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.     

The present day formation of apatite in Mexican continental margin sediments

Results of pore water and sediment analyses from the western Mexican continental margin strongly suggest the present day formation of apatite. The interstitial water phosphate and fluoride profiles indicate chemical removal at a depth which corresponds to a large maximum in the phosphorus content of the sediments. Apatite is identified within this maximum via X-ray diffraction but is elsewhere undetectable in the core. Radioisotopic thorium, uranium, and radium data support the conclusion that this deposit is modern. The present day depositional environment is consistent with those reported by other workers for phosphorite formation with the exception that pore water magnesium is not depleted below its seawater value.     

Quantification of mineral matter in the Argonne Premium Coals using interactive Rietveld-based X-ray diffraction

The mineral matter in the eight reference North American coal samples of the Argonne Premium Coal series has been investigated on a quantitative basis using X-ray diffraction (XRD) techniques. X-ray diffraction data obtained from electronic low-temperature (oxygen–plasma) ash (LTA) residues, from ashes produced by heating the coals in air at 370°C, and also from the raw coals themselves, were evaluated using an interactive data processing system ( ™) based on Rietveld interpretation methods. The results from the three types of material (LTA, 370°C ash and raw coal) were compared for each sample. This allowed the components present in the raw coals in crystalline form to be recognised separately from mineral artifacts produced, particularly in the low-rank coals, from interaction of organically associated elements (Ca, S, etc.) during the two ashing processes.After the allowance for the production of any artifacts, the quantitative mineral assemblages identified from XRD of the raw coals were found to be consistent, even for coals having a relatively low ash percentage (around 5%), with the results obtained from the respective mineral concentrates prepared by the ashing methods. The effects of heating the coal to 370°C could also be distinguished, relative to the raw coal or the LTA, through changes in components such as pyrite and the clay minerals.Although some areas of uncertainty exist, particularly with magnesium in the low-rank coals, the calculated chemical compositions of the coal ash derived from the mineral mixtures identified for each coal were also found to be consistent with the results of direct chemical analysis of the respective coal ash materials.     

Application of Deuterium Excess for Identification of Freshwater Sources in the Bays of Novaya Zemlya Archipelago

Doklady Earth Sciences - An isotopic–geochemical study was carried out for waters of Tsivolkii and Sedov bays (southeastern coast of the Novaya Zemlya Archipelago). The waters of these bays...     

Sphene and zircon in the Highland Range volcanic sequence (Miocene, southern Nevada, USA): elemental partitioning, phase relations, and influence on evolution of silicic magma

Sphene is prominent in Miocene plutonic rocks ranging from diorite to granite in southern Nevada, USA, but it is restricted to rhyolites in coeval volcanic sequences. In the Highland Range volcanic sequence, sphene appears as a phenocryst only in the most evolved rocks (72?C77 mass% SiO₂; matrix glass 77?C78 mass% SiO₂). Zr-in-sphene temperatures of crystallization are mostly restricted to 715 and 755°C, in contrast to zircon (710?C920°C, Ti-in-zircon thermometry). Sphene rim/glass Kds for rare earth elements are extremely high (La 120, Sm 1200, Gd 1300, Lu 240). Rare earth elements, especially the middle REE (MREE), decrease from centers to rims of sphene phenocrysts along with Zr, demonstrating the effect of progressive sphene fractionation. Whole rocks and glasses have MREE-depleted, U-shaped REE patterns as a consequence of sphene fractionation. Within the co-genetic, sphene-rich Searchlight pluton, only evolved leucogranites show comparable MREE depletion. These results indicate that sphene saturation in intruded and extruded magmas occurred only in highly evolved melts: abundant sphene in less silicic plutonic rocks represents a late-stage ??bloom?? in fractionated interstitial melt.     

Seismicity and earthquake focal mechanisms in the Baikal rift zone

The seismicity of the Baikal rift zone is considered on the basis of instrumental and field observations. The spatial pattern of epicentres, the frequency of earthquakes and the relations between seismicity and the elements of fault tectonics are analyzed. The regional and local stress states in the crust of the Pribaikalye region, obtained from studying earthquake focal mechanisms for various energies are summarized.     

Detailed mineralogical-geochemical study of a large spinel Lherzolite xenolith in alkali basalt of Shavaryn Tsaram paleovolcano,Mongolia

Mineralogical-geochemical data obtained on a large xenolith of spinel lherzolite from basanites of Shavaryn Tsaram volcano (Middle Pleistocene) provide evidence that the xenolith was affected by heat and fluid that came from the basalt melt and induced geochemical heterogeneity of the xenolith. Olivine crystals from the central portion of the xenolith contain much more CaO than this mineral from the peripheral zones of the xenolith as well as in xenocrystals of the host basalts. The large xenolith was unevenly annealed by the host basalt melt, and this predetermined the heterogeneous diffusion-controlled “purification” of olivine crystals from their CaO admixture. The xenolith is heterogeneously enriched in LREE and some trace elements (Zr, Hf, Nb, Th, and U), and their distribution demonstrates unclearly pronounced concentric zoning: these elements enriched the outer portions of the xenolith. The enrichment of the xenolith in LREE and other mobile trace elements is explained by their occurrence not only as structurally bound (isomorphic) components in minerals but also in the form of nonstructural admixtures (contaminant), as minute grains of compounds hosted in the interstitial space and tiny cracks cutting mineral grains. The enrichment of the xenolith in these admixtures proceeded via their infiltration-controlled introduction with fluid from the basalt along minute cracks.