基于过氧自由基原位测量的大气臭氧光化学生成速率研究

引用本文: 俞辉, 姚易辰, 徐学哲, 韦娜娜, 赵卫雄, 张为俊. 基于过氧自由基原位测量的大气臭氧光化学生成速率研究[J]. 分析化学, 2023, 51(2): 287-295. doi: 10.19756/j.issn.0253-3820.221313 shu

Citation: YU Hui, YAO Yi-Chen, XU Xue-Zhe, WEI Na-Na, ZHAO Wei-Xiong, ZHANG Wei-Jun. Study on Atmospheric Ozone Photochemical Production Rate Based on In-situ Measurement of Peroxy Radical[J]. Chinese Journal of Analytical Chemistry, 2023, 51(2): 287-295. doi: 10.19756/j.issn.0253-3820.221313 shu

基于过氧自由基原位测量的大气臭氧光化学生成速率研究

俞辉 ^1,2, ,
姚易辰 ^1,2, ,
徐学哲 ^1, ,
韦娜娜 ^1, ,
赵卫雄 ^{1,
,} ,
张为俊 ^1,3,

1.
中国科学院合肥物质科学研究院安徽光学精密机械研究所, 合肥 230031;
2.
中国科学技术大学研究生院科学岛分院, 合肥 230026;
3.
中国科学技术大学环境科学与光电技术学院, 合肥 230026

通讯作者: 赵卫雄,E-mail:wxzhao@aiofm.ac.cn

基金项目:
国家自然科学基金项目(No.U21A2028)、大气重污染成因与治理攻关项目(No.DQGG202117)、中国科学院青年创新促进会项目(No.Y202089)和合肥研究院院长基金项目(No.YZJJ202101)资助。

摘要: 过氧自由基（HO₂和RO₂）是挥发性有机物大气氧化反应过程中的重要中间体，在大气一次污染物降解和二次污染物形成过程中起着承上启下的关键作用，因此，过氧自由基的外场准确测量对研究大气化学反应机理和大气污染成因具有重要意义。本研究利用宽带腔增强吸收光谱-化学放大过氧自由基测量装置，原位在线测量了大气中总过氧自由基（RO₂^*=HO₂+RO₂）的浓度，结合NO的测量，实现了臭氧光化学生成速率（P（O₃））的实时快速测量。利用此装置对2021年淮北市夏季臭氧光化学生成速率进行了研究，结果表明，本地夏季过氧自由基日均峰值体积比为75×10^-12（V/V），臭氧生成速率日均峰值为14×10^-9（V/V）/h，臭氧生成速率对NO的变化更敏感。此外，在污染时段，臭氧光化学生成速率提升显著，对当地臭氧浓度具有重要影响。

关键词:

English

Study on Atmospheric Ozone Photochemical Production Rate Based on In-situ Measurement of Peroxy Radical

1.
Anhui Institute of Optics and Fine Mechanics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China;
2.
Science Island Branch, Graduate School, University of Science and Technology of China, Hefei 230026, China;
3.
School of Environmental Science and Optoelectronics Technology, University of Science and Technology of China, Hefei 230026, China

Corresponding author: ZHAO Wei-Xiong, wxzhao@aiofm.ac.cn

Received Date: 02 June 2022
Revised Date: 29 August 2022
Fund Project:
Supported by the National Natural Science Foundation of China (No. U21A2028), the National Research Program for Key Issues in Air Pollution Control, China (No. DQGG202117), the Youth Innovation Promotion Association, CAS (No. Y202089) and the HFIPS Director′s Fund (No. YZJJ202101).

Abstract: Peroxy radicals (RO₂^* = RO₂ + HO₂) are key intermediates in the atmospheric oxidation of volatile organic compounds, and play a key role in the degradation of primary atmospheric pollution and the formation of secondary pollutants. It is of great significance to accurately measure the concentration of RO₂^* for understanding the atmospheric chemical reaction mechanism and the cause of atmospheric pollution. In this work, a broadband cavity enhanced absorption spectroscopy-chemically amplified peroxy radical instrument was used to measure the peroxy radical in-situ. Combined with the measurement of NO, the photochemical ozone production rate could be determined in real time. Observations were made in Huaibei city during summer 2021, to characterize ozone production. The results showed that the average peaking peroxy radical concentration was 75×10^-12(V/V), while the average ozone peaking production rate was 14×10^-12(V/V) in summer in Huaibei. The ozone production rate was more sensitive to the NO concentration changes. In addition, during the pollution period, the photochemical generation of ozone increased significantly, which made an important contribution to the local high concentration of O₃.

