Radioactive particles often contain very high radioactivity concentrations and are widespread. They pose a potential risk to human health and the environment. Their detection, quantification, and characterization are crucial if we are to understand their impact. Here, we present the use of a real-time autoradiography gaseous detector (using parallel ionization multiplier) to expedite and improve the accuracy of radioactive particle screening in complex environmental samples. First, standard particles were used to assess the detector capabilities (spatial resolution, spectrometry, and artefact contributions), then, we applied the technique to more complex and environmentally relevant samples. The real-time autoradiography technique provides data with a spatial resolution (≲100 µm) suitable for particle analysis in complex samples. Further, it can differentiate between particles predominantly emitting alpha and beta radiation. Here, the technique is applied to radioactive cesium-rich microparticles collected from the Fukushima Daiichi nuclear exclusion zone, showing their accurate detection, and demonstrating the viability of real-time autoradiography in environmental scenarios. Indeed, for more complex samples (radioactive particles in a less radioactive heterogeneous background mix of minerals), the technique permits relatively high selectivity for radioactive particle screening (up to 61.2% success rate) with low false positive percentages (~ 1%).

Margins resulting from continental breakup are generally classified as volcanic (related to flood basalt volcanism from a starting plume head) or non-volcanic (caused by tectonic processes), but many margins (breakups) may actually be hybrids caused by a combination of volcanic and tectonic processes. It has been postulated that the collision of the Hikurangi Plateau with the Gondwana margin similar to 110 Ma ago caused subduction to cease, followed by large-scale extension and ultimately breakoff of the Zealandia micro-continent from West Antarctica through seafloor spreading which started at similar to 85 Ma. Here we report new geochemical (major and trace element and Sr-Nd-Pb-Hf isotope) data for Late Cretaceous (99-69 Ma) volcanism from Zealandia, which include the calc-alkalic, subduction-related Mount Somers (99-96 Ma) and four intraplate igneous provinces: 1) Hikurangi Seamount Province (99-88 Ma), 2) Marlborough Igneous Province (98-94 Ma), 3) Westland Igneous Province (92-69 Ma), and 4) Eastern Chatham Igneous Province (86-79 Ma). Each of the intraplate provinces forms mixing arrays on incompatible-element and isotope ratio plots between HIMU (requiring long-term high mu = U-238/Pb-204) and either a depleted (MORB-source) upper mantle (DM) component or enriched continental (EM) type component (located in the crust and/or upper mantle) or a mixture of both. St. Helena end member HIMU could be the common component in all four provinces. Considering the uniformity in composition of the HIMU end member despite the type of lithosphere (continental, oceanic, oceanic plateau) beneath the igneous provinces, we attribute this component to a sublithospheric source, located beneath all volcanic provinces, and thus most likely a mantle plume. We propose that the plume material rose beneath the active Gondwana margin and flowed along the subducting lithosphere beneath the Hikurangi Plateau and neighboring seafloor and through slab tears/windows beneath the Gondwana (later to become Zealandia) continental lithosphere. We conclude that both plateau collision, resulting in subduction cessation, and the opening of slab tears/windows, allowing hot asthenosphere and/or plume material to upwell to shallow depths, were important in causing the breakup of Zealandia from West Antarctica. Combined tectonic-volcanic processes are also likely to be responsible for causing breakup and the formation of other hybrid type margins. (C) 2019 Elsevier B.V. All rights reserved.

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 Bastnäsfältet 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 δ 18 O 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 δ 18 O (5.0–5.8‰). Plagioclase reveals crystallisation in upper crustal storage reservoirs and shows δ 18 O 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 δ 18 O values. Overall, Toba quartz crystals exhibit comparatively high δ 18 O 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 δ 18 O 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-δ 18 O component into the magma reservoir just prior to eruption. Here we argue that this late-stage low-δ 18 O 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 CO 2 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 CO 2 -dominated vapour phase. The CaO-rich glasses have extremely low δ 11 B values down to −41.5‰, reflecting preferential partitioning of 10 B into the assimilating melt. Loss of 11 B from the reaction site occurs via the CO 2 vapour phase generated during carbonate dissolution, which transports 11 B 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 δ 11 B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

O and C isotope study of Bastnas-type rare earth element mineralisation, Bergslagen, Sweden

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.

This thesis attempts to develop our understanding of volcanic magma plumbing systems and the magmatic processes that operate within them, such as fractional crystallisation, crustal partial melting, assimilation, and magma mixing. I utilise petrology, rock and mineral geochemistry, and isotope systematics to seek to improve our ability to forecast the eruptive frequency and style of active volcanoes, an aspect often lacking in current volcano monitoring efforts. In particular, magma reservoir dynamics are investigated from a mineral scale at Katla volcano in Iceland, to a sub-mineral scale at Merapi, Kelud, and Toba volcanoes in Indonesia.The magma plumbing architecture of Katla volcano on Iceland is explored in the first part of this thesis. Crystalline components within tephra and volcanic rock preserve a record of the physical and chemical evolution of a magma, and are analysed through oxygen isotopic and thermobarometric techniques to temporally constrain changes in reservoir depth and decode the petrogenesis of the lavas. We find both prolonged upper crustal magma storage and shallow level assimilation to be occurring at Katla. The results generated from combining these analytical strands reveal the potential for unpredictable explosive volcanism at this lively Icelandic volcano.The second part of this thesis examines the magma plumbing systems of Merapi, Kelud and Toba volcanoes of the Sunda arc in Indonesia at higher temporal and petrological resolution than possible for Katla (e.g., due to the crystal poor character of the rocks). For this part of the thesis, minerals were analysed in-situ to take advantage of sub-crystal scale isotopic variations in order to investigate processes of shallow-level assimilation in the build-up to particular eruptions. We find that intra-crystal analyses reveal an otherwise hidden differentiation history at these volcanoes, and establish a better understanding as to how they may have rapidly achieved a critical explosive state.The outcomes of this thesis therefore deepen our knowledge of evolutionary trends in magma plumbing system dynamics, and highlight the importance of understanding the geochemical processes that can prime a volcano for eruption. Lastly, I emphasise the vital contribution petrology can make in current volcano monitoring efforts.

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 δ18O values (9.3 to 10.8‰), 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 δ13C and δ18O 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 δ18O data range from un-metamorphosed carbonate (>18‰) to values typical for Vesuvius magmatic rocks (~7.5‰), 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.

Merapi volcano is among the most hazardous volcanoes on the planet. Ancient Javanese folklore describes Merapi's activity as the interaction between the Spirit Kings that inhabit the volcano and the Queen of the South Sea, who resides at Parangtritis beach, 50km SSE of Merapi. The royal palace in Yogyakarta is located half-way along the hypothetical line between Merapi and Parangtritis (the Merapi-Kraton-South Sea axis) to bring balance between these mystical forces. In 2006 and 2010, Merapi erupted explosively and on both occasions, earthquakes shook the region and the eruptions grew more violent in response. These earthquakes appear to influence the sub-volcanic magma supply of Merapi and a positive feedback loop has recently been postulated between the volcano and local earthquake patterns. The 2006 earthquakes clustered along the Opak River fault to the south of the volcano, which trends NE-SW, and reaches the southern sea at Parangtritis beach, the fabled residence of the Queen of the South Sea. Our interpretation of the Merapi-Kraton-South Sea axis is that local folklore was used by ancient people to describe and rationalize the complex interplay between geological processes. We suggest that Merapi displayed volcano-earthquake interaction many times in the past, and not only during its most recent eruptive cycle. Although now shrouded in mystery, these oral traditions can be thought of as an ancient hazard mitigation tool, which makes them likely useful in helping to foster effective dialogues with a variety of target parties and interest groups around the volcano's slopes.

Chemcial fingerprinting of crystal populations from Sekincau, Marapi and Sinabung volcanoes, Sumatra

The role of CO2-rich basement at Merapi; perspectives from petrology, geochemistry, and experiments

Ancient oral tradition describes volcano-earthquake interaction at Merapi volcano, Indonesia

Time-monitored vesiculation and dissolution during magma-carbonate interaction experiments: Merapi (Indonesia) and Vesuvius (Italy).