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介绍了一种基于差分光学吸收光谱(DOAS)方法的OH自由基定标系统, 该系统可产生一定浓度的OH自由基并同时进行精确测量. 系统采用紫外灯185 nm光线分解水汽产生OH自由基, 利用500 W氙灯准直光作为光源; 使用基长1.25 m、反射次数60次、总光程75.0 m的多次反射池来增加OH自由基的吸收光程; 以超高分辨率中阶梯光栅光谱仪(最高分辨率3.3 pm)作为光谱采集系统对光谱信号进行采集, 采用DOAS测量方法获得OH自由基的浓度. 通过改变腔内水汽的浓度, 系统准确测量了5×108-1.8×1010 molecules/cm3浓度范围的OH自由基. 分析了OH自由基测量过程中受到的吸收截面偏差、气压等因素影响, 得到系统总测量误差小于7.3%. 在实验的浓度范围内, 系统可用于大气OH自由基气体扩张激光诱导荧光测量技术的定标.In the present paper, we describe a calibration system for OH radicals based on differential optical absorption spectroscopy (DOAS). In the system OH radicals can be produced by photolysis of H2O which is irradiated by the 185 nm light in a cavity. The produced OH radicals with a certain concentration can be detected exactly. The system consists of a xenon lamp as light source in which the light has been collimated, a 1.25 m multiple-reflection cell in which the light can reflect 60 times to achieve 75.0 m whole path-length, and a double pass high resolution echelle spectrometer that is suitable for the measurement of OH radicals (best resolution: 3.3 pm). Utilizing the system the measurement spectra and lamp spectra can be obtained for OH concentration retrieval. OH concentration can be calculated by DOAS retrieval and during the DOAS retrieval the reference absorption cross section is obtained by applying the Voigt broadening method to the absorption lines. By changing water vapor concentration, the system accurately detects OH concentration ranging from 5×108 molecules/cm3 to 1.8×1010 molecules/cm3. In the concentration range, OH concentration fluctuation is very small. For example, when the volume ratio between water vapor and pure N2 reaches 0.3 L:24.7 L, the fluctuation is just ± 4%. Taking into account the effects of absorption cross section, gas pressure in the cavity and other factors, the total systematic error of the instrument is less than 7.3%. According to the results in the paper, the system can be used for the fluorescence assay by gas expansion technology calibration in field experiments.
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Keywords:
- differential optical absorption spectroscopy /
- OH radicals /
- calibration /
- high resolution spectrometer
[1] 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
[2] Dorn H P, Neuroth R, Brauers T, Brandenburger U, Ehhalt D H 1992 Atmos. Chem. 1715 361
[3] Edwards G D, Cantrell C A, Stephens S, Hill B, Goyea O, Shetter R E, Leon Mauldin R, Kosciuch E, Tanner D J, Eisele F L 2003 Anal. Chem. 75 5317
[4] Brune W H, Stevens P S, Mather J H 1995 J. Atmos. Sci. 52 3328
[5] Chan C Y, Hard T M, Mehrabzadeh A A, George L A, O'Brien R J 1990 J. Geophys. Res. 95 18569
[6] Hard T M, O'Brien R J, Chan C Y, Mehrabzadeh A A 1984 Environ. Sci. Technol. 18 768
[7] Hard T M, George L A, O'Brien R J 1995 J. Atmos. Sci. 52 3354
[8] Heard D E, Pilling M J 2003 Chem. Rev. 103 5163
[9] Creasey D J, Heard D E, Lee J D 2000 Geophys. Res. Lett. 27 1651
[10] Siese M, Becher K H, Brockmann K J 2001 Environ. Sci. Technol. 35 4660
[11] Hard T M, George L A, O'Brien R J 2002 Environ. Sci. Technol. 36 1783
[12] Platt U, Stutz J 2008 Differential Optical Absorption Spectroscopy Principles and Applications (Heidelberg: Springer-Verlag) pp138-141
