Calcium Isotopes (δ44/40Ca) in MPI-DING Reference Glasses, USGS Rock Powders and Various Rocks: Evidence for Ca Isotope Fractionation in Terrestrial Silicates

We report δ^44/40Ca_{(SRM 915a)} values for eight fused MPI‐DING glasses and the respective original powders, six USGS igneous rock reference materials, the U‐Th disequilibria reference material TML, IAEA‐CO1 (Carrara marble) and several igneous rocks (komatiites and carbonatites). Sample selection was guided by three considerations: (1) to address the need for information values on reference materials that are widely available in support of interlaboratory comparison studies; (2) support the development of in situ laser ablation and ion microprobe techniques, which require isotopically homogenous reference samples for ablation; and (3) provide Ca isotope values on a wider range of igneous and metamorphic rock types than is currently available in the scientific literature. Calcium isotope ratios were measured by thermal ionisation mass spectrometry in two laboratories (IFM‐GEOMAR and Saskatchewan Isotope Laboratory) using ⁴³Ca/⁴⁸Ca‐ and ⁴²Ca/⁴³Ca‐double spike techniques and reported relative to the calcium carbonate reference material NIST SRM 915a. The measurement uncertainty in both laboratories was better than 0.2‰ at the 95% confidence level. The impact of different preparation methods on the δ^44/40Ca_{(SRM 915a)} values was found to be negligible. Except for ML3‐B, the original powders and the respective MPI‐DING glasses showed identical δ^44/40Ca_{(SRM 915a)} values; therefore, possible variations in the Ca isotope compositions resulting from the fusion process are excluded. Individual analyses of different glass fragments indicated that the glasses are well homogenised on the mm scale with respect to Ca. The range of δ^44/40Ca_{(SRM 915a)} values in the igneous rocks studied was larger than previously observed, mostly owing to the inclusion of ultramafic rocks from ophiolite sections. In particular, the dunite DTS‐1 (1.49 ± 0.06‰) and the peridotite PCC‐1 (1.14 ± 0.07‰) are enriched in ⁴⁴Ca relative to volcanic rocks (0.8 ± 0.1‰). The Carrara marble (1.32 ± 0.06‰) was also found to be enriched in ⁴⁴Ca relative to the values of assumed precursor carbonates (< 0.8‰). These findings suggest that the isotopes of Ca are susceptible to fractionation at high temperatures by, as yet, unidentified igneous and metamorphic processes.     

Land-use transition for bioenergy and climate stabilization: model comparison of drivers,impacts and interactions with other land use based mitigation options

In this article, we evaluate and compare results from three integrated assessment models (GCAM, IMAGE, and ReMIND/MAgPIE) regarding the drivers and impacts of bioenergy production on the global land system. The considered model frameworks employ linked energy, economy, climate and land use modules. By the help of these linkages the direct competition of bioenergy with other energy technology options for greenhouse gas (GHG) mitigation, based on economic costs and GHG emissions from bioenergy production, has been taken into account. Our results indicate that dedicated bioenergy crops and biomass residues form a potentially important and cost-effective input into the energy system. At the same time, however, the results differ strongly in terms of deployment rates, feedstock composition and land-use and greenhouse gas implications. The current paper adds to earlier work by specific looking into model differences with respect to the land-use component that could contribute to the noted differences in results, including land cover allocation, land use constraints, energy crop yields, and non-bioenergy land mitigation options modeled. In scenarios without climate change mitigation, bioenergy cropland represents 10–18 % of total cropland by 2100 across the different models, and boosts cropland expansion at the expense of carbon richer ecosystems. Therefore, associated emissions from land-use change and agricultural intensification as a result of bio-energy use range from 14 and 113 Gt CO2-eq cumulatively through 2100. Under climate policy, bioenergy cropland increases to 24–36 % of total cropland by 2100.     

