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Abstract: The chemistry of aerosol particles is critical to the influence said particles have over human health, air quality and the distribution of nutrients across the world. Current models estimate that windborne dust represents the movement of thousands of teragrams of solid material of varying composition and solubility across continents and into the world’s oceans. Understanding the composition and surface reactivity of anthropogenic particles from industry, agriculture and vehicle emissions is vital to understanding their potential impact on the world, and the structure and behaviour of inhalable pharmaceuticals is a strong determinant of their efficacy. The following work examines a broad selection of natural and anthropogenic particulate samples with synchrotron-based techniques, including analysis of ship emissions collected directly from stacks for the first time. The effect of simulated atmospheric acid processing on the solubility of iron on coal fly ash is evaluated, and optical trapping is used in conjunction with analytical techniques to observe the influence of relative humidity on the properties of pharmaceutical aerosols and aqueous droplets containing fluorescent protein solutions.

Open Access

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Abstract: Understanding the long-term fate, stability, and bioavailability of uranium (U) in the environment is important for the management of nuclear legacy sites and radioactive wastes. Analysis of U behavior at natural analogue sites permits evaluation of U biogeochemistry under conditions more representative of long-term equilibrium. Here, we have used bulk geochemical and microbial community analysis of soils, coupled with X-ray absorption spectroscopy and μ-focus X-ray fluorescence mapping, to gain a mechanistic understanding of the fate of U transported into an organic-rich soil from a pitchblende vein at the UK Needle's Eye Natural Analogue site. U is highly enriched in the Needle's Eye soils (∼1600 mg kg−1). We show that this enrichment is largely controlled by U(VI) complexation with soil organic matter and not U(VI) bioreduction. Instead, organic-associated U(VI) seems to remain stable under microbially-mediated Fe(III)-reducing conditions. U(IV) (as non-crystalline U(IV)) was only observed at greater depths at the site (>25 cm); the soil here was comparatively mineral-rich, organic-poor, and sulfate-reducing/methanogenic. Furthermore, nanocrystalline UO2, an alternative product of U(VI) reduction in soils, was not observed at the site, and U did not appear to be associated with Fe-bearing minerals. Organic-rich soils appear to have the potential to impede U groundwater transport, irrespective of ambient redox conditions.

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Abstract: Techniques employing synchrotron radiation (SR) have had a major and growing impact on catalytic science. They have made key contributions to our understanding of structural properties of catalytic systems and of structural changes during the operation of a catalytic process. They can also improve our understanding of electronic and vibrational properties, which can contribute to the understanding of mechanisms. SR techniques are now key components of the experimental tool box of the catalytic scientist.

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Abstract: Tuffisite veins are glass-filled fractures formed when magma fragments during degassing within the conduit. These veins form transient channels through which exsolved gases can escape from magma. The purpose of this study is to determine the extent to which chemical heterogeneity within the melt results from gas transport, and assess how this can be used to study magma degassing. Two tuffisite veins from contrasting rhyolitic eruptions at Torfajökull (Iceland) and Chaitén (Chile) were studied in detail. The tuffisite vein from Torfajökull is from a shallow dissected conduit (∼70 ka) that fed a degassed lava flow, while the sample from Chaitén was a bomb ejected during the waning phases of Plinian activity in May 2008. The results of detailed in situ chemical analyses (synchrotron XRF, FTIR, LA-ICP-MS) show that in both veins larger vesiculated fragments are enriched in volatile elements (Torfajökull: H, Li, Cl; Chaitén: Li, Cl, Cu, Zn, As, Sn, Sb) compared to the host, while the surrounding smaller particles are depleted in the Torfajökull vein (Li, Cl, Zn, Br, Rb, Pb), but enriched in the Chaitén vein (K, Cu, Zn, As, Mo, Sb, Pb). The lifespans of both veins and the fluxes of gas and particles through them can be estimated using diffusion profiles and enrichment factors. The Torfajökull vein had a longer lifespan (∼a day) and low particle velocities (∼cm/s), while the Chaitén vein was shorter lived (<1 h) with a high gas velocity (∼m/s). These differences are consistent with the contrasting eruption mechanisms (effusive vs. explosive). The amount of magma that degassed through the Chaitén vein is more than ten times the volume of the vein itself, requiring the vein to tap into pre-exsolved gas pockets. This study highlights that tuffisite veins are highly efficient gas pathways and thereby impart chemical diversity in volatile elements on the melt.

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Abstract: Martian meteorite Northwest Africa (NWA) 8114 – a paired stone to NWA 7034 – provides an opportunity to examine the thermal history of a martian regolith and study near-surface processes and ancient environmental conditions near an impact crater on Mars. Our study reports petrographic and alteration textures and focuses on pyroxene and iron oxide grains. Some of the pyroxene clasts show exsolution lamellae, indicating a high temperature magmatic origin and slow cooling. However, transmission electron microscopy reveals that other predominantly pyroxene clasts are porous and have partially re-crystallised to form magnetite and a K-bearing feldspathic glassy material, together with relict pyroxene. This breakdown event was associated with oxidation, with up to 25% Fe3+/ΣFe in the relict pyroxene measured using Fe-K XANES. By comparison with previous studies, this breakdown and oxidation of pyroxene is most likely to be a result of impact shock heating, being held at a temperature above 700 °C for at least 7 days in an oxidising regolith environment. We report an approximate 40Ar-39Ar maximum age of 1.13 Ga to 1.25 Ga for an individual, separated, augite clast. The disturbed nature of the spectra precludes precise age determination. In section, this clast is porous and contains iron oxide grains. This shows that it has undergone the high temperature partial breakdown seen in other relict pyroxene clasts, and has up to 25% Fe3+/ΣFe. We infer that the age corresponds to the impact shock heating event that led to the high temperature breakdown of many of the pyroxenes, after consolidation of the impact ejecta blanket. High temperatures, above 700 °C, may have been maintained for long enough to remobilise and congruently partially melt some of the alkali feldspar clasts to produce the feldspar veins and aureoles that crosscut, and in some cases surround, the oxidised pyroxene. However, the veins could alternatively be the result of a hydrothermal event in the impact regolith. A simple Fourier cooling model suggests that a regolith of at least five metres depth would be sufficient to maintain temperatures associated with the pyroxene breakdown for over seven days. Low temperature hydrous alteration took place forming goethite, identified via XRD, XANES and FTIR. Comparing with previous studies, the goethite is likely to be terrestrial alteration pseudomorphing martian pyrite.