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波长调制-直接吸收光谱(WM-DAS)同时具有直接吸收光谱(DAS)可测量吸收率函数和波长调制光谱(WMS)高信噪比的优点, 本文首先采用WM-DAS光谱, 在50 cm光程和室温低压下, CO分子近红外4300.7 cm–1谱线吸收率检测限低至4 × 10–7 (200 s); 然后结合120 m长光程Herriott池, 在室温大气压下, 吸收率函数拟合残差标准差达到5.1 × 10–5 (1 s). 最后利用长光程WM-DAS测量系统, 对不同浓度(体积分数为0.44 × 10–6—9.6 × 10–6)CO进行了动态测量, 并将其与腔衰荡光谱(CRDS)进行比较; 实验结果表明: 本文采用的长光程WM-DAS与CRDS方法测量结果相同, 其中长光程WM-DAS系统CO浓度检测限低至0.9 × 10–9 (200 s), 系统简单且测量速度远快于CRDS. 与此同时, 利用建立的长光程WM-DAS测量系统连续监测1个月时间内大气痕量CO浓度及其变化趋势, 测量结果与中国环境监测总站测量结题高度一致.
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关键词:
- 波长调制-直接吸收光谱 /
- 腔衰荡光谱 /
- 吸收率函数 /
- CO浓度监测
Wavelength modulation-direct absorption spectroscopy (WM-DAS) has the advantages of both direct absorption spectroscopy (DAS) measurable absorptivity function and wavelength modulation spectrum (WMS) with high signal-to-noise ratio (SNR). In this paper, the WM-DAS spectrum is used to measure the absorptivity of 4300.7 cm–1 line of CO molecule and the detection limit is as low as 4 × 10–7 (200 s) at 0.5 m optical path, room temperature and low pressure. Then, through combining the WM-DAS spectrum with a 120 m long optical path Herriott cell, at room temperature and atmospheric pressure, the standard deviation of the fitting residual error of the absorptivity function is reduced down to ~5.1 × 10–5 (1 s). Finally, different concentrations of CO are continuously monitored by long-path WM-DAS measurement system, and compared with the results obtained from the cavity ring-down spectroscopy (CRDS). The experimental results show that the measurement results from the long-path WM-DAS and CRDS method are the same. The detection limit of CO concentration in long-path WM-DAS system is as low as 0.9 ppb (200 s), and the WM-DAS system is simple and the measurement speed is much faster than CRDS. At the same time, the long-path WM-DAS system is used to continuously monitor the atmospheric trace CO concentration and trend for one month, and the measured results are highly consistent with those from the China Environmental Monitoring Station.-
Keywords:
- wavelength modulation-direct absorption spectroscopy /
- cavity ring down spectroscopy /
- absorptivity function /
- monitoring of CO concentration
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图 1 实验系统WM-DAS (a)与CRDS (b). ISO, 光纤隔离器; AOM, 声光调制器; APD, 雪崩光电二极管; PD, 光电二极管; DDG, 数字延迟发生器; DAQ, 数据采集卡
Fig. 1. System schematic diagram of WM-DAS (a) and CRDS (b). ISO, fiber isolator; AOM, acousto-optic modulator; APD, avalanche photodiode; PD, photodiode; DDG, digital delay generator; DAQ, digital acquisition.
图 2 (a) WM-DAS波长标定; (b)测量光强It的傅里叶系数
Fig. 2. (a) Wavelength calibration of WM-DAS; (b) Fourier coefficients of the measuring light intensity It.
图 3 (a)压力26 kPa、温度290 K时, WM-DAS单次测量体积分数为101 × 10–6和53 × 10–6的CO吸收率函数; (b) 53 × 10–6标气和纯N2时吸收率峰值的Allan标准差
Fig. 3. (a) CO absorptivity function of 101 × 10–6and 53 × 10–6 measured by WM-DAS at 26 kPa and 290 K; (b) Allan standard deviation of the peak absorptivity at 53 × 10–6 and pure N2.
