I08-Scanning X-ray Microscopy beamline (SXM)
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Open Access
Abstract: Gold nanorods (GNRs) have been fabricated by a novel polymer-immobilised seed mediated method using ultraviolet (UV) photoreduced gold-polymethylmethacrylate
(Au–PMMA) nanocomposites as a seed platform and characterised at sub-micron scale regime with
synchrotron-based techniques; near-edge X-ray absorption fine structure (NEXAFS) spectroscopy
and X-ray fluorescence (XRF) mapping. In this report, it is shown that investigating polymer
nanocomposites using combination of XRF mapping and NEXAFS spectromicroscopy can help
to see the growth phenomenon from different perspective than conventional characterisation
techniques. XRF maps are used to explore distribution of the constituent elements and showing
how polymer matrix making stripe patterns along with regions where GNRs are formed. NEXAFS
carbon (C) K-edge spectra have been taken at three different stages of synthesis: (1) on Au–PMMA
nanocomposites before UV irradiation, (2) after gold nanoparticles formation, and (3) after GNRs formation. It reveals how polymer matrix has been degraded during GNRs formation and avoiding chemically or physically damage to polymer matrix is crucial to control the formation of GNRs.
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Oct 2017
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I08-Scanning X-ray Microscopy beamline (SXM)
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Abstract: The origin and formation of our Solar System is an open research question, which the scientific community is trying to address. In this work was specifically investigated the fine grained matrix which is a mixture of fine-grained materials composed largely of amorphous silicate and sub-micrometre crystals forsterite and enstatite. This is thought to be the remnants of the dust and gas of the protoplanetary disk that allows us to better understand chemical and physical properties of this precursor material. Four pristine primitive meteorites were selected: Acfer 094 (C2-ung.), ALHA77307 (CO3), MIL 07687 (C3-ung.) and QUE 99177 (CR2). The ability of a new generation of SEM-EDX detector was tested, in order to acquire high-resolution element maps of fine grained matrix. This allowed the calculation of abundances, and size distribution of discrete grains of different phases (silicate vs. opaque). Data acquired suggest that the four meteorites can be split into two groups, ALHA77307-MIL 07687 and QUE 99177 and Acfer 094, based on differences in relative abundances and sizes of discrete grains in their matrix. Micro X-ray diffraction was also used for mineralogical phase identification of the matrix constituents allowing the estimation of their modal mineralogy.
MIL 0768 and Acfer 094 were also investigated using Scanning Transmission X-ray Microscopy (STXM) which revealed predominantly oxidising conditions; some reducing conditions are also displayed by some grains, reflecting the mixed redox conditions of the solar nebula.
Measurements of O-isotopic composition of matrix regions were performed, and revealed similarities to values previously reported for IDPs (Starkey et al. 2013,2014 Nakashima et al., 2012, Aleon et al., 2009), rather than those of bulk meteorites (Clayton & Mayeda, 1999). I infer that the observed differences between these matrix components within the meteorite reflect the heterogeneity of the protoplanetary disk. Although these meteorites are pristine, parent body processes have also affected the small matrix grains.
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Nov 2017
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I08-Scanning X-ray Microscopy beamline (SXM)
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Daniela
Medas
,
Ilaria
Carlomagno
,
Carlo
Meneghini
,
Giuliana
Aquilanti
,
Tohru
Araki
,
Diana
Bedolla
,
Carla
Buosi
,
Maria Antonietta
Casu
,
Alessandra
Gianoncelli
,
Andrei C.
Kuncser
,
V. Adrian
Maraloiu
,
Giovanni
De Giudici
Diamond Proposal Number(s):
[16496]
Abstract: Zinc incorporation into marine bivalve shells belonging to different genera (Donax, Glycymeris, Lentidium, and Chamelea) grown in mine-polluted seabed sediments (Zn up to 1% w/w) was investigated using x-ray diffraction (XRD), chemical analysis, soft x-ray microscopy combined with low-energy x-ray fluorescence (XRF) mapping, x-ray absorption spectroscopy (XAS), and transmission electron microscopy (TEM). These bivalves grew their shells, producing aragonite as the main biomineral and they were able to incorporate up to 2.0–80 mg/kg of Zn, 5.4–60 mg/kg of Fe and 0.5–4.5 mg/kg of Mn. X-ray absorption near edge structure (XANES) analysis revealed that for all the investigated genera, Zn occurred as independent Zn mineral phases, i.e., it was not incorporated or adsorbed into the aragonitic lattice. Overall, our results indicated that Zn coordination environment depends on the amount of incorporated Zn. Zn phosphate was the most abundant species in Donax and Lentidium genera, whereas, Chamelea shells, characterized by the highest Zn concentrations, showed the prevalence of Zn-cysteine species (up to 56% of total speciation). Other Zn coordination species found in the investigated samples were Zn hydrate carbonate (hydrozincite) and Zn phosphate. On the basis of the coordination environments, it was deduced that bivalves have developed different biogeochemical mechanisms to regulate Zn content and its chemical speciation and that cysteine plays an important role as an active part of detoxification mechanism. This work represents a step forward for understanding bivalve biomineralization and its significance for environmental monitoring and paleoreconstruction.
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Oct 2018
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I08-Scanning X-ray Microscopy beamline (SXM)
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Diamond Proposal Number(s):
[14946]
Open Access
Abstract: Adsorption of prebiotic building blocks is proposed to have played a role in the emergence of life on Earth. The experimental and theoretical study of this phenomenon should be guided by our knowledge of the geochemistry of the habitable early Earth environments, which could have spanned a large range of settings. Adsorption being an interfacial phenomenon, experiments can be built around the minerals that probably exhibited the largest specific surface areas and were the most abundant, i.e., phyllosilicates. Our current work aims at understanding how nucleotides, the building blocks of RNA and DNA, might have interacted with phyllosilicates under various physico-chemical conditions. We carried out and refined batch adsorption studies to explore parameters such as temperature, pH, salinity, etc. We built a comprehensive, generalized model of the adsorption mechanisms of nucleotides onto phyllosilicate particles, mainly governed by phosphate reactivity. More recently, we used surface chemistry and geochemistry techniques, such as vibrational spectroscopy, low pressure gas adsorption, X-ray microscopy, and theoretical simulations, in order to acquire direct data on the adsorption configurations and localization of nucleotides on mineral surfaces. Although some of these techniques proved to be challenging, questioning our ability to easily detect biosignatures, they confirmed and complemented our pre-established model.
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Nov 2018
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I08-Scanning X-ray Microscopy beamline (SXM)
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Abstract: Primitive CO3 carbonaceous chondrite meteorites provide a detailed record of the geological processes and events that have shaped our solar system over the last 4.5 billion years. They contain a fine-grained (≤ 1 μm) matrix (> 50 vol%) of amorphous and crystalline silicates, oxides, sulphides and metals that have remained largely unaltered since the time they accreted into an asteroid. The matrix of CO3 carbonaceous chondrites also contains ~5 wt% carbon in a wide variety of organic materials including soluble molecules, kerogen-like insoluble organic matter (IOM), and carbonaceous nanoglobules. The formation and evolution of the organic materials and their relationship to the mineralogy remains poorly understood mainly because of the fine-grained and heterogeneous nature of the matrix. However, new analytical techniques are now making it possible to study the relationship between organics and minerals in extra-terrestrial materials in-situ at high spatial resolution. Here, we present C K-edge X-ray absorption near edge structure (XANES) analyses of carbonaceous phases in the CO chondrites DOM 08006, NWA 7892 and Moss.
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Dec 2018
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I08-Scanning X-ray Microscopy beamline (SXM)
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Alastair J. M.
Lough
,
Douglas P.
Connelly
,
William B.
Homoky
,
Jeffrey A.
Hawkes
,
Valerie
Chavagnac
,
Alain
Castillo
,
Majid
Kazemian
,
Ko-ichi
Nakamura
,
Tohru
Araki
,
Burkhard
Kaulich
,
Rachel A.
Mills
Diamond Proposal Number(s):
[12738]
Open Access
Abstract: Iron (Fe) limits primary productivity and nitrogen fixation in large regions of the world’s oceans. Hydrothermal supply of Fe to the global deep ocean is extensive; however, most of the previous work has focused on examining high temperature, acidic, focused flow on ridge axes that create “black smoker” plumes. The contribution of other types of venting to the global ocean Fe cycle has received little attention. To thoroughly understand hydrothermal Fe sources to the ocean, different types of vent site must be compared. To examine the role of more diffuse, higher pH sources of venting, a hydrothermal plume above the Von Damm vent field (VDVF) was sampled for Total dissolvable Fe (unfiltered, TDFe), dissolved Fe (<0.2 μm, dFe) and soluble Fe (<0.02 μm, sFe). Plume particles sampled in situ were characterized using scanning electron microscopy and soft X-ray spectromicroscopy. The VDVF vents emit visibly clear fluids with particulate Fe (TDFe-dFe, >0.2 μm) concentrations up to 196 nmol kg–1 comparable to concentrations measured in black smoker plumes on the Mid-Atlantic Ridge. Colloidal Fe (cFe) and sFe increased as a fraction of TDFe with decreasing TDFe concentration. This increase in the percentage of sFe and cFe within the plume cannot be explained by settling of particulates or mixing with background seawater. The creation of new cFe and sFe within the plume from the breakdown of pFe is required to close the Fe budget. We suggest that the proportional increase in cFe and sFe reflects the entrainment, breakdown and recycling of Fe bearing organic particulates near the vents. Fe plume profiles from the VDVF differ significantly from previous studies of “black smoker” vents where formation of new pFe in the plume decreases the amount of cFe. Formation and removal of Fe-rich colloids and particles will control the amount and physico-chemical composition of dFe supplied to the deep ocean from hydrothermal systems. This study highlights the differences in the stabilization of hydrothermal Fe from an off-axis diffuse source compared to black smokers. Off-axis diffuse venting represent a potentially significant and previously overlooked Fe source to the ocean due to the difficulties in detecting and locating such sites.
