Chemical interdiffusion between Na-series tephritic and phonolitic melts with different H2O content, temperature, and oxygen fugacity values

The diffusive exchange of major elements in Na-series tephrite–phonolite diffusion couples with compositions relevant to the Canary Islands magmatism was determined at 300 MPa and variable H2O concentrations (0.3 wt % to 3.3 wt %), temperatures (1150 to 1300 °C), and fO2 levels (NNO−1.5 to NNO+1.7). Composition-dependent effective binary diffusion coefficients were determined from concentration–distance profiles. Results show a wide range of diffusivities for different cations, consistently following the sequence Na Al K ≥ Mg = Fe = Ca > Si > Ti, with a mild diffusivity contrast (0.2–0.8 log units) between tephritic and phonolitic melts. Na is the fastest component, with diffusivities falling ∼ 1.0 log units above those of Si for any given condition. An anomalously fast Al diffusion is observed, with DAl falling ∼ 0.4 log units above Si and ∼ 0.6 log units below Na, suggesting a prevalence of Al–alkali coupling across our range of run conditions. The relationships between log D and H2O content in melt for all cations in an intermediate composition are strongly nonlinear and can be fitted using an exponential function with a convergence in diffusion coefficients for different temperatures with increasing H2O content. Thus, Arrhenius analyses result in a decrease in activation energies from 222–293 kJ mol−1 at 1.7 wt % H2O to 48–112 kJ mol−1 at 3.0 wt % H2O. These results provide new data on chemical interdiffusion in highly alkaline Na-rich melts and suggest that H2O content plays a key role in increasing the chemical efficiency of magma mixing at low temperatures. The obtained dataset is used to test chemical controls of magma mixing in the El Abrigo ignimbrite, Tenerife, where banded pumices involving basanitic–tephritic to phonolitic magmas are common in several compositionally bimodal ignimbrite units

Alkaline magmas in shallow arc plutonic roots: a field and experimental investigation of hydrous cumulate melting in the southern Adamello batholith

Despite the first-order importance of crystallisation–differentiation for arc magma evolution, several other processes contribute to their compositional diversity. Among them is the remelting of partly crystallised magmas, also known as cumulate melting or ‘petrological cannibalism’. The impact of this process on the plutonic record is poorly constrained. We investigate a nepheline-normative dyke suite close to the Blumone gabbros, a large amphibole-gabbro unit of the Tertiary Southern Alpine Adamello igneous complex. The compositions of the studied dykes are characterised by low SiO2 (43–46 wt. %), MgO (5.0–7.2 wt. %), Ni (18–40 μg/g), and high Al2O3 (20.2–22.0 wt. %) contents. Phenocrystic plagioclase in these dykes exhibits major, trace, and Sr isotope compositions similar to Blumone cumulate plagioclase, suggesting a genetic link between the nepheline-normative dykes and the amphibole-gabbro cumulates. We tested this hypothesis by performing saturation experiments on a nepheline-normative dyke composition in an externally heated pressure vessel at 200 MPa between 975 and 1100 °C at fO2 conditions close to the Ni–NiO buffer. Plagioclase and spinel are near-liquidus phases at and above 1050 °C, contrasting with the typical near-liquidus olivine ± spinel assemblage in hydrous calc-alkaline basalts. The alkaline nature of the dykes results from the abundance of amphibole in the protolith, consistent with melting of amphibole-gabbro cumulates. We modelled the heat budget from the repeated injection of basaltic andesite into a partly crystallised amphibole-gabbro cumulate. The results of this model show that no more than 7% of the cumulate pile reaches temperatures high enough to produce nepheline-normative melts. We propose that such nepheline-normative dykes are a hallmark of hydrous cumulate melting in subvolcanic plumbing systems. Therefore, ne-normative dykes in arc batholiths may indicate periods with high magma fluxes

A New Albite Microanalytical Reference Material from Piz Beverin for Na, Al and Si Determination, and the Potential for New K-Feldspar Reference Materials

