Optimization of Measurement Conditions for Geochemical Survey Sample Analysis by X-ray Fluorescence Spectrometry with Pressed Powder Pellet Sample Preparation
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摘要: 在X射线荧光光谱（XRF）分析中，粉末压片制样是被广泛应用的一种制样方法，但由于存在样品粒度、矿物和基体效应对其测量条件进行优化。本文应用XRF法测量地球化学调查样品中24种主次量元素，综合优化了制样压力、仪器工作电压和工作电流、待测元素分析谱线、探测器的调节和探测效率等实验条件。在最优测量条件下，用土壤和水系沉积物国家标准物质GBW07402、GBW07404、GBW07424、GBW07426、GBW07429验证方法的准确度，结果表明个别元素如GBW07402中的Na2O、GBW07404中的Pb相对误差大于10%，其余元素的相对误差小于10%，但均达到了地球化学调查样品的质量监控要求。经优化的仪器测量条件为我国地球化学调查样品提供了可靠的基础数据。Abstract:
BACKGROUNDPowder compaction is a widely used sample preparation method for X-ray Fluorescence Spectrometry. However, due to the existence of mineral and matrix effects, the measurement conditions should be optimized. OBJECTIVESTo measure 24 major and minor elements in geochemical survey samples. METHODSThe ZSX Primus Ⅱ type Wavelength Dispersive X-ray Fluorescence Spectrometer was used to determine the optimum experimental conditions, such as sample preparation pressure, working voltage and current of the instrument, spectral lines of the elements to be measured and the efficiency of the detector. The optimum experimental conditions were verified by analyzing the National Standard Materials (GBW07402, GBW07404, GBW07424, GBW07426, and GBW07429). RESULTSAccording to the optimum experimental conditions, the National Standard Materials of soil and stream sediments are analyzed. Individual elements such as Na2O in GBW07402 and Pb in GBW07404 have relative errors greater than 10%, and other elements have relative errors less than 10%. The relative errors meet the quality control requirements of geochemical survey samples. CONCLUSIONSThe requirement of data quality monitoring has been achieved for the analysis of geochemical survey samples and the optimized instrument measurement conditions provide reliable basic data for such samples in China. -
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表 1 工作电压对磷、钒等元素激发效率的影响
Table 1. Effect of working voltage on the excitation efficiency of elements such as P and V
工作电压(kV) INa/IBG IMg/IBG IP/IBG IV/IBG ISr/IBG IZr/IBG 30 44.53 35.64 12.70 8.26 2.48 3.74 35 43.24 34.69 11.53 8.63 2.99 4.79 40 40.69 34.11 11.70 9.14 3.33 5.76 45 37.90 32.90 11.50 9.37 3.68 6.46 50 37.07 31.98 10.95 9.51 3.94 7.16 55 36.15 30.99 10.94 9.97 4.22 7.82 60 33.63 30.03 10.59 10.41 4.51 8.21 
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表 2 工作电流对磷和钒激发效率的影响
Table 2. Effect of working current on the excitation efficiency of P and V
工作电流(mA) P V 谱线强度
I(kcps)背景强度
IBG(kcps)I/IBG 谱线强度
I(kcps)背景强度
IBG(kcps)I/IBG 40 5.54 0.52 10.75 10.68 1.06 10.10 45 6.25 0.56 11.08 12.03 1.21 9.90 50 6.95 0.67 10.40 13.34 1.35 9.89 55 7.68 0.68 11.28 14.70 1.46 10.06 60 8.36 0.76 11.01 16.04 1.61 9.98 65 9.08 0.84 10.83 17.42 1.72 10.11 70 9.83 0.89 11.09 18.75 1.89 9.93
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表 3 铜的背景对回归结果的影响
Table 3. Effect of Cu background on regression results
标准物质编号 认定值(μg/g) 原始强度回归结果 相对误差(%) 净强度回归结果 相对误差(%) GBW07301a 28.0 27.9 -0.36 28.0 0.00 GBW07302 4.9 8.4 71.43 4.6 -6.12 GBW07303 177.0 184.2 4.07 183.4 3.62 GBW07304 37.0 34.6 -6.49 37.2 0.54 GBW07305 137.0 138.9 1.39 139.9 2.12 GBW07306 383.0 385.4 0.63 385.6 0.68 GBW07307 38.0 37.3 -1.84 37.5 -1.32 GBW07308 4.1 7.8 90.24 5.0 21.95 GBW07309 32.0 32.3 0.94 32.4 1.25 GBW07310 22.6 26.3 16.37 23.8 5.31 GBW07311 79.0 81.1 2.66 78.9 -0.13 GBW07312 1230.0 1252.6 1.84 1251.2 1.72 GBW07317 11.0 14.5 31.82 11.6 5.45 GBW07318 66.0 59.2 -10.30 61.7 -6.52
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表 4 优化的元素测量条件
Table 4. Optimal measurement conditions of the elements
元素及分析谱线 分光晶体 2θ(°) 计数时间(s) 脉冲高度 衰减器 准直器 探测器 谱峰 背景 谱峰 背景 Na Kα RX-25 46.56 48.90 8 4 110~320 1/1 S4 PC Mg Kα RX-25 38.30 39.75 6 3 90~330 1/1 S4 PC Al Kα PET 144.58 - 4 - 110~320 1/1 S2 PC Si Kα PET 109.01 - 4 - 110~310 1/10 S4 PC P Kα Ge 141.06 143.30 10 5 70~300 1/1 S4 PC K Kα LiF1 136.62 - 4 - 110~290 1/1 S4 PC Ca Kα LiF1 113.11 - 4 - 110~300 1/10 S4 PC Ba Lα LiF1 87.19 88.54 10 5 110~310 1/1 S4 PC Ti Kα LiF1 86.13 - 5 - 90~400 1/1 S2 SC V Kα LiF1 77.02 74.32 20 10 110~290 1/1 S4 PC Cr Kα LiF1 69.35 74.32 20 10 140~310 1/1 S4 PC Mn Kα LiF1 62.96 - 5 - 90~400 1/1 S2 SC Fe Kα LiF1 57.51 - 4 - 90~380 1/10 S2 SC Co Kα LiF1 52.78 53.86 20 10 90~360 1/1 S2 SC Ni Kα LiF1 48.65 49.70 20 10 100~310 1/1 S2 SC Cu Kα LiF1 45.01 46.60 20 10 80~350 1/1 S2 SC Zn Kα LiF1 41.78 42.50 8 4 90~340 1/1 S2 SC Ga Kα LiF1 38.90 39.50 10 5 80~330 1/1 S2 SC As Kα LiF1 33.92 35.24 14 7 80~330 1/1 S2 SC Pb Lβ1 LiF1 28.24 29.60 20 10 90~300 1/1 S2 SC Th Lα LiF1 27.46 29.60 30 15 80~310 1/1 S2 SC Rb Kα LiF1 26.60 25.80 4 2 80~310 1/1 S2 SC Sr Kα LiF1 25.13 25.80 4 2 70~320 1/1 S2 SC Y Kα LiF1 23.77 24.50 10 5 80~320 1/1 S2 SC Zr Kα LiF1 22.52 23.00 6 3 80~310 1/1 S2 SC Nb Kα LiF1 21.38 23.00 10 5 90~310 1/1 S2 SC Bi Lα LiF1 32.99 35.24 10 5 80~300 1/1 S2 SC Rh Kαc LiF1 18.44 - 8 - 80~300 1/1 S2 SC Rh Kα LiF1 17.55 - 8 - 70~300 1/1 S2 SC
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表 5 方法准确度实验数据
Table 5. Accuracy tests of the method
