Atmospheric Chemistry and Physics Discussions www.atmos-chem-phys-discuss.net 1680-7367 1680-7375 8 4 2008 10.5194/acpd-8-15031-2008 http://www.atmos-chem-phys-discuss.net/8/15031/2008/ http://www.atmos-chem-phys-discuss.net/8/15031/2008/acpd-8-15031-2008.html http://www.atmos-chem-phys-discuss.net/8/15031/2008/acpd-8-15031-2008.pdf 15031 15099 2008-08-08 Inverse modeling and mapping US air quality influences of inorganic PM2.5 precursor emissions using the adjoint of GEOS-Chem D. K. Henze dkh2114@columbia.edu J. H. Seinfeld D. T. Shindell Earth Institute, Columbia University, New York, NY, USA Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA, USA NASA Goddard Institute for Space Studies, New York, NY, USA Influences of specific sources of inorganic PM2.5 on peak and ambient aerosol concentrations in the US are evaluated using a combination of inverse modeling and sensitivity analysis. First, sulfate and nitrate aerosol measurements from the IMPROVE network are assimilated using the four-dimensional variational (4D-Var) method into the GEOS-Chem chemical transport model in order to constrain emissions estimates in four separate month-long inversions (one per season). Of the precursor emissions, these observations primarily constrain ammonia (NH3). While the net result is a decrease in estimated US NH3 emissions relative to the original inventory, there is considerable variability in adjustments made to NH3 emissions in different locations, seasons and source sectors, such as focused decreases in the midwest during July, broad decreases throughout the US~in January, increases in eastern coastal areas in April, and an effective redistribution of emissions from natural to anthropogenic sources. Implementing these constrained emissions, the adjoint model is applied to quantify the influences of emissions on representative PM2.5 air quality metrics within the US. The resulting sensitivity maps display a wide range of spatial, sectoral and seasonal variability in the susceptibility of the air quality metrics to absolute emissions changes and the effectiveness of incremental emissions controls of specific source sectors. NH3 emissions near sources of sulfur oxides (SOx) are estimated to most influence peak inorganic PM2.5 levels in the East; thus, the most effective controls of NH3 emissions are often disjoint from locations of peak NH3 emissions. Controls of emissions from industrial sectors of SOx and NOx are estimated to be more effective than surface emissions, and changes to NH3 emissions in regions dominated by natural sources are disproportionately more effective than regions dominated by anthropogenic sources. NOx controls are most effective in northern states in October; in January, SOx controls may be counterproductive. When considering ambient inorganic PM2.5 concentrations, intercontinental influences are small, though transboundary influences within North America are significant, with SOx emissions from surface sources in Mexico contributing almost a fourth of the total influence from this sector. 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.-Atmos., 104, 13 791–13 823, 1999. Baumgardner, R E., Lavery, T F., Rogers, C M., and Isil, S S.: Estimates of the atmospheric deposition of sulfur and nitrogen species: Clean Air Status and Trends Network, 1990–2000, Environ. Sci. Technol., 36, 2614–2629, 2002. Beer, R., Shephard, M W., Kulawik, S., Clough, S A., Eldred, R A., Bowman, K W., Sander, S P., Fisher, B M., Payne, V H., Louo, M., Osterman, G B., and Worden, J R.: First satellite observations of lower tropospheric ammonia and methanol, Geophys. Res. Lett., 35, L09801, \doi10.1029/2008GL033642, 2008. Benkovitz, C M., Scholtz, M T., Pacyna, J., Tarrason, L., Dignon, J., Voldner, E C., Spiro, P A., Logan, J A., and Graedel, T E.: Global gridded inventories of anthropogenic emissions of sulfur and nitrogen, J. Geophys. Res.