Key words:

Peroxyl radicals
/ Broadband cavity enhanced absorption spectroscopy
/ Chemical amplification
/ Field measurement
/ Ozone production rate

1. [1]
  HOFZUMAHAUS A, ROHRER F, LU K, BOHN B, BRAUERS T, CHANG C C, FUCHS H, HOLLAND F, KITA K, KONDO Y, LI X, LOU S, SHAO M, ZENG L, WAHNER A, ZHANG Y. Science, 2009, 324(5935):1702-1704.HOFZUMAHAUS A, ROHRER F, LU K, BOHN B, BRAUERS T, CHANG C C, FUCHS H, HOLLAND F, KITA K, KONDO Y, LI X, LOU S, SHAO M, ZENG L, WAHNER A, ZHANG Y. Science, 2009, 324(5935):1702-1704.
2. [2]
  STONE D, WHALLEY L K, HEARD D E. Chem. Soc. Rev., 2012, 41(19):6348-6404.STONE D, WHALLEY L K, HEARD D E. Chem. Soc. Rev., 2012, 41(19):6348-6404.
3. [3]
  LU X, ZHANG L, WANG X, GAO M, LI K, ZHANG Y, YUE X, ZHANG Y. Environ. Sci. Technol. Lett., 2020, 7(4):240-247.LU X, ZHANG L, WANG X, GAO M, LI K, ZHANG Y, YUE X, ZHANG Y. Environ. Sci. Technol. Lett., 2020, 7(4):240-247.
4. [4]
  TANG Xiao-Yan, ZHANG Yuan-Hang, SHAO Min. Atmospheric Environmental Chemistry. Beijing:Higher Education Press, 2006:32. 唐孝炎, 张远航, 邵敏. 大气环境化学(第二版). 北京:高等教育出版社, 2006:32.
5. [5]
  TAN Z, ROHRER F, LU K, MA X, BOHN B, BROCH S, DONG H, FUCHS H, GKATZELIS G I, HOFZUMAHAUS A, HOLLAND F, LI X, LIU Y, LIU Y, NOVELLI A, SHAO M, WANG H, WU Y, ZENG L, HU M, KIENDLER-SCHARR A, WAHNER A, ZHANG Y. Atmos. Chem. Phys., 2018, 18(16):12391-12411.TAN Z, ROHRER F, LU K, MA X, BOHN B, BROCH S, DONG H, FUCHS H, GKATZELIS G I, HOFZUMAHAUS A, HOLLAND F, LI X, LIU Y, LIU Y, NOVELLI A, SHAO M, WANG H, WU Y, ZENG L, HU M, KIENDLER-SCHARR A, WAHNER A, ZHANG Y. Atmos. Chem. Phys., 2018, 18(16):12391-12411.
6. [6]
  LU K D, ROHRER F, HOLLAND F, FUCHS H, BOHN B, BRAUERS T, CHANG C C, HÄSELER R, HU M, KITA K, KONDO Y, LI X, LOU S R, NEHR S, SHAO M, ZENG L M, WAHNER A, ZHANG Y H, HOFZUMAHAUS A. Atmos. Chem. Phys., 2012, 12(3):1541-1569.LU K D, ROHRER F, HOLLAND F, FUCHS H, BOHN B, BRAUERS T, CHANG C C, HÄSELER R, HU M, KITA K, KONDO Y, LI X, LOU S R, NEHR S, SHAO M, ZENG L M, WAHNER A, ZHANG Y H, HOFZUMAHAUS A. Atmos. Chem. Phys., 2012, 12(3):1541-1569.
7. [7]
  ZHANG G, HU R, XIE P, LOU S, WANG F, WANG Y, QIN M, LI X, LIU X, WANG Y, LIU W. Sci. Total Environ., 2022, 810:152275.ZHANG G, HU R, XIE P, LOU S, WANG F, WANG Y, QIN M, LI X, LIU X, WANG Y, LIU W. Sci. Total Environ., 2022, 810:152275.
8. [8]