Determination of alkali elements is important to Earth scientists, yet suitable and reliable microanalytical reference materials are lacking. This paper proposes a new albite reference material and evaluates the potential for future K-feldspar reference materials. The proposed Piz Beverin albite reference material from Switzerland yields a homogeneous composition at the centimetre- to micrometre-scale for Si, Al and Na with \u3c 2000 μg g-1 total trace elements (mostly heterogeneously distributed Ca, K and Sr). EPMA and LA-ICP-MS measurements confirm a composition of 99.5(2)% albite component, which is supported further by bulk XRF measurements. A round robin evaluation involving nine independent EPMA laboratories confirms its composition and homogeneity for Si, Al and Na. In addition, a set of five distinct clear K-feldspar samples was evaluated as possible reference materials. The first two crystals of adular and orthoclase yield unacceptable inhomogeneities with \u3e 2% relative local variations of Na, K and Ba contents. The three other investigated sets of K-feldspar crystals are yellow sanidine crystals from Itrongay (Madagascar). Despite distinct compositions, EPMA confirms they are each homogeneous at the centimetre to micrometre scale for Si, Al and K and have no apparent inclusions; further investigation to find larger amounts of these materials is therefore justified

A New Albite Microanalytical Reference Material from Piz Beverin for Na, Al and Si Determination, and the Potential for New K-Feldspar Reference Materials

Determination of alkali elements is important to Earth scientists, yet suitable and reliable microanalytical reference materials are lacking. This paper proposes a new albite reference material and evaluates the potential for future K-feldspar reference materials. The proposed Piz Beverin albite reference material from Switzerland yields a homogeneous composition at the centimetre- to micrometre-scale for Si, Al and Na with 2% relative local variations of Na, K and Ba contents. The three other investigated sets of K-feldspar crystals are yellow sanidine crystals from Itrongay (Madagascar). Despite distinct compositions, EPMA confirms they are each homogeneous at the centimetre to micrometre scale for Si, Al and K and have no apparent inclusions; further investigation to find larger amounts of these materials is therefore justified

Fluids as primary carriers of sulphur and copper in magmatic assimilation

Magmas readily react with their wall-rocks forming metamorphic contact aureoles. Sulphur and possibly metal mobilization within these contact aureoles is essential in the formation of economic magmatic sulphide deposits. We performed heating and partial melting experiments on a black shale sample from the Paleoproterozoic Virginia Formation, which is the main source of sulphur for the world-class Cu-Ni sulphide deposits of the 1.1 Ga Duluth Complex, Minnesota. These experiments show that an autochthonous devolatilization fluid effectively mobilizes carbon, sulphur, and copper in the black shale within subsolidus conditions (≤ 700 °C). Further mobilization occurs when the black shale melts and droplets of Cu-rich sulphide melt and pyrrhotite form at ∼1000 °C. The sulphide droplets attach to bubbles of devolatilization fluid, which promotes buoyancy-driven transportation in silicate melt. Our study shows that devolatilization fluids can supply large proportions of sulphur and copper in mafic–ultramafic layered intrusion-hosted Cu-Ni sulphide deposits.</p

Ascent-driven differentiation: a mechanism to keep arc magmas metaluminous?

Arc magmatism is fundamental to the generation of new continental or island arc crust. However, the mechanisms that add to the chemical complexity of natural calc-alkaline magmas ranging from basaltic to rhyolitic compositions are debated. Differentiation mechanisms currently discussed include magma mixing, assimilation, crustal melting, or (fractional) crystallisation. In this contribution, the differentiation of arc magmas by decompression-driven crystallisation is investigated. We performed a set of equilibrium crystallisation experiments at variable crustal pressures (200–800 MPa) on a hydrous high-Al basalt (3.5 wt.% of H2O in the starting material) with run temperatures varying from near-liquidus conditions (1110 °C) to 900 °C. Oxygen fugacity was buffered at moderately oxidising conditions close to the NNO equilibrium. Combining these novel experiments with previous polybaric fractional crystallisation experiments (Marxer et al., Contrib Mineral Petrol 177:3, 2022) we demonstrate the effects of pressure on the crystallisation behaviour of calc-alkaline magmas with respect to liquid and cumulate lines of descent, mineral chemistry, and phase proportions. Decompression shifts the olivine-clinopyroxene cotectic curve towards melt compositions with higher normative clinopyroxene and enlarges the stability field of plagioclase. This exerts a key control on the alumina saturation index of residual liquids. We argue that near-adiabatic (or near-isothermal) decompression accompanied by dissolution of clinopyroxene entrained during residual melt extraction in the lower crust keeps arc magmas metaluminous during crystallisation-driven differentiation thereby closely reproducing the compositional spread observed for natural arc rocks

Polybaric fractional crystallisation of arc magmas: an experimental study simulating trans-crustal magmatic systems

Crystallisation-driven differentiation is one fundamental mechanism proposed to control the compositional evolution of magmas. In this experimental study, we simulated polybaric fractional crystallisation of mantle-derived arc magmas. Various pressure–temperature trajectories were explored to cover a range of potential magma ascent paths and to investigate the role of decompression on phase equilibria and liquid lines of descent (LLD). Fractional crystallisation was approached in a step-wise manner by repetitively synthesising new starting materials chemically corresponding to liquids formed in previous runs. Experiments were performed at temperatures ranging from 1140 to 870 °C with 30 °C steps, and pressure was varied between 0.8 and 0.2 GPa with 0.2 GPa steps. For most fractionation paths, oxygen fugacity (fO2) was buffered close to the Ni-NiO equilibrium (NNO). An additional fractionation series was conducted at fO2 corresponding to the Re-ReO2 buffer (RRO ≈ NNO+2). High-pressure experiments (0.4–0.8 GPa) were run in piston cylinder apparatus while 0.2 GPa runs were conducted in externally heated pressure vessels. Resulting liquid lines of descent follow calc-alkaline differentiation trends where the onset of pronounced silica enrichment coincides with the saturation of amphibole and/or Fe–Ti–oxide. Both pressure and fO2 exert crucial control on the stability fields of olivine, pyroxene, amphibole, plagioclase, and Fe–Ti–oxide phases and on the differentiation behaviour of arc magmas. Key observations are a shift of the olivine–clinopyroxene cotectic towards more clinopyroxene-rich liquid composition, an expansion of the plagioclase stability field and a decrease of amphibole stability with decreasing pressure. Decompression-dominated ascent trajectories result in liquid lines of descent approaching the metaluminous compositional range observed for typical arc volcanic rocks, while differentiation trends obtained for cooling-dominated trajectories evolve to peraluminous compositions, similar to isobaric liquid lines of descent at elevated pressures. Experiments buffered at RRO provide a closer match with natural calc-alkaline differentiation trends compared to fO2 conditions close to NNO. We conclude that decompression-dominated fractionation at oxidising conditions represents one possible scenario for arc magma differentiation.ETH research grantGottfried Wilhelm Leibniz Universität Hannover (1038

Crystallisation and zircon saturation of calc-alkaline tonalite from the Adamello Batholith at upper crustal conditions: an experimental study

The understanding of the geochemical and petrophysical evolution of magmas forming intermediate calc-alkaline batholiths at shallow crustal levels critically depends on knowledge of the phase equilibria relations along the liquid line of descent. Here, we present experimental results for a tonalitic system at a pressure of 200 MPa and under water-saturated conditions. Melting experiments were performed at temperatures between 700 and 1000 °C in externally heated HCM pressure vessels, with oxygen fugacity controlled close to the Ni–NiO buffer equilibrium (NNO) employing an argon–methane mixture as pressure medium and Co–Pd redox sensors to verify fO2 conditions. Natural rock powder of a medium-K tonalite from the Adamello Batholith in Northern Italy served as experimental starting material. Based on compositional data of stable phases in the run products and images of entire run charges, mass balance calculations as well as image processing were performed to investigate the evolution of the crystal/melt ratio with respect to temperature. Furthermore, compositional trends of minerals as well as the liquid line of descent of residual melts were obtained. Orthopyroxene, clinopyroxene and plagioclase were identified as near-liquidus phases (below 990 °C). At 900 °C, amphibole joins the solid-phase assemblage at the expense of clinopyroxene, indicating the existence of a peritectic relationship. After an initial near-linear decrease with temperature, residual melt fractions exhibit a plateau of 45–55 vol. % between 750 and 850 °C, followed by a rapid decrease coinciding with quartz saturation at 725 °C. Compositions of residual liquids evolve along a typical calc-alkaline differentiation trend with decreasing temperature (increasing SiO2 and decreasing TiO2, Al2O3, CaO, MgO and FeO contents) and become peraluminous below 900 °C. Intermediate to acidic rocks from the Adamello follow the experimental liquid line of descent indicating that the observed compositional spread of the natural intermediate composition rock record can be explained by low-pressure magma differentiation and liquid extraction. Experimentally determined zircon saturation levels are at low temperatures distinctly lower compared to existing and often used Zr-saturation models, but fully consistent with observed and modelled Zr-evolution trends from the natural rock record of the Southern Adamello Batholith inferring that zircon saturation in these intermediate to felsic plutonic rocks occurred at 800–830 °C corresponding to a melt fraction of about 50 vol. %.ISSN:0010-7999ISSN:1432-096

Polybaric fractional crystallisation of arc magmas: an experimental study simulating trans-crustal magmatic systems

