Formation of kyanite-quartz veins of the Alpe Sponda, Central Alps, Switzerland: implications for Al transport during regional metamorphism

In this study, we have investigated the formation of quartz-kyanite veins of the Alpe Sponda, Central Alps, Switzerland. We have integrated field observations, fluid inclusion and stable isotope data and combined this with numerical geochemical modeling to constrain the chemical processes of aluminum transport and deposition. The estimated P-T conditions of the quartz-kyanite veins, based on conventional geothermometry (garnet-biotite, white mica solvus and quartz-kyanite oxygen isotope thermometry) and fluid inclusion data, are 550±30°C at 5.0±0.5kbar. Geochemical modeling involved construction of aqueous species predominance diagrams, calculation of kyanite and quartz solubility, and reaction-path simulations. The results of the modeling demonstrate that (1) for the given chemical composition of the vein-forming fluids mixed Al-Si aqueous species are dominant in transporting Al, and that (2) fluid cooling along a small temperature gradient coupled with a pH decrease is able to explain the precipitation of the quartz-kyanite assemblages in the proportions that are observed in the Alpe Sponda veins. We conclude that sufficient amounts of Al can be transported in typical medium- to high-grade regional metamorphic fluids and that immobile behavior of Al is not very likely in advection-dominanted fluid-rock systems in the upper and middle crus

The Grønnedal-Ika Carbonatite-Syenite Complex, South Greenland: Carbonatite Formation by Liquid Immiscibility

The Grønnedal-Ika complex is dominated by layered nepheline syenites which were intruded by a xenolithic syenite and a central plug of calcite to calcite-siderite carbonatite. Aegirine-augite, alkali feldspar and nepheline are the major mineral phases in the syenites, along with rare calcite. Temperatures of 680-910°C and silica activities of 0·28-0·43 were determined for the crystallization of the syenites on the basis of mineral equilibria. Oxygen fugacities, estimated using titanomagnetite compositions, were between 2 and 5 log units above the fayalite-magnetite-quartz buffer during the magmatic stage. Chondrite-normalized REE patterns of magmatic calcite in both carbonatites and syenites are characterized by REE enrichment (LaCN-YbCN = 10-70). Calcite from the carbonatites has higher Ba (∼5490 ppm) and lower HREE concentrations than calcite from the syenites (54-106 ppm Ba). This is consistent with the behavior of these elements during separation of immiscible silicate-carbonate liquid pairs. εNd(T = 1·30 Ga) values of clinopyroxenes from the syenites vary between +1·8 and +2·8, and εNd(T) values of whole-rock carbonatites range from +2·4 to +2·8. Calcite from the carbonatites has δ18O values of 7·8 to 8·6‰ and δ13C values of −3·9 to −4·6‰. δ18O values of clinopyroxene separates from the nepheline syenites range between 4·2 and 4·9‰. The average oxygen isotopic composition of the nepheline syenitic melt was calculated based on known rock-water and mineral-water isotope fractionation to be 5·7 ± 0·4‰. Nd and C-O isotope compositions are typical for mantle-derived rocks and do not indicate significant crustal assimilation for either syenite or carbonatite magmas. The difference in δ18O between calculated syenitic melts and carbonatites, and the overlap in εNd values between carbonatites and syenites, are consistent with derivation of the carbonatites from the syenites via liquid immiscibilit

Fluid mixing from below in unconformity-related hydrothermal ore deposits

This research was partly funded by German Research Foundation (DFG) grant BO 1776/8 and was carried out within the framework of DGMK (German Society for Petroleum and Coal Science and Technology) project 718, funded by the companies ExxonMobil Production Deutschland GmbH, GDF SUEZ E&P Deutschland GmbH, RWE Dea AG, and Wintershall Holding GmbH. Assistance by Simone Kaulfuss, Gabi Stoschek, Sara Ladenburger, Mathias Burisch, and Bernd Steinhilber with sample preparation and crush-leach analyses is gratefully acknowledged. We thank Steve Cox and two anonymous reviewers for their critical comments.Peer reviewedPostprin

The Magmatic to Hydrothermal Evolution of the Intrusive Mont Saint-Hilaire Complex: Insights into the Late-stage Evolution of Peralkaline Rocks

The Cretaceous Mont Saint-Hilaire complex (Quebec, Canada) comprises three major rock units that were emplaced in the following sequence: (I) gabbros; (II) diorites; (III) diverse partly agpaitic foid syenites. The major element compositions of the rock-forming minerals, age-corrected Nd and oxygen isotope data for mineral separates and trace element data of Fe-Mg silicates from the various lithologies imply a common source for all units. The distribution of the rare earth elements in clinopyroxene from the gabbros indicates an ocean island basalt type composition for the parental magma. Gabbros record temperatures of 1200 to 800°C, variable silica activities between 0·7 and 0·3, and fO2 values between −0·5 and +0·7 (log ΔFMQ, where FMQ is fayalite-magnetite-quartz). The diorites crystallized under uniform aSiO2 (aSiO2 = 0·4-0·5) and more reduced fO2 conditions (log ΔFMQ ~ −1) between ~1100 and ~800°C. Phase equilibria in various foid syenites indicate that silica activities decrease from 0·6-0·3 at ~1000°C to <0·3 at ~550°C. Release of an aqueous fluid during the transition to the hydrothermal stage caused aSiO2 to drop to very low values, which results from reduced SiO2 solubilities in aqueous fluids compared with silicate melts. During the hydrothermal stage, high water activities stabilized zeolite-group minerals. Fluid inclusions record a complex post-magmatic history, which includes trapping of an aqueous fluid that unmixed from the restitic foid syenitic magma. Cogenetic aqueous and carbonic fluid inclusions reflect heterogeneous trapping of coexisting immiscible external fluids in the latest evolutionary stage. The O and C isotope characteristics of fluid-inclusion hosted CO2 and late-stage carbonates imply that the surrounding limestones were the source of the external fluids. The mineral-rich syenitic rocks at Mont Saint-Hilaire evolved as follows: first, alkalis, high field strength and large ion lithophile elements were pre-enriched in the (late) magmatic and subsequent hydrothermal stages; second, percolation of external fluids in equilibrium with the carbonate host-rocks and mixing processes with internal fluids as well as fluid-rock interaction governed dissolution of pre-existing minerals, element transport and precipitation of mineral assemblages determined by locally variable parameters. It is this hydrothermal interplay between internal and external fluids that is responsible for the mineral wealth found at Mont Saint-Hilair

Bimodal volcanism in the Hegau region (SW Germany): Differentiation of primitive melilititic to nephelinitic rocks produces evolved nosean phonolites

Peculiar bimodal volcanism in the Hegau region (SW Germany) comprises two contrasting SiO2-undersaturated rock suites. (I) Primitive olivine melilitites and melilite-bearing olivine nephelinites (12–9 Ma) are characterized by high MgO, CaO, Fe2O3, TiO2, Ni, V, F, moderate alkalis, Al2O3, P2O5, Ba, Nb, Zr, and low SiO2, Rb, Pb, and U concentrations. The rocks are composed of forsteritic olivine, diopsidic clinopyroxene, melilite, perovskite, Cr-bearing oxyspinel, F- and Ba-rich mica, and fluorapatite. In rare cases, they contain coeval coarse-grained ijolite patches generated by rapid in-situ fractionation in small melt pockets. (II) Evolved nosean phonolites (14–11 Ma) comprise high alkalis, Al2O3, SiO2, Rb, Nb, Zr, U, Pb, S, and low MgO, CaO, Fe2O3, TiO2, P2O5, Ba, Ni, and V concentrations, and contain abundant Babearing alkali feldspar and nosean-haüyne-sodalitess macrocrysts, aegirine-augitic clinopyrox- ene, as well as accessory apatite, titanite, zircon, and pyrochlore. The melilititic–nephelinitic rocks formed by low degrees of partial melting of a carbonated amphibole ± phlogopite-bearing garnet wehrlite in the uppermost asthenosphere or in the thermal boundary layer and occur also in neighbouring regions. However, their coexistence with evolved nosean phonolites is a unique and so far, unexplained feature in the southern Central European Volcanic Province. Thermodynamic modelling implies that removal of 11–19% oxyspinel, 4–10% olivine, 42–57% clinopyroxene, <3% mica, <9% feldspathoids, <8% feldspar from melilititic–nephelinitic parental melts at upper crustal conditions (~200 MPa) results in significant amounts of phonolitic residues that are compositionally similar to the exposed nosean phonolites. Strongly negative P and Ti anomalies and a trough of MREE in primitive mantlenormalized trace element patterns of phonolites indicate additional fractionation of titanite and apatite, consistent with the mineralogy of coarse-grained (nepheline) syenitic cumulates, which are present as enclaves in both rock suites. The modelling results suggest crystallization of the (nepheline) syenite cumulates between 1050 and 800 ◦C and ascent and eruption of the phonolite residues at no less than ~900 ◦C with complete solidification of the observed assemblage at >750 ◦C. Significant crustal assimilation during fractionation appears unnecessary to explain the mineralogical, mineral chemical, and geochemical characteristics of the phonolites. Prolonged upper crustal differentiation of the magmas in one case (nosean phonolites) and fast ascent of primitive melts in the other (olivine melilitites and melilite-bearing olivine nephelinites) can be explained by stress field changes from an extensional to a more compressive regime, the magma ascent becoming thereby increasingly structurally controlled and supported by brittle deformation

Two distinct age groups of melilitites, foidites, and basanites from the southern Central European Volcanic Province reflect lithospheric heterogeneity

