Grain boundary and volume diffusion experiments in yttrium aluminium garnet bicrystals at 1,723 K: a miniaturized study

Yb-Y inter-diffusion along a single grain boundary of a synthetic yttrium aluminium garnet (YAG) bicrystal has been studied using analytical transmission electron microscopy (ATEM). To investigate the diffusion, a thin-film containing Yb as the diffusant was deposited perpendicular to the bicrystal grain boundary by pulsed laser deposition (PLD). Structural properties and their change with time in both the diffusant source and the grain boundary are reported. The diffusion profiles are incorporated in a numerical diffusion model, which is applied to determine the grain boundary diffusion coefficient, D _gb , at 1.723 K it is equal to 3 × 10⁻¹⁵ m²/s. We find that grain boundary diffusion is 4.85 orders of magnitude faster than volume diffusion, which was determined from the same diffusion experiment. This result is discussed in the context of special versus general grain boundaries. Finally, we successfully tested the capability of synchrotron-based nano-X-ray fluorescence analysis to map micro-chemical patterns in two dimensions with sub-micrometre resolution.     

Low-grade metamorphic rocks from the Pulur complex,NE Turkey: implications for the pre-Liassic evolution of the Eastern Pontides

In the Pulur complex (Sakarya Zone, Eastern Pontides, Turkey) a low-grade tectonometamorphic unit (Doankavak) is exposed in three tectonic windows beneath a complex medium-pressure high-temperature metamorphic unit of late Carboniferous age. The thrust plane between both units is transgressively covered by Liassic conglomerates. The Doankavak unit comprises a sequence of metabasites with MORB-type chemical compositions and phyllites, with subordinate calcareous phyllites, marbles, quarzofeldspathic schists and metacherts. This sequence is interpreted as a former accretionary complex related to the consumption of the Palaeotethys. Mineral parageneses in the metabasites allow for the distinction of two domains with slightly different peak metamorphic conditions, i.e. 375–425 °C/0.5–0.8 GPa (greenschist facies) and 400–470 °C/0.6–1.1 GPa (albite-epidote amphibolite facies). The age of metamorphism is constrained at ~ 260 Ma (early Late Permian) by two Rb-Sr mineral-whole rock ages (hornblende, phengite) and one ⁴⁰Ar/³⁹Ar single step total fusion age (phengite). In conjunction with previous data on other accretionary complexes in the Sakarya zone in Northern Turkey, the data presented in this study suggest a continuous subduction of the Palaeotethys at least from Early/Late Permian to Late Triassic and a discontinuous preservation of accretion complexes in both space and time.     

Isotopic and elemental fractionation of solar wind implanted in the Genesis concentrator target characterized and quantified by noble gases

Abstract– We report concentrations and isotopic compositions of He, Ne, and Ar measured with high spatial resolution along a radial traverse of a silicon carbide (SiC) quadrant of the Genesis mission concentrator target. The Ne isotopic composition maps instrumental fractionation as a function of radial position in the target: the maximum observed isotopic fractionation is approximately 33‰ per mass unit between the center and periphery. The Ne fluence is enhanced by a factor of 43 at the target center and decreases to 5.5 times at the periphery relative to the bulk solar wind fluence. Neon isotopic profiles measured along all four arms of the “gold cross” mount which held the quadrants in the concentrator target demonstrate that the concentrator target was symmetrically irradiated during operation as designed. We used implantation experiments of Ne into SiC and gold to quantify backscatter loss and isotopic fractionation and compared measurements with numerical simulations from the code “stopping and range of ions in matter.” The ²⁰Ne fluence curve as a function of radial distance on the target may be used to construct concentration factors relative to bulk solar wind for accurate corrections for solar wind fluences of other light elements to be measured in the concentrator target. The Ne isotopic composition as a function of the radial distance in the SiC quadrant provides a correction for the instrumental mass‐dependent isotopic fractionation by the concentrator and can be used to correct measured solar wind oxygen and nitrogen isotopic compositions to obtain bulk solar wind isotopic compositions.     

