Excess Silica in Omphacite and the Formation of Free Silica in Eclogite

Silica lamellae in eclogitic clinopyroxene are widely interpreted as evidence of exsolution during decompression of eclogite. However, mechanisms other than exsolution might produce free silica, and the possible mechanisms depend in part on the nature and definition of excess silica. ‘Excess’ silica may occur in both stoichiometric and non-stoichiometric pyroxene. Although the issue has been debated, we show that all common definitions of excess silica in non-stoichiometric clinopyroxene are internally consistent, interchangeable, and therefore equivalent. The excess silica content of pyroxene is easily illustrated in a three-component, condensed composition space and may be plotted directly from a structural formula unit or recalculated end-members. In order to evaluate possible mechanisms for the formation of free silica in eclogite, we examined the net-transfer reactions in model eclogites using a Thompson reaction space. We show that there are at least three broad classes of reactions that release free silica in eclogite: (i) vacancy consumption in non-stoichiometric pyroxene; (ii) dissolution of Ti-phases in pyroxene or garnet; (iii) reactions between accessory phases and either pyroxene or garnet. We suggest that reliable interpretation of the significance of silica lamellae in natural clinopyroxene will require the evaluation not only of silica solubility, but also of titanium solubility, and the possible roles of accessory phases and inclusions on the balance of free silica

MPI-Ding reference glasses for in situ microanalysis: New reference values for element concentrations and isotope ratios

We present new analytical data of major and trace elements for the geological MPI-DING glasses KL2-G, ML3B-G, StHs6/80-G, GOR128-G, GOR132-G, BM90/21-G, T1-G, and ATHO-G. Different analytical methods were used to obtain a large spectrum of major and trace element data, in particular, EPMA, SIMS, LA-ICPMS, and isotope dilution by TIMS and ICPMS. Altogether, more than 60 qualified geochemical laboratories worldwide contributed to the analyses, allowing us to present new reference and information values and their uncertainties (at 95% confidence level) for up to 74 elements. We complied with the recommendations for the certification of geological reference materials by the International Association of Geoanalysts (IAG). The reference values were derived from the results of 16 independent techniques, including definitive (isotope dilution) and comparative bulk (e.g., INAA, ICPMS, SSMS) and microanalytical (e.g., LA-ICPMS, SIMS, EPMA) methods. Agreement between two or more independent methods and the use of definitive methods provided traceability to the fullest extent possible. We also present new and recently published data for the isotopic compositions of H, B, Li, O, Ca, Sr, Nd, Hf, and Pb. The results were mainly obtained by high-precision bulk techniques, such as TIMS and MC-ICPMS. In addition, LA-ICPMS and SIMS isotope data of B, Li, and Pb are presented

Phase relationships in grunerite-garnet-bearing amphibolites in the systemCFMASH, with applications to metamorphic rocks from the Central Zone of the Limpopo Belt, South Africa.

A petrogenetic grid in the model system CaO–FeO–MgO–Al2O3–SiO2–H2O is presented, illustrating the phase relationships among the minerals grunerite, hornblende, garnet, clinopyroxene, chlorite, olivine, anorthite, zoisite and aluminosilicates, with quartz and H2O in excess. The grid was calculated with the computer softwarethermocalc, using an upgraded version of the internally consistent thermodynamic dataset HP98 and non-ideal mixing activity models for all solid solutions. From this grid, quantitative phase diagrams (P–T pseudosections) are derived and employed to infer a P–T path for grunerite–garnet-bearing amphibolites from the Endora Klippe, part of the Venetia Klippen Complex within the Central Zone of the Limpopo Belt. Agreement between calculated and observed mineral assemblages and garnet zonation indicates that this part of the Central Zone underwent a prograde temperature and pressure increase from c. 540 °C/4.5 kbar to 650 °C/6.5 kbar, followed by a post-peak metamorphic pressure decrease. The inferred P–T path supports a geotectonic model suggesting that the area surrounding the Venetia kimberlite pipes represents the amphibolite-facies roof zone of migmatitic gneisses and granulites that occur widely within the Central Zone. In addition, the P–T path conforms to an interpretation that the Proterozoic evolution of the Central Zone was controlled by horizontal tectonics, causing stacking and differential heating at c. 2.0 Ga

Trace element-enriched fluids released during slab dehydration: Implications for oceanic slab-mantle wedge transfer

Mafic blueschists of the Tianshan (NW China) display an interconnected network of eclogite-facies veins derived by prograde blueschist dehydration. The eclogite-facies vein-network in the Tianshan blueschist was found to be the product of hydrofracturing induced by fluids released by the breakdown of glaucophane, paragonite and epidote minerals during blueschist–eclogite transition and, thus represent former fluid pathways within a Paleozoic subduction zone. The veins are predominantly composed of omphacite fibers with minor quartz, calcite, and apatite. The transition from blueschist- to eclogite-facies parageneses occurs as “dehydration” halos along some of these veins. The fluids are interpreted to have been derived from the host blueschist as a result of dehydration reactions at peak metamorphic conditions of 480–600 °C and 18–21 kbar (Gao and Klemd, 2001 and John et al., 2006). The low in trace element fluid caused a strong mobilization of LILE, REE, and high field strength elements (HFSE) in those parts of the host rock with which the passing fluid reacted (John et al., 2006). Hence indicating that so-called immobile elements can be mobilized by reactive flow. Furthermore, field evidence shows that rutile occurs in the form of needle-like segregations in an eclogite boudin and as prismatic crystals in an omphacite-bearing vein cross-cutting foliated host eclogites. Textural and geochemical studies indicate that titanium, niobium and tantalum can be mobilized and transported by fluids which were liberated by means of dehydration of the subduction oceanic crust. Vein-rutile precipitation occurred at sites where evidence for an increasing oxygen fugacity in the acting fluid is found, causing a sudden depletion of the HFSE concentration in the fluid. Such a fluid may act as agent for the subduction component seen in the distinct chemistry of normal island-arc magmas

Trace elements and textures of hydrothermal sphalerite and pyrite in Upper Permian (Zechstein) carbonates of the North German Basin

Deeply buried Upper Permian (Zechstein) carbonates in the southwestern North German Basin host widespread Zn-Fe-Pb sulfide mineralization. The spatial extent of the sediment-hosted mineralization, the geochemical formation conditions, and the number of mineralizing events that are manifested in the Permian sedimentary rocks are an ongoing matter of debate and interest for mineral exploration efforts in the North German Basin. We present detailed petrographic and geochemical data of ore minerals from drill core samples from the Lower Saxony Basin that forms the southwestern part of the North German Basin. Based on these data, we propose and discuss a genetic model for the ore-forming processes. Of particular interest are the sources of metals and sulfur and the timing and temperature at which the sulfides formed. The main sulfide minerals are sphalerite, pyrite, and galena, which commonly occupy mm- to m-scale open space fillings and fractures. Petrographic observations further suggest hydrothermal replacement of the Zechstein Ca2 carbonates, by sulfides, secondary calcite, and anhydrite. Early diagenetic pyrite occurs disseminated in the Zechstein Ca2 carbonates. Scanning electron microscopy, electron microprobe, laser ablation ICP-MS, and sulfur isotope analyses were used to collect petrographic and compositional data on the sphalerite and pyrite. Hydrothermal sphalerite displays cyclical growth patterns and sectoral zoning characterized by colors varying from colorless to black and corresponding indicative variations in their minor and trace element concentrations, e.g., Fe concentrations ranging between below the limit of detection (7.7 ppm) to a maximum of 2.8 wt%. A detailed LA-ICP-MS multielement map illustrates the observed growth patterns and reveals that Mn, Co, Fe, Cu, Ge, Ag, Cd, Hg, Tl, and Pb are the elements that control the distinct color variations. Sectoral zoning is reflected in comparatively high Cu, Ag, and Pb contents, whereas the cyclical growth banding can be retraced by variations in Fe, Co, Cd, Hg, and Tl contents. Calculated temperatures from the trace element signatures using the GGIMFis geothermometer indicate a formation temperature of 148 ± 55 °C for sphalerite. Although the investigated mineralization bears many trademarks of a Mississippi Valley-type (MVT) deposit, the elevated temperatures, a burial depth of around 3.2 km, low concentrations of common strategic elements such as Ga, Ge, and In (< median of 1.3 ppm in sphalerite), as well as the abundance of pyrite represent the unique nature of the Ca2-hosted mineralization. The observed epigenetic ore zones are therefore best described as carbonate replacement mineralization and present an intriguing case study of geochemical exploration in a deeply covered terrane

