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.     

Late-glacial and Holocene vegetation and climatic history of the Cass Basin, central South Island, New Zealand

Lithology, pollen, macrofossils, and stable carbon isotopes from an intermontane basin bog site in southern New Zealand provide a detailed late-glacial and early Holocene vegetation and climate record. Glacial retreat occurred before 17,000 cal yr B.P., and tundra-like grassland–shrubland occupied the basin shortly after. Between 16,500 and 14,600 cal yr B.P., a minor regional expansion of forest patches occurred in response to warming, but the basin remained in shrubland. Forest retreated between 14,600 and 13,600 cal yr B.P., at about the time of the Antarctic Cold Reversal. At 13,600 cal yr B.P., a steady progression from shrubland to tall podocarp forest began as the climate ameliorated. Tall, temperate podocarp trees replaced stress-tolerant shrubs and trees between 12,800 and 11,300 cal yr B.P., indicating sustained warming during the Younger Dryas Chronozone (YDC). Stable isotopes suggest increasing atmospheric humidity from 11,800 to 9300 cal yr B.P. Mild (annual temperatures at least 1°C higher than present), and moist conditions prevailed from 11,000 to 10,350 cal yr B.P. Cooler, more variable conditions followed, and podocarp forest was completely replaced by montane Nothofagus forest at around 7500 cal yr B.P. with the onset of the modern climate regime. The Cass Basin late-glacial climate record closely matches the Antarctic ice core records and is in approximate antiphase with the North Atlantic.     

The “El Pilote” fluorite skarn: A crucial deposit in the understanding and interpretation of the origin and mobilization of F from northern Mexico deposits

Fluorite deposits are widespread in northern Mexico and those deposits have traditionally been categorized as exclusively hydrothermal–magmatic in origin. Recently, two different fluorite-bearing type models have been proposed for the Northern Mexican deposits: (1) MVT-like deposits formed from basinal brines mobilized during the Laramide Orogeny (La Encantada deposit, Gonzalez-Partida et al., [Gonzalez-Partida, E., Carrillo-Chavez, A., Grimmer, J.O.W., Pironon, J., 2002. Petroleum-rich fluid inclusions in fluorite, Purisima mine, Coahuila, Mexico. International Geological Review 44 (8), 751–763.]; Tritlla et al., [Tritlla, J., Gonzalez-Partida, E., Levresse, G., Banks, D., Pironon, J., 2004. Fluorite deposits at Encantada-Buenavista, Mexico: products of Mississippi Valley type processes — a reply. Ore Geology Reviews 25, 329–332.]); and (2) fluorite-bearing skarns in close contact with rhyolite intrusives (Levinson, [Levinson, A.A., 1962. Beryllium–fluorine mineralization at Aguachile Mountain, Coahuila, Mexico. American Mineralogist 47, 67–75.]). The El Pilote fluorite deposit falls into the second category, and is the only known example of a magmatic-related fluorite deposit in the area. The fluorite trace-element patterns from both the El Pilote skarn and La Encantada MVT deposits display comparable and very low relative abundances as well as comparable chondrite-normalized REE patterns; this would suggest that the skarn F-source comes from the remobilization of a MVT fluorite manto.     

Earthquake evidence for compressive stress in the southeast Australian crust

Earthquakes in SE Australia are usually caused by compressive stresses acting in the crust, and are associated with steeply dipping faults. Sometimes the faulting is predominantly strike‐slip, as for the Bowning earthquakes of 1977 and some of the Dalton/Gunning earthquakes; and sometimes it is high‐angle thrust faulting, as for the 1961 Robertson and 1973 Picton earthquakes. No surface expression of the faults associated with any recent earthquakes in SE Australia has been reported.

The directions of the pressure axes, from all the earthquakes for which focal mechanisms have been determined, do not form a consistent pattern. This suggests that the faulting associated with earthquakes in SE Australia is dominated by the geometry of pre‐existing crustal faults or zones of weakness.

In situ stress measurements have not been made near the epicentral areas of the larger recent earthquakes, because of the absence of competent, near‐surface rocks coupled to the crust. However, in the western part of the Lachlan Fold Belt the in situ stress results indicate that the maximum pressure axis is approximately E‐W. The evidence from the focal mechanisms does not preclude the persistence of this stress regime farther to the east, and a regional compressive stress in the crust with an azimuth of about 120° is consistent with most of the earthquake focal mechanisms and the in situ stress measurements throughout SE Australia.     

Transport and accumulation of organochlorines in the ovaries of Atlantic croaker (Micropogonias undulatus)

The role of vitellogenin in the transport of organochlorines was investigated in Atlantic croaker (Micropogonias undulatus) by exposing them through the diet to o,p′-DDT at a concentration of 10.8 μg/100 g fish/day for 14 days or Aroclor 1254 (PCB) at a concentration of 0.5 mg/100 g fish/day for 30 days during gonadal recrudescence. Tissue samples were taken from the fish at various times after initial exposure, and o,p′-DDT and PCBs were extracted in acetonitrile and analyzed by gas chromatography. Analysis of the ovarian tissue collected 2 and 3 weeks from the start of exposure revealed that the o,p′-DDT concentration increases as the gonadosomatic index (GSI) increases (r² = 0.63), with accumulation ranging from less than 1% to as much as 8% of the total dosage. Interestingly, o,p′-DDT did not accumulate in the testes during the same exposure period. Accumulation of PCBs was found to be 40 times higher in the ovaries than in the testes. Gel filtration of plasma from exposed females showed that o,p′-DDT elutes in the low density lipoprotein and vitellogenin fractions. Control plasma incubated with o,p′-DDT at 4 °C for 16 h followed by chromatography on Sepharose 6B gave similar results with an o,p′-DDT concentration of 0.6μg/mg protein in the vitellogenin fraction. Furthermore, both o,p′-DDT and PCBs were found to bind to purified croaker vitellogenin. These results suggest that lipoproteins, including vitellogenin, are involved in the transport and accumulation of organochlorines in the ovaries of exposed fish.     

The X-ray and extreme-ultraviolet flux evolution of SS Cygni throughout outburst

We present the most complete multiwavelength coverage of any dwarf nova outburst: simultaneous optical, Extreme Ultraviolet Explorer and Rossi X-ray Timing Explorer observations of SS Cygni throughout a narrow asymmetric outburst. Our data show that the high-energy outburst begins in the X-ray waveband 0.9–1.4 d after the beginning of the optical rise and 0.6 d before the extreme-ultraviolet rise. The X-ray flux drops suddenly, immediately before the extreme-ultraviolet flux rise, supporting the view that both components arise in the boundary layer between the accretion disc and white dwarf surface. The early rise of the X-ray flux shows that the propagation time of the outburst heating wave may have been previously overestimated.
The transitions between X-ray and extreme-ultraviolet dominated emission are accompanied by intense variability in the X-ray flux, with time-scales of minutes. As detailed by Mauche & Robinson, dwarf nova oscillations are detected throughout the extreme-ultraviolet outburst, but we find they are absent from the X-ray light curve.
X-ray and extreme-ultraviolet luminosities imply accretion rates of  3 × 10¹⁵ g s⁻¹  in quiescence,  1 × 10¹⁶ g s⁻¹  when the boundary layer becomes optically thick, and  ∼10¹⁸ g s⁻¹  at the peak of the outburst. The quiescent accretion rate is two and a half orders of magnitude higher than predicted by the standard disc instability model, and we suggest this may be because the inner accretion disc in SS Cyg is in a permanent outburst state.     

Aetideus and Euaetideus (copepoda: Calanoida) from the Atlantic and Pacific Oceans

The genus Euaetideus Sars, 1925 is here merged with Aetideus Brady, 1883 (Copepoda : Calanoida : Aetideidae). Three new species of the genus Aetideus are described from the Pacific as well as the males of three other known species. A key is given to the known males and females in the genus Aetideus. The closely related genera Paivella and Snelliaetideus are compared with Aetideus.     

1D PetroMod software modeling of the Basrah oil fields, Southern Iraq

1D (Petromod) hydrocarbon charge modeling and source rock characterization of the Lower Cretaceous and Upper Jurassic underlying the prolific Cretaceous and Tertiary reservoirs in the Basra oilfields in southern Iraq. The study is based on well data of the Majnoon, West Qurna, Nahr Umr, Zubair, and Rumaila oil fields. Burial histories indicate complete maturation of Upper Jurassic source rocks during the Late Cretaceous to Paleogene followed by very recent (Neogene) maturation of the Low/Mid Cretaceous succession from early to mid-oil window conditions, consistent with the regional Iraq study of Pitman et al. (Geo Arab 9(4):41–72, 2004). These two main phases of hydrocarbon generation are synchronous with the main tectonic events and trap formation associated with Late Cretaceous closure of the neo-Tethys; the onset of continent–continent collision associated with the Zagros orogeny and Neogene opening of the Gulf of Suez/Red Sea. Palynofacies of the Lower Cretaceous Sulaiy and Lower Yamama Formations and of the Upper Jurassic Najmah/Naokelekan confirm their source rock potential, supported by pyrolysis data. To what extent the Upper Jurassic source rocks contributed to charge of the overlying Cretaceous reservoirs remains uncertain because of the Upper Jurassic Gotnia evaporite seal in between. The younger Cretaceous rocks do not contain source rocks nor were they buried deep enough for significant hydrocarbon generation.     

Travel time controls the magnitude of nitrate discharge in groundwater bypassing the riparian zone to a stream on Virginia's coastal plain

Groundwater that bypasses the riparian zone by travelling along deep flow paths may deliver high concentrations of fertilizer‐derived NO₃^? to streams, or it may be impacted by the NO₃^? removal process of denitrification in streambed sediments. In a study of a small agricultural catchment on the Atlantic coastal plain of Virginia's eastern shore, we used seepage meters deployed in the streambed to measure specific discharge of groundwater and its solute concentrations for various locations and dates. We used values of Cl^? concentration to discriminate between bypass water recharged distal to the stream and that contained high NO₃^? but low Cl^? concentrations and riparian‐influenced water recharged proximal to the stream that contained low NO₃^? and high Cl^? concentrations. The travel time required for bypass water to transit the 30‐cm‐thick, microbially active denitrifying zone in the streambed determined the extent of NO₃^? removal, and hydraulic conductivity determined travel time through the streambed sediments. At all travel times greater than 2 days, NO₃^? removal was virtually complete. Comparison of the timescales for reaction and transport through the streambed sediments in this system confirmed that the predominant control on nitrate flux was travel time rather than denitrification rate coefficients. We conclude that extensive denitrification can occur in groundwater that bypasses the riparian zone, but a residence time in biologically active streambed sediments sufficient to remove a large fraction of the NO₃^? is only achieved in relatively low‐conductivity porous media. Instead of viewing them as separate, the streambed and riparian zone should be considered an integrated NO₃^? removal unit. Copyright © 2011 John Wiley & Sons, Ltd.