Braided peridotite sills and metasomatism in the Rum Layered Suite, Scotland

The Rum Eastern Layered Intrusion (ELI; Scotland) is an open-system layered intrusion constructed of 16 macro-rhythmic units. Each of the macro-rhythmic units consists of a peridotite base and a troctolite (+/- gabbro) top, previously attributed to the fractional crystallisation of a single magma batch. This classic paradigm has been challenged, however, with evidence presented for the emplacement of peridotite sills in Units 9, 10, and 14, such as cross-cutting relationships, upward-oriented apophyses, and lateral discontinuities. To test whether the other major peridotites within the ELI represent sills, we have carried out new field, petrographic, and mineral chemical analyses of the peridotites in Units 7, 8 and 9. The peridotites display large- and small-scale cross-cutting relationships with the overlying troctolite, indicative of an intrusive relationship. The peridotites also show large-scale coalescence and lateral spatial discontinuities such that the ELI unit divisions become arbitrary. Harrisite layers and Cr-spinel seams found throughout Units 7, 8, and 9 suggest the peridotites were constructed incrementally via repeated injections of picritic magma. Our observations allow for distinct subtypes of peridotite to be defined, separated by intrusive contacts, allowing for their relative chronology to be determined. Older, poikilitic peridotite, rich in clinopyroxene, is truncated by younger, well-layered peridotite, containing abundant harrisite layers. In addition to the new peridotite subtypes defined in this study, we find strong evidence for laterally oriented metasomatism within clinopyroxene-rich wehrlites at the top of the Unit 8 peridotite. The wehrlites and surrounding peridotites record a complex series of metasomatic reactions that transformed thin picrite sills into clinopyroxene-rich wehrlites without any evidence for the sort of vertical melt movement typically posited in layered intrusions. The observations presented in this study from the ELI cannot be reconciled with the classic magma chamber paradigm and are better explained by the emplacement of composite sills into pre-existing feldspathic cumulate (gabbro or troctolite). The evidence for sill emplacement presented here suggests that the layered complex was constructed by a combination of sill emplacement and metasomatism, forming many of the unusual (often clinopyroxene-rich) lithologies that surround the sills. The broad-scale formation of the layered peridotites via incremental sill emplacement, suggested by the occurrence of upward-oriented apophyses, coalescence, and lateral discontinuity, could be applied to much larger ultramafic intrusions, which might have formed by similar mechanisms

Chromitite petrogenesis in the mantle section of the Ballantrae Ophiolite Complex (Scotland)

5siPodiform chromitites from the Ballantrae Ophiolite Complex (BOC), NW Scotland, are examined to investigate their petrogenesis and elucidate the nature of melt percolation in the supra-subduction zone oceanic mantle more generally. The mantle portion of the BOC comprises two petrologically distinct serpentinite belts, whose differences have previously been attributed to contrasting degrees of melt extraction. Chromitite occurs in each of the northern and southern serpentinite belts, at Pinbain Bridge and Poundland Burn, respectively. Field relationships suggest that chromitites were formed by melt-rock reaction in channel-like conduits in the upper mantle. Chromitite Cr-spinel compositions from the two localities show marked differences to one another, with the Pinbain Bridge chromitite Cr-spinels being characterised by relatively high Cr# [Cr/(Cr+Al); 0.62-0.65] and lower abundances of certain trace elements (e.g., Ti, Ga, V), whereas the Poundland Burn chromitite Cr-spinels exhibit relatively low Cr# (0.44-0.46) and higher concentrations of these trace elements. The contrasting Cr-spinel compositions are used to estimate parental magma compositions for the chromitites; the Pinbain Bridge chromitites crystallised from magmas resembling arc tholeiites whereas MORB-like magmas were involved in formation of the Poundland Burn chromitites. While it is possible that this dichotomy points to early derivation of the BOC at a MORB spreading centre, with subsequent processing in a supra-subduction zone, we suggest that the differences reflect melt extraction from different parts of an evolving subduction zone, such that the MORB-like magmas were generated in a back-arc setting. This interpretation finds support in the Ti/Fe3# versus Ga/Fe3# systematics of peridotite-hosted accessory Cr-spinel that we present here, as well as previously published trace element data and geochronological constraints on the basalt lava sequences associated with the BOC, which collectively favour formation of the Poundland Burn chromitites in subduction zone mantle.partially_openembargoed_20210616Derbyshire, EJ, O’Driscoll, B, Lenaz, D, Zanetti, A, Gertisser, RDerbyshire, Ej; O’Driscoll, B; Lenaz, D; Zanetti, A; Gertisser,

