电感耦合等离子体串联质谱法测定电解二氧化锰废渣浸出液中的重金属元素

李坦平; 吴宜; 曾利群; 娄晓明; 李爱阳

doi:10.15898/j.cnki.11-2131/td.201911230162

电感耦合等离子体串联质谱法测定电解二氧化锰废渣浸出液中的重金属元素

1.
湖南工学院新型建筑材料研究院, 湖南衡阳 421002

2.
湖南湘潭市华昇环保科技有限公司, 湖南湘潭 411202

基金项目:
国家自然科学基金资助项目（81603400）；湖南省自然科学基金资助项目（2019JJ60026）；湖南省应用特色学科材料科学与工程学科资助项目（湘教通[2018]469号）

详细信息

作者简介: 李坦平, 学士, 教授, 主要从事固体工业废弃物建材资源化利用研究。E-mail:hwl0466@163.com

中图分类号: O657.63;O614

收稿日期: 2019-11-23

修回日期: 2020-01-10

录用日期: 2020-07-03

Determination of Heavy Metal Elements in Leaching Solution of Electrolytic Manganese Dioxide Waste Residue by Inductively Coupled Plasma-Tandem Mass Spectrometry

1.
New Building materials Academy, Hunan Institute of Technology, Hengyang 421002, China

2.
Hunan Xiangtan Huasheng Environmental Protection Technology Co., LTD, Xiangtan 411202, China

Received Date: 23 November 2019

Revised Date: 10 January 2020

Accepted Date: 03 July 2020

摘要

摘要: 电解二氧化锰废渣中的重金属元素在雨水淋滤下，通过地表径流对下游水生态系统及农业生态系统造成不同程度的环境污染和安全隐患，因此，准确测定电解二氧化锰废渣浸出液中的重金属元素含量具有重要的现实意义。电解二氧化锰废渣浸出液中的重金属元素含量通常很低，采用原子吸收光谱法、电感耦合等离子体发射光谱法测定，检出限通常难以满足测定要求。采用电感耦合等离子体质谱法（ICP-MS）测定，消除复杂质谱干扰面临挑战。本文采用电感耦合等离子体串联质谱（ICP-MS/MS）测定电解二氧化锰废渣浸出液中的重金属元素含量。电解二氧化锰废渣中6种重金属元素Cr、Ni、As、Cd、Hg、Pb经硫酸和硝酸混合酸浸出后直接采用ICP-MS/MS进行测定，利用串联质谱的O₂反应模式消除分析过程中Cr、Ni、As、Cd受到的质谱干扰，通过考察不同分析模式下⁵²Cr、⁶⁰Ni、⁷⁵As、¹¹¹Cd的背景等效浓度（BEC），评价质谱干扰对分析结果的影响。结果表明：在MS/MS模式下选择O₂为反应气，采用质量转移法和原位质量法可以消除⁵²Cr、⁶⁰Ni、⁷⁵As、¹¹¹Cd的所有质谱干扰。Cr、Ni、As、Cd、Hg、Pb检出限分别为3.06、9.31、3.50、2.72、2.03、1.89ng/L，加标回收率在95.6%~106.2%之间，相对标准偏差（RSD）≤3.9%。所建立的方法已应用于电解二氧化锰废渣浸出液中重金属元素的测定。
- 电解二氧化锰废渣 /
- 浸出液 /
- 重金属元素 /
- 电感耦合等离子体串联质谱法 /
- 质谱干扰 /
- O₂反应气
Abstract: BACKGROUND The heavy metals in electrolytic manganese dioxide waste residue can cause different degrees of environmental pollution and hidden dangers to downstream aquatic ecosystems and agricultural ecosystems through surface runoff under rainwater leaching. Therefore, it is of great practical significance to determine the content of heavy metal elements in leaching solution of electrolytic manganese dioxide waste residue. Usually, the detection limits of atomic absorption spectrometry and inductively coupled plasma-optical emission spectrometry are insufficient to meet the measurement requirements, since the content of heavy metal elements in the leaching solution of electrolytic manganese dioxide waste residue is typically very low. The challenge is to eliminate complex spectral interference. OBJECTIVES To find an efficient method for the determination of six heavy metal elements in leaching solution of electrolytic manganese dioxide waste residue. METHODS The objective was determined by inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS). The six heavy metal elements Cr, Ni, As, Cd, Hg and Pb in the electrolytic manganese dioxide waste residue were directly measured by ICP-MS/MS after H₂SO₄-HNO₃ mixed acid leaching. The O₂ reaction mode was adopted to eliminate the spectral interference of Cr, Ni, As and Cd during analysis. The background equivalent concentrations (BECs) of ⁵²Cr, ⁶⁰Ni, ⁷⁵As and ¹¹¹Cd in the different analytical mode were investigated to evaluate the influence of spectral interference on the analysis results. RESULTS In the MS/MS mode, O₂ was selected as the reaction gas, and the spectral interference of ⁵²Cr, ⁶⁰Ni, ⁷⁵As and ¹¹¹Cd was eliminated by using mass shift method and on-mass method. The limits of detection for Cr, Ni, As, Cd, Hg and Pb were 3.06, 9.31, 3.50, 2.72, 2.03, 1.89ng/L, respectively. The spiked recoveries were between 95.6% and 106.2%. The relative standard deviation was no higher than 3.9%. CONCLUSIONS The method has been successfully applied to the determination of heavy metal elements in leaching solution of electrolytic manganese dioxide waste residue.
- electrolytic manganese dioxide waste residue /
- leaching solution /
- heavy metal elements /
- inductively coupled plasma-tandem mass spectrometry /
- mass spectral interference /
- O₂ reaction gas