Early Pleistocene banded iron-rich sedimentary rocks at Cape Vani, Milos Island, Greece: A modern analogue of Precambrian banded iron formations?

The genesis of banded iron formations is commonly associated with anoxic and iron-rich (ferruginous) marine conditions throughout the Archean to Palaeoproterozoic, and occasionally in the Neoproterozoic. In recent studies, ~2 million-year-old banded iron-rich sedimentary rocks with alternating Fe- and Si-rich bands occurring in the Cape Vani sedimentary basin on Milos island (Greece) were interpreted to be a modern analogue of Precambrian banded iron formations. This interpretation is mainly due to the discovery of photoferrotrophic-like filamentous fossils in massive iron-rich cherty beddings of another subbasin about 450 m to the south. In this study, we re-examined the stratigraphy and lithology of the Cape Vani basin, carried out detailed petrographic, mineralogical and geochemical investigations of the iron-rich sedimentary rocks, as well as volcaniclastic/volcanic conglomerates and banded hydrothermal veins that are in close spatial association with the iron-rich sedimentary rocks. The Fe2O3 content of the banded iron-rich sedimentary rocks ranges from 0.41 to 11.02 wt% (2.73 wt% on average), far lower than that required per definition for banded iron formations. In addition, the banded iron-rich sedimentary rocks contain substantial clastic materials. Samples with stronger silicification, however, usually contain less clastic materials. The non-clastic components occur as siliceous matrix comprising the same mineral assemblage as the banded hydrothermal veins. These components occur in the interspaces of the clastic materials, within cavities, microfractures and veins crosscutting the layers. Fe2O3, principally reflecting hematite, is intimately linked with the presence of non-clastic materials. Therefore, the non-clastic materials are interpreted as post-depositional products associated with silicification during later stage hydrothermal activities, rather than being syn-depositional as the minerals in Precambrian banded iron formations. Consequently, the Milos banded iron-rich sedimentary rocks cannot be an analogue of Precambrian banded iron formations, seeing their lithological and genetical differences. The geochemical results reveal that both the banded iron-rich sedimentary rocks and the massive iron-rich cherty beddings have the same clastic provenance as the volcaniclastics/volcanic conglomerates, but the massive iron-rich cherty beddings contain more hydrothermal contributions due to more intensive fluid-rock interaction. Thus, the two types of iron-rich sedimentary rocks are considered as clastic sedimentary rocks with varying degrees of hydrothermal overprinting. The massive iron-rich cherty beds were generally subjected to stronger hydrothermal overprinting, and, therefore, contain more siliceous matrix and Fe2O3. The enrichment of Fe is due to post-depositional hydrothermal fluid infiltration to the primary sediment piles. The primary layer planes of the banded iron-rich rocks, their interconnected pores and fractures provided preferential pathways for the hydrothermal fluids, and resulted in denser precipitation of Fe(III) (oxy)hydroxides and SiO2 cement therein. The alternating bands in the banded iron-rich sedimentary rocks, therefore, reflect cyclic permeabilities of the layers (i.e., primary sedimentary planes and porosities), rather than cyclic precipitation of Fe- and Si-minerals. This study also sheds light on an alternative formation mechanism for banded structures in Fe- and Si-rich sedimentary rocks similar to those of Precambrian banded iron formations. © 2022 Elsevier B.V