A new atmospheric aerosol phase equilibrium model (UHAERO): organic systems

In atmospheric aerosols, water and volatile inorganic and organic species are distributed between the gas and aerosol phases in accordance with thermodynamic equilibrium. Within an atmospheric particle, liquid and solid phases can exist at equilibrium. Models exist for computation of phase equilibria for inorganic/water mixtures typical of atmospheric aerosols; when organic species are present, the phase equilibrium problem is complicated by organic/water interactions as well as the potentially large number of organic species. We present here an extension of the UHAERO inorganic thermodynamic model (Amundson et al., 2006c) to organic/water systems. Phase diagrams for a number of model organic/water systems characteristic of both primary and secondary organic aerosols are computed. Also calculated are inorganic/organic/water phase diagrams that show the effect of organics on inorganic deliquescence behavior. The effect of the choice of activity coefficient model for organics on the computed phase equilibria is explored

A new inorganic atmospheric aerosol phase equilibrium model (UHAERO)

A variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium. To achieve computational efficiency a number of the models rely on a priori specification of the phases present in certain relative humidity regimes. Presented here is a new computational model, named UHAERO, that is both efficient and rigorously computes phase behavior without any a priori specification. The computational implementation is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The mathematical details of the solution are given elsewhere. The model computes deliquescence behavior without any a priori specification of the relative humidities of deliquescence. Also included in the model is a formulation based on classical theory of nucleation kinetics that predicts crystallization behavior. Detailed phase diagrams of the sulfate/nitrate/ammonium/water system are presented as a function of relative humidity at 298.15 K over the complete space of composition

A computationally efficient inorganic atmospheric aerosol phase equilibrium model (UHAERO)

A variety of thermodynamic models have been developed to predict inorganic gas-aerosol equilibrium. To achieve computational efficiency a number of the models rely on a priori specification of the phases present in certain relative humidity regimes. Presented here is a new computational model, named UHAERO, that is both efficient and rigorously computes phase behavior without any a priori specification. The computational implementation is based on minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. The mathematical details of the solution are given elsewhere. The model also computes deliquescence and crystallization behavior without any a priori specification of the relative humidities of deliquescence or crystallization. Detailed phase diagrams of the sulfate/nitrate/ammonium/water system are presented as a function of relative humidity at 298.15 K over the complete space of composition

A phase equilibrium model for atmospheric aerosols containing inorganic electrolytes and organic compounds (UHAERO), with application to dicarboxylic acids

Computation of phase and chemical equilibria of water-organic-inorganic mixtures is of significant interest in atmospheric aerosol modeling. A new version of the phase partitioning model, named UHAERO, is presented here, which allows one to compute the phase behavior for atmospheric aerosols containing inorganic electrolytes and organic compounds. The computational implementation of the model is based on standard minimization of the Gibbs free energy using a primal-dual method, coupled to a Newton iteration. Water uptake and deliquescence properties of mixtures of aqueous solutions of salts and dicarboxylic acids, including oxalic, malonic, succinic, glutaric, maleic, malic, or methyl succinic acids, are based on a hybrid thermodynamic approach for the modeling of activity coefficients (Clegg and Seinfeld, 2006a, 2006b). UHAERO currently considers ammonium salts and the neutralization of dicarboxylic acids and sulfuric acid. Phase diagrams for sulfate/ammonium/water/dicarboxylic acid systems are presented as a function of relative humidity at 298.15 K over the complete space of compositions

Mathematical Modeling of Atmospheric Flow and Computation of Convex Envelopes

Atmospheric flow equations govern the time evolution of chemical concentrations in the atmosphere. When considering gas and particle phases, the underlying partial differential equations involve advection and diffusion operators, coagulation effects, and evaporation and condensation phenomena between the aerosol particles and the gas phase. Operator splitting techniques are generally used in global air quality models. When considering organic aerosol particles, the modeling of the thermodynamic equilibrium of each particle leads to the determination of the convex envelope of the energy function. Two strategies are proposed to address the computation of convex envelopes. The first one is based on a primal-dual interior-point method, while the second one relies on a variational formulation, an appropriate augmented Lagrangian, an Uzawa iterative algorithm, and finite element techniques. Numerical experiments are presented for chemical systems of atmospheric interest, in order to compute convex envelopes in various space dimensions

Analysis of a one-dimensional free boundary flow problem

A one-dimensional free surface problem is considered. It consists in Burgers' equation with an additional diffusion term on a moving interval. The well-posedness of the problem is investigated and existence and uniqueness results are obtained locally in time. A semi-discretization in space with a piecewise linear finite element method is considered. A priori and a posteriori error estimates are given for the semi-discretization in space. A time splitting scheme allows to obtain numerical results in agreement with the theoretical investigations