The effects of stress on reactions in the Earth: Sometimes rather mean, usually normal, always important

Abstract

AbstractStress affects chemical processes on all scales in the Earth but the magnitude of its effect is debated. Here, I give a new synthesis of the theory that describes the effects of stress on chemistry, elaborating upon work in Materials Science which is built from fundamental thermodynamic laws, and show its significance in Earth Science. There are separate but compatible relationships describing what happens (1) at interfaces and (2) within grains. (1) The main chemical effects of stress in the Earth are due to variations in normal stress along grain interfaces and between interfaces with different orientations. For reactions involving diffusion these variations give effects on mineral stability broadly equivalent to pressure changes of (molar volume)/(molar volume change during reaction) × (stress variation). The volume ratio is generally large and so the effects of normal stress variations are always important since all stressed rocks have interfaces supporting different normal stresses. There is no global chemical equilibrium in a stressed system, so reaction kinetics contribute to ongoing evolution until stresses relax: this evolution can include deformation by diffusion creep and pressure solution, possibly with new mineral growth. These effects are relevant for predicting the conditions for reactions involving fluids, such as serpentinite formation and breakdown (relevant for the Earth's volatile cycles) and for other reactions such as ringwoodite breakdown (relevant for understanding the 660 km mantle discontinuity). (2) Within stressed solid solution grains it is not possible to define chemical potentials of all chemical components since one has to be specified as “immobile.” The chemical potential of a “mobile” component such as an exchange vector can be defined. It depends on the “partial molar strain,” a second rank tensor defining the variation in unit cell geometry with composition. In cubic crystals the partial molar strain is isotropic and the chemical potential of a mobile component depends on mean stress. In other crystal systems the partial molar strain is anisotropic and the chemical potential depends on a “weighted” mean stress; orientation as well as magnitude of stress has an influence. I propose “chemical palaeopiezometry”—the possibility of measuring past stress levels via chemistry. Examples show that stress variations in hundreds of MPa to GPa are required to produce 2% variations in composition but high stresses and/or precise chemical analyses will allow this proposal to be tested. High stresses around inclusions and dislocations could be targeted. So, the weighted mean stress inside grains has an effect which is relatively minor although potentially valuable in explaining chemical variations; the normal stress at interfaces plays the main role in chemical processes and its effects are of significant magnitude.