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Abstract: Silicified peritidal carbonates of the Tonian Draken Formation, Spitsbergen, contain highly diverse and well-preserved microfossil assemblages dominated by filamentous microbial mats, but also including diverse benthic and/or allochthonous (possibly planktonic) microorganisms. Here, we characterize eight morphospecies in focused ion beam (FIB) ultrathin sections using transmission electron microscopy (TEM) and X-ray absorption near-edge structure (XANES) spectromicroscopy. Raman and XANES spectroscopies show the highly aromatic molecular structure of preserved organic matter. Despite this apparently poor molecular preservation, nano-quartz crystallization allowed for the preservation of various ultrastructures distinguished in TEM. In some filamentous microfossils (Siphonophycus) as well as in all cyanobacterial coccoids, extracellular polysaccharide sheaths appear as bands of dispersed organic nanoparticles. Synodophycus microfossils, made up of pluricellular colonies of coccoids, contain organic walls similar to the F-layers of pleurocapsalean cyanobacteria. In some fossils, internal content occurs as particulate organic matter, forming dense networks throughout ghosts of the intracellular space (e.g., in Salome svalbardensis filaments), or scarce granules (in some Chroococcales). In some chroococcalean microfossils (Gloeodiniopsis mikros, and also possibly Polybessurus), we find layered internal contents that are more continuous than nanoparticulate bands defining the sheaths, and with a shape that can be contracted, folded, or invaginated. We interpret these internal layers as the remains of cell envelope substructures and/or photosynthetic membranes thickened by additional cellular material. Some Myxococccoides show a thick (up to ~ 0.9 μm) wall ultrastructure displaying organic pillars that is best reconciled with a eukaryotic affinity. Finally, a large spheroid with ruptured wall, of uncertain affinity, displays a bi-layered envelope. Altogether, our nanoscale investigations provide unprecedented insights into the taphonomy and taxonomy of this well-preserved assemblage, which can help to assess the nature of organic microstructures in older rocks.

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Abstract: In shallow lakes, mobilization of legacy phosphorus (P) from the sediments can be the main cause for persisting eutrophication after reduction of external P input. In-lake remediation measures can be applied to reduce internal P loading and to achieve ecosystem recovery. The eutrophic shallow peat lake Terra Nova (The Netherlands) was treated with iron (Fe) to enhance P retention in the sediment. This treatment, however, intensified seasonal internal P loading. An earlier study suggested that Fe addition led to increased P binding by easily-reducible Fe(III) associated with organic matter (OM), which readily releases P when bottom waters turn hypoxic. In this complementary study, bulk and micro Fe K-edge and P K-edge X-ray absorption spectroscopy and micro-focused X-ray fluorescence spectroscopy were applied to characterize the P hosting Fe(III) pool. Combined with sequential extraction data, the synchrotron X-ray analyses revealed that a continuum of co-precipitates of Fe(III) with calcium, phosphate, manganese and organic carbon within the OM matrix constitutes the reducible Fe(III) pool. The complementary analyses also shed new light on the interpretation of sequential extraction results, demonstrating that pyrite was not quantitatively extracted by nitric acid (HNO3) and that most of the Fe(II) extracted by hydrochloric acid (HCl) originated from phyllosilicate minerals. Formation of an amorphous inorganic–organic co-precipitate upon Fe addition constitutes an effective P sink in the studied peaty sediments. However, the high intrinsic reactivity of this nanoscale co-precipitate and its fine distribution in the OM matrix makes it very susceptible to reductive dissolution, leading to P remobilization under reducing conditions.

