ACP Atmospheric Chemistry and Physics ACP Atmos. Chem. Phys. 1680-7324 Copernicus Publications Göttingen, Germany 10.5194/acp-8-4947-2008 Twelve years of global observations of formaldehyde in the troposphere using GOME and SCIAMACHY sensors De Smedt I. 1 Müller J.-F. 1 Stavrakou T. 1 van der A R. 2 Eskes H. 2 Van Roozendael M. 2 Belgian Institute for Space Aeronomy (BIRA-IASB), Avenue Circulaire, 3, B-1180, Brussels, Belgium Royal Netherlands Meteorological Institute (KNMI), Wilhelminalaan 10, 3732 GK, De Bilt, The Netherlands 27 08 2008 8 16 4947 4963 Copyright: © 2008 I. De Smedt et al. 2008 This work is licensed under the Creative Commons Attribution 3.0 Unported License. To view a copy of this licence, visit https://creativecommons.org/licenses/by/3.0/ This article is available from https://acp.copernicus.org/articles/8/4947/2008/acp-8-4947-2008.html The full text article is available as a PDF file from https://acp.copernicus.org/articles/8/4947/2008/acp-8-4947-2008.pdf

This work presents global tropospheric formaldehyde columns retrieved from near-UV radiance measurements performed by the GOME instrument onboard ERS-2 since 1995, and by SCIAMACHY, in operation on ENVISAT since the end of 2002. A special effort has been made to ensure the coherence and quality of the CH<sub>2</sub>O dataset covering the period 1996–2007. Optimised DOAS settings are proposed in order to reduce the impact of two important sources of error in the derivation of slant columns, namely, the polarisation anomaly affecting the SCIAMACHY spectra around 350 nm, and a major absorption band of the O<sub>4</sub> collision complex centred near 360 nm. The air mass factors are determined from scattering weights generated using radiative transfer calculations taking into account the cloud fraction, the cloud height and the ground albedo. Vertical profile shapes of CH<sub>2</sub>O are provided by the global CTM IMAGES based on an up-to-date representation of emissions, atmospheric transport and photochemistry. A comprehensive error analysis is presented. This includes errors on the slant columns retrieval and errors on the air mass factors which are mainly due to uncertainties in the a priori profile and in the cloud properties. The major features of the retrieved formaldehyde column distribution are discussed and compared with previous CH<sub>2</sub>O datasets over the major emission regions.

 References Abbot, D. S., Palmer, P. I., Martin, R. V., Chance, K. V., Jacob, D. J., and Guenther, A.: Seasonal and interannual variability of North American isoprene emissions as determined by formaldehyde column measurements from space, Geophys. Res. Lett., 30, 17, 1886, https://doi.org/10.1029/2003GL017336, 2003. Andreae, M. O. and Merlet, P.: Emission of trace gases and aerosols from biomass burning, Glob. Biogeochem. Cyc., 15, 955–966, 2001. Bey, I., Jacob, D. J., Yantosca, R. M., Logan, J. A., Field, B. D., Fiore, A. M., Li, Q., Liu, H. Y., Mickley, L. J., and Schultz, M. G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106(D19), 23 073–23 096, https://doi.org/029/2001JD000807, 2001. Boersma, K. F., Eskes, H. J., and Brinksma., E. J.: Error analysis for tropospheric NO<sub>2</sub> retrieval from space, J. Geophys. Res., 109, D04311, https://doi.org/10.1029/2003JD003962, 