碱溶液提取-离子交换-电感耦合等离子体质谱法测定土壤中六价铬

褚琳琳; 王静云; 金晓霞; 汪碧芬; 孔翠羽

doi:10.15898/j.cnki.11-2131/td.202203240060

碱溶液提取-离子交换-电感耦合等离子体质谱法测定土壤中六价铬

山东省威海生态环境监测中心，山东威海 264200

基金项目:
江西省教育厅科学技术研究项目青年项目(GJJ190613); 山东省高等学校优秀青年创新团队“化学生物学与药学分析创新团队”项目(2019KJM008)

详细信息

作者简介: 褚琳琳，硕士，工程师，主要从事环境样品分析测试工作。E-mail：linlinchu@yeah.net

通讯作者: 金晓霞，硕士，高级工程师，主要从事环境监测工作。E-mail：jczxjxx@126.com

中图分类号: O657.63; O657.31; S151.93

收稿日期: 2022-03-24

修回日期: 2022-05-14

录用日期: 2022-05-24

刊出日期: 2022-09-28

Determination of Hexavalent Chromium in Soil by Inductively Coupled Plasma-Mass Spectrometry with Alkaline Digestion-Ion Exchange

Shandong Weihai Eco-Environment Monitoring Center, Weihai 264200, China

More Information

Corresponding author: JIN Xiaoxia, jczxjxx@126.com

Received Date: 24 March 2022

Revised Date: 14 May 2022

Accepted Date: 24 May 2022

Publish Date: 28 September 2022

摘要

摘要:
六价铬Cr(Ⅵ)是建设用地土壤基本监测指标之一，开展土壤六价铬监测在环境污染防治中具有重要意义。目前测定土壤Cr(Ⅵ)的标准方法为火焰原子吸收分光光度法(FAAS)，其检出限为0.5mg/kg，难以满足低浓度土壤样品中Cr(Ⅵ)的分析。本文采用氢氧化钠-碳酸钠溶液提取土壤中的Cr(Ⅵ)，建立了一种使用电感耦合等离子体质谱法(ICP-MS)结合阳离子交换测定土壤中低浓度Cr(Ⅵ)的方法。结果表明，将碱性提取液稀释10倍并加入3.5g阳离子交换树脂后，溶解性总固体(TDS)质量分数从2.4%降低为0.17%，基体干扰大幅度降低。同时，由于离子交换过程溶出氢离子，使得pH达到适宜的检测范围(7.5±0.5)。此外，优化了前处理条件，提取温度为90~95℃、搅拌速度300r/min、加热时间70min时，Cr(Ⅵ)提取效果最佳，相对误差(RE)仅-1.7%。本方法相对标准偏差(RSD)为3.1%~5.9%，平均相对误差介于-3.8%~-1.1%。使用F检验及t检验比较了ICP-MS法与FAAS法测试高、中、低三种浓度标准物质的结果，二者无显著性差异。由于本法采取稀释、离子交换、内标法等方式降低了基体干扰，结合ICP-MS自身灵敏度高、准确性好的特点，使得方法检出限(MDL)达到0.061mg/kg，显著低于FAAS法检出限(0.5mg/kg)，可用于低浓度土壤Cr(Ⅵ)样品的测定。
- 电感耦合等离子体质谱法 /
- 火焰原子吸收分光光度法 /
- 离子交换 /
- 氢氧化钠-碳酸钠溶液提取 /
- 六价铬
Abstract: BACKGROUND
Hexavalent chromium Cr(Ⅵ) is one of the basic monitoring indicators of soil in construction land. It is of great significance to carry out soil hexavalent chromium monitoring in the prevention and control of environmental pollution. At present, the standard method of hexavalent chromium in soil is flame atomic absorption spectrometry (FAAS). The FAAS method has a high detection limit (0.5mg/kg), and serious matrix effect, and cannot meet the analysis of Cr(Ⅵ) in low-concentration soil samples.
OBJECTIVES
To establish a convenient and high sensitivity method for determination of low-concentration hexavalent chromium in soil.
METHODS
An ion-exchange-inductively coupled plasma-mass spectrometry (ICP-MS) method was developed to determine the content of hexavalent chromium in soil by extracting hexavalent chromium with alkali solution. The resin content, mixing speed, extraction temperature and extraction time were studied. The measurement results were compared with the flame atomic absorption spectrophotometry (FAAS) method.
RESULTS
The results showed that the total dissolved solids (TDS) mass fraction was reduced from 2.4% to 0.17% after the alkaline extraction solution was diluted 10 times and 3.5g of cation exchange resin was added, and the matrix interference was greatly reduced. At the same time, due to the dissolution of hydrogen ions in the ion exchange process, the pH reached a suitable detection range (7.5±0.5). The pretreatment conditions were optimized. When the extraction temperature was 90-95℃, the stirring speed was 300 rpm, and the heating time was 70 min, the extraction effect of Cr(Ⅵ) was the best, and the relative error was -1.7%. The relative standard deviation (RSD) was 3.1%-5.9%, and the average relative error was -3.8% to -1.1%. F test and t test were used to compare the test results of high, medium and low concentration standard substances by ICP-MS and FAAS, and there was no significant difference between the two methods. The method detection limit (MDL) was 0.061 mg/kg.
CONCLUSIONS
Since this method adopts dilution, ion exchange, internal standard method, to reduce matrix interference, combined with the high sensitivity and good accuracy of ICP-MS, the method detection limit (MDL) is significantly lower than the detection limit of FAAS method (0.5mg/kg). This method can be used for the determination of low-concentration soil Cr(Ⅵ) samples.
- inductively coupled plasma-mass spectrometry /
- flame atomic absorption spectrometry /
- ion-exchange /
- sodium hydroxide-sodium carbonate solution digestion /
- hexavalent chromium

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图 1 样品前处理过程图解

Figure 1.

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图 2 阳离子交换树脂加入量对提取液的pH值和标准物质Cr(Ⅵ)测定的影响

Figure 2.

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图 3 不同提取温度下Cr(Ⅵ)浓度及相对误差

Figure 3.

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图 4 不同转速和提取时间下测定标准物质RMH-A048的Cr(Ⅵ)浓度

Figure 4.

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表 1 采用ICP-MS和FAAS法测定土壤中Cr(Ⅵ)的检出限

Table 1. Detection limit of Cr(Ⅵ) in soil by ICP-MS and FAAS

分析方法	提取液平行测定的Cr(Ⅵ)浓度(mg/L)							标准偏差(mg/kg)	方法检出限MDL(mg/kg)
分析方法	1	2	3	4	5	6	7	标准偏差(mg/kg)	方法检出限MDL(mg/kg)
ICP-MS(本文方法)	0.1902	0.2004	0.1578	0.1822	0.1736	0.2148	0.1690	0.01949	0.061
FAAS	2.06	1.90	1.72	1.84	1.68	2.02	1.78	0.145	0.5

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表 2 采用ICP-MS和FAAS法测定Cr(Ⅵ)的精密度及相对误差

Table 2. Precision and relative error of ICP-MS and FAAS determination of Cr(Ⅵ)

标准物质编号	Cr(Ⅵ)浓度标准值(mg/kg)	分析方法	土壤中Cr(Ⅵ)浓度平行测定值(mg/kg)								相对误差(%)	RSD(%)
标准物质编号	Cr(Ⅵ)浓度标准值(mg/kg)	分析方法	1	2	3	4	5	6	7	平均值	相对误差(%)	RSD(%)
RMH-A048	28.8±2.7	ICP-MS	27.1	28.3	26.7	29	27.5	28.3	26.9	27.7	-3.8	3.1
RMH-A048	28.8±2.7	FAAS	28.3	31.1	26.9	27.5	28.3	26.8	27.7	28.1	-2.4	5.2
RMU041	5.10±0.67	ICP-MS	5.11	4.93	5.02	4.67	4.52	4.81	5.30	4.91	-3.7	5.4
RMU041	5.10±0.67	FAAS	4.39	5.73	4.52	4.39	4.64	5.13	4.45	4.75	-6.9	10.6
GBW(E)070251	0.92±0.09	ICP-MS	0.84	0.86	0.93	0.89	0.96	0.99	0.92	0.91	-1.1	5.9
GBW(E)070251	0.92±0.09	FAAS	0.70	0.83	0.96	0.82	0.96	0.91	0.63	0.83	-9.8	15.3

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