-Atmos., 101, 29 239–29 253, 1996. Benkovitz, C. M., Schwartz, S. E., Jensen, M. P., and Miller, M. A.: Attribution of modeled atmospheric sulfate and SO2 in the Northern Hemisphere for June-July 1997, Atmos. Chem. Phys., 6, 4723–4738, 2006. Bey, I., Jacob, D J., Yantosca, R M., Logan, J A., Field, B D., Fiore, A M., Li, Q B., Liu, H. G Y., Mickley, L J., and Schultz, M G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res.-Atmos., 106, 23 073–23 095, 2001. Binkowski, F S. and Roselle, S J.: Models-3 community multiscale air quality (CMAQ) model aerosol component - 1. Model description, J. Geophys. Res.-Atmos., 108, 4183, \doi10.1029/2001JD001409, 2003. 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. Cycles, 11, 561–587, 1997. Brinkman, G., Vance, G., Hannigan, M P., and Milford, J B.: Use of synthetic data to evaluate positive matrix factorization as a source apportionment tool for PM$_2.5$ exposure data, Environ. Sci. Technol., 40, 1892–1901, 2006. Brock, C A., Sullivan, A P., Peltier, R E., Weber, R J., Wollny, A., de~Gouw, J A., Middlebrook, A M., Atlas, E L., Stohl, A., Trainer, M K., Cooper, O R., Fehsenfeld, F C., Frost, G J., Holloway, J., Hübler, G., Neuman, J A., Ryerson, T B., Warneke, C., and Wilson, J C.: Sources of particulate matter in the northeastern United States in summer: 2. Evolution of chemical and microphysical properties, J. Geophys. Res.-Atmos., 113, D08302, \doi10.1029/2007JD009241, 2008. Brown, S S., Ryerson, T B., Wollny, A G., Brock, C A., Peltier, R., Sullivan, A P., Weber, R J., Dube, W P., Trainer, M., Meagher, J F., Fehsenfeld, F C., and Ravishankara, A R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 67–70, 2006. Byrd, R H., Lu, P H., Nocedal, J., and Zhu, C Y.: A Limited Memory Algorithm for Bound Constrained Optimization, Siam J. Sci. Comput., 16, 1190–1208, 1995. Chai, T F., Carmichael, G R., Sandu, A., Tang, Y H., and Daescu, D N.: Chemical data assimilation of Transport and Chemical Evolution over the Pacific (TRACE-P) aircraft measurements, J. Geophys. Res.-Atmos., 111, D02301, \doi10.1029/2005JD005883, 2006. Chai, T F., Carmichael, G R., Tang, Y H., Sandu, A., Hardesty, M., Pilewskie, P., Whitlow, S., Browell, E V., Avery, M A., Nedelec, P., Merrill, J T., Thompson, A M., and Williams, E.: Four-dimensional data assimilation experiments with International Consortium for Atmospheric Research on Transport and Transformation ozone measurements, J. Geophys. Res.-Atmos., 112, D12S15, \doi10.1029/2006jd007763, 2007. Chin, M., Rood, R B., Lin, S J., Muller, J F., and Thompson, A M.: Atmospheric sulfur cycle simulated in the global model GOCART: Model description and global properties, J. Geophys. Res.-Atmos., 105, 24 671–24 687, 2000. Chin, M., Diehl, T., Ginoux, P., and Malm, W.: Intercontinental transport of pollution and dust aerosols: implications for regional air quality, Atmos. Chem. Phys., 7, 5501–5517, 2007. de~Gouw, J A., Brock, C A., Atlas, E L., Bates, T S., Fehsenfeld, F C., Goldan, P D., Holloway, J S., Kuster, W C., Lerner, B M., Matthew, B M., Middlebrook, A M., Onasch, T B., Peltier, R E., Quinn, P K., Senff, C J., Stohl, A., Sullivan, A P., Trainer, M., Warneke, C., Weber, R J., and Williams, E J.: Sources of particulate matter in the northeastern United States in summer: 1. Direct emissions and secondary formation of organic matter in urban plumes, J. Geophys. Res.-Atmos., 113, D08301, \doi10.1029/2007jd009243, 2008. Dentener, F J. and Crutzen, P J.: Reaction of N2O$_5$ on tropospheric aerosols - Impact on the global distributions of NOx, O3, and OH, J. Geophys. Res.