I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[6372, 7487, 8307, 9418, 10328]
Open Access
Abstract: The work described in this thesis features the study of planetary materials, including nakhlite martian meteorites, comet 81P/Wild2 grains, and asteroid Itokawa 25143 particles, using various electron microscopy techniques and X-ray spectroscopy.
Transmission electron microscopy (TEM), Fe-K X-ray absorption spectroscopy (XAS) and in-situ Transmission X-ray Diffraction (XRD) have been used to determine the structure, ferric content and stoichiometry in the secondary phase mineral assemblages of the nakhlites. By measuring the energy position of the Fe-K XANES 1s→3d pre-edge transition centroid, the Fe3+-rich nature of these minerals has been shown. Analyses of the crystalline phyllosilicates in Lafayette found trioctahedral ferric saponite with a 2:1 T-O-T lattice structure and d001-spacings of 0.96 nm, as well as Fe-serpentine with a 1:1 T-O structure and d001-spacings of 0.7 nm. A ferric poorly crystalline or amorphous gel of similar composition to the phyllosilicates was found as fracture fills throughout the other nakhlites.
XRD and Fe-K XAS also allow the mineralogical identification of comet Wild2 terminal grains. The terminal grains of Tracks #170 and #176 are Fe-metal, with hematite subgrain material in #170. The terminal grain of #170 also includes Cr-bearing silicate, similar to the Cr-bearing terminal grain of Track #177. Olivine was found amongst the terminal grains of Track #178 alongside magnetites. The presence of magnetite is consistent with low temperature water-rock interaction similar to a carbonaceous chondrite matrix.
XAS has also been used to study Itokawa particles, finding ferrous olivines and pyroxenes, as well as studying other metals and Ni-bearing phases. Comparisons with the Tuxtuac meteorite showed the similarity of Itokawa particles to that of LL5 and LL6 chondrite materials.
Measuring Fe-K XAS and XRD has proved to be an effective and non-destructive method for mineralogical characterisation of planetary samples, and determining the oxidation state of Fe-silicates, especially on a micron scale. These will be essential techniques for future sample return missions and meteorite finds.
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Jan 2015
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I18-Microfocus Spectroscopy
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Open Access
Abstract: Purpose : The purpose of this study was to investigate the distribution of Ca, Fe and Zn using X-ray fluorescence in human RPE/Bruch’s membrane/choroid with and without early AMD.
Methods : We used a set of unfixed frozen human retinal pigment epithelium (RPE)/choroid samples from young (n=1, female aged 34) and aged donors with (n=4, males, aged 73-78) and without (n=3, one female, aged 75-77) early AMD from Manchester Eye Tissue Repository. Using X-ray fluorescence microscopy (I18 Diamond light source, UK) with a 2 um beam, we obtained high-resolution Ca, Zn, Fe, sulphur, potassium, chloride and phosphorus maps covering areas up to 100 x 600 um2 of 30 um thick sections placed on quartz holders and scanned at room temperature
Results : Calcification was observed in the 3 groups. In the 34-year old sample, sparse small Ca spherules (2x2 um2) at the RPE/Bruch’s membrane interface not colocalising with Zn or Fe. In aged samples, with and without AMD, calcified nodules within RPE cells, at RPE/Bruch’s membrane interface and within druse in AMD. Every calcified nodule colocalised with Zn. Quantification revealed two types (high Zn content, low Zn content). In aged donors without AMD, high-Zn calcified nodules with Ca concentration of 3083+1679 ppm (mean+SD) (maximum 12809+9311) and Zn 66+55 ppm (max 125+75). The average size was 27+15 um2. In aged samples with AMD, high-Zn calcified nodules with average Ca concentration of 4316+1723 ppm (max 13105+7563) and Zn 97+57 ppm (max 201+143). Size 26x10 um2. In the aged non-AMD group, the low zinc-calcification nodules contained an average Ca ppm of 915+259 (max 1475+380) and Zn 33+18 ppm (max 40+21). The average size 28x16 um2. In the AMD group, the low Zn calcified nodules average Ca ppm 1544+1450 (max 3526+5289) and average Zn ppm 47+23 (max 64+37). Average size 19x10 um2. Calcified plaques in Bruch’s membrane from aged donors with and without AMD. Some of these plaques colocalised with Zn and also Fe. Fe-loaded structures in the choriocapillaris underlying calcified nodules and plaques.
Conclusions : Calcific nodules contain zinc in older eyes with and without AMD. Calcified nodules with lower amounts of Ca contained lower amounts of Zn, so the accumulation of Ca may occur in parallel to Zn. It is possible that iron-loaded structures in the choriocapillaris are macrophages.