2004. Bogumil, K., Orphal, J., Homann, T., Voigt, S., Spietz, P., \mboxFleischmann, O. C., Vogel, A., Hartmann, M., Kromminga, H., Bovensmann, H., Frerick, J., and Burrows, J. P.: Measurements of molecular absorption spectra with the SCIAMACHY pre-flight model: instrument characterization and reference data for atmospheric remote-sensing in the 230–2380 nm region, J. Photochem. Photobiology A, 157(2–3), 167–184, 2003. Bovensmann, H., Burrows, J. P., Buchwitz, M., Frerick, J., No\"el, S., Rozanov, V. V., Chance, K. V., and Goede, A. H. P.: \mboxSCIAMACHY – Mission objectives and measurement modes, J. Atmos. Sci., 56(2), 127–150, 1999. Buchwitz, M., de Beek, R., Burrows, J. P., Bovensmann, H., Warneke, T., Notholt, J., Meirink, J. F., Goede, A. P. H., Bergamaschi, P., Körner, S., Heimann, M., Müller, J.-F., and Schulz, A.: Atmospheric methane and carbon dioxide from SCIAMACHY satellite data: Initial comparison with chemistry and transport models, Atmos. Chem. Phys., 5, 941–962, 2005. Burrows, J. P., Dehn, A., Deters, B., Himmelmann, S., Richter, A., Voigt S., and Orphal, J.: Atmospheric remote-sensing reference data from GOME: 1. Temperature-dependent absorption cross sections of NO<sub>2</sub> in the 231–794 nm range, J. Quant. Spectrosc. Rad. Transfer, 60, p. 1025, 1998. Burrows, J. P., Richter, A., Dehn, A., Deters, B., Himmelmann, S., Voigt, S., and Orphal, J.: Atmospheric remote-sensing reference data from GOME: 2. Temperature-dependent absorption cross sections of O3 in the 231–794 nm range, J. Quant. Spectrosc. Rad. Transfer,~61, 509–517, 1999a. Burrows, J. P., Weber, M., Buchwitz, M., Rozanov, V. V., Ladstädter-Weissenmayer, A., Richter, A., de Beek, R., Hoogen, R., Bramstedt, K., Eichmann, K.-U., Eisinger, M., and Perner, D.: The Global Ozone Monitoring Experiment (GOME): mission concept and first scientific results, J. Atmos. Sci., 56, 151–175, 1999b. Cantrell, C. A., Davidson, J. A., McDaniel, A. H., Shetter, R. E., and Calvert, J. G.: Temperature-dependent formaldehyde cross sections in the near-ultraviolet spectral region, J. Phys. Chem., 94, 3902–3908, 1990. Chance, K. and Spurr, R. J. D.: Ring effect studies: Rayleigh scattering including molecular parameters for rotational Raman scattering, and the Fraunhofer spectrum, Applied Optics, 36, 5224–5230, 1997. Chance, K., Palmer, P. I., Spurr, R. J. D., Martin, R. V., Kurosu, T. P. and Jacob, D. J.: Satellite observations of formaldehyde over North America from GOME, Geophys. Res. Lett., 27(21), 3461–3464, 2000. De Smedt, I., Van Roozendael, M., Van der A, R., Eskes, H., and Müller, J.-F.: Retrieval of formaldehyde columns from GOME as part of the GSE PROMOTE and comparison with 3D-CTM calculations, Proceedings of the Atmospheric Science Conference, ESA, 2006. Emmons, L. K., Hauglustaine, D. A., Muller, J.-F., Carroll, M. A., Brasseur, G. P., Brunner, D., Staehelin, J., Thouret, V., Marenco, A.: Data composites of airborne observations of tropospheric ozone and its precursors, J. Geophys. Res., 105, 16, 20 497–20 538, 2000. Eisinger, M. and Burrows, J. P.: Tropospheric sulfur dioxide observed by the ERS-2 GOME instrument, Geophys. Res. Lett., 25(22), 4177–4180, 1998. Eskes, H. J., Isaksen, I. S. A., Zerefos, C. S., Platt, U., Hansen, G., Zehner, C., Casale, R.: GOME assimilated and validated ozone and NO2 fields