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| Determining five oxides in manganese ores using inductively coupled plasma-optical emission spectroscopy |
ZHANG Peng-peng1,2( ), XU Bing-xu3(), HU Meng-ying1,2, Xu Jin-li1,2, LIU Bin1,2, ZHANG Ling-huo1,2, BAI Jin-feng1,2 |
1. Institute of Geophysical and Geochemical Exploration, Chinese Academy of Geological Sciences, Langfang 065000, China
2. Key Laboratory of Geochemical Exploration, Ministry of Natural Resources, Langfang 065000, China
3. Institute of Comprehensive Utilization of Mineral Resources, Chinese Academy of Geological Sciences, Chengdu 610041, China |
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Abstract Manganese ores are significant raw materials in the iron and steel industry. Accurately determining their major components is critical for the analysis of manganese ore composition. Based on three acid dissolution systems, i.e., aqua regia (HNO3+HC), tetracid (HNO3+HF+HClO4+HCl), and pentaacid (HNO3+HF+H2SO4+HClO4+HCl) solutions, and three extraction conditions, i.e., hydrochloric acid, nitric acid, and aqua regia, this study determined five oxides in manganese ores using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The results indicate that the pentaacid or pentaacid solution and the extraction with hydrochloric acid achieved encouraging determination results. Spectral lines with wavelengths of 766.490 nm (K), 184.006 nm (Ca), 589.592 nm (Na), 279.553 nm (Mg), and 396.152 nm (Al) were analyzed. The possible interference in the determination process was eliminated based on the standard solution matrix matching principle. The detection limits of Na, Mg, K, Ca, and Al were 0.000 27%, 0.000 21%, 0.000 15%, 0.000 17%, and 0.000 23%, respectively. The determination results of all five oxides in two national primary reference materials for manganese ores showed relative standard deviations (RSD) not exceeding 5.0%, suggesting fair precision. The verification results of all five oxides in five reference materials showed relative errors (RE) below 10%, demonstrating high accuracy, with the measured values roughly consistent with the recommended values. The spiked determination of five oxides in five manganese ores with unknown content yielded recovery rates ranging from 90% to 110%, suggesting that the accuracy met the analytical requirements. Therefore, the ICP-OES method simplifies sample pretreatment, improves efficiency, and reduces costs, thereby applying to batch sample analysis. The verification using reference materials demonstrates that its accuracy and precision meet industrial standards, establishing the ICP-OES method as an effective approach for determining the five oxides in manganese ore samples.
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Received: 11 October 2023
Published: 30 December 2025
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Corresponding Authors:
XU Bing-xu
E-mail: zhangpengpeng@mail.cgs.gov.cn;994814561@qq.com
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| 参数 | 数值 | 参数 | 数值 | | 等离子体功率/W | 1150 | 长波积分时间/s | 20 | | 雾化器压力/psi | 30 | 短波积分时间/s | 10 | | 辅助气流量/(L·min-1) | 1.0 | 冷却气流量/(L·min-1) | 14 | | 蠕动泵速/(r·min-1) | 60 | 清洗时间/s | 20 |
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Instrument operating parameters
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| 氧化物 | 标准物质 | 认定值/% | 王水溶样
测定值/% | 四酸溶样
测定值/% | 五酸溶样
测定值/% | 测定值与认定值误差/% | | 王水溶样 | 四酸溶样 | 五酸溶样 | | Na2O | GBW07261 | 0.04 | 0.047 | 0.040 | 0.044 | 19.00 | 0.50 | 10.00 | | GBW07262 | 0.05 | 0.054 | 0.052 | 0.054 | 8.40 | 4.00 | 8.00 | | MgO | GBW07261 | 0.64 | 0.577 | 0.599 | 0.601 | 9.84 | 6.30 | 6.06 | | GBW07262 | 1.44 | 1.436 | 1.474 | 1.436 | 0.22 | 2.40 | 0.23 | | K2O | GBW07261 | 1.00 | 0.981 | 0.993 | 0.951 | 1.87 | 0.67 | 4.87 | | GBW07262 | 0.46 | 0.425 | 0.439 | 0.422 | 7.57 | 4.39 | 8.22 | | CaO | GBW07261 | 1.06 | 1.042 | 1.066 | 1.104 | 1.67 | 0.57 | 4.24 | | GBW07262 | 3.60 | 3.330 | 3.460 | 3.419 | 7.50 | 3.88 | 5.03 | | Al2O3 | GBW07261 | 2.20 | 2.108 | 2.204 | 2.207 | 4.16 | 0.21 | 0.32 | | GBW07262 | 3.00 | 2.929 | 2.974 | 2.897 | 2.34 | 0.85 | 3.42 |
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Comparison of analysis results of different melting method
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| 氧化物 | 标准物质 | 认定
值/% | 盐酸浸提
测定值/% | 硝酸浸提
测定值/% | 王水浸提
测定值/% | | Na2O | GBW07261 | 0.04 | 0.043 | 0.049 | 0.046 | | GBW07262 | 0.05 | 0.053 | 0.050 | 0.045 | | MgO | GBW07261 | 0.64 | 0.61 | 0.56 | 0.58 | | GBW07262 | 1.44 | 1.51 | 1.39 | 1.35 | | K2O | GBW07261 | 1.00 | 0.97 | 0.54 | 0.96 | | GBW07262 | 0.46 | 0.45 | 0.26 | 0.40 | | CaO | GBW07261 | 1.06 | 1.11 | 1.11 | 1.09 | | GBW07262 | 3.60 | 3.63 | 3.59 | 3.23 | | Al2O3 | GBW07261 | 2.20 | 2.24 | 1.68 | 2.18 | | GBW07262 | 3.00 | 3.13 | 2.65 | 2.77 |
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Effects of different extraction acids on determination results
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| 元素 | 测定值/(mg·L-1) | | 1%Mn | 4%Mn | 8%Mn | 10%Mn | 20%Mn | 25%Mn | | K | 10.17 | 10.14 | 10.05 | 10.05 | 10.99 | 11.20 | | Ca | 9.96 | 9.92 | 9.83 | 9.67 | 10.90 | 11.14 | | Na | 9.74 | 9.93 | 9.97 | 10.05 | 13.82 | 14.85 | | Mg | 10.02 | 9.90 | 9.78 | 9.51 | 9.49 | 9.44 | | Al | 10.24 | 10.15 | 10.48 | 10.83 | 12.25 | 12.99 |
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Effect of Mn matrix mass concentration on the determination results of K、Ca、Na、Mg and Al
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| 元素 | 波长 | 相关系数 | 线性方程 | 检出限/
10-6 | | K | 766.490 | 0.9999 | y=1.3565×103x+15.949 | 1.5 | | Ca | 184.006 | 0.9999 | y=6.0257×10x+4.8343 | 1.7 | | Na | 589.592 | 0.9999 | y=2.9602×103x+54.545 | 2.7 | | Mg | 279.553 | 0.9994 | y=3.1583×104x+2.4967×103 | 2.1 | | Al | 396.152 | 0.9993 | y=9.1696×102x+8.9783 | 2.3 |
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Linear equation, correlation coefficient and detection limit of calibration curve
