蒋涛; 朱志强; 卢爱民

doi:10.15898/j.cnki.11-2131/td.2016.05.004

利用微波等离子体炬四极杆质谱在线测定稀土矿样中的多种稀土元素

1.
中国武警后勤部疾病预防控制中心, 北京 102613

2.
东华理工大学江西省质谱科学与仪器重点实验室, 江西南昌 330013

3.
上饶师范学院化学化工学院, 江西上饶 334001

基金项目:
国家科技部项目国家重大仪器专项（2011YQ14015009）；国家自然科学基金资助项目（21565003）

详细信息

作者简介: 初晨, 学士, 研究方向为分析化学。E-mail:13810747783@163.com

通讯作者: 朱志强, 博士, 副教授, 研究方向为质谱分析。E-mail:zhiqiangz@iccas.ac.cn

中图分类号: O614.33;O657.63

收稿日期: 2016-03-28

修回日期: 2016-06-15

录用日期: 2016-09-09

Direct Determination of Rare Earth Elements in REE Ores Using Microwave Plasma Torch Coupled with Quadrupole Mass Spectrometry

1.
Center for Disease Control and Prevention, Logistics Department of Chinese Armed Police Force, Beijing 102613, China

2.
Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China Institute of Technology, Nanchang 330013, China

3.
School of Chemistry and Chemical Engineering, Shangrao Normal University, Shangrao 334001, China

More Information

Corresponding author: Zhi-qiang ZHU, zhiqiangz@iccas.ac.cn

Received Date: 28 March 2016

Revised Date: 15 June 2016

Accepted Date: 09 September 2016

摘要

摘要: 随着稀土的应用越来越广泛，开发稀土元素的快速在线检测技术已日趋成为行业发展的需求。本文以微波等离子体炬（MPT）为离子源，以四极杆质谱仪（QMS）作为质量分析器建立了一种快速、直接检测水样中稀土元素的质谱检测方法，并将其应用于分析稀土矿样中的多种稀土元素。研究表明，应用MPT-QMS测定水样中的钇、镧、铈、钕、铕五种稀土元素，检出限（LOD）可达11.0~60.5 μg/L, 测定范围为50~1000 μg/L。当分析固体稀土矿样时，样品经酸溶处理后通过气动雾化形成气溶胶，再进行冷却干燥，气溶胶由MPT的中心管道进入等离子体中，产生稀土元素复合离子，再引入QMS中进行分析，即可以定量地测定矿样中稀土元素的含量。同一样品用电感耦合等离子体质谱（ICP-MS）进行对比实验，两者的检测结果在数量级上接近，证明了MPT-QMS方法在半定量的意义下是准确、可靠的，因而这种快速的检测方法可发展成为水体中金属元素的现场分析方法，应用于环境水、生活水质量在线监测等领域。
- 微波等离子体炬 /
- 等离子体质谱 /
- 稀土元素 /
- 在线检测
Abstract: With the widespread application of rare earth elements analysis, the development of rapid detection technology of rare earth elements has increasingly become a necessity within the industry. Microwave Plasma Torch (MPT) as the ion source and Quadrupole Mass Spectrometry (QMS) as the mass analyzer to develop a method for fast detection of rare earth elements (REEs) in water and ore samples has been developed and discussed in this paper. With the MPT-QMS method, for elements Y, La, Ce, Nd, Eu in water samples, the limits of detection (LODs) are 11.0-60.5 μg/L, and the linear ranges are 50-1000 μg/L. When analyzing ore samples, the samples were firstly digested by acid solution and the sample solution formed an aerosol, which was then cooled to keep it dry. The aerosol entered the plasma by the centre tube of the MPT and formed REE ions. These ions enter the QMS, and concentrations of REE elements can be quantitatively determined. Repeated analyses of the same sample by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) yield similar results, indicating that the semi-quantitative analyses of MPT-QMS are precise and reliable. Therefore, MPT coupled with QMS is suitable for portable, rapid analysis of metal elements in water and can be used in the field of in situ quality monitoring of environmental and drinking water.
- microwave plasma torch /
- Plasma Mass Spectrometry /
- rare earth element /
- on-line determination

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图 1 MPT-QMS实验装置示意图

Figure 1.

