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.     

Rate of growth of the preserved North American continental crust: Evidence from Hf and O isotopes in Mississippi detrital zircons

Detrital zircons from the Mississippi River have been analyzed for U-Th-Pb, Lu-Hf and O isotopes to constrain the rate of growth of the preserved North American continental crust. One hundred and forty two concordant zircon U/Pb dates on grains mounted in epoxy, obtained by Excimer laser ablation ICP-MS method, resolved six major periods of zircon crystallization: 0-0.25, 0.3-0.6, 0.95-1.25, 1.3-1.5, 1.65-1.95 and 2.5-3.0 Ga. These age ranges match the ages of the recognized lithotectonic units of the North American continent in the hinterland of the Mississippi River. Ninety-six zircons mounted on tape, which show no age zonation and were within 7.5% of concordance, were selected to represent the six U/Pb age time intervals and analyzed for Lu-Hf and O isotope by laser ablation MC-ICP-MS and SHRIMP II, respectively. The δ¹⁸O values of the zircons show a small step increase in the maximum δ¹⁸O values at the Archean-Proterozoic boundary from 7.5‰ in the Archean to 9.5‰, and rarely 13‰, in the Proterozoic and Phanerozoic. However, the average value of δ¹⁸O in zircons changes little with time, showing that the increase in the maximum δ¹⁸O values between 2.5 and 2.0 Ga, which can be attributed to an increase in the sediment content of the source regions of younger granitoids, is largely balanced by an increase in zircons with anomalously low δ¹⁸O, which can be attributed to hydrothermally altered crust in the granitoid source region.εHf_i values for the zircons range from 13.1 to −26.9. Zircons derived from juvenile crust, which we define as having mantle δ¹⁸O (4.5-6.5‰) and lying within error of the Hf depleted mantle growth curve, are rare or absent in the Mississippi basin. The overwhelming majority of zircons crystallized from melted pre-existing continental crust, or mantle-derived magmas that were contaminated by continental crust. The average time difference between primitive crust formation and remelting for each of the recognized lithotectonic time intervals, which is defined as crustal incubation time in this study, is 890 ± 460 Myr. There is also a suggestion that the crustal incubation time increases with decreasing age in the Mississippi basin, which is consistent with the declining role of radioactive heat production in the lower crust with time.The average Hf model age (1.94 Ga), weighted by fraction of zircons in the river load is in reasonable agreement with the Nd model age (1.7 Ga) for the Mississippi River. However, if the zircons are weighted by the area of North America covered by the six recognized periods of zircon crystallization the average model age is 2.35 Ga, which compares favorably with an area weighted Nd model age of 2.36 Ga. Our preferred approach is to use the measured O isotope values to constrain variations in the ¹⁷⁶Lu/¹⁷⁷Hf ratio of the granitic source region from which the zircons crystallized, making the assumption that zircons with mantle-like O isotopic ratios have higher ¹⁷⁶Lu/¹⁷⁷Hf than zircons with higher O isotope values. This method gives an average Hf model age of 2.53 Ga, which is 180 Myr older than the constant ¹⁷⁶Lu/¹⁷⁷Hf calculation.The area weighted zircon Hf model ages show two distinct periods of crust formation for the North American continent, 1.6-2.2 and 2.9-3.4 Ga. At least 50% of the preserved North American continental crust was extracted from the mantle by 2.9 Ga and 90% by 1.6 Ga. Two similar periods of crustal growth are also recognized in Gondwana (Hawkesworth C. J. and Kemp A. I. S. (2006) Using hafnium and oxygen isotopes in zircons to unravel the record of crustal evolution. Chem. Geol.226, 144-162.), suggesting that these may be periods of global continental crustal growth. However, we stress that more data from other continents are required before the hypothesis of episodic global continental growth can be accepted with confidence.     

Statistical Modeling of Monthly Anomalies of Atmospheric Precipitations for the Region of the Ukraine and Black Sea

The data array accumulated for the period 1946–1995 is used to select the most significant predictor of monthly anomalies of precipitation in the region of the Ukraine and Black Sea, namely, a large-scale circulation in a sector covering the North Atlantic and Europe. Three large-scale predictors (geopotential at a level of 500GPa, sea-level pressure, and the difference between the geopotentials at levels of 500 and 1000GPa) give almost identical results: their correlation with anomalies of precipitation is equal to 0.7–0.8 in winter and 0.4–0.5 in summer. The predominant mechanism of the influence of circulation on precipitations at low frequencies is the response of the trajectories of European cyclones to changes in the upper-tropospheric jet currents in the Atlantic-European sector described as the superposition of the North-Atlantic oscillation and the Eurasian mode. The decomposition of the fields of precipitations and circulation in the eigenmodes of the canonical correlation analysis opens a possibility of direct computation of the monthly average fields of precipitations for the entire territory of the Ukraine and Black Sea region according to the large-scale geopotential fields.     

Distribution of heavy metals in the core sediments of a tropical wetland system

Five sediment cores from the fresh water region of the Vembanad wetland system were studied for the trace element contents The average concentration of iron, manganese, nickel, copper, zinc, cadmium, lead, mercury and chromium were determined. The core samples were collected using gravity type corer, digested with a mixture of nitric acid and perchloric acid and analyzed by atomic absorption spectrophotometry. Heavy metals such as iron, copper, nickel and zinc reported enrichment towards the surface of the core sediment sample collected from the centre of the lake. Lead, cadmium and mercury showed uniform distribution through out the core. Quality of the sediments were evaluated based on sediment quality guidelines, pollution load index, sum of toxic units and with effect range low/effect range median and threshold effect level/probable effect level values of Environmental Protection Agency guidelines. The degree of contamination for each station was determined. The concentration of different heavy metals has been compared with the world average concentration of shale values. Results of the analysis showed that Vembanad lake is facing serious metal pollution with increased rate of deposition.     

Dynamics of Saxothuringian subduction channel/wedge constrained by phase‐equilibria modelling and micro‐fabric analysis

Subduction and exhumation dynamics can be investigated through analysis of metamorphic and deformational evolution of associated high‐grade rocks. The Erzgebirge anticline, which forms at the boundary between the Saxothuringian and Teplá‐Barrandian domains of the Bohemian Massif, provides a useful study area for these processes owing to the occurrence of numerous meta‐basites preserving eclogite facies assemblages, and coesite and diamond bearing quartzofeldspathic lithologies indicating subduction to deep mantle depths. The prograde and retrograde evolution of meta‐basite from the Czech portion of the Erzgebirge anticline has been constrained through a combination of thermodynamic modelling and conventional thermobarometry. Garnet growth zoning indicates that the rocks underwent burial and heating to peak conditions of 2.6 GPa and at least 615 °C. Initial exhumation occurred with concurrent cooling and decompression resulting in the growth of amphibole and zoisite poikiloblasts overgrowing and including the eclogite facies assemblage. The development of clinopyroxene–plagioclase–amphibole symplectites after omphacite and Al‐rich rims on matrix amphibole indicate later heating at the base of the lower crust. Omphacite microstructures, in particular grain size analysis and lattice‐preferred orientations, indicate that the prograde evolution was characterized by a constrictional strain geometry transitioning into plane strain and oblate fabrics during exhumation. The initial constrictional strain pattern is interpreted as being controlled by competing slab pull and crustal buoyancy forces leading to necking of the subducting slab. The transition to plane strain and flattening geometries represents transfer of material from the subducting lithosphere into a subduction channel, break‐off of the dense slab and rebound of the buoyant crustal material.     

