A continuous phase gradient in a “monocrystalline” pyrrhotite

X-ray diffraction and microprobe analyses of pseudomonocrystalline fragments of pyrrhotite from Bodenmais, Bavaria, revealed continuous gradients in composition and phase distribution. The gradients extend from the well-developed (0001) cleavage surfaces 15–30 μm into the bulk of the crystals. The phase gradient is made up two low-temperature pyrrhotites with monoclinic (4C) and hexagonal (5C) symmetry. The fraction of monoclinic pyrrhotite, expressed on the basis of recorded X-ray intensities, I, decreases exponentially according to I _(mon)/I _(hex)+I _(mon)] = EXP (aX+b) where a is a constant ranging from ?0.04 to ?0.25, X is the depth from the (0001) cleavage surface in μm, and b is a constant determined by the intensity ratios obtained from the untreated cleavage surfaces. The phase gradient developed during retrograde reactions from a continuous composition gradient. This primary gradient was caused by the extraction of iron from a disordered, high-temperature hexagonal pyrrhotite during oxidation of the cleavage surfaces at temperatures above 254° C (upper stability limit of 4C pyrrhotite), probably above 308° C. The length of the c axis of the monoclinic superstructure slightly increases with the increase in iron and decrease in vacancy content of the bulk. This expansion is probably due to a minor compositional variation of the monoclinic phase controlled by the availability of vacancies during the transition to low-temperature phases.