Determination of 18 Minor Elements in the Structural Superimposed Halo Samples from Gold Deposits by Wavelength Dispersive X-ray Fluorescence Spectrometry with Pressed-powder Pellets
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摘要: 金矿床型构造叠加晕样品中的砷锑铋银锡钨等金属元素含量对金矿多期次多阶段成矿具有指示意义。此类样品采集于金矿中，样品各元素含量范围大，从克吨级至百分之几，分布也不均匀。采用常规的检测方法分析时，存在元素间干扰不易消除、记忆效应严重等问题。本文建立了粉末压片-波长色散X射线荧光光谱法测定金矿型构造叠加晕样品中砷锑铋等18种次量元素的定量分析方法。通过研究角度扫描图，选择了干扰少、强度高的分析线；充分混匀样品，消除了偏析效应；选用与样品基体类似的国家标准样品建立工作曲线，通过数学校正和内标法校正了谱线重叠干扰和基体效应。方法检出限为0.14~2.23 μg/g，精密度（RSD，n=12）小于4%。本方法可快速、准确地测定金矿床型构造叠加晕样品中各元素的含量。Abstract:
BACKGROUND Elements As, Sb, Bi, Ag, Sn, W, Mo, Cu, Pb, Zn, Co, Cr, Ni, Ti, V, Mn, Sr and Ba in structural superimposed halo samples of gold deposits were of significance to the multi-phases and multi-stage mineralization of the gold deposits. This kind of sample is collected in the gold mine. The content of each element is very different and the distribution is uneven, from the ppm level to a few percent. OBJECTIVES To overcome the problems of conventional detection methods, such as difficult to eliminate inter-element interference and serious memory effects. METHODS The contents of 18 elements in structural superimposed haloes of gold ore were studied by pressed-powder pellets Wavelength Dispersive XRF. RESULTS By studying the angle scanning chart, the analysis line with least interference and high intensity is selected, and the segregation effect is eliminated by fully mixing the sample. The detection limits of this method are 0.14-2.23 μg/g, and the precision (RSD, n=12) is less than 4%. CONCLUSIONS The method can rapidly and accurately determine the contents of all elements in structural superimposed halo samples of gold deposits. -
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表 1 仪器测量条件
Table 1. Measurement conditions of elements by XRF instrument
分析线 晶体 检测器 准直器 滤光片 PHD(%) 电压
(kV)电流
(mA)2θ(°) 仪器背景(°) 阈值 窗口 低端 高端 Ag Kα1, 2 LiF200 SC 0.4 Cu 0.27 40 103 50 50 16.065 -0.645 0.403 As Kβ1, 3 LiF200 SC 0.4 None 40 104 50 50 30.451 -0.450 0.440 Ba Lβ1 LiF200 FPC 0.4 Al 0.50 30 120 50 50 79.255 -0.740 1.190 Bi Lα1 LiF220 SC 0.4 None 40 110 50 50 47.361 -0.300 0.500 Co Kα1 LiF200 FPC 0.4 None 30 120 50 50 77.827 -0.600 0.600 Cr Kα1, 2 LiF200 FPC 0.4 None 30 120 50 50 69.354 -0.800 0.950 Cu Kα1, 2 LiF200 SC 0.4 None 40 120 50 50 45.027 -0.723 0.838 Mn Kα1, 2 LiF200 FPC 0.4 None 30 120 50 50 62.973 -0.890 0.950 Mo Kα1, 2 LiF200 SC 0.4 None 59 86 50 50 20.332 -0.346 0.500 Ni Kα1, 2 LiF200 SC 0.4 None 40 115 50 50 48.667 -0.445 0.654 Pb Lβ1 LiF200 SC 0.4 None 40 120 50 50 28.242 -0.745 0.560 Rh Kαcom LiF200 SC 0.4 Cu 0.27 40 100 50 50 26.073 0 1.700 Sb Lβ1 LiF200 FPC 1.00 None 55 90 30 80 106.426 -1.395 1.750 Sn Lα1 LiF200 FPC 1.00 None 55 90 30 80 126.765 0 2 Sr Kα1 LiF220 SC 0.4 None 40 120 50 50 35.831 -0.677 0.725 Ti Kα1, 2 LiF200 FPC 0.4 None 55 120 50 50 86.137 -0.856 0.809 V Kα1 LiF220 FPC 0.4 None 60 85 50 50 123.058 -0.850 0 W Lα1 LiF200 SC 0.4 None 40 120 50 50 43.018 -0.621 0.872 Zn Kα1, 2 LiF200 SC 0.4 None 40 120 50 50 41.799 -0.546 0.680 
