André Jorge Pinto

Palaeopascichnus is an Ediacaran organism, whose phylogenetic affiliation and functional anatomy are both shrouded in mystery. Different studies and assessments have interpreted this fossil as macrophytes or foraminifera-like protists. Currently ongoing discussions concerns the possible phylogenetic relation between Palaeopascichnus and modern xenophyophores; benthic organisms that built agglutinated tests. We present micro-XRD, SEM-EDS and three-dimensional microtomographic data on a possible Palaeopascichnus specimen from the Ediacaran Fara Formation, in Wadi Bani Awf, Jabal Akhdar, Oman. The unique preservation of this specimen as a full positive epirelief of drusy calcite growths represents a new taphotype for this organism, enabling a more accurate observation of chamber structure and better morphological characterization. The data gathered concerning both chamber´s dimensions and morphology does not point towards an affiliation with any known Paleopascichnus species, except for much smaller P. jiumenensis. Therefore, it is possible that this specimen represents a new, previously unknown species.

Weathering products of sphalerite-bearing ores play an important role in controlling the fate of Zn in the environment. In this framework, the relative stability of Zn carbonates is of special relevance for the common case of ore weathering by carbonated groundwater in the presence of calcium carbonates. We investigated the experimental (co)nucleation and growth of Zn and Ca carbonates at 25 °C in finite double diffusion silica hydrogel media with the purpose of deciphering the system’s reactive pathway and unraveling the major governing factors behind the obtained mineral assemblages. The crystallized solids were carefully extracted two months post-nucleation and studied with micro-Raman spectroscopy, micro X-ray diffraction (XRD), scanning electron microscopy, and electron microprobe (EMP) methods. The obtained results indicate that the grown Zn-bearing phases corresponded to smithsonite and/or Zn hydroxyl carbonate, while CaCO₃ polymorphs aragonite and calcite were also crystallized. Moreover, the observed mineral textural relationships reflected the interplay between supersaturation with respect to CaCO₃/pCO₂ and the grown Zn-bearing carbonate. Experiments conducted in more supersaturated conditions with respect to CaCO₃ polymorphs (higher pCO₂) favored the precipitation of smithsonite, while the opposite was true for the obtained Zn hydroxyl carbonate phase. The gathered Raman, XRD, and EMP data indicate that the latter phase corresponded to a non-stoichiometric, poorly crystalline solid.

The present study showcases a series of crystallization experiments using a specially designed double diffusion system to grow crystals belonging to the calcium carbonate–phosphate system. The experimental U-shaped device comprised two vertical solution containers, separated by a horizontal column of silica hydrogel. Each container was filled with 0.5 M CaCl₂ and 0.5 M Na₂CO₃ solutions, which diffused through the gel column over time. Na₃PO₄ solutions, with 50 and 500 ppm concentrations, were incorporated into the gel in different experiments, resulting in a homogeneous distribution of phosphate concentrations within the diffusion column. After 15- and 30-day incubation periods post-nucleation, the crystals formed in different sections of the gel were carefully extracted and studied with scanning electron microscopy and electron microprobe. Additionally, Raman spectra were collected from the samples using a confocal Raman microscope, providing further insights into their molecular composition and structural properties. The obtained results show that under the induced experimental conditions (i) phosphate incorporates into calcite’s structure, and (ii) the growth of calcium phosphates in the presence of carbonate ions involves the sequential, heterogeneous nucleation of CO₃-bearing OCP/HAP-like phases, with Raman spectral characteristics very similar to those of bioapatites.

The present study showcases a series of crystallization experiments using a specially designed double diffusion system to grow crystals belonging to the calcium carbonate-phosphate system. The experimental U-shaped device comprised two vertical solution containers, separated by a horizontal column of silica hydrogel. Each container was filled with 0.5 M CaCl2 and 0.5 M Na2CO3 solutions, which diffused through the gel column over time. Na3PO4 solutions, with 50 and 500 ppm concentrations, were incorporated into the gel in different experiments, resulting in a homogeneous distribution of phosphate concentrations within the diffusion column. After 15 and 30 days incubation period post-nucleation, the crystals formed in different sections of the gel were carefully extracted and studied with scanning electron microscopy and electron microprobe. Additionally, Raman spectra were collected from the samples using a confocal Raman microscope, providing further insights into their molecular composition and structural properties. The obtained results show that under the induced experimental conditions (i) phosphate incorporates into calcite´s structure, and (ii) the growth of calcium phosphates in the presence of carbonate ions involves the sequential, heterogeneous nucleation of CO3-bearing OCP/HAP-like phases with Raman spectral characteristics very similar to those of bioapatites.

Rutile, a common accessory mineral in a wide variety of rocks, is the most stable naturally occurring TiO₂ polymorph. The relationship between its trace element composition and formation conditions has provided geoscientists with discriminant tools for fingerprinting geological processes, such as magmatic evolution and subduction zone metamorphism, alongside applications to the study of sediment provenance. In the present work, volcaniclastic rock samples belonging to Fara and Saiq Formations, outcropping in Jebel Akhdar mountains, Oman, are studied with Raman spectroscopy and Electron Microprobe (EMP) aiming: of (i) the identification of different naturally-occurring TiO₂ polymorphs, (ii) the evaluation of their trace element contents in relation with hydrothermal alteration features, and (iii) the analysis of the mineral reactive pathways behind the observed textural relationships. Raman investigations demonstrated that interstitial, fine-grained TiO₂ corresponds to anatase, whereas rutile occurs as isolated single grains. EMP determinations further revealed that an identified Nb-enrichment in anatase is coupled with a corresponding Nb-depletion in rutile. The combination of the obtained results with petrographic observations enabled unravelling the TiO₂ reactive pathways affecting the studied samples. Thus, a coupled polymorphic dissolution-precipitation reaction assisting rutile-to-anatase conversion has been defined, together with the role of Nb in further stabilizing the structure of the lower temperature polymorph. Semi-quantitative thermometric considerations suggest that rutile substrates are likely of magmatic origin, whereas anatase formation is clearly associated with a lower temperature aqueous environment. The gathered results raise fundamental questions concerning the application of commonly used rutile-based geochemical and thermometric tools.