傅里叶红外光谱气体检测限的定性分析

王钰豪; 刘建国; 徐亮; 成潇潇; 邓亚颂; 沈先春; 孙永丰; 徐寒杨

doi:10.7498/aps.71.20212366

摘要

傅里叶红外光谱仪检测和定量气态化合物的最小量取决于所测气体光谱的信噪比. 为了使用傅里叶变换红外吸收光谱测量CO₂, CO, CH₄和N₂O等温室气体, 对混合气体的信噪比和仪器检测限进行了研究. 提出通过HITRAN模拟光谱计算仪器的气体检测限并分析波段等因素的影响. 此外, 搭建实验平台来验证基于HITRAN模拟光谱计算的检测限近似作为仪器实际测量检测限的精确程度, 并分析了两者具有误差的原因和现有实验平台的不足及优化方案.

关键词:

Abstract

The minimum amount that can be detected and quantitatively analyzed by Fourier infrared spectrometer depends on the signal-to-noise ratio of the measured gas spectrum. In order to use Fourier transform infrared absorption spectroscopy to measure CO₂, CO, CH₄, N₂O and other greenhouse gases, the signal-to-noise ratio and instrument detection limit of the mixed gas are studied. We propose a method to calculate the gas detection limit of the instrument through the HITRAN simulation spectrum. In addition, we build an experimental platform to verify the accuracy of the detection limit approximation based on the HITRAN simulation spectrum calculation, which serves as the actual measurement detection limit of the instrument, and we also analyze the reasons why there appears the error between the existing experimental platform and optimization scheme and their deficiencies as well.

Keywords:

Fourier transform infrared spectroscopy /
spectral simulation /
detection limit /
greenhouse gas

作者及机构信息

1.
中国科学技术大学环境科学与光电技术学院, 合肥　230026

2.
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, 中国科学院环境光学与技术重点实验室, 合肥　230031

通信作者: 徐亮, xuliang@aiofm.ac.cn

基金项目: 国家自然科学基金(批准号: 41941011)、中国科学院前沿科学重点研究项目(批准号: QYZDY-SSW-DQC016)和国家重点研发计划(批准号: 2019YFF0303400)资助的课题.

Authors and contacts

1.
School of Environmental Science and Optoelectronic Technology, University of Science and Technology of China, Heifei 230026, China

2.
Key Laboratory of Environmental Optics and Technology, Anhui Institute of Optics and Fine Mechanics, Hefei Institutes of Physical Science, Chinese Academy of Science, Hefei 230031, China

Corresponding author: Xu Liang, xuliang@aiofm.ac.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 41941011), the Key Research Program of Frontier Sciences, Chinese Academy of Sciences (Grant No. QYZDY-SSW-DQC016), and the National Key Research and Development Program of China (Grant No. 2019YFF0303400).

