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The presently increasing demand for rare earth elements (REE), particularly in high-tech and "green energy" applications, has led to global interest in the distribution, origins and formation conditions of REE deposits. The World's first hard-rock REE sources, the polymetallic deposits of Bastnasfaltet in Bergslagen, central Sweden, were also the place of the original discovery of several REE and many of their host minerals. Similar deposits with high concentrations of REE occur along a >100 km corridor in the region and they share a number of geological and mineralogical features; all comprising Palaeoproterozoic, skarn-hosted magnetite-REE mineralisation of ambiguous origin. Here we report oxygen isotope data for magnetite and quartz, and oxygen and carbon isotope data for carbonates from ten of these classic deposits, to model and assess their mode of origin. Combined with existing geological observations, the isotope results support an origin in a c. 1.9 Ga shallow-marine back-arc, sub-seafloor setting, where felsic magmatic-sourced, high-temperature fluids reacted with pre-existing limestone interlayers, leading to localised skarn formation and magnetite-REE-mineral precipitation. These findings help us to better understand the geological processes that have produced economic REE mineralisation and may assist future exploration for these critical commodities.

The island of Bali in Indonesia is home to two active stratovolcanoes, Agung and Batur, but relatively little is known of their underlying magma plumbing systems. Here we define magma storage depths and isotopic evolution of the 1963 and 1974 eruptions using mineral-melt equilibrium thermobarometry and oxygen and helium isotopes in mineral separates. Olivine crystallised from a primitive magma and has average delta O-18 values of 4.8%. Clinopyroxene records magma storage at the crust-mantle boundary, and displays mantle-like isotope values for Helium (8.62 R-A) and delta O-18 (5.0-5.8%). Plagioclase reveals crystallisation in upper crustal storage reservoirs and shows delta O-18 values of 5.5-6.4%. Our new thermobarometry and isotope data thus corroborate earlier seismic and InSAR studies that inferred upper crustal magma storage in the region. This type of multi-level plumbing architecture could drive replenishing magma to rapid volatile saturation, thus increasing the likelihood of explosive eruptions and the consequent hazard potential for the population of Bali.

Quartz is a common phase in high-silica igneous rocks and is resistant to post-eruptive alteration, thus offering a reliable record of magmatic processes in silicic magma systems. Here we employ the 75 ka Toba super-eruption as a case study to show that quartz can resolve late-stage temporal changes in magmatic δ¹⁸O values. Overall, Toba quartz crystals exhibit comparatively high δ¹⁸O values, up to 10.2‰, due to magma residence within, and assimilation of, local granite basement. However, some 40% of the analysed quartz crystals display a decrease in δ¹⁸O values in outermost growth zones compared to their cores, with values as low as 6.7‰ (maximum ∆_core−rim = 1.8‰). These lower values are consistent with the limited zircon record available for Toba, and the crystallisation history of Toba quartz traces an influx of a low-δ¹⁸O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ¹⁸O component is derived from hydrothermally-altered roof material. Our study demonstrates that quartz isotope stratigraphy can resolve magmatic events that may remain undetected by whole-rock or zircon isotope studies, and that assimilation of altered roof material may represent a viable eruption trigger in large Toba-style magmatic systems.

Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low delta B-11 values down to -41.5%, reflecting preferential partitioning of B-10 into the assimilating melt. Loss of B-11 from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports B-11 away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low delta B-11 melt values in arc magmas could flag shallow-level additions to the subduction cycle.

We conducted quantitative textural analysis of vesicles in high temperature and pressure carbonate assimilation experiments (1200 °C, 0.5 GPa) to investigate CO2 generation and subsequent bubble migration from carbonate into magma. We employed Mt. Merapi (Indonesia) and Mt. Vesuvius (Italy) compositions as magmatic starting materials and present three experimental series using (1) a dry basaltic-andesite, (2) a hydrous basaltic-andesite (2 wt% H2O), and (3) a hydrous shoshonite (2 wt% H2O). The duration of the experiments was varied from 0 to 300 s, and carbonate assimilation produced a CO2-rich fluid and CaO-enriched melts in all cases. The rate of carbonate assimilation, however, changed as a function of melt viscosity, which affected the 2D vesicle number, vesicle volume, and vesicle size distribution within each experiment. Relatively low-viscosity melts (i.e. Vesuvius experiments) facilitated efficient removal of bubbles from the reaction site. This allowed carbonate assimilation to continue unhindered and large volumes of CO2 to be liberated, a scenario thought to fuel sustained CO2-driven eruptions at the surface. Conversely, at higher viscosity (i.e. Merapi experiments), bubble migration became progressively inhibited and bubble concentration at the reaction site caused localised volatile over-pressure that can eventually trigger short-lived explosive outbursts. Melt viscosity therefore exerts a fundamental control on carbonate assimilation rates and, by consequence, the style of CO2-fuelled eruptions.

Limestone assimilation and skarn formation are important processes in magmatic systems emplaced within carbonate-rich crust and can affect the composition of the magma and that of associated volcanic gas. In this study we focus on marble and calc-silicate (skarn) xenoliths from contact reactions between magma and carbonate wall-rock of the Vesuvius volcanic system. We present new elemental and C-O isotope data for marble and skarn xenoliths as well as for igneous rocks collected from the AD 79 (Pompeii) and AD 472 (Pollena) eruptions. The igneous samples have consistently high delta O-18 values (9.3 to 10.8 parts per thousand), but low H2O contents (<= 1.5%), indicating that magma-crust interaction prior to eruption took place. The marble xenoliths, in turn, record initial decarbonation reactions and fluid-mass exchange in their textures and delta C-13 and delta O-18 ranges, while the skarn xenoliths reflect prolonged magma-carbonate interaction and intense contact metamorphism. Skarn-xenoliths record Ca and Mg release from the original carbonate and uptake of Al and Si and span the full delta O-18 data range from unmetamorphosed carbonate (>18 parts per thousand) to values typical for Vesuvius magmatic rocks (similar to 7.5 parts per thousand), which implies that skarn xenoliths comprise carbonate and magmatic components. Textural and chemical evidence suggest that direct carbonate dissolution into the host magmas occurred as well as post-metamorphic skarn recycling, resulting in progressive Ca and Mg liberation from the skarn xenoliths into the magma. Magma-carbonate interaction is an additional source of CO2 during carbonate break-down and assimilation and we calculate the amount of extra volatile components likely liberated by contact metamorphic reactions before and during the investigated eruptions. We find that the extra CO2 added into the volcanic system could have outweighed the magmatic CO2 component by >= factor seven and thus likely increased the intensity of both the Pompeii and the Pollena eruptive events.