High resolution analysis of uranium and thorium concentration as well as U-series isotope distributions in a Neanderthal tooth from Payre (Ardèche, France) using laser ablation ICP-MS

We have mapped U (²³⁸U) and Th (²³²Th) elemental concentrations as well as U-series isotope distributions in a Neanderthal tooth from the Middle Palaeolithic site of Payre using laser ablation ICP-MS. The U-concentrations in an enamel section varied between 1 and 1500 ppb. The U-concentration maps show that U-migration through the external enamel surface is minute, the bulk of the uranium having migrated internally via the dentine into the enamel. The uranium migration and uptake is critically dependent on the mineralogical structure of the enamel. Increased U-concentrations are observed along lineaments, some of which are associated with cracks, and others may be related to intra-prismatic zones or structural weaknesses reaching from the dentine into the enamel. The uranium concentrations in the dentine vary between about 25,000 and 45,000 ppb. Our systematic mapping of U-concentration and U-series isotopes provides insight into the time domain of U-accumulation. Most of the uranium was accumulated in an early stage of burial, with some much later overprints. None of the uranium concentration and U-series profiles across the root of the tooth complied with a single stage diffusion-adsorption (D-A) model that is used for quality control in U-series dating of bones and teeth. Nevertheless, in the domains that yielded the oldest apparent U-series age estimates, U-leaching could be excluded. This means that the oldest apparent U-series ages of around 200 ka represent a minimum age for this Neanderthal specimen. This is in good agreement with independent age assessments (200-230 ka) for the archaeological layer, in which it was found.The Th elemental concentrations in the dental tissues were generally low (between about 1 and 20 ppb), and show little relationship with the nature of the tissue.     

Corrosion-induced gas generation in a nuclear waste repository: Reactive geochemistry and multiphase flow effects

Corrosion of steel canisters, stored in a repository for spent fuel and high-level nuclear wastes, leads to the generation and accumulation of H₂ gas in the backfilled emplacement tunnels, which may significantly affect long-term repository safety. Previous studies have used H₂ generation rates based on the volume of the waste or canister material and the stoichiometry of the corrosion reaction. However, Fe corrosion and H₂ generation rates vary with time, depending on factors such as amount of Fe, water availability, water contact area and aqueous and solid chemistry. To account for these factors and feedback mechanisms, a chemistry model was developed related to Fe corrosion, coupled with two-phase (liquid and gas) flow phenomena that are driven by gas-pressure buildup associated with H₂ generation and water consumption. Results indicate that by dynamically calculating H₂ generation rates based on a simple model of corrosion chemistry, and by coupling this corrosion reaction with two-phase flow processes, the degree and extent of gas-pressure buildup could be much smaller compared to a model that neglects the coupling between flow and reactive transport mechanisms. By considering the feedback of corrosion chemistry, the gas pressure increases initially at the canister, but later decreases and eventually returns to a stabilized pressure that is slightly higher than the background pressure. The current study focuses on corrosion under anaerobic conditions for which the coupled hydrogeochemical model was used to examine the role of selected physical parameters on H₂ gas generation and corresponding pressure buildup in a nuclear waste repository. The developed model can be applied to evaluate the effect of water and mineral chemistry of the buffer and host rock on the corrosion reaction for future site-specific studies.     

Calculations of the seasonal loadings of North Sea sediments with persistent aromatic organochlorines

The content and distribution of ΣPCB (as the sum of 24 individual components), HCB and p,p′-DDE was determined in sediments taken from the North Sea during two seasons. The mass-balance of aromatic organochlorine compounds in the upper 2 cm of sediments is calculated and dicussed in relation to pollutant dispersal.     

Physical conditions in eruptive prominences at several solar radii

SMM data from the Corograph/Polarimeter experiment giving intensities of H and continuum emission in eight erupting prominences are analyzed to obtain the physical conditions in the regions of H emission. Since the H intensity depends upon three unknowns whereas only two independent observations are available, it is necessary to assume one additional condition in order to obtain unique solutions. Solutions are chosen that give the maximum expansion of the prominence volume as reflected by minimum values of the electron density. These solutions correspond closely with those giving the best agreement between the gas pressure in the prominence and the ambient coronal pressure. Electron densities are found to be of the order of 10⁸ cm^-3 at temperatures near 2 × 10⁴ K.The National Center for Atmospheric Research is operated by the University Corporation for Atmospheric Research under sponsorship of the National Science Foundation.     

