微波消解电感耦合等离子体质谱法测量气态元素汞

周枫然; 王德发; 张体强; 叶菁; 冯和平

doi:10.12338/j.issn.2096-9015.2022.0158

微波消解电感耦合等离子体质谱法测量气态元素汞

doi: 10.12338/j.issn.2096-9015.2022.0158

周枫然^1,,
王德发^{1, 2},
张体强^{1, 2, ,},
叶菁¹,
冯和平¹

1.
中国计量科学研究院，北京 100029
2.
国家气体产品质量监督检验中心，北京 100029

基金项目: 中央级公益性科研院所基本科研业务费（AKY1620）。

详细信息

作者简介:
周枫然（1997 -），中国计量科学研究院在读研究生，研究方向：元素分析，邮箱：15652393599@163.com

通讯作者:
张体强（1982-），中国计量科学研究院副研究员，研究方向：气体分析计量，邮箱：zhangtq@nim.ac.cn

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出版历程
- 收稿日期: 2022-07-05
- 录用日期: 2022-07-18
- 网络出版日期: 2022-09-07
- 刊出日期: 2022-10-18

Determination of Gaseous Elemental Mercury by Microwave Digestion and Inductively Coupled Plasma Mass Spectrometry Analysis

ZHOU Fengran^1
,,
WANG Defa^{1, 2},
ZHANG Tiqiang^{1, 2
, ,},
YE Jing¹,
FENG Heping¹

1.
National Institute of Metrology, Beijing 100029, China
2.
National Quality Inspection and Testing Center for Gas Products, Beijing 100029, China

摘要

摘要: 气态汞浓度测量技术的提升有助于大气汞的准确监测，可进一步为我国履行《关于汞的水俣公约》提供技术支持，推动汞的污染防治工作。使用微波消解电感耦合等离子体质谱法测量气态汞浓度，研究了样品制备时活性炭粒径和气体流量对活性炭吸附汞效果的影响，样品预处理过程中消解温度、HNO₃和HCl的比例以及消解时间对消解效果的影响，并且为电感耦合等离子体质谱测量建立了外标定量方法。结果显示，50目的活性炭及较低的气体流量更利于气态汞的吸附；消解温度为190℃、HNO₃与HCl配比为5∶3、消解时间为50 min时消解效果最好。在此方法中，线性相关系数R²为0.9999，检出限为0.0509 ng·g⁻¹，线性好、检出限低，可用于气态元素汞的测量。采用外标法依据汞单元素有证标准物质对样品进行了定值，该值与动态发生汞标准的理论值间相对偏差均小于2.5%，证明此方法具有较高的准确性，进一步验证了动态发生法制备汞标准气体的量值准确性。
- 气态元素汞 /
- 微波消解 /
- 电感耦合等离子体质谱法 /
- 外标法
Abstract: The improvement of gaseous mercury concentration measurement technology is conducive to the accurate monitoring of atmospheric mercury, which can further provide technical support to the implementation of the “Minamata Convention on Mercury” and promote the prevention and control of mercury pollution in China. In this paper, a microwave digestion and inductively coupled plasma mass spectrometry (ICP-MS) was developed to measure the concentration of gaseous mercury. Specifically, the factors affecting the experimental results were evaluated, including (1) the factors of activated carbon particle size and gas flow to mercury adsorption in sample preparation, and (2) the factors of digestion temperature, volume ratio of HNO₃∶HCl and digestion time to the digestion efficiency in sample pretreatment. The external standard method for the quantitative determination of mercury based on ICP-MS was also established. The results showed that 50 mesh activated carbon and lower gas flow were more favorable for the adsorption of gaseous mercury, and the best efficient digestion was obtained when the digestion temperature was 190℃, the volume ratio of HNO₃∶HCl was 5∶3, and the digestion time was 50 min. In this method, the linear correlation coefficient R² is 0.9999 and the detection limit is 0.0509 ng·g⁻¹, which shows good linearity and a lower detection limit for the measurement of gaseous elemental mercury. The samples were determined by the external standard method based on the certified reference material of single elemental mercury. The differences between the results calculated by the external standard method and the theoretical data are less than 2.5%, which proves the high accuracy of this method and further verifies the accuracy of the quantity of mercury gas standard prepared by the dynamical generation method.
- gaseous elemental mercury /
- microwave digestion /
- ICP-MS /
- external standard method

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图 1 工作曲线

Figure 1. working curve

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表 1 ICP-MS仪器工作参数

Table 1. Operating parameters of ICP-MS

参数	条件
RF功率/W	1550
采样深度/mm	10
载气流速/（L·min⁻¹）	1.07
积分时间/s	0.3
采集时间/s	40.14

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表 2 活性炭粒径和气体流量对采样的影响

Table 2. The influence of activated carbon particle size and gas flow on the collection of samples

样品	c /µg·m⁻³	q/mL·min⁻¹	t/h	结果
样品	c /µg·m⁻³	q/mL·min⁻¹	t/h	30目	50目
1	10	258	2	√	√
2	10	258	2	√	√
3	10	597	2	×	√
4	10	597	2	×	√
5	10	750	2	×	×
6	10	750	2	×	×
7	22	258	2	×	√
8	22	258	2	×	√
9	22	597	2	×	√
10	22	597	2	×	√

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表 3 消解时间对消解效果的影响

Table 3. The influence of time on digestion efficiency

样品	t_dig/min	离子强度/ CPS
1	40	82090
2	40	84416
3	50	87005
4	50	88596
5	60	85017
6	60	84968

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表 4 消解温度对消解效果的影响

Table 4. The influence of temperature on digestion efficiency

样品	T_dig/℃	离子强度/ CPS
1	180	114432
2	180	113608
3	190	142492
4	190	146542
5	200	135939
6	200	137083

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表 5 消解酸对消解效果的影响

Table 5. The influence of digestive acid on digestion efficiency

样品	HNO₃/mL	HCl/ mL	离子强度/ CPS
1	6	2	133194
2	6	2	132945
3	5	3	158719
4	5	3	158181
5	4	4	156534
6	4	4	156217

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表 6 工作标准系列溶液配制数据

Table 6. The preparation data of working standard solutions

序号	1	2	3	4	5
v /mL	0	0.1	0.2	0.4	0.8
v_2%HCl /mL	10	9.9	9.8	9.6	9.2
m₇/g	0	0.1004	0.2013	0.3920	0.8044
m₈/g	10	10.0600	10.0598	10.0124	9.8073
c_Hg/ ng·g⁻¹	0	0.4949	0.9924	1.9417	4.0677

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表 7 工作标准系列溶液的质谱测量数据

Table 7. The mass spectrometry data for measurement of mercury standard solution

c_Hg / ng·g⁻¹	0.0000	0.4949	0.9924	1.9417	4.0677
离子强度/ CPS	838	24429	48181	93914	199116
相对标准偏差	0.86%	0.69%	0.70%	0.25%	0.20%

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表 8 样品制备的参数

Table 8. The parameters for sample preparation

参数	样品1	样品2	样品3	样品4	样品5
m₁/g	29.5072	29.6451	29.9120	29.5833	29.6763
m₂/g	29.6367	29.7669	30.0414	29.7056	29.8089
m_C1/g	0.1295	0.1218	0.1294	0.1223	0.1326
c /µg·m⁻³	10.00	10.00	10.00	10.00	10.00
q/mL·min⁻¹	258.8	258.8	258.8	258.8	258.8
t /min	40	40	40	40	38
m_Hg/µg	0.104	0.104	0.104	0.104	0.098
m₃/g	93.7879	95.2588	94.6019	94.8694	94.5125
m₄/g	93.9075	95.3691	94.7129	94.9889	94.6293
m_C2/g	0.1196	0.1103	0.1110	0.1195	0.1168
m₅/g	51.3738	51.3155	17.9974	17.9321	51.3799
m₆/g	147.7002	151.7624	117.8900	116.3892	148.5025
m_s/g	96.3264	100.4469	99.8926	98.4571	97.1226
c_h/ng·g⁻¹	0.9925	0.9333	0.8890	1.0274	0.8919

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表 9 样品的质谱检测数据与结果

Table 9. The mass spectrometry data and results of samples

	样品1	样品2	样品3	样品4	样品5
c_h/ng·g⁻¹	0.9925	0.9333	0.8890	1.0274	0.8919
吸附样品离子强度/ CPS	82649	80304	75691	85692	77081
空白样品离子强度/ CPS	33168	33835	31327	34514	32661
c_m/ng·g⁻¹	1.0144	0.9526	0.9095	1.0492	0.9106
相对偏差/%	2.20	2.07	2.31	2.12	2.10
回收率/%	102.2	102.0	102.3	102.1	102.1
回收率相对标准偏差（RSD）	0.1%

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