From laboratory to application

The great value of kinetic theory is that it frees us from many of the constraints of the equilibrium model and its variants (partial equilibrium, local equilibrium, and so on see Chapter 2). In early studies (e.g., Lasaga, 1984), geochemists were openly optimistic that the results of laboratory experiments could be applied directly to the study of natural systems. Transferring the laboratory results to field situations, however, has proved to be much more challenging than many first imagined. 

Many minerals have been found to dissolve and precipitate in nature at dramatically different rates than they do in laboratory experiments. As first pointed out by Paces (1983) and confirmed by subsequent studies, for example, albite weathers in the field much more slowly than predicted on the basis of reaction rates measured in the laboratory. The discrepancy can be as large as four orders of magnitude (Brantley, 1992, and references therein). As we calculate in Chapter 26, furthermore, the measured reaction kinetics of quartz (SiC 2) suggest that water should quickly reach equilibrium with this mineral, even at low temperatures. Equilibrium between groundwater and quartz, however, is seldom observed, even in aquifers composed largely of quartz sand. 

Geochemists (e.g., Aagaard and Helgeson, 1982) commonly attribute such discrepancies to difficulties in representing the surface area As of minerals in natural samples. In the laboratory, the mineral is fresh and any surface coatings have been removed. The same mineral in the field, however, may be shielded with oxide, hy- 

Even where it is not occluded, the mineral surface may not be reactive. In the va-dose zone, the surface may not be fully in contact with water or may contact water only intermittently. In the saturated zone, a mineral may touch virtually immobile water within isolated portions of the sediment s pore structure. Fluid chemistry in such microenvironments may bear little relationship to the bulk chemistry of the pore water. Since groundwater flow tends to be channeled through the most permeable portions of the subsurface, furthermore, fluids may bypass many or most of the mineral grains in a sediment or rock. The latter phenomenon is especially pronounced in fractured rocks, where only the mineral surfaces lining the fracture may be reactive. 

There are other important factors beyond the state of the surface that may lead to discrepancies between laboratory and field studies. Measurement error in the laboratory, first of all, is considerable. Brantley (1992) notes that rate constants determined by different laboratories generally agree to within only a factor of about 30. Agreement to better than a factor of 5, she reasons, might not be an attainable goal. 

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