Dynamics of Magma Mixing in Partially Crystallized Magma Chambers: Textural and Petrological Constraints from the Basal Complex of the Austurhorn Intrusion (SE Iceland)

The Tertiary Austurhorn intrusive complex in SE Iceland represents an exhumed magma chamber that has recorded an extensive history of magma mixing and mingling. The basal part of the intrusion consists predominantly of granophyres that have been intensively and repeatedly intruded by more mafic magma. This association of granophyres, basic and hybrid rocks at Austurhorn is referred to in the literature as a ‘net-veined' complex, but field relations suggest a much more complex emplacement history. Here we present petrological and physical constraints on the various processes that resulted in magma mixing and mingling and the formation of different generations of hybrid rocks at Austurhorn. The complexity of the mixing and mingling processes increases towards the inferred centre of the intrusion, where chaotic hybrid rocks dominate the exposed lithology. Complex cross-cutting relations between different hybrid generations strongly suggest multiple magma injection and reheating events in the basal part of the shallow magma chamber. Model calculations employing distribution coefficients based on rare earth element concentrations reveal that early stage hybrid magma generations formed by pure endmember mixing between felsic and mafic magma with about 10% mafic fraction in the hybrids. With repeated injections of mafic magma into the base of the magma chamber, the intruding magma interacted to a greater extent with pre-existing hybrids. This led to the formation of hybrid magma compositions that are shifted towards the mafic endmember over time, with up to 30% of the mafic fraction in the hybrids. These mixing processes are recorded in the zonation patterns of clinopyroxene and plagioclase phenocrysts; the latter have been divided into four main groups by cross-correlation analysis. Melt viscosity calculations were performed to constrain the possible conditions of magma mixing and the results indicate that the interaction of the contrasting magmas most probably occurred at temperatures of approximately 1000°C up to 1120°C. This suggests that the initiation of effective magma mixing requires local superheating of the felsic magmas, thereby confining the process to areas of localized, substantial mafic magma injectio

Mineral resorption triggers explosive mixed silicate–carbonatite eruptions

Historic eruptions of Earth's only active carbonatite volcano, Oldoinyo Lengai (Tanzania), have repeatedly switched from low energy carbonatite lava extrusion to highly energetic explosive silicate volcanism, most recently in 1966–67 and 2007–08. The explosive eruptions produce strongly Si-undersaturated peralkaline silicate ashes with unusually high (Na + K)/Al of 3.4–6.3 when compared to the average peralkalinity of ∼0.8 in the East African Rift System. A series of experiments in the carbonatite–clinopyroxene system at 750–1150 °C, 0.1 GPa, reveal that augitic clinopyroxene breaks down peritectically at >900 °C yielding strongly peralkaline conjugated silicate- and carbonatite melts. The clinopyroxene-derived silicate melt dissolves (Na,K)_2O from the (Na,K)_2CO_3-component of the carbonatite leading to high peralkalinities and to liberation of excess CO_2, since the solubility of carbon dioxide in silicate liquids is ≪1 wt.% at subvolcanic pressures. Carbonatite injection into subvolcanic clinopyroxene-rich crystal mushes hence explains the occurrence of strongly peralkaline silicate melts and provides a mechanism for CO_2-driven explosive eruptions. The silicate melt compositions mostly depend on the (Na + K)/Ca ratio of the intruding carbonatite, the silicate ashes erupted in 1966–67 and 2007–08 require an interaction of a clinopyroxene-rich crystal mush with a slightly less evolved alkali-carbonatite than presently erupted at Oldoinyo Lengai. The mechanism identified here, where mineral breakdown induced melt hybridization triggers volatile saturation and highly explosive volcanism is generally applicable to igneous systems that involve carbonatites or other low-viscosity CO_2-bearing alkaline silicate melts