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表 2 分析元素的测量范围
Table 2. Measurement ranges of the elements
分析元素 测量范围(μg/g) Ag 1.00~1010 As 5.00~2800 Ba 10.0~1200 Bi 3.00~140 Co 1.00~100 Cr 3.00~500 Cu 3.00~28000 Mn 20.0~10000 Mo 3.00~2200 Ni 2.00~150 Pb 5.00~21700 Sb 2.00~1400 Sn 3.00~400 Sr 5.00~1100 Ti 50.0~14200 W 3.00~518 Zn 10.0~42600 V 5.00~300
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表 3 XRF与其他测定方法比对
Table 3. Comparison of analytical results with XRF and others analytical methods
元素 Y41 Y42 Y43 Y44 本方法
(μg/g)常规方法
(μg/g)相对偏差
(%)本方法
(μg/g)常规方法
(μg/g)相对偏差
(%)本方法
(μg/g)常规方法
(μg/g)相对偏差
(%)本方法
(μg/g)常规方法
(μg/g)相对偏差
(%)Ag 44.1 39.2 5.9 50.2 48.1 2.1 14.4 13.8 2.1 12.4 12.7 -1.20 As 17.8 20.4 -6.8 8.18 9.61 -8.0 12.7 14.3 -5.9 6.78 7.12 -2.45 Ba 546 564 -1.6 645 682 -2.8 712 697 1.1 3321 3301 0.30 Bi 9.21 10.2 -5.1 12.8 13.6 -3.0 8.28 9.82 -8.5 5.34 5.77 -3.87 Co 24.9 26 -2.2 17.6 19.1 -4.1 9.76 10.6 -4.1 6.29 6.19 0.80 Cr 123 118 2.1 99.4 107 -3.7 108 102 2.9 11.4 11.7 -1.30 Cu 38066 38243 -0.2 1811 1872 -1.7 428 416 1.4 2170 2155 0.35 Mn 675 708 -2.4 1231 1264 -1.3 553 586 -2.9 412 419 -0.84 Mo 48.2 46.1 2.2 68.4 62.4 4.6 51.5 54.4 -2.7 12.4 11.8 2.48 Ni 132 126 2.3 13.8 14.6 -2.8 18.9 21.4 -6.2 874 856 1.04 Pb 16405 16672 -0.8 16494 16129 1.1 200 214 -3.4 385 379 0.79 Sb 212 197 3.7 39.9 42.1 -2.7 25.2 23.7 3.1 6.21 6.41 -1.58 Sn 28.2 26.5 3.1 13.3 14.9 -5.7 17.8 15.3 7.6 14.8 15.1 -1.00 Sr 129 121 3.2 124 118 2.5 214 207 1.7 77.5 78.1 -0.39 Ti 2316 2386 -1.5 346 361 -2.1 1286 1264 0.9 964 956 0.42 W 750 723 1.8 116 128 -4.9 140 131 3.3 25.6 26.1 -0.97 Zn 1079 1120 -1.9 35.6 36.4 -1.1 54.7 56.9 -2.0 521 534 -1.23 V 157 148 3.0 25.0 26.0 -2.0 25.7 27.0 -2.5 64.1 64.6 -0.39 注：相对偏差=(本方法分析结果-两方法分析结果平均值)/两方法分析结果平均值×100。
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表 4 方法精密度
Table 4. Precision tests of the method
元素 GBW07311 GBW07405 测量平均值
(μg/g)RSD
(%)测量平均值
(μg/g)RSD
(%)Ag 3.50 2.06 4.54 3.46 As 258 1.75 423 0.71 Ba 265 1.15 304 0.50 Bi 52.4 1.62 42.9 0.94 Co 8.19 0.75 13.6 1.47 Cr 45.9 1.28 113 1.02 Cu 82.0 0.46 150 2.67 Mn 2513 0.17 1370 0.37 Mo 6.10 1.83 4.73 1.64 Ni 15.0 2.15 42.8 0.71 Pb 631 0.42 553 1.45 Sb 15.5 1.98 37.1 1.48 Sn 384 1.04 18.8 1.92 Sr 32.9 1.32 43.0 1.81 Ti 2127 0.24 6338 0.39 W 134 2.29 35.2 1.15 Zn 374 1.74 504 0.72 V 52.6 3.67 165 1.86
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表 5 方法检出限
Table 5. Detection limits of the method
分析元素 检出限(μg/g) Ag 0.21 As 0.82 Ba 2.23 Bi 0.51 Co 0.18 Cr 0.46 Cu 0.18 Mn 0.34 Mo 0.47 Ni 0.14 Pb 0.66 Sb 0.19 Sn 0.24 Sr 0.63 Ti 1.21 W 0.43 Zn 0.15 V 0.81
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