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图 2 (a)钇、(b)镧、(c)铈、(d)铕的MPT-QMS特征质谱图

Figure 2.

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图 3 矿样消解液稀释100倍所得质谱图

Figure 3.

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表 1 MPT-QMS和ICP-MS对标准样品中各元素的分析结果

Table 1. Experimental results of MPT-QMS and ICP-MS for five rare earth elements

元素	MPT-QMS方法技术指标					稀土矿样测定结果(mg/L)		相似度(%)
元素	线性方程	R	线性范围 (μg/L)	最低检出限 (μg/L)	相对标准偏差 RSD(%)	MPT-QMS法	ICP-MS法	相似度(%)
Y	y=0.23285x-47.554	0.9903	200~1000	60.51	5.4~11.2	57.798	58.473	98.8456
La	y=0.0741x-1.591	0.9680	50~300	17.12	2.7~13.8	164.383	164.956	99.6526
Ce	y=0.0566x-3.413	0.9852	50~600	21.51	1.6~8.6	212.488	212.938	99.7887
Nd	y=0.1347x-12.92	0.9868	50~1000	23.45	1.3~10.2	71.998	72.756	98.9581
Eu	y=0.121x-4.265	0.9903	10~1000	11.03	3.8~19.0	5.803	5.901	98.3054

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参考文献(29)