图 4 激光电流以锯齿波形式扫描时, 衰荡时间(黑色)与激光电流(蓝色)的关系
Fig. 4. Relationship between the decay time (black) and the laser current (blue) when the laser current is scanned in the form of saw tooth wave.
图 5 (a) WM-DAS测量的CO(4300.7 cm–1)吸收系数函数, 采集103周期, 总用时1 s; (b) CRDS测量的CO(6383.09 cm–1、线强度约为4300.7 cm–1的0.77 %)吸收系数函数, 平均103次, 总用时4 h
Fig. 5. (a) CO (4300.7 cm–1) absorption coefficient function measured by WM-DAS, 103 cycles of collection, and the total time is ~1 second; (b) absorption coefficient function of CO (6383.09 cm–1, the line strength is about 0.77% of 4300.7 cm–1) measured by CRDS, with an average of 103 times, with a total time of 4 hours.
图 6 WM-DAS和CRDS两种方法测量CO浓度的Allan标准差
Fig. 6. Allan standard deviation of CO concentration measured by WM-DAS and CRDS.
图 7 不同浓度配比下, WM-DAS(红色)和CRDS(蓝色)连续测量结果 (a) 低浓度(1.3 × 10–6—9.6 × 10–6); (b) 极低浓度(0.44 × 10–6—1.33 × 10–6)
Fig. 7. Continuous measurement results of WM-DAS (red) and CRDS (blue) under different concentration ratios: (a) Low concentration (1.3 × 10–6–19.6 × 10–6) (b) extremely low concentration (0.44 × 10–6–11.33 × 10–6).
图 8 WM-DAS和CRDS测量的不同浓度下CO的吸收系数(去除了CRDS测量的吸收系数基线以便于比较)
Fig. 8. Absorption coefficient of CO measured by WM-DAS and CRDS at different concentrations (the baseline of absorption coefficient measured by CRDS is removed).
图 9 大气痕量CO连续监测原始数据(绿色)及24 h平均(蓝色), 以及监测总站测量的CO(红色)及PM2.5(黑色)
Fig. 9. Atmospheric trace CO continuous monitoring raw data (green) and 24-hour average (blue), CO (red) and PM2.5 (black) measured by the monitoring station.
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[1] Zellweger C, Steinbrecher R, Laurent O, Lee H, Kim S, Emmenegger L, Steinbacher M, Buchmann B 2019 Atmos. Meas. Tech. 12 5863
Google Scholar
[2] Chen H, Karion A, Rella C W, Winderlich J, Gerbig C, Filges A, Newberger T, Sweeney C, Tans P P 2013 Atmos. Meas. Tech. 6 1031
Google Scholar
[3] van der Laan S, Neubert R E M, Meijer H A J 2009 Atmos. Meas. Tech. 2 549
Google Scholar
[4] Hammer S, Griffith D W T, Konrad G, Vardag S, Caldow C, Levin I 2013 Atmos. Meas. Tech. 6 1153
Google Scholar
[5] Adámek P, Olejníček J, Čada M, Kment Š, Hubička Z 2013 Opt. Lett. 38 2428
Google Scholar
[6] Goldenstein C S, Spearrin R M, Jeffries J B, Hanson R K 2016 Prog. Energy Combust. 60 132
[7] Witzel O, Klein A, Meffert C, Wagner S, Kaiser S, Schulz C, Ebert V 2013 Opt. Express 21 19951
Google Scholar
[8] Hanson R K 2011 Proc. Combust. Inst. 33 1
Google Scholar
[9] Pal M, Maity A, Pradhan M 2018 Laser Phys. 28 105702
Google Scholar
[10] Maity A, Pal M, Banik1 G D, Maithani S, Pradhan M 2017 Laser Phys. Lett. 14 115701
Google Scholar
[11] Zhou S, Liu N W, Shen C Y, Zhang L, He T B, Yu B L, Li J S 2019 Spectrochim. Acta A 2019 223 117332
