Progressive veining during peridotite carbonation: insights from listvenites in Hole BT1B, Samail ophiolite (Oman)

The reaction of serpentinized peridotites with CO2-bearing fluids to listvenite (quartz-carbonate rocks) requires massive fluid flux and significant permeability despite increase in solid volume. Listvenite and serpentinite samples from Hole BT1B of the Oman Drilling Project help to understand mechanisms and feedbacks during vein formation in this process. Samples analyzed in this study contain abundant magnesite veins in closely spaced, parallel sets and younger quartz-rich veins. Cross-cutting relationships suggest that antitaxial, zoned carbonate veins with elongated grains growing from a median zone towards the wall rock are among the earliest structures to form during carbonation of serpentinite. Their bisymmetric chemical zoning of variable Ca and Fe contents, a systematic distribution of SiO2 and Fe-oxide inclusions in these zones, and cross-cutting relations with Fe-oxides and Cr-spinel indicate that they record progress of reaction fronts during replacement of serpentine by carbonate in addition to dilatant vein growth. Euhedral terminations and growth textures of carbonate vein fill together with local dolomite precipitation and voids along the vein – wall rock interface suggest that these antitaxial veins acted as preferred fluid pathways allowing infiltration of CO2-rich fluids necessary for carbonation to progress. Fluid flow was probably further enabled by external tectonic stress, as indicated by closely spaced sets of subparallel carbonate veins. Despite widespread subsequent quartz mineralization in the rock matrix and veins, which most likely caused a reduction in the permeability network, carbonation proceeded to completion in listvenite horizons.

Garnet Chemical Zoning Based Thermobarometry: Method Evaluation and Applications in the Menderes Massif, Western Turkey

The garnet chemical zoning method (GZM) is a reliable thermodynamic approach for forward modeling pressure-temperature (P-T) paths using observed garnet and bulk rock compositions. However, intracrystalline diffusion is known to compromise the integrity of GZM modeled garnet-growth P-T paths. For this reason, extracting reliable metamorphic estimates from garnet-bearing schists in the Central Menderes Massif (CMM), western Turkey, has been difficult. To evaluate the impact of diffusion on GZM, we simulate garnet growth and diffusion for an average metapelite using the program Theria_G. Modeled garnet compositions from four simulations are used to estimate P-T conditions and paths by GZM, which are compared against Theria_G specified P-T-t trajectories. Factors influencing results are heating/cooling rate, grain size, and peak T. At a maximum T of 610 °C, both undiffused and diffused garnet compositions returned estimates comparable to prescribed conditions regardless of heating/cooling rate. Diffused profiles from simulations reaching a maximum T of 670 °C also reproduced prescribed P-T paths if tectonism occurred at high heating/cooling rates (50 °C/my). From these insights and additional Theria_G simulation-derived observations for CMM garnets, we deduce that metamorphism in the region exceeded 650 °C and achieved a maximum burial P between 8–10 kbar prior to Cenozoic exhumation.

A Distal, High-grade Irish-type Orebody: Petrographic, Sulfur Isotope, and Sulfide Chemistry of the Island Pod Zn-Pb Orebody, Lisheen, Ireland

Irish-type Zn-Pb deposits are important global sources of zinc, but despite a fundamental understanding of ore genesis within the Irish orefield, a detailed understanding of fluid migration and chemical evolution pathways related to sulfide and carbonate precipitation is lacking. We present the first petrographic, paragenetically constrained sulfur isotope and mineral chemistry study of mineralization at the Island Pod orebody, Lisheen deposit. The Island Pod orebody comprises high-grade mineralization that is less deformed than elsewhere in the Irish orefield. Consequently, studies of the Island Pod orebody and its mineralization provide information on the evolving nature of hydrothermal fluids involved in ore deposition. The Island Pod orebody consists almost exclusively of pyrite, sphalerite, and galena, with several stages of calcite and dolomite precipitation. Pre-ore, diagenetic pyrite is commonly overgrown by early main ore-stage pyrite, with both phases frequently replaced by main ore-stage sphalerite. In many cases, early main ore-stage pyrite is texturally zoned and exhibits chemical zoning patterns, reflecting that episodic influxes of hydrothermal fluids contained variable concentrations of As, Co, Ni, and Tl. The main ore stage was dominated by the formation of sphalerite and galena from mineralizing fluids that were depleted in these trace elements (e.g., As, Co, Tl) compared to the early main ore stage. Sulfur isotope analysis reveals four distinctive but slightly overlapping isotopic groupings, corresponding to different mineral and paragenetic stages: (1) δ34S values range from –47.7 to –30.7‰, associated with diagenetic pyrite; (2) δ34S values range from –34.3 to –14.7‰, related to early main ore-stage pyrite; (3) δ34S values range from –15.5 to + 1.7‰, corresponding to main ore-stage sphalerite; and (4) δ34S values range from –11.1 to + 17.4‰, associated with galena. Large variations in S isotope composition are common at intragrain and at other small spatial scales. The textures, paragenetic sequence, and ranges in δ34S values are consistent with hydrothermal sulfide deposition where the fluids containing bacteriogenic sulfide mixed with metal-bearing fluids. Replacement and remobilization from other Lisheen orebodies may have contributed to some of the higher sulfur isotope ratios observed in the Island Pod orebody. The excellent preservation of sulfide textures in the Island Pod orebody observed during this study demonstrates that it is an ideal location to study hydrothermal fluid evolution, including episodic fluid flow, mixing, precipitation, and compositional variations during the early main ore stage. In other Irish Zn-Pb orebodies, these early-ore textures are often obscured due to more complex dissolution and replacement processes, making interpretation of the early hydrothermal activity challenging. Consequently, the petrographic, mineral chemistry, and sulfur isotope studies of the Island Pod orebody presented here contribute to an enhanced understanding of ore-forming processes in similar deposits, where mineralization is often associated with more complex deformation or repeated pulses of hydrothermal activity.