[1]	胡斌, 殷俊.稀土元素分离检测技术新进展[J].中国稀土学报, 2006, 24(5):513-522. doi: 10.1016/S1002-0721(06)60154-3 Hu B, Yin J.Progress of Separation and Determination Methods for Rare Earth Elements[J].Journal of the Chinese Rare Earth Society, 2006, 24(5):513-522. doi: 10.1016/S1002-0721(06)60154-3
[2]	Packard H.AES Detector for GC[J].Analytical Chemistry, 1995, 67:742A.
[3]	Barnes IV J H, Gr∅n, Hieftje G M.Characterization of an Argon Microwave Plasma Torch Coupled to a Mattauch-Herzog Geometry Mass Spectrometer[J].Journal of Analytical Atomic Spectrometry, 2002, 17(9):1132-1136. doi: 10.1039/B202201J
[4]	吴石头, 王亚平, 孙德忠, 等.电感耦合等离子体发射光谱法测定稀土矿石中的15种稀土元素——四种前处理方法的比较[J].岩矿测试, 2014, 33(1):12-19. http://www.ykcs.ac.cn/ykcs/ch/reader/create_pdf.aspx?file_no=20140104&year_id=2014&quarter_id=1&falg=1 Wu S T, Wang Y P, Sun D Z, et al.Determination of 15 Rare Earth Elements in Rare Earth Ores by Inductively Coupled Plasma-Atomic Emission Spectrometry:A Comparison of Four Difference[J].Rock and Mineral Analysis, 2014, 33(1):12-19. http://www.ykcs.ac.cn/ykcs/ch/reader/create_pdf.aspx?file_no=20140104&year_id=2014&quarter_id=1&falg=1
[5]	苏宇亮, 方黎.离子色谱法在饮用水水质分析中的应用[J].净水技术, 2005, 24(2):62-65. http://www.cnki.com.cn/Article/CJFDTOTAL-ZSJS200502018.htm Su Y L, Fang L.Application of Ion-Chromatography Technique in Drinking Water Analysis[J].Water Purification Technology, 2005, 24(2):62-65. http://www.cnki.com.cn/Article/CJFDTOTAL-ZSJS200502018.htm
[6]	Liu Q L, Feng L X, Yuan C X, et al.A Highly Selective Fluorescent Probe for Cadmium Ions in Aqueous Solution and Living Cells[J].Chemical Communications, 2014, 50:2498-2501. doi: 10.1039/c3cc48668k
[7]	Doner G, Ege A.Determination of Copper, Cadmium and Lead in Seawater and Mineral Water by Flame Atomic Absorption Spectrometry after Coprecipitation with Aluminum Hydroxide[J].Analytical Chimica Acta, 2005, 547:14-17. doi: 10.1016/j.aca.2005.02.073
[8]	Veillon C.Trace Element Analysis of Biological Samples[J].Analytical Chemistry, 1986, 58:851A-866A. http://pubs.acs.org/doi/pdf/10.1021/ac00121a715
[9]	Kipphardt H, Czerwensky M, Matschat R.ICP-MS Analysis of High Purity Molybdenum Used as SI-traceable Standard of High Metrological Quality[J].Journal of Analytical Atomic Spectrometry, 2005, 20:28-34. doi: 10.1039/b409973g
[10]	Keyes W R, Turnlund J R.Determination of Molybdenum and Enriched Mo Stable Isotope Concentrations in Human Blood Plasma by Isotope Dilution ICP-MS[J].Journal of Analytical Atomic Spectrometry, 2002, 17:1153-1156. doi: 10.1039/b202250h
[11]	Townsend A T, Miller K A, McLean S, et al.The Determination of Copper, Zinc, Cadmium and Lead in Urine by High Resolution ICP-MS[J].Journal of Analytical Atomic Spectrometry, 1998, 13:1213-1219. doi: 10.1039/a805021j
[12]	金钦汉, 杨广德, 于爱民, 等.一种新型的等离子体光源[J].吉林大学自然科学学报, 1985(1):90-92. http://www.cnki.com.cn/Article/CJFDTOTAL-JLDX198501012.htm Jin Q H, Yang D G, Yu A M, et al.A Novel Plasma Emission Source[J].Acta Scientiarum Naturalium Universitatis Jilinensis, 1985(1):90-91. http://www.cnki.com.cn/Article/CJFDTOTAL-JLDX198501012.htm
[13]	Jin Q H, Zhu C, Border M W, et al.A Microwave Plasma Torch Assembly for Atomic Emission Spectrometry[J].Spectrochimica Acta Part B:Atomic Spectroscopy, 1991, 46(3):417-430. doi: 10.1016/0584-8547(91)80039-6
[14]	Wan T Q, Yu D D, Zhang T Q, et al.A Rapid Method for Detection of Gunshot Residue Using Microwave Plasma Torch-Mass Spectrometry[J].Procedia Engineering, 2010, 7:22-27. doi: 10.1016/j.proeng.2010.11.004
[15]	张体强, 金伟, 周建光, 等.微波等离子体常压解吸电离质谱法快速检测化学药剂中的活性成分[J].高等学校化学学报, 2012, 33(9):1938-1944. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201209012.htm Zhang T Q, Jin W, Zhou J G, et al.Rapid Detection of Active Pharmaceutical Ingredients in Drugs by Microwave Plasma Atmospheric Pressure Desorption Ionization Mass Spectrometry[J].Chemical Journal of Chinese Universities, 2012, 33(9):1938-1944. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201209012.htm
[16]	Jin Q, Zhu C, Border M W, et al.A Microwave Plasma Torch Assembly for Atomic Emission Spectrometry[J].Spectrochimaica Acta Part B:Atomic Spectroscopy, 1991, 46(3):417-430. doi: 10.1016/0584-8547(91)80039-6