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Jul 2019
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I08-Scanning X-ray Microscopy beamline (SXM)
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Aug 2018
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I08-Scanning X-ray Microscopy beamline (SXM)
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Abstract: Fluoroacetate (FA), a plant toxin and intermediate product of anticancer agents, integrates itself into the Krebs cycle by substituting for acetate to form fluorocitrate. The function of this key metabolic cycle in glucose metabolism is disabled when fluorocitrate binds to aconitase. FA purportedly disrupts the Krebs cycle selectively in non-neuronal cells, i.e. glia/astrocytes, making it the substance of choice by which to assess the importance of glia for brain function in the living animal. However, since acetate, considered a marker of glial oxidative metabolism, can also be transported into neurons begs the question whether FA uptake, metabolism, and compartmentation is glial-selective in vivo, and whether this can be experimentally imaged; as important, is whether the first phase of brain glucose metabolism, i.e. glycolysis is affected. Dynamic cerebral 18FDG (glucose) PET in the living rat, and low energy x-ray fluorescence chemical imaging of such brains, albeit freeze substitution-fixed and epon infiltrated, were implemented to address these questions, and enabled testing our working hypothesis that sexual dimorphism of brain structure and function extends to metabolism as well.
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Aug 2018
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I08-Scanning X-ray Microscopy beamline (SXM)
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Diamond Proposal Number(s):
[19228, 22730]
Abstract: Hydrothermal carbonisation (HTC) has been demonstrated to be a sustainable thermochemical process, capable of producing functionalised carbon materials for a wide range of applications. In order to better apply such materials, the local chemistry and reaction pathways governing hydrothermal carbon growth must be understood. We report the use of scanning transmission X-ray microscopy (STXM) to observe chemical changes in functionality of carbon between the interface and bulk regions of HTC. Spatially-resolved, element-specific X-ray photo-absorption spectra show the presence of differing local carbon chemistry between bulk “core” and interface “shell” regions of a glucose-derived hydrothermal carbon spherule. STXM provides direct evidence to suggest that mechanistic pathways differ between the core and shell of the hydrothermal carbon. In the shell region, at the water-carbon interface, more aldehyde and/or carboxylic species are suspected to provide a reactive interface for bridging reactions to occur with local furan-based monomers. In contrast, condensation reactions appear to dominate in the core, removing aryl-linking units between polyfuranic domains. The application of STXM to HTC presents opportunities for a more comprehensive understanding of the spatial distribution of carbon species within hydrothermal carbon, especially at the solvent-carbon interface.
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Jan 2020
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I08-Scanning X-ray Microscopy beamline (SXM)
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Diamond Proposal Number(s):
[12738]
Abstract: Iron (Fe) limits or co-limits primary productivity and nitrogen fixation in large regions of the world's oceans, and the supply of Fe from hydrothermal vents to the deep ocean is now known to be extensive. However, the mechanisms that control the amount of hydrothermal Fe that is stabilized in the deep ocean, and thus dictate the impact of hydrothermal Fe sources on surface ocean biogeochemistry, are unclear. To learn more, we have examined the dispersion of total dissolvable Fe (TDFe), dissolved Fe (dFe) and soluble Fe (sFe) in the buoyant and non-buoyant hydrothermal plume above the Beebe vent field, Caribbean Sea. We have also characterized plume particles using electron microscopy and synchrotron based spectromicroscopy.
We show that the majority of dFe in the Beebe hydrothermal plume was present as colloidal Fe (dFe − sFe = cFe). During ascent of the buoyant plume, a significant fraction of particulate Fe (pFe = TDFe − dFe) was lost to settling and exchange with colloids. Conversely, the opposite was observed in the non-buoyant plume, where pFe concentrations increased during non-buoyant plume dilution, cFe concentrations decreased apparently due to colloid aggregation. Elemental mapping of carbon, oxygen and iron in plume particles reveals their close association and indicates that exchanges of Fe between colloids and particles must include transformations of organic carbon and Fe oxyhydroxide minerals. Notably, sFe is largely conserved during plume dilution, and this is likely to be due to stabilization by organic ligands, in contrast to the more dynamic exchanges between pFe and cFe.
This study highlights that the size of the sFe stabilizing ligand pool, and the rate of iron-rich colloid aggregation will control the amount and physico-chemical composition of dFe supplied to the ocean interior from hydrothermal systems. Both the ligand pool, and the rate of cFe aggregation in hydrothermal plumes remain uncertain and determining these are important intermediate goals to more accurately assess the impact of hydrothermalism on the ocean's carbon cycle.
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Jan 2019
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