Magmatic and metasomatic effects of magma-carbonate interaction recorded in calc-silicate xenoliths from Merapi volcano (Indonesia)

Magma-carbonate interaction is an increasingly recognised process occurring at active volcanoes worldwide, with implications for the magmatic evolution of the host volcanic systems, their eruptive behaviour, volcanic CO2 budgets, and economic mineralisation. Abundant calc-silicate skarn xenoliths are found at Merapi volcano, Indonesia. We identify two distinct xenolith types: magmatic skarn xenoliths, which contain evidence of formation within the magma, and exoskarn xenoliths, which more likely represent fragments of crystalline metamorphosed wall-rocks. The magmatic skarn xenoliths comprise distinct compositional and mineralogical zones with abundant Ca-enriched glass (up to 10 wt% relative to lava groundmass), mineralogically dominated by clinopyroxene (En15-43Fs14-36Wo41-51) + plagioclase (An37-100) ± magnetite in the outer zones towards the lava contact and by wollastonite ± clinopyroxene (En17-38Fs8-34Wo49-59) ± plagioclase (An46-100) ± garnet (Grs0-65Adr24-75Sch0-76) ± quartz in the xenolith cores. These zones are controlled by Ca transfer from the limestone protolith to the magma and by transfer of magma-derived elements in the opposite direction. In contrast, the exoskarn xenoliths are unzoned and essentially glass-free, representing equilibration at sub-solidus conditions. The major mineral assemblage in the exoskarn xenoliths is wollastonite + garnet (Grs73-97Adr3-24) + Ca-Al-rich clinopyroxene (CaTs0-38) + anorthite ± quartz, with variable amounts of either quartz or melilite (Geh42-91) + spinel. Thermobarometric calculations, fluid inclusion microthermometry and newly calibrated oxybarometry based on Fe3+/ΣFe in clinopyroxene indicate magmatic skarn xenolith formation conditions of ∼850 ± 45 °C, < 100 MPa and at an oxygen fugacity between the NNO and HM buffer. The exoskarn xenoliths, in turn, formed at 510-910 °C under oxygen fugacity conditions between NNO and air. These high oxygen fugacities are likely imposed by the large volumes of CO2 liberated from the carbonate. Halogen and sulphur-rich mineral phases in the xenoliths testify to the infiltration by a magmatic brine. In some xenoliths this is associated with the precipitation of copper-bearing mineral phases by sulphur dissociation into sulphide and sulphate, indicating potential mineralisation in the skarn system below Merapi. Compositions of many xenolith clinopyroxene and plagioclase crystals overlap with that of magmatic minerals, suggesting that the crystal cargo in Merapi magmas may contain a larger proportion of skarn-derived xenocrysts than previously recognised. Assessment of xenolith formation timescales demonstrates that magma-carbonate interaction and associated CO2 release could affect eruption intensity, as recently suggested for Merapi and similar carbonate-hosted volcanoes elsewhere

Structural features and stability of Spanish sepiolite as a potential catalyst

Abstract Sepiolite-based catalysts loaded with potassium hydroxide were prepared via the wet impregnation and ion-exchange methods and evaluated as catalysts in base-assisted reactions, such as transesterification of renewable oils. The structural features of these catalysts were characterised in detail by variable-temperature in situ X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy with energy-dispersive X-ray analysis and in situ FTIR spectroscopy. Although a high yield of fatty acid methyl esters was achieved in transesterification reactions in the presence of K-containing sepiolite, this system showed significant deactivation due to its structural degradation and loss of the active component during the reaction and regeneration cycles. This work demonstrates for the first time how the thermal and structural stability of sepiolite based systems can affect their performance, which is an essential issue that has not been sufficiently addressed in recent research related to the catalytic applications of these materials

Eruptive history of the Late Quaternary Ciomadul (Csomád) volcano, East Carpathians, part II: magma output rates

This study, which builds on high-precision unspiked Cassignol-Gillot K-Ar age determinations, presents an advanced DEMbased volumetrical analysis to infer long-term magma output rates for the Late Quaternary Ciomadul (Csomád) dacitic lava dome complex (East Carpathians, Romania). The volcanic field of Ciomadul developed on the erosional surface of Lower Cretaceous flysch and ~ 2 Ma old andesites and experienced an extended eruptive history from ~ 850 to < 30 ka. Predominantly effusive activity took place during the first stage (~ 850 to ~ 440 ka), producing volumetrically minor, isolated, peripheral domes. Subsequently, after a ~ 250 ky repose interval, a voluminous central dome cluster developed in the second stage (~ 200 to < 30 ka). During the youngest phase of evolution (~ 60 to < 30 ka), highly explosive eruptions also occurred, resulting in the formation of two craters (Mohos and St. Ana). The calculated ~ 8.00 ± 0.55 km3 total volume of the lava domes, which includes the related volcaniclastic (1.57 km3 ) as well as erosionally removed (0.18 km3 ) material, is in line with dimensions of other medium-sized dacitic lava domes worldwide. This volume was extruded at an average long-term magma output rate of 9.76 km3 / My (0.0098 km3 /ky). However, most of the domes (7.53 ± 0.51 km3 ) were formed in the 200 to < 30 ka period, implying a significantly increased magma output rate of 37.40 km3 /My (0.0374 km3 /ky), more than 30 times higher than in the first stage. Within these long-term trends, individual lava domes of Ciomadul (e.g. those with volumes between 0.02 and 0.40 km3 ) would have been emplaced at much higher rates over a period of years to tens of years. The active periods, lasting up to hundreds of years, would have been followed by repose periods ~ 30 times longer. The most recent eruption of Ciomadul has been dated here at 27.7 ± 1.4 ka. This age, which is in agreement with radiocarbon dates for the onset of lake sediment accumulation in St. Ana crater, dates fragmented lava blocks which are possibly related to a disrupted dome. This suggests that during the last, typically explosive, phase of Ciomadul, lava dome extrusion was still ongoing. In a global context, the analysis of the volumetric dynamism of Ciomadul’s activity gives insights into the temporal variations in magma output; at lava domes, short-term (dayor week-scale) eruption rates smooth out in long-term (millenia-scale) output rates which are tens of times lower

Crustal CO2 contribution to subduction zone degassing recorded through calc-silicate xenoliths in arc lavas

Interaction between magma and crustal carbonate at active arc volcanoes has recently been proposed as a source of atmospheric CO2, in addition to CO2 released from the mantle and subducted oceanic crust. However, quantitative constraints on efciency and timing of these processes are poorly established. Here, we present the frst in situ carbon and oxygen isotope data of texturally distinct calcite in calc-silicate xenoliths from arc volcanics in a case study from Merapi volcano (Indonesia). Textures and C-O isotopic data provide unique evidence for decarbonation, magma-fuid interaction, and the generation of carbonate melts. We report extremely light δ13CPDB values down to −29.3‰ which are among the lowest reported in magmatic systems so far. Combined with the general paucity of relict calcite, these extremely low values demonstrate highly efcient remobilisation of crustal CO2 over geologically short timescales of thousands of years or less. This rapid release of large volumes of crustal CO2 may impact global carbon cycling

Carbonate Assimilation at Merapi Volcano, Java, Indonesia: Insights from Crystal Isotope Stratigraphy

