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.     

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.     

Simultaneous quantification of dissolved organic carbon fractions and copper complexation using solid-phase extraction

Trace metal cycling in natural waters is highly influenced by the amount and type of dissolved organic C (DOC). Although determining individual species of DOC is unrealistic, there has been success in classifying DOC by determining operationally defined fractions. However, current fractionation schemes do not allow for the simultaneous quantification of associated trace metals. Using operational classifications, a scheme was developed to fractionate DOC based on a set of seven solid-phase extraction (SPE) cartridges. The cartridges isolated fractions based on a range of specific mechanisms thought to be responsible for DOC aggregation in solution, as well as molecular weight. The method was evaluated to determine if it can identify differences in DOC characteristics, including differences in Cu–DOC complexation. Results are that: (1) cartridge blanks were low for both DOC and Cu, (2) differences are observed in the distribution of DOC amongst the fractions from various sources that are consistent with what is known about the DOC materials and the mechanisms operative for each cartridge, (3) when present as a free cation, Cu was not retained by non-cationic cartridges allowing the method to be used to assess Cu binding, (4) the capability of the method to provide quantitative assessment of Cu–DOC complexation was demonstrated for a variety of DOC standards, (5) Cu was found to preferentially bind with high molecular weight fractions of DOC, and (6) estimated partitioning coefficients and conditional binding constants for Cu were similar to those reported elsewhere. The method developed describes DOC characteristics based on specific bonding mechanisms (hydrogen, donor–acceptor, London dispersion, and ionic bonding) while simultaneously quantifying Cu–DOC complexation. The method provides researchers a means of describing not only the extent of DOC complexation but also how that complex will be behave in natural waters.     

Rutile occurrence and trace element behavior in medium-grade metasedimentary rocks: example from the Erzgebirge, Germany

Metamorphic textures in medium-grade (~500–550°C) metasedimentary rocks from the Erzgebirge give evidence of prograde rutile crystallization from ilmenite. Newly-crystallized grains occur as rutile-rich polycrystalline aggregates that pseudomorph the shape of the ilmenites. In-situ trace element data (EMP and SIMS) show that rutiles from the higher-grade samples record large scatter in Nb content and have Nb/Ti ratios higher than coexisting ilmenite. This behavior can be predicted using prograde rutile crystallization from ilmenite and indicates that rutiles are reequilibrating their chemistry with remaining ilmenites. On the contrary, rutiles from the lowest grade samples (~480°C) have Nb/Ti ratios that are similar to the ones in ilmenite. Hence, rutiles from these samples did not equilibrate their chemistry with remaining ilmenites. Our data suggest that temperature may be one of the main factors determining whether or not the elements are able to diffuse between the phases and, therefore, reequilibrate. Newly-crystallized rutiles yield temperatures (from ~500 to 630°C, Zr-in-rutile thermometry) that are in agreement with the metamorphic conditions previously determined for the studied rocks. In quartzites from the medium-grade domain (~530°C), inherited detrital rutile grains are detected. They are identified by their distinct chemical composition (high Zr and Nb contents) and textures (single grains surrounded by fine grained ilmenites). Preliminary calculation, based on grain size distribution of rutile in medium-grade metapelites and quartzites that occur in the studied area, show that rutiles derived from quartzites can be anticipated to dominate the detrital rutile population, even if quartzites are a minor component of the exposure.     

A note on first-order normalizations of perturbed Keplerian systems

Techniques are developed to facilitate the transformation of a perturbed Keplerian system into Deláunay normal form at first order. The implicit dependence of the Hamiltonian on 1, the mean anomaly, through the explicit variable f, the true anomaly, or E, the eccentric anomaly, is removed through first order for terms of the form: