Application of micro-XRF technology to rapid and nondestructive detection of inorganic elements in ocean minerals
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摘要:
深海固体矿产主要由铁锰结核、富钴结壳和多金属热液硫化物组成，元素在矿产中原位的分布和含量，对了解矿物成因、品位以及评估其经济价值有重要指示作用。本研究利用微区XRF分析技术对铁锰结核、富钴结壳、热液硫化物3种大洋类型矿产样品，进行高分辨、原位和无损的多元素空间分布检测，结果显示了不同元素在3种类型矿物中的空间分布特征。通过对测试数据进一步处理和优化成图流程，可以获得特定元素在矿物中半定量分布图，并对不同元素在矿物空间分布的差异性和相关性进行对比分析，从而建立一种肉眼可见的测试大洋矿产资源样品中元素原位分布的新方法。
Abstract:A great amount of solid minerals, such as ferromanganese nodules, cobalt-bearing crusts and polymetallic hydrothermal sulfides, occur in the deep ocean. The in-situ distribution of the contents of various elements in the minerals are important indicators to their genesis, identification, grade and evaluation of economic value. In this study, three types of mineral samples, including ferromanganese nodules, cobalt-bearing crusts and polymetallic hydrothermal sulfides, were analyzed with micro-XRF technology, and high-resolution, in-situ and non-destructive multi-element mapping analysis was adopted to reveal the difference in spatial distribution of different elements in different types of mineral samples. Through the analysis of test data and the optimization of mapping process, we can compare the correlation and difference in specific element distribution and semi-quantitative content, so as to establish a new method for disclosing the visible deep-sea mineral element distribution psatterns.
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Key words:
- nodules /
- crusts /
- hydrothermal sulfides /
- micro-XRF /
- element distribution /
- in situ /
- nondestructive
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表 1 微区XRF在结核、结壳样品中的平行性验证
Table 1. Verification of parallelism of micro-XRF in nodule and crust samples
元素 结核样品 结壳样品点1 结壳样品点2 5次点扫
均值/%5次点扫标准
偏差/%相对标准
偏差/%5次点扫
均值/%5次点扫标准
偏差/%相对标准
偏差/%5次点扫
均值/%5次点扫标准
偏差/%相对标准
偏差/%Mg 0.098 0.035 35.3 0.113 0.023 20.0 0.063 0.046 74.1 Al 0.597 0.020 3.3 0.320 0.018 5.5 1.820 0.107 5.9 Si 1.873 0.013 0.7 1.961 0.050 2.6 7.834 0.303 3.9 P 0.252 0.004 1.8 0.382 0.009 2.3 0.286 0.036 12.7 S 0.222 0.006 2.7 0.259 0.002 0.8 0.170 0.017 10.0 Cl 2.296 0.019 0.8 1.348 0.028 2.1 1.569 0.012 0.8 K 0.788 0.004 0.5 0.682 0.005 0.8 1.354 0.039 2.9 Ca 4.011 0.012 0.3 5.147 0.017 0.3 5.857 0.026 0.4 Ti 2.391 0.006 0.3 2.668 0.008 0.3 1.777 0.009 0.5 V 0.258 0.006 2.5 0.329 0.009 2.8 0.281 0.022 7.7 Cr 0.286 0.008 2.9 0.245 0.009 3.7 0.499 0.010 2.1 Mn 50.880 0.037 0.1 44.081 0.049 0.1 34.971 0.461 1.3 Fe 32.746 0.069 0.2 39.651 0.079 0.2 41.289 0.154 0.4 Co 1.269 0.007 0.5 1.066 0.012 1.1 0.506 0.031 6.2 Ni 0.761 0.004 0.5 0.534 0.003 0.6 0.594 0.008 1.4 Cu 0.303 0.004 1.5 0.170 0.004 2.2 0.252 0.005 1.8 Zn 0.157 0.008 5.0 0.150 0.010 6.4 0.142 0.007 5.2 Sr 0.081 0.002 2.4 0.104 0.002 2.3 0.107 0.003 2.8 Pb 0.730 0.014 2.0 0.788 0.014 1.7 0.629 0.012 1.9 
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表 2 微区XRF在热液硫化物样品中的平行性验证
Table 2. Verification of parallelism of micro-XRF in hydrothermal sulfide
元素 热液硫化物点1 热液硫化物点2 热液硫化物点3 5次点扫
均值/%5次点扫标准
偏差/%相对标准
偏差/%5次点扫
均值/%5次点扫标准
偏差/%相对标准
偏差/%5次点扫
均值/%5次点扫标准
偏差/%相对标准
偏差/%Al 0.484 0.065 13.5 0.178 0.022 12.3 0.180 0.022 12.4 Si 1.076 0.242 22.5 0.102 0.013 12.7 1.045 0.021 2.0 S 26.594 0.917 3.4 42.930 0.424 1.0 34.685 0.084 0.2 Cl 1.954 0.279 14.3 0.671 0.419 62.4 3.446 0.021 0.6 K 0.161 0.008 4.8 0.066 0.005 7.0 0.324 0.015 4.8 Ca 0.067 0.034 49.8 0.008 0.001 7.2 0.034 0.003 7.6 V 0.098 0.013 13.3 0.204 0.038 18.8 2.422 0.031 1.3 Cr 1.102 0.200 18.2 54.463 0.681 1.2 19.171 0.059 0.3 Fe 39.325 0.472 1.2 0.017 0.001 8.1 0.023 0.002 7.1 Cu 27.629 0.633 2.3 0.223 0.005 2.4 6.521 0.133 2.0 Zn 1.511 0.235 15.5 1.138 0.106 9.3 32.146 0.240 0.7
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表 3 微区XRF在黄铁矿标样中的准确度验证
Table 3. Accuracy verification of micro-XRF in pyrite standard sample
黄铁矿标样K18 点1/% 点2/% 点3/% 3次点扫相对标准偏差/% 3次点扫均值/% 标样理论值/% 检测误差/% Fe 43.01 43.51 43.36 0.59 43.29 46.64 7.18 S 53.38 53.32 52.93 0.46 53.21 53.19 0.04
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表 4 微区XRF在闪锌矿标样中的准确度验证
Table 4. Accuracy verification of micro-XRF in sphalerite standard sample
闪锌矿标样 K52 点1/% 点2/% 点3/% 3次点扫相对标准偏差/% 3次点扫均值/% 标样理论值/% 检测误差/% Zn 62.96 62.33 63.62 1.02 62.97 66.96 5.96 S 33.68 33.72 33.41 0.50 33.60 32.71 2.72
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表 5 不同单点驻留时间下的微区XRF面扫结果比对
Table 5. Comparison of micro-XRF area scanning results under different point dwell time
元素 100ms/% 50 ms/% 30 ms/% 20 ms/% 10 ms/% Al 0.11 0.13 0.10 0.12 0.12 Si 0.52 0.53 0.52 0.52 0.51 S 43.35 43.24 43.34 43.23 43.33 Cl 4.00 3.91 3.90 3.94 3.95 K 0.02 0.02 0.02 0.02 0.03 Ca 0.10 0.11 0.11 0.11 0.11 Cr 1.67 1.67 1.70 1.67 1.67 Fe 45.90 46.06 46.02 46.07 45.99 Cu 1.39 1.40 1.38 1.40 1.38 Zn 2.86 2.87 2.84 2.86 2.86 As 0.05 0.05 0.05 0.05 0.05 Cd 0.02 0.02 0.02 0.02 0.02
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