Recent basaltic andesite lavas from Merapi volcano contain abundant, complexly zoned, plagioclase phenocrysts, analysed here for their petrographic textures, major element composition and Sr isotope composition. Anorthite (An) content in individual crystals can vary by as much as 55 mol% (An40-95) across internal resorption surfaces with a negative correlation between high An mol% (>70), MgO wt% and FeO wt%. In situ Sr isotope analyses of zoned plagioclase phenocrysts show that the 87Sr/86Sr ratios of individual zones range from 0·70568 to 0·70627. The upper end of this range is notably more radiogenic than the host basaltic andesite whole-rocks (< 0·70574). Crystal zones with the highest An content have the highest 87Sr/86Sr values, requiring a source or melt with elevated radiogenic Sr, rich in Ca and with lower Mg and Fe. Recent Merapi eruptive rocks contain abundant xenoliths, including metamorphosed volcanoclastic sediment and carbonate country rock (calc-silicate skarns) analysed here for petrographic textures, mineralogy, major element composition and Sr isotope composition. The xenoliths contain extremely calcic plagioclase (up to An100) and have whole-rock 87Sr/86Sr ratios of 0·70584 to 0·70786. The presence of these xenoliths and their mineralogy and geochemistry, coupled with the 87Sr/86Sr ratios observed in different zones of individual phenocrysts, indicate that magma-crust interaction at Merapi is potentially more significant than previously thought, as numerous crystal cores in the phenocrysts appear to be inherited from a metamorphosed sedimentary crustal source. This has potentially significant consequences for geochemical mass-balance calculations, volatile saturation and flux and eruptive behaviour at Merapi and similar island arc volcanic systems elsewher

Sr isotopes indicate millennial-scale formation of metal-rich layers by reactive melt percolation in an open-system layered intrusion

&amp;lt;p&amp;gt;In order to test whether the crystal mushes that form layered mafic intrusions can behave as open systems, we investigated mineral-scale textural, chemical and Sr isotopic heterogeneity in the c. 60 Ma Rum intrusion, Scotland. Within Unit 10 of the Rum intrusion, intercumulus plagioclase and clinopyroxene crystals in peridotite 1-2 cm above and below millimetric Cr-spinel seams exhibit complex optical and chemical zoning (Hepworth et al. 2017). These Cr-spinel seams are closely associated with sulphide and platinum-group element (PGE) mineralization. High precision Sr isotopic analyses (undertaken by thermal ionisation mass spectrometry) of individual intracrystal zones (sampled by micromilling) in intercumulus plagioclase and clinopyroxene from within the PGE-enriched Cr-spinel seams have revealed significant intra-crystalline heterogeneity. &amp;lt;sup&amp;gt;87&amp;lt;/sup&amp;gt;Sr/&amp;lt;sup&amp;gt;86&amp;lt;/sup&amp;gt;Sr heterogeneity is present between plagioclase crystals, between clinopyroxene and plagioclase, and within plagioclase crystals, throughout the studied section. The preservation of Sr isotope heterogeneities at 10-100 &amp;amp;#181;m length-scales implies cooling of the melts that formed the precious metal-rich layers at rates &amp;gt;1 &amp;amp;#176;C per year, and cooling to diffusive closure within 10s-100s of years. The combined textural observations and intra-crystal plagioclase &amp;lt;sup&amp;gt;87&amp;lt;/sup&amp;gt;Sr/&amp;lt;sup&amp;gt;86&amp;lt;/sup&amp;gt;Sr data also highlight the importance of repeated cycles of dissolution and recrystallization within the crystal mush, and together with recent documentation of &amp;amp;#8216;out-of-sequence&amp;amp;#8217; layers in other layered intrusions (Mungall et al. 2016; Wall et al. 2018), raise the prospect that basaltic magmatic systems may undergo repeated self-intrusion during solidification.&amp;lt;/p&amp;gt;&amp;lt;p&amp;gt;Hepworth, L.N., O&amp;amp;#8217;Driscoll, B., Gertisser, R., Daly, J.S. and Emeleus, H.C. 2017. Journal of Petrology 58, 137-166; Mungall, J. E., Kamo, S. L. &amp;amp; McQuade, S. 2016. Nature Communications 7, 13385; Wall, C. J., Scoates, J. S., Weis, D., Friedman, R. M., Amini, M. &amp;amp; Meurer, W. P. 2018. Journal of Petrology 59, 153&amp;amp;#8211;190.&amp;lt;/p&amp;gt; </jats:p