Determination of Selenium, Major and Minor Elements in Selenium-rich Soil Samples by X-ray Fluorescence Spectrometry with Powder Pellet Preparation
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摘要:
目前土壤中Se主要采用原子荧光光谱法测定，存在用酸量大、前处理相对复杂等缺点，对于高含量Se的测定则需要高倍稀释，无疑会扩大分析误差。本文采用粉末压片波谱-能谱复合X射线荧光光谱法测定湖北富硒土壤样品中的Se等17个主次量元素，波谱分析10个元素的同时，能谱分析As、Cu、Rb、Sr、Zr、Ba、Ni等7个元素，大幅节省了测定时间。通过将不同国家标准物质按比例混合的方式配置混合标准样品，解决了现有Se标准物质在5~72μg/g含量范围不足的问题。对于高含量Se的测定，通过谱图分析，波谱数据优于能谱数据，对其精密度、准确度考核，相对标准偏差（RSD）小于10%，高含量Se样品的RSD小于0.70%，能够满足Se含量大于3.00μg/g土壤样品的定量分析要求，同时可提供16个主次量元素的定量或近似定量分析结果。
Abstract:BACKGROUND At present, the content of Se in soil is mainly determined by atomic fluorescence spectrometry, which has disadvantages such as large usage of acid and relatively complex pretreatment. Determination of high content of Se requires high dilution, which expands the analysis error.
OBJECTIVES To establish a method for the determination of Se and other elements in Se-rich soil samples by wavelength dispersive and energy dispersive X-ray fluorescence (WD-ED XRF).
METHODS WD-ED XRF was used to determine 17 major and minor elements such as Se in Hubei selenium-rich soil samples with powder pellet. While 10 elements were analyzed by WD-XRF, As, Cu, Rb, Sr, Zr, Ba, Ni were analyzed by ED-XRF, which significantly reduced the measurement time.
RESULTS By mixing different certified reference materials in proportion to configure mixed certified reference materials, the problem of insufficient content of the existing Se reference materials in the range of 5-72μg/g was solved. For the determination of high content Se, the relative standard deviation was less than 10%, and the RSD of high content Se sample was less than 0.70%, through the precision and accuracy assessment.
CONCLUSIONS The proposed method satisfies the quantitative analysis of soil samples with Se content greater than 3.00μg/g, and provides the quantitative or approximate quantitative analysis results of 16 major and minor elements.
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表 1 波长色散-能量色散X射线荧光光谱仪测量条件
Table 1. Measurement conditions of elements by WD-ED X-ray fluorescence spectrometer
波长色散测量条件 元素 谱线 电压(kV) 电流(mA) 滤光片 分析晶体 准直器(μm) 探测器 脉高分析器 2θ(º) 低限 高限 峰值 背景 Na Kα12 30 120 None PX1 700 Flow 25 75 27.7034 1.8196 Mg Kα12 30 120 None PX1 700 Flow 28 72 22.9178 1.8228 Al Kα12 30 120 None PE 300 Flow 27 73 144.8636 -1.8032 Si Kα12 30 120 None PE 300 Flow 34 66 109.0776 1.5716 P Kα12 30 120 None Ge 300 Flow 30 67 140.9834 -1.1014 K Kα12 30 120 None LiF200 300 Flow 33 66 136.6882 -2.7074 Ca Kα12 30 120 None LiF200 300 Flow 33 66 113.1246 2.0476 Ti Kα12 60 60 Al/200 LiF200 300 Flow 37 62 86.1620 -1.3728 Mn Kα12 60 60 Al/200 LiF220 150 Flow 39 59 95.1696 1.5694 Fe Kα12 60 60 Al/200 LiF220 150 