地质样品铊同位素分析预处理方法优化

柒锦捷; 余红霞; 徐庆鸿; 袁永海; 杨锋; 张惠评

doi:10.15898/j.ykcs.202311070174

地质样品铊同位素分析预处理方法优化

1.
桂林理工大学地球科学学院，广西桂林 541006

2.
桂林理工大学，广西隐伏金属矿产勘查重点实验室，广西桂林 541006

基金项目: 国家重点研发计划项目(2021YFC2900100)；广西研究生创新项目(YCBZ2022119)

详细信息

作者简介: 柒锦捷，硕士研究生，地球化学专业。E-mail：495898865@qq.com

通讯作者: 袁永海，高级实验师，主要从事原子光谱分析方法研究。E-mail：Hg20109@163.com。

中图分类号: O657.63

收稿日期: 2023-11-07

修回日期: 2024-01-11

录用日期: 2024-02-22

刊出日期: 2024-04-30

Optimization of Pretreatment Method for Tl Isotope Analysis of Geological Samples

1.
College of Earth Sciences, Guilin University of Technology, Guilin 541006, China

2.
Guangxi Key Laboratory of Hidden Metal Mineral Exploration, Guilin University of Technology, Guilin 541006, China

More Information

Corresponding author: YUAN Yonghai, Hg20109@163.com

Received Date: 07 November 2023

Revised Date: 11 January 2024

Accepted Date: 22 February 2024

Publish Date: 30 April 2024

摘要

摘要:
铊同位素体系可以示踪天体演化、古环境变化、矿床成因及污染物迁移等地质过程。然而，目前用于铊同位素分析的样品消解和离子交换方法耗时较长，往往需要两周甚至更久；为了提高化学前处理效率，本文采用微波消解法分解样品，以AG1-X8阴离子交换树脂纯化铊，采用多接收器电感耦合等离子体质谱(MC-ICP-MS)测试，仪器的质量歧视用铅同位素标准溶液(NIST SRM981)校正。通过考察消解条件、淋洗曲线和基质效应，结果表明：采用微波消解法，在2mL硝酸-2mL氢氟酸-0.5mL高氯酸的混合酸体系中选用适当的消解程序可以将0.2g土壤标准物质GBW07406消解完全，总耗时不超过2h；利用AG1-X8树脂，上样后，依次以2mL 2mol/L硝酸-1%溴水淋洗6次、2mL超纯水淋洗1次和2mL 0.1mol/L盐酸-6%二氧化硫淋洗5次(收集铊)，可有效地纯化铊；常见共存元素的干扰实验结果显示，树脂填充量为2mL时，该淋洗流程所允许上样溶液中含有三价铁和三价铝离子的量分别不应超过2.56mmol和4.90mmol，否则会使铊的回收率降低。将此方法应用于4个地质标准物质中铊同位素比值的测定，ε²⁰⁵Tl_{GSB Tl}的精密度(2SD，n=6)均优于0.3；与文献的结果对比显示，标准物质NOD-P-1、GBW07406和GSP-2的ε²⁰⁵Tl差值(ε²⁰⁵Tl_{NIST 997}−ε²⁰⁵Tl_{GSB Tl})均为0.8，NOD-A-1的ε²⁰⁵Tl差值为0.7，说明方法具有较好的准确性；此外，可以估算标准物质GSB 04-1758-2004相对于NIST 997的ε²⁰⁵Tl值应约等于0.8。
- 硝酸-氢氟酸-高氯酸 /
- 微波消解 /
- AG1-X8阴离子交换树脂 /
- 铊同位素组成 /
- 多接收器电感耦合等离子体质谱法
Abstract:
The thallium (Tl) isotope system can be utilized to track various geological processes, but the current sample digestion and ion exchange methods used for Tl isotope analysis take a long time. To improve the efficiency of chemical pretreatment of samples for Tl isotope analysis, the samples were decomposed by the microwave digestion method. In the mixed acid system of 2mL HNO₃, 2mL HF and 0.5mL HClO₄, 0.2g of GBW07406 could be completely dissolved by selecting the digestion procedure. The slurry was then loaded on AG1-X8 resin, followed by eluting with 2mL 2mol/L HNO₃-1% Br₂ for 6 times, 2mL H₂O for 1 time, and 2mL 0.1mol/L HCl-6% SO₂ for 5 times (Tl collection). The amount of Fe³⁺ and Al³⁺ allowed in the sample solution should not exceed 2.56mmol and 4.90mmol respectively, otherwise the recovery rate of Tl will be reduced. Measurement ε²⁰⁵Tl values for four geological reference materials (NOD-P-1, NOD-A-1, GBW07406 and GSP-2) by multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS) showed a good precision (2SD better than 0.3, n=6) and a fixed difference of 0.8 compared with the value in the literature, indicating that the ε²⁰⁵Tl value of GSB04-1758-2004 with respect to NIST 997 should be approximately equal to 0.8. The BRIEF REPORT is available for this paper at http://www.ykcs.ac.cn/en/article/doi/10.15898/j.ykcs.202311070174.
- HNO₃-HF-HClO₄ /
- microwave digestion /
- AG1-X8 anion exchange resin /
- Tl isotope composition /
- multi-collector inductively coupled plasma-mass spectrometry

HTML全文

图 1 铊的淋洗曲线(AG1-X8树脂，100～200目)，其中2mol/L硝酸-1%溴水洗脱基体元素，超纯水洗脱残留NO₃⁻和BrO⁻，0.1mol/L盐酸-6%二氧化硫收集铊

Figure 1.

