Abstract
An instrument for measuringtropospheric OH/HO2 radicals by laser-inducedfluorescence developed in our laboratory is presentedin detail. It is based on FAGE (fluorescence assay bygas expansion) technique and OH is both excited anddetected at 308 nm corresponding to its A-X(0,0) band.The alignment of the laser beam, the design of thesample gas inlet, and the devices for the fluorescencedetection are optimized so as to reduce the backgroundsignal while keeping the OH sensitivity as high aspossible. A thermalized position of the expanding gasbeam is probed in our system and we did not observe asevere decrease of the HOx sensitivities under humidconditions. An optical fiber is used for deliveringthe laser light to the fluorescence detection cellmounted outside at a high position. Thus the laserbeam alignment is by far simplified and is made highlyreproducible, once settled properly. For thecalibration, two methods are employed: a system withlaser absorption measurements of OH and a system ofsimultaneous photolysis of H2O and O2. Thecalibration factors are compared well within thecombined uncertainty. Using the latter system, theconversion efficiency of HO2 to OH by NO additionis measured to be around 90%. The detection limitsfor OH and HO2 (S/N = 2) are estimated to be3.3 × 106 and 3.6 × 106cm−3 at noon,respectively, with an integration time of 1 min. Theresults of test observations at our institute are alsopresented.
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Armerding, W., Spiekermann, M., Walter, J., and Comes, F. J., 1995: MOAS: An absorption laser spectrometer for sensitive and local monitoring of tropospheric OH and other trace gases, J. Atmos. Sci. 52, 3381-3392.
Aschmutat, U., Hessling, M., Holland, F., and Hofzumahaus, A., 1993: A tunable source of hydroxyl (OH) and hydroperoxy (HO2) radicals: in the range between 106 and 109 cm-3, Physico-Chem. Behaviour Atmos. Poll. 2, 811-816.
Brune, W. H., Stevens, P. S., and Mather, J. H., 1995: Measuring OH and HO2 in the troposphere by laser-induced fluorescence at low pressure, J. Atmos. Sci. 52, 3328-3336.
Brune, W. H. et al., 1998: Airborne in-situ OH and HO2 observations in the cloud-free troposphere and lower stratosphere during SUCCESS, Geophys. Res. Lett. 25, 1701-1704.
Cantrell, C. A., Shetter, R. E., Calvert, J. G., Eisele, F. L., Williams, E., Baumann, K., Brune, W. H., Stevens, P. S., and Mather, J. M., 1997a: Peroxy radicals from photostationary state deviations and steady state calculations during the Tropospheric OH Photochemistry Experiments at Idaho Hill, Colorado, 1993, J. Geophys. Res. 102, 6369-6378.
Cantrell, C. A., Zimmer, A., and Tyndall, G. S., 1997b: Absorption cross sections for water vapor from 183 to 193 nm, Geophys. Res. Lett. 24, 2195-2198.
Carslaw, N., Creasey, D. J., Heard, D. E., Lewis, A. C., McQuaid, J. B., Pilling, M. J., Monks, P. S., Bandy, B. J., and Penkett, S. A., 1999: Modeling OH, HO2, and RO2 radicals in the marine boundary layer 1. Model construction and comparison with field measurements, J. Geophys. Res. 104, 30,241-30,255.
Chan, C. Y., Hard, T. M., Mehrabzadeh, A. A., George, L. A., and O'Brien, R. J., 1990: Third-generation FAGE instrument for tropospheric hydroxyl radical measurement, J. Geophys. Res. 95, 18,569-18,576.
Copeland, R. A. and Crosley, D. R., 1986: Temperature dependent electronic quenching of OH(A2∑, v' = 0) between 230 K and 310 K, J. Chem. Phys. 84, 3099-3105.
Creasey, D. J., Halford-Maw, P. A., Heard, D. E., Pilling, M. J., and Whitaker, B. J., 1997a: Implementation and initial deployment of a field instrument for measurement of OH and HO2 in the troposphere by laser-induced fluorescence, J. Chem. Soc. Faraday Trans. 93, 2907-2913.
Creasey, D. J., Heard, D. E., Pilling, M. J., Whitaker, B. J., Berzins, M., and Fairlie, R., 1997b: Visualisation of a supersonic free-jet expansion using laser-induced fluorescence spectroscopy: Application to the measurement of rate constants at ultralow temperatures, Appl. Phys. B 65, 375-391.
Crosley, D. R., 1995: The measurement of OH and HO2 in the atmosphere, J. Atmos. Sci. 52, 3299-3314.
