Interference of the Spectral Line Mζ in the M Energy Level Series of Ce on the F Element Kα Peak in Monazite Samples
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摘要:
超轻元素氟（F）的定量分析一直是电子探针（EPMA）矿物分析的难点之一，高分辨定性分析、主量元素谱线干扰峰扣除是F元素准确定量分析的前提。本文以独居石样品中F元素(F含量很低甚至接近0)为研究对象，通过与磷灰石、InP、CeAl2、LaF3标准样品的高分辨定性分析谱图比较、分析，结果表明高含量P元素的Kα三阶线不会对F元素的Kα峰产生干扰，但Ce元素的M能级谱线Mζ会对F元素的Kα峰产生干扰，Ce元素含量高的独居石需要通过干扰峰扣除进行F元素的准确定量分析；稀土元素的M能级谱线Mα、 Mβ、Mζ对超轻元素谱峰的干扰需要引起重视，通过定性分析谱图进行必要的干扰峰修正。
Abstract:Quantitative analysis of the ultra-light element fluorine (F) has always been one of the difficulties in electron probe microanalysis (EPMA). High-resolution qualitative analysis and proper subtraction of spectral interferences from major elements are prerequisites for accurate F quantification. This study focuses on F in monazite samples with very low F content or even close to 0. Through comparison and analysis of high-resolution qualitative analysis spectra with apatite, InP, CeAl2, and LaF3 samples, it is found that the third-order line of high-content P Kα does not interfere with the F Kα peak, but the spectral line Mζ of the M energy level series of Ce interferes with the F Kα peak. Monazite with high Ce content needs accurate quantitative analysis of F through interference peak subtraction. The interference of the M-level spectral lines (including Mα, Mβ, Mζ) of rare earth elements on ultra-light element peaks needs to be taken seriously, and the necessary interference correction should be made through qualitative analysis of the spectra.
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Key words:
- electron probe microanalysis /
- qualitative analysis /
- monazite /
- apatite /
- interference peak subtraction
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表 1
$ \mathbf{F\ }\mathbf{K}_{\text{α }} $ 、$ \mathbf{P}\mathbf{\ K}_{\text{α }\left(3\right)} $ 、$ \mathbf{C}\mathbf{e}\mathbf{\ M}_{\text{ζ }} $ 的波长$ \left(\mathit{\lambda }\right) $ 和LDE1和TAP两种分光晶体对应的L值Table 1. The wavelength
$ \left(\lambda \right) $ of$ \mathrm{F}\mathrm{\ K}_{\text{α}} $ ,$ \mathrm{P\ }\mathrm{K}_{\text{α}\left(3\right)} $ , and$ \mathrm{C}\mathrm{e}\mathrm{\ M}_{\text{ζ }} $ and L values corresponding to LDE1 and TAP crystals.三阶线 $ \lambda\mathrm{\ \left(nm\right)} $ $ L=\dfrac{R}{d}n\lambda\ \left(\mathrm{m}\mathrm{m}\right) $ LDE1 TAP $ \mathrm{F}\mathrm{\ K}_{\text{α}} $ 1.832 85.493 199.154 $ \mathrm{P\ }\mathrm{K}_{\text{α}\; \left(3\right)} $ 0.6158 $ \approx $ 1.832÷386.212 200.828 $ \mathrm{C}\mathrm{e}\mathrm{\ M}_{\text{ζ }} $ 1.835 85.633 199.48 
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表 2 本文实验样品中F、P、Ce三种元素的质量浓度
Table 2. Mass concentrations of elements F, P, and Ce in the experimental samples used in this paper.
实验样品 元素F含量（%） 元素P含量（%） 元素Ce含量（%） 化学成分特点 独居石 很少或接近0 13.14 29.56 含Ce、P、低F InP 0 21.17 0 含P、不含F、Ce 磷灰石 3.70 16.47 0.75 含F、Ce、P CeAl2 0 0 72.23 含Ce，不含F、P LaF3 29.51 0 0 含F，不含Ce、P
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表 3 独居石定量分析条件
Table 3. Quantitative analysis conditions of monazite
元素 分光晶体 峰位计数时间(s) 背景计数时间(s) 标准样品 标准样品来源 谱线 U PETJ 10 5 沥青铀矿 国家标准物质 Mα Th PETJ 10 5 Th SPI Mα Ca PETJ 10 5 磷灰石 SPI Kα La PETJ 10 5 独居石 SPI Lα Ce PETJ 10 5 独居石 SPI Lα Si TAP 10 5 石英 SPI Kα Gd LIFH 10 5 Gd SPI Lβ Dy LIFH 10 5 独居石 SPI Lα Sm LIFH 10 5 独居石 SPI Lα Pr LIFH 10 5 PrF3 SPI Lβ Nd LIFH 10 5 独居石 SPI Lα F LDE1 10 5 磷灰石 SPI Kα Pb PETH 10 5 方铅矿 SPI Mα P PETH 10 5 磷灰石 SPI Kα Y PETH 10 5 Y SPI Lα
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表 4 扣除
$ \mathbf{C}\mathbf{e}\mathbf{\ M}_{\text{ζ }} $ 峰对$ \mathbf{F}\mathbf{\ K}_{\text{α }} $ 的干扰前后的独居石定量分析结果Table 4. Quantitative analysis results of monazite before and after removing the interference of
$ \mathrm{C}\mathrm{e}\;{\mathrm{M}}_{\text{ζ }} $ peak on$ {\mathrm{F}\;\mathrm{K}}_{\text{α}} $ .元素
Element扣除Ce干扰前含量 扣除Ce干扰后含量 Mass(%) Cation Mass(%) Cation P2O5 26.84 5.53 26.85 5.53 Ce2O3 24.85 2.21 24.87 2.21 ThO2 11.98 0.66 11.98 0.66 Nd2O3 11.03 0.96 11.03 0.96 La2O3 9.72 0.87 9.71 0.87 Sm2O3 3.31 0.28 3.31 0.28 Pr2O3 2.82 0.25 2.81 0.25 Gd2O3 2.59 0.21 2.59 0.21 Y2O3 2.09 0.27 2.09 0.27 SiO2 1.8 0.44 1.8 0.44 Dy2O3 0.91 0.07 0.91 0.07 CaO 0.89 0.23 0.89 0.23 F 0.55 0.42 0.01 0.01 =O −0.23 — −0.01 — UO2 0.52 0.03 0.52 0.03 PbO 0.30 0.02 0.30 0.02 Total 99.96 12.44 99.66 12.04 注：“—”无此数据。
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