ALBERT

Description: Investigation by Raman spectroscopy of samples from different geological settings shows that the occurrence of TiO2 polymorphs other than rutile can hardly be predicted, and furthermore, the occurrence of anatase is more widespread than previously thought. Metamorphic pressure and temperature, together with whole rock chemistry, control the occurrence of anatase, whereas variation of mineral assemblage characteristics and/or fluid occurrence or composition takes influence on anatase trace element characteristics and re-equilibration of relict rutiles. Evaluation of trace element contents obtained by electron microprobe in anatase, brookite, and rutile shows that these vary significantly between the three TiO2 phases. Therefore, on the one hand, an appropriation to source rock type according to Nb and Cr contents, but as well application of thermometry on the basis of Zr contents, would lead to erroneous results if no phase specification is done beforehand. For the elements Cr, V, Fe, and Nb, variation between the polymorphs is systematic and can be used for discrimination on the basis of a linear discriminant analysis. Using phase group means and coefficients of linear discriminants obtained from a compilation of analyses from samples with well-defined phase information together with prior probabilities of groupings from a natural sample compilation, one is able to calculate phase grouping probabilities of any TiO2 analysis containing at least the critical elements Cr, V, Fe, and Nb. An application of this calculation shows that for the appropriation to the phase rutile, a correct-classification rate of 99.5% is obtained. Hence, phase specification by trace elements proves to be a valuable tool besides Raman spectroscopy.

Description: Metamorphic textures in medium-grade (~500– 550°C) metasedimentary rocks from the Erzgebirge give evidence of prograde rutile crystallization from ilmenite. Newly-crystallized grains occur as rutile-rich polycrystalline aggregates that pseudomorph the shape of the ilmenites. In-situ trace element data (EMP and SIMS) show that rutiles from the higher-grade samples record large scatter in Nb content and have Nb/Ti ratios higher than coexisting ilmenite. This behavior can be predicted using prograde rutile crystallization from ilmenite and indicates that rutiles are reequilibrating their chemistry with remaining ilmenites. On the contrary, rutiles from the lowest grade samples (~480°C) have Nb/Ti ratios that are similar to the ones in ilmenite. Hence, rutiles from these samples did not equilibrate their chemistry with remaining ilmenites. Our data suggest that temperature may be one of the main factors determining whether or not the elements are able to diffuse between the phases and, therefore, reequilibrate. Newly-crystallized rutiles yield temperatures (from ~500 to 630°C, Zr-in-rutile thermometry) that are in agreement with the metamorphic conditions previously determined for the studied rocks. In quartzites from the medium-grade domain (~530°C), inherited detrital rutile grains are detected. They are identified by their distinct chemical composition (high Zr and Nb contents) and textures (single grains surrounded by fine grained ilmenites). Preliminary calculation, based on grain size distribution of rutile in medium-grade metapelites and quartzites that occur in the studied area, show that rutiles derived from quartzites can be anticipated to dominate the detrital rutile population, even if quartzites are a minor component of the exposure.

Description: Serpentinization-fueled systems in the cool, hydrated forearc mantle of subduction zones may provide an environment that supports deep chemolithoautotrophic life. Here, we examine serpentinite clasts expelled from mud volcanoes above the Izu–Bonin–Mariana subduction zone forearc (Pacific Ocean) that contain complex organic matter and nanosized Ni–Fe alloys. Using time-of-flight secondary ion mass spectrometry and Raman spectroscopy, we determined that the organic matter consists of a mixture of aliphatic and aromatic compounds and functional groups such as amides. Although an abiotic or subduction slab-derived fluid origin cannot be excluded, the similarities between the molecular signatures identified in the clasts and those of bacteria-derived biopolymers from other serpentinizing systems hint at the possibility of deep microbial life within the forearc. To test this hypothesis, we coupled the currently known temperature limit for life, 122 °C, with a heat conduction model that predicts a potential depth limit for life within the forearc at ∼10,000 m below the seafloor. This is deeper than the 122 °C isotherm in known oceanic serpentinizing regions and an order of magnitude deeper than the downhole temperature at the serpentinized Atlantis Massif oceanic core complex, Mid-Atlantic Ridge. We suggest that the organic-rich serpentinites may be indicators for microbial life deep within or below the mud volcano. Thus, the hydrated forearc mantle may represent one of Earth’s largest hidden microbial ecosystems. These types of protected ecosystems may have allowed the deep biosphere to thrive, despite violent phases during Earth’s history such as the late heavy bombardment and global mass extinctions.

Description: Halogen contents for the widely distributed reference glasses BHVO-2G, BIR-1G, BCR-2G, GSD-1G, GSE-1G, NIST SRM 610 and NIST SRM 612 were investigated by pyrohydrolysis combined with ion chromatography, total reflection X-ray fluorescence analysis, instrumental neutron activation analysis, the noble gas method, electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry. Glasses BHVO-2G, GSD-1G and GSE-1G have halogen contents that can be reproduced at the 15% level by all bulk techniques and cover a significant range in halogen mass fractions for F (~ 20 – 300 μg g-1), Cl (~ 70 – 1220 μg g-1) and Br (~ 0.2 – 285 μg g-1) and I (~ 9 – 3560 ng g-1). The BIR-1G glass has low F (〈 15 μg g-1), Cl (~ 20 μg g-1), Br (15 ng g-1) and I (3 ng g-1). The halogen contents for the silica-rich NIST SRM 610 and 612 glasses were poorly reproduced by the different techniques. The relatively high Cl, Br and I abundances in glasses GSD-1G and GSE-1G mean that these glasses are well suited for calibrating spatially resolved micro-analytical studies on silicate glasses, melt and fluid inclusions. Combined electron probe microanalysis and laser ablation inductively coupled plasma mass spectrometry data for glass GSE-1G demonstrate homogeneity at the 10% level for Cl and Br. This article is protected by copyright. All rights reserved.

Description: Serpentinite mud volcanoes from the Mariana forearc comprise B-rich mantle wedge peridotites serpentinized by slab fluids. The major component of these rocks are serpentine group minerals [Mg3Si2O5(OH)4], showing highly variable textural and geochemical features. Micro-Raman spectroscopy reveals that the serpentine minerals are well-crystallized lizardite and chrysotile. In situ SIMS spot analyses and element mapping via ToF-SIMS show that B is evenly distributed across serpentine grains, suggesting that serpentine, both lizardite and chrysotile in different textural regions, can host significant amounts of B (up to ~200 {micro}g/g) into its crystal structure. As such structurally bound B can only be released during recrystallization or serpentine breakdown, our results have implications for modeling of the efficiency of cross-arc fluid mobile element recycling in subduction zones and stress the importance of the hydrated forearc mantle as a reservoir for fluid mobile elements.

Description: The Lower Carboniferous flysch of the Istanbul Zone in Turkey is an over 1500 m thick turbiditic sandstone-shale sequence marking the onset of the Variscan deformation in the Pontides. It overlies Lower Carboniferous black cherts and is unconformably overlain by Lower Triassic continental sandstones and conglomerates. The petrography of the Carboniferous sandstones and the geochronology and geochemistry of the detrital zircons and rutiles were studied to establish the provenance of the clastic rocks. The sandstones are feldspathic to lithic greywackes and subgreywackes with approximately equal amounts of quartz, feldspar and lithic clasts. The amount of quartz and lithic fragments decreases upwards in the sequence at the expense of feldspar. The lithic fragments are dominated by intermediate volcanic rocks, followed by metamorphic and sedimentary rock fragments. Coarse lithic fragments are generally granitoidic. In the discrimination diagrams, sandstone samples lie mainly in the field of dissected arc. A total of 218 detrital zircons and 35 detrital rutiles from four sandstone samples were analysed with laser ablation ICP-MS. The detrital zircons show a predominantly bimodal age distribution with Late Devonian to Early Carboniferous (390 to 335 Ma) and Cambrian-Neoproterozoic (640 to 520 Ma) ages. The remaining 9 % of the analysed zircons are in the 1700-2750 Ma range; zircons of the 700-1700 Ma age range are absent. The REE patterns and Th/U ratios of the zircons are consistent with a magmatic origin. With one exception (Neoproterozoic), the rutile ages are Late Devonian-Early Carboniferous and their geochemistry indicates that they were derived from amphibolite-facies metamorphic rocks. Sandstone petrography and detrital zircon-rutile ages suggest one dominant source for the Lower Carboniferous sandstones: a Late Devonian to Early Carboniferous magmatic and metamorphic province with overprinted Neoproterozoic basement. Late Devonian-Early Carboniferous magmatic and metamorphic rocks are unknown from the Eastern Mediterranean region. They are, however, widespread in central Europe. The Istanbul Zone is commonly correlated with the Avalonian terrranes in central Europe, which collided with the Armorican terranes during Carboniferous times, resulting in the Variscan orogeny. The Carboniferous flysch of the Istanbul Zone must have been derived from a colliding Armorican terrane, as indicated by the absence of 700-1700 Ma zircons and by Late Devonian-Early Carboniferous magmatism, typical features of the Armorican terranes. This suggests that during Carboniferous times the Istanbul terrane was located close to the Bohemian Massif and has been translated by strike-slip along the Trans-European Suture Zone to its Cretaceous position north of the Black Sea.

Description: Kesebolite-(Ce), ideal formula CeCa2Mn(AsO4)[SiO3]3, is a new mineral (IMA No. 2019-097) recovered from mine dumps at the Kesebol Mn-(Fe-Cu) deposit in Västra Götaland, Sweden. It occurs with rhodonite, baryte, quartz, calcite, talc, andradite, rhodochrosite, K-feldspar, hematite, gasparite-(Ce), chernovite-(Y) and ferriakasakaite-(Ce). It forms mostly euhedral crystals, with lengthwise striation. The mineral is dark grayish-brown to brown, translucent, with light brown streak. It is optically biaxial (+), with weak pleochroism, and ncalc = 1.74. H = 5–6 and VHN100 = 825. Fair cleavage is observed on {100}. The calculated density is 3.998(5) g·cm−3. Kesebolite-(Ce) is monoclinic, P21/c, with unit-cell parameters from X-ray single-crystal diffraction data: a = 6.7382(3), b = 13.0368(6), c = 12.0958(6) Å, β = 98.578(2)°, and V = 1050.66(9) Å3, with Z = 4. Strongest Bragg peaks in the X-ray powder pattern are: [I(%), d(Å) (hkl)] 100, 3.114 (20-2); 92, 2.924 (140); 84, 3.138 (041); 72, 2.908 (014); 57, 3.228 (210); 48, 2.856 (042); 48, 3.002 (132). The unique crystal structure was solved and refined to R1 = 4.6%. It consists of 6-periodic single silicate chains along (001); these are interconnected to infinite (010) strings of alternating, corner-sharing MnO6 and AsO4 polyhedra, altogether forming a trellis-like framework parallel to (100).