Scint 31 69 85.6652 -1.0046 V Kα12 60 60 Al/200 LiF220 300 Flow 26 69 123.1436 -0.6186 Cr Kα12 60 60 Al/200 LiF200 150 Flow 35 60 69.3302 0.8222 Se Kα12 60 60 None LiF200 300 Scint 19 78 31.8598 0.7874 能量色散测量条件 元素 谱线 能量 解谱类型 电压(kV) 电流(mA) 滤光片 衰减器 探测器 背景 感兴趣区(keV) 低限 高限 As Kβ13 11.72 ED-R 60 60 Al/200 D=0.6 SDD Yes 11.47 11.83 Ba Kα12 32.06 ED-R 60 60 Brass/400 D=3.0 SDD Yes 31.57 32.58 Br Kα12 11.91 ED-R 60 60 Al/200 D=0.6 SDD Yes 11.88 12.00 Cu Kα12 8.04 ED-R 60 60 Al/200 D=0.6 SDD Yes 7.91 8.25 Ga Kα12 9.24 ED-R 60 60 Al/200 D=0.6 SDD Yes 9.01 9.43 Ge Kα12 9.87 ED-R 60 60 Al/200 D=0.6 SDD Yes 9.80 10.04 Ni Kα12 7.47 ED-R 60 60 Al/200 D=0.6 SDD Yes 7.33 7.63 Pb Lβ1 12.61 ED-R 60 60 Al/200 D=0.6 SDD Yes 12.36 12.87 Rb Kα12 13.37 ED-R 60 60 Al/200 D=0.6 SDD Yes 13.16 13.60 Se Kα12 11.21 ED-R 60 60 Al/200 D=0.6 SDD Yes 10.90 11.48 Sr Kα12 14.14 ED-R 60 60 Al/200 D=0.6 SDD Yes 13.87 14.41 Ti Kα12 4.51 ED-R 60 60 Al/200 D=0.6 SDD Yes 4.28 4.67 Y Kα12 14.93 ED-R 60 60 Al/200 D=0.6 SDD Yes 14.95 15.24 Zn Kα12 8.63 ED-R 60 60 Al/200 D=0.6 SDD Yes 8.45 8.81 Zr Kα12 15.75 ED-R 60 60 Al/200 D=0.6 SDD Yes 15.40 16.07 Rh Kα12 19.18 ED-R 60 60 Al/200 D=0.6 SDD Yes 18.32 19.83 
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表 2 配置的混合标准样品信息
Table 2. Information of mixed reference materials
混合标准样品编号 采用的标准物质编号 称样质量(g) Se含量(μg/g) HC-Se1 GBW07280 4.0000 72.19 GBW07407 6.0000 HC-Se2 GBW07166 4.0017 32.54 GBW07449 6.0028 HC-Se3 GBW07268 4.0042 20.36 GBW07406 5.8799 HC-Se4 GBW07283 4.0002 12.24 GBW07401 5.5382 HC-Se5 GBW07278 4.0003 5.78 GBW07403 6.0002
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表 3 方法检出限
Table 3. Detection limit of the methods
元素 方法检出限(μg/g) 元素 方法检出限(μg/g) Na2O 33.03 As 0.41 MgO 17.33 Cu 1.25 Al2O3 101.6 Rb 0.83 SiO2 79.02 Sr 1.00 P2O5 5.93 Zr 0.97 K2O 6.17 Ba 3.75 TiO2 26.46 Se(能谱) 0.45 MnO 6.39 Se(波谱) 0.91 Fe2O3 6.28 Ni 1.69
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表 4 方法精密度与准确度
Table 4. Precision and accuracy tests of the method
元素 GBW07347(n=10) GBW07277(n=10) 平均值(%) 标准值(%) RSD (%) 平均值(%) 标准值(%) RSD (%) Na2O 1.6 2.46 2.90 0.47 0.32 3.72 MgO 1.57 1.6 1.75 8.22 8.59 3.01 Al2O3 13.14 15.95 1.77 2.48 2.66 6.00 SiO2 49.65 51.24 0.74 15.43 13.74 1.64 P2O5 0.17 0.18 1.61 0.03 0.05 6.29 K2O 2.44 2.6 7.83 0.58 0.51 3.17 TiO2 0.76 0.75 2.95 0.23 0.1 7.88 MnO 0.09 0.09 1.89 0.06 0.06 1.81 Fe2O3 12.57 13.05 0.65 1.75 1.24 1.84 元素 GBW07347(n=10) GBW07277(n=10) 平均值(μg/g) 标准值(μg/g) RSD (%) 平均值(μg/g) 标准值(μg/g) RSD (%) As 15.43 24.2 8.17 94051 93300 0.31 Cu 6086 5000 1.06 249 140 1.53 Rb 77.69 52.7 1.35 20.68 无定值 5.88 Sr 429 399 0.66 477 无定值 0.92 Zr 136 134 2.04 - 无定值 - Ba 553 576 0.61 143 无定值 1.45 Se 3.79 4 9.44 26.05 28 0.61 Ni 2400 2390 1.11 - 33.6 -
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