for scientific users and model validation, Final Report (http://www.knmi.nl/goa), European Commission, Fifth Framework Programme, Environment and Sustainable Development, 1998–2002, 2003a. Eskes, H. J. and Boersma, K. F.: Averaging kernels for DOAS total-column satellite retrievals, Atmos. Chem. Phys., 3, 1285–1291, 2003b. Fishman, J., Hoell Jr., J. M., Bendura, R. J., McNeal, R. J., and Kirchhoff, V. W. J. H.: NASA GTE TRACE-A experiment (September–October 1992): Overview, J. Geophys. Res., 101(D19), 23 865–23 880, https://doi.org/10.1029/96JD00123, 1996. Fu, T.-M., Jacob, D. J., Palmer, P. I., Chance, K., Wang, Y. X., Barletta, B., Blake, D. R., Stanton, J. C., Pilling, M. J.: Space-based formaldehyde measurements as constraints on volatile organic compound emissions in East and South Asia, J. Geophys. Res., 112, D06312, https://doi.org/10.1029/2006JD007853, 2007. Frankenberg, C., Meirink, J. F., vanWeele, M., Platt, U.,Wagner, T.: Assessing methane emissions from global space-borne observations, Science, 308, 5724, 1010–1014, https://doi.org/10.1126/science.1106644, 2005. Giglio, L.: Characterization of the tropical diurnal fire cycle using VIRS and MODIS observations, Rem. Sens. Environ., 108, 407–421, 2007. Grainger, J. F. and Ring, J.: Anomalous Fraunhofer line profiles, Nature, 193, p. 762, 1962. Gratien, A., Picquet-Varrault, B., Orphal, J., Perraudin, E., Doussin, J.-F., Flaud, J.-M.: Laboratory intercomparison of the formaldehyde absorption cross sections in the infrared (1660–1820 cm<sup>&minus;1</sup>) and ultraviolet (300–360 nm) spectral regions, J. Geophys. Res., 112(D5), D05305, https://doi.org/10.1029/2006JD007201, 2007. Greenblatt, G. D., Orlando, J. J., Burkholder, J. B., and Ravishankara, A. R.: Absorption measurements of oxygen between 330 and 1140 nm, J. Geophys. Res., 95(D11), 18 577–18 582, https://doi.org/10.1029/90JD01375, 1990. Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., McKay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A global model of natural volatile organic compound emissions, J. Geophys. Res., 100(D5), 8873–8892, https://doi.org/10.1029/94JD02950, 1995. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of the global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181–3210, 2006. Heckel, A , A Richter, T Tarsu, F Wittrock, C Hak, I Pundt, W Junkermann, and J P Burrows, MAX-DOAS measurements of formaldehyde in the Po-Valley, Atmos. Chem. Phys., 5, 909–918, 2005. Jones, N. B., Riedel, K., Allan, W., Wood, S.,~Palmer, P I.,~Chance, K., and Notholt, J.: Long-term tropospheric formaldehyde concentrations deduced from ground-based fourier transform solar infrared measurements, Atmos. Chem. Phys.,~7,~14 543–14 568,~2007. Khokhar, M. F., Frankenberg, C., Beirle, S., Kühl, S., Van Roozendael, M., Richter, A., Platt U., and Wagner, T.: Satellite observations of atmospheric SO2 from volcanic eruptions during the time period of 1996 to 2002, J. Adv. Space Res., 36(\refeq5), 879–887, https://doi.org/10.1016/j.asr.2005.04.114, 2005. Koelemeijer, R. B. A., Stammes, P., Hovenier, J. W., and de Haan, J. F.: Global distributions of effective cloud fraction and cloud top pressure derived from oxygen A band spectra measured by the Global Ozone Monitoring Experiment: comparison to ISCCP data, J. Geophys. Res., 107(D12), 