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Towards an understanding of climate proxy formation in the Chew Bahir basin, southern Ethiopian Rift
(2018)
Deciphering paleoclimate from lake sediments is a challenge due to the complex relationship between climate parameters and sediment composition. Here we show the links between potassium (K) concentrations in the sediments of the Chew Bahir basin in the Southern Ethiopian Rift and fluctuations in the catchment precipitation/evaporation balance. Our micro-X-ray fluorescence and X-ray diffraction results suggest that the most likely process linking climate with potassium concentrations is the authigenic illitization of smectites during episodes of higher alkalinity and salinity in the closed -basin lake, due to a drier climate. Whole-rock and clay size fraction analyses suggest that illitization of the Chew Bahir clay minerals with increasing evaporation is enhanced by octahedral Al-to-Mg substitution in the clay minerals, with the resulting layer charge increase facilitating potassium-fixation. Linking mineralogy with geochemistry shows the links between hydroclimatic control, process and formation of the Chew Bahir K patterns, in the context of well-known and widely documented eastern African climate fluctuations over the last 45,000 years. These results indicate characteristic mineral alteration patterns associated with orbitally controlled wet-dry cycles such as the African Humid Period (similar to 15-5 ka) or high-latitude controlled climate events such as the Younger Dryas (similar to 12.8-11.6 ka) chronozone. Determining the impact of authigenic mineral alteration on the Chew Bahir records enables the interpretation of the previously established pXRF-derived aridity proxy K and provides a better paleohydrological understanding of complex climate proxy formation.
The paper presents the first study of heavy-mineral sand beaches from the Mediterranean coast of Annaba/Algeria. The studied beaches run along the basement outcrops of the Edough massif, which are mainly composed by micaschists, tourmaline-rich quartzo-feldspathic veins, gneisses, skarns and marbles. Sand samples were taken from three localities (Ain Achir, Plage-Militaire and El Nasr). The heavy-mineral fraction comprises between 74 and 91 vol%. The garnets of the beaches are almandine rich and tourmalines vary with respect to their location from schorl to dravite. Tourmaline at Ain Achir and the Plage-Militaire is schorlits, while at El Nasr beach dravite is ubiquitous. The World Shale Average normalised REE of the sands and the basement outcrops reveal: (i) Ain Achir beach: REE pattern of sand and the coastal rocks from the studied beaches reflects a multiple sources; (ii) Plage-Militaire: the sand and the coastal outcrops show similar LREE and a strong enrichment in HREE, suggesting the presence HREE-rich phases found as inclusions in staurolite; (iii) El Nasr: two types of sand patterns are found: one with flat REE pattern similar to the proximal rocks and other one enriched in HREE suggesting a mixed source.
Whilst correlations have been made between the loess of Europe and China, deposits in Central Asia have remained largely overlooked by scientific investigation. The nature of the relationship between loess accumulation and palaeoclimate at the core of the Eurasian loess belt is particularly poorly understood. Here we reconstruct palaeoenvironmental change in Central Asia over the last 40 ky based on data from the Remizovka loess profile, in the northern foothills of the Tian Shan in southern Kazakhstan. Our interpretations are based on synthesis of chronostratigraphic, colour and magnetic susceptibility data, supported by chronostratigraphies from two additional sites nearby, Maibulak and Valikhanova. All three sites record substantially increased loess accumulation during late MIS 3 into the global last glacial maximum (gLGM). At Remizovka, increased loess flux occurred in two pulses at c. 38-25 ka and 22-18 ka, with the intervening period involving incipient pedogenesis. At Maibulak, two loess pulses at c. 40-30 ka and c. 28-22 ka are separated by a weakly developed paleosol which may date to the same time as pedogenesis at Remizovka. There is additional possible periglacial influence at Maibulak from c. 40-33.5 ka. At Valikhanova, there is some age overlap between paleosol and loess samples, but overall loess accumulation appears to have increased at c. 42-35 ka, c. 30 ka and the gLGM, with pedogenesis occurring >40 ka and c. 32 ka. At all three sites, Holocene loess accumulation is minimal; this period is characterised by pedogenesis. The chronostratigraphic variability between our sites highlights a need to interrogate climate-driven models for loess formation in piedmont environments. We interpret our data in the context of regional palaeoenvironmental archives to indicate that loess accumulation increased coeval with MIS 3 glacial advance in the Tian Shan, which was facilitated by northward expansion of the Asian monsoon and associated increase in precipitation. We hypothesise that increased ice volume impeded teleconnections with the temperate zone westerlies to the north; these were compressed against the piedmont resulting in increased wind strength and facilitating increased loess flux. Peak loess accumulation during the gLGM occurred under colder, drier climatic conditions, with reduced but sustained glacial ice volume and persistent influence of the westerlies in the arid Central Asian piedmont loess belt. In the absence of more widespread, reliably dated palaeoenvironmental records from the region, our data become of critical importance for understanding past environmental conditions in Central Asia, relative to elsewhere in Eurasia and globally.