  YANG X, LU K, MA X, LIU Y, WANG H, HU R, LI X, LOU S, CHEN S, DONG H, WANG F, WANG Y, ZHANG G, LI S, YANG S, YANG Y, KUANG C, TAN Z, CHEN X, QIU P, ZENG L, XIE P, ZHANG Y. Sci. Total Environ., 2021, 772:144829.YANG X, LU K, MA X, LIU Y, WANG H, HU R, LI X, LOU S, CHEN S, DONG H, WANG F, WANG Y, ZHANG G, LI S, YANG S, YANG Y, KUANG C, TAN Z, CHEN X, QIU P, ZENG L, XIE P, ZHANG Y. Sci. Total Environ., 2021, 772:144829.
9. [9]
  XUE L K, SAUNDERS S M, WANG T, GAO R, WANG X F, ZHANG Q Z, WANG W X. Geosci. Model Dev., 2015, 8(10):3151-3162.XUE L K, SAUNDERS S M, WANG T, GAO R, WANG X F, ZHANG Q Z, WANG W X. Geosci. Model Dev., 2015, 8(10):3151-3162.
10. [10]
  PENG X, WANG W, XIA M, CHEN H, RAVISHANKARA A R, LI Q, SAIZ-LOPEZ A, LIU P, ZHANG F, ZHANG C, XUE L, WANG X, GEORGE C, WANG J, MU Y, CHEN J, WANG T. Natl. Sci. Rev., 2021, 8(7):nwaa304.PENG X, WANG W, XIA M, CHEN H, RAVISHANKARA A R, LI Q, SAIZ-LOPEZ A, LIU P, ZHANG F, ZHANG C, XUE L, WANG X, GEORGE C, WANG J, MU Y, CHEN J, WANG T. Natl. Sci. Rev., 2021, 8(7):nwaa304.
11. [11]
  WHALLEY L K, STONE D, DUNMORE R, HAMILTON J, HOPKINS J R, LEE J D, LEWIS A C, WILLIAMS P, KLEFFMANN J, LAUFS S, WOODWARD-MASSEY R, HEARD D E. Atmos. Chem. Phys., 2018, 18(4):2547-2571.WHALLEY L K, STONE D, DUNMORE R, HAMILTON J, HOPKINS J R, LEE J D, LEWIS A C, WILLIAMS P, KLEFFMANN J, LAUFS S, WOODWARD-MASSEY R, HEARD D E. Atmos. Chem. Phys., 2018, 18(4):2547-2571.
12. [12]
  TAN Z, MA X, LU K, JIANG M, ZOU Q, WANG H, ZENG L, ZHANG Y. Sci. Total Environ., 2021, 800:148868.TAN Z, MA X, LU K, JIANG M, ZOU Q, WANG H, ZENG L, ZHANG Y. Sci. Total Environ., 2021, 800:148868.
13. [13]
  MIHELCIC D, VOLZ-THOMAS A, PATZ H W, KLEY D, MIHELCIC M. J. Atmos. Chem., 1990, 11(3):271-297.MIHELCIC D, VOLZ-THOMAS A, PATZ H W, KLEY D, MIHELCIC M. J. Atmos. Chem., 1990, 11(3):271-297.
14. [14]
  FUCHS H, BRAUERS T, HÄSELER R, HOLLAND F, MIHELCIC D, MÜSGEN P, ROHRER F, WEGENER R, HOFZUMAHAUS A. Atmos. Meas. Tech., 2009, 2(1):55-64.FUCHS H, BRAUERS T, HÄSELER R, HOLLAND F, MIHELCIC D, MÜSGEN P, ROHRER F, WEGENER R, HOFZUMAHAUS A. Atmos. Meas. Tech., 2009, 2(1):55-64.
15. [15]
  FUCHS H, HOLLAND F, HOFZUMAHAUS A. Rev. Sci. Instruments, 2008, 79(8):084104.FUCHS H, HOLLAND F, HOFZUMAHAUS A. Rev. Sci. Instruments, 2008, 79(8):084104.
16. [16]
  WHALLEY L K, BLITZ M A, DESSERVETTAZ M, SEAKINS P W, HEARD D E. Atmos. Meas. Tech., 2013, 6(12):3425-3440.WHALLEY L K, BLITZ M A, DESSERVETTAZ M, SEAKINS P W, HEARD D E. Atmos. Meas. Tech., 2013, 6(12):3425-3440.
17. [17]
  CANTRELL C A, STEDMAN D H, WENDEL G J. Anal. Chem., 1984, 56(8):1496-1502.CANTRELL C A, STEDMAN D H, WENDEL G J. Anal. Chem., 1984, 56(8):1496-1502.
18. [18]
