Redistribution of HFSE elements during rutile replacement by titanite

Titanite growth at the expense of rutile during retrograde hydration of eclogite into amphibolite is a common phenomenon. We investigated an amphibolite sample from the Tromsø eclogite facies terrain in Northern Norway to gain insight into the trace element distribution between rutile and titanite during incomplete resorption of the rutile by titanite. Patchy compositional zoning of Al, Ti, and F in titanite relates to the presence of a fluid with variable Ti/Al and/or F during its growth. Laser ablation ICP–MS and electron microprobe data for high field strength elements (HFSE: Nb, Zr, Ta, and Hf) of rutile resorbed by titanite indicate a pronounced enrichment of these elements in the rim of a large single rutile crystal (~8 mm) and a systematic decrease towards uniform HFSE contents in the large core. HFSE contents of smaller rutile grains (~0.5 mm) and rutile inclusions (<100 μm) in the titanite overgrowth are similar or higher than in the rims of large rutile crystals. Element profiles from the rim inward demonstrate that HFSE enrichment in rutile is controlled by diffusion. HFSE ratios in diffusion-altered rutile show systematic variations compared with the uniform core composition of the large rutile. Modelling of Zr and Nb diffusion in rutile indicates that diffusion coefficients in rutile in fluid-dominated natural systems must be considerably higher than those determined experimentally at 1 bar in dry systems. Variations of HFSE contents in the newly formed titanite show no systematic spatial distribution. HFSE ratios in titanite and the rims of rutile are different, indicating different solid/fluid distribution coefficients in these minerals. Element fractionation by diffusion into the relict rutile and during fluid-mediated growth of new titanite could substantially change the HFSE budget of these minerals and could affect their use for geochemical tracing and other applications, such as Zr-based geothermobarometry.     

Climatology of Ozone, PAN, CO, and NMHC in the Free Troposphere Over the Southern North Atlantic

Free tropospheric measurements of ozone, peroxyacetylnitrate andprecursors (CO, NMHC) that were made within the framework of the EUROTRACsub-project TOR (Tropospheric Ozone Research) between 1990 and 1995 at theGAW station Izana, Tenerife (28°18N, 16°30W) arediscussed. The average annual cycles reveal the importance of transport fromnorthern mid-latitudes and the role of photo-chemistry. According toair-mass trajectories, which were supplied to us from AEROCE(Atmosphere/Ocean Chemistry Experiment), transport from northernmid-latitudes is associated with high precursor concentrations in winter,whereas ozone concentrations in winter are not much influenced by transportpatterns, suggesting a rather uniform distribution over the northern part ofthe Northern Hemisphere around mean value of 43 ± 5 ppb. In summer,high ozone concentrations of up to 90 ppb are often encountered duringtransport from north, while the levels of precursors are much lower than inwinter, because of photochemical destruction. Trajectories from southerlylatitudes and the Sahara usually have the lowest ozone concentrationsassociated with them.     

Enhanced red fluorescence emission in the oxygen minimum zone of the Arabian Sea

 Depth profiles of fluorescence at several excitation and emission wavelengths were measured along with CTD data during the cruise So119 of RV Sonne in the Arabian Sea from 12 May to 10 June 1997. In addition to chlorophyll fluorescence from phytoplankton in the near-surface layer, the profiles in the oxygen minimum region well below the euphotic zone show enhanced red fluorescence. Red fluorescence intensity is inversely related to the oxygen concentration in intermediate and deep waters. A relationship to characteristic water masses of the region cannot be found in the data, and this holds also with chemical data such as DOC. Absorbance spectra of water samples taken in the oxygen minimum zone show an absorption band at 420 nm wavelength with about 50 nm bandwidth, much weaker than gelbstoff absorbance in the same wavelength range. The absorption band remains stable after sample filtration with 0.45 μm glass fibre filters. Hence, the size of the absorbing matter is in the range of dissolved molecules or particles much smaller than 1 μm. Fluorescence spectra of unfiltered samples with 420 nm excitation show a weak emission band at 600 nm and a more pronounced one at 660 nm wavelength. The trailing edge of the 660 nm band falls into the range of chlorophyll emission, thus giving rise to the observed depth profiles of red fluorescence in the oxygen minimum zone. Red fluorescence measured on samples remain stable during a few hours after sampling even in the presence of oxygen. It is not detectable after several weeks of sample storage in the dark and cannot be reproduced even after depletion of dissolved oxygen. Received: 22 May 2002 / Accepted: 18 February 2003 Responsible Editor: Andreas Oschlies Acknowledgements. This work was supported by a grant from the Federal Minister of Education and Technology, Bonn, within the frame work of the JGOFS Arabian Sea program. We are grateful to the captain and the crew of RV Sonne for their support. We are indebted to Mrs. Kirsten Neumann from the Institute of Marine Chemistry and Biogeochemistry of the University of Hamburg for providing the oxygen data, and to Mr. Nikolai Delling from the same institute for making the DOC and chlorophyll data available to us.     

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.     

Study of inorganic ligand-chromium(III)-surface ternary complexes by ESR spectroscopy

Cr(III) sorbed at the solid/water interface of latex and hectorite was studied by ESR spectroscopy in the presence of different inorganic ligands. The ESR spectra of the surface obtained in the presence of selenite, phosphate and fluoride can be explained in terms of ternary surface complex formation. This is contrasted by the behaviour of sulfate and selenate ions which were found to have no effect on the ligand field of Cr(III), either in the adsorbed state or in solution.     

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.