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.     

Continental crust in Gorny Altai: nature and composition of protoliths

The history of the Vendian–Early Paleozoic formation of protoliths of continental crust in the Gorny Altai segment of the Central Asian fold belt is considered, and their composition, isotopic characteristics, and formation mechanisms are estimated. We have established two stages of crust-forming processes in Gorny Altai: Early and Late Caledonian, with the different structures of formed geoblocks and nature and compositions of crustal protoliths. At the Early Caledonian stage, fragments of oceanic lithosphere of basic composition (MORB, OIT, OIB) (T_Nd(DM-2st) = 0.65–1.1 Ga) formed, as well as island arcs with andesite-basaltic and andesitic protoliths with low contents of incompatible elements (T_Nd(DM-2st) = 0.7–0.9 Ga). At the Late Caledonian stage, the redistribution of the substance of these blocks and the external supply of material led to the formation of heterogeneous crust of turbidite basins with an oceanic basement and andesite-dacitic upper-crustal protoliths (T_Nd(DM-2st) varies from 0.8–0.9 Ga in the framing of the volcanic arc of Altaids to 1.4–1.6 Ga at the boundary of the Altai–Mongolian microcontinent).     

4D architecture and tectonic evolution of the Laverton region,eastern Yilgarn Craton,Western Australia

The Laverton region, located in the eastern Yilgarn Craton (EYC) Western Australia, is second only to the Kalgoorlie region for gold endowment. The integration of high-density, potential-field data, regional- and camp-scale seismic reflection data, regional- and mine-scale structural analysis, and geochronologically-constrained stratigraphy, provided new insights into the 4D architecture and tectonic evolution of Laverton region.     

Decolorization of different azo dyes by Phanerochaete chrysosporium RP78 under optimal condition

Detoxification of synthetic dyes is one of the main challenges in clearing textile industry wastes. Biodegradation of azo-dyes using Phanerochaete chrysosporium is one the most environmentally friendly methods available. The main enzymes responsible for mycodecolorization process are lignin and manganese peroxidases. Here, optimization of expression conditions has been carried out with manipulating culture condition and nutrient sources. Therefore, the effects of buffer and temperature as well as nitrogen source on lignin peroxidase and manganese peroxidase production were investigated at two levels and four levels, respectively. For this purpose, P. chrysosporium RP78 based on Taguchi design of experiment has been applied. Maximum lignin and manganese peroxidase activities of 182 ± 2.5 U/L and 850 ± 41 U/L were obtained under predicted optimum conditions, respectively. Thereby, about 100 % decolorization was achieved after 24 h for two most widely used groups of azo dyes in textile industry consisting reactive and acidic. The physical adsorption of the azo dyes by mycelia was not significant which indicated that the enzymatic degradation of the dyes was occurred. Time profile of these enzymes showed that manganese peroxidase was peaked on 9^th day while lignin peroxidase peaked on 13^th day and remained stable in the culture. The extracellular expression profiles of both were studied by 2 dimensional gel electrophoresis to partially characterize the enzymes.     

Assessment of airborne bacteria and fungi in an indoor and outdoor environment

Airborne indoor and outdoor bacteria and fungi were assessed during the spring season using conventional methods to investigate the enumeration and identification of airborne micro-organisms. This was determined through air quality sampling using the ‘open plate technique’. The air samples were collected during the spring season (March-May) from four different locations. Conventional enumeration of airborne micro-organisms relies on culture-based or microscopic methods. Although a culture-based analysis is most widely used for bio-aerosol, four public places located in urban residential areas were selected for indoor/outdoor air bio-pollutant measurement. The public places included kitchens, classrooms, recreational areas, laboratories. Public parks are an important facility associated with the environmental exposure of children. Cultivation and total microscopic enumeration methods were employed for the sample analysis. 26 groups of bacteria and fungi, either of human or environmental origin were detected. Environmental agents generally predominated while significantly higher counts were detected as the level of hygiene or standard of housing dropped. Seven genera of fungi, mainly members of the genus Aspergillum, were isolated from all residents. Bacteria shows higher growth numbers as opposed to the slow growing fungi. Sample collection and pretreatment, determination techniques and performance results are summarized and discussed.     

Tidal variability in the water quality of an urbanized estuary

Tide and water quality data were collected concurrently in the Hackensack River estuary (HRE), a tidal tributary of the New York-new Jersey Harbor estuary. Harmonic analyses of tidal elevation data indicate that HRE tides are predominantly semidiurnal, though modulated by diurnal and fortnightly components. Nearly uniform tidal ranges (averaging approximately 1.6 m) were observed at three stations within the HRE. Periodogram estimates reveal significant tidal variability for the water quality parameter NH₄−N under dry-weather conditions. Lag correlation analyses associate NH₄−N concentration variations with water level fluctuations. Longitudinal profile plots for NH₄−N reveal a consistent pattern of tidal translations, with peak concentrations oscillating about a major wastewater discharger. These analyses suggest that the distribution of NH₄−N concentrations in the HRE is controlled primarily by major point source loadings and horizontal advection. A simplified, one-dimensional model is used to describe this distribution. Effects of tidal variability in masking water quality status and waak trends are also analyzed. These analyses highlight the potential importance of short-term water quality variability in tidal estuaries where concentration gradients are large.     

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

Dissolution and precipitation rates of brucite (Mg(OH)₂) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10⁻⁴ to 3 M), saturation index (−12 < log Ω < 0.4) and aqueous magnesium concentrations (10⁻⁶ to 5·10⁻⁴ M). Brucite surface charge and isoelectric point (pH_IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH_IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m²) and lack of dependence on ionic strength predicts the dominance of >MgOH₂⁺ species at pH < 8 and their progressive replacement by >MgOH° and >MgO⁻ as pH increases to 10-12. Rates are proportional to the square of >MgOH₂⁺ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH₂⁺ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: