Composition-Induced Variations in SIMS Instrumental Mass Fractionation during Boron Isotope Ratio Measurements of Silicate Glasses

An analytical artefact is reported here related to differences in instrumental mass fractionation between NIST SRM glasses and natural geological glasses during SIMS boron isotope determinations. The data presented demonstrated an average 3.4‰ difference between the NIST glasses and natural basaltic to rhyolitic glasses mainly in terms of their sputtering-induced fractionation of boron isotopes. As no matrix effect was found among basaltic to rhyolitic glasses, instrumental mass fractionation of most natural glass samples can be corrected by using appropriate glass reference materials. In order to confirm the existence of the compositionally induced variations in boron SIMS instrumental mass bias, the observed offset in SIMS instrumental mass bias has been independently reproduced in two laboratories and the phenomenon has been found to be stable over a period of more than one year. This study highlights the need for a close match between the chemical composition of the reference material and the samples being investigated.     

On the inclusion of ground-based gravity measurements to the calibration process of a global rainfall-discharge reservoir model: case of the Durzon karst system (Larzac, southern France)

This work examines the relevance of the inclusion of ground-based gravity data in the calibration process of a global rainfall-discharge reservoir model. The analysis is performed for the Durzon karst system (Larzac, France). The first part of the study focuses on the hydrological interpretation of the ground-based gravity measurements. The second part of the study investigates further the information content of the gravity data with respect to water storage dynamics modelling. The gravity-derived information is found unable to either reduce equifinality of the single-objective, discharge-based model calibration process or enhance model performance through assimilation.     

A data exploration framework for validation and setup of hydrological models

Over the course of hydrological research projects often a large number of heterogeneous data sets are acquired from sources as diverse as boreholes, gauging stations or satellite imagery. This data then need to be integrated into models for the simulation of hydrological processes. We propose a framework for exploration of geoscientific data and visually guided preparation of such models. Data sets from a large number of sources can be imported, combined and validated to avoid potential problems due to artefacts or inconsistencies between data sets in a subsequent simulation. Boundary conditions and domain discretisations for surface and subsurface models can be created and tested regarding criteria indicating possible numerical instabilities. All data sets including simulation results can be integrated into a user-controlled 3D scene and aspects of the data can be enhanced using a number of established visualisation techniques including thresholding and user-defined transfer functions. We present the application of this framework for the preparation of a model for simulation of groundwater flow in a river catchment in southwest Germany investigated in the scope of the WESS project.     

Cathodoluminescence of authigenic albite

Authigenic albites in carbonate rocks typically grow in a high-grade diagenetic to low-grade metamorphic environment and often show Roc-Tourné-twinning sensu Füchtbauer. Based on an investigation of four Middle to South European occurrences, they show Mn²⁺- and Fe³⁺-activated cathodoluminescence (CL), as revealed by combined high resolution spectroscopy of cathodoluminescence emission (HRS-CL), electron paramagnetic resonance (EPR), and proton-induced X-ray emission (μPIXE).     

Thermal modeling of Carboniferous to Triassic sediments of the Karawanken Range (Southern Alps) as a tool for paleogeographic reconstructions in the Alpine–Dinaridic–Pannonian realm

Vitrinite reflectance was measured in Late Carboniferous to Triassic shales, siltstones and marls of the Karawanken Range. Thermal models of the central South-Karawanken Range were calibrated on the basis of these data. They suggest an eroded overburden of more than 3,200 m of Jurassic to Cretaceous sediments and a heat flow in the range of 42 to 60 mW m^?2 during the time of maximum subsidence. Because the reconstructed thermal history of the South-Karawanken Range is very similar to the thermal history of the Generoso basin (western Southern Alps), these data provide strong evidence for a deep basinal position of the Southern Karawanken Range during Jurassic to Cretaceous times. A vitrinite reflectance anomaly at the northern margin of the South-Karawanken Range is explained by advective heat transport during the Oligocene. The heat source for the anomalies at the western margin of the Seeberg Rise and in the area between the Periadriatic Lineament and the Donat Fault Zone is unknown. Vitrinite reflectance in Late Triassic sediments indicates the South-Karawanken Range and the South-Zala Unit of the Pannonian basement as exotic blocks in the Sava Composite Unit. This is explained by Miocene displacement of structural units, which were derived from different paleogeographical segments of the Permo-Mesozoic western Tethyan margin.     

