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Mineral replacement reactions mediated by fluids are common in sedimentary basins, where they influence geochemical cycles. Phosphorous (P) pollution of soils, sediments and water bodies is currently a widespread problem. Some apatite accumulations in sediments may have formed through the interaction of P-bearing aqueous solutions with mineral surfaces that result in mineral replacement reactions. Here, we investigate the pseudomorphic replacement of anhydrite single crystals by aggregates of β-tricalcium phosphate and hydroxyapatite upon interaction with a P-bearing solution at temperatures between 120 and 200 °C. SEM imaging is used to study the texture of the aggregates. Rietveld refinement of the X-ray diffraction patterns and Raman spectra analysis of the reacted samples provide information on the kinetics of the replacement. At all temperatures β-tricalcium phosphate forms alongside hydroxyapatite at early stages of the replacement reaction. At T ≥ 180 °C, hydroxyapatite/β-tricalcium phosphate ratio rapidly increases, and hydroxyapatite is the only phase in fully replaced samples. At T < 180 °C hydroxyapatite/β-tricalcium phosphate ratio increases slowly and fully replaced samples still contain significant amounts of β-tricalcium phosphate. The progress of the replacement is facilitated by the formation of porosity. The evolution of the hydroxyapatite/β-tricalcium phosphate ratio and the crystal habit of both phases strongly influence the arrangement of this porosity. The empirical activation energy Ea (kJ/mol) of the replacement reaction is determined by the Avrami and the iso-conversion methods. Both approaches yield an Ea of ~40 kJ/mol. Anhydrite dissolution appears as the rate-limiting process and the overall kinetics of the replacement reaction is controlled by the rate diffusion of dissolved species through the porosity network. The ripening of the metastable β-tricalcium phosphate into hydroxyapatite affects the characteristics of the porosity network and further modulates the kinetics of the replacement. These results may improve the understanding of the mechanisms of P-sequestration by mineral surfaces through coupled dissolution–precipitation reactions and shed light on the origin of apatite accumulations associated to evaporitic sedimentary rocks. [ABSTRACT FROM AUTHOR]

Many studies have improved our understanding of the mode of preservation at the Crato fossil Lagerstätte. The high degree of preservation of the Crato mineralized insects is thought to be a consequence of the diffusion of ions through carcasses and envelopment by bacteria that, in turn, created microenvironmental conditions that led to mineralization, mainly pyritization. Pyritized insects have been oxidized by in situ weathering to more stable oxide/hydroxy minerals during Quaternary time. This transformation is essential to maintain the palaeontological information acquired during microbially induced pyritization in an oxidizing atmosphere. However, intense weathering can diminish or obscure the morphological fidelity, and little attention has been paid to the post-diagenetic processes experienced by these fossils. Here, we aim to determine the degree of alteration undergone by Crato pyritized insects using the following combination of analytical tools: scanning electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared and Raman spectroscopy. Our results show that well-preserved insects are preferentially replaced by haematite and poorly preserved fossils are replaced by goethite. In addition, we recorded three types of post-diagenetic alteration: insects with iron-oxide overgrowths; insects associated with black coatings, sometimes with the formation of dendrites; and insects preserved as an impression, where only the outline of the body remains. All of these alterations have the potential to distort or tarnish palaeontological information. Here, we measured the effects of such telodiagenetic alterations at macro and micro scales. Therefore, this taphonomic approach has wide applicability wherever fine-grained deposits bearing mineralized insects are found. [ABSTRACT FROM AUTHOR]

Over the almost 190 years-long research of the Ditrău Alkaline Massif (Eastern Carpathians, Romania), felsic rocks have been regarded as homogeneous, uniform units of the igneous complex. Nevertheless, our detailed textural study revealed that the felsic suite (diorite–alkaline feldspar syenite and nepheline-bearing syenite–granite series) cropping out north of the Jolotca Creek valley is more heterogenous at micro-scale than previously thought. This heterogeneity partly derives from abundant mafic mineral-rich clusters; nevertheless, felsic minerals also exhibit various, remarkable textural features. Outcrop to micro-scale traits of felsic crystal settling, mafic mineral aggregates and flow fabrics along with metamorphic country rock xenoliths suggest that the studied rocks crystallized under dynamic magmatic conditions. Cumulate formation, shear flow, convection currents as well as various open-system magmatic processes (e.g., magma recharge, magma mixing and mingling, crystal or mush transfer and recycling, country rock assimilation) played a significant role in the petrogenesis of the examined felsic suite. Based on field observations as well as on the microtextural relationship of the minerals, two major groups of felsic rocks were distinguished: (1) felsic rocks (lacking or containing sparse mafic minerals) spatially associated with mafic rocks and (2) felsic rocks (with mafic minerals and clots) spatially unassociated with mafic rocks. Rocks of the former group are dominated by plagioclase, accompanied by minor alkaline feldspar, biotite and accessory titanite. Distinct structural and textural features suggest the physical accumulation of the rock-forming phases. Such textural properties can also be observed in some rocks of the second group. Isolated mafic minerals are rather scarce in the latter; nevertheless, different types of aggregates made up of either identical or various mafic phases are more common. Clustered minerals are either intact or show different stages of alteration. A detailed petrographic study of the above-mentioned peculiarities has been implemented in order to define their potential origin(s) and petrogenetic significance. [ABSTRACT FROM AUTHOR]

• CaCO 3 is rapidly converted to CaF 2 by the action of a KF solution at room temperature. • The volumetric reaction deficit is about 1/3. • About 2% of potassium enters into CaF 2 lattice. • The KCaF 3 compound is unstable at temperatures below 500 °C. Conversion of microcrystalline calcium carbonate powder to fluorite by reacting it with potassium fluoride solution is studied. The reaction occurs at room temperature and yields a white flowing powder. Rhombohedral CaCO 3 microcrystals are replaced by an ensemble of CaF 2 nanoparticles sized ca. 20 nm, which in part fill in the volume of the precursor microcrystals. The product calcium fluoride contains about 2 mol% KF. KCaF 3 is not produced by the reaction, and KCaF 3 is a high-temperature compound stable above 500 оС. [Display omitted] [ABSTRACT FROM AUTHOR]