ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-10743-2011 TES ammonia retrieval strategy and global observations of the spatial and seasonal variability of ammonia Shephard M. W. 1 7 Cady-Pereira K. E. 2 Luo M. 3 Henze D. K. 4 Pinder R. W. 5 Walker J. T. 5 Rinsland C. P. 8 9 Bash J. O. 5 Zhu L. 4 Payne V. H. 2 Clarisse L. 6 Environment Canada, Downsview, Ontario, Canada Atmospheric and Environmental Research, Inc., Lexington, Massachusetts, USA Jet Propulsion Laboratory, California Institute of Technology Pasadena, CA, USA University of Colorado, Boulder, Colorado, USA US Environmental Protection Agency, Research Triangle Park, North Carolina, USA Spectroscopie de l'Atmosphere, Service de Chimie Quantique et Photophysique, Universite Libre de Bruxelles (U.L.B.), Brussels, Belguim presently at: Atmospheric and Climate Applications (ACApps), Inc., East Gwillimbury, Ontario, Canada formerly at: NASA Langley Research Center, Hampton, VA, USA deceased 31 10 2011 11 20 10743 10763 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/11/10743/2011/acp-11-10743-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/10743/2011/acp-11-10743-2011.pdf

Presently only limited sets of tropospheric ammonia (NH<sub>3</sub>) measurements in the Earth's atmosphere have been reported from satellite and surface station measurements, despite the well-documented negative impact of NH<sub>3</sub> on the environment and human health. Presented here is a detailed description of the satellite retrieval strategy and analysis for the Tropospheric Emission Spectrometer (TES) using simulations and measurements. These results show that: (i) the level of detectability for a representative boundary layer TES NH<sub>3</sub> mixing ratio value is ~0.4 ppbv, which typically corresponds to a profile that contains a maximum level value of ~1 ppbv; (ii) TES NH<sub>3</sub> retrievals generally provide at most one degree of freedom for signal (DOFS), with peak sensitivity between 700 and 900 mbar; (iii) TES NH<sub>3</sub> retrievals show significant spatial and seasonal variability of NH<sub>3</sub> globally; (iv) initial comparisons of TES observations with GEOS-CHEM estimates show TES values being higher overall. Important differences and similarities between modeled and observed seasonal and spatial trends are noted, with discrepancies indicating areas where the timing and magnitude of modeled NH<sub>3</sub> emissions from agricultural sources, and to lesser extent biomass burning sources, need further study.

 References % vor jede Referenz Adams, P. J., Seinfeld, J. H., and Koch, D. M.: Global concentrations of tropospheric sulfate, nitrate, and ammonium aerosol simulated in a general circulation model, J. Geophys. Res., 104, 13791–13823, 1999. Adon, M., Galy-Lacaux, C., Yoboué, V., Delon, C., Lacaux, J. P., Castera, P., Gardrat, E., Pienaar, J., Al Ourabi, H., Laouali, D., Diop, B., Sigha-Nkamdjou, L., Akpo, A., Tathy, J. P., Lavenu, F., and Mougin, E.: Long term measurements of sulfur dioxide, nitrogen dioxide, ammonia, nitric acid and ozone in Africa using passive samplers, Atmos. Chem. Phys., 10, 7467–7487, http://dx.doi.org/10.5194/acp-10-7467-2010doi:10.5194/acp-10-7467-2010, 