高钙碳酸盐岩样品中微量钛ICP-MS测试方法

陈菲菲; 金斌; 杨梦娜; 陈瑜; 冉敬; 徐国栋

doi:10.15898/j.ykcs.202402280023

高钙碳酸盐岩样品中微量钛ICP-MS测试方法

中国地质调查局成都地质调查中心，四川成都 610081

详细信息

作者简介:
陈菲菲，硕士，高级工程师，主要从事分析化学及地球化学研究。E-mail：cfffair2008@163.com

通讯作者:
冉敬，教授级高级工程师，主要从事岩石矿物分析测试工作。E-mail：27341937@qq.com。

中图分类号: P618.88；O657.63
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出版历程
- 收稿日期: 2024-02-27
- 修回日期: 2024-05-23
- 录用日期: 2024-06-19
- 网络出版日期: 2024-08-08

Determination of Trace Ti in High Calcium Carbonate Rocks by ICP-MS

Chengdu Center, China Geological Survey, Chengdu 610081, China

摘要

摘要:
硅酸岩中的主量元素钛(Ti)在碳酸盐岩中含量一般低于3.5mg/g，其中绝大部分低于1mg/g，目前常用于硅酸岩中Ti含量(通常大于0.1%)测试的X射线荧光光谱法已无法满足碳酸盐岩中微量Ti的准确测试要求。本文尝试用电感耦合等离子体质谱测试碳酸盐岩中的Ti含量，讨论分析了Ti的5个测试同位素(⁴⁶Ti、⁴⁷ Ti、⁴⁸ Ti、⁴⁹ Ti、⁵⁰ Ti)在碳酸盐岩基体中的受干扰情况，确定了适合的测试同位素⁴⁸Ti，从而提出碳酸盐岩中微量Ti的ICP-MS测试方法。按照该方法测试并校正5个国家一级标准物质中Ti浓度，测定值与标准值相符，相对标准偏差(RSD，n=10)小于7.3%。在同一实验条件下，测试未知碳酸盐岩样品溶液Ti浓度并加以校正，与国家标准方法二安替比林甲烷光度法及电感耦合等离子体发射光谱法(ICP-OES)测定结果进行方法比对，与两者的相对标准偏差均小于允许限。方法加标回收率为83%～107%。该方法适用于CaO含量范围在31%～56%，Ti含量范围在14～3346μg/g的碳酸盐岩样品的测试，为高钙高镁碳酸盐岩中微量Ti的测试提供了方法参考。
- 碳酸盐岩 /
- 电感耦合等离子体质谱法 /
- Ti /
- 同位素选择
Abstract:
The content of Ti in carbonate rocks is generally lower than 3.5mg/g, and most of it is below 1mg/g. X-ray fluorescence spectrometry (XRF), which is commonly used to measure Ti content in silicic rocks (usually more than 0.1%), cannot meet the requirements of accurate measurement of trace Ti in carbonate rocks. This paper reports on the attempts to test Ti in carbonate rock by inductively coupled plasma-mass spectrometry (ICP-MS), discusses and analyzes the interference of 5 test isotopes of Ti (⁴⁶Ti, ⁴⁷Ti, ⁴⁸Ti, ⁴⁹Ti, ⁵⁰Ti) in carbonate solution matrix, and determines the suitable test isotope ⁴⁸Ti. Then the ICP-MS method for the determination of trace Ti in carbonate rock is proposed. According to the method, the concentration of Ti in 5 first-class national standard materials was tested and corrected. The measured values were consistent with the certified values, and the relative standard deviation (RSD, n=10) was less than 7.3%. The concentration of Ti in the unknown carbonate sample solution was measured and corrected under the same experimental conditions, and this method was compared with the national standard method of diantipyrine methane spectrophotometry and inductively coupled plasma-optical emission spectrometry (ICP-OES) method, and the relative standard deviation with these two methods were less than the allowable limit. The recoveries were 83%−107%. This method is suitable for the determination of carbonate samples with 31%−56% CaO and 14−3346μg/g Ti, and provides a reference for the determination of trace Ti in carbonate rocks with high calcium and magnesium.
- carbonate rocks /
- inductively coupled plasma-mass spectrometry /
- Ti /
- isotope selection

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图 1 单标溶液中Ca对Ti各同位素的干扰程度

△Ti表示Ca在各Ti测试同位素处的贡献值。(a) Ca对⁴⁶Ti测试值的贡献；(b) Ca对⁴⁷Ti测试值的贡献；(c) Ca对⁴⁸Ti测试值的贡献；(d) Ca对⁴⁹Ti测试值的贡献；(e) Ca对⁵⁰Ti测试值的贡献。

Figure 1. Diagrams of interference degree of Ca on each isotope of Ti in single element standard solutions

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图 2 国家一级标准物质中CaO对Ti各同位素的干扰程度

△Ti表示国家标准物质中CaO在各Ti测试同位素处的贡献值。(a) CaO对⁴⁶Ti测试值的贡献；(b) CaO对⁴⁷Ti测试值的贡献；(c) CaO对⁴⁸Ti测试值的贡献；（d） CaO对⁴⁹Ti测试值的贡献；(e) CaO对⁵⁰Ti测试值的贡献。

Figure 2. Interference degree of CaO on each isotope of Ti in first class national standard materials

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表 1 碳酸盐岩国家一级标准物质Ti含量测定值与标准值对比

Table 1 Comparison of analytical values and certified values of Ti content in carbonate rock national standard materials