Mechanism and geochemical implications of the Late Holocene organic carbon burial event: an example from the southwest coast of India

Carbonaceous clay found in the palaeo-deposits of Meenachil River basin was analysed for the total organic carbon, nitrogen and textural characters. Radiocarbon dating of this clay formation and the embedded carbonized wood fragments was also done. The values obtained for the organic carbon, nitrogen and C/N ratio of the carbonaceous clay exhibited a very remarkable range, suggestive of different environmental conditions of formation. It is evident from the present study that since the lignin and cellulose are the dominant components of terrestrial higher plants, allochthonous and submerged organic matter have high C/N ratio. The radio carbon dating of the sediment and wood samples suggested that the palaeo-deposits of Meenachil River basin were formed as result of many transgrassive–regressive episodes, which had started even before the formation of Vembanad Lake. The formation of carbonaceous clay, as found sandwiched in palaeo-deposits, was due to the global eustatic sea-level fluctuations and tectonism.     

Paleoclimatic implications of glacial and postglacial refugia for Pinus pumila in western Beringia

Palynological results from Julietta Lake currently provide the most direct evidence to support the existence of a glacial refugium for Pinus pumila in mountains of southwestern Beringia. Both percentages and accumulation rates indicate the evergreen shrub survived until at least ∼ 19,000 ¹⁴C yr BP in the Upper Kolyma region. Percentage data suggest numbers dwindled into the late glaciation, whereas pollen accumulation rates point towards a more rapid demise shortly after ∼ 19,000 ¹⁴C yr BP. Pinus pumila did not re-establish in any great numbers until ∼ 8100 ¹⁴C yr BP, despite the local presence ∼ 9800 ¹⁴C yr BP of Larixdahurica, which shares similar summer temperature requirements. The postglacial thermal maximum (in Beringia ∼ 11,000-9000 ¹⁴C yr BP) provided Pinus pumila shrubs with equally harsh albeit different conditions for survival than those present during the LGM. Regional records indicate that in this time of maximum warmth Pinus pumila likely sheltered in a second, lower-elevation refugium. Paleoclimatic models and modern ecology suggest that shifts in the nature of seasonal transitions and not only seasonal extremes have played important roles in the history of Pinus pumila over the last ∼ 21,000 ¹⁴C yr BP.     

Postglacial vegetation history of Mitkof Island, Alexander Archipelago, southeastern Alaska

An AMS radiocarbon-dated pollen record from a peat deposit on Mitkof Island, southeastern Alaska provides a vegetation history spanning ∼12,900 cal yr BP to the present. Late Wisconsin glaciers covered the entire island; deglaciation occurred > 15,400 cal yr BP. The earliest known vegetation to develop on the island (∼12,900 cal yr BP) was pine woodland (Pinus contorta) with alder (Alnus), sedges (Cyperaceae) and ferns (Polypodiaceae type). By ∼12,240 cal yr BP, Sitka spruce (Picea sitchensis) began to colonize the island while pine woodland declined. By ∼11,200 cal yr BP, mountain hemlock (Tsuga mertensiana) began to spread across the island. Sitka spruce-mountain hemlock forests dominated the lowland landscapes of the island until ∼10,180 cal yr BP, when western hemlock (Tsuga heterophylla) began to colonize, and soon became the dominant tree species. Rising percentages of pine, sedge, and sphagnum after ∼7100 cal yr BP may reflect an expansion of peat bog habitats as regional climate began to shift to cooler, wetter conditions. A decline in alders at that time suggests that coastal forests had spread into the island's uplands, replacing large areas of alder thickets. Cedars (Chamaecyparis nootkatensis, Thuja plicata) appeared on Mitkof Island during the late Holocene.     

Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone.Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (> 99.85 mol.% of ∑[C₁–C₄, CO₂]). Molecular ratios of LMWHC (C₁/[C₂ + C₃] > 1000) and stable isotopic compositions of methane (δ¹³C = ? 53.5‰ V-PDB; D/H around ? 175‰ SMOW) indicated predominant microbial methane formation. C₁/C₂₊ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by > 0.03 mol.% (∑[C₁–C₄, CO₂]) relative to the other gas types and the virtual lack of ¹⁴C–CH₄ indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely.As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% ∑(C₁–C₄, CO₂)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of ¹⁴C–CH₄ (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.