New mesoporous silk fibroin (SF)/silica hybrids were processed via a one-pot soft and energy-efficient sol-gel chemistry and self-assembly from a silica precursor, an acidic or basic catalyst, and the ionic liquid 1-butyl-3-methylimidazolium chloride, acting as both solvent and mesoporosity-inducer. The as-prepared materials were obtained as slightly transparent-opaque, amorphous monoliths, easily transformed into powders, and stable up to ca. 300 degrees C. Structural data suggest the formation of a hexagonal mesostructure with low range order and apparent surface areas, pore volumes, and pore radii of 205-263 m(2) g(-1), 0.16-0.19 cm(3) g(-1), and 1.2-1.6 nm, respectively. In all samples, the dominating conformation of the SF chains is the beta-sheet. Cytotoxicity/bioactivity resazurin assays and fluorescence microscopy demonstrate the high viability of MC3T3 pre-osteoblasts to indirect (>= 99 +/- 9%) and direct (78 +/- 2 to 99 +/- 13%) contact with the SF/silica materials. Considering their properties and further improvements, these systems are promising candidates to be explored in bone tissue engineering. They also offer excellent prospects as electrolytes for solid-state electrochemical devices, in particular for fuel cells.
Background. Metal recycling factories (MRFs) have developed rapidly in Nigeria as recycling policies have been increasingly embraced. These MRFs are point sources for introducing potentially toxic elements (PTEs) into environmental media. Objectives. The aim of this study was to determine the constituents (elemental and mineralogy) of the wastes (slag and particulate matter, (PM)) and soils around the MRFs and to determine the level of pollution within the area. Methods. Sixty samples (30 slag samples, 15 soil samples and 15 PM samples) were collected for this study. The soils, slag and PM samples were analyzed for elemental constituents using inductively coupled plasma optical emission spectrometry. Mineralogy of the PM was determined using scanning electron microscope-energy dispersive spectroscopy (SEM-EDS), and soil mineralogy was determined by an X-ray diffractometer (XRD). Results. The results of the soil analyses revealed the following concentrations for the selected metals in mg/kg include lead (Pb) (21.0-2399.0), zinc (Zn) (56.0-4188.0), copper (Cu) (10.0-1470.0), nickel (Ni) (6.0-215.0), chromium (Cr) (921.0-1737.0) and cadmium (Cd) (below detectable limit (Bdl)-18.1). For the slags the results were Pb (68.0-.333.0), Zn (1364.0-3062), Cu (119.0-1470.0), Ni (12.0-675.0), Cr (297-1737) and Cd (Bdl-15.8). The results in µg/g for the metal analysis in PM were Pb (4.6-160.0), Zn (18.0-471.0), Cu (2.5-11.0), Ni (0.8-4.2), and Cr (2.5-11.0), while Cd was undetected. The slags are currently utilized for filling the foundations of buildings and roads, providing additional pathways for the introduction of PTEs into the environment from the suspended materials generated from mechanical breakdown of the slags. Conclusions. The MRFs were found to have impacted the quality of environmental media through the introduction of PTEs, impairing soil quality, in addition to PM, which can have detrimental health consequences. Further studies on the health implications of these pollutants and their impacts on human health are needed. Competing Interests. The authors declare no competing financial interests
Hexagonal p-type semiconductor CuS nanoplates were synthesized via a hot injection method from bis(trimethylsilyl) sulfide and the ionic liquid precursor bis(N-dodecylpyridinium) tetrachloridocuprate( II). The particles have a broad size distribution with diameters between 30 and 680 nm and well-developed crystal habits. The nanoplates were successfully incorporated into organic photovoltaic (OPV) cells as hole conduction materials. The power conversion efficiency of OPV cells fabricated with the nanoplates is 16% higher than that of a control device fabricated without the nanoplates. (C) 2018 Author(s).