4151, https://doi.org/10.1029/2001JD000840, 2002. Koelemeijer, R. B. A., de Haan, J. F., and Stammes, P.: A database of spectral surface reflectivity in the range 335–772 nm derived from 5.5 years of GOME observations, J. Geophys. Res., 108(D2), 4070, https://doi.org/10.1029/2002JD002429, 2003. Kromminga, H., Orphal, J., Spietz, P., Voigt, S., and Burrows, J. P.: New measurements of OClO absorption cross sections in the 325–435 nm and their temperature dependence between 213–293 K, J. Photochem. Photobio. A., 157, 149–160, 2003. Kühl, S., Wilms-Grabe, W., Beirle, S., Frankenberg, C., Grzegorski, M., Hollwedel, J., Khokhar, F., Kraus, S., Platt, U., Sanghavi, S., von Friedeburg, C., and Wagner, T. P.: Stratospheric chlorine activation in the arctic winters 1995/1996 to 2001/2002 derived from GOME OClO measurements, Adv. Space Res., 34, 798–803, 2004. Kylling, K., Stamnes, P., and~Tsay, S.-C.: A reliable and efficient two-stream algorithm for spherical radiative transfer: Documentation of accuracy in realistic layered media, J. Atmos. Phys., 21, 115–150, 1995. Marbach, T., Beirle, S., Hollwedel, J., Platt, U., and Wagner, T.: Identification of tropospheric emission sources from satellite observations: Synergistic use of trace gas measurements of formaldehyde (HCHO), and nitrogen dioxide (NO$_2)$, Proceedings of the ENVISAT & ERS Symposium, ESA publication SP-572, (CD-ROM), 2004. Martin, R. V., Chance, K., Jacob, D. J., Kurosu, T. P., Spurr, R. J. D., Bucsela, E., Gleason, J. F., Palmer, P. I., Bey, I., Fiore, A. M., Li, Q., Yantosca, R. M., and Koelemeijer, R. B. A.: An improved retrieval of tropospheric nitrogen dioxide from GOME, J. Geophys. Res., 107(D20), 4437, https://doi.org/10.1029/2001JD001027, 2001. Martin, R. V., Jacob, D. J., Chance, K. V., Kurosu, T. P., Palmer, P. I., and Evans, J.: Global inventory on nitrogen dioxide emissions constrained by space-based observations of NO<sub>2</sub> Columns, J. Geophys. Res., 108(D17), 4537, https://doi.org/10.1029/2003JD003453, 2003. Martin, R. V., Parrish, D. D., Ryerson, T. B., Nicks Jr., D. K., Chance, K., Kurosu, T. P., Fried, A., Wert, B. P., Jacob, D.J., and Sturges, E. D.: Evaluation of GOME satellite measurements of tropospheric NO2 and HCHO using regional data from aircraft campaigns in the southeastern US, J. Geophys. Res., 109, D24307, https://doi.org/10.1029/2004JD004869, 2004. Meller, R., and Moortgat, G. K.: Temperature dependence of the absorption cross section of HCHO between 223 and 323 K in the wavelength range 225–375 nm, J. Geophys. Res., 105(D6), 7089–7102, https://doi.org/10.1029/1999JD901074, 2000. Millet, D, Jacob, D. J., Turquety, S., Hudman, R. C., Wu, S., Fried, A., Walega, J., Heikes, B. G., Blake, D. R., Singh, H. B., Anderson, B. E., and Clarke, A. D.: Formaldehyde distribution over North America: Implications for satellite retrievals of formaldehyde columns and isoprene emissions, J. Geophys. Res., 111, D24S02, https://doi.org/10.1029/2005JD006853, 2006. Monks, P.: Gas-phase radical chemistry in the troposphere, Chem. Soc. Rev., 34, 376-395., 2005. Müller, J.-F. and Stavrakou, T.: Inversion of CO and NO<sub>x</sub> emissions using the adjoint of the IMAGES model, Atmos. Chem. Phys., 5, 1157–1186, 2005. Müller, J.