A first-order analysis of solute flux statistics in aquifers: The combined effect of pore-scale dispersion, sampling, and linear sorption kinetics

[1] We consider steady groundwater flow of uniform mean in aquifers of random, spatially variable, hydraulic conductivity. Analytical expressions for the statistical moments of mass fluxes of sorbing solutes in presence of pore-scale dispersion are derived, where the reactive solutes undergo first-order sorption kinetics. The developments which lead to the analytical formulation of the solute flux are rigorous in the first-order analysis framework, and results obtained are valid for weakly heterogeneous formations. The methodology is exemplified for a two-dimensional aquifer, assuming that the source is of small transverse extent compared to the heterogeneity length scales. The examples show that pore-scale dispersion has a relatively small effect on the mean point flux, whereas the point flux variance shows much larger sensitivity to pore-scale dispersion. The variance first decreases as the reaction rate departs from the nonreactive limit, but for equilibrium reactions it is of the same order as for nonreactive solutes. The effect of averaging the solute flux over a finite sampling area is also investigated. It is found that for the expected area-averaged flux the mixing effect induced by sampling tends to supersede that caused by pore-scale dispersion. On the contrary, pore-scale dispersion may have a strong effect on the flux variance also when sampling effects are taken into account.