Characterization of hydrothermally generated oil from the Uzon caldera,Kamchatka

This paper reports the analyses of unusual oils that accumulate in the Uzon Caldera, situated in the central volcanic region of Kamchatka, Russia. Gas chromatography–mass spectrometry (GC–MS) was used to determine the primary constituents, and the ¹³C and ¹⁴C compositions provided information about the potential source and age of the oils. The ¹⁴C ages determined are 1030 ± 40 a BP (measured) or 940 ± 40 a BP (conventional). The δ¹³C value is −30.6‰ versus the PDB standard, a value consistent with a biological origin. The nearly contemporary age of the C content indicates a geologically recent origin from biogenic detritus and not by synthesis from mantle C. The biogenic origin is supported by the presence of sterane and hopane biomarkers and the δ¹³C value of the bulk oil. The overall compositions of the oils indicate that they are derived from rapid hydrothermal alteration of algal/bacterial mat detritus buried by volcanic ashfall deposits of the Uzon Caldera. The oils represent the youngest hydrothermal petroleum reported to date.     

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.     

Origin of petroliferous bitumen from the Büyük Menderes–Gediz geothermal graben system,Denizli – Sarayköy,western Turkey

The KB-5 well is located at the intersection of the geothermally active Menderes and Gediz graben systems in western Turkey. Significant volumes of “petroleum-like material” (PLM) with its associated thermal water (120 °C) erupted onto the surface during drilling from a depth of 120–132 m (i.e., from the claystone and marl-rich Early to Middle Pliocene Kolonkoya formation). The purpose of this paper is: (1) to characterize this PLM, (2) to assess the source characteristics from which the PLM was likely generated, and (3) to recognize the generation mechanism considering the geothermal-gradual versus the hydrothermal-rapid processes. Analytical organic geochemistry using thin layer chromatographic separation followed by gas chromatography–mass spectrometry (GC–MS) was carried out.     

Characteristics of lipid tracer compounds transported to the Arabian Gulf by runoff from rivers and atmospheric dust transport

River runoff and atmospheric fallout (dust and air particulate matter) are major input sources of natural and anthropogenic terrestrial organic and inorganic components to the Arabian seas. In this study, we report on the various lipid tracer compounds that might be transported to the Arabian Gulf by rivers, dust, and air particulate matter. These are based on geochemical analysis of sediment, dust, and particulate samples collected from Iraq, Kuwait, and Saudi Arabia. The samples were extracted with a dichloromethane/methanol mixture and analyzed by gas chromatography-mass spectrometry. The extractable organic compounds (lipids) in the samples include n-alkanes, n-alkanoic acids, n-alkanols, methyl n-alkanoates, steroids, triterpenoids, carbohydrates, and petroleum hydrocarbons. The steroids and triterpenoids were major components in river and wetland samples. The major sources of these lipids were from natural vegetation, microbial (plankton and bacteria) residues in the sediments, sand, and soils, with some contribution from anthropogenic sources. Accordingly, these sources could be major inputs to the Arabian seas besides the autochthonous marine products. Future studies of the organic and inorganic biogeochemistry on river, dust, and coastal areas are needed to characterize the various regional sources, transformation, and diagenetic processes of the organic matter en route to the marine environment.     

Extended saturated and monoaromatic tricyclic terpenoid carboxylic acids found in Tasmanian tasmanite

A series of tricyclic terpenoid carboxylic acids (C₂₀–C₄₀) was found in the acidic fraction of Tasmanian tasmanite bitumen, occurring as a mixture of stereoisomers with mainly the 13β(H), 14α(H)-and 13α(H),14α(H)-configurations. These dominant acidic tricyclic constituents have the same carbon skeleton as the ubiquitous tricyclic terpane biomarkers. A novel series of ring-C monoaromatic tricyclic terpenoid carboxylic acids was also characterized. The series ranges from C₁₉ to C₃₉ and is the acidic counterpart of the recently described series of monoaromatic tricyclic terpanes.     

13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500°C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of ¹³C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The ¹³C CP/MAS results appear to provide a good measure of thermal alteration.     

Stereochemical studies of acyclic isoprenoid compounds—V. Oxidation products of Green River Formation oil shale kerogen

Gas chromatographic analysis of the major isoprenoid carboxylic acids and the major ketone (6,10,14-trimethylpentadecan-2-one), derived from successive chromic acid oxidations of the kerogen of Green River Formation oil shale, indicates that their stereochemistry is compatible with the hypothesis that phytol or a derivative with the same carbon skeleton and stereochemistry was incorporated into the kerogen matrix.     

Organic geochemical evidence for a regional stratigraphic thermal event in East China

A systematic investigation of the petroleum exploratory well N-13 within the Huangqiao region, Lower Yangtze Basin, East China, has been carried out using multiple analytical techniques of organic geochemistry. The past occurrence of a thermal event has been recognized based on changes in optical vitrinite reflectance (R_o), pyrolysis peak temperature (T_max) and chemical hydrogen index (HI), potential degradation rate (D), the atomic H/C ratio and dimethylphenanthrene ratios (DPR, DPR₁ and DPR₂) in the sedimentary rocks. The geological significance of this thermal event is discussed in this paper.     

Composition and sources of organic matter in atmospheric PM10 over a two year period in Beijing, China

The solvent-extractable organic compounds of atmospheric PM₁₀ samples, collected over two years beginning in 2003 at urban and suburban sites of Beijing, were characterized using gas chromatography–mass spectrometry (GC–MS). The elemental carbon (EC) contents were determined and ranged from 4.3 to 42 μg m^− 3. Organic compounds in total extracts were identified and included unresolved complex mixture (UCM) and series of n-alkanes, n-alkanols, n-alkanoic acids, polycyclic aromatic hydrocarbons (PAHs); saccharides, alkanedioic acids, steroids, and other biomarkers and source tracers. The seasonal variations of their relative abundances are discussed. The abundance order for the major molecular classes in the particulate organic matter (POM) was the following: UCM > saccharides > n-alkanoic acids >n-alkanes > n-alkanols > PAHs > hydroxy-PAHs > other biomarker tracers. Based on the genetic significance of the molecular tracers, the dominant sources of POM are proposed for the two sampling sites. The emissions from fossil fuel use (both coal and petroleum products), biomass combustion, other pyrolysis sources, higher plant wax, and secondary products contribute > 98.0% of the POM mass. The fossil fuel use (average = 65% of POM) is the largest contributor and derives mainly from vehicular traffic.     

Organic geochemistry of geographically unrelated tasmanites

The biomarker analysis of three tasmanite rock samples from Tasmania, Alaska and Brazil showed an unusually high tricyclic terpane concentration relative to hopanes and steranes. A possible product-precursor relationship is advanced, associating Tasmanaceae alage with these tricyclic terpanes. These results support the search of possible precursor molecules in present day organisms which may be taxonomically related to these algae.