Carbonatites in oceanic hotspots

An analysis of the global array of ocean island volcanics shows that carbonatites only form in those hotspots that have the lowest Si- and highest alkali-contents among their primitive melts, such as the Cape Verde and Canary (Islands) hotspots. Fractionated melts from these two hotspots reach, at any given SiO_2, several wt% higher total alkali contents than for ocean islands without carbonatites. This is because their strongly silica-undersaturated primitive melts fractionate at low SiO_2 to high alkali contents, driving the evolving melt into the silicate-carbonatite miscibility gap. Instead, moderately alkaline magmas fractionate toward the alkali-feldspar thermal divide and do not reach liquid immiscibility. Low SiO_2 and high alkalis are the combined result of comparatively deep and low-degree mantle melting, the latter is corroborated by the highest high-field-strength and rare earth element concentrations in the Cape Verde and Canary primitive melts. CO_2 in the source facilitates low melt SiO_2, but enrichment in CO_2 relative to other hotspots is not required. The oceanic hotspots with carbonatites are among those with the thickest thermal lithosphere supporting a deep origin of their asthenospheric parent melts, an argument that could be expanded to continental hotspot settings

Fractional crystallization of Si-undersaturated alkaline magmas leading to unmixing of carbonatites on Brava Island (Cape Verde) and a general model of carbonatite genesis in alkaline magma suites

The carbonatites of Brava Island, Cape Verde hot spot, allow to investigate whether they represent small mantle melt fractions or form through extreme fractionation and/or liquid immiscibility from CO2-bearing silicate magmas. The intrusive carbonatites on Brava Island are part of a strongly silica-undersaturated pyroxenite, ijolite, nephelinite, nepheline syenite, combeite–foiditite, carbonatite series. The major and trace element composition of this suite is reproduced by a model fractionating olivine, clinopyroxene, perovskite, biotite, apatite, titanite, sodalite and FeTi oxides, all present as phenocrysts in the rocks corresponding to their fractionation interval. Fractionation of ~90 wt% crystals reproduces the observed geochemical trend from the least evolved ultramafic dikes (bulk X Mg = 0.64) to syenitic compositions. The modelled fractional crystallization leads to alkali enrichment, driving the melt into the carbonatite–silicate miscibility gap. An initial CO2 content of 4000 ppm is sufficient to saturate in CO2 at the point where the rock record suggests continuing unmixing carbonatites from nephelinites to nepheline syenites after 61 wt% fractionation. Such immiscibility is also manifested in carbonatite and silicate domains on a hand-specimen scale. Furthermore, almost identical primary clinopyroxene, biotite and carbonate compositions from carbonatites and nephelinites to nepheline syenites substantiate their conjugate character and our unmixing model. The modelled carbonatite compositions correspond to the natural ones except for their much higher alkali contents. The alkali-poor character of the carbonatites on Brava and elsewhere is likely a consequence of the release of alkali-rich CO2 + H2O fluids during final crystallization, which cause fenitization in adjacent rocks. We propose a general model for carbonatite generation during alkaline magmatism, where the fractionation of heavily Si-undersaturated, alkaline parent melts results in alkali and CO2 enrichment in the evolving melt, ultimately leading to immiscibility between carbonatites and evolved Si-undersaturated alkaline melts. Early saturation in feldspathoids or feldspars would limit alkali enrichment preventing the formation of carbonatites. The complete and continuous fractionation line from almost primitive melts to syenitic compositions on Brava underlines the possibly important role of intrusives for hot spot volcanism.ISSN:0010-7999ISSN:1432-096

