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An NO2 sensor based on a fiber coupled broadband LED source with a Herriott multi-pass cell is developed and demonstrated for calibrating aerosol absorption photoacoustic (PA) spectrometer. At first, a Herriott multi-pass cell with an effective optical path of 26.1 m is designed based on the theory of light transmission, for increasing the light absorption of NO2 in the cell. It is difficult to obtain a high-quality beam of LED by using the conventional collimating method that enables the collimated output beam to transmit back and forth in the multi-pass cell, due to the large emitting surface and divergence angle of the LED. So, in the present work, the emission of the LED is coupled into a single model fiber, and then collimated by using a lens. The LED spectrum does not change before and after fiber coupling. The collimated beam with a central wavelength of 438.5 nm is coupled into the multi-pass cell. The output beam passing through the multi-pass cell is detected by using a spectrometer for retrieving the NO2 concentration. Finally, an expected concentration detection limit of 1 μmol/mol (3σ) is achieved within 1 s acquisition time and the signal-to-noise ratio (SNR) is 40. By analyzing the result measured with 46 μmol/mol NO2, a measurement precision of 0.1% is achieved. In order to calibrate the aerosol absorption PA spectrometer, the NO2 sensor and the aerosol absorption PA spectrometer based on 450 nm are used to measure different concentrations of NO2, simultaneously. The results show that the measured NO2 concentration has a good linear relationship with the PA spectrum signal, and the linearity is better than 99.9%. This good linear relationship further shows the feasibility and reliability of the NO2 sensor. The slope of calibration curve after normalizing the power is 0.95 nV/(mW·Mm-1). Using this calibration result, the PA signal measured with aerosol absorption PA spectrometer is transformed into the absorption coefficient. The developed NO2 measuring system based on a broadband LED light source and Herriott multi-pass cell has the advantages of low cost, simple structure and easy use. It can be used to calibrate the aerosol absorption PA spectrometer, and also to measure NO2 in industry.
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Keywords:
- broadband LED source /
- absorption cell /
- broadband absorption spectroscopy /
- nitrogen dioxide
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图 1 基于光学模拟软件的模拟结果
Figure 1. Simulation results based on optical simulation software.
图 2 研制的NO2测量吸收池实物图
Figure 2. Photo of developed absorption cell for NO2 measurement.
图 3 实验装置图
Figure 3. Experimental setup.
图 4 通过光纤耦合前后的归一化的光强分布
Figure 4. Normalized light intensity distribution before and after fiber coupling.
图 5 LED的发射谱(蓝线)和NO2的吸收截面(黑线)
Figure 5. LED emission spectrum (blue line) and the absorption cross section of NO2 (black line).
图 6 通过多通池后的光强分布, N2(蓝线), NO2(红线)
Figure 6. Light intensity after passing the multi-pass cell in N2(blue line) and in 42.14 μmol/mol NO2(red line).
图 7 (a)实验中42.14
$\rm{\mu mol}/\rm{mol}$ NO2的吸收光谱(蓝线)及拟合光谱(红线); (b)拟合残差Figure 7. (a)Experimental absorption spectra of NO2(blue line) and the fitted absorption spectrum for 42.14 μmol/mol NO2(red line); (b)fit residual.
图 8 宽带LED光谱(红线)和光声光谱(蓝线)同时、连续测量NO2结果
Figure 8. NO2 measurement continuously with broadband LED absorption spectroscopy (red line) and PA spectroscopy (blue line), simultaneously.
图 9 光声光谱仪的标定结果
Figure 9. The calibration results of PA spectrometer.
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[1] Jacobson M Z 2001 Nature 409 695
Google Scholar
[2] Ramanathan V, Carmichael G H 2008 Nat. Geosci. 1 221
Google Scholar
[3] Ackerman A S, Toon O B, Stevens D E, Heymsfield A J, Ramanathan V, Welton E J 2000 Science 288 1042
Google Scholar
[4] Lohmann U, Feichter J 2005 Atmos. Chem. Phys. 5 715
Google Scholar
[5] Ajtai T, Filep Á, Schnaiter M, Linke C, Vragel M, Bozóki Z, Szabó G, Leisner T 2010 J. Aerosol Sci. 41 1020
Google Scholar
[6] Sheridan P J, Arnott W P, Ogren J A, Andrews E, Atkinson D B, Covert D S, Moosmüller H, Petzold A, Schmid B, Strawa A W, Varma R, Virkkula A 2005 Aerosol Sci. Technol. 39 1
Google Scholar
[7] Petzold A, Schloesser H, Sheridan P J, Arnott W P, Ogren J A, Virkkula A 2005 Aerosol Sci. Technol. 39 40
Google Scholar
[8] Tomberg T, Vainio M, Hieta T, Halonen L 2018 Sci. Rep. 8 1848
Google Scholar
[9] Havey D K, Bueno P A, Gillis K A, Hodges J T, Mulholland G W, Zee R D, Zachariah M R 2010 Anal. Chem. 82 7935
Google Scholar
[10] Liu K, Guo X Y, Yi H M, Chen W D, Zhang W J, Gao X M 2009 Opt. Lett. 34 1594
Google Scholar
[11] Liu K, Mei J X, Zhang W J, Chen W D, Gao X M 2017 Sens. Actuator, B 251 632
Google Scholar
[12] Liu Q, Huang H H, Wang Y, Wang G S, Cao Z S, Liu K, Chen W D, Gao X M 2014 Chin. Phys. B 23 064205
Google Scholar
[13] Tian G X, Moosmüller H, Arnott W P 2009 Aerosol Sci. Technol. 43 1084
Google Scholar
[14] Lack D A, Lovejoy E R, Baynard T, Pettersson A, Ravishankara A R 2006 Aerosol Sci. Technol. 40 697
Google Scholar
[15] Arnott W P, Moosmüller H, Walker J W 2000 Rev. Sci. Instrum. 71 4545
Google Scholar
[16] 吴涛, 赵卫雄, 李劲松, 张为俊, 陈卫东, 高晓明 2008 光谱学与光谱分析 28 2469
Google Scholar
Wu T, Zhao W X, Li J S, Zhang W J, Chen W D, Gao X M 2008 Spectrosc. Spectr. Anal. 28 2469
Google Scholar
[17] 董美丽, 赵卫雄, 程跃, 胡长进, 顾学军, 张为俊 2012 物理学报 61 060702
Dong M L, Zhao W X, Cheng Y, Hu C J, Gu X J, Zhang W J 2012 Acta Phys. Sin. 61 060702
[18] Wu T, Zhao W X, Chen W D, Zhang W J, Gao X M 2008 Appl. Phys. B 94 85
[19] Gherman T, Venables D S, Vaughan S, Orphai J, Ruth A A 2008 Environ. Sci. Technol. 42 890
Google Scholar
[20] Liu K, Lewicki R, Tittel F K 2016 Sens. Actuator, B 237 887
Google Scholar
[21] The HITRAN database: http://hitran.iao.ru [2019-2-25]
[22] Herriott D, Kogelnik H, Kompfner R 1964 Appl. Opt. 3 523
Google Scholar
[23] Robert C 2007 Appl. Opt. 46 5408
Google Scholar
[24] Fang B, Zhao W X, Xu X Z, Zhou J C, Ma X, Wang S, Zhang W J, Venables D S, Chen W D 2017 Opt. Express 25 26910
Google Scholar
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