-Atmos., 98, 7149–7163, 1993. Dubovik, O., Lapyonok, T., Kaufman, Y J., Chin, M., Ginoux, P., Remer, L A., and Holben, B N.: Inversion of global distribution of aerosol sources using MODIS and AERONET data, Optica Pura y Aplicada, 37, 3349–3358, 2004. Dubovik, O., Lapyonok, T., Kaufman, Y. J., Chin, M., Ginoux, P., Kahn, R. A., and Sinyuk, A.: Retrieving global aerosol sources from satellites using inverse modeling, Atmos. Chem. Phys., 8, 209–250, 2008. 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.-Atmos., 108(D2), 4100, \doi10.1029/2002JD002378, 2003. Elbern, H., Schmidt, H., and Ebel, A.: Variational data assimilation for tropospheric chemistry modeling, J. Geophys. Res.-Atmos., 102, 15 967–15 985, 1997. Elbern, H., Schmidt, H., Talagrand, O., and Ebel, A.: 4D-varational data assimilation with an adjoint air quality model for emission analysis, Environ. Modell. Softw., 15, 539–548, 2000. Environmental Protection Agency (EPA), Latest findings on national air quality: 2001 status and trends, Tech. rep., 2002. Environmental Protection Agency (EPA), TTN NAAQS - PM$_2.5$ - NAAQS Implementation PM$_2.5$ Designations – Technical Information, 2004. Evans, M J. and Jacob, D J.: Impact of new laboratory studies of N2O$_5$ hydrolysis on global model budgets of tropospheric nitrogen oxides, ozone, and OH, Geophys. Res. Lett., 32, L09813, doi:10.1029/2005GL022469, 2005. Fisher, M. and Lary, D J.: Lagrangian four-dimensional variational data assimilation of chemical species, Q. J. R. Meteorol. Soc., 121, 1681–1704, 1995. Giering, R. and Kaminski, T.: Recipes for adjoint code construction, ACM Transactions on Mathematical Software, 24, 437–474, 1998. Gilliland, A. and Abbitt, P J.: A sensitivity study of the discrete Kalman filter (DKF) to initial condition discrepancies, J. Geophys. Res.-Atmos., 106, 17 939–17 952, 2001. Gilliland, A B., Dennis, R L., Roselle, S J., and Pierce, T E.: Seasonal NH3 emission estimates for the eastern United States based on ammonium wet concentrations and an inverse modeling method, J. Geophys. Res.-Atmos., 108, 4477, \doi10.1029/2002JD003063, 2003. Gilliland, A B., Appel, K W., Pinder, R W., and Dennis, R L.: Seasonal NH3 emissions for the continental United States: Inverse model estimation and evaluation, Atmos. Environ., 40, 4986–4998, 2006. Hakami, A., Henze, D K., Seinfeld, J H., Chai, T., Tang, Y., Carmichael, G R., and Sandu, A.: Adjoint inverse modeling of black carbon during the Asian Pacific Regional Aerosol Characterization Experiment, J. Geophys. Res.-Atmos., 110, D14301, \doi10.1029/2004JD005671, 2005. Hakami, A., Seinfeld, J H., Chai, T F., Tang, Y H., Carmichael, G R., and Sandu, A.: Adjoint sensitivity analysis of ozone nonattainment over the continental United States, Environ. Sci. Technol., 40, 3855–3864, 2006. Hakami, A., Henze, D K., Seinfeld, J H., Singh, K., Sandu, A., Kim, S., Byun, D., and Li, Q.: The adjoint of CMAQ, Environ. Sci. Technol., 41, 7807–7817, 2007. Hansen, P C.: Rank-Deficient and Discrete Ill-Posed Problems: Numerical Aspects of Linear Inversion, SIAM, Philadelphia, USA, 1998. Heald, C L., Jacob, D J., Park, R J., Russell, L M., Huebert, B J., Seinfeld, J H., Liao, H., and Weber, R J.: A large organic aerosol source in the free troposphere missing from current models, Geophys. Res. Lett., 32, L18809, \doi10.1029/2005GL023831, 2005. Heald, C L., Jacob, D J., Park, R J., Alexander, B., Fairlie, T D., Chu, D A., and Yantosca, R M.: Transpacific transport of Asian anthropogenic aerosols and its impact on surface air quality in the United States, J. Geophys. Res.-Atmos., 111, D14310, \doidoi:10.1029/2005JD006847, 2006a. Heald, C L., Jacob, D J., Turquety, S., Hudman, R C., Weber, R J., Sullivan, A P., Peltier, R E., Atlas, E L., de~Gouw, J A., Warneke, C., Holloway, J S., Neuman, J A., Flocke, F M., and Seinfeld, J H.: Concentrations and sources of organic carbon aerosols in the free troposphere over North America, J. Geophys. Res.-Atmos., 111, D23S47, \doi10.1029/2006JD007705, 2006b. Henze, D K., Seinfeld, J H., Liao, W., Sandu, A., and Carmichael, G R.: Inverse modeling of aerosol dynamics: Condensational growth, J. Geophys. Res.-Atmos., 109, D14201, \doi10.1029/2004JD004593, 2004. Henze, D. K., Hakami, A., and Seinfeld, J. H.: Development of the adjoint of GEOS-Chem, Atmos. Chem. Phys., 7, 2413–2433, 2007. Jacob, D J., Liu, H., Mari, C., and Yantosca, B M.: Harvard wet deposition scheme for GMI, http://gmi.gsfc.nasa.gov/models/jacob_wetdep.pdf, 2000. Jaffe, D., McKendry, I., Anderson, T., and Price, H.: Six "new" episodes of trans-Pacific transport of air pollutants, Atmos. Environ., 37, 391–404, \doiPii S1352-2310(02)00862-2, 2003. Kalnay, E.: Atmospheric Modeling, Data Assimilation and Predictability, Cambridge University Press, Cambridge, United Kingdom, 2003. Kim, S W., Heckel, A., McKeen, S A., Frost, G J., Hsie, E Y., Trainer, M K., Richter, A., Burrows, J P., Peckham, S E., and Grell, G A.: Satellite-observed US power plant NOx emission reductions and their impact on air quality, Geophys. Res. Lett., 33, L22812, \doi10.1029/2006gl027749, 2006. Kleeman, M J. and Cass, G R.: A 3D Eulerian source-oriented model for an externally mixed aerosol, Environ. Sci. Technol., 35, 4834–4848, 2001. Knipping, E M., Kumar, N., Pun, B K., Seigneur, C., Wu, S Y., and Schichtel, B A.: Modeling regional haze during the BRAVO study using CMAQ-MADRID: 2. Source region attribution of particulate sulfate compounds, J. Geophys. Res.-Atmos., 111, D06303, \doi10.1029/2004JD005609, 2006. Koo, B., Dunker, A M., and Yarwood, G.: Implementing the decoupled direct method for sensitivity analysis in a particulate matter air quality model, Environ. Sci. Technol., 41, 2847–2854, 2007. Kopacz, M., Jacob, D., Henze, D K., Heald, C L., Streets, D G., and Zhang, Q.: A comparison of analytical and adjoint Bayesian inversion methods for constraining Asian sources of CO using satellite (MOPITT) measurements of CO columns, J. Geophys. Res.-Atmos., in press, 2008. Lee, S., Liu, W., Wang, Y., Russell, A G., and Edgerton, E S.: Source apportionment of PM$_2.5$: Comparing PMF and CMB results for four ambient monitoring sites in the southeastern United States, Atmos. Environ., 42, 4126–4137, 2008. Li, Q B., Jacob, D J., Logan, J A., Bey, I., Yantosca, R M., Liu, H Y., Martin, R V., Fiore, A M., Field, B D., Duncan, B N., and Thouret, V.: A tropospheric ozone maximum over the Middle East, Geophys. Res. Lett., 28, 3235–3238, 2001. Liao, H., Henze, D K., Seinfeld, J H., Wu, S., and Mickley, L J.: Biogenic secondary organic aerosol over the United States: Comparison of climatological simulations with observations, J. Geophys. Res.-Atmos., 112, D06201, \doi10.1029/2006JD007813, 2007. Lions, J L.: Optimal Control of Systems Governed by Partial Differential Equations, Springer-Verlag, Berlin, 1971. Liu, J., Mauzerall, D. L., and Horowitz, L. W.: Source-receptor relationships between East Asian sulfur dioxide emissions and Northern Hemisphere sulfate concentrations, Atmos. Chem. Phys., 8, 3721–3733, 2008. Malm, W C., Sisler, J F., Huffman, D., Eldred, R A., and Cahill, T A.: Spatial and seasonal trends in particle concentration and optical extinction in the United States, J. Geophys. Res.-Atmos., 99, 1347–1370, 1994. Marchuk, G.: Numerical solution of the problems of the dynamics of the atmosphere and the ocean (In Russian), Gidrometeoizdat, 1974. Martien, P T. and Harley, R A.: Adjoint sensitivity analysis for a three-dimensional photochemical model: Application to Southern California, Environ. Sci. Technol., 40, 4200–4210, 2006. Martien, P T., Harley, R A., and Cacuci, D G.: Adjoint sensitivity analysis for a three-dimensional photochemical model: Implementation and method comparison, Environ. Sci. Technol., 2006. Martin, R V., Jacob, D J., Logan, J A., Bey, I., Yantosca, R M., Staudt, A C., Li, Q B., Fiore, A M., Duncan, B N., Liu, H Y., Ginoux, P., and Thouret, V.: Interpretation of TOMS observations of tropical tropospheric ozone with a global model and in situ observations, J. Geophys. Res.-Atmos., 107, 4351, 2002. Martin, R V., Jacob, D J., Yantosca, R M., Chin, M., and Ginoux, P.: Global and regional decreases in tropospheric oxidants from photochemical effects of aerosols, J. Geophys. Res.-Atmos., 108, 4097, \doi10.1029/2002JD002622, 2003. Mendoza-Dominguez, A. and Russell, A G.: Iterative inverse modeling and direct sensitivity analysis of a photochemical air duality model, Environ. Sci. Technol., 34, 4974–4981, 2000. Mendoza-Dominguez, A. and Russell, A G.: Emission strength validation using four-dimensional data assimilation: Application to primary aerosol and precursors to ozone and secondary aerosol, J. Air & Waste Manage. Assoc, 51, 1538–1550, 2001. Menut, L.: Adjoint modeling for atmospheric pollution process sensitivity at regional scale, J. Geophys. Res.-Atmos., 108, 8562, \doi10.1029/2002JD002549, 2003. Muller, J. F. and Stavrakou, T.: Inversion of CO and NOx emissions using the adjoint of the IMAGES model, Atmos. Chem. Phys., 5, 1157–1186, 2005. Napelenok, S L., Cohan, D., Hu, Y., and Russel, A G.: Decoupled direct 3D sensitivity analysis for particulate matter (DDM-3D\/PM), Atmos. Environ., 40, 6112–6121, 2006. Nester, K. and Panitz, H J.: Sensitivity analysis by the adjoint chemistry transport model DRAIS for an episode in the Berlin Ozone (BERLIOZ) experiment, Atmos. Chem. Phys., 6, 2091–2106, 2006. Nowak, J B., Huey, L G., Russell, A G., Tian, D., Neuman, J A., Orsini, D., Sjostedt, S J., Sullivan, A P., Tanner, D J., Weber, R J., Nenes, A., Edgerton, E., and Fehsenfeld, F C.: Analysis of urban gas phase ammonia measurements from the 2002 Atlanta Aerosol Nucleation and Real-Time Characterization Experiment (ANARChE), J. Geophys. Res.-Atmos., 111, D17308, \doi10.1029/2006JD007113, 2006. 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, \doi10.1029/2003JD004473, 2004. Park, R J., Jacob, D J., Kumar, N., and Yantosca, R M.: Regional visibility statistics in the United States: Natural and transboundary pollution influences, and implications for the Regional Haze Rule, Atmos. Environ., 40, 5405–5423, 2006. Pinder, R W., Adams, P J., Pandis, S N., and Gilliland, A B.: Temporally resolved ammonia emission inventories: Current estimates, evaluation tools, and measurement needs, J. Geophys. Res.-Atmos., 111, D16310, \doi10.1029/2005JD006603, 2006. Pinder, R W., Adams, P J., and Pandis, S N.: Ammonia emission controls as a cost-effective strategy for reducing atmospheric particulate matter in the eastern United States, Environ. Sci. Technol., 41, 380–386, 2007. Pope, C A.: Review: Epidemiological basis for particulate air pollution health standards, Aerosol Sci. Tech., 32, 4–14, 2000. Pope, C A., Burnett, R T., Thun, M J., Calle, E E., Krewski, D., Ito, K., and Thurston, G D.: Lung cancer, cardiopulmonary mortality, and long-term exposure to fine particulate air pollution, J. Am. Med. Assoc., 287, 1132–1141, 2002. Quelo, D., Mallet, V., and Sportisse, B.: Inverse modeling of NOx emissions at regional scale over northern France: Preliminary investigation of the second-order sensitivity, J. Geophys. Res.-Atmos., 110, D24310, \doi10.1029/2005JD006151, 2005. Quinn, P K., Bates, T S., Coffman, D., Onasch, T B., Worsnop, D., Baynard, T., de~Gouw, J A., Goldan, P D., Kuster, W C., Williams, E., Roberts, J M., Lerner, B., Stohl, A., Pettersson, A., and Lovejoy, E R.: Impacts of sources and aging on submicrometer aerosol properties in the marine boundary layer across the Gulf of Maine, J. Geophys. Res.-Atmos., 111, D23S36, \doi10.1029/2006jd007582, 2006. Reiss, R., Anderson, E L., Cross, C E., Hidy, G., Hoel, D., McClellan, R., and Moolgavkar, S.: Evidence of health impacts of sulfate- and nitrate-containing particles in ambient air, Inhal Toxicol, 19, 419–449, \doi10.1080/08958370601174941, 2007. Rodgers, C D.: Inverse Methods for Atmospheric Sounding, vol 2 of \em Series on Atmospheric, Oceanic and Planetary Physics\/, World Scientific, Singapore, 2000. Sandu, A., Daescu, D N., Carmichael, G R., and Chai, T F.: Adjoint sensitivity analysis of regional air quality models, J. Comput. Phys., 204, 222–252, 2005a. Sandu, A., Liao, W., Carmichael, G R., Henze, D K., and Seinfeld, J H.: Inverse modeling of aerosol dynamics using adjoints: Theoretical and numerical considerations, Aerosol Sci. Tech., 39, 677–694, 2005b. Schmidt, H. and Martin, D.: Adjoint sensitivity of episodic ozone in the Paris area to emissions on the continental scale, J. Geophys. Res.-Atmos., 108, \doi10.1029/2001JD001583, 2003. Schwartz, J., Laden, F., and Zanobetti, A.: The concentration-response relation between PM$_2.5$ and daily deaths, Environ. Health Perspect., 110, 1025–1029, 2002. Schwartz, J., Coull, B., Laden, F., and Ryan, L.: The effect of dose and timing of dose on the association between airborne particles and survival, Environ. Health Perspect., 116, 64–69, \doiDoi 10.1289/Ehp.9955, 2008. Stavrakou, T. and Muller, J F.: Grid-based versus big region approach for inverting CO emissions using Measurement of Pollution in the Troposphere (MOPITT) data, J. Geophys. Res.-Atmos., 111, D15304, \doi10.1029/2005JD006896, 2006. Stavrakou, T., Müller, J.-F., Boersma, K F., Smedt, I D., and van~der A., R J.: Assessing the distribution and growth rates of NOx emission sources by inverting a 10-year record of NO2 satellite columns, Geophys. Res. Lett., 35, L10801, \doi10.1029/2008GL033521, 2008. Stephen, K. and Aneja, V P.: Trends in agricultural ammonia emissions and ammonium concentrations in precipitation over the Southeast and Midwest United States, Atmos. Environ., 42, 3238–3252, 2008. Stier, P., Seinfeld, J H., Kinne, S., Feichter, J., and Boucher, O.: Impact of nonabsorbing anthropogenic aerosols on clear-sky atmospheric absorption, J. Geophys. Res.-Atmos., 111, D18201, \doi10.1029/2006jd007147, 2006. Surratt, J D., Kroll, J H., Kleindienst, T E., Edney, E O., Claeys, M., Sorooshian, A., Ng, N L., Offenberg, J H., Lewandowski, M., Jaoui, M., Flagan, R C., and Seinfeld, J H.: Evidence for organosulfates in secondary organic aerosol, Environ. Sci. Technol., 41, 517–527, 2007. Takahama, S., Wittig, A E., Vayenas, D V., Davidson, C I., and Pandis, S N.: Modeling the diurnal variation of nitrate during the Pittsburgh Air Quality Study, J. Geophys. Res.-Atmos., 109, D16S06, \doi10.1029/2003JD004149, 2004. Tarantola, A.: Inverse problem theory and model parameter estimation, SIAM, 2005. Tarantola, A.: Popper, Bayes and the inverse problem, Nat. Phys., 2, 492–494, 2006. Thacker, W C.: The role of the Hessian matrix in fitting models to measurements, J. Geophys. Res.-Oceans, 94, 6177–6196, 1989. Thornton, J. and Abbatt, J. P D.: Measurements of HO2 uptake to aqueous aerosol: Mass accomodation coefficients and net reactive loss, J. Geophys. Res.-Atmos., 110, D08309, \doi10.1029/2004JD005402, 2005. Tziperman, E. and Thacker, W C.: An optimal-control/adjoint-equations approach to studying the oceanic general circulation, J. Phys. Oceonogr., 19, 1471–1485, 1989. van~der A., R J., Eskes, H J., Boersma, K F., van Noije, T. P C., Roozendael, M V., Smedt, I D., Peters, D. H. M U., and Meijer, E W.: Trends, seasonal variability and dominant NOx source derived from a ten year record of NO2 measured from space, J. Geophys. Res.-Atmos., 113, D04302, \doi10.1029/2007JD009021, 2008. Vautard, R., Beekmann, M., and Menut, L.: Applications of adjoint modelling in atmospheric chemistry: Sensitivity and inverse modelling, Environ. Modell. Softw., 15, 703–709, 2000. Vayenas, D V., Takahama, S., Davidson, C I., and Pandis, S N.: Simulation of the thermodynamics and removal processes in the sulfate-ammonia-nitric acid system during winter: Implications for PM$_2.5$ control strategies, J. Geophys. Res.-Atmos., 110, D07S14, \doi10.1029/2004JD005038., 2005. Wang, Y H., Jacob, D J., and Logan, J A.: Global simulation of tropospheric O3-NOx-hydrocarbon chemistry 1. Model formulation, J. Geophys. Res.-Atmos., 103, 10 713–10 725, 1998. Wesely, M L.: Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical-models, Atmos. Environ., 23, 1293–1304, 1989. West, J J., Ansari, A S., and Pandis, S N.: Marginal PM$_2.5$: Nonlinear aerosol mass response to sulfate reductions in the Eastern United States, J. Air Waste Manage. Assoc., 49, 1415–1424, 1999. Wu, S.-Y., Hu, J.-L., Zhang, Y., and Aneja, V P.: Modeling atmospheric transport and fate of ammonia in North Carolina–Part II: Effect of ammonia emissions on fine particulate matter formation, Atmos. Environ., 42, 3437–3451, 2008. Yevich, R. and Logan, J A.: An assessment of biofuel use and burning of agricultural waste in the developing world, Global Biogeochem. Cycles, 17()4, 1095, doi:10.1029/2002GB001952, 2003. Yienger, J., Galanter, M., Holloway, J., Phadnis, M., Guttikunda, S K., Carmichael, G R., Moxim, W J., and Levy, H I.: The episodic nature of air pollution transport from Asia to North America, J. Geophys. Res.-Atmos., 105, 26 931–26 945, 2000. Ying, Q. and Kleeman, M J.: Source contributions to the regional distribution of secondary particulate matter in California, Atmos. Environ., 40, 736, 2006. Ying, Q., Fraser, M P., Griffin, R J., Chen, J J., and Kleeman, M J.: Verification of a source-oriented externally mixed air quality model during a severe photochemical smog episode, Atmos. Environ., 41, 1521–1538, 2007. Yu, S., Eder, B., Dennis, R., Chu, S.-H., and Schwartz, S.: New unbiased symmetric metrics for the evaluation of air quality models, Atmos. Sci. Letters, 7, 26–34, \doi10.1002/asl.125, 2006. Yu, S., Mathur, R., Schere, K., Kang, D., Pleim, J., Young, J., Tong, D., Pouliot, G., McKeen, S A., and Rao, S T.: Evaluation of real-time PM$_2.5$ forecasts and process analysis for PM$_2.5$ formation over the eastern United States using the Eta-CMAQ forecast model during the 2004 ICARTT study, J. Geophys. Res.-Atmos., 113, D06204, \doi10.1029/2007JD009226, 2008. Yu, S C., Dennis, R., Roselle, S., Nenes, A., Walker, J., Eder, B., Schere, K., Swall, J., and Robarge, W.: An assessment of the ability of three-dimensional air quality models with current thermodynamic equilibrium models to predict aerosol NO3-, J. Geophys. Res.-Atmos., 110, D07S13, \doi10.1029/2004jd004718, 2005. Zhang, Y., Wu, S.-Y., Krishnan, S., Wang, K., Queen, A., Aneja, V P., and Arya, S P.: Modeling agricultural air quality: Current status, major challenges, and outlook, Atmos. Environ., 42, 3218–3237, 2008. Zhu, C., Byrd, R H., Lu, P., and Nocedal, J.: L-BFGS-B: A limited memory FORTRAN code for solving bound constrained optimization problems, Tech. rep., Northwestern University, 1994.