混合熔剂熔融ICP-OES内标法同时测定铝土矿中铝等十种元素

doi:10.3964/j.issn.1000-0593(2025)12-3387-07

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摘要：铝土矿是我国战略性矿产之一，准确、高效地分析其主要及共伴生的有益有害元素含量对铝土矿的矿床评价和综合利用有重要意义。目前铝土矿系统分析仍以传统化学法、原子吸收法单元素测定为主，分析效率较低，亟待开发一种简单高效的铝土矿中多元素同时测定方法。电感耦合等离子体发射光谱法（ICP-OES）同时测定铝土矿中的多元素含量，关键点在于难熔铝土矿样品高效分解方法的选择、高倍稀释条件下提高测定精密度和准确度的方法、基体及共存元素干扰的消除等。提出一种无水碳酸钠-硼酸混合熔剂熔融，超声提取，ICP-OES离线内标法同时测定铝土矿中铝、硅、铁、钛、锶、锂、铬、钒、锆、钪十种元素的分析方法。系统探究了混合熔剂用量、熔融温度对样品分解效果的影响，0.1 g样品加入0.7 g混合熔剂，在1 000 ℃下熔融20 min保证样品分解完全；优化了熔融物提取条件，选择15%盐酸超声提取，提取效率高且不产生硅酸沉淀；根据铝土矿中各元素含量、谱线灵敏度及谱线干扰情况，优选了待测元素分析谱线；通过对比Cd 214.438 nm、Cd 228.802 nm、Co 228.616 nm、Co 345.351 nm对10种元素的校正效果，选择Co 228.616 nm、Co 345.351 nm为内标谱线分别校正不同元素，提高了待测元素测定结果的精密度；系统考察了不同浓度铝对其他元素的干扰情况，发现不同元素受铝干扰的程度存在差异，该方法样品稀释2 500倍后待测溶液中铝的浓度一般不超过200 μg·mL^-1，对其他元素的干扰可以忽略。该方法各元素的检出限为0.5 μg·g^-1~0.1%，通过标准物质验证，除锂元素外，其他元素的相对标准偏差（RSD，n=12）均小于5%。主量元素（Al₂O₃、SiO₂、Fe₂O₃、TiO₂）测定结果的相对误差（RE）为-1.81%~1.61%，其中Al₂O₃为-0.65%~0.28%，其他元素测定结果的相对误差为-10.53%~12.78%，测定值与认定值基本一致。该方法方便快捷，检出限低，测定结果准确度高、精密度好，适用于不同含量范围铝土矿样品中多元素同时分析。

关键词：电感耦合等离子体发射光谱法；铝土矿；多元素同时分析；混合熔剂熔融；内标法

Abstract：Bauxite is one of the strategic minerals in China. Accurate and efficient analysis of the contents of major, associated beneficial, and harmful elements is of great significance for evaluating and comprehensively utilizing bauxite. At present, the systematic analysis of bauxite is still dominated by traditional chemical methods and atomic absorption spectrometry, with relatively low analytical efficiency. It is necessary to develop a simple, efficient, and simultaneous multi-element analysis method for bauxite. The key points of simultaneously determining the multi-element content in bauxite by inductively coupled plasma optical emission spectrometry (ICP-OES) include selecting efficient decomposition methods for refractory bauxite samples, improving the precision and accuracy of determination under high dilution conditions, and eliminating matrix and coexisting element interferences. This study proposes a method for 10 elements (Al, Si, Fe, Ti, Sr, Li, Cr, V, Zr, Sc) in bauxite using mixed-flux fusion-ICP-OES with an offline internal standard. The effects of mixed flux dosage and melting temperature on sample decomposition efficiency were systematically investigated. 0.1 g sample was added to 0.7 g mixed flux and melted at 1 000 ℃ for 20 min to ensure complete decomposition of the sample; the extraction conditions of the fused samples were optimized. Ultrasonic extraction with 15% hydrochloric acid was selected, as it offers high extraction efficiency without silicic acid precipitation. Based on the content of various elements in bauxite, the sensitivity and interference of spectral lines, the analytical spectral lines of the determined elements were selected. By comparing the correction effects of Cd 214.438 nm, Cd 228.802 nm, Co 228.616 nm, and Co 345.351 nm on the 10 elements, Co 228.616 nm and Co 345.351 nm were selected as internal standard lines to correct different elements, respectively, which significantly improved the precision of the determined elements. The interference of aluminum at different concentrations on other elements was systematically investigated, and it was found that the degree of interference varied among elements. The concentration of aluminum in the sample solution (dilution of 2 500 times) was generally not more than 200 μg·mL^-1, and the interference on other elements could be ignored. The detection limit for each element in this method ranged from 0.5 μg·g^-1 to 0.1%. According to the verification of certified reference materials, the relative standard deviation (RSD, n= 12) of all elements except lithium was less than 5%. The relative error (RE) of major elements (Al₂O₃, SiO₂, Fe₂O₃, TiO₂) ranged from -1.81% to 1.61% (e. g., Al₂O₃: -0.65%~0.28%), while the relative error of other elements ranged from -10.53% to 12.78%. The determination values were basically consistent with the certified values. This method is convenient and fast, with a low detection limit, high accuracy, and good precision, and is suitable for the simultaneous analysis of multiple elements in bauxite with different contents.

