Uncertainty propagation in geochemical calculations: non-linearity in solubility equilibria

Uncertainty in the results of geochemical equilibrium calculations may be estimated from input uncertainties using either derivative approximations or Monte Carlo simulations. While derivative methods are fast and convenient for many equilibria, inherently non-linear aspects of solubility equilibria may lead to a failure of the linear approximation and thus to asymmetric and/or bimodal uncertainty in calculated concentrations. In these cases, the use of derivative methods and the assumption of Gaussian uncertainty in the calculated concentrations misrepresent the propagated uncertainty. Equilibria with gibbsite, calcite, and the chromate analog of jarosite are examined.