-F., Stavrakou, T., Wallens, S., De Smedt, I., Van Roozendael, M., Potosnak, M., Rinne, J., Munger, B., Goldstein, A., and Guenther, A.: Global isoprene emissions estimates using MEGAN, ECMWF analyses and a detailed canopy environment model, Atmos. Chem. Phys., 8, 1329–1341, 2008. Olivier, J. G. J., Berdowski, J. J. M., Peters, J. A. H. W., Bakker, J. Visschedijk, A. J. H., and Bloos, J.-P. J.: Applications of EDGAR. Including a description of EDGAR 3.0: reference database with trend data for 1970–1995, RIVM report no. 773301 001/NOP report no. 410200 051, RIVM, Bilthoven, 51–85, 2001. Platt, U.: Differential optical absorption spectroscopy (DOAS), in: Air Monitoring by Spectroscopic Techniques, edited by: Sigrist, M. W., Chemical Analysis Series, Wiley, New York, USA, 127, 27–84, 1994. Palmer, P. I., Jacob, D. J., Chance, K., Martin, R. V., Spurr, R. J. D., Kurosu, T. P., Bey, I., Yantosca, R., Fiore, A., and Li, Q.: Air-mass factor formulation for spectroscopic measurements from satellites: application to formaldehyde retrievals from GOME, J. Geophys. Res., 106(D13), 14 539–14 550, https://doi.org/10.1029/2000JD900772, 2001. Palmer, P. I., Jacob, D. J., Fiore, A. M., Martin, R. V., Chance, K., and Kurosu, T. P.: Mapping isoprene emissions over North America using formaldehyde column observations from space, J. Geophys. Res., 108(D6), 4180, https://doi.org/10,1029/2002JD002153, 2003. Palmer, P. I., Abbot, D. S., Fu, T.-M., Jacob, D. J., Chance, K., Kurosu, T., Guenther, A., Wiedinmyer, C., Stanton, J., Pilling, M., Pressley, S., Lamb, B., and Sumner, A. L.: Quantifying the seasonal and interannual variability of North American isoprene emissions using satellite observations of formaldehyde column, J. Geophys. Res., 111, D12315, https://doi.org/10.1029/2005JD006689, 2006. Richter, A., Wittrock, F., Eisinger, M., and Burrows, J. P.: GOME observations of tropospheric BrO in northern hemispheric spring and summer 1997, Geophys. Res. Lett., 25, 2683–2686, 1998. Richter, A. and Wagner, T.: Diffuser plate spectral structures and their influence on GOME slant columns, Tech. rep., Inst. Env. Phys., Univ. Bremen and Inst. Env. Phys., Univ. Heidelberg, 2001. Richter, A. and Burrows, J. P.: Tropospheric NO<sub>2</sub> from GOME measurements, Adv. Space Res., 29, 1673–1683, 2002. Richter, A., Wittrock, F., Weber, M., Beirle, S., Kühl, S., Platt, U., Wagner, T., Wilms-Grabe, W., and Burrows, J. P.: GOME observations of stratospheric trace gas distributions during the splitting vortex event in the Antarctic winter 2002 Part I: Measurements, J. Atmos. Sci., 62(\refeq3), 778–785, 2005a. Richter, A., Burrows, J. P., Nüß, H., Granier, C., and Niemeier, U.: Increase in tropospheric nitrogen dioxide over China observed from space, Nature, 437, 129–132, https://doi.org/10.1038/nature04092, 2005b. Rodgers, C. D.: Inverse Methods for Atmospheric Sounding, Theory and Practice, World Scientific Publishing, Singapore-New-Jersey-London-Hong Kong, 105–106, 2000. Saunders, S. M., Jenkin, M. E.,Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, 2003. Seinfeld, J. H., Pandis, S. N.: Atmospheric Chemistry and Physics: From air pollution to climate change, Wiley-Interscience, 204–283, 2006. Singh, H. B., Brune, W. H., Crawford, J. H., Jacob, D. J., and Russell, P. B.: Overview of the summer 2004 Intercontinental Chemical Transport Experiment–North America (INTEX-A), J. Geophys. Res., 111, D24S01, https://doi.org/10.1029/2006JD007905, 2006. Shim, C., Wang, Y., Choi, Y., Palmer, P. I., Abbot, D. S., and Chance, K.: Constraining global isoprene emissions with Global Ozone Monitoring Experiment (GOME) formaldehyde column measurements, J. Geophys. Res., 110, D24301, https://doi.org/10.1029/2004JD005629, 2005. Stavrakou, T., Müller, J.