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图 1 在MS/MS模式下采用O₂反应气消除质谱干扰的工作原理

Figure 1.

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图 2 O₂流速对测定混合标准溶液中Cr、Ni、As、Cd的影响

Figure 2.

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表 1 不同质谱模式下分析元素的背景等效浓度

Table 1. Background equivalent concentrations of analytes in different mass spectrometric mode

同位素	潜在质谱干扰	背景等效浓度(ng/L)
同位素	潜在质谱干扰	SQ(无气体模式)	SQ(He碰撞模式)	MS/MS(O₂反应模式)
⁵²Cr	⁴⁰Ar¹²C, ³⁵Cl¹⁶O¹H, ³⁶Ar¹⁶O, ³⁸Ar¹⁴N	31600	53.7	23.4
⁶⁰Ni	⁵⁹Co¹H, ²³Na³⁶Ar¹H, ²³Na³⁷Cl	78.9	40.5	5.28
⁷⁵As	⁴⁰Ar³⁵Cl, ⁵⁹Co¹⁶O, ¹⁵⁰Nd⁺⁺, ¹⁵⁰Sm⁺⁺	1050	22.8	13.0
¹¹¹Cd	⁹⁵Mo¹⁶O	216	84.6	19.2
²⁰²Hg	¹⁸⁶W¹⁶O	10.3	17.1	16.6
²⁰⁸Pb	¹⁹²Os¹⁶O	11.2	15.8	20.5

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表 2 校准数据与检出限 (n=11)

Table 2. Calibration data and detection limits (n=11)

待测元素	监测离子	内标分配	线性范围 (μg/L)	线性相关系数	检出限 (ng/L)
Cr	⁵²Cr¹⁶O⁺	⁴⁵Sc¹⁶O⁺	10.2~500	1.0000	3.06
Ni	⁶⁰Ni¹⁶O⁺	⁴⁵Sc¹⁶O⁺	31.3~500	0.9999	9.31
As	⁷⁵As¹⁶O⁺	⁸⁹Y¹⁶O⁺	11.7~500	0.9998	3.50
Cd	¹¹¹Cd⁺	¹⁰³Rh⁺	9.07~50	1.0000	2.72
Hg	²⁰²Hg⁺	²⁰⁹Bi⁺	6.77~50	0.9999	2.03
Pb	²⁰⁸Pb⁺	²⁰⁹Bi⁺	6.30~500	1.0000	1.89

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表 3 分析方法的准确度和精密度 (n=6)

Table 3. Accuracy and precision of analytical method (n=6)

待测元素	加标值 (μg/L)	测定值 (μg/L)	加标回收率 (%)	RSD (%)
	2.00	1.88	94.0	2.8
Cr	10.0	10.3	103.0	2.2
	50.0	51.6	103.2	1.9
	2.00	2.05	102.5	2.6
Ni	10.0	9.87	98.7	3.0
	50.0	51.8	103.6	2.5
	2.00	1.95	97.5	1.7
As	10.0	10.4	104.0	3.1
	50.0	52.3	104.6	2.0
	2.00	1.92	96.0	2.3
Cd	10.0	9.37	93.7	3.9
	50.0	53.6	107.2	3.2
	2.00	1.90	95.0	2.7
Hg	10.0	9.62	96.2	3.4
	50.0	47.3	94.6	2.5
	2.00	2.07	103.5	1.8
Pb	10.0	10.1	101.0	2.1
	50.0	48.4	96.8	2.9

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表 4 电解二氧化锰废渣浸出液的分析结果 (n=6)

Table 4. Analytical results of leaching solution of electrolytic manganese dioxide waste residue (n=6)

待测元素	元素测定值(μg/L)
待测元素	样品A	样品B	样品C	样品D
Cr	46.2±1.70	32.8±1.26	61.3±2.19	13.4±0.51
Ni	0.71±0.028	0.92±0.037	0.38±0.014	0.25±0.010
As	3.06±0.12	1.37±0.048	0.88±0.035	5.41±0.16
Cd	0.072±0.005	0.040±0.003	0.052±0.003	0.087±0.005
Hg	0.053±0.004	0.031±0.002	0.016±0.001	0.023±0.002
Pb	0.38±0.011	0.69±0.025	0.45±0.018	0.82±0.034

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