Reactions leading to the formation and breakdown of stilpnomelane in the Otago Schist, New Zealand

Semi-pelitic rocks ranging in grade from the prehnite–pumpellyite to the greenschist facies from southeastern Otago, New Zealand, have been investigated in order to evaluate the reactions leading to formation and breakdown of stilpnomelane. Detrital grains of mica and chlorite along with fine-grained authigenic illite and chlorite occur in lower-grade rocks with compactional fabric parallel to bedding. At higher grades, detrital grains have undergone dissolution, and metamorphic phyllosilicates have crystallized with preferred orientation (sub)parallel to bedding, leading to slaty cleavage. Stilpnomelane is found in metapelites of the pumpellyite–actinolite facies and the chlorite zone of the greenschist facies, but only rarely in the biotite zone of the greenschist facies. Illite or phengite is ubiquitous, whereas chlorite occurs only rarely with stilpnomelane upgrade of the pumpellyite-out isograd. Chemical and textural relationships suggest that stilpnomelane formed from chlorite, phengite, quartz, K-feldspar and iron oxides. Stilpnomelane was produced by grain-boundary replacement of chlorite and by precipitation from solution, overprinting earlier textures. Some relict 14 Å chlorite layers are observed by TEM to be in the process of transforming to 12 Å stilpnomelane layers. The AEM analyses show that Fe is strongly partitioned over Mg into stilpnomelane relative to chlorite (KD#2.5) and into chlorite relative to phengite (KD#1.9). Modified A∞FM diagrams, projected from the measured phengite composition rather than from ideal 33102 are used to elucidate reactions among chlorite, stilpnomelane, phengite and biotite. In addition to pressure, temperature and bulk rock composition, the stilpnomelane-in isograd is controlled by variations in K, Fe3+/Fe2+, O/OH and 2 contents, and the locus of the isograd is expected to vary in rocks of different oxidation states and permeabilities. Biotite, quartz and less phengitic muscovite form from stilpnomelane, chlorite and phengite in the biotite zone. Projection of bulk rock compositions from phengite, 2 2 and 2 reveals that they lie close to the polyhedra defined by the A∞FM minerals and albite. Other extended A∞FM diagrams, such as one projected from phengite, 2 24 2 and 2 may prove useful in the evaluation of other low-grade assemblages.