A fresh view on the structure and twinning of owyheeite, a rod-polytype and twofold superstructure.

Owyheeite [Cu0.09 (1)Ag2.77 (4)Pb10.23 (4)Sb10.89 (5)S28.00 (5)] crystallizes as a twofold superstructure with P21/n symmetry and pseudo-orthorhombic metrics [a = 8.1882 (3) Å, b = 27.2641 (7) Å, c = 22.8679 (7) Å, ß = 90.293 (3)°, V = 5105.0 (3) Å3, Z = 4]. Owyheeite is systematically twinned by reflection at (021) or equivalently (021). Twinning is explained by describing a simplified Pmcn archetype structure as polytype built of two kinds of rods, which contact via electron-pair micelles. A procedure of generating hypothetical polytypes by tiling space with partially overlapping equivalent regions is described.

The parisite-(Ce) enigma: challenges in the identification of fluorcarbonate minerals.

A multi-methodological study was conducted in order to provide further insight into the structural and compositional complexity of rare earth element (REE) fluorcarbonates, with particular attention to their correct assignment to a mineral species. Polycrystals from La Pita Mine, Municipality de Maripí, Boyacá Department, Colombia, show syntaxic intergrowth of parisite-(Ce) with röntgenite-(Ce) and a phase which is assigned to B 3 S 4 (i.e., bastnäsite-3-synchisite-4; still unnamed) fluorcarbonate. Transmission electron microscope (TEM) images reveal well-ordered stacking patterns of two monoclinic polytypes of parisite-(Ce) as well as heavily disordered layer sequences with varying lattice fringe spacings. The crystal structure refinement from single crystal X-ray diffraction data - impeded by twinning, complex stacking patterns, sequential and compositional faults - indicates that the dominant parisite-(Ce) polytype M 1 has space group Cc. Parisite-(Ce), the B 3 S 4 phase and röntgenite-(Ce) show different BSE intensities from high to low. Raman spectroscopic analyses of parisite-(Ce), the B 3 S 4 phase and röntgenite-(Ce) reveal different intensity ratios of the three symmetric CO3 stretching bands at around 1100 cm-1. We propose to non-destructively differentiate parisite-(Ce) and röntgenite-(Ce) by their 1092 cm-1 / 1081 cm-1 ν1(CO3) band height ratio.

Fossil microbial shark tooth decay documents in situ metabolism of enameloid proteins as nutrition source in deep water environments.

Alteration of organic remains during the transition from the bio- to lithosphere is affected strongly by biotic processes of microbes influencing the potential of dead matter to become fossilized or vanish ultimately. If fossilized, bones, cartilage, and tooth dentine often display traces of bioerosion caused by destructive microbes. The causal agents, however, usually remain ambiguous. Here we present a new type of tissue alteration in fossil deep-sea shark teeth with in situ preservation of the responsible organisms embedded in a delicate filmy substance identified as extrapolymeric matter. The invading microorganisms are arranged in nest- or chain-like patterns between fluorapatite bundles of the superficial enameloid. Chemical analysis of the bacteriomorph structures indicates replacement by a phyllosilicate, which enabled in situ preservation. Our results imply that bacteria invaded the hypermineralized tissue for harvesting intra-crystalline bound organic matter, which provided nutrient supply in a nutrient depleted deep-marine environment they inhabited. We document here for the first time in situ bacteria preservation in tooth enameloid, one of the hardest mineralized tissues developed by animals. This unambiguously verifies that microbes also colonize highly mineralized dental capping tissues with only minor organic content when nutrients are scarce as in deep-marine environments.

Synthetic aenigmatite analog Na2(Mn5.26Na0.74)Ge6O20: structure and crystal chemical considerations.

Disodium hexamanganese(II,III) germanate is the first aenigmatite-type compound with significant amounts of manganese. Na(2)(Mn(5.26)Na(0.74))Ge(6)O(20) is triclinic and contains two different Na positions, six Ge positions and 20 O positions (all with site symmetry 1 on general position 2i of space group P1). Five out of the seven M positions are also on general position 2i, while the remaining two have site symmetry 1 (Wyckoff positions 1f and 1c). The structure can be described in terms of two different layers, A and B, stacked along the [011] direction. Layer A contains pyroxene-like chains and isolated octahedra, while layer B is built up by slabs of edge-sharing octahedra connected to one another by bands of Na polyhedra. The GeO(4) tetrahedra show slight polyhedral distortion and are among the most regular found so far in germanate compounds. The M sites of layer A are occupied by highly charged (trivalent) cations, while in layer B a central pyroxene-like zigzag chain can be identified, which contains divalent (or low-charged) cations. This applies to the aenigmatite-type compounds in general and to the title compound in particular.

High pressure minerals in the Château-Renard (L6) ordinary chondrite: implications for collisions on its parent body.

We report the first discoveries of high-pressure minerals in the historical L6 chondrite fall Château-Renard, based on co-located Raman spectroscopy, scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy and electron backscatter diffraction, electron microprobe analysis, and transmission electron microscopy (TEM) with selected-area electron diffraction. A single polished section contains a network of melt veins from ~40 to ~200 µm wide, with no cross-cutting features requiring multiple vein generations. We find high-pressure minerals in veins greater than ~50 µm wide, including assemblages of ringwoodite + wadsleyite, ringwoodite + wadsleyite + majorite-pyropess, and ahrensite + wadsleyite. In association with ahrensite + wadsleyite at both SEM and TEM scale, we find a sodic pyroxene whose Raman spectrum is indistinguishable from that of jadeite but whose composition and structure are those of omphacite. We discuss constraints on the impact record of this meteorite and the L-chondrites in general.