2010. Beer, R., Shephard M. W., Kulawik, S. S., Clough, S. A., Eldering, A., Bowman, K. W., Sander, S. P., Fisher, B. M., Payne, V. H., Luo, M., Osterman, G. B., and Worden, J. R.: First satellite observations of lower tropospheric ammonia and methanol, Geophys. Res. Lett., 35, L09801, http://dx.doi.org/10.1029/2008GL033642doi:10.1029/2008GL033642, 2008. Blanchard, C. L. and Tanenbaum, S.: Analysis of Inorganic Particulate Matter Formation in the Midwestern United States Final Report Prepared for Lake Michigan Air Directors Consortium, 30 November 2008, Albany, CA, USA, 2008. Bouwman, A. F., Lee, D. S., Asman, W. A. H., Dentener, F. J., VanderHoek, K. W., and Olivier, J. G. J.: A global high-resolution emission inventory for ammonia, Global Biogeochem. Cy., 11, 561–587, 1997 Burgess, A. B., Budhia, A., Grainer, B. G., and Stephenson, D.: Progress in tropospheric ammonia retrieval from the MIPAS satellite instrument, Adv. Space Res., $37$, 2218–2221, 2006. Bowman, K. W., Rodgers, C. D., Sund-Kulawik, S., Worden, J., Sarkissian, E., Osterman, G., Steck, T., Luo, M., Eldering, A., Shephard, M. W., Worden, H., Clough, S. A., Brown, P. D., Rinsland, C. P., Lampel, M., Gunson, M., and Beer, R.: Tropospheric emission spectrometer: Retrieval method and error analysis, IEEE T. Geosci. Remote, 44, 1297–1307, http://dx.doi.org/10.1109/TGRS.2006.871234doi:10.1109/TGRS.2006.871234, 2006. Carfrae, J. A., Sheppard, L. J., Raven, J., Stein, W., Leith, I. D., Theobald, A., and Crossley, A.: Early effects of atmospheric ammonia deposition on Calluna vulgaris (L.) hull growing on an ombrotrophic peat bog, Water Air Soil Pollut. Focus, 4, 229–239, 2004. Charlson, R. J., Langner, J., Rodhe, H., Leovy, C. B., and Warren, S. G.: Perturbation of the Northern-Hemisphere Radiative Balance by Backscattering from Anthropogenic Sulfate Aerosols, Tellus A, 43, 152–163, 1991. Clough, S. A., Shephard, M. W., Mlawer, E. J., Delamere, J. S., Iacono, M. J., Cady-Pereira, K., Boukabara, S., and Brown, R. D.: Atmospheric radiative transfer modeling: a summary of the AER codes, J. Quant. Spectrosc. Ra., 91, 233–244, 2005. Clarisse, L., Clerbaux, C., Dentener, F., Hurtmans, D., and Coheur, P.-F.: Global ammonia distribution derived from infrared satellite observations, Nature Geosci., 2, 479–483, http://dx.doi.org/10.1038/ngeo551doi:10.1038/ngeo551, 2009. Clarisse, L., Shephard, M. W., Dentener, F., Hurtmans, D., Cady-Pereira, K., Karagulian, F., Van Damme, M., Clerbaux, C., and Coheur P.-F.: Satellite monitoring of ammonia: A case study of the San Joaquin Valley, J. Geophys. Res., 115, D13302, http://dx.doi.org/10.1029/2009JD013291doi:10.1029/2009JD013291, 2010. Clough, S. A., Shephard, M. W., Worden, J., Brown, P. D., Worden, H. M., Luo, M., Rodgers, C. D., Rinsland, C. P., Goldman, A., Brown, L., Kulawik, S. S., Eldering, A., Lampel, M. C., Osterman, G., Beer, R., Bowman, K., Cady-Pereira, K. E., and Mlawer, E. J.: Forward Model and Jacobians for Tropospheric Emission Spectrometer Retrievals, IEEE T. Geosci. Remote, 44, 1308–1323, 2006. Duncan, B. N., Martin, R. V., Staudt, A. C., Yevich, R., and Logan, J. A.: Interannual and seasonal variability of biomass burning emissions constrained by satellite observations, J. Geophys. Res., 108, 4100, http://dx.doi.org/10.1029/2002JD002378doi:10.1029/2002JD002378, 2003 Eldering, A., Kulawik, S. S., Worden, J., Bowman, K., and Osterman, G.: Implementation of cloud retrievals for TES atmospheric retrievals: 2. Characterization of cloud top pressure and effective optical depth retrievals, J. Geophys. Res., 113, D16S37, http://dx.doi.org/10.1029/2007JD008858doi:10.1029/2007JD008858, 2008. Erisman, J. W., Galloway, J. A., Sutton, M. S., Klimont, Z., and Winiwater, W.: How a century of ammonia synthesis changed the world, Nature Geosci., 1, 636–639, 2008. Fisher, J. A., Jacob, D. J., Wang, Q., Bahreini, R., Carouge, C. C., Cubison, M. J., Dibb, J. E., Diehl, T., Jimenez, J. L., Leibensperger, E. M., Meinders, M. B. J., Pye, H. O. T., Quinn, P. K., Sharma, S., van Donkelaar, A., and Yantosca, R. M.: Sources, distribution, and acidity of sulfate-ammonium aerosol in the Arctic in winter-spring, Atmos. Environ., http://dx.doi.org/10.1016/j.atmosenv.2011.08.030doi:10.1016/j.atmosenv.2011.08.030, in press, 2011. Galloway, J. N., Townsend, A. R., Erisman, J. W., Bekunda, M., Cai, Z., Freney, J. R., Martinelli, L. A., Seitzinger, S. P., and Sutton, M. A.: Transformation of the Nitrogen Cycle: Recent Trends, Questions, and Potential Solutions, Science, 320, 889–892, http://dx.doi.org/10.1126/science.1136674doi:10.1126/science.1136674, 2008. Gilliland, A. B., Dennis, R. L., Roselle, S. J., and Pierce, T. E.: Seasonal NH<sub>3</sub> emission estimates for the eastern United States based on ammonium wet concentrations and an inverse modeling method, J. Geophys. Res., 108, 4477, http://dx.doi.org/10.1029/2002JD003063doi:10.1029/2002JD003063, 2003. Gilliland, A. B., Appel, K. W, Pinder, R. W., and Dennis, R. L.: Seasonal NH<sub>3</sub> emissions for the continental United States: Inverse model estimation and evaluation, Atmos. Environ., $40$, 4986–4998, 2006. Henze, D. K., Hakami, A., and Seinfeld, J. H.: Development of the adjoint of GEOS-Chem, Atmos. Chem. Phys., 7, 2413–2433, http://dx.doi.org/10.5194/acp-7-2413-2007doi:10.5194/acp-7-2413-2007, 2007. Henze, D. K., Seinfeld, J. H., and Shindell, D. T.: Inverse modeling and mapping US air quality influences of inorganic PM$_2.5$ precursor emissions using the adjoint of GEOS-Chem, Atmos. Chem. Phys., 9, 5877–5903, http://dx.doi.org/10.5194/acp-9-5877-2009doi:10.5194/acp-9-5877-2009, 2009. Ianniello, A., Spataro, F., Esposito, G., Allegrini, I., Rantica, E., Ancora, M. P., Hu, M., and Zhu, T.: Occurrence of gas phase ammonia in the area of Beijing (China), Atmos. Chem. Phys., 10, 9487–9503, http://dx.doi.org/10.5194/acp-10-9487-2010doi:10.5194/acp-10-9487-2010, 2010. JPL, TES Level 2 Data User's Guide, edited by Osterman, G., available online at: http://tes.jpl.nasa.gov/uploadedfiles/TES_L2_Data_Users_Guide-1.pdf, 2006. Kleiner, I., Tarrago, G., Cottaz, C., Sagui, L., Brown, L. R., Poynter, R. L., Pickett, H. M., Chen, P., Pearson, J. C., Sams, R. L., Blake, G. A., Matsuura, S., Nemtchinov, V., Varanasi, P., Fusina, F., and Dilonardo, G. Di.: NH3 and