Patterns of rare earth and other trace elements in different size fractions of clays of Campanian–Maastrichtian deposits from the Portuguese western margin (Aveiro and Taveiro Formations)

The Upper Cretaceous (Campanian–Maastrichtian) Taveiro and Aveiro Formations belong to the northern sector of the Lusitanian basin (Portuguese western margin). The Taveiro Formation was deposited in alluvial fans, including mud flow beds, lakes and sinuous rivers. The Aveiro Formation was deposited in a flat region with low hydrodynamics channels, with the formation of a barrier island-tidal system. The reconstruction of this sedimentary basin may be difficult due to its complex architecture. This work aims a methodology to be used in the reconstruction of Cretaceous sedimentary environments of the Lusitanian basin, through the establishment of geochemical patterns of different size fractions of those deposits. Chemical analysis was performed by instrumental neutron activation analysis (INAA), and the mineralogical composition obtained by X-ray diffractometry (XRD). The whole rock and different size fractions (? ≥ 125 μm, 63–125 μm, 20–63 μm, 2–20 μm and ? < 2 μm) of selected samples were studied aiming the rare earth elements (REE) and other trace elements distribution and its correlation with the grain size and mineralogy.The results obtained for the studied Cretaceous sediments showed that REE patterns and other trace elements distribution in the different size fractions may be used as a tool to differentiate deposits within and between sedimentary formations. Within the Taveiro Formation, REE are concentrated in the silt fractions (20–63 μm and 2–20 μm) of the Reveles deposit, and in the clay size fraction of S. Pedro deposit, which is richer in kaolinite. The 1st transition elements, particularly Zn, are correlated with the presence of smectite in the clay fraction of Reveles deposit. In the sand and silt size fractions (>2 μm) of samples from Taveiro Formation correlations were found between: Ga and 1st transition elements, and phyllosilicates; Cs and mica; and Rb and Ba, and K–feldspars.The Bustos deposit (Aveiro Formation) samples are very fine-grained and with a high proportion of the fine silt fraction where REE are concentrated, especially the heavy ones. Incorporation of MREE, Co and U in carbonates of the coarser fraction appears to occur. The abundances of the 1st transition elements, Ga and As, are correlated with phyllosilicates.Significant differences were found in the trace elements patterns of the various analysed size fractions of the Lusitanian basin of Cretaceous sediments, between and even within formations, which can be used as a methodological approach for a fine paleogeographic reconstruction.     

Thermal expansion and high-temperature P21/c–C2/c phase transition in clinopyroxene-type LiFeGe2O6 and comparison to NaFe(Si,Ge)2O6

A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) Å, β = 108.844(6)°, V = 442.75(16) ų, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the $(\bar{1}\,0\,1) A synthetic clinopyroxene with composition LiFe³⁺Ge₂O₆, monoclinic s.g. P2₁/c, a = 9.8792(7), b = 8.8095(5), c = 5.3754(3) ?, β = 108.844(6)°, V = 442.75(16) ?³, has been studied by in situ low- and high-temperature single-crystal X-ray diffraction. The variation of lattice parameters and the intensity of the b-type reflections (h + k = 2n + 1, only present in the P-symmetry) with increasing temperature showed a displacive phase transition from space group P2₁/c to C2/c at a transition temperature T _tr = 789 K, first order in character, with a sudden volume increase of 1.6% and a decrease of β by 1° at the transition. This spontaneous dilatation is reversible, shows a limited hysteresis of ±10°C, and corresponds to the vanishing of the b-type reflections, thus indicating a symmetry increase to space group C2/c. Below T _tr an expansion is observed for all the cell parameters, while the β angle remained almost constant; at T > T _tr the thermal volume expansion is due to dilatation of the structure in the ([`1] 0 1)(\bar{1}\,0\,1) plane, mostly along [0 1 0], and pure shear in the (0 1 0) plane due to the decrease of β. From comparison with silicate analogues, the germanate clinopyroxenes are more expansible, while the P2₁/c expands more than the C2/c phase. The evolution of Q ² (calculated as the normalized intensity of b-type reflections) with T in the framework of the Landau theory has been done using a standard expression for a first order phase transition. We observe a jump of Q ₀² = 0.538(2) at T _tr, with T _c of 481(7) K, b/a = −2,290 K, and c/a = 3,192 K, and thus far from being tri-critical point. A closely related composition (LiFe³⁺Si₂O₆) shows an equivalent phase transition at 228 K, which is very close to the tri-critical point and 561 K cooler. This result indicates that a change in the composition of tetrahedral sites can have dramatic effects on the P2₁/c ↔ C2/c displacive phase transition in clinopyroxenes. The major changes observed in the evolution of the crystal structure with T are observed in the M2 polyhedron, with a volume decrease by ca. 13.3%, compared to ca. 1.3% observed in the M1 polyhedron. The tetrahedra behave as rigid units with neither a significant change of volume at T > T _tr (<1‰), nor a change of tilting of the basal plane. No change in coordination is observed at T > T _tr in the M2 polyhedron, which remains sixfold coordinated although a strong deformation of this polyhedron is observed. This deformation is related to a strong change by 51.4° at T _tr of the kinking angle (O3–O3–O3 angle) of the B-chain of tetrahedra, which switches from O-rotated to S-rotated [from 143.3(5)° to 194.7(6)°]. The A-chain is S-rotated at T < T _tr [206.8(5)° at 703 K] and extends by 12° at the transition.     

Chemical and structural study of 1M- and 2M 1-phlogopites coexisting in the same Kasenyi kamafugitic rock (SW Uganda)

In the present work, crystal chemical variations between 1M and 2M ₁ phlogopites coexisting in the same rock sample from kamafugite of Kasenyi (southwest Uganda, west branch of the East African Rift) were explored by electron probe microanalyses, single crystal X-ray diffraction and M?ssbauer spectroscopy. Chemical analyses revealed close similarity both within and between the two polytypic arrangements as well as high TiO₂ (~4.9?wt%) and Al₂O₃ (~12.9?wt%), and low Cr₂O₃ (~0.8?wt%), F (~0.3?wt%) and BaO (~0.2?wt%) contents. Room temperature ⁵⁷Fe M?ssbauer investigation proved that the studied mica is a tetraferriphlogopite with: ^IVFe³⁺?=?19(1)?%, ^VIFe²⁺?=?58(1)?%, ^VIFe³⁺?=?23(1)?%. Single crystal refinement showed that both polytypes have narrow range of variation in terms of some relevant unit cell parameters and similar values in terms of mean bond lengths, mean atomic numbers and distortion parameters. Similar substitutions were active in the structure of the 1M and 2M ₁ studied phlogopites. However, in 2M ₁ polytypes the oxy-type substitutions were found to occur to a greater extent. Comparison of unit layer of 1M mica (in the 2M ₁ setting) with that of the 2M ₁ ones showed that the 2M ₁ polytypes are affected to different extent by relative shifts of the upper and lower triads of octahedral oxygens along the ±b directions. This effect did not cause any symmetry lowering in the T-O-T layer of the studied samples.     

The age and source of late Hercynian magmatism in the central Alps: evidence from precise U−Pb ages and initial Hf isotopes

This study presents U–Pb ages for zircon, titanite, allanite and epidote, and initial Hf isotopic compositions for zircon of Upper Carboniferous granites, diorites and syenites from the Aar massif, central Alps. The rocks were emplaced during three magmatic pulses after Hercynian collisional tectonics: (A) a shoshonitic-ultrapotassic series at 334±2.5 Ma; (B) scattered diorites and granites at 308–310 Ma; and (C) a high-K cale-alkaline granite batholith at 298±2 Ma. Inheritance of old zircons is negligible among all three groups. The Southern Aar granite, in contrast, is a syn-tectonic, probably ca. 350 Ma old granite that contains large amounts of inherited Precambrian zircons. Alpine metamorphism caused weak lead loss in many analyzed zircon fractions, but left the titanite U–Pb system undisturbed: thorites were almost completely reset by Alpine and recent lead loss. Mineral isochrons defined by titanite, allanite, epidote and apatite yield initial Pb isotopic compositions that are in agreement with the model values of Stacey and Kramers. Initial Hf isotopic compositions range from _Hf=–8 to +3.5. The data follow a trend of increasing _Hf with decreasing age. The _Hf versus element concentration relationships suggest mixing between a mantle and a crustal component. These relationships can be explained in terms of generation of the melts from a subcontinental mantle that had been enriched during subduction events at about 1 Ga and by 300 Ma had developed an isotopic signature distinct from that of MORB-type mantle. Further contamination of the melts occurred during ascent and differentiation in the crust. This late Hercynian magmatism can be related to post-collisional strike-slip tectonics.     

Computer simulation studies of Crystallization under confinement conditions

Crystallization under confinement conditions is a very important process in geochemistry and geophysics. Computer simulations of fluids in nanometer scale pore spaces can provide a unique microscopic insight into the structure, dynamics and forces arising from the crystallization process. We discuss in this paper molecular dynamics computer simulations of crystallization in pores of nanometer dimensions. The crystallization pressure due to the freezing of a model of Argon in a nanopore is computed using molecular dynamics simulations. We also investigate the influence of pore geometry in determining the dynamics of confined fluids, as well as mass separation in binary mixtures. It turns out that the pore geometry reveals itself as an important variable, leading to 1) new mechanisms for fast diffusion in confined spaces, and 2) accumulation of solute in specific regions inside the pore.     

Estimation of aquifer hydraulic parameters from surface geophysical measurements: a case study of the Upper Cretaceous aquifer, central Sinai, Egypt

The integration of geophysical data with direct hydrogeological measurements can provide a minimally invasive approach to characterize the subsurface at a variety of resolutions and over many spatial scales. The field of hydrogeophysics has attracted much attention during the last two decades. In this domain, the geophysical data inverted to geophysical models are interpreted in terms of the hydrogeology to serve as a basis for the definition of hydraulic models in the areas of interest. The hydraulic conductivity (K) value measured in a reference borehole has been combined with the electrical conductivity obtained from nearby geo-electromagnetic sounding data in the Cenomanian (Upper Cretaceous) aquifer, central Sinai, Egypt. The resulting relation was interpreted with Dar Zarrouk parameters to infer the transmissivity variations at other vertical electrical sounding locations, where K values are unknown. Coincident transient electromagnetic data have been adopted to increase accuracy while interpreting the aquifer geoelectrical properties. The results indicate that the transmissivity values in the aquifer of interest vary from 2,446 to 9,694 m²/day, and K varies from 12.9 to 57.0 m/day throughout the studied area.     

Description and recognition of potassic-richterite,an amphibole supergroup mineral from the Pajsberg ore field,Värmland,Sweden

Mineralogy and Petrology - Potassic-richterite, ideally AKB(NaCa)CMg5TSi8O22W(OH)2, is recognized as a valid member of the amphibole supergroup (IMA-CNMNC 2017–102). Type material is from the...