文章全文 : translate this paragraph

参考文献

[1]	Arevalo-Martinez D L, Beyer M, Krumbholz M, Piller I, Kock A, Steinhoff T, Körtzinger A, Bange H W 2013 Ocean Sci. 9 1071 Google Scholar
[2]	Baer D, Gupta M, Leen J B, Berman E 2012 American Laboratory 44 20
[3]	Schibig M F, Steinbacher M, Buchmann B, Van Der Laan-Luijkx I, van Der Laan S, Ranjan S, Leuenberger M C 2015 Atmos. Meas. Tech. 8 57 Google Scholar
[4]	Bacsik Z, Mink J, Keresztury G 2004 Appl. Spectrosc. Rev. 39 295 Google Scholar
[5]	程巳阳, 徐亮, 高闽光, 金岭, 李胜, 冯书香, 刘建国, 刘文清 2013 物理学报 62 124206 Google Scholar Cheng S Y, Xu L, Cao M G, Jin L, Li S, Feng S X, Liu J G, Liu W Q 2013 Acta Phys. Sin. 62 124206 Google Scholar
[6]	焦洋, 徐亮, 高闽光, 金岭, 童晶晶, 李胜, 魏秀丽 2013 物理学报 62 140705 Google Scholar Jiao Y, Xu L, Gao M G, Jin L, Tong J J, Li S, Wei X L 2013 Acta Phys. Sin. 62 140705 Google Scholar
[7]	Griffith D W T, Jamie I, Esler M, Wilson S R, Parkes S D, Waring C, Bryant G W 2006 Isot. Environ. Health Stud. 42 9 Google Scholar
[8]	Griffith D W T, Deutscher N M, Caldow C, Kettlewell G, Riggenbach M, Hammer S 2012 Atmos. Meas. Tech. 5 2481 Google Scholar
[9]	Smale D, Sherlock V, Griffith D T, Moss R, Brailsford G, Nichol S, Kotkamp M 2019 Atmos. Meas. Tech. 12 637 Google Scholar
[10]	Bak J, Clausen S 1999 Appl. Spectrosc. 53 697 Google Scholar
[11]	Griffiths P R 1972 Anal. Chem. 44 1909 Google Scholar
[12]	Griffiths P R, De Haseth J A 2007 Fourier Transform Infrared Spectrometry (Vol. 171) (New Jersey: John Wiley & Sons, Inc) pp161–164
[13]	Esler M B, Griffith D W T, Wilson S R, Steele L P 2000 Anal. Chem. 72 206 Google Scholar
[14]	Esler M B, Griffith D W T, Wilson S R, Steele L P 2000 Anal. Chem. 72 216 Google Scholar
[15]	Haaland D M, Easterling R G, Vopicka D A 1985 Appl. Spectrosc. 39 73 Google Scholar
[16]	Zimmermann B, Kohler A 2013 Appl Spectrosc 67 892 Google Scholar
[17]	Liu T T, Liu H, Chen Z Z, Lesgold A M 2018 IEEE Trans. Ind. Inf. 14 5268 Google Scholar
[18]	Liu H, Li Y, Zhang Z, Liu S, Liu T 2018 Opt. Express 26 22837 Google Scholar
[19]	Liu L, Huan H, Li W, Mandelis A, Wang Y, Zhang L, Zhang X, Yin X, Wu Y, Shao X 2021 Photoacoustics 21 100228 Google Scholar
[20]	Hill C, Gordon I E, Kochanov R V, Barrett L, Wilzewski J S, Rothman L S 2016 J. Quant. Spectrosc. Radiat. Transfer 177 4 Google Scholar
[21]	Kochanov R V, Gordon I, Rothman L, Wcisło P, Hill C, Wilzewski J 2016 Spectrosc. Radiat. Transfer 177 15 Google Scholar
[22]	Gordon I E, Rothman L S, Hargreaves R, Hashemi R, Karlovets E, Skinner F, Conway E, Hill C, Kochanov R, Tan Y 2021 Transfer 277 107949
[23]	Manning C J, Griffiths P R 1997 Appl. Spectrosc. 51 1092 Google Scholar

施引文献

图 1 各气体在分辨率为1 cm^–1、光程为24 m下的吸光度光谱

Fig. 1. Absorbance spectrum of each gas at a resolution of 1 cm^–1 and an optical path of 24 m.

下载: 全尺寸图片幻灯片

图 2 透过率光谱的最小透过率与光程、分辨率的关系

Fig. 2. Relationship of the minimum transmittance of the transmittance spectrum to the optical path and resolution.

下载: 全尺寸图片幻灯片

图 3 叠加噪声的透过率仿真光谱　(a)未叠加噪声与叠加噪声的仿真光谱图对比; (b)随机100次叠加0.001标准偏差的噪声的仿真光谱图的反演浓度

Fig. 3. Transmittance simulation spectrum with noise added: (a) Comparing the simulated spectrogram with no noise added and noise added; (b) inversion concentration of simulated spectra with noise with 0.01 standard deviation added randomly 100 times.

下载: 全尺寸图片幻灯片

图 4 仪器主机

Fig. 4. Instrument host.

下载: 全尺寸图片幻灯片

图 5 光谱拟合结果　(a) 2097—2242 cm^–1拟合N₂O和CO; (b) 3001—3150 cm^–1拟合CH₄; (c) 2150—2310 cm^–1拟合¹²CO₂和¹³CO₂

Fig. 5. Spectral fitting results of analysis bands: (a) Fitting N₂O and CO at 2097−2242 cm^–1; (b) fitting CH₄ at 3001−3150 cm^–1; (c) fitting ¹²CO₂ and ¹³CO₂ at 2150− 2310 cm^–1

下载: 全尺寸图片幻灯片

图 6 MCT和MIP检测限测量结果

Fig. 6. Measurement results of MCT and MIP detection limit.

下载: 全尺寸图片幻灯片

图 7 均方根噪声直接反演CO₂浓度的拟合结果

Fig. 7. Fitting results of direct inversion of CO₂ volume concentration by root mean square noise.

下载: 全尺寸图片幻灯片

表 1 WMO范围内建议的测量网络兼容性

Table 1. Recommended measurement network compatibility within WMO.

Component	Wave number/cm^–1	Extended network compatibility goal	Range in unpolluted troposphere	Range covered by the WMO scale
CO₂/(μmol·mol^–1)	2150—2310	0.2	380—450	250—520
N₂O/(nmol·mol^–1)	2097—2242	0.3	325—335	260—370
CO/(nmol·mol^–1)	2097—2242	5	30—300	30—500
CH₄/(nmol·mol^–1)	2810—3150	5	1750—2100	300—5900

下载: 导出CSV

表 2 检测限结果对比

Table 2. Retrieving concentration from actual spectral data of low noise detector.