The choice of a thermodynamic formulation dramatically affects modelled chemical zoning in minerals

Quantifying natural processes that shape our planet is a key to understanding the geological observations. Many phenomena in the Earth are not in thermodynamic equilibrium. Cooling of the Earth, mantle convection, mountain building are examples of dynamic processes that evolve in time and space and are driven by gradients. During those irreversible processes, entropy is produced. In petrology, several thermodynamic approaches have been suggested to quantify systems under chemical and mechanical gradients. Yet, their thermodynamic admissibility has not been investigated in detail. Here, we focus on a fundamental, though not yet unequivocally answered, question: which thermodynamic formulation for petrological systems under gradients is appropriate—mass or molar? We provide a comparison of both thermodynamic formulations for chemical diffusion flux, applying the positive entropy production principle as a necessary admissibility condition. Furthermore, we show that the inappropriate solution has dramatic consequences for understanding the key processes in petrology, such as chemical diffusion in the presence of pressure gradients.

Re-Evaluation of the First Metamorphic P-T Path Using QuiG Barometry and Equilibrium Thermodynamics

Quartz in garnet (“QuiG”) barometry is a relatively new technique that uses physical properties of minerals to estimate the pressure of garnet nucleation and growth history independent of chemical equilibrium. QuiG barometry was used to determine pressures of garnet growth and compared to thermodynamically calculated P-T conditions for two samples (FH-1M and Z3H) from the Lower Shieferhülle (Formation), Tauern Window, Austria. FH-1M was the first sample for which a P-T path was calculated through inversion of chemical zoning in garnet (Selverstone et al., 1984). Mineral Assemblage Diagrams (MADs) and geothermobarometric techniques were used to determine P-T conditions for garnet nucleation and peak metamorphism. No MAD reproduced either the results of Selvserstone et al. (1984) or petrologic observations such as mineral assemblages and likely P-T conditions as determined using independent thermobarometers. Thermobarometrically calculated rim conditions were consistent between our study and previous work in the Lower Schieferhülle. However, without appropriate inclusion assemblages and compositions, the accuracy of calculated core P-T conditions could not be independently assessed using thermobarometry for either rock. QuiG isomekes from both samples are broadly consistent with growth of garnet during exhumation with heating as originally proposed by Selverstone et al. (1984). However, the QuiG isomekes for Z3H suggest that 90% or more of the Z3H garnet grew over small changes in pressure and temperature or along a QuiG isomeke (heating with a slight increase in pressure). These results support the accuracy of prior P-T paths and their tectonic interpretations. However, inconsistencies between QuiG barometry vs. thermodynamic calculations remain unresolved.

Quantitative chemical mapping of plagioclase as a tool for the interpretation of volcanic stratigraphy: an example from Saint Kitts, Lesser Antilles

Establishing a quantitative link between magmatic processes occurring at depth and volcanic eruption dynamics is essential to forecast the future behaviour of volcanoes, and to correctly interpret monitoring signals at active centres. Chemical zoning in minerals, which captures successive events or states within a magmatic system, can be exploited for such a purpose. However, to develop a quantitative understanding of magmatic systems requires an unbiased, reproducible method for characterising zoned crystals. We use image segmentation on thin section scale chemical maps to segment textural zones in plagioclase phenocrysts. These zones are then correlated throughout a stratigraphic sequence from Saint Kitts (Lesser Antilles), composed of a basal pyroclastic flow deposit and a series of fall deposits. Both segmented phenocrysts and unsegmented matrix plagioclase are chemically decoupled from whole rock geochemical trends, with the latter showing a systematic temporal progression towards less chemically evolved magma (more anorthitic plagioclase). By working on a stratigraphic sequence, it is possible to track the chemical and textural complexity of segmented plagioclase in time, in this case on the order of millennia. In doing so, we find a relationship between the number of crystal populations, deposit thickness and time. Thicker deposits contain a larger number of crystal populations, alongside an overall reduction in this number towards the top of the deposit. Our approach provides quantitative textural parameters for volcanic and plutonic rocks, including the ability to measure the amount of crystal fracturing. In combination with mineral chemistry, these parameters can strengthen the link between petrology and volcanology, paving the way towards a deeper understanding of the magmatic processes controlling eruptive dynamics.