Lithostratigraphy and U-Pb zircon dating in the overturned limb of the Siviez-Mischabel nappe: a new key for Middle Penninic nappe geometry.

Detailed field work and zircon analysis have improved the knowledge of the lithostratigraphy at the base of the Siviez-Mischabel nappe in the Mattertal (St-Niklaus-Törbel area). They confirm the existence of an overturned limb and clarify the structure of the St-Niklaus syncline. The following formations can be observed:

• Polymetamorphic gneisses; composed of paragneisses, amphibolites and micaschists (Bielen Unit, pre-Ordovician).
• Fine-grained, greyish quartzite and graywacke with kerogen-rich horizons (Törbel Formation, presumed Carboniferous).
• Green or white micaschists characterized by brown carbonate spots associated with white conglomeratic quartzites (Moosalp Formation, Early Permian).
• Massive, green or white, fine grained, microconglomeratic or conglomeratic quartzites with characteristic pink quartz pebbles (Bruneggjoch Formation, Late Permian-Early Triassic).

This coherent overturned sequence can be observed from the St-Niklaus area to the Moosalp pass to the north. Detailed mapping revealed that the St-Niklaus syncline is symmetrical and connects the overturned limb of the Siviez-Mischabel nappe to the normal series of the Upper Stalden zone. U-Pb zircon geochronology on magmatic and detrital zircons allowed constraining ages of these formations. Detrital zircons display ages ranging from 2900 ± 50 to 520 ± 4 Ma in the Törbel Formation, and from 514 ± 6 to 292 ± 9 Ma in the Moosalp Formation. In addition, the Permian Randa orthogneiss is intrusive into the polymetamorphic gneisses and into the Permo-Carboniferous metasediments of the overturned limb of the Siviez-Mischabel nappe. This revision clarified also the lithostratigraphy of the nearby and subjacent Lower Stalden zone composed of an overturned limb with Permo-Carboniferous formations. This has critical implications for the tectonic setting of the nappes in the region, speaking for few recumbent folds with well preserved normal and overturned limbs instead of a succession of imbricate thrust sheets in a normal stratigraphic position.     

Timing and rate of granulite facies metamorphism and cooling from multi-mineral chronology on migmatitic gneisses,Sierras de La Huerta and Valle Fértil,NW Argentina

Migmatitic paragneisses of the Valle Fértil–La Huerta Ranges at the Western margin of the Sierras Pampeanas are composed of garnet–cordierite–plagioclase–biotite–quartz-bearing units that experienced peak metamorphic conditions of ca. 800 °C at 6–7 kbar. Based on petrological studies, pseudosection modeling and petrographic observations, an anticlockwise P–T path with a small pressure increment is proposed. Rare earth element LA-ICP-MS patterns acquired from rutile bearing garnets suggest a single stage of garnet growth at high-T at pressures above the ilmenite–rutile transition. U–Pb dating of zircon rims from the migmatites indicates two distinct metamorphic U–Pb ages of 525 ± 9 Ma and 478 ± 9 Ma. The older age is suggested to record an amphibolite facies event of the Pampean orogeny. The younger metamorphic age is contemporary with igneous zircons from metatonalites and pegmatites that yield 478 ± 4 Ma. We suggest that the prograde high-T metamorphic Famatinian event is associated with the emplacement of large magmatic bodies in which large-scale magmatic activity gave rise to an increased geothermal gradient of about 35 °C/km. Sm–Nd garnet ages of 447 ± 3 Ma indicate a time span of around 30 Ma for which temperatures above the garnet closure temperature prevailed. Using U–Pb, Sm–Nd and Rb–Sr isotope systems, a cooling rate of 3 to 6 °C/Myr is inferred.     

