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.     

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.     

GPS for real-time earthquake source determination and tsunami warning systems

We identify the key design aspects of a GPS-based system (and in the future, GNSS-based systems) that could contribute to real-time earthquake source determination and tsunami warning systems. Our approach is based on models of both transient and permanent displacement of GPS stations caused by large earthquakes, while considering the effect of GPS errors on inverted earthquake source parameters. Our main conclusions are that (1) the spatial pattern, magnitude, and timing of permanent displacement of GPS stations can be inverted for the earthquake source and so predict the 3D displacement field of the ocean bottom, thus providing the initial conditions for tsunami models, and (2) there are no inherently limiting factors arising from real-time orbit and positioning errors, provided sufficient near-field GPS stations are deployed. This signal could be readily exploited by GPS networks currently in place, and will be facilitated by the IGS Real-Time Project as it comes to fruition.     

Petrogenesis of voluminous mid-Tertiary ignimbrites of the Sierra Madre Occidental,Chihuahua, Mexico

The mid-Tertiary ignimbrites of the Sierra Madre Occidental of western Mexico constitute the largest continuous rhyolitic province in the world. The rhyolites appear to represent part of a continental magmatic arc that was emplaced when an eastward-dipping subduction zone was located beneath western Mexico.In the Batopilas region of the northern Sierra Madre Occidental the mid-Tertiary Upper Volcanic sequence is composed predominantly of rhyolitic ignimbrites, but volumetrically minor lava flows as mafic as basaltic andesite are also present. The basaltic andesite to rhyolite series is calc-alkalic and contains 1% K₂O at 60% SiO₂. Trace element abundances of a typical ignimbrite with 73% SiO₂ are Sr 225 ppm, Rb 130 ppm, Y 32 ppm, Th 12 ppm, Zr 200 ppm, and Nb 15 ppm. The entire series plots as coherent and continuous trends on variation diagrams involving major and trace elements, and the trends are distinct from those of geographicallyassociated rocks of other suites. We interpret these and other geochemical variations to indicate that the rocks are comagmatic. Mineral chemistry, Sr isotopic data, and REE modelling support this interpretation.Least squares calculations show that the major element variations are consistent with formation of the basaltic andesite to rhyolite series by crystal fractionation of observed phenocryst phases in approximate modal proportions. In addition, calculations modelling the behavior of Sr with the incompatible trace element Th favor a fractional crystallization origin over a crustal anatexis origin for the rock series. The fractionating minerals included plagioclase (> 50%), and lesser amounts of Fe-Ti oxides, pyroxenes, and/or hornblende. The voluminous ignimbrites represent no more than 20% of the original mass of a mantle-derived mafic parental magma.     

Geologic sources and geographic distribution of sand tempers in prehistoric potsherds from the Mariana Islands

Temper sands in prehistoric potsherds of the Mariana Islands include terrigenous detritus derived from Paleogene volcanic bedrock and calcareous grains derived chiefly from modern fringing reefs, but also in part from uplifted Neogene limestones overlying volcanic bedrock. Calcareous sands are nondiagnostic of island of origin, but volcanic sands and the terrigenous component of hybrid sands composed of mixed terrigenous and calcareous grain types can be traced to geologic sources on Saipan and Guam, the only occupied islands where volcanic bedrock is extensively exposed. Quartzose tempers of several types were derived exclusively from dacitic volcanic rocks on Saipan. Nonquartzose tempers of andesitic parentage derive from both Saipan and Guam, but abundance of orthopyroxene as well as clinopyroxene is diagnostic of Saipan andesitic tempers, the presence of olivine is diagnostic of selected tempers from Guam, and placer temper sands rich in heavy ferromagnesian minerals occur only in sherds on Guam. Temper analysis documents widespread ceramic transfer from Saipan to other islands throughout Mariana prehistory, and more restricted ceramic transfer from Guam to nearby Rota, although the origin of some andesitic temper types is petrographically indeterminate. © 2001 John Wiley & Sons, Inc.     

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.