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Abstract: The nature of the magma plumbing system of Large Igneous Provinces is still poorly understood. Among these exceptional magmatic events from Earth’s past, the end-Triassic Central Atlantic Magmatic Province (CAMP) and the end-Cretaceous Deccan Traps (Deccan) coincided in time with two of the most catastrophic biotic crises during the Phanerozoic. In order to constrain the architecture of their magma plumbing system, glomerocrysts containing abundant bubble-bearing melt inclusions from basaltic lava flows of both CAMP and Deccan were investigated via in situ geochemical and microstructural analyses. The analysed glomerocrysts, dominated by augitic clinopyroxene crystals, represent fragments of a crystal mush entrained by basaltic magmas before eruption. The analysed melt inclusions, consisting of an intermediate to felsic composition glass and CO2-bearing bubbles, represent relics of interstitial melts and fluids within a porous crystal framework forming the crystal mush. The different volume proportions between bubbles and whole inclusions reveal that melt entrapment occurred after volatile exsolution. The minimum observed bubble/inclusion fraction indicates that the CO2 concentration in CAMP and Deccan melts was at least 0.3 wt.%, consistent with a maximum entrapment pressure of about 0.5 GPa at CO2–H2O fluid-saturated conditions. The MgO-rich composition of host clinopyroxene crystals and whole rocks is in contrast with the SiO2-rich composition of (trachy-) andesitic to rhyolitic glass of melt inclusions, pointing to disequilibrium conditions. Thermodynamic and geochemical modelling shows that fractional crystallization alone cannot explain the evolved composition of glass in melt inclusions starting from their whole rock composition. On one side, the oxygen isotope composition of clinopyroxene crystals in glomerocrysts ranges from + 3.9 (± 0.3) to + 5.8 (± 0.3) ‰ and their sample-averaged oxygen isotope composition spans from + 4.4 (N = 10) to + 5.6 (N = 10) ‰, implying that glomerocrysts crystallized from mafic melts with normal (i.e., mantle-like) to slightly low δ18O values. On the other side, the oxygen isotope composition of glass in melt inclusions ranges from + 5.5 (± 0.4) to + 22.1 (± 0.4) ‰, implying that melt inclusions entrapped intermediate to felsic melts with normal (i.e., mantle-like) to extremely high δ18O values, typical of (meta-) sedimentary rocks. Some melt inclusions are compatible with fractionation from the same mafic melts that crystallized their host mineral phase, but most melt inclusions are compatible with variable degrees of crustal assimilation and partial mixing, potentially followed by minor post-entrapment isotope re-equilibration. In the CAMP, where sedimentary basins are abundant, (meta-) pelites and occasionally granitoids were the most likely assimilants. On the contrary, in the Deccan, where sedimentary basins are rare, granitoids and metapelites were the most likely assimilants. Oxygen isotope compositions of glass in melt inclusions, spanning from mantle-like to crust-dominated signatures, suggest that the CO2 within their coexisting bubbles likely derived partly from the mantle and partly from assimilated crustal materials. The investigated glomerocrysts and their bubble-bearing melt inclusions are relics of a multiphase (i.e., solid + liquid + gas phases) crystal mush revealing a dynamic evolution for the magma plumbing system of both CAMP and Deccan, where crystals, silicate melts and exsolved fluids coexisted and interacted through most of the transcrustal section.

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Abstract: The plumes of Enceladus contain a non-ice component that originates from aqueous processes occurring within the interior 1,2. The ocean of Enceladus is thought to be connected to the surface across a range of time scales. These processes range from the rapid eruption of cryovolcanic plumes to slow crustal convection on geological timescales3,4. In every case, the system will have a temperature and geochemical evolution as it freezes, with the history of evolution recorded in the sequence of mineral precipitation. Analogously to igneous and metamorphic petrology, we can explore the mineralogy and its context to reconstruct the history of that sample. Most importantly, for astrobiological investigations, the formation and cryo-petrological study of inorganic salts can be used to identify sites of recent exposure on the surface. Synchrotron X-ray techniques allow fast, high-resolution probing of these systems with X-ray light. By exploring large, multi-component samples with multiple techniques, with variable temperature over time we can reveal many emergent processes that may not be predictable with simple phase diagrams. We use a combination of synchrotron powder X-ray diffraction (PXRD) and X-ray microtomography (µCT) across multiple beamlines at Diamond Light Source (I11, I12 and DIAD). Using a multi-modal approach, we present an in-situ study of the low-temperature phase behaviour of Na-Cl-HCO3 fluids. We employ K11-DIAD (Dual Imaging and Diffraction) to carry out ‘image-guided diffraction’ on an Enceladus-type sample frozen in real-time. DIAD’s unique capabilities allow us not only to study microstructure down to 1 µm but also to carry out spatially resolved XRD and identify solid phases present. We present, for the first time, the use of dual imaging and diffraction of a Na-Cl-CO₃ solution frozen in real time in 3 dimensions [Figure 1]. DIAD’s imaged guided diffraction provides spatially-resolved XRD, allowing us to probe different regions of our sample and identify the formation of Na2CO₃ hydrates. We show the influence of carbonate chemistry on the sequence of cryogenic precipitation and the development of complex microstructures. These results provide insights into crustal transport processes and will help with interpreting observational data from upcoming Galilean missions.

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Abstract: Mangroves provide fundamental ecosystem services; however, the growing impact of human activities has resulted in increased pollution pressure, such as chemical contaminants. The redox processes are major biogeochemical players in the fate of contaminants. We investigate the effects of the redox environment on As(V) and Cr(VI) adsorbed on goethite (i.e., Fe(III)-oxide) over 40 days of incubation in columns containing mangrove soil subjected to seawater saturation cycles. Our spectroscopic data highlighted a less Fe(III)-ordered arrangement on goethite over time; As(V) is strongly bound to goethite, which delayed until 20 days its remobilization and reduction to As(III). After 40 days, the goethite held ∼50% of the initial As, but it was 15% as As(III). On the other hand, Cr(VI) was desorbed almost completely in less than 10 days, and the residual Cr ions bound to goethite were almost totally converted to Cr(III). Our study stresses the importance of individual time-dependence in evaluating chemical speciation changes among potential toxic elements in wetland systems, such as mangroves and artificial wetlands designed to water treatment or soil remediation.