Dorn, H-P., Brandenburger, U., Brauers, T., and Hausmann, M., 1995a: A new in situ laser longpath absorption instrument for the measurement of tropospheric OH radicals, J. Atmos. Sci. 52, 3373-3380.
Dorn, H-P., Neuroth, R., and Hofzumahaus, A., 1995b: Investigation of OH absorption cross sections of rotational transitions in the A2∑+, v' = 0 ← X 2П, v” = 0 band under atmospheric conditions: Implications for tropospheric long-path absorption measurements, J. Geophys. Res. 100, 7397-7409.
Ehhalt, D. H., 1999: Photooxidation of trace gases in the troposphere, plenary lecture, Phys. Chem. Chem. Phys. 1, 5401-5408.
Eisele, F. L., Tanner, D. J., Cantrell, C. A., and Calvert, J. G., 1996: Measurements and steady state calculations of OH concentrations at Mauna Loa Observatory, J. Geophys. Res. 101, 14,665-14,679.
Eisele, F. L., Mount, G. H., Fehsenfeld, F. C., Harder, J., Marovich, E., Parrish, D. D., Roberts, J., Trainer, M., and Tanner, D., 1994: Intercomparison of tropospheric OH and ancillary trace gas measurements at Fritz Peak Observatory, Colorado, J. Geophys. Res. 99, 18,605-18,626.
Faloona, I. et al., 2000: Observations of HOx and its relationship with NOx in the upper troposphere during SONEX, J. Geophys. Res. 105, 3771-3783.
Felton, C. C., Sheppard, J. C., and Campbell, M. J., 1990: The radiochemical hydroxyl radical measurement method, Environ. Sci. Technol. 24, 1841-1847.
Hard, T. M., O'Brien, R. J., Chan, C. Y., and Mehrabzadeh, A. A., 1984: Tropospheric free radical determination by FAGE, Environ. Sci. Technol. 18, 768-777.
Hard, T. M., Chan, C. Y., Mehrabzadeh, A. A., and O'Brien, R. J., 1992: Diurnal HO2 cycles at clean air and urban sites in the troposphere, J. Geophys. Res. 97, 9785-9794.
Hard, T. M., George, L. A., and O'Brien, R. J., 1995: FAGE determination of tropospheric HO and HO2, J. Atmos. Sci. 52, 3354-3372.
Hofzumahaus, A. and Holland, F., 1993: Laser-induced fluorescence based detection system for measurement of tropospheric OH using 308 nm excitation at low pressure, in H. I. Schiff and U. Platt (eds), Optical Methods in Atmoshperic Chemistry, Proc. SPIE 1715, pp. 163-173.
Hofzumahaus, A., Aschmutat, U., Hessling, M., Holland, F., and Ehhalt, D. H., 1996: The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign, Geophys. Res. Lett. 23, 2541-2544.
Hofzumahaus, A., Brauers, T., Aschmutat, U., Brandenburger, U., Dorn, H.-P., Hausmann, M., Heß ling, M., Holland, F., Plass-Dülmer, C., Sedlacek, M., Weber, M., and Ehhalt, D. H., 1997: Reply, Geophys. Res. Lett. 24, 3039-3040.
Hofzumahaus, A. et al., 1998: Intercomparison of tropospheric OH measurements by different laser techniques during the POPCORN campaign 1994, J. Atmos. Chem. 31, 227-246.
Holland, F., Hessling, M., and Hofzumahaus, A., 1995: In situ measurement of tropospheric OH radicals by laser-induced fluorescence-A description of the KFA instrument, J. Atmos. Sci. 52, 3393-3401.
Holland, F., Aschmutat, U., Heß ling, M., Hofzumahaus, A., and Ehhalt, D. H., 1998: Highly time resolved measurements of OH during POPCORN using laser-induced fluorescence spectroscopy, J. Atmos. Chem. 31, 205-225.
Kanaya, Y., Sadanaga, Y., Matsumoto, J., Sharma, U. K., Hirokawa, J., Kajii, Y., and Akimoto, H., 1999: Nighttime observation of the HO2 radical by an LIF based instrument at Oki island, Japan, and its possible origins, Geophys. Res. Lett. 26, 2179-2182.
Kanaya, Y., Sadanaga, Y., Matsumoto, J., Sharma, U. K., Hirokawa, J., Kajii, Y., and Akimoto, H., 2000: Daytime HO2 concentrations at Oki island, Japan, in summer 1998: Comparison between measurement and theory, J. Geophys. Res., in press.
Krol, M., van Leeuwen, J., and Lelieveld, J., 1998: Global OH trend inferred from methylchloroform measurements, J. Geophys. Res. 103, 10,697-10,711.