	Componentsequence
	CO₂/(μmol·mol^–1)	N₂O/(nmol·mol^–1)	CO/(nmol·mol^–1)	CH₄/(μmol·mol^–1)
DL of MCT detector experimental measurement	6.95634	30.01392	32.98644	0.01947
DL of simulated spectrum detection	3.24915	15.63831	41.69358	0.02526
DL of MIP detector experimental measurement	2.43627	6.35112	16.89	0.012

下载: 导出CSV

[1]	Arevalo-Martinez D L, Beyer M, Krumbholz M, Piller I, Kock A, Steinhoff T, Körtzinger A, Bange H W 2013 Ocean Sci. 9 1071 Google Scholar
[2]	Baer D, Gupta M, Leen J B, Berman E 2012 American Laboratory 44 20
[3]	Schibig M F, Steinbacher M, Buchmann B, Van Der Laan-Luijkx I, van Der Laan S, Ranjan S, Leuenberger M C 2015 Atmos. Meas. Tech. 8 57 Google Scholar
[4]	Bacsik Z, Mink J, Keresztury G 2004 Appl. Spectrosc. Rev. 39 295 Google Scholar
[5]	程巳阳, 徐亮, 高闽光, 金岭, 李胜, 冯书香, 刘建国, 刘文清 2013 物理学报 62 124206 Google Scholar Cheng S Y, Xu L, Cao M G, Jin L, Li S, Feng S X, Liu J G, Liu W Q 2013 Acta Phys. Sin. 62 124206 Google Scholar
[6]	焦洋, 徐亮, 高闽光, 金岭, 童晶晶, 李胜, 魏秀丽 2013 物理学报 62 140705 Google Scholar Jiao Y, Xu L, Gao M G, Jin L, Tong J J, Li S, Wei X L 2013 Acta Phys. Sin. 62 140705 Google Scholar
[7]	Griffith D W T, Jamie I, Esler M, Wilson S R, Parkes S D, Waring C, Bryant G W 2006 Isot. Environ. Health Stud. 42 9 Google Scholar
[8]	Griffith D W T, Deutscher N M, Caldow C, Kettlewell G, Riggenbach M, Hammer S 2012 Atmos. Meas. Tech. 5 2481 Google Scholar
[9]	Smale D, Sherlock V, Griffith D T, Moss R, Brailsford G, Nichol S, Kotkamp M 2019 Atmos. Meas. Tech. 12 637 Google Scholar
[10]	Bak J, Clausen S 1999 Appl. Spectrosc. 53 697 Google Scholar
[11]	Griffiths P R 1972 Anal. Chem. 44 1909 Google Scholar
[12]	Griffiths P R, De Haseth J A 2007 Fourier Transform Infrared Spectrometry (Vol. 171) (New Jersey: John Wiley & Sons, Inc) pp161–164
[13]	Esler M B, Griffith D W T, Wilson S R, Steele L P 2000 Anal. Chem. 72 206 Google Scholar
[14]	Esler M B, Griffith D W T, Wilson S R, Steele L P 2000 Anal. Chem. 72 216 Google Scholar
[15]	Haaland D M, Easterling R G, Vopicka D A 1985 Appl. Spectrosc. 39 73 Google Scholar
[16]	Zimmermann B, Kohler A 2013 Appl Spectrosc 67 892 Google Scholar
[17]	Liu T T, Liu H, Chen Z Z, Lesgold A M 2018 IEEE Trans. Ind. Inf. 14 5268 Google Scholar
[18]	Liu H, Li Y, Zhang Z, Liu S, Liu T 2018 Opt. Express 26 22837 Google Scholar
[19]	Liu L, Huan H, Li W, Mandelis A, Wang Y, Zhang L, Zhang X, Yin X, Wu Y, Shao X 2021 Photoacoustics 21 100228 Google Scholar
[20]	Hill C, Gordon I E, Kochanov R V, Barrett L, Wilzewski J S, Rothman L S 2016 J. Quant. Spectrosc. Radiat. Transfer 177 4 Google Scholar
[21]	Kochanov R V, Gordon I, Rothman L, Wcisło P, Hill C, Wilzewski J 2016 Spectrosc. Radiat. Transfer 177 15 Google Scholar
[22]	Gordon I E, Rothman L S, Hargreaves R, Hashemi R, Karlovets E, Skinner F, Conway E, Hill C, Kochanov R, Tan Y 2021 Transfer 277 107949
[23]	Manning C J, Griffiths P R 1997 Appl. Spectrosc. 51 1092 Google Scholar

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