标准物质编号	CaO含量（%）	Ti含量（μg/g）
GBW07128	41.95	132
GBW07128	41.95	132
GBW07129	55.49	42
GBW07131	30.93	78
GBW07133	53.83	174
GBW07135	43.76	2580

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表 2 碳酸盐岩国家一级标准物质Ti含量测定值与标准值对比

Table 2 Comparison of analytical values and certified values of Ti content in carbonate rock national standard materials

国家标准物质编号	Ti含量标准值 (μg/g)	Ti含量测定值(μg/g)
国家标准物质编号	Ti含量标准值 (μg/g)	⁴⁶Ti	⁴⁷Ti	⁴⁸Ti	⁴⁹Ti	⁵⁰Ti
GBW07128	132	223	214	474	225	219
GBW07129	42	127	128	492	130	123
GBW07131	78	143	141	314	142	138
GBW07133	174	256	242	544	231	232
GBW07135	2580	2628	2628	3158	2602	2635

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表 3 碳酸盐岩中Ti元素的潜在干扰离子

Table 3 Potential interference ions of Ti in carbonate rocks

Ti的测试同位素	Ti自然丰度 (%)	潜在干扰离子
⁴⁶Ti	7.93	⁴⁶Ca⁺、³²S¹⁴N⁺、³⁰Si¹⁶O⁺、²⁸Si¹⁸O⁺、⁹²Zr²⁺、⁹²Mo²⁺
⁴⁷Ti	7.28	⁴⁶CaH⁺、³¹P¹⁶O⁺、¹²C³⁵Cl⁺、¹⁵N¹⁶O₂、⁹⁴Zr²⁺、⁹⁴Mo²⁺、⁷Li⁴⁰Ar⁺、¹¹B³⁶Ar⁺
⁴⁸Ti	73.94	⁴⁸Ca⁺、³⁶Ar¹²C⁺、⁹⁶Zr²⁺、⁹⁶Mo²⁺、⁹⁶Ru²⁺、³²S¹⁶O⁺
⁴⁹Ti	5.51	⁴⁸CaH⁺、⁹⁸Mo²⁺、⁹⁸Ru²⁺、³³S¹⁶O⁺、³¹P¹⁸O⁺
⁵⁰Ti	5.34	⁵⁰Cr⁺、⁵⁰V⁺、¹⁴N³⁶Ar⁺、¹¹B³⁶Ar⁺、¹⁰⁰Ru²⁺、¹⁰⁰Mo²⁺、³⁴S¹⁶O⁺

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表 4 方法准确度

Table 4 Accuracy of the method

标准物质编号	Ti含量标准值 (μg/g)	Ti含量校正值 (μg/g)	相对误差 (%)	允许限 (%)
GBW07128	132	145	10.0	12.1
GBW07129	42	38.7	7.86	14.9
GBW07131	78	85.7	9.84	13.3
GBW07133	174	193	11.1	11.5
GBW07135	2580	2725	5.60	6.64

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表 5 加标回收率

Table 5 Recovery of standard addition

标准物质编号	试样Ti含量测得量 (μg)	Ti加标量 (μg)	加标试样Ti含量测得量 (μg)	回收率 (%)	回收率允许限 (%)
GBW07128	145.0	100	228.0	83.0	10～110
GBW07129	46	50	99.4	107.0
GBW07131	86	50	133.0	94.6

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表 6 方法精密度

Table 6 Precision of the method

标准物质编号	Ti含量分次测定值 (μg/g)					Ti含量平均值 (μg/g)	RSD (%)
GBW07129	38.7	42.3	36.2	40.9	45	41	7.3
GBW07129	40.6	45.7	42.5	38	40	41	7.3
GBW07133	174	165	178	166	165	170	3.8
GBW07133	183	170	166	164	165	170	3.8
GBW07135	2725	2561	2560	2559	2559	2613	3.3
GBW07135	2559	2788	2536	2684	2602	2613	3.3

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表 7 不同方法测定Ti含量结果比对

Table 7 Comparison of Ti content determined by different methods

样品编号	本文方法Ti含量测定值(μg/g)	二安替比林甲烷光度法			ICP-OES法
样品编号	本文方法Ti含量测定值(μg/g)	测定值 (μg/g)	相对偏差 (%)	允许限 (%)	测定值 (μg/g)	相对偏差 (%)	允许限 (%)
1	14.7	16	6.6	25.0	12.4	17.4	18.0
2	30.0	32	4.8	22.2	25.2	17.6	22.6
3	125	143	13.7	17.1	123	1.16	12.3
4	254	277	8.6	15.1	246	3.28	10.8
5	3346	3301	1.4	8.9	3270	2.30	6.27
6	756	764	1.1	12.2	723	4.41	8.70
7	535	544	1.6	13.1	548	2.36	9.27
8	1481	1501	1.4	10.6	1530	3.28	7.49
9	14.0	18	22.9	24.8	16.3	15.3	17.7
10	1051	1068	1.6	11.4	965	8.46	11.5
注：相对偏差= $\left(\left\|X_{\text {测 }}-\bar{X}\right\| / \bar{X}\right) \times 100 \%$ ；其中 $X_{\text {测 }}$ 为本方法测定值， $\bar{X}$ 为本方法测定值与二安替比林甲烷光度法或ICP-OES法测定值的平均值；允许限= $C \times\left(14.37 \bar{X}^{-0.1263}-7.659\right)$ ，其中C=1， $\bar{X}$ 为本方法测定值与二安替比林甲烷光度法或ICP-OES法测定值的平均值。

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