Lanzendorf, E. J., Hanisco, T. F., Donahue, N. M., and Wennberg, P. O., 1997: Comment on: 'The measurement of tropospheric OH radicals by laser-induced fluorescence spectroscopy during the POPCORN field campaign' by Hofzumahaus et al. and 'Intercomparison of tropospheric OH radical measurements by multiple folded long-path laser absorption and laser induced fluorescence' by Brauers et al., Geophys. Res. Lett. 24, 3037-3038.
Mather, J. H., 1994: Measurement of tropospheric OH and HO2 by laser-induced fluorescence, PhD thesis, The Pennsylvania State University.
Mather, J. H., Stevens, P. S., and Brune, W. H., 1997: OH and HO2 measurements using laser-induced fluorescence, J. Geophys. Res. 102, 6427-6436.
Mauldin, R. L., Frost, G. J., Chen, G., Tanner, D. J., Prevot, A. S. H., Davis, D. D., and Eisele, F. L., 1998: OH measurements during the first aerosol characterization experiment (ACE 1): Observations and model comparisons, J. Geophys. Res. 103, 16,713-16,729.
Mauldin, R. L., Tanner, D. J., and Eisele, F. L., 1999: Measurements of OH during PEM-Tropics A., J. Geophys. Res. 104, 5817-5827.
McKeen, S. A., Mount, G., Eisele, F., Williams, E., Harder, J., Goldan, P., Kuster, W., Liu, S. C., Baumann, K., Tanner, D., Fried, A., Sewell, S., Cantrell, C., and Shetter, R., 1997: Photochemical modeling of hydroxyl and its relationship to other species during the Tropospheric OH Photochemistry Experiment, J. Geophys. Res. 102, 6467-6493.
Mihelcic, D., Klemp, D., Müsgen, P., Pätz, H. W., and Volz-Thomas, A., 1993: Simultaneous measurements of peroxy and nitrate radicals at Schauinsland, J. Atmos. Chem. 16, 313-335.
Mount, G. H., Brault, J. W., Johnston, P. V., Marovich, E., Jakoubek, R. O., Volpe, C. J., Harder, J., and Olson, J., 1997: Measurement of tropospheric OH by long-path laser absorption at Fritz Peak Observatory, Colorado, during the OH Photochemistry Experiment, fall 1993, J. Geophys. Res. 102, 6393-6413.
Prinn, R. G., Weiss, R. F., Miller, B. R., Huang, J., Alyea, F. N., Cunnold, D. M., Fraser, P. J., Hartley, D. E., and Simmonds, P. G., 1995: Atmospheric trends and lifetime of CH3CCl3 and global OH concentrations, Science 269, 187-192.
Stevens, P. S., Mather, J. H., and Brune, W. H., 1994: Measurement of tropospheric OH and HO2 by laser-induced fluorescence, J. Geophys. Res. 99, 3543-3557.
Stevens, P. S., Mather, J. H., Brune, W. H., Eisele, F., Tanner, D., Jefferson, A., Cantrell, C., Shetter, R., Sewall, S., Fried, A., Henry, B., Williams, E., Baumann, K., Goldan, P., and Kuster, W., 1997: HO2/OH and RO2/HO2 ratios during the Tropospheric OH Photochemistry Experiment: Measurement and theory, J. Geophys. Res. 102, 6379-6391.
Tanner, D. J. and Eisele, F. L., 1995: Present OH measurement limits and associated uncertainties, J. Geophys. Res. 100, 2883-2892.
Wennberg, P. O. et al., 1994: Aircraft-borne, laser-induced fluorescence instrument for the in situ detection of hydroxyl and hydroperoxyl radicals, Rev. Sci. Instrum. 65, 1858-1876.
Wennberg, P. O. et al., 1998: Hydrogen radicals, nitrogen radicals, and the production of O3 in the upper troposphere, Science 279, 49-53.
Wysong, I. J., Jeffries, J. B., and Crosley, D. R., 1990: Quenching of A2∑+ OH at 300 K by several collidars, J. Chem. Phys. 92, 5218-5222.
Zeng, G., Heard, D. E., Pilling, M. J., and Robertson, S. H., 1998: A master equation study of lasergenerated interference in the detection of hydroxyl radicals using laser-induced fluorescence, Geophys. Res. Lett. 25, 4497-4500.
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Kanaya, Y., Sadanaga, Y., Hirokawa, J. et al. Development of a Ground-Based LIF Instrument for Measuring HOx Radicals: Instrumentation and Calibrations. Journal of Atmospheric Chemistry 38, 73–110 (2001). https://doi.org/10.1023/A:1026559321911
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DOI: https://doi.org/10.1023/A:1026559321911