Abstract
Mineral compositions are used to infer pressures, temperatures, and
timescales of geological processes. The thermodynamic techniques
underlying these inferences assume a uniform, constant pressure.
Nonetheless, convergent margins generate significant non-hydrostatic
(unequal) stresses, violating the uniform pressure assumption and
creating uncertainty. Materials scientists F. Larché and J. Cahn derived
an equation suitable for non-hydrostatically stressed geologic
environments that links stress and equilibrium composition in elastic,
multi-component crystals. However, previous works have shown that for
binary solid solutions with ideal mixing behavior, hundreds of MPa to
GPa-level stresses are required to shift mineral compositions by a few
hundredths of a mole fraction, limiting the equation’s applicability.
Here, we apply Larché and Cahn’s equation to garnet, clinopyroxene, and
plagioclase solid solutions, incorporating for the first time non-ideal
mixing behavior and more than two endmembers. We show that non-ideal
mixing increases predicted stress-induced composition changes by up to
an order of magnitude. Further, incorporating additional solid solution
endmembers changes the predicted stress-induced composition shifts of
the other endmembers being considered. Finally, we demonstrate that
Larché and Cahn’s approach yields positive entropy production, a
requirement for any real process to occur. Our findings reveal that
stresses between tens and a few hundred MPa can shift mineral
compositions by several hundredths of a mole fraction. Consequently,
mineral compositions could plausibly be used to infer stress states. We
suggest that stress-composition effects could develop via
intracrystalline diffusion in any high-grade metamorphic setting, but
are most likely in hot, dry, and strong rocks such as lower crustal
granulites.