  HERNÁNDEZ M D A, BURKERT J, REICHERT L, STÖBENER D, MEYER-ARNEK J, BURROWS J P, DICKERSON R R, DODDRIDGE B G. J. Geophys. Res.:Atmos., 2001, 106(D18):20833-20846.HERNÁNDEZ M D A, BURKERT J, REICHERT L, STÖBENER D, MEYER-ARNEK J, BURROWS J P, DICKERSON R R, DODDRIDGE B G. J. Geophys. Res.:Atmos., 2001, 106(D18):20833-20846.
19. [19]
  LIU Y, MORALES-CUETO R, HARGROVE J, MEDINA D, ZHANG J. Environ. Sci. Technol., 2009, 43(20):7791-7796.LIU Y, MORALES-CUETO R, HARGROVE J, MEDINA D, ZHANG J. Environ. Sci. Technol., 2009, 43(20):7791-7796.
20. [20]
  WOOD E C, CHAREST J R. Anal. Chem., 2014, 86(20):10266-10273.WOOD E C, CHAREST J R. Anal. Chem., 2014, 86(20):10266-10273.
21. [21]
  GEORGE M, ANDRÉS HERNÁNDEZ M D, NENAKHOV V, LIU Y, BURROWS J P. Atmos. Meas. Tech., 2020, 13(5):2577-2600.GEORGE M, ANDRÉS HERNÁNDEZ M D, NENAKHOV V, LIU Y, BURROWS J P. Atmos. Meas. Tech., 2020, 13(5):2577-2600.
22. [22]
  CHEN Y, YANG C, ZHAO W, FANG B, XU X, GAI Y, LIN X, CHEN W, ZHANG W. Analyst, 2016, 141(20):5870-5878.CHEN Y, YANG C, ZHAO W, FANG B, XU X, GAI Y, LIN X, CHEN W, ZHANG W. Analyst, 2016, 141(20):5870-5878.
23. [23]
  YANG C, ZHAO W, FANG B, XU X, ZHANG Y, GAI Y, ZHANG W, VENABLES D S, CHEN W. Anal. Chem., 2018, 90(5):3307-3312.YANG C, ZHAO W, FANG B, XU X, ZHANG Y, GAI Y, ZHANG W, VENABLES D S, CHEN W. Anal. Chem., 2018, 90(5):3307-3312.
24. [24]
  YANG C, ZHAO W, FANG B, YU H, XU X, ZHANG Y, GAI Y, ZHANG W, CHEN W, FITTSCHEN C. Anal. Chem., 2019, 91(1):776-779.YANG C, ZHAO W, FANG B, YU H, XU X, ZHANG Y, GAI Y, ZHANG W, CHEN W, FITTSCHEN C. Anal. Chem., 2019, 91(1):776-779.
25. [25]
  WASHENFELDER R A, WAGNER N L, DUBE W P, BROWN S S. Environ. Sci. Technol., 2011, 45(7):2938-2944.WASHENFELDER R A, WAGNER N L, DUBE W P, BROWN S S. Environ. Sci. Technol., 2011, 45(7):2938-2944.
26. [26]
  MIN K E, WASHENFELDER R A, DUBÉ W P, LANGFORD A O, EDWARDS P M, ZARZANA K J, STUTZ J, LU K, ROHRER F, ZHANG Y, BROWN S S. Atmos. Meas. Tech., 2016, 9(2):423-440.MIN K E, WASHENFELDER R A, DUBÉ W P, LANGFORD A O, EDWARDS P M, ZARZANA K J, STUTZ J, LU K, ROHRER F, ZHANG Y, BROWN S S. Atmos. Meas. Tech., 2016, 9(2):423-440.
27. [27]
  THALMAN R, VOLKAMER R. Atmos. Meas. Tech., 2010, 3(6):1797-1814.THALMAN R, VOLKAMER R. Atmos. Meas. Tech., 2010, 3(6):1797-1814.
28. [28]
  ZHAO W, XU X, DONG M, CHEN W, GU X, HU C, HUANG Y, GAO X, HUANG W, ZHANG W. Atmos. Meas. Tech., 2014, 7(8):2551-2566.ZHAO W, XU X, DONG M, CHEN W, GU X, HU C, HUANG Y, GAO X, HUANG W, ZHANG W. Atmos. Meas. Tech., 2014, 7(8):2551-2566.
29. [29]