Neutral sodium atoms release from the surface of the Moon induced by meteoroid impacts

In this work, we calculate the vapour and neutral Na production rates on the Moon, as due to the impacts of meteoroids in the radius range of 10⁻⁸–0.15 m. We limit our calculations to this size range, since meteoroids with radius larger than 0.15 m have not been found to be important for the production of the exosphere in a time interval comparable with that of the observations.
We have considered a new dynamical model of the flux of meteoroids at the heliocentric distance of the Moon, regarding objects in the radius range of 10⁻²–0.15 m. Instead, the flux of smaller meteoroids (radius range 10⁻⁸–10⁻² m) has been calculated using the two distributions adopted by Cintala and Love & Brownlee.
The results of our model are that (i) the neutral Na production rate is  ∼3–4.9 × 10⁴ atoms cm⁻² s⁻¹  , slightly larger than the previous estimates  (∼2–3 × 10⁴ atoms cm⁻² s⁻¹)  , and (ii) only about 6 per cent of neutral Na is produced by the impacts of meteoroids in the size range 10⁻³–0.15 m, whereas about 94 per cent of the Na comes from the  10⁻⁵–10⁻³ m  size range.     

Unique isoprene oxidation products demonstrate chlorine atom chemistry occurs in the Houston,Texas urban area

As part of the 2000 Texas Air Quality Study (TexAQS), we studied the isoprene oxidation process under ambient conditions to discern the presence of chlorine atom (Cl) chemistry in the Houston, Texas urban area. By measuring chloromethylbutenone (CMBO) and an isomer of chloromethylbutenal (CMBA), we clearly observed sixteen episodes of active Cl chemistry during the 24-day experiment. Estimated median Cl concentration during each of these episodes was between the detection limit of ~10² atoms cm⁻³ and 50 _{- 30} ^{+ 70} ×10⁴ 50_{ - 30}^{ + 70} \times {10^4} atoms cm⁻³. Cl concentration during all the episodes averaged 7.6 _{- 2.0} ^{+ 4.7} ×10⁴ 7.6_{ - 2.0}^{ + 4.7} \times {10^4} atoms cm⁻³ and thus amounted to less than 3% of the OH concentration during the same periods. During the episodes, the fraction of oxidation chemistry initiated by Cl ranged from 3–43% and was strongly dependent on the quantity and type of hydrocarbons present in the atmosphere. Because of its intermittent presence and low concentration, Cl is not a broadly influential oxidant in the Houston, Texas urban area.     

Water renewal estimates for aquaculture developments in the Richibucto estuary,Canada

Water renewal in semi-enclosed coastal areas is crucial for the supply of oxygen and seston and for the removal of organic loadings from finfish or shellfish aquaculture sites. Water renewal depends on hydrodynamic processes and can have a complex spatial distribution due to irregular topographic features. This study describes some physical oceanography observations gathered in the Richibucto estuary, New Brunswick, Canada, and provides an estimate of the spatial distribution of water renewal in the North Arm, a location in the estuary where the largest American oyster (Crassostrea virginica) aquaculture operation in eastern Canada is located. The estuary changes from a well mixed estuary to a partially stratified estuary depending on runoff conditions. Tides are mixed but mainly diurnal due to the nearby presence of the second M₂ amphidromic point in the Gulf of St. Lawrence. Tidal amplitudes vary from 0.3 to 0.6 m and show a slight increase some 35 km upstream. Currents in the main channel can reach over 0.60 m s⁻¹ during ebb and 0.3 m s⁻¹ during flood, with a slack water period of approximately 8 h. Low frequency sea level fluctuations have a range of 0.5 m at the mouth and are coherent within the estuary. Hydrodynamic and advection-dispersion models are used to calculate the spatial distribution of the local renewal time (LRT) in the North Arm for high and low freshwater discharge conditions, using the dissolved tracer method. Results show that the LRT varies from less than 5 d at the downstream end of the North Arm to over 100 d further upstream. When averaged over the entire North Arm, the integral renewal time (IRT) is estimated to vary only from 8 to 21 d depending on the season. The LRT and IRT estimates are major improvements over conventional renewal estimates using tidal prism methods.     

Dynamo currents representing geomagnetic L variation demonstrated by a multi-layer ionospheric model

A multi-layer ionospheric model and lunar (2,2) tidal mode have been used to calculate dynamo current systems representing lunar geomagnetic semidiurnal variations. Since both the height variation of the ionospheric conductivities and latitudinal dependence of the height of the conductivity peaks have been taken into account, the dynamo current systems agree with equivalent ones (estimated from geomagnetic data) better than those for a thin shell model of the ionospheric conductivity, especially in the polar region.