In large-scale air quality simulations we are interested in the influence factors which cause changes of pollutants, and optimization methods which improve forecasts. The solutions to these problems can be achieved by incorporating adjoint models, which are efficient in computing the derivatives of a functional with respect to a large number of model parameters. In this research we employ first order adjoints in air quality simulations. Moreover, we explore theoretically the computation of second order adjoints for chemical transport models, and illustrate their feasibility in several aspects. We apply first order adjoints to sensitivity analysis and data assimilation. Through sensitivity analysis, we can discover the area that has the largest influence on changes of ozone concentrations at a receptor. For data assimilation with optimization methods which use first order adjoints, we assess their performance under different scenarios. The results indicate that the L-BFGS method is the most efficient. Compared with first order adjoints, second order adjoints have not been used to date in air quality simulation. To explore their utility, we show the construction of second order adjoints for chemical transport models and demonstrate several applications including sensitivity analysis, optimization, uncertainty quantification, and Hessian singular vectors. Since second order adjoints provide second order information in the form of Hessian-vector product instead of the entire Hessian matrix, it is possible to implement applications for large-scale models which require second order derivatives. Finally, we conclude that second order adjoints for chemical transport models are computationally feasible and effective. / Master of Science

A deep scientific understanding of complex physical systems, such as the atmosphere, can be achieved neither by direct measurements nor by numerical simulations alone. Data assimilation is a rigorous procedure to fuse information from a priori knowledge of the system state, the physical laws governing the evolution of the system, and real measurements, all with associated error statistics. Data assimilation produces best (a posteriori) estimates of model states and parameter values, and results in considerably improved computer simulations. The acquisition and use of observations in data assimilation raises several important scientific questions related to optimal sensor network design, quantification of data impact, pruning redundant data, and identifying the most beneficial additional observations. These questions originate in operational data assimilation practice, and have started to attract considerable interest in the recent past. This dissertation advances the state of knowledge in four dimensional variational (4D-Var) - data assimilation by developing, implementing, and validating a novel computational framework for estimating observation impact and for optimizing sensor networks. The framework builds on the powerful methodologies of second-order adjoint modeling and the 4D-Var sensitivity equations. Efficient computational approaches for quantifying the observation impact include matrix free linear algebra algorithms and low-rank approximations of the sensitivities to observations. The sensor network configuration problem is formulated as a meta-optimization problem. Best values for parameters such as sensor location are obtained by optimizing a performance criterion, subject to the constraint posed by the 4D-Var optimization. Tractable computational solutions to this "optimization-constrained" optimization problem are provided. The results of this work can be directly applied to the deployment of intelligent sensors and adaptive observations, as well as to reducing the operating costs of measuring networks, while preserving their ability to capture the essential features of the system under consideration. / Ph. D.