Petrographic observations and in situ U–Pb ages of melilitites, foidites, basanites, phonolites, and trachytes from the southern part of the Central European Volcanic Province (CEVP) and related plutonic inclusions therein reveal two distinct age groups separated by a gap of ~ 20 Myr. A late Cretaceous to early Eocene group (~ 73–47 Ma; Taunus, Lower Main plain, Odenwald and Kraichgau area, Bonndorfer Graben and Freiburger Bucht area, Vosges and Pfälzerwald) is characterized by nephelinites and basanites mostly devoid of melilite and perovskite, and by rare haüynites, and trachytes. In contrast, a late Oligocene to late Miocene group (~ 27–9 Ma; Lorraine, southern Upper Rhine Graben, Urach, Hegau area) is dominated by melilitites, melilite-bearing nephelinites (both carrying perovskite), and phonolites. Both magmatic episodes are related to domal topographic uplift, erosion, and formation of major angular unconformities in the Upper Rhine Graben, suggesting an association with dynamic topography interrupted by phases of subsidence (or abatements of uplift). The investigated rocks in the southern CEVP (south of a line Eifel–Vogelsberg–Rhön–Heldburg), except for the Kaiserstuhl volcanic complex, mostly comprise small and isolated occurrences or monogenetic volcanic fields, whereas the northern CEVP is dominated by large volcanic complexes and dyke swarms, which are mostly SiO$_2$-saturated to weakly SiO$_2$-undersaturated. In the northern CEVP, evidence of spatially varying but recurrent volcanic activity exists since the Eocene, lacking the distinct 20 Myr gap as documented from the southern CEVP. While the temporal and spatial distribution of volcanism are a result of the Cretaceous to Miocene tectonic evolution in Central Europe, further studies are needed to explain the petrographic differences between the two age groups in the south

Sideritization and silification of unconformity-related hydrothermal baryte veins near Grünau, south Namibia

The development of economic mineralization within unconformity related hydrothermal vein type deposits is a topic of basic (but also economic) significance. In particular late-stage processes like pseudo- or perimorphic replacements can significantly influence the mineralogy and hence processability of ore deposits. This study aims to shed light on such late stage processes leading to the mineralogical modification of primary hydrothermal veins by pseudomorphous and perimorphous replacements of quartz after hydrothermal gangue minerals like carbonates, baryte and fluorite; whereas the genesis of pseudomorphic replacements of baryte by siderite and a contemporaneous perimorphic overgrowth of quartz has not been studied in detail so far. To study this process, hydrothermal veins of the south Namibian hydrothermal vein type district, which are related to the breakup of Pangea are chosen as natural laboratories. Fluid inclusion data together with a detailed petrography of the paragenetic sequence and fluid inclusion assemblages reveal a temperature drop from early quartz I at ∼170 °C down to ∼80 °C in quartz III at almost constant salinities of 23.1 to 24.5 wt% (NaCl+CaCl2). The chemistry of the observed fluid inclusion assemblages is in accordance with previous microthermometry studies carried out in the same hydrothermal vein type district indicating an identical provenance of the fluids recognized in the other deposits (e.g., Aukam and Garub). Hence it is likely that a high salinity basement brine of cryogenic origin has been mixed with a Nama Group limestone derived fluid to form the primary mineralization. Mixing of two chemically-contrasted fluids is also depicted by the trace elements studied in the youngest quartz generation whereas the application of the TitaniQ thermometer provide evidence for a temperature of about 320 °C in the deep-seated reservoir which became afterwards mixed with Nama Group limestone derived fluids. Thermodynamic modelling based on the gathered fluid data and data from analogue studies, provide evidence that siderite pseudomorphs after baryte form under reducing conditions, under which sulfate is reduced and the dissolution of baryte promotes siderite and pyrite precipitation. Hence, the present study contributes to the still weakly developed understanding how post-precipitation processes influences the mineralogy of hydrothermal veins

Zahvala autorima Sestrinski glasnik/Nursing Journal 2013 godina Thanking to authors Sestrinski glasnik/Nursing Journal year 2013

Earth’s surface and mantle sulphur reservoirs are connected via subduction, crustal recycling and volcanism. Although oceanic hotspot lavas currently provide the best constraints on the deep sulphur cycle, their restricted age range (&lt;200 Ma) means they cannot reveal temporal variations in crustal recycling over Earth history. Sulphur-rich alkaline magmas offer the solution because they are associated with recycled sources (i.e. metasomatized lithospheric mantle and plumes) and, crucially, are found throughout the geological record. Here, we present a detailed study of sulphur isotope fractionation in a Mesoproterozoic alkaline province in Greenland and demonstrate that an enriched subduction-influenced source (δ34S of +1 to +5‰) can be reconstructed. A global δ34S compilation reveals secular variation in alkaline magma sources which support changes in the composition of the lithospheric mantle and/or Ga timescales for deep crustal recycling. Thus, alkaline magmas represent a powerful yet underutilized repository for interrogating crustal recycling through geological time