Noble gas composition of the solar wind as collected by the Genesis mission

We present the elemental and isotopic composition of noble gases in the bulk solar wind collected by the NASA Genesis sample return mission. He, Ne, and Ar were analyzed in diamond-like carbon on a silicon substrate (DOS) and ^84,86Kr and ^129,132Xe in silicon targets by UV laser ablation noble gas mass spectrometry. Solar wind noble gases are quantitatively retained in DOS and with exception of He also in Si as shown by a stepwise heating experiment on a flown DOS target and analyses on other bulk solar wind collector materials. Solar wind data presented here are absolutely calibrated and the error of the standard gas composition is included in stated uncertainties. The isotopic composition of the light noble gases in the bulk solar wind is as follows: ³He/⁴He: (4.64 ± 0.09) × 10⁻⁴, ²⁰Ne/²²Ne: 13.78 ± 0.03, ²¹Ne/²²Ne: 0.0329 ± 0.0001, ³⁶Ar/³⁸Ar 5.47 ± 0.01. The elemental composition is: ⁴He/²⁰Ne: 656 ± 5, and ²⁰Ne/³⁶Ar 42.1 ± 0.3. Genesis provided the first Kr and Xe data on the contemporary bulk solar wind. The preliminary isotope and elemental composition is: ⁸⁶Kr/⁸⁴Kr: 0.302 ± 0.003, ¹²⁹Xe/¹³²Xe: 1.05 ± 0.02, ³⁶Ar/⁸⁴Kr 2390 ± 150, and ⁸⁴Kr/¹³²Xe 9.5 ± 1.0. The ³He/⁴He and the ⁴He/²⁰Ne ratios in the Genesis DOS target are the highest solar wind values measured in exposed natural and artificial targets. The isotopic composition of the other noble gases and the Kr/Xe ratio obtained in this work agree with data from lunar samples containing “young” (∼100 Ma) solar wind, indicating that solar wind composition has not changed within at least the last 100 Ma. Genesis could provide in many cases more precise data on solar wind composition than any previous experiment. Because of the controlled exposure conditions, Genesis data are also less prone to unrecognized systematic errors than, e.g., lunar sample analyses. The solar wind is the most authentic sample of the solar composition of noble gases, however, the derivation of solar noble gas abundances and isotopic composition using solar wind data requires a better understanding of fractionation processes acting upon solar wind formation.     

Garnet reaction rims from the breakdown of Staurolite in polymetamorphic micashists from the Rappold complex, Austroalpine basement, Eastern Alps

In polymetamorphic pelites of the Rappold complex in the Wölz crystalline basement (Eastern Alps) reaction rim garnets at staurolite-quartz interfaces (type I) and single grain garnets along previous staurolite-white mica interfaces (type II) were formed. The garnet reaction rims were formed during the Cretaceous amphibolite facies metamorphic overprint of the pre-existing mineral assemblages comprising garnet, staurolite, and kyanite from an amphibolite facies metamorphic event probably of Variscian age. The newly formed garnet may take the form of reaction rims along the margins of large pre-existing staurolite blasts. The initial growth increments of garnet have low grossular content, and reaction rim growth was controlled by the transfer of Fe, Mg and Mn components from the staurolite-garnet interface to the quartz-garnet interface. Later garnet growth increments have relatively high grossular content due to consumption of matrix plagioclase, which was destabilized by successive pressure increase. The grossular content of newly formed garnet shows systematic increase towards sites where plagioclase breaks down indicating that transport of calcium through the matrix was sluggish. On the basis of reaction microstructures it is demonstrated that the mineral assemblage garnet?+?kyanite?+?biotite?+?paragonite was formed at the conditions of eo-alpine amphibolite facies overprint while staurolite and plagioclase broke down successively with increasing pressure.     

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.     

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.     

Beyond headline mitigation numbers: we need more transparent and comparable NDCs to achieve the Paris Agreement on climate change

Nationally determined contributions (NDCs) were key to reaching the Paris Agreement and will be instrumental in implementing it. Research was quick to identify the ‘headline numbers’ of NDCs: if these climate action plans were fully implemented, global mean warming by 2100 would be reduced from approximately 3.6 to 2.7°C above pre-industrial levels (Höhne et al. Climate Pol 17:1–17, 2016; Rogelj et al. Nature 534:631–639, 2016). However, beyond these headline mitigation numbers, NDCs are more difficult to analyse and compare. UN climate negotiations have so far provided limited guidance on NDC formulation, which has resulted in varying scopes and contents of NDCs, often lacking details concerning ambitions. If NDCs are to become the long-term instrument for international cooperation, negotiation, and ratcheting up of ambitions to address climate change, then they need to become more transparent and comparable, both with respect to mitigation goals, and to issues such as adaptation, finance, and the way in which NDCs are aligned with national policies. Our analysis of INDCs and NDCs (Once a party ratifies the Paris Agreement, it is invited to turn its Intended Nationally Determined Contribution (INDC) into an NDC. We refer to results from our INDC analysis rather than our NDC analysis in this commentary unless otherwise stated.) shows that they omit important mitigation sectors, do not adequately provide details on costs and financing of implementation, and are poorly designed to meet assessment and review needs.     

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.