Simultaneous Determination of Au and Associated Elements Ag, Cu, Pb, Zn, As and Sb in Gold Ore by ICP-MS with Hypochloric Acid Oxidation
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摘要:
金矿石是重要的战略性矿产资源，除需检测金含量外，还需检测银铜铅锌砷锑等伴生元素含量。由于金矿石中往往含有碳质物和硫化物，对金的浸出有影响，现有方法需要焙烧-消解-预富集后测定，矿物中硫化砷、氧化砷、卤化锑等化合物沸点均低于565℃，金矿石在650℃焙烧时砷、锑极易损失，因此银铜铅锌砷锑需单独消解测定，极为繁琐。本文利用次氯酸的强氧化性，在硝酸介质中氧化碳质物与硫化物替代焙烧样品，结合离线内标建立了电感耦合等离子体质谱(ICP-MS)同时测定金银铜铅锌砷锑的方法。研究了次氯酸用量、消解时间、内标和干扰元素对分析结果的影响，结果表明10.0000g样品加入20mL硝酸和5mL次氯酸于电热板沸腾溶解近干，可将碳质物与硫化物完全氧化，稀释因子为1000时金银铜铅锌砷锑的检出限分别为0.03、0.05、0.19、0.26、0.22、0.27、0.05µg/g。应用本方法对高品位碲金矿成分分析标准物质(GBW07858、GBW07859)进行测定，结果与标准值相符；对5个不同类型的金矿石实际样品进行测定，结果与《金矿石化学分析方法》(GB/T 20899—2019)单独测定结果相符，各元素相对误差均≤5.32%，相对标准偏差(RSD，n=7)≤4.71％。本方法解决了金与银铜铅锌砷锑等伴生元素无法同时测定的问题，并省去了焙烧样品与金预富集步骤，流程简便。
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关键词:
- 次氯酸 /
- 电感耦合等离子体质谱法 /
- 金矿石 /
- 金 /
- 伴生元素
Abstract:Gold ore contains a certain amount of gold, silver, copper, lead, zinc, arsenic, and antimony. Gold needs to be determined after roasting, digestion and enrichment; arsenic and antimony are lost after roasting, while silver, copper, lead, zinc, arsenic and antimony need to be separately determined, which is extremely cumbersome. The experiment utilized the oxidizing properties of hypochlorous acid to oxidize carbonaceous materials and sulfides in a nitric acid medium instead of sample roasting. Combined with offline internal standards, a method was established for the simultaneous determination of gold, silver, copper, lead, zinc, arsenic, and antimony by ICP-MS. The amount of hypochlorous acid, digestion time, internal standard selection, and interfering elements were optimized. The results showed that the carbonaceous and sulfides materials were oxidized under the conditions of 10.0000g of the sample, 20mL of nitric acid and 5mL of hypochlorous acid with using a heating plate to deal with them until near-dryness. According to the experimental method, gold, silver, copper, lead, zinc, arsenic, and antimony were determined in five different types of gold ore samples, the results were consistent with the national standard method, and the relative standard deviations (RSDs, n=7) were less than 4.71%. This method solves the problem of simultaneous determination of gold, silver, copper, lead, zinc, arsenic and antimony, which is simple and convenient. The BRIEF REPORT is available for this paper at
http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202403130044 .-
Key words:
- hypochloric acid /
- inductively coupled plasma-mass spectrometry /
- gold ore /
- gold /
- associated elements
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表 1 电感耦合等离子体质谱分析工作条件
Table 1. The instrument parameters of ICP-MS
工作参数 设定值 工作参数 设定值 ICP射频功率 1550W Omega透镜 10V 载气流速 0.7L/min 反应池入口 −30V 雾室温度 2℃ 反应池出口 −50V 采样深度 7mm 偏转电压 10V 提取透镜1 0V 泵速 30r/min 提取透镜2 −140V 雾化器气体流速 0.80L/min Omega偏置电压 −80V 氧化物产率 0.67% 
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表 2 次氯酸用量与氧化时间关系
Table 2. The relationship between the dosage of hypochlorous acid and oxidation time
样品名称 次氯酸用量
(mL)完全氧化时间
(min)活性炭 3 11 4 8 5 5 6 4 石墨 3 19 4 16 5 10 6 9
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表 3 金和银加入标准回收试验
Table 3. The recovery tests of Au and Ag
样品名称 元素 加标量
(µg/g)测得总量
(µg/g)回收率
(%)活性炭 Au 5.00 4.98 97.0 Ag 5.00 4.94 103.0 石墨 Au 5.00 5.02 97.4 Ag 5.00 4.97 100.5
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表 4 各元素检出限和测定范围
Table 4. Detection limits and measurement ranges of each element
元素 空白测定值
(µg/g)标准偏差
(µg/g)检出限
(µg/g)测定范围
(µg/g)197Au 0.03 0.02 0.03 0.02 0.01 0.03 0.03 0.03 0.04 0.03 0.03 0.008 0.03 0.12～20 107Ag 0.09 0.08 0.05 0.04 0.04 0.05 0.06 0.07 0.05 0.06 0.06 0.016 0.05 0.20～1000 63Cu 0.35 0.36 0.41 0.37 0.42 0.31 0.45 0.41 0.46 0.53 0.45 0.062 0.19 0.76～2000 208Pb 0.42 0.41 0.51 0.42 0.53 0.36 0.58 0.51 0.48 0.62 0.61 0.086 0.26 1.04～2000 66Zn 0.47 0.49 0.53 0.42 0.51 0.65 0.57 0.55 0.54 0.58 0.66 0.072 0.22 0.88～2000 75As 0.52 0.54 0.61 0.55 0.63 0.46 0.67 0.51 0.59 0.76 0.48 0.089 0.27 1.08～2000 121Sb 0.11 0.12 0.10 0.14 0.09 0.10 0.12 0.11 0.10 0.12 0.11 0.014 0.05 0.20～2000
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表 5 标准物质测定结果
Table 5. Determination results of national standard materials
标准物质
编号元素 本法测定值(µg/g) RSD
(%)标准值
(µg/g)相对误差
(%)7次平行测定值 平均值 GBW07858 Au 19.1 19.3 19.4 19.2 19.4 19.6 19.2 19.3 0.87 19.6±0.4 1.53 Ag 44.0 44.1 44.8 43.5 44.2 44.8 44.1 44.2 1.04 44.2±1.4 0.00 Cu 53.4 52.3 53.2 53.5 54.1 54.5 53.2 53.5 1.32 53.4±3.6 0.19 Pb 68.7 70.1 70.5 71.1 69.2 69.1 71.6 70.0 1.56 70.3±2.8 0.43 Zn 96.3 97.2 97.8 99.2 100 98.5 101 98.6 1.66 99±4 0.40 As 12.2 12.3 12.4 12.3 12.6 12.5 12.3 12.4 1.12 12.5±0.8 0.80 Sb 3.35 3.33 3.25 3.26 3.41 3.38 3.34 3.33 1.76 3.35±0.28 0.60 GBW07859 Au 31.2 30.4 32.1 32.2 31.5 31.5 32.1 31.6 2.03 32.1±0.7 1.56 Ag 67.6 67.4 68.5 67.5 67.6 68.5 67.4 67.8 0.73 67.4±2.8 0.59 Cu 65.1 66.7 65.8 64.2 65.9 66.4 67.8 66.0 1.75 65±4.4 1.54 Pb 87.6 86.4 85.8 87.6 86.9 87.2 86.2 86.8 0.81 87.8±3.9 1.14 Zn 114 115 116 118 119 111 117 116 2.33 112±6 3.57 As 12.3 12.5 12.6 12.5 12.3 12.1 12.2 12.4 1.47 12.1±0.8 2.48 Sb 4.32 4.33 4.44 4.31 4.36 4.34 4.46 4.37 1.37 4.38±0.34 0.23
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表 6 本文方法与国家标准分析方法比对实验结果
Table 6. Determination results of proposed method in this study and national standard method
实际样品编号 元素 本法测定值(µg/g) RSD
(%)国标法
测定均值
(µg/g)相对误差*
(%)7次平行测定值 平均值 S1 Au 0.22 0.21 0.22 0.22 0.24 0.21 0.22 0.22 4.55 0.23 4.44 Ag 5.41 5.53 5.29 5.35 5.26 5.13 5.05 5.29 3.08 5.41 2.27 Cu 123 125 131 133 128 124 130 128 2.99 123 3.76 Pb 266 261 262 269 256 263 271 264 1.93 271 2.62 Zn 87.4 83.6 87.4 85.6 88.6 85.4 90.9 87.0 2.74 85.0 2.33 As 33.6 34.5 34.1 33.2 32.4 34.6 34.4 33.8 2.39 34.5 1.97 Sb 11.2 10.8 11.3 10.6 11.5 11.3 10.8 11.1 3.03 10.7 3.41 S2 Au 17.9 18.1 18.5 17.7 17.9 18.4 18.6 18.2 1.90 18.3 0.78 Ag 10.7 10.0 9.79 10.3 10.50 10.2 10.1 10.2 3.01 10.7 4.53 Cu 541 540 539 544 551 547 542 543 0.79 538 1.00 Pb 43.6 43.0 42.2 41.3 40.5 39.7 39.9 41.5 3.70 43.5 4.82 Zn 121 115 124 126 116 119 128 121 4.09 115 5.32 As 52.6 53.6 53.3 55.1 50.5 54.3 56.2 53.7 3.42 53.1 1.04 Sb 127 123 128 119 127 131 125 126 3.07 122 3.00 S3 Au 1.12 1.07 1.16 1.18 1.11 1.15 1.07 1.12 3.84 1.15 2.39 Ag 10.1 10.4 10.6 10.4 10.2 9.87 9.95 10.2 2.59 10.1 1.15 Cu 93.2 93.6 96.2 95.4 97.8 97.1 94.6 95.4 1.82 94.2 1.28 Pb 682 688 699 693 682 687 693 689 0.91 696 0.99 Zn 243 245 241 235 247 238 248 242 1.96 241 0.59 As 12.9 12.3 12.8 13.6 13.4 14.2 13.5 13.2 4.71 12.7 4.19 Sb 2.31 2.19 2.26 2.48 2.23 2.31 2.37 2.31 4.18 2.39 3.53 S4 Au 3.30 3.25 3.24 3.40 3.27 3.34 3.42 3.32 2.16 3.30 0.52 Ag 115 119 115 119 121 123 124 119 2.97 115 3.78 Cu 104 109 105 111 112 106 107 108 2.82 107 0.67 Pb 524 513 516 519 515 525 513 518 0.96 511 1.33 Zn 206 204 201 199 208 207 205 204 1.59 201 1.62 As 1163 1152 1181 1133 1154 1151 1153 1155 1.25 1147 0.72 Sb 949 955 957 948 955 957 964 955 0.56 945 1.05 S5 Au 8.40 8.41 8.65 8.34 8.40 8.51 8.47 8.45 1.21 8.42 0.41 Ag 65.6 67.1 65.5 64.2 63.5 65.8 65.1 65.3 1.78 65.1 0.24 Cu 1269 1253 1256 1264 1261 1269 1252 1261 0.57 1250 0.84 Pb 1690 1675 1681 1672 1695 1677 1680 1681 0.49 1685 0.21 Zn 855 843 865 851 859 864 854 856 0.90 854 0.22 As 438 423 426 435 432 437 433 432 1.30 430 0.46 Sb 71.1 71.6 73.4 70.8 73.5 72.8 74.2 72.5 1.82 72.1 0.53 注：“*”代表该相对误差的计算是以国标法测定平均值为真实值。
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[1] Kerr R A. Is the world tottering on the precipice of peak gold?[J]. Science, 2012, 335(6072): 1038−1039. doi: 10.1126/science.335.6072.1038
[2] 王安建, 袁小晶. 大国竞争背景下的中国战略性关键矿产资源安全思考[J]. 中国科学院院刊, 2022, 37(11): 1550−1559. doi: 10.16418/j.issn.1000-3045.20220817001
Wang A J, Yuan X J. Security of China’s strategic and critical minerals under background of great power competition[J]. Bulletin of Chinese Academy of Sciences, 2022, 37(11): 1550−1559. doi: 10.16418/j.issn.1000-3045.20220817001
[3] 王登红. 关键矿产的研究意义、矿种厘定、资源属性、找矿进展、存在问题及主攻方向[J]. 地质学报, 2019, 93(6): 1189−1209. doi: 10.19762/j.cnki.dizhixuebao.2019186
Wang D H. Study on critical mineral resources: Significance of research, determination of types, attributes of resources, progress of prospecting, problems of utilization, and direction of exploitation[J]. Acta Geologica Sinica, 2019, 93(6): 1189−1209. doi: 10.19762/j.cnki.dizhixuebao.2019186
[4] 王楠, 孙旭东, 霍地. 小火试金分离富集火焰原子吸收光谱法测定矿石样品中的金[J]. 光谱学与光谱分析, 2019, 39(8): 2614−2617. doi: 10.3964/j.issn.1000-0593(2019)08-2614-04
Wang N, Sun X D, Huo D. Determination of gold in mineral samples by flame atomic absorption spectrometry after the separation and preconcentration with small fire assay[J]. Spectroscopy and Spectral Analysis, 2019, 39(8): 2614−2617. doi: 10.3964/j.issn.1000-0593(2019)08-2614-04
[5] 郭晓瑞, 樊蕾, 王甜甜, 等. 锑试金-微波消解-高分辨率连续光源火焰原子吸收光谱法测定金矿石中金[J]. 冶金分析, 2022, 42(12): 45−51. doi: 10.13228/j.boyuan.issn1000-7571.011859
Guo X R, Fan L, Wang T T, et al. Determination of gold in gold ore by high resolution continuum source flame atomic absorption spectrometry combined with antimony fire assay and microwave digestion[J]. Metallurgical Analysis, 2022, 42(12): 45−51. doi: 10.13228/j.boyuan.issn1000-7571.011859
[6] 孙启亮, 毛香菊, 郭晓瑞, 等. 铅试金富集-高分辨率连续光源石墨炉原子吸收光谱法测定地球化学样品中痕量金铂钯[J]. 冶金分析, 2021, 41(7): 10−16. doi: 10.13228/j.boyuan.issn1000-7571.011416
Sun Q L, Mao X J, Guo X R, et al. Determination of trace gold, platinum and palladium in geological samples by lead fire assay pre-concentration high resolution continuum source graphite furnace atomic absorption spectrometry[J]. Metallurgical Analysis, 2021, 41(7): 10−16. doi: 10.13228/j.boyuan.issn1000-7571.011416
[7] 王小强, 赵亚男, 梁倩, 等. 泡沫塑料富集-火焰原子吸收光谱法测定金矿石中金[J]. 中国无机分析化学, 2022, 12(3): 110−114. doi: 10.3969/j.issn.2095-1035.2022.03.016
Wang X Q, Zhao Y N, Liang Q, et al. Determination of gold in gold ores by flame atomic absorption spectrometry with foam plastics enrichment[J]. Chinese Journal of Inorganic Analytical Chemistry, 2022, 12(3): 110−114. doi: 10.3969/j.issn.2095-1035.2022.03.016
[8] Ramesh S L, Anjaiah K V, Mathur R, et al. Determination of gold in rocks, ores, and other geological materials by atomic absorption techniques[J]. Atomic Spectroscopy, 2001, 22(1): 263−269.
[9] Volzhenin A V, Petrova N I, Medvedev N S, et al. Determination of gold and palladium in rocks and ores by atomic absorption spectrometry using two-stage probe atomization[J]. Journal of Analytical Chemistry, 2017, 72(2): 156−162. doi: 10.1134/s1061934817020150
[10] 王鹏, 门倩妮, 甘黎明, 等. 基于RSM模型对石墨炉原子吸收法分析痕量金测定条件的优化研究[J]. 光谱学与光谱分析, 2022, 42(8): 2334−2339. doi: 10.3964/j.issn.1000-0593(2022)08-2334-06
Wang P, Men Q N, Gan L M, et al. Research on optimization of determination conditions for trace gold analysis by graphite furnace atomic absorption spectrometry based on RSM model[J]. Spectroscopy and Spectral Analysis, 2022, 42(8): 2334−2339. doi: 10.3964/j.issn.1000-0593(2022)08-2334-06
[11] Dyachenko E N, Kolpakova N A, Oskina U A. Determination of gold by stripping voltammetry in platinum gold ore mineral raw materials on grafite electrode modified by bismuth[J]. Procedia Chemistry, 2014, 10: 47−50. doi: 10.1016/j.proche.2014.10.010
[12] Kolpakova N A, Oskina Y A, Panova S M, et al. Determination of Au, Pt, Pd in gold ore mineral raw materials by stripping voltammetry[J]. MATEC Web of Conferences, 2016, 85: 01012. doi: 10.1051/matecconf/20168501012
[13] 马景治, 李策, 张明杰, 等. 王水溶样-电感耦合等离子体质谱(ICP-MS)法测定地质样品中的金[J]. 中国无机分析化学, 2020, 10(2): 48−51. doi: 10.3969/j.issn.2095-1035.2020.02.010
Ma J Z, Li C, Zhang M J, et al. Direct determination of gold in geological samples by inductively coupled plasma mass spectrometry with aqua regia sampling preparation[J]. Chinese Jouranl of Inorganic Analytical Chemistry, 2020, 10(2): 48−51. doi: 10.3969/j.issn.2095-1035.2020.02.010
[14] Yim S A, Choi M S, Chae J S. Direct determination of gold in rock samples using collision cell quadrupole ICP-MS[J]. Journal of the American Society for Mass Spectrometry, 2012, 23(1): 17−18. doi: 10.1007/s13361-011-0270-1
[15] Tao D Y, Guo W, Xie W K, et al. Rapid and accurate determination of gold in geological materials by an improved ICP-MS method[J]. Microchemical Journal, 2017, 135: 221−225. doi: 10.1016/j.microc.2017.09.014
[16] Tavakoli L, Yamini Y, Ebrahimzadeh H. Development of cloud point extraction for simultaneous extraction and determination of gold and palladium using ICP-OES[J]. Journal of Hazardous Materials, 2008, 152(2): 737−743. doi: 10.1016/j.jhazmat.2007.07.039
[17] Rastegarzadeh S, Pourreza N, Larki A. Determination of trace silver in water, wastewater and ore samples using dispersive liquid–liquid microextraction coupled with flame atomic absorption spectrometry[J]. Journal of Industrial and Engineering Chemistry, 2015, 24: 297−301. doi: 10.1016/j.jiec.2014.09.045
[18] Rodrigo M P, Paulina V B, Marcela M B, et al. Validation of the ASTM E1898-21 method with estimation of analytical uncertainty for the determination of silver by FAAS[J]. MAPAN, 2023, 38(4): 1005−1018. doi: 10.1007/s12647-023-00678-2
[19] 陈祝海. 电感耦合等离子体原子发射光谱法测定金矿石中铅锌砷铋镉汞[J]. 黄金, 2020, 41(4): 79−82. doi: 10.11792/hj20200418
Chen Z H. Determination of Pb, Zn, As, Bi, Cd and Hg in gold ores by inductively coupled plasma-atomic emission spectroscopy[J]. Gold, 2020, 41(4): 79−82. doi: 10.11792/hj20200418
[20] 徐进力, 邢夏, 张勤, 等. 电感耦合等离子体发射光谱法直接测定铜矿石中银铜铅[J]. 岩矿测试, 2010, 29(4): 377−382. doi: 10.15898/j.cnki.11-2131/td.2010.04.006
Xu J L, Xing X, Zhang Q, et al. Direct determination of silver copper lead and zinc in copper ores by inductively coupled plasma atomic emission spectrometry[J]. Rock and Mineral Analysis, 2010, 29(4): 377−382. doi: 10.15898/j.cnki.11-2131/td.2010.04.006
[21] Rito B, Almeida D, Coimbra C. Post-measurement compressed calibration for ICP-MS-based metal quantification in mine residues bioleaching[J]. Scientific Reports, 2022, 12(1): 16007−16007. doi: 10.1038/s41598-022-19620-8
[22] Xiong C X, Liu Y R, Gu J P. Rapid determination of As, Sb, Bi and Hg in gold ore samples by AFS with L-cysteine as a prereducer[J]. Advanced Materials Research, 2011, 1362(304): 328−333. doi: 10.4028/www.scientific.net/AMR.304.328
[23] Mattiazzi P, Bohrer D, Viana C, et al. Determination of antimony in pharmaceutical formulations and beverages using high-resolution continuum-source graphite furnace atomic absorption spectrometry[J]. Journal of AOAC International, 2017, 100(3): 737−742. doi: 10.5740/jaoacint.16-0389
[24] Unutkan T, Koyuncu I, Diker C, et al. Accurate and sensitive analytical strategy for the determination of antimony: Hydrogen assisted T-shaped slotted quartz tube-atom trap-flame atomic absorption spectrometry[J]. Bulletin of Environmental Contamination and Toxicology, 2019, 102(1): 122−127. doi: 10.1007/s00128-018-2504-4
