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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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Abstract: Magmatic systems are dominated by five volatiles, namely H2O, CO2, F, Cl, and S (the igneous quintet). Multiple studies have measured partitioning of four out of these five volatiles (H2O, CO2, F, and Cl) between nominally volatile-free minerals and melts, whereas the partitioning of sulfur is poorly known. To better constrain the behavior of sulfur in igneous systems we measured the partitioning of sulfur between clinopyroxene and silicate melts over a range of pressure, temperature, and melt composition from 0.8 to 1.2 GPa, 1000 to 1240 °C, and 49 to 66 wt% SiO2 (13 measurements). Additionally, we determined the crystal-melt partitioning of sulfur for plagioclase (6 measurements), orthopyroxene (2 measurements), amphibole (2 measurements), and olivine (1 measurement) in some of these same run products. Experiments were performed at high and low oxygen fugacities, where sulfur in the melt is expected to be dominantly present as an S6+ or an S2– species, respectively. When the partition coefficient is calculated as the total sulfur in the crystal divided by the total sulfur in the melt, the partition coefficient varies from 0.017 to 0.075 for clinopyroxene, from 0.036 to 0.229 for plagioclase, and is a maximum of 0.001 for olivine and of 0.003 for orthopyroxene. The variation in the total sulfur partition coefficient positively correlates with cation-oxygen bond lengths in the crystals; the measured partition coefficients increase in the order: olivine < orthopyroxene < clinopyroxene ≤ amphibole and plagioclase. At high oxygen fugacities in hydrous experiments, the clinopyroxene/melt partition coefficients for total sulfur are only approximately one-third of those measured in low oxygen fugacity, anhydrous experiments. However when the partition coefficient is calculated as total sulfur in the crystal divided by S2– in the melt, the clinopyroxene/melt partition coefficients for experiments with melts between ~51 and 66 wt% SiO2 can be described by a single mean value of 0.063 ± 0.010 (1σ standard deviation about the mean). These two observations support the hypothesis that sulfur, as S2–, replaces oxygen in the crystal structure. The results of hydrous experiments at low oxygen fugacity and anhydrous experiments at high oxygen fugacity suggest that oxygen fugacity has a greater effect on sulfur partitioning than water. Although the total sulfur clinopyroxene-melt partition coefficients are affected by the Mg/(Mg+Fe) ratio of the crystal, partition coefficients calculated using S2– in the melt display no clear dependence upon the Mg# of the clinopyroxene. Both the bulk and the S 2– partition coefficients appear unaffected by IVAl in the clinopyroxene structure. No effect of anorthite content nor of iron concentration in the crystal was seen in the data for plagioclase-melt partitioning. The data obtained for orthopyroxene and olivine were too few to establish any trends. The partition coefficients of total sulfur and S 2– between the crystals studied and silicate melts are typically lower than those of fluorine, higher than those of carbon, and similar to those of chlorine and hydrogen. These sulfur partition coefficients can be combined with analyses of volatiles in nominally volatile-free minerals and previously published partition coefficients of H2O, C, F, and Cl to constrain the concentration of the igneous quintet, the five major volatiles in magmatic systems.

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Abstract: This research aimed to find the best phenotype of the brown algae Fucus vesiculosus (kelp) which has the greater potential to become a sorption byproduct for Zn removal from contaminated waters. Thus, the Zn uptake capacity and sorption mechanisms of the kelp collected from the Baltic Sea shore was, for the first time, investigated under various conditions, and compared to the phenotype habiting on the Irish Sea shore. Sorption studies were performed investigating the effect of algal dosage, Zn sources as well as algal harvesting time of the year on Zn uptake capacity. The results suggested that the Baltic algae is a better biosorbent for Zn uptake. Sorption mechanisms were studied by employing various indirect and direct approaches, more importantly, including high resolution synchrotron X-Ray Fluorescence and X-Ray Absorption Spectroscopy (XAS) and molecular modelling (MM). The results revealed that alginate and cellulose are among the main polysaccharide bonding Zn at algal surface, via coordination with O atoms from carboxyl and hydroxyl groups. XAS results giving direct measurements of Zn bonding environment on algal surface are supported by MM outputs and suggested that Zn is surrounded by ca. 5 O atoms at interatomic distances varying from 1.94 to 2.02 Å. The results contribute to understanding sorption mechanisms which can further lead to finding the best eluent for Zn desorption from the used biomass, bio sorbent reconditioning and reuse in multiple sorption desorption cycles as well as process optimization before industrial scaling up.

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Abstract: Biometals such as iron, copper, potassium, and zinc are essential regulatory elements of several biological processes. The homeostasis of biometals is often affected in age-related pathologies. Notably, impaired iron metabolism has been linked to several neurodegenerative disorders. Autophagy, an intracellular degradative process dependent on the lysosomes, is involved in the regulation of ferritin and iron levels. Impaired autophagy has been associated with normal pathological aging, and neurodegeneration. Non-mammalian model organisms such as Drosophila have proven to be appropriate for the investigation of age-related pathologies. Here, we show that ferritin is expressed in adult Drosophila brain and that iron and holoferritin accumulate with aging. At whole-brain level we found no direct relationship between the accumulation of holoferritin and a deficit in autophagy in aged Drosophila brain. However, synchrotron X-ray spectromicroscopy revealed an additional spectral feature in the iron-richest region of autophagy-deficient fly brains, consistent with iron–sulfur. This potentially arises from iron–sulfur clusters associated with altered mitochondrial iron homeostasis.

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Abstract: The complexity and heterogeneity of bone chemistry makes it difficult to discern information on physiological and taphonomic processes stored within the bone matrix. Analysis of archaeological and palaeontological bone becomes more difficult because in many cases the most pivotal specimens are too scientifically valuable for destructive analysis. This problem is further escalated by the fact that the heterogeneity of the bone may cause small “pockets” of preservation that can be missed during sampling. Therefore, a non-destructive technique that can spatially resolve such heterogeneity within the bone is needed. Here we use microfocus, non-destructive synchrotron-based X-Ray Fluorescence (XRF) imaging and X-ray Absorption Spectroscopy (XAS) to map the organic constituents within extant and fossil bovid bones. XAS analysis of sulfur allowed organic sulfur (within collagen as methionine) to be distinguished from inorganic sulfate (within bone apatite). Mapping and quantification of organic sulfur within the samples were made by setting the beam to the methionine resonance, allowing for the detection, distribution and quantification of collagen present by using organic sulfur as an internal marker. Results show organic sulfur to be distributed in small “pockets” throughout the bone matrix in both extant and fossil specimens. Significant loss of collagen (organic sulfur) was seen in specimens between 100 ka and 650 ka with little organic sulfur preservation persisting after this date. Comparison of residual organic sulfur concentrations as a function of sample age revealed a second order rate law for organic sulfur oxidation (k ≈ 1 × 10−5 y−1) within bone. These results show that non-destructive, synchrotron-based XRF mapping of organic sulfur is a useful tool for not only calculating rates of collagen degradation through time, but also identifying areas of potential collagen preservation for other paleobiological applications such as proteomics and stable isotope analyses.