  FANG B, ZHAO W, XU X, ZHOU J, MA X, WANG S, ZHANG W, VENABLES D S, CHEN W. Opt. Express, 2017, 25(22):26910-26922.FANG B, ZHAO W, XU X, ZHOU J, MA X, WANG S, ZHANG W, VENABLES D S, CHEN W. Opt. Express, 2017, 25(22):26910-26922.
30. [30]
  ANDERSON D C, PAVELEC J, DAUBE C, HERNDON S C, KNIGHTON W B, LERNER B M, ROSCIOLI J R, YACOVITCH T I, WOOD E C. Atmos. Chem. Phys., 2019, 19(5):2845-2860.ANDERSON D C, PAVELEC J, DAUBE C, HERNDON S C, KNIGHTON W B, LERNER B M, ROSCIOLI J R, YACOVITCH T I, WOOD E C. Atmos. Chem. Phys., 2019, 19(5):2845-2860.
31. [31]
  ORLANDO J J, TYNDALL G S. Chem. Soc. Rev., 2012, 41(19):6294-6317.ORLANDO J J, TYNDALL G S. Chem. Soc. Rev., 2012, 41(19):6294-6317.
32. [32]
  GRIFFITH S M, HANSEN R F, DUSANTER S, MICHOUD V, GILMAN J B, KUSTER W C, VERES P R, GRAUS M, DE GOUW J A, ROBERTS J, YOUNG C, WASHENFELDER R, BROWN S S, THALMAN R, WAXMAN E, VOLKAMER R, TSAI C, STUTZ J, FLYNN J H, GROSSBERG N, LEFER B, ALVAREZ S L, RAPPENGLUECK B, MIELKE L H, OSTHOFF H D, STEVENS P S. J. Geophys. Res. Atmos., 2016, 121(8):4211-4232.GRIFFITH S M, HANSEN R F, DUSANTER S, MICHOUD V, GILMAN J B, KUSTER W C, VERES P R, GRAUS M, DE GOUW J A, ROBERTS J, YOUNG C, WASHENFELDER R, BROWN S S, THALMAN R, WAXMAN E, VOLKAMER R, TSAI C, STUTZ J, FLYNN J H, GROSSBERG N, LEFER B, ALVAREZ S L, RAPPENGLUECK B, MIELKE L H, OSTHOFF H D, STEVENS P S. J. Geophys. Res. Atmos., 2016, 121(8):4211-4232.
33. [33]
  TAN Z, FUCHS H, LU K, HOFZUMAHAUS A, BOHN B, BROCH S, DONG H, GOMM S, HÄSELER R, HE L, HOLLAND F, LI X, LIU Y, LU S, ROHRER F, SHAO M, WANG B, WANG M, WU Y, ZENG L, ZHANG Y, WAHNER A, ZHANG Y. Atmos. Chem. Phys., 2017, 17(1):663-690.TAN Z, FUCHS H, LU K, HOFZUMAHAUS A, BOHN B, BROCH S, DONG H, GOMM S, HÄSELER R, HE L, HOLLAND F, LI X, LIU Y, LU S, ROHRER F, SHAO M, WANG B, WANG M, WU Y, ZENG L, ZHANG Y, WAHNER A, ZHANG Y. Atmos. Chem. Phys., 2017, 17(1):663-690.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

基于过氧自由基原位测量的大气臭氧光化学生成速率研究

通讯作者: 赵卫雄,E-mail:wxzhao@aiofm.ac.cn

English

Study on Atmospheric Ozone Photochemical Production Rate Based on In-situ Measurement of Peroxy Radical

Corresponding author: ZHAO Wei-Xiong, wxzhao@aiofm.ac.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

基于过氧自由基原位测量的大气臭氧光化学生成速率研究

通讯作者: 赵卫雄,E-mail:wxzhao@aiofm.ac.cn

English

Study on Atmospheric Ozone Photochemical Production Rate Based on In-situ Measurement of Peroxy Radical

Corresponding author: ZHAO Wei-Xiong, wxzhao@aiofm.ac.cn

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？

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