Crystal chemistry and hydrogen bonding of rustumite Ca10(Si2O7)2(SiO4)(OH)2Cl2 with variable OH, Cl, F

Three samples of the skarn mineral rustumite Ca10(Si2O7)2(SiO4)(OH)2Cl2, space group C2/c, a ≈7.6, b ≈ 18.5, c ≈ 15.5 Å, β ≈ 104°, with variable OH, Cl, F content were investigated by electron microprobe, single-crystal X-ray structure refinements, and Raman spectroscopy. “Rust1LCl” is a low chlorine rustumite Ca10(Si2O7)2(SiO4)(OH1.88F0.12)(Cl1.28,OH0.72) from skarns associated with the Rize batholith near Ikizedere, Turkey. “Rust2F” is a F-bearing rustumite Ca10(Si2O7)2(SiO4)(OH1.13F0.87) (Cl1 96OH0.04) from xenoliths in ignimbrites of the Upper Chegem Caldera, Northern Caucasus, Russia. “Rust3LClF” represents a low-Cl, F-bearing rustumite Ca10(Si2O7)2(SiO4)0.87(H4O4)0.13(OH1.01F0.99) (Cl1.00 OH1.00) from altered merwinite skarns of the Birkhin massif, Baikal Lake area, Eastern Siberia, Russia. Rustumite from Birkhin massif is characterized by a significant hydrogarnet-like or fluorine substitution at the apices of the orthosilicate group, leading to specific atomic displacements. The crystal structures including hydrogen positions have been refined from single-crystal X-ray data to R1 = 0.0205 (Rust1_LCl), R1 = 0.0295 (Rust2_F), and R1 = 0.0243 (Rust3_LCl_F), respectively. Depletion in Cl and replacement by OH is associated with smaller unit-cell dimensions. The substitution of OH by F leads to shorter hydrogen bonds O-H⋯F instead of O-H⋯OH. Raman spectra for all samples have been measured and confirm slight strengthening of the hydrogen bonds with uptake of F.This study discusses the complex crystal chemistry of the skarn mineral rustumite and may provide a wider understanding of the chemical reactions related to contact metamorphism of limestones.

Resolving Cl and SO4 Profiles in a Clay-Rich Rock Sequence

The chloride and sulfate concentration profiles in a 260 m thick clay-rich Mesozoic sediment sequence have been analyzed by various methods. Chloride data generally indicate a good consistency between different methods if anion exclusion is accounted for in leaching tests. For sulfate, however, there is an apparent inconsistency between leaching data and those obtained from the other methods, which points to the dissolution of a sulfur-bearing mineral. Traces of diagenetic gypsum seem to be a likely source, but other sulfur minerals cannot be ruled out.

Calibration of cosmogenic noble gas production in ordinary chondrites based on 36 Cl- 36 Ar ages. Part 1: Refined produced rates for cosmogenic 21 Ne and 38 Ar

We measured the concentrations and isotopic compositions of He, Ne, and Ar in bulk samples and metal separates of 14 ordinary chondrite falls with long exposure ages and high metamorphic grades. In addition, we measured concentrations of the cosmogenic radionuclides 10Be, 26Al, and 36Cl in metal separates and in the nonmagnetic fractions of the selected meteorites. Using cosmogenic 36Cl and 36Ar measured in the metal separates, we determined 36Cl-36Ar cosmic-ray exposure (CRE) ages, which are shielding-independent and therefore particularly reliable. Using the cosmogenic noble gases and radionuclides, we are able to decipher the CRE history for the studied objects. Based on the correlation 3He/21Ne versus 22Ne/21Ne, we demonstrate that, among the meteorites studied, only one suffered significant diffusive losses (about 35%). The data confirm that the linear correlation 3He/21Ne versus 22Ne/21Ne breaks down at high shielding. Using 36Cl-36Ar exposure ages and measured noble gas concentrations, we determine 21Ne and 38Ar production rates as a function of 22Ne/21Ne. The new data agree with recent model calculations for the relationship between 21Ne and 38Ar production rates and the 22Ne/21Ne ratio, which does not always provide unique shielding information. Based on the model calculations, we determine a new correlation line for 21Ne and 38Ar production rates as a function of the shielding indicator 22Ne/21Ne for H, L, and LL chondrites with preatmospheric radii less than about 65 cm. We also calculated the 10Be/21Ne and 26Al/21Ne production rate ratios for the investigated samples, which show good agreement with recent model calculations.

Cl. v. Martini Trosti Grammatica ebraea, eademque universalis recognita et locupletata vice tertia...

autore Andrea Sennerto

Atomization Energies of LnX Molecules (Ln = Sm, Eu, and Yb; X = Cl, Br, and I)

The gas phase equilibria Ba + LnX = BaX + Ln (Ln = Sm, Eu, Yb; X = Cl, Br, I) were investigated by Knudsen effusion mass spectrometry using a low energy of ionizing electrons to avoid fragmentation processes. The BaX molecules were used as references with well-established bond energies. The atomization enthalpies ΔatH0° of the LnX molecules were determined to be 427 ± 9 (SmCl), 409 ± 9 (EuCl), 366 ± 9 (YbCl), 360 ± 10 (SmBr), 356 ± 13 (EuBr), 316 ± 9 (YbBr), 317 ± 10 (SmI), 293 ± 10 (EuI), and 283 ± 10 (YbI) kJ·mol−1.

Grammatica Ebraea Martinio-Buxtorfiana : Seu Grammatica Petri Martinii Navarri, quam ex accuratissimis aliorum Grammaticis; praecipuè verò Cl. Buxtorfii suisque etiam observationibus Sixtinus Amama Innumeris in locis ita mutavit, correxit & auxit, ut nova meritò Grammatica dici possit.

Teilw. in hebr. Schr.

Grammatica Ebræa Martino-Buxtorfiana. Seu, Grammatica Petri Martinii Navarri, quam ex accuratissimis aliorum Grammaticis, precipue verò Cl. Buxtorfii, suisque etiam observationibus Sixtinvs Amana, Innumeris in locis ita mutavit, correxit & auxit, ut nova meritò Grammatica dici possit. ...

Teilw. in hebr. Schr.

Morphological ripening of fluid inclusions and coupled zone-refining in quartz crystals revealed by cathodoluminescence imaging: Implications for CL-petrography, fluid inclusion analysis and trace-element geothermometry

Cathodoluminescence (CL) studies have previously shown that some secondary fluid inclusions in luminescent quartz are surrounded by dark, non-luminescent patches, resulting from fracture-sealing by late, trace-element-poor quartz. This finding has led to the tacit generalization that all dark CL patches indicate influx of low temperature, late-stage fluids. In this study we have examined natural and synthetic hydrothermal quartz crystals using CL imaging supplemented by in-situ elemental analysis. The results lead us to propose that all natural, liquid-water-bearing inclusions in quartz, whether trapped on former crystal growth surfaces (i.e., of primary origin) or in healed fractures (i.e., of pseudosecondary or secondary origin), are surrounded by three-dimensional, non-luminescent patches. Cross-cutting relations show that the patches form after entrapment of the fluid inclusions and therefore they are not diagnostic of the timing of fluid entrapment. Instead, the dark patches reveal the mechanism by which fluid inclusions spontaneously approach morphological equilibrium and purify their host quartz over geological time. Fluid inclusions that contain solvent water perpetually dissolve and reprecipitate their walls, gradually adopting low-energy euhedral and equant shapes. Defects in the host quartz constitute solubility gradients that drive physical migration of the inclusions over distances of tens of μm (commonly) up to several mm (rarely). Inclusions thus sequester from their walls any trace elements (e.g., Li, Al, Na, Ti) present in excess of equilibrium concentrations, thereby chemically purifying their host crystals in a process analogous to industrial zone refining. Non-luminescent patches of quartz are left in their wake. Fluid inclusions that contain no liquid water as solvent (e.g., inclusions of low-density H2O vapor or other non-aqueous volatiles) do not undergo this process and therefore do not migrate, do not modify their shapes with time, and are not associated with dark-CL zone-refined patches. This new understanding has implications for the interpretation of solids within fluid inclusions (e.g., Ti- and Al-minerals) and for the elemental analysis of hydrothermal and metamorphic quartz and its fluid inclusions by microbeam methods such as LA-ICPMS and SIMS. As Ti is a common trace element in quartz, its sequestration by fluid inclusions and its depletion in zone-refined patches impacts on applications of the Ti-in-quartz geothermometer.