组分 测试项目 GBW
07402GBW
07404GBW
07424GBW
07426GBW
07429认定值(%) 1.62 0.11 2.13 1.99 1.25 Na2O 测定值(%) 1.82 0.12 2.01 1.73 1.22 相对误差(%) 12.3 9.1 -5.6 -13.1 -2.4 认定值(%) 1.04 0.49 1.31 2.41 1.78 MgO 测定值(%) 1.11 0.49 1.41 2.59 1.8 相对误差(%) 6.7 0.0 7.6 7.5 1.1 认定值(%) 10.31 23.45 13.8 13.27 15.27 Al2O3 测定值(%) 10.14 23.48 13.74 12.71 14.95 相对误差(%) -1.6 0.1 -0.4 -4.2 -2.1 认定值(%) 73.35 50.95 65.5 60.01 63.63 SiO2 测定值(%) 72.43 49.49 64.71 59.21 64.12 相对误差(%) -1.3 -2.9 -1.2 -1.3 0.8 认定值(%) 2.54 1.03 2.65 2.61 2.35 K2O 测定值(%) 2.47 1.05 2.67 2.68 2.38 相对误差(%) -2.8 1.9 0.8 2.7 1.3 认定值(%) 2.36 0.26 2.62 5.83 1.54 CaO 测定值(%) 2.35 0.29 2.72 5.92 1.64 相对误差(%) -0.4 11.5 3.8 1.5 6.5 认定值(%) 3.52 10.3 4.17 4.7 6.44 TFe2O3 测定值(%) 3.46 10.44 4.29 4.76 6.39 相对误差(%) -1.7 1.4 2.9 1.3 -0.8 认定值(μg/g) 446 695 496 708 558 P 测定值(μg/g) 432.7 678.8 535.4 703.7 558.2 相对误差(%) -3.0 -2.3 7.9 -0.6 0.0 认定值(μg/g) 930 213 614 493 718 Ba 测定值(μg/g) 922.6 231.1 606.4 470.2 744.4 相对误差(%) -0.8 8.5 -1.2 -4.6 3.7 认定值(μg/g) 2710 10800 4210 3950 5310 Ti 测定值(μg/g) 2800.1 11246.8 4274.4 3936.5 5424.9 相对误差(%) 3.3 4.1 1.5 -0.3 2.2 认定值(μg/g) 62 247 75 86 119 V 测定值(μg/g) 64.2 252.8 69.4 87.7 119.8 相对误差(%) 3.5 2.3 -7.5 2.0 0.7 认定值(μg/g) 47 370 58 59 87 Cr 测定值(μg/g) 47.8 377.9 57.9 64.3 86.2 相对误差(%) 1.7 2.1 -0.2 9.0 -0.9 认定值(μg/g) 510 1420 682 776 964 Mn 测定值(μg/g) 519.4 1515.2 718.4 772.4 985.8 相对误差(%) 1.8 6.7 5.3 -0.5 2.3 认定值(μg/g) 8.7 22.3 11.7 12.6 17.6 Co 测定值(μg/g) 8.5 22.5 11.4 12.8 17.9 相对误差(%) -2.3 0.9 -2.6 1.6 1.7 认定值(μg/g) 19.4 64 25.9 32.4 41.5 Ni 测定值(μg/g) 18.4 64.1 25.5 32.3 39.7 相对误差(%) -5.2 0.2 -1.5 -0.3 -4.3 认定值(μg/g) 16.3 40 19.3 29 36.8 Cu 测定值(μg/g) 17.3 41.3 20.4 30.1 38.4 相对误差(%) 6.1 3.2 5.7 3.8 4.3 认定值(μg/g) 42 210 60 78 94 Zn 测定值(μg/g) 39.6 215.3 59.8 75.9 92.5 相对误差(%) -5.7 2.5 -0.3 -2.7 -1.6 认定值(μg/g) 12 30.6 18.2 16.9 20.5 Ga 测定值(μg/g) 12 30.2 17.7 16.8 20.1 相对误差(%) 0.0 -1.3 -2.7 -0.6 -2.0 认定值(μg/g) 20 58 22.4 18.9 37.8 Pb 测定值(μg/g) 19.5 55.2 24.7 20.2 38.6 相对误差(%) -2.5 -4.8 10.3 6.9 2.1 认定值(μg/g) 88 75 108 94 116 Rb 测定值(μg/g) 86.8 73.9 107.7 93.3 115.5 相对误差(%) -1.4 -1.5 -0.3 -0.7 -0.4 认定值(μg/g) 187 77 226 239 116 Sr 测定值(μg/g) 182 78.4 231.6 239.5 114.8 相对误差(%) -2.7 1.8 2.5 0.2 -1.0 认定值(μg/g) 22 39 26.5 26.5 32.7 Y 测定值(μg/g) 20.7 39.2 26.5 26 32.9 相对误差(%) -5.9 0.5 0.0 -1.9 0.6 认定值(μg/g) 219 500 349 195 272 Zr 测定值(μg/g) 203.9 513.1 347.9 190.9 277.3 相对误差(%) -6.9 2.6 -0.3 -2.1 1.9 认定值(μg/g) 27 38 16.5 12 18.5 Nb 测定值(μg/g) 27.5 38.2 15.5 12.3 19.5 相对误差(%) 1.9 0.5 -6.1 2.5 5.4
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