[12] Tang Y Y, Liu W Q, Kan R F, Liu J G, He Y B, Zhang Y J, Xu Z Y, Ruan J, Geng H 2011 Opt. Express 19 20224
Google Scholar
[13] Kasyutich1 V L, Holdsworth R J, Martin P A 2008 Appl. Phys. B 92 271
Google Scholar
[14] Stefan´ski P, Lewicki R, Sanchez N P, Tarka J, Griffin R J, Razeghi M, Tittel F K 2014 Appl. Phys. B 117 519
Google Scholar
[15] Qiao S D, Ma Y F, He Y, Patimisco P, Sampaolo A, Spagnolo V 2021 Opt. Express 29 25100
Google Scholar
[16] Dang J M, Yu H Y, Sun Y J, Wang Y D 2017 Infrared Phys. Technol. 82 183
Google Scholar
[17] Li J S, Parchatka U, Fischer H 2013 Sens. Actuators, B 182 659
Google Scholar
[18] Wei M, Ye Q H, Kan R F, Chen B, Yang C G, Xu Z Y, Chen X, Ruan J, Fan X L, Wang W, Hu M, Liu J G 2016 Chin. Phys. B 25 094210
Google Scholar
[19] Lan L J, Ding Y J, Peng Z M, Du Y J, Liu Y F, Li Z 2014 Appl. Phys. B 117 543
Google Scholar
[20] Silva M L, Wainner R T, Sonnenfroh D M, Rosen D I, Allen M G, Risby T H 2005 Proc. SPIE, November 17, 2005 p6010
[21] Hangauer A, Chen J, Strzoda R, Ortsiefer M, Amann M C 2008 Opt. Lett. 33 1566
Google Scholar
[22] Hangauer A, Chen J, Strzoda R, Fleischer M, Amann M C 2013 Opt. Express 22 13680
[23] Ortsiefer M, Neumeyr C, Rosskopf J, Arafin S, Böhm G, Hangauer A, Chen J, Strzoda R, M.-C. Amann M C 2011 Proc. SPIE 7945 794509
Google Scholar
[24] Ma Y F, Yu G, Zhang J B, Yu X, Sun R 2015 J. Opt. 17 055401
Google Scholar
[25] Lou D C, Rao W, Wang K, Song J L, Jiang Y J 2020 Global Intelligent Industry Conference 2020 Proc. SPIE March 18, 2021, p117801P
[26] 陈兵, 周泽义, 康鹏, 刘安雯, 胡水明 2015 光谱学与光谱分析 35 971
Google Scholar
Chen B, Zhou Z Y, Kang P, Liu A W, Hu S M 2015 Spectrosc. Spect. Anal. 35 971
Google Scholar
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Google Scholar
[28] Peng Z M, Du Y J, Ding Y J 2020 Sensors 20 616
Google Scholar
[29] Maity A, Pal M, Banik1 G D, Maithani S, Pradhan M 2017 Laser Physics Letters 14 115701
[30] Mazurenka M, Wada R, Shillings A J L, Butler T J A, Beames J M, Orr-Ewing A J 2005 Appl. Phys. B 81 135
Google Scholar
[31] Li J D, Du Y J, Ding Y J, Peng Z M 2020 J. Quant. Spectrosc. Radiat. Transfer 254 107216
Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
[36] Zhao G, Tan W, Jia M Y, Hou J J, Ma W G, Dong L, Zhang L, Feng X X, Wu X C, Yin W B, Xiao L T, Axner O, Jia S T 2016 Sensors 16 1544
Google Scholar
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Google Scholar
Wang Z, Du Y J, Ding Y J, Peng Z M 2020 Acta Phys. Sin. 69 064204
Google Scholar
[38] 王振, 杜艳君, 丁艳军, 彭志敏 2019 68 204204
Google Scholar
Wang Z, Du Y J, Ding Y J, Peng Z M 2019 Acta Phys. Sin. 68 204204
Google Scholar
[39] Wang Z, Du Y J, Ding Y J, Peng Z M 2020 Sensors 20 585
Google Scholar
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