Calibration of subsurface batch and reactive-transport models involving complex biogeochemical processes

In this study, the calibration of subsurface batch and reactive-transport models involving complex biogeochemical processes was systematically evaluated. Two hypothetical nitrate biodegradation scenarios were developed and simulated in numerical experiments to evaluate the performance of three calibration search procedures: a multi-start non-linear regression algorithm (i.e. multi-start Levenberg–Marquardt), a global search heuristic (i.e. particle swarm optimization), and a hybrid algorithm that combines the particle swarm procedure with a regression-based “polishing” step. Graphical analysis of the selected calibration problems revealed heterogeneous regions of extreme parameter sensitivity and insensitivity along with abundant numbers of local minima. These characteristics hindered the performance of the multi-start non-linear regression technique, which was generally the least effective of the considered algorithms. In most cases, the global search and hybrid methods were capable of producing improved model fits at comparable computational expense. In other cases, the multi-start and hybrid calibration algorithms yielded comparable fitness values but markedly differing parameter estimates and associated uncertainty measures.