ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-8-7779-2008 Measurement of glyoxal using an incoherent broadband cavity enhanced absorption spectrometer Washenfelder R. A. 1 2 Langford A. O. 2 Fuchs H. 1 2 Brown S. S. 2 Cooperative Institute for Research in Environmental Sciences, 216 UCB, University of Colorado, Boulder, CO 80309, USA Chemical Sciences Division, National Oceanic and Atmospheric Administration, 325 Broadway, Boulder, CO 80305, USA 23 12 2008 8 24 7779 7793 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/8/7779/2008/acp-8-7779-2008.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/8/7779/2008/acp-8-7779-2008.pdf

We describe an instrument for simultaneous measurements of glyoxal (CHOCHO) and nitrogen dioxide (NO<sub>2</sub>) using cavity enhanced absorption spectroscopy with a broadband light source. The output of a Xenon arc lamp is coupled into a 1 m optical cavity, and the spectrum of light exiting the cavity is recorded by a grating spectrometer with a charge-coupled device (CCD) array detector. The mirror reflectivity and effective path lengths are determined from the known Rayleigh scattering of He and dry zero air (N<sub>2</sub>+O<sub>2</sub>). Least-squares fitting, using published reference spectra, allow the simultaneous retrieval of CHOCHO, NO<sub>2</sub>, O<sub>4</sub>, and H<sub>2</sub>O in the 441 to 469 nm spectral range. For a 1-min sampling time, the precision (&plusmn;1σ) on signal for measurements of CHOCHO and NO<sub>2</sub> is 29 pptv and 20 pptv, respectively. We directly compare measurements made with the incoherent broadband cavity enhanced absorption spectrometer with those from cavity ringdown instruments detecting CHOCHO and NO<sub>2</sub> at 404 and 532 nm, respectively, and find linear agreement over a wide range of concentrations. The instrument has been tested in the laboratory with both synthetic and real air samples, and the demonstrated sensitivity and specificity suggest a strong potential for field measurements of both CHOCHO and NO<sub>2</sub>.

 References % vor jede Referenz Ball, S. M. and Jones, R. L.: Broad-band cavity ring-down spectroscopy, Chem. Rev., 103, 5239–5262, 2003. % vor jede Referenz Ball, S. M., Langridge, J. M., and Jones, R. L.: Broadband cavity enhanced absorption spectroscopy using light emitting diodes, Chem. Phys. Lett., 398, 68–74, 2004. % vor jede Referenz Bandow, H., Washida, N., and Akimoto, H.: Ring-cleavage reactions of aromatic hydrocarbons studied by FT-IR spectroscopy: 1. Photooxidation of toluene and benzene in the NO$_x$-air system, B. Chem. Soc. Jpn., 58, 2531–2540, 1985. % vor jede Referenz Bodhaine, B. A., Wood, N. B., Dutton, E. G., and Slusser, J. R.: On Rayleigh optical depth calculations, J. Atmos. Ocean. Tech., 16, 1854–1861, 1999. % vor jede Referenz Brown, S. S., Ravishankara, A. R., and Stark, H.: Simultaneous kinetics and ring-down: Rate coefficients from single cavity loss temporal profiles, J. Phys. Chem.-US A, 104, 7044–7052, 2000. % vor jede Referenz Carter, W. P. L. and Atkinson, R.: Development and evaluation of a detailed mechanism for the atmospheric reactions of isoprene and NO<sub>x</sub>, Int. J. Chem. Kinet., 28, 497–530, 1996. % vor jede Referenz Chen, Y. Q. and Zhu, L.: Wavelength-dependent photolysis of glyoxal in the 290–420 nm region, J. Phys. Chem.-US A, 107, 4643–4651, 2003. % vor jede Referenz Dube, W. P., Brown, S. S., Osthoff, H. D., Nunley, M. R., Ciciora, S. J., Paris, M. W., McLaughlin, R. J., and Ravishankara, A. R.: Aircraft instrument for simultaneous, in situ measurement of NO<sub>3</sub> and N<sub>2</sub>O$_5$ via pulsed cavity ring-down spectroscopy, Rev. Sci. Instrum., 77, 034101, doi:10.1063/1.2176058, 2006. % vor jede Referenz Feierabend, K. J., Zhu, L., Talukdar, R. K., and Burkholder, J. B.: Rate coefficients for the OH+HC(O)C(O)H (glyoxal) reaction between 210 and 390 K, J. Phys. Chem.-US A, 112, 73–82, 2008. % vor jede Referenz Fick, J., Pommer, L., Nilsson, C., and Andersson, B.: Effect of OH radicals, relative humidity, and time on the composition of the products formed in the ozonolysis of alpha-pinene, Atmos. Environ., 37, 4087–4096, 2003. % vor jede Referenz Fiedler, S. E., Hese, A., and Ruth, A. A.: Incoherent broad-band cavity-enhanced absorption spectroscopy, Chem. Phys. Lett., 371, 284–294, 2003. % vor jede Referenz Flad, J. E., Brown, S. S., Burkholder, J. B., Stark, H., and Ravishankara, A. R.: Absorption cross sections for the Ã<sup>2</sup>A" (0,9&deg;,0)$\longleftarrow$X<sup>2</sup>A' (0,0$^1$,0) band of the HCO radical Physical Chemistry, Chem. Phys., 8, 3636–3642, 2006. % vor jede Referenz Francois, S., Perraud, V., Pflieger, M., Monod, A., and Wortham, H.: Comparative study of glass tube and mist chamber sampling techniques for the analysis of gaseous carbonyl compounds, Atmos. Environ., 39, 6642–6653, 2005. % vor jede Referenz Fung, K. and Grosjean, D.: Determination of nanogram amounts of carbonyls as 2,4-dinitrophenylhydrazones by high-performance liquid-chromatography, Anal. Chem., 53, 168–171, 1981. % vor jede Referenz Gherman, T., Venables, D. S., Vaughan, S., Orphal, J., and Ruth, A. A.: Incoherent broadband cavity-enhanced absorption spectroscopy in the near-ultraviolet: Application to HONO and NO<sub>2</sub>, Environ. Sci. Technol., 42, 890–895, 2008. % vor jede Referenz Goldan, P. D., Kuster, W. C., and Albritton, D. L.: A dynamic dilution system for the production of sub-ppb concentrations of reactive and labile species, Atmos. Environ., 20, 1203–1209, 1986. % vor jede Referenz Greenblatt, G. D., Orlando, J. J., Burkholder, J. B., and Ravishankara, A. R.: Absorption measurements of oxygen between 330 nm and 1140 nm, J. Geophys. Res.-Atmos., 95, 18577–18582, 1990. % vor jede Referenz Grosjean, D., Grosjean, E., and Moreira, L. F. R.: Speciated ambient carbonyls in Rio de Janeiro, Brazil, Environ. Sci. Technol., 36, 1389–1395, 2002. % vor jede Referenz Grosjean, E., Green, P. G., and Grosjean, D.: Liquid chromatography analysis of carbonyl (2,4-dinitrophenyl)hydrazones with detection by diode array ultraviolet spectroscopy and by atmospheric pressure negative chemical ionization mass spectrometry, Anal. Chem., 71, 1851–1861, 1999. % vor jede Referenz Harder, J. W. and Brault, J. W.: Atmospheric measurements of water vapor in the 442-nm region, J. Geophys. Res.-Atmos., 102, 6245–6252, 1997. % vor jede Referenz Harder, J. W., Brault, J. W., Johnston, P. V., and Mount, G. H.: Temperature dependent NO<sub>2</sub> cross sections at high spectral resolution, J. Geophys. Res.-Atmos., 102, 3861–3879, 1997. % vor jede Referenz Hastings, W. P., Koehler, C. A., Bailey, E. L., and De Haan, D. O.: Secondary organic aerosol formation by glyoxal hydration and oligomer formation: Humidity effects and equilibrium shifts during analysis, Environ. Sci. Technol., 39, 8728–8735, 2005. % vor jede Referenz Ho, S. S. H. and Yu, J. Z.: Determination of airborne carbonyls: Comparison of a thermal desorption/GC method with the standard DNPH/HPLC method, Environ. Sci. Technol., 38, 862–870, 2004. % vor jede Referenz Huisman, A. J., Hottle, J. R., Coens, K. L., DiGangi, J. P., Galloway, M. M., Kammrath, A., and Keutsch, F. N.: Laser-induced phosphorescence for the in situ detection of glyoxal at part per trillion mixing ratios, Anal. Chem., 80, 5884–5891, 2008. % vor jede Referenz Jang, M. S. and Kamens, R. M.: Characterization of secondary aerosol from the photooxidation of toluene in the presence of NO<sub>x</sub> and 1-propene, Environ. Sci. Technol., 35, 3626–3639, 2001. % vor jede Referenz Jang, M. S., Czoschke, N. M., Lee, S., and Kamens, R. M.: Heterogeneous atmospheric aerosol production by acid-catalyzed particle-phase reactions, Science, 298, 814–817, 2002. % vor jede Referenz Kawamura, K., Steinberg, S., and Kaplan, I. R.: Homologous series of C-1-C-10 monocarboxylic acids and C-1-C-6 carbonyls in Los Angeles air and motor vehicle exhausts, Atmos. Environ., 34, 4175–4191, 2000. % vor jede Referenz Kroll, J. H., Ng, N. L., Murphy, S. M., Flagan, R. C., and Seinfeld, J. H.: Chamber studies of secondary organic aerosol growth by reactive uptake of simple carbonyl compounds, J. Geophys. Res.-Atmos., 110, L18808, doi:10.1029/2005JD006004, 2005. % vor jede Referenz Langford, A. O. and Moore, C. B.: Reaction and relaxation of vibrationally excited formyl radicals, J. Chem. Phys., 80, 4204–4210, 1984. % vor jede Referenz Langford, A. O., Schofield, R., Daniel, J. S., Portmann, R. W., Melamed, M. L., Miller, H. L., Dutton, E. G., and Solomon, S.: On the variability of the Ring effect in the near ultraviolet: understanding the role of aerosols and multiple scattering, Atmos. Chem. Phys., 7, 575–586, 2007. % vor jede Referenz Langridge, J. M., Ball, S. M., and Jones, R. L.: A compact broadband cavity enhanced absorption spectrometer for detection of atmospheric NO<sub>2</sub> using light emitting diodes, Analyst, 131, 916–922, 2006. % vor jede Referenz Langridge, J. M., Le Crane, J., Ball, S. M., and Jones, R. J.: Broadband Cavity Enhanced Absorption Spectroscopy: an in-situ DOAS for atmospheric measurements, Eos Trans. AGU, 88, Fall Meet. Suppl., Abstract A51H-07, 2007. % vor jede Referenz Lee, Y. N., Zhou, X., Kleinman, L. I., Nunnermacker, L. J., Springston, S. R., Daum, P. H., Newman, L., Keigley, W. G., Holdren, M. W., Spicer, C. W., Young, V., Fu, B., Parrish, D. D., Holloway, J., Williams, J., Roberts, J. M., Ryerson, T. B., and Fehsenfeld, F. C.: Atmospheric chemistry and distribution of formaldehyde and several multioxygenated carbonyl compounds during the 1995 Nashville Middle Tennessee Ozone Study, J. Geophys. Res.-Atmos., 103, 22449–22462, 1998. % vor jede Referenz Liggio, J., Li, S. M., and McLaren, R.: Reactive uptake of glyoxal by particulate matter, J. Geophys. Res.-Atmos., 110, D10304, doi:10.1029/2004JD005113, 2005. % vor jede Referenz Munger, J. W., Jacob, D. J., Daube, B. C., Horowitz, L. W., Keene, W. C., and Heikes, B. G.: Formaldehyde, glyoxal, and methylglyoxal in air and cloudwater at a rural mountain site in Central Virginia, J. Geophys. Res.-Atmos., 100, 9325–9333, 1995. % vor jede Referenz Osthoff, H. D., Brown, S. S., Ryerson, T. B., Fortin, T. J., Lerner, B. M., Williams, E. J., Pettersson, A., Baynard, T., Dube, W. P., Ciciora, S. J., and Ravishankara, A. R.: Measurement of atmospheric NO<sub>2</sub> by pulsed cavity ring-down spectroscopy, J. Geophys. Res.-Atmos., 111, D12305, doi:10.1029/2005JD006942, 2006. % vor jede Referenz Paul, J. B., Lapson, L., and Anderson, J. G.: Ultrasensitive absorption spectroscopy with a high-finesse optical cavity and off-axis alignment, Appl. Optics, 40, 4904–4910, 2001. % vor jede Referenz Platt, U., Perner, D., and Patz, H. W.: Simultaneous measurement of atmospheric CH<sub>2</sub>O, O<sub>3</sub>, and NO<sub>2</sub> by differential optical-absorption, J. Geophys. Res.-Oc. Atm., 84, 6329–6335, 1979. % vor jede Referenz Read, K. A., Mahajan, A. S., Carpenter, L. J., Evans, M. J., Faria, B. V. E., Heard, D. E., Hopkins, J. R., Lee, J. D., Moller, S. J., Lewis, A. C., Mendes, L., McQuaid, J. B., Oetjen, H., Saiz-Lopez, A., Pilling, M. J., and Plane, J. M. C.: Extensive halogen-mediated ozone destruction over the tropical Atlantic Ocean, Nature, 453, 1232–1235, 2008. % vor jede Referenz Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Keller-Rudek, H., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation Number 15, JPL Publication 06-2, Jet Propulsion Laboratory, Pasadena, USA, 2006. % vor jede Referenz Scherer, J. J., Paul, J. B., OKeefe, A., and Saykally, R. J.: Cavity ringdown laser absorption spectroscopy: History, development, and