References

AMTD

Atmospheric Measurement Techniques Discussions

AMTD

1867-8610

Copernicus GmbH

Göttingen, Germany

10.5194/amtd-3-2681-2010

Inherent calibration of a novel LED-CE-DOAS instrument to measure iodine oxide, glyoxal, methyl glyoxal, nitrogen dioxide, water vapour and aerosol extinction in open cavity mode

Thalman

¹ Volkamer

¹ ²

Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA

Cooperative Institute for Research in the Environmental Sciences CIRES, Boulder, CO 80309, USA

24 06 2010

3 3 2681 2721

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The combination of Cavity Enhanced Absorption Spectroscopy (CEAS) with broad-band light sources (e.g. Light-Emitting Diodes, LEDs) lends itself to the application of cavity enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) to perform sensitive and selective point measurements of multiple trace gases and aerosol extinction with a single instrument. In contrast to other broad-band CEAS techniques, CE-DOAS relies only on the measurement of relative intensity changes, i.e. does not require knowledge of the light intensity in the absence of trace gases and aerosols (I0). We have built a prototype LED-CE-DOAS instrument in the blue spectral range (420–490 nm) to measure nitrogen dioxide (NO2), glyoxal (CHOCHO), methyl glyoxal (CH3COCHO), iodine oxide (IO), water vapour (H2O) and oxygen dimers (O4). We demonstrate the first CEAS detection of methyl glyoxal, and the first CE-DOAS detection of CHOCHO and IO. A further innovation consists in the measurement of extinction losses from the cavity, e.g. due to aerosols, at two wavelengths by observing O4 (477 nm) and H2O (443 nm) and measuring the pressure, relative humidity and temperature independently. This approach is demonstrated by experiments where laboratory aerosols of known size and refractive index were generated and their extinction measured. The measured extinctions were then compared to the theoretical extinctions calculated using Mie theory (3–7×10-7 cm-1). Excellent agreement is found from both the O4 and H2O retrievals. This enables the first inherently calibrated CEAS measurement in open cavity mode (mirrors facing the open atmosphere), and eliminates the need for sampling lines to supply air to the cavity, and/or keep the cavity enclosed and aerosol free. Measurements in open cavity mode are demonstrated for CHOCHO, CH3COCHO, NO2, H2O and aerosol extinction at 477 nm and 443 nm. Our prototype LED-CE-DOAS provides a low cost, yet research grade innovative instrument for applications in simulation chambers and in the open atmosphere.

References 1

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.

Betterton, E. A. and Hoffmann, M. R.: Henry's law constants of some environmentally important aldehydes, Envir. Sci. Technol., 22, 1415–1418, 1988.

Biskos, G., Paulsen, D., Russell, L. M., Buseck, P. R., and Martin, S. T.: Prompt deliquescence and efflorescence of aerosol nanoparticles, Atmos. Chem. Phys., 6, 4633–4642, doi:10.5194/acp-6-4633-2006, 2006.

Bloss, C., Wagner, V., Bonzanini, A., Jenkin, M. E., Wirtz, K., Martin-Reviejo, M., and Pilling, M. J.: Evaluation of detailed aromatic mechanisms (MCMv3 and MCMv3.1) against environmental chamber data, Atmos. Chem. Phys., 5, 623–639, doi:10.5194/acp-5-623-2005, 2005.

Brown, S. S.: Absorption spectroscopy in high-finesse cavities for atmospheric studies, Chem. Rev., 103, 5219–5238, 2003.

Dibble, T. S.: Intramolecular Hydrogen Bonding and Double H-Atom Transfer in Peroxy and Alkoxy Radicals from Isoprene, J. Phys. Chem. A, 108, 2199–2207, 2004a.

Dibble, T. S.: Prompt Chemistry of Alkenoxy Radical Products of the Double H-Atom Transfer of Alkoxy Radicals from Isoprene, J. Phys. Chem. A, 108, 2208–2215, 2004b.

Dixneuf, S., Ruth, A. A., Vaughan, S., Varma, R. M., and Orphal, J.: The time dependence of molecular iodine emission from Laminaria digitata, Atmos. Chem. Phys., 9, 823–829, doi:10.5194/acp-9-823-2009, 2009.

Fayt, C. and Van Roosendael, M.: WinDOAS User Manual, 2001.

Fiedler, S. E., Hese, A., and Ruth, A. A.: Incoherent broad-band cavity-enhanced absorption spectroscopy, Chem. Phys. Lett., 371, 284–294, 2003.

Frankenberg, C., Platt, U., and Wagner, T.: Iterative maximum a posteriori (IMAP)-DOAS for retrieval of strongly absorbing trace gases: Model studies for CH4 and CO2 retrieval from near infrared spectra of SCIAMACHY onboard ENVISAT, Atmos. Chem. Phys., 5, 9–22, doi:10.5194/acp-5-9-2005, 2005.

Fu, T. M., Jacob, D. J., Wittrock, F., Burrows, J. P., Vrekoussis, M., and Henze, D. K.: Global budgets of atmospheric glyoxal and methylglyoxal, and implications for formation of secondary organic aerosols, J. Geophys. Res., 113, doi:10.1029/2007JD009505, D15303, 2008.

Galloway, M. M., Chhabra, P. S., Chan, A. W. H., Surratt, J. D., Flagan, R. C., Seinfeld, J. H., and Keutsch, F. N.: Glyoxal uptake on ammonium sulphate seed aerosol: reaction products and reversibility of uptake under dark and irradiated conditions, Atmos. Chem. Phys., 9, 3331–3345, doi:10.5194/acp-9-3331-2009, 2009.

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 NO2, Envir. Sci. Technol., 42, 890–895, 2008.

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, Envir. Sci. Technol., 39, 8728–8735, 2005.

Hermans, C.,Measurement of absorption cross sections and spectroscopic molecular parameters: O2 and its collisonal induced absorption: http://www.aeronomie.be/spectrolab/o2.htm4-9-20104-26-3010.

Herriott, D. R. and Schulte, H. J.: Folded Optical Delay Lines, Appl.Opt., 4, 883–889, 1965.

Hönninger, G.: Referenzspektren reaktiver Halogenverbindungen für DOAS-Messungen, 1999.

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.

Ip, H. S. S., Huang, X. H. H., and Yu, J. Z.: Effective Henry's law constants of glyoxal, glyoxylic acid, and glycolic acid, Geophys. Res. Lett., 36, L01802, doi:10.1029/2008GL036212, 2009.

Jang, M., Czoschke, N. M., Lee, S., and Kamens, R. M.: Heterogeneous Atmospheric Aerosol Production by Acid-Catalyzed Particle-Phase Reactions, Science, 298, 814–817, 2002.

Kern, C., Trick, S., Rippel, B., and Platt, U.: Applicability of light-emitting diodes as light sources for active differential optical absorption spectroscopy measurements, Appl. Opt., 45, 2077–2088, 2006.

Kurosu, T., Chance, K., and Volkamer, R.: Global measurements of OClO, BrO, HCHO, and CHO-CHO from the Ozone Monitoring Instruments on EOS Aura, EOS Trans. EGU, 86, Fall Meet. Suppl. Abstract A54B-01, 2005.

Langridge, J. M., Ball, S. M., and Jones, R. L.: A compact broadband cavity enhanced absorption spectrometer for detection of atmospheric NO2 using light emitting diodes, Analyst, 131, 916–922, 2006.

Langridge, J. M., Ball, S. M., Shillings, A. J. L., and Jones, R. L.: A broadband absorption spectrometer using light emitting diodes for ultrasensitive, in situ trace gas detection, Rev. Sci. Instrum., 79, 2008a.

Langridge, J. M., Laurila, T., Watt, R. S., Jones, R. L., Kaminski, C. F., and Hult, J.: Cavity enhanced absorption spectroscopy of multiple trace gas species using a supercontinuum radiation source, Opt. Express, 16, 10178–10188, 2008b.

Liggio, J., Li, S. M., and McLaren, R.: Reactive uptake of glyoxal by particulate matter, J. Geophys. Res., 110, doi:10.1029/2004JD005113, D10304, 2005.

Martin, J. C. G., Spietz, P., and Burrows, J. P.: Kinetic and mechanistic studies of the I-2/O-3 photochemistry, J. Phys. Chem. A, 111, 306–320, 2007.

Meinen, J., Thieser, J., Platt, U., and Leisner, T.: Using a high finesse optical resonator to provide a long light path for differential optical absorption spectroscopy: CE-DOAS, Atmos. Meas. Tech., 8, 10665–10695, 2008.