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Jun 2020
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I18-Microfocus Spectroscopy
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Open Access
Abstract: Neoplastic and healthy brain tissues were analysed to discern the changes in the spatial distribution and overall concentration of elements using micro X-ray fluorescence spectroscopy. High-resolution distribution maps of minor and trace elements such as P, S, Cl, K, Ca, Fe, Cu and Zn made it possible to distinguish between homogeneous cancerous tissue and areas where some structures could be identified, such as blood vessels and calcifications. Concentrations of the elements in the selected homogeneous areas of brain tissue were compared between tumours with various malignancy grades and with the controls. The study showed a decrease in the average concentration of Fe, P, S and Ca in tissues with high grades of malignancy as compared to the control group, whereas the concentration of Zn in these tissues was increased. The changes in the concentration were found to be correlated with the tumour malignancy grade. The efficacy of micro X-ray fluorescence spectroscopy to distinguish between various types of cancer based on the concentrations of studied elements was confirmed by multivariate discriminant analysis. Our analysis showed that the most important elements for tissue classification are Cu, K, Fe, Ca, and Zn. This method made it possible to correctly classify histopathological types in 99.93% of the cases used to build the model and in as much as 99.16% of new cases
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Dec 2015
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[13939, 14440]
Open Access
Abstract: The imaging of catalysts and other functional materials under reaction conditions has advanced significantly in recent years. The combination of the computed tomography (CT) approach with methods such as X-ray diffraction (XRD), X-ray fluorescence (XRF) and X-ray absorption near-edge spectroscopy (XANES) now enables local chemical and physical state information to be extracted from within the interiors of intact materials which are, by accident or design, inhomogeneous. In this work, we follow the phase evolution during the initial reduction step(s) to form Co metal, for Co-containing particles employed as Fischer–Tropsch synthesis (FTS) catalysts; firstly, working at small length scales (approx. micrometre spatial resolution), a combination of sample size and density allows for transmission of comparatively low energy signals enabling the recording of ‘multimodal’ tomography, i.e. simultaneous XRF–CT, XANES–CT and XRD–CT. Subsequently, we show high-energy XRD–CT can be employed to reveal extent of reduction and uniformity of crystallite size on millimetre-sized TiO2 trilobes. In both studies, the CoO phase is seen to persist or else evolve under particular operating conditions and we speculate as to why this is observed.
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Nov 2017
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I18-Microfocus Spectroscopy
I20-Scanning-X-ray spectroscopy (XAS/XES)
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Abstract: Energy scale calibration and reliable intensity measurement are the main issues related to the collection of good spectroscopy data. The accurate determination of the energy scale is often established by using foils of optimum thickness to calibrate the monochromator. However, mechanical issues with the monochromator, movement of the source, or even the resolution of the spectrometer can have an effect on the measured energy scale. For the issue of accurate intensity measurements, calibrated detectors are necessary to ensure a reliable measurement of the spectroscopic signal, both in transmission and fluorescence detection modes. In this paper a review of the most common techniques used for energy calibration and for collecting X-ray absorption spectroscopy data is given, together with a brief description of the factors that have an impact on the intensity of the measured signal. A brief description of the versatile X-ray absorption spectroscopy beamline, I20, at Diamond Light Source is also presented, giving particular emphasis on how the beamline design has been undertaken to tackle these key issues. In particular, the use of a four-bounce monochromator will be discussed, highlighting the advantages of the device for the measurement of spectroscopy data.
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Nov 2012
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I18-Microfocus Spectroscopy
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Abstract: The chemistry of molybdenum species in artificial corrosion pits on 316L stainless steel was investigated using X-ray absorption spectroscopy (XANES). It was found that the K-edge spectra are consistent with the presence of an Mo(III) species. The presence of Mo(VI) polymolybdates as been proposed to explain the well-known beneficial effects of Mo in decreasing the susceptibility of stainless steel to localised corrosion, but no evidence of these species was found. High resolution measurements (with a spatial resolution of 3.5 μm in the vertical direction) through the dissolving metal interface did not detect the presence of any different Mo-containing species in the vicinity of the salt film. However, the spatial resolution was insufficient to detect the presence of submonolayer species on the dissolving metal surface that have been proposed to block active dissolution.
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Jan 2011
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[9418]
Abstract: The terminal grains of the Stardust keystones have preserved the least thermally altered Comet Wild2 samples and some of the most pristine cometary material currently available for analysis. The micron-scale of the terminal grains requires synchro-tron analyses to perform X-ray diffraction (XRD) and X-ray Absorption, Fluorescence (XAS, XRF). In par-ticular, we have studied Fe oxides in order to be able to make increasingly detailed comparisons to carbo-naecous chondrites and understand the variation in Fe oxidation state within Wild2 [1,2]. Fe oxides, includ-ing magnetite or magnetite-hematite mixtures have been identified along track walls [1,3] and leave a characteristic oxidized iron signature on keystone Fe-K XANES and XRF maps. However, the potential ef-fects of capture heating, and terrestrial oxidation, has meant that the origin of the scattered Fe oxides has required further study through comparison to a terminal grain.