Fuzzy characterization of near-earth-asteroids

Due to close encounters with the inner planets, Near-Earth-Asteroids (NEAs) can have very chaotic orbits. Because of this chaoticity, a statistical treatment of the dynamical properties of NEAs becomes difficult or even impossible. We propose a new way to classify NEAs by using methods from Fuzzy Logic. We demonstrate how a fuzzy characterization of NEAs can be obtained and how a subsequent analysis can deliver valid and quantitative results concerning the long-term dynamics of NEAs.     

Early diagenesis of redox-sensitive trace metals in the Peru upwelling area - response to ENSO-related oxygen fluctuations in the water column

Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ∼0 to 93 μM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Niño Southern Oscillation (ENSO).Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ precipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.     

Hydrochemical Groundwater Evolution in the Bunter Sandstone Sequence of the Odenwald Mountain Range,Germany: A Laboratory and Field Study

Field and laboratory investigations were performed to identify the principal mechanisms of the hydrochemical groundwater evolution among low mineralised groundwater in the Triassic Bunter sandstone aquifer of the Odenwald low mountain range, central Germany. Hydrochemical composition comprises low pH, SO₄-rich shallow groundwaters issued by springs (Ca-Mg-SO₄-type) grading to SO₄-poor deep groundwaters with near-neutral pH (Ca-HCO₃-type). Batch experiments of the original rock were run to determine primary mineral alteration reactions and the origin of dissolved ions. Principal experimental reactions comprise the decomposition of anorthite, K-feldspar, biotite and jarosite as mineral components of the original sandstone rock and the formation of clay minerals of the smectite group (Ca-montmorillonite, beidellite), and iron hydroxides as secondary minerals. Mobilisation of fluid inclusion in quartz grains contributes to Na and Cl concentrations in the leachates. The evolution of deep groundwater circulation proceeds by mineral alteration reactions calculated by the inverse modelling of both primary and secondary minerals to produce low-T mineral phases. The dissolution of K-feldspar converts Ca-montmorillonite to illite (illitisation). The formation of Na-beidellite correlates with decreasing concentration of Na in solution. Mineral reactions further proceed to the formation of kaolinite as stable mineral phase. As indicated by modelled adsorption curves, the decrease of SO₄ concentrations during groundwater evolution relates to the adsorption of SO₄ on iron hydroxides. The leaching of calcite indicated for individual groundwaters relates to the distribution of loess in the appropriate catchment areas.     

Impact of Oyster Farming on Diagenetic Processes and the Phosphorus Cycle in Two Estuaries (Brittany,France)

This study aims to compare the impact of oyster cultures on diagenetic processes and the phosphorus cycle in the sediments of the Aber Benoît and the Rivière d’Auray, estuary of Brittany, France. Our results showed clear evidence of the seasonal impact of oyster cultures on sediment characteristics (grain size and organic matter parameters) and the phosphorus cycle, especially in the Aber Benoît. At this site, seasonal variations in sulfide and Fe concentrations in pore waters, as well as Fe–P concentrations in the solid phase, highlighted a shift from a system governed by iron reduction (Reference) to a system governed by sulfate reduction (beneath oyster). This could be partly explained by the increase in labile organic matter (i.e., biodeposits) beneath oysters, whose mineralization by sulfate led to high sulfide concentrations in pore waters (up to 4,475 µmol l^?1). In turn, sulfide caused an enhanced release of phosphate in the summer, as adsorption sites for phosphate decreased through the formation of iron–sulfide compounds (FeS and FeS₂). In the Aber Benoît, dissolved Fe/PO₄ ratios could be used as an indicator of phosphate release into oxic water. Low Fe/PO₄ ratios in the summer indicated higher effluxes of phosphate toward the water column (up to 47 µmol m^?2 h^?1). At other periods, Fe/PO₄ ratios higher than 2 mol/mol indicated very low phosphate fluxes. In contrast, in the Rivière d’Auray, the occurrence of macroalgae, stranding regularly all over the site, clearly masked the impact of oyster cultures on sediment properties and the phosphorus cycle and made the use of Fe/PO₄ ratios more difficult in terms of indicators of phosphate release.