大气挥发性有机物实时在线监测的双极性质子转移反应质谱仪研制

引用本文: 张强领, 邹雪, 梁渠, 张亚婷, 易明建, 王鸿梅, 黄超群, 沈成银, 储焰南. 大气挥发性有机物实时在线监测的双极性质子转移反应质谱仪研制[J]. 分析化学, 2018, 46(4): 471-478. doi: 10.11895/j.issn.0253-3820.171234 shu

Citation: ZHANG Qiang-Ling, ZOU Xue, LIANG Qu, ZHANG Ya-Ting, YI Ming-Jian, WANG Hong-Mei, HUANG Chao-Qun, SHEN Cheng-Yin, CHU Yan-Nan. Development of Dipolar Proton Transfer Reaction Mass Spectrometer for Real-time Monitoring of Volatile Organic Compounds in Ambient Air[J]. Chinese Journal of Analytical Chemistry, 2018, 46(4): 471-478. doi: 10.11895/j.issn.0253-3820.171234 shu

大气挥发性有机物实时在线监测的双极性质子转移反应质谱仪研制

1.
中国科学院合肥物质科学研究院, 医学物理与技术中心, 医学物理与技术安徽省重点实验室, 合肥 230031;
2.
中国科学技术大学, 合肥 230026;
3.
中国科学院安徽光学精密机械研究所, 合肥 230031;
4.
安徽省环境科学研究院大气环境研究所, 合肥 230026
基金项目:
本文系国家重点研发计划项目（No.2016YFC0200200）、国家自然科学基金项目（Nos.21777163，21477132，21577145）和国家科技支撑计划项目（No.2014BAC22B06）资助

摘要: 大气中挥发性有机物（VOCs）能参与光化学反应，导致臭氧和气溶胶等二次污染物的产生，实时精准地监测VOCs对于大气污染成因研究具有重要意义。在质子转移反应质谱（PTR-MS）研究基础上，本工作研制一套用于大气VOCs实时在线监测的双极性质子转移反应质谱仪（Dipolar proton transfer reaction mass spectrometer，DP-PTR-MS）。相比单一反应离子H₃O⁺的常规PTR-MS，DP-PTR-MS中有正负3种反应离子（H₃O⁺、OH^-、（CH₃）₂COH⁺），可根据实际检测需要选择切换，提高定性能力，并有效扩展检测范围。其中，H₃O⁺反应离子用于检测质子亲和势大于H₂O的VOCs；OH^-反应离子可与H₃O⁺反应离子配合识别VOCs，还可用于检测CO₂等无机物；（CH₃）₂COH⁺反应离子可在排除干扰的情况下准确检测NH₃。利用6种标准气体测定DP-PTR-MS检出限和灵敏度，结果表明，DP-PTR-MS对甲苯的检出限为7×10^-12（V/V），对氨气的灵敏度为126.0 cps/10^-9（V/V）。利用DP-PTR-MS对合肥市区大气VOCs开展连续78 h实时在线监测验证实验，结果表明，DP-PTR-MS可对大气中10^-12（V/V）量级VOCs进行长期实时在线监测，可作为大气污染成因研究和痕量VOCs排放监测的重要工具。

关键词:

English

Development of Dipolar Proton Transfer Reaction Mass Spectrometer for Real-time Monitoring of Volatile Organic Compounds in Ambient Air

1.
Anhui Province Key Laboratory of Medical Physics and Technology, Center of Medical Physics and Technology, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China;
2.
University of Science and Technology of China, Hefei 230026, China;
3.
Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China;
4.
Institute of Atmospheric Environment, Research Academy of Environmental Sciences of Anhui Province, Hefei 230026, China
Received Date: 06 September 2017
Revised Date: 28 December 2017
Fund Project:
This work was supported by the National Key R&D Program of China (No.2016YFC0200200), the National Natural Science Foundation of China (Nos.21777163, 21477132, 21577145) and the National Science and Technology Support Program of China (No.2014BAC22B06).

Abstract: Volatile organic compounds (VOCs) in ambient air can participate in photochemical reactions, which lead to the generation of secondary pollutants such as ozone and aerosol. So real-time and accurate monitoring of atmospheric VOCs plays an important role in the study of the causes of air pollution. On the basis of proton transfer reaction mass spectrometry (PTR-MS) research, a novel dipolar proton transfer reaction mass spectrometer (DP-PTR-MS) for real-time and on-line monitoring atmospheric VOCs was developed. Compared with the conventional PTR-MS with one kind of reagent ion H₃O⁺, DP-PTR-MS had three kinds of reagent ions H₃O⁺, OH^-, (CH)₂COH⁺, which could be switched according to the actual detection need. So DP-PTR-MS can improve the qualitative ability and expand the detection range effectively. The reagent ion H₃O⁺ can be used for detecting VOCs whose proton affinities are greater than that of H₂O. The reagent ion OH^- can be used to identify VOCs cooperating with the reagent ion H₃O⁺, and can also be used for detecting some inorganic substances such as CO₂. The reagent ion (CH₃)₂COH⁺ can be used for accurately detecting NH₃ under interference elimination circumstances. The limit of detection (LOD) and sensitivity of DP-PTR-MS were measured by using six kinds of standard gases. The results showed that the LOD for detecting toluene was 7×10^-12 (V/V) and the sensitivity for detecting ammonia has reached 126 cps/10^-9(V/V). The ambient air in Hefei city was on-line and real-time monitored for continuous 78 hours with DP-PTR-MS. The results showed that the newly developed DP-PTR-MS could be used for long-term and real-time monitoring atmospheric VOCs with the concentration of 10^-12(V/V) level. DP-PTR-MS is an important tool for the study of the causes of atmospheric pollution and the monitoring of trace VOCs emissions.