application to pulsed molecular beams, Chem. Rev., 97, 25–51, 1997. % vor jede Referenz Seinfeld, J. H. and Pankow, J. F.: Organic atmospheric particulate material, Annu. Rev. Phys. Chem., 54, 121–140, 2003. % vor jede Referenz Shardanand, S. and Rao, A. D. P.: Absolute Rayleigh scattering cross sections of gases and freons of stratospheric interest in the visible and ultraviolet regions, NASA Technical Note, 1977. % vor jede Referenz Sneep, M. and Ubachs, W.: Direct measurement of the Rayleigh scattering cross section in various gases, J. Quant. Spectrosc. Ra., 92, 293–310, 2005. % vor jede Referenz Spaulding, R. S., Talbot, R. W., and Charles, M. J.: Optimization of a mist chamber (cofer scrubber) for sampling water-soluble organics in air, Environ. Sci. Technol., 36, 1798–1808, 2002. % vor jede Referenz Spaulding, R. S., Schade, G. W., Goldstein, A. H., and Charles, M. J.: Characterization of secondary atmospheric photooxidation products: Evidence for biogenic and anthropogenic sources, J. Geophys. Res.-Atmos., 108, 4247, doi:10.1029/2002JD002478, 2003. % vor jede Referenz Tomasi, C., Vitale, V., Petkov, B., Lupi, A., and Cacciari, A.: Improved algorithm for calculations of Rayleigh-scattering optical depth in standard atmospheres, Appl. Optics, 44, 3320–3341, 2005. % vor jede Referenz Triki, M., Cermak, P., Mejean, G., and Romanini, D.: Cavity-enhanced absorption spectroscopy with a red LED source for NO<sub>x</sub> trace analysis, Appl. Phys. B-Laser O., 91, 195–201, 2008. % vor jede Referenz Tuazon, E. C., Atkinson, R., Macleod, H., Biermann, H. W., Winer, A. M., Carter, W. P. L., and Pitts, J. N.: Yields of glyoxal and methylglyoxal from the NO<sub>x</sub>-air photooxidations of toluene and m-xylene and p-xylene, Environ. Sci. Technol., 18, 981–984, 1984. % vor jede Referenz Vandaele, A. C., Hermans, C., Fally, S., Carleer, M., Colin, R., Merienne, M. F., Jenouvrier, A., and Coquart, B.: High-resolution Fourier transform measurement of the NO<sub>2</sub> visible and near-infrared absorption cross sections: Temperature and pressure effects, J. Geophys. Res.-Atmos., 107, 4348, doi:10.1029/2001JD000971, 2002. % vor jede Referenz Venables, D. S., Gherman, T., Orphal, J., Wenger, J. C., and Ruth, A. A.: High sensitivity in situ monitoring of NO<sub>3</sub> in an atmospheric simulation chamber using incoherent broadband cavity-enhanced absorption spectroscopy, Environ. Sci. Technol., 40, 6758–6763, 2006. % vor jede Referenz Volkamer, R., Molina, L. T., Molina, M. J., Shirley, T., and Brune, W. H.: DOAS measurement of glyoxal as an indicator for fast VOC chemistry in urban air, Geophys. Res. Lett., 32, L08806, doi:10.1029/2005GL022616, 2005a. % vor jede Referenz Volkamer, R., Spietz, P., Burrows, J., and Platt, U.: High-resolution absorption cross-section of glyoxal in the UV-vis and IR spectral ranges, J. Photoch. Photobio. A., 172, 35–46, 2005b. % vor jede Referenz Volkamer, R., Martini, F. S., Molina, L. T., Salcedo, D., Jimenez, J. L., and Molina, M. J.: A missing sink for gas-phase glyoxal in Mexico City: Formation of secondary organic aerosol, Geophys. Res. Lett., 34, L19807, doi:10.1029/2007GL030752, 2007. % vor jede Referenz Wittrock, F., Richter, A., Oetjen, H., Burrows, J. P., Kanakidou, M., Myriokefalitakis, S., Volkamer, R., Beirle, S., Platt, U., and Wagner, T.: Simultaneous global observations of glyoxal and formaldehyde from space, Geophys. Res. Lett., 33, L16804, doi:10.1029/2006GL026310, 2006. % vor jede Referenz Yu, J. Z., Jeffries, H. E., and Lelacheur, R. M.: Identifying airborne carbonyl-compounds in isoprene atmospheric photooxidation products by their PFBHA oximes using gas-chromatography ion-trap mass-spectrometry, Environ. Sci. Technol., 29, 1923–1932, 1995. % vor jede Referenz Zhu, L., Kellis, D., and Ding, C. F.: Photolysis of glyoxal at 193, 248, 308 and 351 nm, Chem. Phys. Lett., 257, 487–491, 1996.