[13] Li A 2008 Ph. D. Dissertation (Hefei: Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences) (in Chinese) [李昂 2008博士学位论文(合肥: 中国科学院安徽光学精密机械研究所)]
[14] Faloona I C, Tan D, Lesher R L, Hazen N L, Frame C L, Simpas J B, Harder H, Martinez M, Carlo P D, Ren X, Brune W H 2004 J. Atmos. Chem. 47 139
[15] Cantrell C A, Zimmer A, Tyndall G S 1997 Geophys. Res. Lett. 24 2195
[16] Hausmann M, Brandenburger U, Brauers T, Dorn H P 1997 J. Geophys. Res. 102 16011
[17] Whiting E E 1968 J. Quant. Spectrosc. Radiat. Transfer 8 1379
[18] Leonard C 1990 Ph. D. Dissertation (Hannover: Hannover University)
[19] Qin M, Xie P H, Liu J G, Liu W Q, Fang W, Lu F, Li A, Lu Y H, Wei Q N, Dou K, Zhang W J 2005 Spectrosc. Spect. Anal. 25 1463 (in Chinese) [秦敏, 谢品华, 刘建国, 刘文清, 方武, 陆钒, 李昂, 陆亦怀, 魏庆农, 窦科, 张为俊 2005 光谱学与光谱分析 25 1463]
[20] Dusanter S, Vimal D, Stevens P S 2008 Atmos. Chem. Phys. 8 321
[21] Kanaya Y, Sadanaga Y, Hirokawa J, Kajii Y, Akinoto H 2001 J. Geophys. Res. 38 73
[22] Dorn H P, Neuroth R, Hofzumahaus A 1995 J. Geophys. Res. 100 7397
[23] Hofzumahaus A, Dorn H P, Callies J, Platt U, Ehhalt D H 1991 Atmos. Environ. A 25 2017
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[1] 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
[2] Dorn H P, Neuroth R, Brauers T, Brandenburger U, Ehhalt D H 1992 Atmos. Chem. 1715 361
[3] Edwards G D, Cantrell C A, Stephens S, Hill B, Goyea O, Shetter R E, Leon Mauldin R, Kosciuch E, Tanner D J, Eisele F L 2003 Anal. Chem. 75 5317
[4] Brune W H, Stevens P S, Mather J H 1995 J. Atmos. Sci. 52 3328
[5] Chan C Y, Hard T M, Mehrabzadeh A A, George L A, O'Brien R J 1990 J. Geophys. Res. 95 18569
[6] Hard T M, O'Brien R J, Chan C Y, Mehrabzadeh A A 1984 Environ. Sci. Technol. 18 768
[7] Hard T M, George L A, O'Brien R J 1995 J. Atmos. Sci. 52 3354
[8] Heard D E, Pilling M J 2003 Chem. Rev. 103 5163
[9] Creasey D J, Heard D E, Lee J D 2000 Geophys. Res. Lett. 27 1651
[10] Siese M, Becher K H, Brockmann K J 2001 Environ. Sci. Technol. 35 4660
[11] Hard T M, George L A, O'Brien R J 2002 Environ. Sci. Technol. 36 1783
[12] Platt U, Stutz J 2008 Differential Optical Absorption Spectroscopy Principles and Applications (Heidelberg: Springer-Verlag) pp138-141
[13] Li A 2008 Ph. D. Dissertation (Hefei: Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences) (in Chinese) [李昂 2008博士学位论文(合肥: 中国科学院安徽光学精密机械研究所)]
[14] Faloona I C, Tan D, Lesher R L, Hazen N L, Frame C L, Simpas J B, Harder H, Martinez M, Carlo P D, Ren X, Brune W H 2004 J. Atmos. Chem. 47 139
[15] Cantrell C A, Zimmer A, Tyndall G S 1997 Geophys. Res. Lett. 24 2195
[16] Hausmann M, Brandenburger U, Brauers T, Dorn H P 1997 J. Geophys. Res. 102 16011
[17] Whiting E E 1968 J. Quant. Spectrosc. Radiat. Transfer 8 1379
[18] Leonard C 1990 Ph. D. Dissertation (Hannover: Hannover University)
[19] Qin M, Xie P H, Liu J G, Liu W Q, Fang W, Lu F, Li A, Lu Y H, Wei Q N, Dou K, Zhang W J 2005 Spectrosc. Spect. Anal. 25 1463 (in Chinese) [秦敏, 谢品华, 刘建国, 刘文清, 方武, 陆钒, 李昂, 陆亦怀, 魏庆农, 窦科, 张为俊 2005 光谱学与光谱分析 25 1463]
[20] Dusanter S, Vimal D, Stevens P S 2008 Atmos. Chem. Phys. 8 321
[21] Kanaya Y, Sadanaga Y, Hirokawa J, Kajii Y, Akinoto H 2001 J. Geophys. Res. 38 73
[22] Dorn H P, Neuroth R, Hofzumahaus A 1995 J. Geophys. Res. 100 7397
[23] Hofzumahaus A, Dorn H P, Callies J, Platt U, Ehhalt D H 1991 Atmos. Environ. A 25 2017
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