Meller, R., Raber, W., Crowley, J. N., Jenkin, M. E., and Moortgat, G. K.: The UV-visible absorption spectrum of methylglyoxal, J. Photochem. Photobio., A, 62, 163–171, 1991.

Miles, R. E. H., Rudic, S., Orr-Ewing, A. J., and Reid, J. P.: Measurements of the wavelength dependent extinction of aerosols by cavity ring down spectroscopy, Phys. Chem. Chem. Phys., 12, 3914–3920, 2010.

Myriokefalitakis, S., Vrekoussis, M., Tsigaridis, K., Wittrock, F., Richter, A., Brühl, C., Volkamer, R., Burrows, J. P., and Kanakidou, M.: The influence of natural and anthropogenic secondary sources on the glyoxal global distribution, Atmos. Chem. Phys., 8, 4965–4981, doi:10.5194/acp-8-4965-2008, 2008.

Okeefe, A. and Deacon, D. A. G.: Cavity Ring-Down Optical Spectrometer for Absorption-Measurements Using Pulsed Laser Sources, Rev. Sci. Instrum., 59, 2544–2551, 1988.

Orphal, J. and Ruth, A. A.: High-resolution Fourier-transform cavity-enhanced absorption spectroscopy in the near-infrared using an incoherent broad-band light source, Opt. Express, 16, 19232–19243, 2008.

Platt, U., Meinen, J., Pöhler, D., and Leisner, T.: Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) - applicability and corrections, Atmos. Meas. Tech., 2, 713-723, doi:10.5194/amt-2-713-2009, 2009.

Platt, U. and Stutz, J.: Differential optical absorption spectroscopy: principles and applications, 1, Springer Verlag, Berlin, Germany, 2008.

Pope, C. A. and Dockery, D. W.: Health effects of fine particulate air pollution: Lines that connect, J. Air Waste Manage. Assoc., 56, 709–742, 2006.

Rothman, L. S., Gordon, I. E., Barbe, A., Benner, D. C., Bernath, P. F., Birk, M., Boudon, V., Brown, L. R., Campargue, A., Champion, J. P., Chance, K., Coudert, L. H., Dana, V., Devi, V. M., Fally, S., Flaud, J. M., Gamache, R. R., Goldman, A., Jacquemart, D., Kleiner, I., Lacome, N., Lafferty, W. J., Mandin, J. Y., Massie, S. T., Mikhailenko, S. N., Miller, C. E., Moazzen-Ahmadi, N., Naumenko, O. V., Nikitin, A. V., Orphal, J., Perevalov, V. I., Perrin, A., Predoi-Cross, A., Rinsland, C. P., Rotger, M., Simeckov$\beta $, M., Smith, M. A. H., Sung, K., Tashkun, S. A., Tennyson, J., Toth, R. A., Vandaele, A. C., and Vander Auwera, J.: The HITRAN 2008 molecular spectroscopic database, J. Quant. Spectrosc. Radiat. Transfer, 110, 533–572, 2006.

Schuster, G., Labazan, I., and Crowley, J. N.: A cavity ring down/cavity enhanced absorption device for measurement of ambient NO3 and N2O$_5$, Atmos. Meas. Tech., 2, 1–13, doi:10.5194/amt-2-1-2009, 2009.

Sihler, H., Kern, C., Pohler, D., and Platt, U.: Applying light-emitting diodes with narrowband emission features in differential spectroscopy, Opt.Lett., 34, 3716–3718, 2009.

Sinreich, R., Volkamer, R., Filsinger, F., Frieß, U., Kern, C., Platt, U., Sebasti$\acute\rm a$n, O., and Wagner, T.: MAX-DOAS detection of glyoxal during ICARTT 2004, Atmos. Chem. Phys., 7, 1293–1303, doi:10.5194/acp-7-1293-2007, 2007.

Stavrakou, T., Müller, J.-F., De Smedt, I., Van Roozendael, M., Kanakidou, M., Vrekoussis, M., Wittrock, F., Richter, A., and Burrows, J. P.: The continental source of glyoxal estimated by the synergistic use of spaceborne measurements and inverse modelling, Atmos. Chem. Phys., 9, 8431–8446, doi:10.5194/acp-9-8431-2009, 2009.