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图 2 三氧化二铁、氧化钙和三氧化二铝对铊回收率的影响(n=3)

Figure 2.

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图 3 铊标准溶液GSB 04-1758-2004测量结果的稳定性(n=40)

Figure 3.

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表 1 MC-ICP-MS和ICP-MS仪器主要工作参数

Table 1. Main operation conditions of MC-ICP-MS and ICP-MS instruments

工作参数	设定值
工作参数	MC-ICP-MS	ICP-MS
冷却气(Ar)流速(L/min)	16.00	14.95
辅助气(Ar)流速(L/min)	0.86	0.28
雾化气(Ar)流速(L/min)	0.05	0.92
射频功率(W)	1152	1470
积分时间(s)	4.194	/
每组测量次数	30	/
测量组数	1	/

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表 2 地质标准物质和同位素标准溶液的详细信息

Table 2. Details of geological reference materials and isotope reference solutions

标准物质编号	样品类型	研制单位	推荐值
标准物质编号	样品类型	研制单位	铊	铅
NIST SRM 981	铅同位素标准溶液	美国标准与技术研究院(NIST)	/	10μg/mL
GSB 04-1758-2004	铊标准溶液	中国有色金属及电子材料分析测试中心	1000μg/mL	/
NOD-P-1	铁锰结核	美国地质调查局(USGS)	210±2μg/g	560±6μg/g
NOD-A-1	铁锰结核	美国地质调查局(USGS)	120±1.0μg/g	846±8.2μg/g
GBW07406	土壤	中国地质科学院地球物理地球化学勘查研究所	2.2±0.6μg/g	314±25μg/g
GSP-2	花岗岩	美国地质调查局(USGS)	1.1±0.1μg/g	43±3μg/g

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表 3 样品处理微波消解程序

Table 3. Microwave digestion procedure for sample pretreatment

步骤	消解温度 (℃)	消解功率 (W)	加热时间 (min)	保持时间 (min)
1	120	400	5	5
2	150	800	5	5
3	190	1200	5	20

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表 4 铊同位素的离子交换流程(2mL AG1-X8树脂，100～200目)

Table 4. Chemical purification procedure for Tl isotopes (2mL AG1-X8 resin, 100-200 mesh)

步骤	淋洗液	淋洗液体积 (mL)	淋洗次数	实验目的
1	0.1mol/L盐酸-6%二氧化硫	1	2	清洗树脂
2	超纯水	1	2	清洗树脂
3	2mol/L硝酸-1%溴水	2	2	清洗/平衡树脂
4	2mol/L硝酸-1%溴水	2	/	装载样品
5	2mol/L硝酸-1%溴水	2	6	洗脱基质
6	超纯水	2	1	洗脱NO₃⁻和BrO⁻
7	0.1mol/L盐酸-6%二氧化硫	2	5	收集铊

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表 5 不同无机酸种类及用量的消解效果对比(n=3)

Table 5. Comparison of digestion effects of different types and volumes of inorganic acids (n=3)

混合酸体系	实验组号	混合酸体系各酸用量 (mL)	样品消解效果观察	铊回收率 (%)
硝酸-氢氟酸- 盐酸-过氧化氢	1-1	1+1+1+1	有少量不溶白色沉淀	84.7
	1-2	2+2+2+1	黄色消解液清澈透亮	98.4
	1-3	5+3+3+1	黄色消解液清澈透亮	98.6
硝酸-氢氟酸- 高氯酸	2-1	1+1+0.5	有少量不溶白色沉淀	81.9
	2-2	2+2+0.5	黄色消解液清澈透亮	98.2
	2-3	5+3+0.5	黄色消解液清澈透亮	99.0

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表 6 消解温度和保持时间的正交试验结果(n=3)

Table 6. Orthogonal test results of digestion temperature and holding time (n=3)

编号	因素水平		铊回收率 (%)
编号	消解温度(℃)	时间(min)	铊回收率 (%)
1	180	15	86.6
2	180	20	93.1
3	190	15	94.0
4	190	20	98.2
5	200	15	97.8
6	200	20	99.1

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表 7 地质标准物质中铊同位素组成的测定结果及文献对比

Table 7. Comparison of analytical results of Tl isotope composition in geological reference materials determined by this method and those in the literatures

标准物质编号	岩性	ε²⁰⁵Tl_{GSB Tl} (2SD)	ε²⁰⁵Tl_{NIST 997} (2SD)	测量次数 (n)	数据来源	ε²⁰⁵Tl差值
NOD-P-1	铁锰结核	/	3.3±0.7	6	［5］	0.8
NOD-P-1	铁锰结核	2.5±0.2	/	6	本文研究	0.8
NOD-A-1	铁锰结核	/	10.7±0.5	6	［28］	0.7
NOD-A-1	铁锰结核	10.0±0.3	/	6	本文研究	0.7
GBW07406	土壤	/	−2.2±0.2	4	［5］	0.8
GBW07406	土壤	−3.0±0.2	/	6	本文研究	0.8
GSP-2	花岗岩	/	−2.5±0.6	9	［4］	0.8
GSP-2	花岗岩	−3.3±0.3	/	6	本文研究	0.8

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