Growth of, and diffusion in, olivine in ultra-fast ascending basalt magmas from Shiveluch volcano.

Complex core-rim zoning of Mg-Fe-Ni-Ca-Cr-Al-P in high-Mg olivine crystals from a tuff ring of Shiveluch volcano, Kamchatka, enables reconstruction of the entire olivine crystallization history from mantle conditions to eruption. Bell-shaped Fo86-92 and Ni profiles in crystal cores were formed by diffusion after mixing with evolved magma. Diffusion proceeded to the centres of crystals and completely equilibrated Fo and Ni in some crystals. Diffusion times extracted from Fo and Ni core profiles range from 100 to 2000 days. During subsequent mixing with mafic mantle-equilibrated melt, the cores were partially dissolved and overgrown by Fo90 olivine. Times extracted from Fo and Ni diffusion profiles across the resorption interface between the core and its overgrowth range within 1-10 days, which corresponds to the time of magma ascent to the surface. The overgrowth shows identical smooth Fo-Ni decreasing zoning patterns for all crystals towards the margin, indicating that all crystals shared the same growth history after last mixing event prior to eruption. At the same time, Ca, and to an even greater extent Cr, Al, and P have oscillatory growth patterns in the crystals overgrowth. Our data show that magma ascent can be extremely short during maar/tuff ring eruption.

Calcification of the acetabular labrum of the hip: prevalence in the general population and relation to hip articular cartilage and fibrocartilage degeneration.

BACKGROUND: Meniscal calcification is considered to play a relevant role in the pathogenesis of osteoarthritis of the knee. Little is known about the biology of acetabular labral disease and its importance in hip pathology. Here, we analyze for the first time the calcification of the acetabular labrum of the hip (ALH) and its relation to hip cartilage degeneration. METHODS: In this cross-sectional post-mortem study of an unselected sample of the general population, 170 ALH specimens and 170 femoral heads from 85 donors (38 female, 47 male; mean age 62.1 years) were analyzed by high-resolution digital contact radiography (DCR) and histological degeneration grade. The medial menisci (MM) from the same 85 donors served as an intra-individual reference for cartilage calcification (CC). Scanning electron microscopy (SEM), energy dispersive analysis (ED) and Raman spectroscopy were performed for characterization of ALH CC. RESULTS: The prevalence of CC in the ALH was 100% and that in the articular cartilage of the hip (ACH) was 96.5%. Quantitative analysis revealed that the amount of ALH CC was higher than that in the ACH (factor 3.0, p < 0.001) and in the MM (factor 1.3, p < 0.001). There was significant correlation between the amount of CC in the fibrocartilage of the left and right ALH (r = 0.70, p < 0.001). Independent of age, the amount of ALH CC correlated with histological degeneration of the ALH (Krenn score) (r = 0.55; p < 0.001) and the ACH (Osteoarthritis Research Society International (OARSI), r = 0.69; p < 0.001). Calcification of the ALH was characterized as calcium pyrophosphate dihydrate deposition. CONCLUSION: The finding that ALH fibrocartilage is a strongly calcifying tissue is unexpected and novel. The fact that ALH calcification correlates with cartilage degeneration independent of age is suggestive of an important role of ALH calcification in osteoarthritis of the hip and renders it a potential target for the prevention and treatment of hip joint degeneration.

GZ7 and GZ8 - Two Zircon Reference Materials for SIMS U-Pb Geochronology.

Here, we document a detailed characterisation of two zircon gemstones, GZ7 and GZ8. Both stones had the same mass at 19.2 carats (3.84 g) each; both came from placer deposits in the Ratnapura district, Sri Lanka. The U-Pb data are in both cases concordant within the uncertainties of decay constants and yield weighted mean 206Pb/238U ages (95% confidence uncertainty) of 530.26 Ma ± 0.05 Ma (GZ7) and 543.92 Ma ± 0.06 Ma (GZ8). Neither GZ7 nor GZ8 have been subjected to any gem enhancement by heating. Structure-related parameters correspond well with the calculated alpha doses of 1.48 × 1018 g-1 (GZ7) and 2.53 × 1018 g-1 (GZ8), respectively, and the (U-Th)/He ages of 438 Ma ± 3 Ma (2s) for GZ7 and 426 Ma ± 9 Ma (2s) for GZ8 are typical of unheated zircon from Sri Lanka. The mean U mass fractions are 680 µg g-1 (GZ7) and 1305 µg g-1 (GZ8). The two zircon samples are proposed as reference materials for SIMS (secondary ion mass spectrometry) U-Pb geochronology. In addition, GZ7 (Ti mass fractions 25.08 µg g-1 ± 0.18 µg g-1; 95% confidence uncertainty) may prove useful as reference material for Ti-in-zircon temperature estimates.

Copper complexes as catalyst precursors in the electrochemical hydrogen evolution reaction.

