Calibration source for OH radical based on synchronous photolysis

Wang Feng-Yang; Hu Ren-Zhi; Xie Pin-Hua; Wang Yi-Hui; Chen Hao; Zhang Guo-Xian; Liu Wen-Qing

doi:10.7498/aps.69.20200153

Abstract

OH radical is the most important oxidant in the atmosphere, and controls the tropospheric concentration of tropospheric trace gases such as CO, SO₂, NO₂, CH₄ and other volatile organic compounds. Accurate measurement of the concentration of OH radical in troposphere is the key to clarifying the formation mechanism of secondary pollution in China. The laser-induced fluorescence (LIF) technique is widely used in tropospheric OH radical field observation due to its high sensitivity, high selectivity, and small interference. However, the LIF technique is not an absolute measurement technology. In recent years, OH radical measurements and simulations in many field observations show that the improvement of accuracy of calibration is a way to reduce the differences. Currently, the common calibration methods are ozone-alkene method and water photolysis method. Further improving the accuracy of calibration is a key factor to ensure the accurate measurement of OH radicals. In this paper, a portable calibration method of OH radicals based on simultaneous photolysis is introduced. The synthetic air with a certain water vapor concentration is irradiated in laminar flow by 185 nm light of mercury lamp, and the photolysis of water vapor and O₂ produce OH, HO₂ radicals and O₃. The concentration of OH radicals is calculated by oxygen concentration, water vapor concentration, ozone concentration, oxygen absorption cross section and water vapor absorption cross section. The water vapor is measured by a high-precision temperature and humidity probe, and the systematic error of the probe is corrected by 911-0016 ammonia (NH₃, H₂O) analyzer. As the ozone concentration is only 0.5－1 ppb in the calibration, the commercial ozone analyzer cannot meet the requirement for the measurement. A high-precision ozone analyzer O₃-CRDS based on cavity-ring-down spectrocopy is built to achieve the detection limit of 15 ppt (1σ). Using the O₃-CRDS analyzer, the concentration distribution coefficient of ozone in laminar flow along the radial direction of the flow tube (P = 1.9) is measured. Because the absorption cross section of oxygen at 185 nm is seriously affected by oxygen column concentration and the characteristics of mercury lamp, the oxygen absorption cross section is remeasured based on Lambert’s law, which is

$ \sigma_{\rm O_2} $

= (1.25 ± 0.08)×10^–20 cm². The portable calibration device is established by establishing the corresponding relationship between ozone concentration and light intensity. By changing the concentration of water vapor in the flow tube, the OH radicals with concentrations in a range of 3×10⁸－2.8×10⁹ cm^–3 are produced, which are used to calibrate the atmospheric OH radical measurement instrument based on LIF technique. The fluorescence signal has a good correlation with the concentration of OH. The calibration device of OH radical is used to calibrate the LIF system during “a comprehensive study of the ozone formation mechanism in Shenzhen” (STORM) field observation in Autumn 2018. The calibration results under the field condition show that the calibration uncertainty of the calibration device for LIF instrument is 13.0%, which has good stability and accuracy.

Keywords:

Authors and contacts

1.
Key Laboratory of Environmental Optics and Technology, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei 230031, China
2.
University of Science and Technology of China, Hefei 230026, China
3.
CAS Center for Excellence in Regional Atmospheric Environment, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361000, China
4.
University of Chinese Academy of Sciences, Beijing 100049, China
5.
College of Mechanical Engineering, Suzhou University of Science and Technology, Suzhou 215009, China

Corresponding author: Hu Ren-Zhi, rzhu@aiofm.ac.cn ; Xie Pin-Hua, phxie@aiofm.ac.cn ;

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References

[1]	Guo S, Hu M, Zamora M L, Peng J F, Shang D J, Zheng J, Du Z F, Wu Z, Shao M, Zeng L M, Molina M J, Zhang R Y 2014 Proc. Natl. Acad. Sci. U.S.A. 111 17373 Google Scholar
[2]	Huang R J, Zhang Y L, Bozzetti C, Ho K F, Cao J J, Han Y M, Daellenbach K R, Slowik J G, Platt S M, Canonaco F, Zotter P, Wolf R, Pieber S M, Bruns E A, Crippa M, Ciarelli G, Piazzalunga A, Schwikowski M, Abbaszade G, Schnelle-Kreis J, Zimmermann R, An Z S, Szidat S, Baltensperger U, El Haddad I, Prevot A S H 2014 Nature 514 218 Google Scholar
[3]	Ehhalt D H 1999 Phys. Chem. Chem. Phys. 1 5401 Google Scholar
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[13]	Ren X R, Olson J R, Crawford J H, Brune W H, Mao J Q, Long R B, Chen Z, Chen G, Avery M A, Sachse G W, Barrick J D, Diskin G S, Huey L G, Fried A, Cohen R C, Heikes B, Wennberg P O, Singh H B, Blake D R, Shetter R E 2008 J. Geophys. Res. Atmos. 113 D05310 Google Scholar
[14]	Whalley L K, Edwards P M, Furneaux K L, Goddard A, Ingham T, Evans M J, Stone D, Hopkins J R, Jones C E, Karunaharan A, Lee J D, Lewis A C, Monks P S, Moller S J, Heard D E 2011 Atmos. Chem. Phys. 11 7223 Google Scholar
[15]	Faloona I C, Tan D, Lesher R L, Hazen N L, Frame C L, Simpas J B, Harder H, Martinez M, Di Carlo P, Ren X R, Brune W H 2004 J. Atmos. Chem. 47 139 Google Scholar
[16]	Hofzumahaus A, Heard D E 2016 Assessment of Local HOx and ROx Measurement Techniques: Achievements, Challenges, and Future Directions - Outcome From the International HOx Workshop 2015 endorsed by IGAC Forschungzentrum Juelich, Germany, March 23−25, 2015, p1
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[21]	Kanaya Y, Sadanaga Y, Hirokawa J, Kajii Y, Akimoto H 2001 J. Atmos. Chem. 38 73 Google Scholar
[22]	Kono M, Lewis B R, Baldwin K G H, Gibson S T 2003 J. Chem. Phys. 118 10924 Google Scholar
[23]	Lanzendorf E J, Hanisco T F, Donahue N M, Wennberg P O 1997 Geophys. Res. Lett. 24 3037 Google Scholar
[24]	Creasey D J, Heard D E, Lee J D 2000 Geophys. Res. Lett. 27 1651 Google Scholar
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[26]	Li Z Y, Hu R Z, Xie P H, Chen H, Liu X Y, Liang S X, Wang D, Wang F Y, Wang Y H, Lin C, Liu J G, Liu W Q 2019 Atmos. Meas. Tech. 12 3223 Google Scholar
[27]	Cantrell C A, Zimmer A, Tyndall G S 1997 Geophys. Res. Lett. 24 2687 Google Scholar

Cited By

图 1 流动管层流分布示意图

Figure 1. Schematic diagram of laminar distribution in the flow tube

DownLoad: Full-Size Img PowerPoint

图 2 同步光解H₂O和O₂装置示意图

Figure 2. System diagram of synchronous photolysis of H₂O and O₂.

DownLoad: Full-Size Img PowerPoint

图 3 O₃-CRDS示意图

Figure 3. Schematic diagram of O₃-CRDS.

DownLoad: Full-Size Img PowerPoint

图 4 (a) 当仪器只采样零空气时, 黑点代表1 s平均的数据, 红点代表30 s的平均数据; (b)臭氧浓度的Allan方差

Figure 4. (a) When the instrument only samples zero air, the black point represents the average data of 1 s, and the red point represents the average data of 30 s; (b) Allan variance of ozone concentration.

DownLoad: Full-Size Img PowerPoint

图 5 臭氧浓度分布因子P测量结果

Figure 5. Measurement results of ozone concentration distribution factor P.

DownLoad: Full-Size Img PowerPoint

图 6 (a) 汞灯光强随N₂O浓度变化; (b) 光强与臭氧浓度的关系

Figure 6. (a) Light intensity at 185 nm as a function of N₂O concentration; (b) relationship between light intensity and ozone concentration.

DownLoad: Full-Size Img PowerPoint

图 7 标定装置产生的OH自由基浓度对应LIF-OH系统荧光计数

Figure 7. Concentration of OH radicals produced by the calibration device corresponds to the fluorescence count of LIF-OH system.

DownLoad: Full-Size Img PowerPoint

图 8 使用OH自由基标定装置外场标定LIF-OH系统的结果

Figure 8. Calibration results of LIF-OH instrument by OH radical calibration source under field conditions.

DownLoad: Full-Size Img PowerPoint

表 1 OH自由基标定装置不确定度

Table 1. Uncertainty of OH radical calibration source.

误差源	不确定度	来源
臭氧分布系数P	6.0%	测量
臭氧灵敏度Q_v	2.9%	测量
PD光强 I'	1.0%	测量
水汽浓度[H₂O]	2.0%	测量
氧气吸收截面$ \sigma _{\rm O_2} $	7.0%	测量
水汽吸收截面$ {\sigma _{{{\rm{H}}_2}{\rm{O}}}} $	3.0%	引用
标定装置产生OH自由基误差	10.4%	计算

