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The extent of natural weathering of phiogopite crystals in a karstic environment and the composition of its weathering products have been examined through a multi-method investigation carried out on a volcanoclastic deposit discovered in the Grotta del Cervo cave, Pietrasecca, central Italy. Phlogopite crystals are a mixture of 1M and 2M1 polytypes and show mixed- layering with a low amount (1-4%) of smectite in the glass groundmass. Phiogopite crystals vary in composition from phlogopite to ferroan phiogopite. Their average structural formula is (K0.92Na0.03Ba0.03Ca0.02) (Mg2.05Al0.01Fe2+0.19Fe3+0.04Mn0.01Ti0.15 0.19 (Si2.63Al1.37)O10.16(OH1.57F0.27). Micromorphological, X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), scanning electron microscopy (SEM), and microprobe analyses (EMPA) showed that the mineralogical evolution of phiogopite crystals is consistent with in-situ pseudomor- phic weathering of mica to Al-rich dlioctahedral (rather than Mg-rich) clay minerals (beideffite-like) via phlogopite-smectite mixed-layer phases. The main mechanism of transformation is a layer-by-layer modification in which water composition, enriched in Si and Al from glass dissolution, is a major control. Mg loss, Ca and Na exchange for K, enrichment in Si and Al are the main processes required for beidellitization of phiogopite. Glass alteration produced sequentially smectite, chabazite, phillipsite and analcime, as leaching progressed and the interstitial fluids became increasingly alkaline. The type of zeolite found in the several samples (in the chabazite, phillipsite, analcime series) indicates that the alteration extent increases from wall to the ceiling and to the floor of the cave. [ABSTRACT FROM AUTHOR]

Decomposing fungi translocate manganese (Mn) as demonstrated by the fact that Mn has been found to accumulate on decomposing leaves associated with individual fungal hyphae forming insoluble Mn(III,IV) oxides that remain concentrated in diffuse patches. Here, we studied Mn translocation and precipitation by the saprophytic fungus Alternaria sp. strain FBL507 both on naturally decomposing oak leaves and in vitro experiments. Manganese was translocated and precipitated in beads and encrustations along the fungal hyphae. The combination of X-ray diffraction and scanning electron microscopy-energy dispersive X-ray spectroscopy chemical data showed that the precipitates found on leaves were rhodochrosite (MnCO3), birnessite ([Na, Ca, K]Mn2O4× 1.5H2O) and possibly Mn oxalate. The precipitates on wood were an amorphous Mn-O compound, probably MnO. Thus, Mn oxidation state in the precipitates spanned from +2 to +4, with +3 and +4 only in the birnessite on the leaves. In vitro experiments showed that Mn precipitates formed in living hyphae, suggesting the possibility that Mn precipitation is actively produced by the fungus. Such a possibility raises interesting questions regarding the role of readily available Mn in the activity of saprophytic fungi and other soil microorganisms, such as would result in a large involvement of Mn in the cycles of the major nutrient elements.