[17]	Huang M, Hanselman D S, Jin Q, et al.Non-thermal Features of Atmospheric-pressure Argon and Helium Microwave-induced Plasmas Observed by Laser-light Thomson Scattering and Rayleigh Scattering[J].Spectrochim Acta Part B, 1990, 45B:1339-1352. http://www.sciencedirect.com/science/article/pii/058485479080187N
[18]	Zhang T Q, Zhou W, Jin W, et al.Direct Desorption/Ionization of Analysis by Microwave Plasma Torch for Ambient Mass Spectrometric Analysis[J].Journal of Mass Spectrometry, 2013, 48(6):669-676. doi: 10.1002/jms.3212
[19]	Jin Q, Wang F, Zhu C, et al.Atomic Emission Detector for Gas Chromatography and Supercritical Fluid Chromatography[J].Journal of Analytical Atomic Spectrometry, 1990, 5:487-494. doi: 10.1039/ja9900500487
[20]	杨美玲, 钟涛, 裴妙荣, 等.气动雾化进样-微波等离子体炬质谱法快速测定水样中的钙离子[J].岩矿测试, 2015, 34(5):586-591. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20150515&flag=1 Yang M L, Zhong T, Pei M R, et al.Rapid Determination of Calcium Ions in Water by Microwave Plasma Torch-Mass Spectrometry Coupled with Pneumatic Nebulization[J].Rock and Mineral Analysis, 2015, 34(5):586-591. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20150515&flag=1
[21]	钟涛, 杨美玲, 裴妙荣, 等.微波等离子体炬-质谱法测定饮用水中微量钙[J].高等学校化学学报, 2016, 37(1):26-30. http://www.cjcu.jlu.edu.cn/CN/10.7503/cjcu20150503 Zhong T, Yang M L, Pei M R, et al.Determination of Trace-amount Calcium in Drinking Water by Microwave Plasma Torch Mass Spectrometry[J].Chemical Journal of Chinese Universities, 2016, 37(1):26-30. http://www.cjcu.jlu.edu.cn/CN/10.7503/cjcu20150503
[22]	Xiong X H, Jiang T, Zhou R Z, et al.Microwave Plasma Torch Mass Spectrometry for the Direct Detection of Copper and Molybdenum Ions in Aqueous Liquids[J].Journal of Mass Spectrometry, 2016, 51:369-377. doi: 10.1002/jms.3768
[23]	蒋涛, 熊小红, 周炜, 等.两种微波等离子体炬质谱测定水中铅的对比研究[J].分析测试学报, 2016, 35(6):648-653. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201606003.htm Jiang T, Xiong X H, Zhou W, et al.Direct Detection of Lead in Aqueous Solution Using Two Kinds of Microwave Plasma Torch Coupled Mass Spectrometry[J].Journal of Instrumental Analysis, 2016, 35(6):648-653. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201606003.htm
[24]	蒋涛, 刘秋菊, 易兰芳, 等.微波等离子体炬质谱直接分析水中镉的研究[J].分析测试学报, 2016, 35(1):79-84. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201601017.htm Jiang T, Liu Q J, Yi L F, et al.Direct Detection of Cadmium in Aqueous Solution Using Microwave Plasma Torch Coupled with Quadrupole Mass Spectrometry[J].Journal of Instrumental Analysis, 2016, 35(1):79-84. http://www.cnki.com.cn/Article/CJFDTOTAL-TEST201601017.htm
[25]	Xiong X H, Jiang T, Qi W H, et al.Some Rare Earth Elements Analysis by Microwave Plasma Torch Coupled with the Linear Ion Trap Mass Spectrometry[J].International Journal of Analytical Chemistry, 2015, ID156509. http://www.sinoms.net/uploadfile/201512/20151216093756269.pdf
[26]	Jiang T, Xiong X H, Wang S X.Direct Mass Spectro-metric Analysis of Zinc and Cadmium in Water by Microwave Plasma Torch Coupled with a Linear Ion Trap Mass Spectrometer[J].International Journal of Mass Spectrometry, 2016, 399-400:33-39. doi: 10.1016/j.ijms.2016.02.007
[27]	许华磊, 凌星, 张小华, 等.微波等离子体炬质谱仪的研制[J].分析化学, 2015, 43(12):1955-1961. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201512030.htm Xu H L, Ling X, Zhang X H, et al.Development of Microwave Plasma Torch Mass Quadrupole Spectrometer[J].Chinese Journal of Analytical Chemistry, 2015, 43(12):1955-1961. http://www.cnki.com.cn/Article/CJFDTOTAL-FXHX201512030.htm
[28]	Ding J H, Gu H W, Yang S P, et al.Selective Detection of Diethylene Glycol in Toothpaste Products Using Neutral Desorption Reactive Extractive Electrospray Ionization Tandem Mass Spectrometry[J].Analytical Chemistry, 2009, 81(20):8632-8638. doi: 10.1021/ac9013594
[29]	Balaram V.Recent Trends in the Instrumental Analysis of Rare Earth Elements in Geological and Industrial Materials[J].Trends in Analytical Chemistry, 1996, 15(9):475. doi: 10.1016/S0165-9936(96)00058-1