The article describes the surface modification of 3D printed poly(lactic acid) (PLA) scaffolds with calcium phosphate (CP)/gelatin and CP/chitosan hybrid coating layers. The presence of gelatin or chitosan significantly enhances CP co-deposition and adhesion of the mineral layer on the PLA scaffolds. The hydrogel/CP coating layers are fairly thick and the mineral is a mixture of brushite, octacalcium phosphate, and hydroxyapatite. Mineral formation is uniform throughout the printed architectures and all steps (printing, hydrogel deposition, and mineralization) are in principle amenable to automatization. Overall, the process reported here therefore has a high application potential for the controlled synthesis of biomimetic coatings on polymeric biomaterials.
The article describes the surface modification of 3D printed poly(lactic acid) (PLA) scaffolds with calcium phosphate (CP)/gelatin and CP/chitosan hybrid coating layers. The presence of gelatin or chitosan significantly enhances CP co-deposition and adhesion of the mineral layer on the PLA scaffolds. The hydrogel/CP coating layers are fairly thick and the mineral is a mixture of brushite, octacalcium phosphate, and hydroxyapatite. Mineral formation is uniform throughout the printed architectures and all steps (printing, hydrogel deposition, and mineralization) are in principle amenable to automatization. Overall, the process reported here therefore has a high application potential for the controlled synthesis of biomimetic coatings on polymeric biomaterials.
The precise determination of the stable C and O isotope fractionation between water and calcite (CC) and water and aragonite (AR) is of special interest for climate reconstructions, e.g. paleotemperatures. Previous studies reported results from both laboratory and field experiments, but their results are only partly consistent. Here we present C and O isotope data of a stalagmite from the Swiss Alps, which shows CC-AR transitions along individual growth layers. Using detailed analyses both laterally and perpendicular to such layers we examined the difference in the C and O isotope fractionation factor of the HCO3- - CC and the HCO3- - AR system. For O this difference is similar to the water-CC and water-AR offset provided in experimental studies. The O isotope fractionation difference in the water-CC and water-AR system is comparable to those determined in laboratory studies but shows a statistically significant correlation with the CaCO3 precipitation rate. For C we found a fractionation difference, which is independent of CaCO3 precipitation rate and with slightly smaller values for the fractionation offset between HCO3- - CC and HCO3- - AR compared to literature values. However, we also found an unexpected decrease in delta C-13 along growth layers, which contradicts the widely used concept of Rayleigh fractionation during CO2 degassing and CaCO3 precipitation. The results of this study can be used e.g., to correct stable isotope time series of stalagmites showing CC-AR transitions along their growth axes. (C) 2018 Elsevier Ltd. All rights reserved.
The synthesis, structure, and photocatalytic water splitting performance of two new titania (TiO2)/gold(Au)/Bombyx mori silk hybrid materials are reported. All materials are monoliths with diameters of up to ca. 4.5 cm. The materials are macroscopically homogeneous and porous with surface areas between 170 and 210 m(2)/g. The diameter of the TiO2 nanoparticles (NPs) - mainly anatase with a minor fraction of brookite - and the Au NPs are on the order of 5 and 7-18 nm, respectively. Addition of poly(ethylene oxide) to the reaction mixture enables pore size tuning, thus providing access to different materials with different photocatalytic activities. Water splitting experiments using a sunlight simulator and a Xe lamp show that the new hybrid materials are effective water splitting catalysts and produce up to 30 mmol of hydrogen per 24 h. Overall the article demonstrates that the combination of a renewable and robust scaffold such as B. mori silk with a photoactive material provides a promising approach to new monolithic photocatalysts that can easily be recycled and show great potential for application in lightweight devices for green fuel production.