[25] 范凡, 温宏利, 屈文俊, 等. 王水溶样-等离子体质谱法同时测定地质样品中砷锑铋银镉铟[J]. 岩矿测试, 2009, 28(4): 333−336. doi: 10.3969/j.issn.0254-5357.2009.04.006
Fan F, Wen H L, Qu W J, et al. Determination of arsenic, antimony, bismuth, silver, cadmium and indium in geological samples by inductively coupled plasma-mass spectrometry with aqua regia sample digestion[J]. Rock and Mineral Analysis, 2009, 28(4): 333−336. doi: 10.3969/j.issn.0254-5357.2009.04.006
[26] Maja W, Anna S M, Pawel P. Improvement in the single and simultaneous generation of As, Bi, Sb and Se hydrides using a vapor generation accessory (VGA) coupled to axially viewed inductively coupled plasma optical emission spectrometry (ICP-OES)[J]. Analytical Methods, 2017, 9(5): 871−880. doi: 10.1039/c6ay02932a
[27] 郑智慷, 曾江萍, 王家松, 等. 常压密闭微波消解-电感耦合等离子体发射光谱法测定锑矿石中的锑[J]. 岩矿测试, 2020, 39(2): 208−215. doi: 10.15898/j.cnki.11-2131/td.201906110084
Zheng Z K, Zeng J P, Wang J S, et al. Determination of antimony in antimony ores by inductively coupled plasma-optical emission spectrometry with microwave digestion[J]. Rock and Mineral Analysis, 2020, 39(2): 208−215. doi: 10.15898/j.cnki.11-2131/td.201906110084
[28] 罗永红, 韦真周, 张相钰, 等. 湿法氧化除硫碳-活性炭富集-原子吸收分光光度法测定矿石中的金[J]. 湿法冶金, 2016, 35(2): 167−170. doi: 10.13355/j.cnki.sfyj.2016.02.021
Luo Y H, Wei Z Z, Zhang X Y, et al. Determination of gold in ore by oxidation removal sulphur and carbon-activated carbon enrichment-atomic absorption spectrophotometry[J]. Hydrometallurgy of China, 2016, 35(2): 167−170. doi: 10.13355/j.cnki.sfyj.2016.02.021
[29] 葛艳梅. 王水溶样-火焰原子吸收光谱法直接测定高品位金矿石的金量[J]. 岩矿测试, 2014, 33(4): 491−496. doi: 10.15898/j.cnki.11-2131/td.2014.04.005
Ge Y M. Direct determination of high grade gold in ore by flame atomic absorption spectrometry with aqua regia sampling preparation[J]. Rock and Mineral Analysis, 2014, 33(4): 491−496. doi: 10.15898/j.cnki.11-2131/td.2014.04.005
[30] Rodriguez N, Yoho M, Landsberger S. Determination of Ag, Au, Cu and Zn in ore samples from two Mexican mines by various thermal and epithermal NAA techniques[J]. Journal of Radio analytical and Nuclear Chemistry, 2016, 37(2): 955−961. doi: 10.1007/s10967-015-4277-0
[31] 张洁, 阳国运. 电感耦合等离子体质谱法测定金矿石中金[J]. 冶金分析, 2018, 38(11): 18−23. doi: 10.13228/j.boyuan.issn1000-7571.010426
Zhang J, Yang G Y. Determination of gold in gold ore by inductively coupled plasma mass spectrometry[J]. Metallurgical Analysis, 2018, 38(11): 18−23. doi: 10.13228/j.boyuan.issn1000-7571.010426
[32] 杨艳明. 电感耦合等离子体质谱法测定水系沉积物中银铜砷锑铋镉[J]. 冶金分析, 2019, 39(7): 58−64. doi: 10.13228/j.boyuan.issn1000-7571.010632
Yang Y M. Determination of silver, copper, arsenic, antimony, bismuth and cadmium in stream sediment by inductively coupled plasma mass spectrometry[J]. Metallurgical Analysis, 2019, 39(7): 58−64. doi: 10.13228/j.boyuan.issn1000-7571.010632
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