Rate controls on the chemical weathering of natural polymineralic material. I. Dissolution behaviour of polymineralic assemblages determined using batch and unsaturated column experiments

Chemical weathering rates for a mudstone obtained from a mining environment were investigated using a combination of batch reactors and hydrologically unsaturated column experiments. Results of tracer tests were combined with relationships between solute concentrations, mass fluxes, flow rates and residence times, and used to calculate element release rates and infer rate-controlling mechanisms for the two different experimental environments. Elements that eluted from column experiments exhibited either: (1) concentrations independent of flow rate and column length coupled with mass flux increasing with flow rate, or (2) an inverse relationship between concentration and flow rate coupled with mass flux increasing with both column length and flow rate. The former is attributed to equilibrium-controlled release of particular elements (Si, Al), while the latter is ascribed to transport-controlled release of others (Mg, Mn, Ca, Na, K, S). Tracer tests using NaBr solutions revealed that some elements were also affected by ion exchange (Mg, Mn, Ca, Na), but these effects were temporary and did not mask underlying dissolution rate-controlling mechanisms. Analysis of characteristic diffusive lengths was used to distinguish between transport rates limited by the transfer of solutes between immobile and mobile water within the columns, and rates limited by slow diffusion across partially reacted mineral layers. The analysis suggests that transfer between immobile and mobile water limited the element release rates, with diffusion hindered by low diffusion coefficients within the unsaturated medium, and by low interfacial areas between mobile and immobile fluids. Results of the batch experiments showed different characteristics. Element concentrations either rose to a plateau or increased linearly with time. Rate-controlling mechanisms associated with these characteristics were equilibrium (Fe) and surface kinetic reactions (Si, Mg, Mn, Ca, K, S), respectively. Surface area-normalized element release rates for Mg, Mn, Ca and S are consistently a factor of 4 higher than those from the column experiments. This is a significant difference and cannot be attributed to differences in mineral preparation or to factors influencing individual minerals. It must, therefore, reflect the difference in the rate-controlling mechanism, that is, transport vs. surface-kinetic control. These results suggest that some proportion of the commonly recorded discrepancy between laboratory and