-F., De Smedt, I., Van Roozendael, M., van der Werf, G., Giglio, L.: One decade of pyrogenic NMVOC emissions deduced from HCHO satellite data, Proceedings of the 2nd ACCENT Symposium, Urbino, Italy, July 2007. Stavrakou, T., Müller, J.-F., De Smedt, I., van Roozendael, M., van der Werf, G., Giglio, L., and Guenther, A.: Evaluating the performance of pyrogenic and biogenic emission inventories against one decade of space-based formaldehyde columns, Atmos. Chem. Phys. Discuss., accepted, 2008. Taylor, J. R.: An introduction to error analysis, University Science Books, 81–91 and 153–159, 1982. Theys, N., Van Roozendael, M., Hendrick, F., Fayt, C., Hermans, C., Baray, J.-L., Goutail, F., Pommereau, J.-P., and De Mazière, M.: Retrieval of stratospheric and tropospheric BrO columns from multi-axis DOAS measurements at Reunion Island (21&deg;S, 56&deg;E), Atmos. Chem. Phys., 7, 4733–4749, 2007. Thomas, W., Hegels, E., Slijkhuis, S., Spurr, R., and Chance, K.: Detection of biomass burning combustion products in Southeast Asia from backscatter data taken by the GOME spectrometer, Geophys. Res. Lett., 25, 1317–1320, 1998. van der A, R. J., Peters, D. H. M. U., Eskes, H., Boersma, K. F., Van Roozendael, M., De Smedt, I., Kelder, H. M.: Detection of the trend and seasonal variation in tropospheric NO<sub>2</sub> over China, J. Geophys. Res., 111, D12317, https://doi.org/10.1029/2005JD006594, 2006. van der Werf, G. R., Randerson, J. T., Collatz, G. J., Giglio, L., Kasibhatla, P. S., Arellano Jr., A. F., Olsen, S. C., and Kasischke, E. S.: Continental scale partitioning of fire emissions during the 1997 to 2001 El Nino/La Nina period, Science, 303, 73–76, 2004. van der Werf, G. R., Randerson, J. T., Giglio, L., Collatz, G. J., Kasibhatla, P. S., A., Arellano Jr., F.: Interannual variability in global biomass burning emissions from 1997 to 2004, Atmos. Chem. Phys., 6, 3423–3441, 2006. Vountas, M., Rozanov, V. V., and Burrows, J. P.: Ring effect: Impact of rotational raman scattering on radiative transfer in earth's atmosphere, J. Quant. Spectrosc. Radiat. Transfer., 60, 943–961, 1998. Wahner, A., Ravishankara, A. R., Sander, S. P., andFriedl, R. R.: Absorption cross section of BrO between 312 and 385 nm at 298 and 223 K, Chem. Phys. Lett., 152, 507–512, 1988. Wenig, M., Spichtinger, N., Stohl, A., Held, G., Beirle, S.,Wagner, T., Jahne, B., and Platt, U.: Intercontinental transport of nitrogen oxide pollution plumes, Atmos. Chem. Phys., 3, 387–393, 2003. Wittrock, F., Richter, A., Ladstätter-Weißenmayer, A., and Burrows, J. P.: Global observations of formaldehyde, Proceedings of the ERS-ENVISAT symposium, ESA publication SP-461, CD-ROM, ISBN 92-9092-685-6, 2000. Wittrock, F.: The Retrieval of oxygenated volatile organic compounds by remote sensing techniques, PhD Thesis, Bremen University, 2006. 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, https://doi.org/10.1029/2006GL026310, 2006.