Clay mineral distribution in surface sediments of the South Atlantic: sources, transport, and relation to oceanography

Surface samples, mostly from abyssal sediments of the South Atlantic, from parts of the equatorial Atlantic, and of the Antarctic Ocean, were investigated for clay content and clay mineral composition. Maps of relative clay mineral content were compiled, which improve previous maps by showing more details, especially at high latitudes. Large-scale relations regarding the origin and transport paths of detrital clay are revealed. High smectite concentrations are observed in abyssal regions, primarily derived from southernmost South America and from minor sources in Southwest Africa. Near submarine volcanoes of the Antarctic Ocean (South Sandwich, Bouvet Island) smectite contents exhibit distinct maxima, which is ascribed to the weathering of altered basalts and volcanic glasses. The illite distribution can be subdivided into five major zones including two maxima revealing both South African and Antarctic sources. A particularly high amount of Mg- and Fe-rich illites are observed close to East Antarctica. They are derived from biotite-bearing crystalline rocks and transported to the west by the East Antarctic Coastal Current. Chiorite and well-crystallized dioctaedral illite are typical minerals enriched within the Subantarctic and Polarfrontal-Zone but of minor importance off East Antarctica. Kaolinite dominates the clay mineral assemblage at low latitudes, where the continental source rocks (West Africa, Brazil) are mainly affected by intensive chemical weathering. Surprisingly, a slight increase of kaolinite is observed in the Enderby Basin and near the Filchner-Ronne Ice shelf.

The investigated area can be subdivided into ten, large-scale clay facies zones with characteristic possible source regions and transport paths. Clay mineral assemblages of the largest part of the South Atlantic, especially of the western basins are dominated by chlorite and illite derived from the Antarctic Peninsula and southernmost South America and supported by advection within the Circumantarctic Deep Water flow. In contrast, the East Antarctic provinces are relatively small. Assemblages of the eastern basins north of 30°S are strongly influenced by African sources, controlled by weathering regimes on land and by a complex interaction of wind, river and deep ocean transport. The strong gradient in clay mineral composition at the Brazilian slope indicate a relatively low contribution of tropically derived assemblages to the western basins.     

Biosiliceous particle flux in the Southern Ocean

The flux of diatom valves and radiolarian shells obtained during short-term and annual sediment trap experiments at seven localities in the Atlantic sector of the Antarctic Ocean (in the Drake Passage, Bransfield Strait, Powell Basin, NW and SE Weddell Sea and the Polar Front north of Bouvet Island) is summarized and discussed. The deployment of time-series sediment traps provided annual flux records between 1983 and 1990. The biosiliceous particle flux is characterized by significant seasonal and interannual variations. Flux pulses, accounting for 70–95% of the total annual flux, occur during austral summer, with a duration ranging between about 2 and 9 weeks. The annual values of vertical diatom and radiolarian flux range between 0.26 × 10⁹ and more than 26 × 10⁹ valves m⁻² and between 0.21 × 10⁴ and 70 × 10⁴ shells m⁻², respectively. Interannual differences in the particle flux range over a factor of 10. Grazers play an important role in controlling the quantity, timing and pattern of the vertical biosiliceous particle flux.The flux pattern of diatoms and radiolarians is similar at most of the sites investigated and shows a close relationship between the production of siliceous phytoplankton and proto-zooplankton. At some sites, however, the radiolarian flux pattern indicates probably phytoplankton production which is not documented by direct signals in the trap record.During their transfer through the water column to the ocean floor, the composition of the biosiliceous particles is altered mechanically (breakdown by grazing Zooplankton) and by dissolution, which significantly affects especially diatoms and phaeodarians in the upper portion of the water column and at the sediment-water interface.Significant lateral transport of suspended biosiliceous particles was observed in the bottom water layer in regions adjacent to shelf areas (Bransfield Strait), and in the vicinity of topographic elevations (Maud Rise), indicating considerable redistribution of biogenic silica in these regions.