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Mar 2014
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I18-Microfocus Spectroscopy
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Abstract: Zinc is known to play an important role in many cellular processes, and the levels of zinc are controlled by specific transporters from the ZIP (SLC39A) influx transporter group and the ZnT (SLC30A) efflux transporter group. The distribution of zinc was measured in 59 samples of invasive ductal carcinoma of breast using synchrotron radiation micro probe x-ray fluorescence facilities. The samples were formalin fixed paraffin embedded tissue micro arrays (TMAs) enabling a high throughput of samples and allowing us to correlate the distribution of trace metals with tumour cell distribution and, for the first time, important biological variables. The samples were divided into two classes, 34 oestrogen receptor positive (ER+ve) and 25 oestrogen receptor negative (ER-ve) based on quantitative immunohistochemistry assessment. The overall levels of zinc (i.e. in tumour and surrounding tissue) in the ER+ve samples were on average 60% higher than those in the ER-ve samples. The zinc levels were higher in the ER+ve tumour areas compared to the ER-ve tumour areas with the mean levels in the ER+ve samples being approximately 80% higher than the mean ER-ve levels. However, the non-tumour tissue regions of the samples contained on average the same levels of zinc in both types of breast cancers. The relative levels of zinc in tumour areas of the tissue were compared with levels in areas of non-tumour surrounding tissue. There was a significant increase in zinc in the tumour regions of the ER+ve samples compared to the surrounding regions (P < 0.001) and a non-significant increase in the ER-ve samples. When comparing the increase in zinc in the tumour regions expressed as a percentage of the surrounding non-tumour tissue zinc level in the same sample, a significant difference between the ER+ve and ER-ve samples was found (P < 0.01).
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Jun 2009
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B18-Core EXAFS
I18-Microfocus Spectroscopy
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Abstract: Zircon (ZrSiO4) is a durable mineral found in most igneous rocks; it is highly retentive of the trace element concentrations it acquires at crystallisation, and its high initial concentrations of U and Th relative to Pb make it the most important mineral for radiometric dating. Therefore, it is a valuable archive of magmatic processes, particularly with regard to those occurring on the early Earth. Based on crystal chemistry, anomalous Ce and Eu concentrations in zircon relative to other rare earth elements (REE) seem likely to reflect the oxidation state of the magma. Zircons were grown experimentally under controlled conditions of oxygen fugacity (fO2) and the crystals and coexisting glass were analysed by SIMS and LA-ICP-MS to examine the covariation of the partition coefficients of Ce and Eu, as well as those of other trace elements. This revealed that with increasing fO2, Ce becomes more compatible and Eu and U become less compatible. There is a narrow window of fO2s in which a Ce and a Eu anomaly coexist. Literature data allow the partitioning data obtained for the heavy REE in this study to be extrapolated to other temperatures. To allow extrapolation of the partitioning experiments, Ce- and Eu-doped glasses of various melt compositions were prepared at a range of fO2s and temperatures. X-ray absorption near edge structure (XANES) spectroscopy of these glasses was carried out at the LIII-edge of these elements to determine their oxidation state ratios. Because of beam damage effects for the Eu-bearing glasses, a limited number of XANES spectra were recorded in situ at 1400 °C, and some samples were analysed by electron paramagnetic resonance spectroscopy. The results obtained were compared to trace element concentrations in zircons from some natural samples, and suggestions for future work made.
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Jul 2012
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I18-Microfocus Spectroscopy
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Diamond Proposal Number(s):
[15771]
Abstract: This study presents a multifaceted approach of Zn adsorption onto dry Fucus vesiculosus originating from the Irish Sea. Metal chemistry as well as algae surface charge properties were characterized before adsorption. Zn adsorption tests were run as function of: pH, algae concentration and metal source. A comparison with Co, Cd, and Cu adsorption – in mono-ion solutions was also performed. Adsorption kinetics, fitted with pseudo-first order (PFO) and pseudo-second order (PSO) kinetic model, allowed the uptake parameters to be found and a comparison of kinetic rates. Synchrotron X-Ray-Florescence and X-Ray Absorption Spectroscopy measurements of Zn on algae after exposure permitted the extraction of direct information about Zn spatial distribution and bonding environment. The results showed that the carboxylic groups are the ones involved in the heterogeneously distributed Zn adsorption at low pH, Zn being coordinated with 5 - 6 O at bond distances varying from 1.98-2.03 Å - as in Zn alginate. Synchrotron results provide confirmation that, relative to Zn, alginate is one of the main algae components responsible for metal binding.
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Nov 2018
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