ACPD Atmospheric Chemistry and Physics Discussions ACPD 1680-7375 Copernicus GmbH Göttingen, Germany 10.5194/acpd-11-23469-2011 ANISORROPIA: the adjoint of the aerosol thermodynamic model ISORROPIA Capps S. L. 1 Henze D. K. 2 Hakami A. 3 Russell A. G. 4 Nenes A. 1 5 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA Deparment of Mechanical Engineering, University of Colorado, Boulder, CO, USA Department of Civil and Environmental Engineering, Carleton University, Ottawa, ON, Canada School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA, USA School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA 19 08 2011 11 8 23469 23511 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-discuss.net/11/23469/2011/acpd-11-23469-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys-discuss.net/11/23469/2011/acpd-11-23469-2011.pdf

We present the development of ANISORROPIA, the discrete adjoint of the ISORROPIA thermodynamic equilibrium model that treats the Na<sup>+</sup>-SO<sub>4</sub><sup>2&minus;</sup>-HSO<sub>4</SUB><sup>&minus;</sup>-NH<sub>4</sub><sup>+</sup>-NO<sub>3</sub><sup>&minus;</sup>-Cl<sup>&minus;</sup>-H<sub>2</sub>O aerosol system, and we demonstrate its sensitivity analysis capabilities. ANISORROPIA calculates sensitivities of an inorganic species in aerosol or gas phase with respect to the total concentrations of each species present with only a two-fold increase in computational time over the forward model execution. Due to the highly nonlinear and discontinuous solution surface of ISORROPIA, evaluation of the adjoint required a new, complex-variable version of the the model, which determines first-order sensitivities with machine precision and avoids cancellation errors arising from finite difference calculations. The adjoint is verified over an atmospherically relevant range of concentrations, temperature, and relative humidity. We apply ANISORROPIA to recent field campaign results from Atlanta, GA, USA, and Mexico City, Mexico, to characterize the inorganic aerosol sensitivities of these distinct urban air masses. The variability in the relationship between PM<sub>2.5</sub> mass and precursor concentrations shown has important implications for air quality and climate. ANISORROPIA enables efficient elucidation of aerosol concentration dependence on aerosol precursor emissions in the context of atmospheric chemical transport model adjoints.

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