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[en] The crystal structure of aragonite (a=4.9611(4), b=7.9672(6), c=5.7407(4) A, cell content: 4xCaCO3, space group: Pmcn) was refined with 1180 neutron diffraction data to Rsub(w)=0.014. The atomic parameters of earlier X-ray refinements were essentially confirmed, but were now determined with considerably higher accuracy. The aplanarity of the carbonate group is 0.0280(5) A, a value greater by 0.010 A than that in dolomite. (Author)
[en] The influence of milling on the transformations of the calcium carbonate phase has been studied using a laboratory centrifuge mill as well as a high energy planetary mill for grinding. The second one was fitted with two motors for freely selecting the translation and rotation movements of the grinding jars and therefore to vary the relative contribution of the shear and impact forces. The transformation phase of the calcite and aragonite has been observed although it is not thermodynamically aided. This transformation is helped by the application of shear forces more than by the energy released by the impact of the balls against the grinding material. A mechanism is proposed that explains this behavior (CW)
[en] In this article, the results of a treatment applied to dolomitic stones using an isopropyl colloidal solution based on calcium hydroxide nanoparticles with a concentration of 2.0g/l are presented. The consolidation process in the stone has been checked before and after 28 days of exposure to 75% relative humidity. Morphologic and structural studies of the consolidating product confirmed the carbonation process. X ray diffraction, electron microscopy (TEM and ESEM), and electron diffraction carried out on the consolidating product have confirmed the transformation of portlandite phase to calcium carbonate polymorph, calcite, aragonite and vaterite. Petrophysical tests performed on the stone before and after the application of the product have shown the improvement in the physical and hydrical properties due to the increase in the ultrasound velocity and density of the material, and a decrease in the capillarity coefficient and open porosity without significant changes in colour and brightness. The application of the consolidating product in the proposed experimental conditions is a natural method, compatible with the petrological characteristics of the substrate, without secondary damages on the stone, being an effective method to improve the durability of carbonate stones. (Author) 26 refs.
[en] The stabilisation of strong textures in mollusc shells has for long been a strong drawback towards precise structural determinations of these natural biocomposites. We demonstrate here on several crossed lamellar and nacre layers from two gastropods (Charonia lampas lampas and Haliotis tuberculata tuberculata) and one bivalve (Pinctada maxima), that on real specimens (without grinding or specific preparation), the textural information can be used efficiently for precise structural determination of the biogenic aragonite. This is done through the combination of orientation distribution function and cyclic Rietveld refinements on several hundreds to thousands of diffractions diagrams.
[en] Red abalone (Haliotis rufescens) nacre is a layered composite biomineral that contains crystalline aragonite tablets confined by organic layers. Nacre is intensely studied because its biologically controlled microarchitecture gives rise to remarkable strength and toughness, but the mechanisms leading to its formation are not well understood. Here we present synchrotron spectromicroscopy experiments revealing that stacks of aragonite tablet crystals in nacre are misoriented with respect to each other. Quantitative measurements of crystal orientation, tablet size, and tablet stacking direction show that orientational ordering occurs not abruptly but gradually over a distance of 50 (micro)m. Several lines of evidence indicate that different crystal orientations imply different tablet growth rates during nacre formation. A theoretical model based on kinetic and gradual selection of the fastest growth rates produces results in qualitative and quantitative agreement with the experimental data and therefore demonstrates that ordering in nacre is a result of crystal growth kinetics and competition either in addition or to the exclusion of templation by acidic proteins as previously assumed. As in other natural evolving kinetic systems, selection of the fastest-growing stacks of tablets occurs gradually in space and time. These results suggest that the self-ordering of the mineral phase, which may occur completely independently of biological or organic-molecule control, is fundamental in nacre formation
[en] The polymorphic phase transformation of thermally treated pearl powder was investigated by X-ray diffraction and thermoanalytical techniques. The phase transformation was based on quantification of the calcite content at various temperatures using Rietveld refinement analysis. The results show that the phase transformation of pearl aragonite occurred within a temperature range of 360–410 °C, which is 50–100 °C lower than the range for non-biomineralized aragonite. These thermoanalytical results suggest that the phase transformation of pearl aragonite may occur immediately after the thermal decomposition of the organic matrix in the pearl powder. An important finding is that decomposition of the organic matrix may greatly facilitate such transformation by releasing additional space for an easier structural reconstruction during the phase transformation process. - Highlights: ► Providing a new method to describe the polymorphic transition of pearl powder ► The phase transition sketch was exhibited by XRD phase quantitative analysis. ► There are dozens of degrees in advance comparing to natural aragonite. ► The phase transition occurs following the thermal decomposition of organism
[en] Complete text of publication follows. The aim of the work is the identification of the sulphurated phase's outbreak on an aragonite, dolomite and calcite-based original rock inside an abandoned mine. The studied Blende/Galena (ZnS/PbS) Mine, located in Lanestosa (Bizkaia, North of Spain) was operative until 1950. After decades, the area has only supported wild life and thus nowadays it could be considered as a polluted site which has become naturalized. The main alteration factors inside the mine are percolated water, gases come from the outside (CO2, O2) and biological activities. Mining activities generates loads of ore minerals and unwanted materials that with the time impact the surrounding environment. The waste includes granular, broken rock and soils ranging in size from the fine sand to large boulders, with the content of fine material largely dependent on the nature of the formation and extraction methods employed during mining. Waste materials geochemistry varies widely from mine to mine and may vary significantly at individual mines over time as different lithologic strata are exposed and geochemical processes alter characteristics of the waste. In order to determine the finest mineral composition in the galleries, several samples were collected. Once dried in a fume hood and sieved, the portions below 250 μm were subjected to non-destructive Raman spectroscopic analysis. The measurements reflected the ore precursors (primary phases: Blende, and Galena), several primary carbonates (dolomite, calcite and aragonite) with secondary minerals in trace levels (Brookite, Libethenite, Fluorapatita, Anatasa, Quartz, Apatite, Augite, Diopside, Anthracite, Hematite, Cosalite, Epidote, Rutile) and transformation products, probably of recent formation (Smithsonite, Massicot, Plattnerite, Gypsum, Siderite, Mendiphite, Escorodite, Gauberite, Goethite or Mascagnite). The origin of the secondary mineral may be related to percolated rain and snow water. This hypothesis is based in the acidic snow water collected in January of 2009 (pH?5). Acid water dissolves all carbonates and all those soluble salts leached in surface (ZnCO3 or PbCO3). Finally, a basic thermodynamic model has been developed in order to explain the primary mineral phases transformation to the secondary ones. Acknowledgements. This work was financially supported by the BERRILUR II Project (ref. IE06-179, ETORTEK, Basque Government).