Herein, we report the synthesis and species distribution of copper(ii) complexes based on two different ligand scaffolds and the application of the two complexes in the electrochemical proton reduction catalysis. The ligands bind to one or two copper(II) ions and the pH-dependent mono/dinuclear equilibrium depends on the steric bulk of the ligands. The two water soluble copper(II) complexes were investigated for their activities in the electrochemical hydrogen evolution reaction (HER). In both complexes the copper(ii) ions have a N4-coordination environment composed of N-heterocycles, although in different coordination geometries (SPY-5 and TBPY-5). The solutions of the complexes were highly active catalysts in water at acidic pH but the complexes decompose under catalytic conditions. They act as precursors for highly active copper(0) and Cu2O deposits at the electrode surface, which are in turn the active catalysts. The absence or presence of the ligands has neither an influence on the catalytic activity of the solutions nor an influence on the activity of the deposit formed during controlled potential electrolysis. Finally, we can draw some conclusions on the stability of copper catalysts in the aqueous electrochemical HER.

Release of zirconia nanoparticles at the metal stem-bone cement interface in implant loosening of total hip replacements.

In a previous failure analysis performed on femoral components of cemented total hip replacements, we determined high volumes of abraded bone cement. Here, we describe the topography of the polished surface of polymethyl methacrylate (PMMA) bone cement containing zirconia radiopacifier, analyzed by scanning electron microscopy and vertical scanning interferometry. Zirconia spikes protruded about 300nm from the PMMA matrix, with pits of former crystal deposition measuring about 400nm in depth. We deduced that the characteristically mulberry-shaped agglomerates of zirconia crystals are ground and truncated into flat surfaces and finally torn out of the PMMA matrix. Additionally, evaluation of in vitro PMMA-on-PMMA articulation confirmed that crystal agglomerations of zirconia were exposed to grain pullout, fatigue, and abrasion. In great quantities, micron-sized PMMA wear and zirconia nanoparticles accumulate in the cement-bone interface and capsular tissues, thereby contributing to osteolysis. Dissemination of nanoparticles to distant lymph nodes and organs of storage has been reported. As sufficient information is lacking, foreign body reactions to accumulated nanosized zirconia in places of long-term storage should be investigated. STATEMENT OF SIGNIFICANCE: The production of wear particles of PMMA bone cement in the interface to joint replacement devices, presents a local challenge. The presence of zirconia particles results in frustrated digestion attempts by macrophages, liberation of inflammatory mediators, and necrosis leading to aseptic inflammation and osteolyses. Attempts to minimize wear of articulating joints reduced the attention to the deterioration of cement cuffs. We therefore investigated polished surfaces of retrieved cuffs to demonstrate their morphology and to measure surface roughness. Industrially admixed agglomerates of the radiopacifier are abraded to micron and nano-meter sized particles. The dissemination of zirconia particles in the reticulo-endothelial system to storage organs is a possible burden. Research to replace the actual contrast media by non-particulate material deserves more attention.

Arctic sea-ice decline archived by multicentury annual-resolution record from crustose coralline algal proxy.

Northern Hemisphere sea ice has been declining sharply over the past decades and 2012 exhibited the lowest Arctic summer sea-ice cover in historic times. Whereas ongoing changes are closely monitored through satellite observations, we have only limited data of past Arctic sea-ice cover derived from short historical records, indirect terrestrial proxies, and low-resolution marine sediment cores. A multicentury time series from extremely long-lived annual increment-forming crustose coralline algal buildups now provides the first high-resolution in situ marine proxy for sea-ice cover. Growth and Mg/Ca ratios of these Arctic-wide occurring calcified algae are sensitive to changes in both temperature and solar radiation. Growth sharply declines with increasing sea-ice blockage of light from the benthic algal habitat. The 646-y multisite record from the Canadian Arctic indicates that during the Little Ice Age, sea ice was extensive but highly variable on subdecadal time scales and coincided with an expansion of ice-dependent Thule/Labrador Inuit sea mammal hunters in the region. The past 150 y instead have been characterized by sea ice exhibiting multidecadal variability with a long-term decline distinctly steeper than at any time since the 14th century.

Description of an aerodynamic levitation apparatus with applications in Earth sciences.

BACKGROUND: In aerodynamic levitation, solids and liquids are floated in a vertical gas stream. In combination with CO2-laser heating, containerless melting at high temperature of oxides and silicates is possible. We apply aerodynamic levitation to bulk rocks in preparation for microchemical analyses, and for evaporation and reduction experiments. RESULTS: Liquid silicate droplets (~2 mm) were maintained stable in levitation using a nozzle with a 0.8 mm bore and an opening angle of 60°. The gas flow was ~250 ml min-1. Rock powders were melted and homogenized for microchemcial analyses. Laser melting produced chemically homogeneous glass spheres. Only highly (e.g. H2O) and moderately volatile components (Na, K) were partially lost. The composition of evaporated materials was determined by directly combining levitation and inductively coupled plasma mass spectrometry. It is shown that the evaporated material is composed of Na > K >> Si. Levitation of metal oxide-rich material in a mixture of H2 and Ar resulted in the exsolution of liquid metal. CONCLUSIONS: Levitation melting is a rapid technique or for the preparation of bulk rock powders for major, minor and trace element analysis. With exception of moderately volatile elements Na and K, bulk rock analyses can be performed with an uncertainty of ± 5% relative. The technique has great potential for the quantitative determination of evaporated materials from silicate melts. Reduction of oxides to metal is a means for the extraction and analysis of siderophile elements from silicates and can be used to better understand the origin of chondritic metal.