Pervasive fluid-rock interaction in subducted oceanic crust revealed by oxygen isotope zoning in garnet

Dehydration reactions in the subducting slab liberate fluids causing major changes in rock density, volume and permeability. Although it is well known that the fluids can migrate and interact with the surrounding rocks, fluid pathways remain challenging to track and the consequences of fluid-rock interaction processes are often overlooked. In this study, we investigate pervasive fluid-rock interaction in a sequence of schists and mafic felses exposed in the Theodul Glacier Unit (TGU), Western Alps. This unit is embedded within metaophiolites of the Zermatt-Saas Zone and reached eclogite-facies conditions during Alpine convergence. Chemical mapping and in situ oxygen isotope analyses of garnet from the schists reveal a sharp chemical zoning between a xenomorphic core and a euhedral rim, associated to a drop of ~ 8‰ in δ18O. Thermodynamic and δ18O models show that the large amount of low δ18O H2O required to change the reactive bulk δ18O composition cannot be produced by dehydration of the mafic fels from the TGU only, and requires a large contribution of the surrounding serpentinites. The calculated time-integrated fluid flux across the TGU rocks is 1.1 × 105 cm3/cm2, which is above the open-system behaviour threshold and argues for pervasive fluid flow at kilometre-scale under high-pressure conditions. The transient rock volume variations caused by lawsonite breakdown is identified as a possible trigger for the pervasive fluid influx. The calculated schist permeability at eclogite-facies conditions (~ 2 × 10–20 m2) is comparable to the permeability determined experimentally for blueschist and serpentinites.

Zonality of ore-forming chrome spinels of medium-chrome and aluminous chromitites of the Voikaro-Syninsky massif

Relevance of the work. The conditions for the formation of chromium ores in alpine-type ultramafites remain a topical subject of research. In recent years, scientific papers have focused on the issue of changing the chemical composition of ore-forming minerals and chromium ores under the influence of deformation and dynamic recrystallization processes accompanying metamorphism. The results of such studies make it possible to formulate a new model of the formation of chromium mineralization taking into account a significant amount of geological data indicating that alpine-type ultramafic rocks are “mantle tectonites”. In our work, we have studied zonal ore-forming spinels from chrome ores of the Polar Urals. The results of the study make it possible to associate the formation of chemical zoning in minerals and ore bodies with recrystallization under the influence of stress tension. Purpose of the work – study of the conditions for the formation of chemical zoning of chromium spinels from alumina and medium chromium ores of the Voikaro-Syninsky massif. Results. Zonal ore-forming spinels from medium-chromium and aluminous chromitites of the Voikaro-Syninsky massif (Polar Urals) have been studied. It was found that replacement rims are developed along the grains of oreforming spinels with an increased content of Cr2 O3 and an oxidation state of iron in relation to the core, as well as a reduced content of Al2 O3 . The oxidation state of iron in the rims of most grains does not exceed the values typical for unaltered ore-forming spinels. T–fO2 parameters of zoning formation in spinels were determined by oxythermobarometry. Comparison with zoned chrome spinels of the Golyamo Kamenyane massif (Bulgaria). Conclusion. Metamorphic transformations of alumina and medium-chromium chromitites of the Voikaro-Syninsky massif, occurring under subcrustal conditions under the action of directional stress at relatively constant T–fO2 parameters, lead to an increase in the chromium content of the ore mineral.

Time scales for pluton growth, magma chamber formation and super-eruptions

Generation of silicic magmas leads to emplacement of granite plutons, huge explosive volcanic eruptions and physical and chemical zoning of continental and arc crust1-7. While the time scales for silicic magma generation in the deep and middle crust are prolonged8 magma transfer into the upper crust followed by eruption is episodic and can be rapid9-12. Ages of inherited zircons and sanidines from four Miocene ignimbrites in the Central Andes indicate a gap of 4.6 Myr between the start of pluton emplacement and onset of super-eruptions, with a 1 Myr cyclicity. Here we show that inherited sanidine crystals were stored at temperatures <470oC prior to incorporation in the magma. Our observations are explained by silicic melt segregation in a middle crustal hot zone with episodic melt ascent from an unstable layer at the top of the zone with a time scale governed by the rheology of the upper crust. After thermal incubation of the growing batholith, large magma chambers formed in only a few thousand years or less by dyke transport from the hot zone melt layer. Instability and disruption of earlier plutonic rock occurred in a few decades or less just prior to or during super-eruptions.