A common origin of carbonatite magmas

The more than 500 fossil Ca-carbonatite occurrences on Earth are at odds with the only active East African Rift carbonatite volcano, Oldoinyo Lengai (Tanzania), which produces Na-carbonatite magmas. The volcano’s recent major explosive eruptions yielded a mix of nephelinitic and carbonatite melts, supporting the hypothesis that carbonatites and spatially associated peralkaline silicate lavas are related through liquid immiscibility. Nevertheless, previous eruption temperatures of Na-carbonatites were 490–595 °C, which is 250–450 °C lower than for any suitable conjugate silicate liquid. This study demonstrates experimentally that moderately alkaline Ca-carbonatite melts evolve to Na-carbonatites through crystal fractionation. The thermal barrier of the synthetic Na-Ca-carbonate system, held to preclude an evolution from Ca-carbonatites to Na-carbonatites, vanishes in the natural system, where continuous fractionation of calcite + apatite leads to Na-carbonatites, as observed at Oldoinyo Lengai. Furthermore, saturating the Na-carbonatite with minerals present in possible conjugate nephelinites yields a parent carbonatite with total alkali contents of 8–9 wt%, i.e., concentrations that are realistic for immiscible separation from nephelinitic liquids at 1000–1050 °C. Modeling the liquid line of descent along the calcite surface requires a total fractionation of ∼48% calcite, ∼12% apatite, and ∼2 wt% clinopyroxene. SiO2 solubility only increases from 0.2 to 2.9 wt% at 750–1200 °C, leaving little leeway for crystallization of silicates. The experimental results suggest a moderately alkaline parent to the Oldoinyo Lengai carbonatites and therefore a common origin for carbonatites related to alkaline magmatism.ISSN:0091-7613ISSN:1943-268

A tool to distinguish magmatic from secondarily recrystallized carbonatites—Calcite/apatite rare earth element partitioning

Crustal geochemical signatures in carbonatites may arise from carbon recycling through the mantle or from fluid-mediated interaction with the continental crust. To distinguish igne-ous from fluid-mediated processes, we experimentally determined rare earth element (REE) partitioning between calcite/melt and apatite/melt at subvolcanic emplacement conditions (1-2 kbar, 750-1000 degrees C). Our data allow modeling of calcite-apatite (Cc/Ap) partition coef-ficients (D), representing a new tool to bypass the previously required but largely unknown carbonatite melt composition. Experimentally determined magmatic calcite/apatite REE patterns are flat, as DLa D Cc /Ap/ Cc Ap Lu / is similar to 0.75, and they show a slight U-shape that becomes more pronounced with temperature decreasing from 1000 to 750 degrees C. Application to texturally well-equilibrated natural Ca-carbonatites and calcite-bearing nephelinites shows that some calcite-apatite pairs follow this pattern and, hence, confirm the magmatic nature of the car-bonates. DLaD Cc/Ap / values of other mineral pairs range from 10-2 to 10-3, which, together Cc/Ap Lu with a substantial light REE depletion in the calcite, is interpreted as fluid-mediated light REE removal during secondary calcite recrystallization. Calcite/apatite REE distributions are well suited to evaluate whether a carbonatite mineralogy is primary and magmatic or has been affected by secondary recrystallization. In this sense, our tool provides information about the sample's primary or secondary nature, which is essential when assigning isotopic crustal signatures (in Ca, C, or Sr) or REE patterns to related geologic processes.ISSN:0091-7613ISSN:1943-268

Effect of water on the glass transition of a potassium-magnesium carbonate melt

Calorimetric measurements of the glass transition temperatures (Tg) of hydrous carbonate melts are reported on a near-eutectic composition of 55 mol% K2CO3 - 45 mol% MgCO3 with up to 42 mol% bulk H2O dissolved in the carbonate melt. Hydrous melts were quenched from 750°C to transparent and crystal-free glasses and were subsequently analysed for water content before and after measuring Tg by high-sensitivity differential scanning calorimetry. The glass transition and limited fictive temperatures as a function of the water content were determined at 10 K/min cooling/heating rates resulting in Tg ranging from 245°C at nominally anhydrous conditions to 83°C in the presence of 42 mol% H2O in the glass. Through a generalized Gordon-Taylor analysis, the factors k (7.27), k0 (3.2) and the interaction parameter Ax (0.49) were derived. The limited fictive temperature of a hypothetically, zero water containing 55 mol% K2CO3 - 45 mol% MgCO3 glass is 232 ± 5°C (505 K). The high value of the interaction parameter A indicates strong specific molecular interactions between water and the carbonates in the glassy state and a large decrease in the excess enthalpy of mixing during the conversion of the glassy into the liquid state at the glass transition. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.ISSN:1364-503XISSN:1471-296