微波消解-双浊点萃取ICP-MS测定地球化学样品中的痕量铂钯钌铑

沈宇; 张尼; 高小红; 李展; 李日升; 郑建斌

doi:10.15898/j.cnki.11-2131/td.2016.03.007

微波消解-双浊点萃取ICP-MS测定地球化学样品中的痕量铂钯钌铑

1.
西安西北有色地质研究院有限公司, 陕西西安 710054

2.
西北大学分析科学研究所, 陕西省电分析化学重点实验室, 陕西西安 710069

基金项目:
陕西省科技计划项目(2015KJXX-81);陕西省工业科技攻关项目(2015GY54)

详细信息

作者简介: 沈宇,在读博士研究生,工程师,从事无机元素分析和方法研究工作。E-mail:shenyusherry@163.com

通讯作者: 郑建斌,博士生导师,教授,从事电化学分析研究。E-mail:zhengjb@nwu.edu.cn

中图分类号: O657.63;O614.82

收稿日期: 2015-11-26

修回日期: 2016-04-28

录用日期: 2016-05-20

Determination of Pt, Pd, Ru, Rh in Geochemical Samples by ICP-MS with Microwave Digestion and Dual-cloud Point Extraction

1.
Xi'an Northwest Geological Research Institute for Nonferrous Metals, Xi'an 710054, China

2.
Institute of Analytical Science, Northwest University, Shannxi Provincal Key Laboratory of Electroanalytical Chemistry, Xi'an 710069, China

More Information

Corresponding author: Jian-bin ZHENG, zhengjb@nwu.edu.cn

Received Date: 26 November 2015

Revised Date: 28 April 2016

Accepted Date: 20 May 2016

摘要

摘要: 传统浊点萃取技术是将待测元素富集在黏稠的表面活性剂相中,溶液的黏度会对等离子体检测信号产生影响,通常使用甲醇作为稀释剂降低有机相黏度,有机成分也对等离子体的稳定性产生影响,同时有机物在进样管路上的吸附还会提高待测元素的记忆效应,因而限制了ICP-MS在浊点萃取中的应用。本文建立了双浊点萃取技术ICP-MS测定地球化学样品中铂钯钌铑的分析方法。样品用微波消解处理后,以DDTP为螯合剂,Triton X-114为表面活性剂,对消解溶液第一次浊点萃取,再在有机相中加入硝酸,通过加热完成第二次浊点萃取,使铂钯钌铑由有机相进入水相,铂钯钌铑的富集因子分别为45、33、18和35,高于单次浊点萃取的富集因子,ICP-MS检出限分别为0.05、0.02、0.10和0.03μg/L。本方法通过两次浊点萃取过程实现了基体复杂的地球化学样品中痕量铂族元素的同时富集,提高了ICP-MS的稳定性。
- 地球化学样品 /
- 铂族元素 /
- 双浊点萃取 /
- 有机相 /
- 水相 /
- 电感耦合等离子体质谱法
Abstract: Traditional cloud point extraction methods commonly enrich elements in the viscous surfactant. However, the viscosity of the solution will adversely affect the detection signal of the plasma. Harmful agents such as methanol are usually adopted as a thinner to reduce the viscosity of the organic phase, but the organic component affects the stability of the plasma, and organic absorption on the injection tube will enhance elemental memory effect. These disadvantages limit the widespread application of Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) in cloud point extraction. A method to determine Pt, Pd, Ru, Rh in geochemical samples by ICP-MS based dual-cloud point extraction has been established, and is reported in this paper. After the microwave digestion procedure, first cloud point extraction is performed on the sample solution using DDTP as the sequestrant and Triton X-114 as the surfactant. HNO₃ is added into the organic phase, and second cloud point extraction is performed by heating so that Pt, Pd, Ru, Rh enter the water phase from the organic phase. Enrichment factors are 45, 33, 18, 35, and detection limits are 0.05, 0.02, 0.10 and 0.03 μg/L for Pt, Pd, Ru and Rh, respectively. The proposed method succeeds in the simultaneous enrichment of trace platinum group elements in complex matrix geochemical samples, improving the stability of the ICP-MS measurement.
- geochemical samples /
- platinum group elements /
- dual-cloud point extraction /
- organic phase /
- aqueous phase /
- Inductively Coupled Plasma-Mass Spectrometry

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图 1 不同浓度的硝酸对各金属离子萃取的影响

Figure 1.

