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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: Microglia and astrocytes can quench metal toxicity to maintain tissue homeostasis, but with age, increasing glial dystrophy alongside metal dyshomeostasis may predispose the aged brain to acquire neurodegenerative diseases. The aim of the present study was to investigate age-related changes in brain metal deposition along with glial distribution in normal C57Bl/6J mice aged 2-, 6-, 19- and 27-months (n = 4/age). Using synchrotron-based X-ray fluorescence elemental mapping, we demonstrated age-related increases in iron, copper, and zinc in the basal ganglia (p < 0.05). Qualitative assessments revealed age-associated increases in iron, particularly in the basal ganglia and zinc in the white matter tracts, while copper showed overt enrichment in the choroid plexus/ventricles. Immunohistochemical staining showed augmented numbers of microglia and astrocytes, as a function of aging, in the basal ganglia (p < 0.05). Moreover, qualitative analysis of the glial immunostaining at the level of the fimbria and ventral commissure, revealed increments in the number of microglia but decrements in astroglia, in older aged mice. Upon morphological evaluation, aged microglia and astroglia displayed enlarged soma and thickened processes, reminiscent of dystrophy. Since glial cells have major roles in metal metabolism, we performed linear regression analysis and found a positive association between iron (R2 = 0.57, p = 0.0008), copper (R2 = 0.43, p = 0.0057), and zinc (R2 = 0.37, p = 0.0132) with microglia in the basal ganglia. Also, higher levels of iron (R2 = 0.49, p = 0.0025) and zinc (R2 = 0.27, p = 0.040) were correlated to higher astroglia numbers. Aging was accompanied by a dissociation between metal and glial levels, as we found through the formulation of metal to glia ratios, with regions of basal ganglia being differentially affected. For example, iron to astroglia ratio showed age-related increases in the substantia nigra and globus pallidus, while the ratio was decreased in the striatum. Meanwhile, copper and zinc to astroglia ratios showed a similar regional decline. Our findings suggest that inflammation at the choroid plexus, part of the blood-cerebrospinal-fluid barrier, prompts accumulation of, particularly, copper and iron in the ventricles, implying a compromised barrier system. Moreover, age-related glial dystrophy/senescence appears to disrupt metal homeostasis, likely due to induced oxidative stress, and hence increase the risk of neurodegenerative diseases.

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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.

Open Access

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Abstract: In this work, the effects of the protozoan Neospora caninum on the bioenergetics, chemical composition, and elemental content of human brain microvascular endothelial cells (hBMECs) were investigated. We showed that N. caninum can impair cell mitochondrial (Mt) function and causes an arrest in host cell cycling at S and G2 phases. These adverse effects were also associated with altered expression of genes involved in Mt energy metabolism, suggesting Mt dysfunction caused by N. caninum infection. Fourier Transform Infrared (FTIR) spectroscopy analysis of hBMECs revealed alterations in the FTIR bands as a function of infection, where infected cells showed alterations in the absorption bands of lipid (2924 cm−1), amide I protein (1649 cm−1), amide II protein (1537 cm−1), nucleic acids and carbohydrates (1092 cm−1, 1047 cm−1, and 939 cm−1). By using quantitative synchrotron radiation X-ray fluorescence (μSR-XRF) imaging and quantification of the trace elements Zn, Cu and Fe, we detected an increase in the levels of Zn and Cu from 3 to 24 h post infection (hpi) in infected cells compared to control cells, but there were no changes in the level of Fe. We also used Affymetrix array technology to investigate the global alteration in gene expression of hBMECs and rat brain microvascular endothelial cells (rBMVECs) in response to N. caninum infection at 24 hpi. The result of transcriptome profiling identified differentially expressed genes involved mainly in immune response, lipid metabolism and apoptosis. These data further our understanding of the molecular events that shape the interaction between N. caninum and blood-brain-barrier endothelial cells.

Open Access

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Abstract: Global resources of heavy Rare Earth Elements (REE) are dominantly sourced from Chinese regolith-hosted ion-adsorption deposits in which the REE are inferred to be weakly adsorbed onto clay minerals. Similar deposits elsewhere might provide alternative supply for these high-tech metals, but the adsorption mechanisms remain unclear and the adsorbed state of REE to clays has never been demonstrated in situ. This study compares the mineralogy and speciation of REE in economic weathering profiles from China to prospective regoliths developed on peralkaline rocks from Madagascar. We use synchrotron X-ray absorption spectroscopy to study the distribution and local bonding environment of Y and Nd, as proxies for heavy and light REE, in the deposits. Our results show that REE are truly adsorbed as easily leachable 8- to 9-coordinated outer-sphere hydrated complexes, dominantly onto kaolinite. Hence, at the atomic level, the Malagasy clays are genuine mineralogical analogues to those currently exploited in China.