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| 编号 | GBW07261 | GBW07262 | | Na2O | MgO | K2O | CaO | Al2O3 | Na2O | MgO | K2O | CaO | Al2O3 | | 1 | 0.043 | 0.59 | 0.99 | 1.06 | 2.29 | 0.049 | 1.54 | 0.45 | 3.46 | 3.21 | | 2 | 0.044 | 0.58 | 0.97 | 1.04 | 2.22 | 0.044 | 1.46 | 0.44 | 3.36 | 3.10 | | 3 | 0.046 | 0.60 | 1.00 | 1.07 | 2.28 | 0.048 | 1.53 | 0.46 | 3.51 | 3.32 | | 4 | 0.043 | 0.58 | 0.97 | 1.06 | 2.27 | 0.044 | 1.50 | 0.45 | 3.48 | 3.24 | | 5 | 0.044 | 0.60 | 1.00 | 1.05 | 2.24 | 0.044 | 1.47 | 0.44 | 3.41 | 3.22 | | 6 | 0.042 | 0.58 | 0.96 | 1.02 | 2.22 | 0.044 | 1.48 | 0.44 | 3.38 | 3.12 | | 7 | 0.043 | 0.57 | 0.94 | 1.00 | 2.09 | 0.044 | 1.42 | 0.43 | 3.34 | 3.06 | | 8 | 0.041 | 0.55 | 0.91 | 0.98 | 2.07 | 0.044 | 1.39 | 0.42 | 3.23 | 2.93 | | 9 | 0.042 | 0.61 | 1.00 | 1.07 | 2.29 | 0.048 | 1.44 | 0.42 | 3.29 | 3.06 | | 10 | 0.041 | 0.63 | 1.03 | 1.09 | 2.30 | 0.045 | 1.41 | 0.42 | 3.24 | 2.99 | | 平均值/% | 0.043 | 0.59 | 0.98 | 1.04 | 2.23 | 0.045 | 1.47 | 0.44 | 3.37 | 3.12 | | 标准值/% | 0.04 | 0.64 | 1.00 | 1.06 | 2.20 | 0.05 | 1.44 | 0.46 | 3.60 | 3.00 | | RSD/% | 4.08 | 3.93 | 3.31 | 3.29 | 3.71 | 4.60 | 3.43 | 3.19 | 2.92 | 3.96 |
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Precision of the method
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| 氧化物 | 标准物质 | 认定值
/% | 测定值/% | 准确度
/% | 回收
率/% | | 本文方法 | 传统方法 | | Na2O | GBW07261 | 0.04 | 0.043 | 0.044 | 7.50 | | | GBW07262 | 0.05 | 0.054 | 0.054 | 8.00 | | | GBW07264 | 0.03 | 0.032 | 0.033 | 6.67 | | | GBW07265 | 0.02 | 0.021 | 0.020 | 5.00 | | | GBW07266 | 0.04 | 0.044 | 0.044 | 10.0 | | | 未知样品1 | | 0.78 | 0.78 | | 94.4 | | 未知样品2 | | 1.28 | 1.29 | | 103.1 | | 未知样品3 | | 1.08 | 1.07 | | 98.2 | | 未知样品4 | | 0.87 | 0.87 | | 93.2 | | 未知样品5 | | 0.61 | 0.62 | | 93.0 | | MgO | GBW07261 | 0.64 | 0.59 | 0.58 | -7.44 | | | GBW07262 | 1.44 | 1.48 | 1.48 | 3.08 | | | GBW07264 | 0.10 | 0.10 | 0.11 | 1.51 | | | GBW07265 | 3.50 | 3.58 | 3.58 | 2.34 | | | GBW07266 | 3.82 | 3.92 | 3.94 | 2.67 | | | 未知样品1 | | 5.35 | 5.36 | | 92.3 | | 未知样品2 | | 4.42 | 4.41 | | 96.2 | | 未知样品3 | | 5.09 | 5.06 | | 108.7 | | 未知样品4 | | 5.08 | 5.07 | | 100.3 | | 未知样品5 | | 5.50 | 5.03 | | 101.6 | | K2O | GBW07261 | 1.00 | 0.98 | 0.97 | -1.56 | | | GBW07262 | 0.46 | 0.45 | 0.43 | -1.25 | | | GBW07264 | 0.72 | 0.74 | 0.73 | 2.83 | | | GBW07265 | 0.46 | 0.45 | 0.44 | -0.26 | | | GBW07266 | 0.70 | 0.70 | 0.71 | 0.94 | | | 未知样品1 | | 1.73 | 1.72 | | 93.0 | | 未知样品2 | | 3.59 | 3.59 | | 93.7 | | 未知样品3 | | 2.67 | 2.65 | | 101.2 | | 未知样品4 | | 2.21 | 2.20 | | 94.1 | | 未知样品5 | | 1.24 | 1.24 | | 92.5 | | CaO | GBW07261 | 1.06 | 1.05 | 1.03 | -0.54 | | | GBW07262 | 3.60 | 3.44 | 3.42 | -4.38 | | | GBW07264 | 0.05 | 0.05 | 0.05 | -1.44 | | | GBW07265 | 14.7 | 13.9 | 13.8 | -5.00 | | | GBW07266 | 19.8 | 18.8 | 18.9 | -5.05 | | | 未知样品1 | | 17.76 | 17.75 | | 96.3 | | 未知样品2 | | 13.74 | 13.75 | | 96.1 | | 未知样品3 | | 15.93 | 15.94 | | 98.3 | | 未知样品4 | | 16.74 | 16.72 | | 110.0 | | 未知样品5 | | 19.26 | 19.24 | | 101.1 | | Al2O3 | GBW07261 | 2.20 | 2.22 | 2.21 | 1.12 | | | GBW07262 | 3.00 | 3.15 | 3.12 | 5.23 | | | GBW07264 | 8.97 | 8.27 | 8.24 | 7.79 | | | GBW07265 | 1.68 | 1.72 | 1.71 | 2.94 | | | GBW07266 | 2.49 | 2.63 | 2.61 | 5.97 | | | 未知样品1 | | 5.73 | 5.71 | | 98.2 | | 未知样品2 | | 9.54 | 9.52 | | 100.7 | | 未知样品3 | | 8.19 | 8.17 | | 96.4 | | 未知样品4 | | 7.02 | 7.01 | | 109.1 | | 未知样品5 | | 4.21 | 4.21 | | 101.5 |
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Accuracy test of the method
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