Key words：Inductively coupled plasma optical emission spectrometry; Bauxite; Simultaneous multi-element analysis; Mixed flux fusion; Internal standard method

收稿日期: 2025-05-07 修订日期: 2025-09-24

中图分类号:

O657.3

基金资助: 国家重点研发计划课题（2021YFC2903001）资助

通讯作者: 阳国运，白金峰 E-mail: 731757094@qq.com；bjinfeng@mail.cgs.gov.cn

作者简介: 张灵火，1992年生，中国地质科学院地球物理地球化学勘查研究所工程师 e-mail: zhanglinghuo@mail.cgs.gov.cn

引用本文:

张灵火，阳国运，马娜，张鹏鹏，陈海杰，徐进力，白金峰. 混合熔剂熔融ICP-OES内标法同时测定铝土矿中铝等十种元素[J]. 光谱学与光谱分析, 2025, 45(12): 3387-3393.
ZHANG Ling-huo, YANG Guo-yun, MA Na, ZHANG Peng-peng, CHEN Hai-jie, XU Jin-li, BAI Jin-feng. Simultaneous Determination of Ten Elements Including Aluminum in Bauxite by Mixed Flux Fusion-ICP-OES With Internal Standard Method. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(12): 3387-3393.

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[1] YU Wen-chao, DU Yuan-sheng, ZHOU Jin-tao, et al(余文超, 杜远生, 周锦涛, 等). Acta Geologica Sinica(地质学报), 2023, 97(9): 3056.
[2] DU Tian-jun, QIAO Li-jun, ZHAO Ya-nan, et al(杜天军, 乔丽君, 赵亚男, 等). Chinese Journal of Inorganic Analytical Chemistry(中国无机分析化学), 2023, 13(10): 1083.
[3] Putzolu F, Papa A P, Mondillo N, et al. Minerals, 2018, 8(7): 298.
[4] Zhu K Y, Su H M, Jiang S Y. Ore Geology Reviews, 2019, 114: 103144.
[5] ZHANG Ying-ying, SHI Lei(张莹莹, 石磊). Physical Testing and Chemical Analysis (Part B: Chemical Analysis) (理化检验-化学分册), 2021, 57(9): 813.
[6] XIA Chuan-bo, ZHAO Wei, JIANG Yun, et al(夏传波, 赵伟, 姜云, 等). Metallurgical Analysis(冶金分析), 2020, 40(7): 29.
[7] LIU Gui-lei, XU Chun-xue, CHEN Zong-ding, et al(刘贵磊, 许春雪, 陈宗定, 等). Rock and Mineral Analysis(岩矿测试), 2020, 39(5): 670.
[8] LÜ Shan-sheng, CHEN Qing-lin, LAI Xuan-han, et al(吕善胜, 陈晴林, 赖宣汉, 等). Physical Testing and Chemical Analysis (Part B: Chemical Analysis)(理化检验-化学分册), 2021, 57(7): 654.
[9] Zhang W, Qi L, Hu Z C, et al. Geostandards and Geoanalytical Research, 2016, 40(2): 195.
[10] HU Xuan(胡璇). Rock and Mineral Analysis(岩矿测试), 2020, 39(6): 954.
[11] SUN Hong-bin, LIU Gui-lei, ZHAO Huai-ying, et al (孙红宾, 刘贵磊, 赵怀颖, 等). Chinese Journal of Analysis Laboratory(分析试验室), 2017, 36(12): 1429.
[12] PAN Qian-ni, LIU Wei, HE Yu-shan, et al(潘倩妮, 刘伟, 何雨珊, 等). Rock and Mineral Analysis(岩矿测试), 2024, 43(3): 459.
[13] YS/T 575.1—2007 Nonferrous Metals Industry Standard of the People's Republic of China, Methods for Chemical Analysis of Bauxite-Part 1: Determination of Aluminium Oxide Content-EDTA Titrimetric Method (YS/T 575.1—2007中华人民共和国有色金属行业标准铝土矿石化学分析方法第1部分: 氧化铝含量的测定EDTA滴定法). National Development and Reform Commission(中华人民共和国国家发展和改革委员会), 2007.
[14] ZHAO Hui, ZHANG Lai-ping, YU Jun-ming, et al(赵辉, 章来平, 于君明, 等). Physical Testing and Chemical Analysis (Part B: Chemical Analysis) (理化检验-化学分册), 2020, 56(3): 352.