Crystallisation-driven differentiation is one fundamental mechanism proposed to control the compositional evolution of magmas. In this experimental study, we simulated polybaric fractional crystallisation of mantle-derived arc magmas. Various pressure–temperature trajectories were explored to cover a range of potential magma ascent paths and to investigate the role of decompression on phase equilibria and liquid lines of descent (LLD). Fractional crystallisation was approached in a step-wise manner by repetitively synthesising new starting materials chemically corresponding to liquids formed in previous runs. Experiments were performed at temperatures ranging from 1140 to 870 °C with 30 °C steps, and pressure was varied between 0.8 and 0.2 GPa with 0.2 GPa steps. For most fractionation paths, oxygen fugacity (fO₂) was buffered close to the Ni-NiO equilibrium (NNO). An additional fractionation series was conducted at fO₂ corresponding to the Re-ReO₂ buffer (RRO ≈ NNO+2). High-pressure experiments (0.4–0.8 GPa) were run in piston cylinder apparatus while 0.2 GPa runs were conducted in externally heated pressure vessels. Resulting liquid lines of descent follow calc-alkaline differentiation trends where the onset of pronounced silica enrichment coincides with the saturation of amphibole and/or Fe–Ti–oxide. Both pressure and fO₂ exert crucial control on the stability fields of olivine, pyroxene, amphibole, plagioclase, and Fe–Ti–oxide phases and on the differentiation behaviour of arc magmas. Key observations are a shift of the olivine–clinopyroxene cotectic towards more clinopyroxene-rich liquid composition, an expansion of the plagioclase stability field and a decrease of amphibole stability with decreasing pressure. Decompression-dominated ascent trajectories result in liquid lines of descent approaching the metaluminous compositional range observed for typical arc volcanic rocks, while differentiation trends obtained for cooling-dominated trajectories evolve to peraluminous compositions, similar to isobaric liquid lines of descent at elevated pressures. Experiments buffered at RRO provide a closer match with natural calc-alkaline differentiation trends compared to fO₂ conditions close to NNO. We conclude that decompression-dominated fractionation at oxidising conditions represents one possible scenario for arc magma differentiation.ISSN:0010-7999ISSN:1432-096

Polybaric fractional crystallisation of arc magmas: an experimental study simulating trans-crustal magmatic systems

Crystallisation-driven differentiation is one fundamental mechanism proposed to control the compositional evolution of magmas. In this experimental study, we simulated polybaric fractional crystallisation of mantle-derived arc magmas. Various pressure–temperature trajectories were explored to cover a range of potential magma ascent paths and to investigate the role of decompression on phase equilibria and liquid lines of descent (LLD). Fractional crystallisation was approached in a step-wise manner by repetitively synthesising new starting materials chemically corresponding to liquids formed in previous runs. Experiments were performed at temperatures ranging from 1140 to 870 °C with 30 °C steps, and pressure was varied between 0.8 and 0.2 GPa with 0.2 GPa steps. For most fractionation paths, oxygen fugacity (fO₂) was buffered close to the Ni-NiO equilibrium (NNO). An additional fractionation series was conducted at fO₂ corresponding to the Re-ReO₂ buffer (RRO ≈ NNO+2). High-pressure experiments (0.4–0.8 GPa) were run in piston cylinder apparatus while 0.2 GPa runs were conducted in externally heated pressure vessels. Resulting liquid lines of descent follow calc-alkaline differentiation trends where the onset of pronounced silica enrichment coincides with the saturation of amphibole and/or Fe–Ti–oxide. Both pressure and fO₂ exert crucial control on the stability fields of olivine, pyroxene, amphibole, plagioclase, and Fe–Ti–oxide phases and on the differentiation behaviour of arc magmas. Key observations are a shift of the olivine–clinopyroxene cotectic towards more clinopyroxene-rich liquid composition, an expansion of the plagioclase stability field and a decrease of amphibole stability with decreasing pressure. Decompression-dominated ascent trajectories result in liquid lines of descent approaching the metaluminous compositional range observed for typical arc volcanic rocks, while differentiation trends obtained for cooling-dominated trajectories evolve to peraluminous compositions, similar to isobaric liquid lines of descent at elevated pressures. Experiments buffered at RRO provide a closer match with natural calc-alkaline differentiation trends compared to fO₂ conditions close to NNO. We conclude that decompression-dominated fractionation at oxidising conditions represents one possible scenario for arc magma differentiation.ISSN:0010-7999ISSN:1432-096