PH<sub>3</sub> parameters: the 2000 HITRAN update and new parameters J. Quant. Spectrosc. Ra., 82, 293–312, 2003. Kulawik, S. S., Worden, J., Eldering, A., Bowman, K., Gunson, M., Osterman, G. B., Zhang, L., Clough, S. A., Shephard, M. W., and Beer, R.: Implementation of cloud retrievals for Tropospheric Emission Spectrometer (TES) atmospheric retrievals: part 1. Description and characterization of errors on trace gas retrievals, J. Geophys. Res., 111, D24204, http://dx.doi.org/10.1029/2005JD006733doi:10.1029/2005JD006733, 2006. Moncet, J.-L., Uymin, G., Lipton, A. E., and Snell, H. E.: Infrared radiance modeling by optimal spectral sampling, J. Atmos. Sci., 65, 3917–3934, 2008. Massad, R.-S., Nemitz, E., and Sutton, M. A.: Review and parameterisation of bi-directional ammonia exchange between vegetation and the atmosphere, Atmos. Chem. Phys., 10, 10359–10386, http://dx.doi.org/10.5194/acp-10-10359-2010doi:10.5194/acp-10-10359-2010, 2010. Paerl, H. W., Dennis, R. L., and Whitall, D. R.,: Atmospheric deposition of nitrogen: Implications for nutrient over-enrichment of coastal waters, Estuaries, 24, 667–693, 2002. Park, R. J., Jacob, D., Field, B. D., Yantosca, R., and Chin, M.: Natural and transboundary pollution influences on sulfate-nitrate-ammonium aerosols in the United States: Implications for policy, J. Geophys. Res.-Atmos., 109,~D15204, http://dx.doi.org/10.1029/2003JD004473doi:10.1029/2003JD004473, 2004. Payne, V. H., Clough, S. A., Shephard, M. W., Nassar, R., and Logan, J. A.: Information-centered representation of retrievals with limited degrees of freedom for signal: Application to methane from the Tropospheric Emission Spectrometer, J. Geophys. Res., 17, 1095, http://dx.doi.org/10.1029/2008JD010155doi:10.1029/2008JD010155, 2009. Perrino, C., Catrambone, M., Di Menno Di Bucchianico, A., and Allergrini, I.: Gaseous ammonia in the urban area of Rome, Italy and its relationship with traffic emissions, Atmos. Environ., 36, 5385–5394, 2002. Pinder, R. W., Gilliand, A. B., and Dennis, R. L.: Environmental impact of atmospheric NH<sub>3</sub> emissions under present and future conditions in the eastern United States, Geophys. Res. Lett., 35, L12808, http://dx.doi.org/10.1029/2008GL033732doi:10.1029/2008GL033732, 2008. Pinder, R. W., Walker, J. T., Bash, J. O., Cady-Pereira, K. E., Henze, D. K., Luo, M., and Shephard, M. W.: Quantifying spatial and temporal variability in atmospheric ammonia with in situ and space-based observations, Geophys. Res. Lett., 38, L04802, http://dx.doi.org/10.1029/2010GL046146doi:10.1029/2010GL046146, 2011. Pope, C. A.: Epidemiology of fine particulate air pollution and human health: Biologic mechanisms and who's at risk?, Environ. Health Perspect., 108, 713–723, 2000. Rodgers, C. D.: Inverse methods for atmospheric Sounding: Theory and Practice, World Sci., Hackensack, NJ, 2000. Rothman, L. S., Barbe, A., Benner, D. C., Brown, L. R., Camy-Peyret, C., Carleer, M. R., Chance, K., Clerbeaux, C., Dana, V., Devi, V. M., Fayt, A., Flaud, J.-M., Gamache, R. R., Goldman, A., Jacquemart, D., Jucks, K. W, Lafferty, W. J, Mandin J.-Y., Massie, S. T., Newnham, D. A., Perrin, A., Rinsland, C. P., Schroeder, J., Smith, M. A., Tang, K., Toth, R. A., Vander Auwera, J., Varanasi, P., and Yoshino, K.: The HITRAN molecular spectroscopic database: edition 2000 including updates through 2001, J. Quant. Spectrosc. Ra., 82, 5–44, 2003. Rothman, L. S., Jaquemart, D., Barbe, A., Benner, C. D., Birk, M., Brown, L. R., Carleer, M. R., Chackerian, C., Chance, K., Coudert, L. H., Dana, V., Devi, V. M., Flaud, J.-M., Gamache, R. R., Goldman, A., Hartmann, J.-M., Jucks, K. W., Maki, A. G., Mandin, J.-Y., Massie, S. T., Orphal, J., Perrin, A., Rinsland, C. P., Smith, M. A. H., Tennyson, J., Tolchenov, R. N., Toth, R. A., Vander Auwera, J., Varanasi, P., and Wagner, G.: The HITRAN 2004 molecular spectroscopic database, J. Quant. Spectrosc. Ra., 96, 139–204, 2005. Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, John Wiley, Hoboken, NJ, 1988. Shephard, M. W., Worden, H. M., Cady-Pereira, K. E., Lampel, M., Luo, M., Bowman, K. W., Sarkissian, E., Beer, R., Rider, D. M., Tobin, D. C., Revercomb, H. E., Fisher, B. M., Tremblay, D., Clough, S. A., Osterman, G. B., and Gunson, M.: Tropospheric Emission Spectrometer Spectral Radiance Comparisons, J. Geophys. Res., 113, D15S05, http://dx.doi.org/10.1029/2007JD008856doi:10.1029/2007JD008856, 2008. Shephard, M. W., Clough, S. A., Payne, V. H., Smith, W. L., Kireev, S., and Cady-Pereira, K. E.: Performance of the line-by-line radiative transfer model (LBLRTM) for temperature and species retrievals: IASI case studies from JAIVEx, Atmos. Chem. Phys., 9, 7397–7417, http://dx.doi.org/10.5194/acp-9-7397-2009doi:10.5194/acp-9-7397-2009, 2009. Streets, D. G., Bond, T. C., Carmichael, G. R., Fernandes, S. D., Fu, Q., Klimont, Z., Nelson, S. M., Tsai, N. Y., Wang, M. Q., Woo, J.-H., and Yarber, K. F.: An inventory of gaseous and primary aerosol emissions in Asia in the year 2000, J. Geophys. Res, 108, 8809, http://dx.doi.org/10.1029/2002JD003093doi:10.1029/2002JD003093, 2003. Wang, Y., Jacob D. J., and Logan J. A.: Global simulation of tropospheric O<sub>3</sub>-NO<sub>x</sub>- hydrocarbon chemistry, 1. Model formulation, J. Geophys. Res., 103, 10713–10726, 1998. Vestreng, V. and Klein, H.: Emission data reported to UNECE/EMEP: Quality insurance and trend analysis and presentation of Web-Dab, MSC-W Status Rep. 2002, 101 pp., Norw. Meteorol. Inst., Oslo, Norway. Whitehead, J. D., Longley, I. D., and Gallagher, M. W.: Seasonal and Diurnal Variation in Atmospheric Ammonia in an Urban Environment Measured Using a Quantum Cascade Laser Absorption Spectrometer, Water Air Soil Pollut., 183, 317–329, http://dx.doi.org/10.1007/s11270-007-9381-5doi:10.1007/s11270-007-9381-5, 2007. Worden, J., Kulawik, S. S., Shephard, M. W., Clough, S. A., Worden, H., Bowman, K., and Goldman, A.: Predicted errors of tropospheric emission spectrometer nadir retrievals from spectral window selection, J. Geophys. Res., 109, D09308, http://dx.doi.org/10.1029/2004JD004522doi:10.1029/2004JD004522, 2004. Yevich, R. and Logan, J. A.: An assessment of biofuel use and burning of agricultural waste in the developing world, Global Biogeochem. Cy., 17, 1095, http://dx.doi.org/10.1029/2002GB001952doi:10.1029/2002GB001952, 2003.