DownLoad: CSV

[1]	Guo S, Hu M, Zamora M L, Peng J F, Shang D J, Zheng J, Du Z F, Wu Z, Shao M, Zeng L M, Molina M J, Zhang R Y 2014 Proc. Natl. Acad. Sci. U.S.A. 111 17373 Google Scholar
[2]	Huang R J, Zhang Y L, Bozzetti C, Ho K F, Cao J J, Han Y M, Daellenbach K R, Slowik J G, Platt S M, Canonaco F, Zotter P, Wolf R, Pieber S M, Bruns E A, Crippa M, Ciarelli G, Piazzalunga A, Schwikowski M, Abbaszade G, Schnelle-Kreis J, Zimmermann R, An Z S, Szidat S, Baltensperger U, El Haddad I, Prevot A S H 2014 Nature 514 218 Google Scholar
[3]	Ehhalt D H 1999 Phys. Chem. Chem. Phys. 1 5401 Google Scholar
[4]	Jaegle L, Jacob D J, Brune W H, Faloona I, Tan D, Heikes B G, Kondo Y, Sachse G W, Anderson B, Gregory G L, Singh H B, Pueschel R, Ferry G, Blake D R, Shetter R E 2000 J. Geophys. Res. Atmos. 105 3877 Google Scholar
[5]	陆克定, 张远航 2010 化学进展 22 500 Lu K D, Zhang Y H 2010 Prog. Chem. 22 500
[6]	Hofzumahaus A, Rohrer F, Lu K D, Bohn B, Brauers T, Chang C, Fuchs H, Holland F, Kita K, Kondo Y, Li X, Lou S R, Shao M, Zeng L M, Wahner A, Zhang Y H 2009 Science 324 1702 Google Scholar
[7]	Brauers T, Aschmutat U, Brandenburger U, Dorn H P, Hausmann M, Heßling M, Hofzumahaus A, Holland F, Plass-Dülmer C, Ehhalt D H 1996 Geophys. Res. Lett. 23 2545 Google Scholar
[8]	Mauldin R L, Cantrell C A, Zondlo M, Kosciuch E, Eisele F L, Chen G, Davis D, Weber R, Crawford J, Blake D, Bandy A, Thornton D 2003 J. Geophys. Res. Atmos. 108 8796 Google Scholar
[9]	Thomas L A G, Hard M 1995 Atmos. Sci. 52 3354 Google Scholar
[10]	Stone D, Whalley L K, Heard D E 2012 Chem. Soc. Rev. 41 6348 Google Scholar
[11]	Novelli A, Hens K, Ernest C T, Kubistin D, Regelin E, Elste T, Plass-Duelmer C, Martinez M, Lelieveld J, Harder H 2014 Atmos. Meas. Tech. 7 3413 Google Scholar
[12]	Lu K D, Hofzumahaus A, Holland F, Bohn B, Brauers T, Fuchs H, Hu M, Haeseler R, Kita K, Kondo Y, Li X, Lou S R, Oebel A, Shao M, Zeng L M, Wahner A, Zhu T, Zhang Y H, Rohrer F 2013 Atmos. Chem. Phys. 13 1057 Google Scholar
[13]	Ren X R, Olson J R, Crawford J H, Brune W H, Mao J Q, Long R B, Chen Z, Chen G, Avery M A, Sachse G W, Barrick J D, Diskin G S, Huey L G, Fried A, Cohen R C, Heikes B, Wennberg P O, Singh H B, Blake D R, Shetter R E 2008 J. Geophys. Res. Atmos. 113 D05310 Google Scholar
[14]	Whalley L K, Edwards P M, Furneaux K L, Goddard A, Ingham T, Evans M J, Stone D, Hopkins J R, Jones C E, Karunaharan A, Lee J D, Lewis A C, Monks P S, Moller S J, Heard D E 2011 Atmos. Chem. Phys. 11 7223 Google Scholar
[15]	Faloona I C, Tan D, Lesher R L, Hazen N L, Frame C L, Simpas J B, Harder H, Martinez M, Di Carlo P, Ren X R, Brune W H 2004 J. Atmos. Chem. 47 139 Google Scholar
[16]	Hofzumahaus A, Heard D E 2016 Assessment of Local HOx and ROx Measurement Techniques: Achievements, Challenges, and Future Directions - Outcome From the International HOx Workshop 2015 endorsed by IGAC Forschungzentrum Juelich, Germany, March 23−25, 2015, p1
[17]	Hard T M, George L A, O'Brien R J 2002 Environ. Sci. Technol. 36 1783 Google Scholar
[18]	Dusanter D V S, Stevens P S 2008 Atmos. Chem. Phys. 8 321 Google Scholar
[19]	Bloss W J, Lee J D, Bloss C, Heard D E, Pilling M J, Wirtz K, Martin-Reviejo M, Siese M 2004 Atmos. Chem. Phys. 4 571 Google Scholar
[20]	Schultz M, Heitlinger M, Mihelcic D, Volz-Thomas A 1995 J. Geophys. Res. 100 18811 Google Scholar
[21]	Kanaya Y, Sadanaga Y, Hirokawa J, Kajii Y, Akimoto H 2001 J. Atmos. Chem. 38 73 Google Scholar
[22]	Kono M, Lewis B R, Baldwin K G H, Gibson S T 2003 J. Chem. Phys. 118 10924 Google Scholar
[23]	Lanzendorf E J, Hanisco T F, Donahue N M, Wennberg P O 1997 Geophys. Res. Lett. 24 3037 Google Scholar
[24]	Creasey D J, Heard D E, Lee J D 2000 Geophys. Res. Lett. 27 1651 Google Scholar
[25]	Hofzumahaus A, Brauers T, Aschmutat U, Brandenburger U, Dorn H P, Hausmann M, Heßling M, Holland F, Plass-Dülmer C, Sedlacek M, Weber M, Ehhalt D H 1997 Geophys. Res. Lett. 24 3039 Google Scholar
[26]	Li Z Y, Hu R Z, Xie P H, Chen H, Liu X Y, Liang S X, Wang D, Wang F Y, Wang Y H, Lin C, Liu J G, Liu W Q 2019 Atmos. Meas. Tech. 12 3223 Google Scholar
[27]	Cantrell C A, Zimmer A, Tyndall G S 1997 Geophys. Res. Lett. 24 2687 Google Scholar

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