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The influence of crystallography and kinetics on phengite breakdown reactions in a low-pressure metamorphic aureole
Authors:R H Worden  G T R Droop  P E Champness
Institution:(1) Department of Geology, Manchester University, Oxford Road, M13 9PL Manchester, UK;(2) Present address: Sunbury Research Centre, BP International Ltd, Chertsey Road, TW16 7LN Sunbury on Thames, Middlesex, UK
Abstract:A natural example of phengite that had undergone partial thermal decomposition at a pressure of about 0.5 kbar and a temperature of about 680° C in a contact aureole was exmined in the transmission electron microscope (TEM). Partially pseudomorphed phengites were found to consist of combinations of phengite, biotite, K-feldspar, mullite, sillimanite, spinel and cordierite. Different areas within individual, partially pseudomorphed, phengite grains show various degrees of reaction and different reaction products; the cores are the least reacted and the margins have reacted most. In the cores the assemblage Al-, Mg-enriched phengite+biotite +K-feldspar+mullite±spinel has formed, whereas the assemblage K-feldspar+mullite+sillimanite+spinel +biotite+cordierite has formed at the edges. According to our thermodynamic calculations, the breakdown of phengite should have produced cordierite+spinel +corundum+K-feldspar in regions isolated from the influx of SiO2 and cordierite+andalusite+quartz+K-feldspar in regions near the edge of the grains that were essentially saturated with SiO2. Chemical equilibrium was not achieved in any part of the partially pseudomorphed phengites on a micron scale or larger. Breakdown theoretically should have been complete by about 550° C; the reaction temperature was overstepped by at least 130° C for 20–25 years. The variations in the degree and type of reaction are probably due partly to the availability of suitable nucleation sites in different regions, partly to the need to remove H2O from reaction sites and partly to the influence of SiO2, which diffused into the grains during metamorphism. The presence of SiO2 lowers the equilibrium temperatures. Thus there is a higher driving force for breakdown near the grain boundaries than in the cores. Most of the products show an orientation relationship with the parent phengite and have consistent habit planes; they have their closest-packed planes and closest-packed directions parallel to one another and to those of phengite. Such relationships minimize the strain and surface energies at nucleation and favour most rapid nucleation and growth of the reaction products. The great structural similarity of biotite to phengite resulted in its having the highest rate of nucleation and growth of any product and it occurred in all areas of the phengite pseudomorphs studied. Mullite and sillimanite were produced metastably. Mullite has more rapid nucleation kinetics than other aluminosilicates because it is structurally disordered. Sillimanite formed rather than andalusite in regions of the partially pseudomorphed phengites where the reaction reached an advanced stage, because the reaction from phengite to andalusite requires an energetically unfavourable change in aluminium co-ordination state.
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