Taraborrelli, D., Lawrence, M. G., Butler, T. M., Sander, R., and Lelieveld, J.: Mainz Isoprene Mechanism 2 (MIM2): an isoprene oxidation mechanism for regional and global atmospheric modelling, Atmos. Chem. Phys., 9, 2751–2777, doi:10.5194/acp-9-2751-2009, 2009.

Triki, M., Cermak, P., Mejean, G., and Romanini, D.: Cavity-enhanced absorption spectroscopy with a red LED source for NOx trace analysis, Appl. Phys. B, 91, 195–201, 2008.

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 NO2 visible and near-infrared absorption cross sections: Temperature and pressure effects, J. Geophys. Res., 107, 4348, doi:10.1029/2001JD000971, 2002.

Varma, R. M., Venables, D. S., Ruth, A. A., Heitmann, U., Schlosser, E., and Dixneuf, S.: Long optical cavities for open-path monitoring of atmospheric trace gases and aerosol extinction, Appl. Opt., 48, B159–B171, 2009.

Vaughan, S., Gherman, T., Ruth, A. A., and Orphal, J.: Incoherent broad-band cavity-enhanced absorption spectroscopy of the marine boundary layer species I-2, IO and OIO, Phys. Chem. Chem. Phys., 10, 4471–4477, 2008.

Venables, D. S., Gherman, T., Orphal, J., Wenger, J. C., and Ruth, A. A.: High sensitivity in situ monitoring of NO3 in an atmospheric simulation chamber using incoherent broadband cavity-enhanced absorption spectroscopy, Envir. Sci. Technol., 40, 6758–6763, 2006.

Villalobos-Pietrini, R., Hernandez-Mena, L., Amador-Munoz, O., Munive-Colin, Z., Bravo-Cabrera, J. L., Gómez-Arroyo, S., Frias-Villegas, A., Waliszewski, S., Ramirez-Pulido, J., and Ortiz-Muniz, R.: Biodirected mutagenic chemical assay of PM10 extractable organic matter in Southwest Mexico City, Mutat.Res./Gen.Toxicol.Environ.Mutag., 634, 192–204, 2007.

Volkamer, R., Barnes, I., Platt, U., Molina, L. T., and Molina, M. J.: Remote Sensing of Glyoxal by Differential Optical Absorption Spectroscopy (DOAS): Advancements in Simulation Chamber and Field Experiments, 2005a.

Volkamer, R., Coburn, S., Dix, B., and Sinreich, R.: The Eastern Pacific Ocean is a source for short lived trace gases: Glyoxal and Iodine Oxide, April, 2010.

Volkamer, R., Etzkorn, T., Geyer, A., and Platt, U.: Correction of the oxygen interference with UV spectroscopic (DOAS) measurements of monocyclic aromatic hydrocarbons in the atmosphere, Atmos. Environ., 32, 3731–3747, 1998.

Volkamer, R., Ziemann, P. J., and Molina, M. J.: Secondary Organic Aerosol Formation from Acetylene (C$2$H2): seed effect on SOA yields due to organic photochemistry in the aerosol aqueous phase, Atmos. Chem. Phys., 9, 1907–1928, doi:10.5194/acp-9-1907-2009, 2009.

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, 2005b.

Volkamer, R., San Martini, F., 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.

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. Photochem. Photobio., A, 172, 35–46, 2005c.

Vrekoussis, M., Wittrock, F., Richter, A., and Burrows, J. P.: Temporal and spatial variability of glyoxal as observed from space, Atmos. Chem. Phys., 9, 4485–4504, doi:10.5194/acp-9-4485-2009, 2009.

Washenfelder, R. A., Langford, A. O., Fuchs, H., and Brown, S. S.: Measurement of glyoxal using an incoherent broadband cavity enhanced absorption spectrometer, Atmos. Chem. Phys., 8, 7779–7793, doi:10.5194/acp-8-7779-2008, 2008.

White, J. U.: Long Optical Paths of Large Aperture, J. Opt. Soc. Am., 32, 285–288, 1942.

Wiedensohler, A.: An approximation of the bipolar charge distribution for particles in the submicron size range, J. Aerosol Sci., 19, 387–389, 1988.

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.

Wu, T., Zhao, W., Chen, W., Zhang, W., and Gao, X.: Incoherent broadband cavity enhanced absorption spectroscopy for in situ measurements of NO2 with a blue light emitting diode, Appl. Phys. B, 94, 85–94, 2009.