Biologically mediated crystallization of buddingtonite in the Paleoproterozoic; organic-igneous interactions from the Volyn Pegmatite, Ukraine

The Volyn pegmatites from Volodarsk-Volynskyi in the Zhytomyr Oblast, NW Ukraine, are associated with granites genetically related to the Paleoproterozoic Korosten pluton. Their late-stage evolution is characterized by the formation of opal-cemented breccia. A polymineralic pseudomorph after beryl within the breccia includes bertrandite (+ or -euclase) + F-muscovite (with tobelite component) + buddingtonite + organic matter (OM) + opal (+ traces of K-feldspar, albite, columbite, FeS (sub 2) , barite, REE-minerals). Sector-zoned and platy to fibrous buddingtonite has variable (K+Na)- vs. NH (sub 4) -contents (electron microprobe analyses) and some H (sub 2) O or H (sub 3) O (super +) , as indicated by microscope infrared spectroscopy. We suggest that ammonium was produced by decay of OM, which is partly preserved in the pseudomorph. Energy-dispersive electron microprobe data of the OM show with increasing O-decreasing C-N-content due to degassing; the OM contains the high field strength elements Zr (< or =7 at%), Y (< or =3 at%), Sc (< or =0.8 at%), REE (< or =0.3 at%), Th (< or =0.2 at%), and U (< or =1.25 at%), which increase with increasing O-content. Transmission electron microscopy of the OM confirms the presence of N; Zr, Si, and O (with other HFSE) are concentrated in nanometer-sized areas and at the transition from OM to opal in nanometer-sized platy Zr-Si-O crystals. C-rich areas are amorphous but show poorly developed lattice fringes. OM is present in the pseudomorph also as brown pigmentation of opal and in pegmatitic beryl from Volyn as a component in late stage fluid inclusions, identified by C-H vibrational bands in infrared spectra. Stable isotope investigations of C and N of buddingtonite, black opal and kerite (fibrous OM known from the literature to occur in the Volyn pegmatites and interpreted as microfossils) indicate a biogenic origin of the OM. We propose that OM in the pseudomorph is condensed kerite, which achieved the high concentrations of high field strength elements via fluid-pegmatite interaction. Although no age determination of minerals in the pseudomorph is available, textural arguments and phase equilibria indicate its formation in a late stage of the pegmatite evolution, at P-T conditions below approximately 100 MPa/150 degrees C. We favor a conceptual model for the formation of the Volyn buddingtonite in analogy to Phanerozoic occurrences of buddingtonite, where over and around the shallow anorthosite-granite Korosten pluton hydrothermal convection cells introduced N-bearing hydrocarbons and its precursors into the cooling igneous rocks. Due to the elevated temperature, the OM disintegrated into degassing volatile and non-volatile residual components analogous to petroleum maturation. Organic N, released as NH (sub 4) , was then incorporated into buddingtonite.