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表 1 本文方法与其他方法对比

Table 1. Comparison of analytical results of PGEs determined by this method and other methods

样品类型	测定元素	表面活性剂	螯合试剂	稀释剂	检测手段	富集因子	检出限	线性范围	文献
环境样品	Cd²⁺ Pb²⁺ Pd²⁺ Ag⁺	Triton X-114	2-苯并咪唑乙硫醚	甲醇	FAAS	48 39 32 42	1.4 μg/L 2.8 μg/L 1.6 μg/L 1.4 μg/L	-	^[14]
土壤和岩石样品	Pd Ag Au	Triton X-114	4-对氯苯基-1-(2-吡啶)-氨基硫脲	甲醇	ETAAS	52 46 56	0.12 μg/L 0.08 μg/L 0.30 μg/L	0~125 μg/L 0~50 μg/L 0~100 μg/L	^[15]
矿石和标准物质	Au Pd	Triton X-114	1,8-二氨基-4,5-二羟基-9,10-蒽二酮	硝酸	ICP-OES	8.6 20.2	0.5 μg/L 0.3 μg/L	0.5~1000 μg/L	^[16]
街尘	Pt	Triton X-100	十六烷基三甲基溴化铵	甲醇	ICP-MS	13	10 pg/g	100~50000 ng/L	^[17]
环境样品	Pt Pd	Triton X-100	2-巯基苯并噻唑	盐酸	ICP-MS	6 6	0.22 ng/g 0.17 ng/g	-	^[18]
地球化学样品	Pt Pd Rh Ru	Triton X-114	O,O-二乙基二硫代磷酸铵	硝酸	ICP-MS	45 33 18 35	0.05 μg/L 0.02 μg/L 0.10 μg/L 0.03 μg/L	0.0005~0.3 μg/mL	本文
注：表格中的“-”表示文献中未列出。

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表 2 方法准确度及精密度

Table 2. Accuracy and precision tests of the method

铂族元素	GBW07291			GBW07293
铂族元素	标准值(ng/g)	测定值 (ng/g)	RSD (%)	标准值 (ng/g)	测定值 (ng/g)	RSD (%)
Pt	58	49	3.0	440	392	2.8
Pd	60	51	3.3	568	497	3.0
Ru	2.5	1.8	5.7	13	9.5	4.1
Rh	4.3	3.2	4.9	22	16	3.9

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表 3 实际样品分析

Table 3. Analytical results of the actual samples

样品编号	元素	元素含量测定值(ng/g)		ICP-MS(n=3)精密度 (%)	对数误差
样品编号	元素	d-CPE	火试金/树脂吸附	ICP-MS(n=3)精密度 (%)	对数误差
S-1	Pt	1.3	1.1	2.9	0.03
	Pd	2.1	2.5	2.6	0.06
	Ru	0.58	0.49	3.3	0.10
	Rh	0.89	0.86	4.1	0.09
S-2	Pt	6.3	6.6	2.2	0.07
	Pd	3.3	3.1	2.3	0.06
	Ru	2.1	1.8	2.9	0.10
	Rh	2.6	2.6	3.5	0.07
S-3	Pt	29	30	1.9	0.01
	Pd	16.8	15.9	1.5	0.03
	Ru	0.83	0.77	3.0	0.10
	Rh	0.53	0.49	3.6	0.11
S-4	Pt	18.3	19.2	1.9	0.03
	Pd	13.6	12.8	1.2	0.05
	Ru	0.66	0.64	3.6	0.13
	Rh	1.9	2.3	2.9	0.09
注：“对数误差”参见DZ/T 0130—2006《地质矿产实验室测试质量管理规范》。

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