Key words:

Dipolar proton transfer reaction mass spectrometry
/ Volatile organic compounds
/ Real-time
/ On-line monitoring

1. [1]
  Jenkin M E, Derwent R G, Wallington T J. Atmos. Environ.,2017,163:128-137
2. [2]
  ZHAN Xue-Fang, DUAN Yi-Xiang. Chinese J. Anal. Chem.,2011,39(10):1611-1618 詹雪芳, 段忆翔.分析化学,2011,39(10):1611-1618
3. [3]
  Omori Y, Tanimoto H, Inomata S, Ikeda K, Iwata T, Kameyama S, Uematsu M, Gamo T, Ogawa H, Furuya K. J. Geophys. Res.Atmos.,2017,122(13):7216-7231
4. [4]
  Zou X, Kang M, Li A Y, Shen C Y, Chu Y N. Anal. Chem.,2016,88(6):3144-3148
5. [5]
  Li K, Li J L, Wang W G, Tong S R, Liggio J, Ge M F. Atmos. Environ.,2017,164:117-127
6. [6]
  Malecha K T, Nizkorodov S A. J. Phys. Chem. A,2017,121(26):4961-4967
7. [7]
  Erasmus S W, Muller M, Alewijn M, Koot A H, Van Ruth S M, Hoffman L C. Food Chem.,2017,233:331-342
8. [8]
  Landy P, Pollien P, Rytz A, Leser M E, Sagalowicz L, Blank I, Spadone J C. J. Agric. Food Chem., 2007,55(5):1915-1922
9. [9]
  Lindinger W, Hansel A, Jordan A. Inter. J. Mass Spectrom.,1998,173(3):191-241
10. [10]
  Zou X, Zhou W Z, Lu Y, Shen C Y, Hu Z T, Wang H Z, Jiang H H, Chu Y N. J. Gastroenterol. Hepatol., 2016,31(11):1837-1843
11. [11]
  SHEN Chen-Yin, LI Jian-Quan, WANG Hong-Zhi, ZHI Zhong-Hua, WANG Hong-Mei, LIU Sheng, JIANG Hai-He, CHU Yan-Nan. Chinese J. Anal. Chem.,2012,40(5):773-777 沈成银, 李建权, 王宏志, 志中华, 王鸿梅, 黄超群, 刘升, 江海河, 储焰南.分析化学,2012,40(5):773-777
12. [12]
  Guo T, Du X B, Peng Z, Xu L, Dong J G, Li J Q, Cheng P, Zhou Z. Rapid Commun. Mass Spectrom.,2017,31(17):1424-1430
13. [13]
  Gonzalez-Mendez R, Watts P, Olivenza-Leon D, Reich D F, Mullock S J, Corlett C A, Cairns S, Hickey P, Brookes M, Mayhew C A. Anal. Chem.,2016,88(21):10624-10630
14. [14]
  Hansel A, Jordan A, Holzinger R, Prazeller P, Vogel W, Lindinger W. Inter. J. Mass Spectrom.,1995,149:609-619
15. [15]
  Pan Y, Zhang Q L, Zhou W Z, Zou X, Wang H M, Huang C Q, Shen C Y, Chu Y N.J. Am. Soc. Mass Spectrom.,2017,28(5):873-879
16. [16]
  Kang M, Zou X, Lu Y, Wang H M, Shen C Y, Jiang H H, Chu Y N. Chem. Res. Chinese Univers.,2016,32(4):565-569
17. [17]
  Coles K F, Popper F. Industrial Engineer. Chem.,1950,42(7):1434-1438
18. [18]
  Ambrose D, Sprake C H S, Townsend R. J. Chem. Thermodyn.,1974,6(7):693-700
19. [19]
  Ikezoe S, Matsuoka M, Takebe A. Gas Phase Ion-molecule Reaction Rate Constants Through986, Maruzen Company, Ltd., Tokyo,1987
20. [20]
  Shen C Y, Niu W Q, Huang C Q, Xia L, Lu Y, Wang S L, Wang H Z, Jiang H H, Chu Y N. Inter. J. Mass Spectrom.,2014,371:36-41
21. [21]
  Shen C Y, Li J Q, Wang Y J, Wang H M, Han H Y, Chu Y N. Inter. J. Environ. Anal. Chem.,2012,92(3):289-301
22. [22]
  Hunter E P L, Lias S G. J. Phys. Chem. Reference Data,1998,27(3):413-656
23. [23]
  Guo Y X, Tang Q H, Gong D Y, Zhang Z Y. Remote Sensing Environ.,2017,198:140-149
24. [24]
  Lin C, Liou N, Sun E. J. Air Waste Manage. Assoc.,2008,58(6):821-828

扫一扫看文章

计量

PDF下载量: 8
文章访问数: 1261
HTML全文浏览量: 41

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

大气挥发性有机物实时在线监测的双极性质子转移反应质谱仪研制

English

Development of Dipolar Proton Transfer Reaction Mass Spectrometer for Real-time Monitoring of Volatile Organic Compounds in Ambient Air

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

大气挥发性有机物实时在线监测的双极性质子转移反应质谱仪研制

English

Development of Dipolar Proton Transfer Reaction Mass Spectrometer for Real-time Monitoring of Volatile Organic Compounds in Ambient Air

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs