FTIR-derived characteristics of fossil-gymnosperm leaf remains of Cordaites principalis and Cordaites borassifolius (Pennsylvanian, Maritimes Canada and Czech Republic)

Cordaites principalis and Cordaites borassifolius, gymnosperm trees of the Carboniferous, are distinguished based on compression and cuticular morphology. A new distinction between them is suggested on the basis of differences in functional groups. Cuticular and compression spectra of C. borassifolius have lower CH₂/CH₃ ratios, suggesting more branched aliphatic chains in comparison with cuticles and compressions of C. principalis. Other differences are observed with Fourier transform infrared spectroscopy (FTIR) technique, but they vary from sample to sample of the two species to suggest other than chemotaxonomic-based sources of variations.     

Chemometric study of functional groups in different layers of Trigonocarpus grandis ovules (Pennsylvanian seed fern, Canada)

We examined four dispersed, coalified ovules, Trigonocarpus grandis, of medullosalean seed-fern affinity from the Late Pennsylvanian age Sydney Coalfield, Canada, which represent the larger type of the 7–8 cm trigonocarpalean form species. At first glance it appears that the ovules are preserved like the usual Carboniferous foliar compressions, i.e. one coalified layer with one preserved anatomical tissue, the cuticle. However, careful sample preparation uncovered at least three coalified layers, and Schulze’s oxidative maceration process, which dissolves the coalified material, revealed several tissue layers. Altogether, eight sample forms were defined: (i) coalified layer, (ii) cuticle A, (iii) cupric + vitrain, (iv) vitrain, (v) cupric, (vi) cuticle B, (vii) alkaline solution and (viii) added coal seam material. The purpose of the study was twofold: first, to systematically analyze the forms by way of Fourier transform infrared (FTIR) spectrometry to fill a gap in chemical information that exits for coalified trigonocarpalean ovules of Carboniferous seed ferns; second, to use principal component analysis to focus on groupings as a function of chemical structure (functional groups) and to assess the different fossil forms in terms of FTIR chemical parameters, based on a 8 × 49 data matrix.Results include distinction among the three coaly sample forms, coalified layer (i), cupric + vitrain (iii) and cupric (v), based mainly, but not exclusively, on differences in carbonyl content, as well as length and branching of the polymethylenic chains. Important to note is the high aliphatic content of the cuticles as a signature of the biomacromolecules cutan/cutin. In particular, new insights into the structure of the original ovule are presented, and differences in chemistry are mainly a result of the complex structure of the precursor plant organ.     

Functional groups of fossil marattialeans: chemotaxonomic implications for Pennsylvanian tree ferns and pteridophylls

Marattialean-fossil foliage, assigned to Pecopteris Brongniart, was an important and widespread floral component in Late Pennsylvanian mires, with phylogenetic affinity to extant marattialean taxa in tropical regions. Marattialean fossil taxonomy is, however, still uncertain. Specimens from the Pilsen limnic Basin, Westphalian D, Czech Republic, represent fertile marattialean foliage of Pecopteris (Asterotheca) nyranensis and Pecopteris (Asterotheca) miltonii, and sterile foliage of Pecopteris aspidioides and Pecopteris polypodioides. Taxonomic parameters for their assignments included cuticle, stomatal morphologies (studied for the first time), and in situ reproductive organs and spores. Chemotaxonomic interpretations hinge on fidelity of preservation of compounds, or molecular fragments thereof, that were synthesized by the once-living plants. This preservation state was possibly due to the thermal history (maximum temperature of 130 °C) in the Pilsen Basin, acidic preservation conditions, lithology and facies stability.Although subtle, the four pecopterid species are differentiable from one another by combined FTIR characteristics, supporting taxonomy. The ratio of CH₂/CH₃ is hypothesized to be a chemotaxonomic parameter for Pennsylvanian pteridophylls, both in seed and true ferns that have previously been studied. It will, however, be supplemented by additional biochemical markers.     

C NMR, micro-FTIR and fluorescence spectra, and pyrolysis-gas chromatograms of coalified foliage of late Carboniferous medullosan seed ferns, Nova Scotia, Canada: Implications for coalification and chemotaxonomy

The cuticles and cuticle-free compressions of three Carboniferous medullosan seed-fern leaf species (Macroneuropteris scheuchzeri, Neuropteris ovata var. simonii and Alethopteris lesquereuxii) were analyzed by elemental, ¹³C nuclear magnetic resonance (NMR), micro-FTIR (Fourier transform infrared) and coal petrographic techniques. The 13C NMR spectra of the cuticle-free compressions and the associated whole coal (high volatile A/B bituminous coal rank) are generally similar and consist of a large aromatic carbon peak, a smaller aliphatic carbon peak and a shoulder on the aromatic peak, representing phenolic carbons. In contrast, the ¹³C NMR spectra of the cuticles from the same leaves have a predominant peak for aliphatic carbons and a much smaller aromatic carbon peak. This difference in aromaticity between the cuticles and the cuticle-free compressions is also reflected in the higher atomic H/C ratios of the cuticles. Micro-FTIR spectra of the cuticles show oxygenated functional groups (carboxyl and ketone) similar to those in modern cuticles but their most characteristic feature is very strong bands in the aliphatic stretching region. The cuticle-free compressions (mainly vitrinite), in turn, show the absence or significant reduction in oxygenated functional groups, reduction in aliphatic stretching bands and, usually, increased absorbance of aromatic out-of-plane deformation in the 700–900 cm⁻¹ region. Fluorescence spectra for the cuticles from all three species show a great similarity with a λ_max at 580–590 nm, probably reflecting a similardegree of coalification, which is consistent with the similar vitrinite reflectance (R_r) and H/C and O/C ratios of the cuticlefree compressions.These results indicate that leaf cuticle-free compressions, which were initially cellulose rich ( 90% cellulose and hemicellulose, < 10% lignin), can alter, during peatification and coalification, to a macromolecular structure similar to that of coalified wood (initially 50% cellulose and hemicellulose, 30%–50% lignin). Thus, a lignin-enriched structure is not a prerequisite for the formation of the macromolecular structure of vitrinite. In addition, the micro-FTIR spectra reveal the complexity of the molecular structure in coalified seed-fern leaves. The micro-FFIR data reveal some significant differences among the cuticles that may be of chemotaxonomic value. Clearly, a combination of macro- and micro-techniques offers a better basis for the interpretation of the molecular structure of pre-macerals and their alteration during peatification and coalification. Also, the data presented in this paper provide important new information that extends the data from morphological and cuticular taxonomic studies of some seed ferns. The data are encouraging preliminary advances in the chemotaxonomy of medullosan seed fern species.Pyrolysis-gas chromatography (PY-GC) data for the cuticles of three seed-fern leaves indicate distinct chemical signatures for the two neuropterid leaves as compared to the Alethopteris leaf. This perhaps indicates a chemotaxomic factor, or it could be related to the greater thickness of the cuticle of Alethopteris. Mass spectrometric data are needed to identify individual components in the PY-GC chromatograms.     

Pyrolytic and spectroscopic studies of Eocene resin from Vastan lignite Mine,Cambay basin,Western India

The molecular structure of an Eocene fossil resin (Vastan, Cambay basin, Western India) has been investigated with complimentary spectroscopic techniques. The FTIR spectrum shows strong aliphatic CH _x (3000–2800 and 1460–1450 cm⁻¹) and CH₃ (1377 cm⁻¹) absorptions and less intense aromatic C=C (1560–1610 cm⁻¹) absorptions. The major products from analytical pyrolysis are cadalene based bicyclic sesquiterpenoids including some bicadinenes and bicadinanes. The polycadinane products confirm the fossil material as an Angiosperm dammar resin, associated with inputs of tropical rain forests supported by past climates.     

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin,West-Central Alabama

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO_2, CH₄, approximately equimolar CO₂ + CH₄ mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45–150 µm, 1–2 mm, and 5–10 mm) of crushed coal were performed at 40 °C and 35 °C over a pressure range of 1.4–6.9 MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO₂ adsorption on both dry and water-saturated coal is much more rapid than CH₄ adsorption; (2) water saturation decreases the rates of CO₂ and CH₄ adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO₂ or CH₄ adsorption if the coal is not previously exposed to CO₂; (3) retention of adsorbed CO₂ on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45–150 μm size fraction compared to the two coarser fractions.     

Thermal maturity and organic composition of Pennsylvanian coals and carbonaceous shales, north-central Texas: Implications for coalbed gas potential

Thermal maturity was determined for about 120 core, cuttings, and outcrop samples to investigate the potential for coalbed gas resources in Pennsylvanian strata of north-central Texas. Shallow (< 600 m; 2000 ft) coal and carbonaceous shale cuttings samples from the Middle-Upper Pennsylvanian Strawn, Canyon, and Cisco Groups in Archer and Young Counties on the Eastern Shelf of the Midland basin (northwest and downdip from the outcrop) yielded mean random vitrinite reflectance (R_o) values between about 0.4 and 0.8%. This range of R_o values indicates rank from subbituminous C to high volatile A bituminous in the shallow subsurface, which may be sufficient for early thermogenic gas generation. Near-surface (< 100 m; 300 ft) core and outcrop samples of coal from areas of historical underground coal mining in the region yielded similar R_o values of 0.5 to 0.8%. Carbonaceous shale core samples of Lower Pennsylvanian strata (lower Atoka Group) from two deeper wells (samples from ~ 1650 m; 5400 ft) in Jack and western Wise Counties in the western part of the Fort Worth basin yielded higher R_o values of about 1.0%. Pyrolysis and petrographic data for the lower Atoka samples indicate mixed Type II/Type III organic matter, suggesting generated hydrocarbons may be both gas- and oil-prone. In all other samples, organic material is dominated by Type III organic matter (vitrinite), indicating that generated hydrocarbons should be gas-prone. Individual coal beds are thin at outcrop (< 1 m; 3.3 ft), laterally discontinuous, and moderately high in ash yield and sulfur content. A possible analog for coalbed gas potential in the Pennsylvanian section of north-central Texas occurs on the northeast Oklahoma shelf and in the Cherokee basin of southeastern Kansas, where contemporaneous gas-producing coal beds are similar in thickness, quality, and rank.     

Methane and carbon dioxide adsorption–diffusion experiments on coal: upscaling and modeling

Numerical modelling of the processes of CO₂ storage in coal and enhanced coalbed methane (ECBM) production requires information on the kinetics of adsorption and desorption processes. In order to address this issue, the sorption kinetics of CO₂ and CH₄ were studied on a high volatile bituminous Pennsylvanian (Upper Carboniferous) coal (VR_r=0.68%) from the Upper Silesian Basin of Poland in the dry and moisture-equilibrated states. The experiments were conducted on six different grain size fractions, ranging from <0.063 to 3 mm at temperatures of 45 and 32 °C, using a volumetric experimental setup. CO₂ sorption was consistently faster than CH₄ sorption under all experimental conditions. For moist coals, sorption rates of both gases were reduced by a factor of more than 2 with respect to dry coals and the sorption rate was found to be positively correlated with temperature. Generally, adsorption rates decreased with increasing grain size for all experimental conditions.Based on the experimental results, simple bidisperse modelling approaches are proposed for the sorption kinetics of CO₂ and CH₄ that may be readily implemented into reservoir simulators. These approaches consider the combination of two first-order reactions and provide, in contrast to the unipore model, a perfect fit of the experimental pressure decay curves. The results of this modeling approach show that the experimental data can be interpreted in terms of a fast and a slow sorption process. Half-life sorption times as well as the percentage of sorption capacity attributed to each of the two individual steps have been calculated.Further, it was shown that an upscaling of the experimental and modelling results for CO₂ and CH₄ can be achieved by performing experiments on different grain size fractions under the same experimental conditions.In addition to the sorption kinetics, sorption isotherms of the samples with different grain size fractions have been related to the variations in ash and maceral composition of the different grain size fractions.     

Geochemistry,Petrography and Spectroscopy of Organic Matter of Clay‐Associated Kerogen of Ypresian Series: Gafsa‐Metlaoui Phosphatic Basin,Tunisia

This work presents geochemical characterization of isolated kerogen out of clay fraction using petrography studies, infrared absorption and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy, with N‐alkane distributions of saturated hydrocarbon. Mineralogical study of clay mineral associations was carried out using X‐ray diffraction (XRD), on Ypresian phosphatic series from Gafsa‐Metlaoui basin, Tunisia. The XRD data indicate that smectite, palygorskite and sepiolite are the prevalent clay minerals in the selected samples. In this clay mineral association, the N‐alkane (m/z = 57) distribution indicates that the marine organic matter is plankton and bacterial in origin. The kerogens observed on transmitted light microscopy, however, appear to be totally amorphous organic matter, without any appearance of biological form. The orange gel‐like amorphous organic matter with distinct edges and homogenous texture is consistent with a high degree of aliphaticity. This material has relatively intense CH₂ and CH₃ infrared bands in ¹³C NMR peaks. This aliphatic character is related to bacterial origin. Brown amorphous organic matter with diffuse edges has a lower aliphatic character than the previous kerogen, deduced from relatively low CH₂ and CH₃ infrared and ¹³C NMR band intensities.     

Environmental control of carbon isotope variations in Pennsylvania black-shale sequences, Midcontinent, U.S.A.

A reversal of the conventional carbon isotope relationship, “terrestrial-lighter-than-marine” organic matter, has been documented for two Pennsylvanian (Desmoinesian) cyclothemic sequence cores from the Midcontinent craton of the central United States. “Deep” water organic-rich phosphatic black shales contain a significant proportion of algal-derived marine organic matter (as indicated by organic petrography, Rock-Eval hydrogen index and ratios) and display the lightest δ¹³C-values (max −27.80‰ for kerogen) while shallower water, more oxic facies (e.g. fossiliferous shales and limestones) contain dominantly terrestrial organic matter and have heavier δ¹³C_kerogen-values (to −22.87‰ for a stratigraphically adjacent coal). δ¹³C-values for extract fractions were relatively homogeneous for the organic-rich black shales with the lightest fraction (often the aromatics) being only 1‰, or less, more negative than the kerogen. Differences between extract fractions and kerogens were much greater for oxic facies and coals (e.g. saturates nearly 5‰ lighter than the kerogen).A proposed depositional model for the black shales calls upon a large influx of nutrients and humic detritus to the marine environment from the laterally adjacent, extremely widespread Pennsylvanian (peat) swamps which were rapidly submerged by transgression of the epicontinental seas. In this setting marine organisms drew upon a CO₂-reservoir which was in a state of disequilibrium with the atmosphere, being affected by isotopically light “recycled-CO₂” derived from the decomposition of peaty material in the water column and possibly from the anoxic diagenesis of organic matter in the sediments.     

Late Quaternary vegetation changes around Lake Rutundu,Mount Kenya,East Africa: evidence from grass cuticles,pollen and stable carbon isotopes

Woody, subalpine shrubs and grasses currently surround Lake Rutundu, Mount Kenya. Multiple proxies, including carbon isotopes, pollen and grass cuticles, from a 755‐cm‐long core were used to reconstruct the vegetation over the past 38 300 calendar years. Stable carbon‐isotope ratios of total organic carbon and terrestrial biomarkers from the lake sediments imply that the proportion of terrestrial plants using the C₄ photosynthetic pathway was greater during the Late Pleistocene than in the Holocene. Pollen data show that grasses were a major constituent of the vegetation throughout the Late Pleistocene and Holocene. The proportion of grass pollen relative to the pollen from other plants was greatest at the last glacial maximum (LGM). Grass cuticles confirm evidence that C₄ grass taxa were present at the LGM and that the majority followed the cold‐tolerant NADP‐MEC₄ subpathway. Copyright © 2003 John Wiley & Sons, Ltd.     

Detailed compositional analysis of gas seepage at the National Carbon Storage Test Site,Teapot Dome,Wyoming, USA

A baseline determination of CO₂ and CH₄ fluxes and soil gas concentrations of CO₂ and CH₄ was made over the Teapot Dome oil field in the Naval Petroleum Reserve No. 3 (NPR-3) in Wyoming, USA. This was done in anticipation of experimentation with CO₂ sequestration in the Pennsylvanian Tensleep Sandstone underlying the field at a depth of 1680 m.The baseline data were collected during the winter, 2004 in order to minimize near-surface biological activity in the soil profile. The baseline data were used to select anomalous locations that may be the result of seeping thermogenic gas, along with background locations. Five 10-m holes were drilled, 3 of which had anomalous gas microseepage, and 2 were characterized as “background.” These were equipped for nested gas sampling at depths of 10-, 5-, 3-, 2-, and 1-m depths. Methane concentrations as high as 170,000 ppmv (17%) were found, along with high concentrations of C₂H₆, C₃H₈, n-C₄H₁₀, and i-C₄H₁₀. Much smaller concentrations of C₂H₄ and C₃H₆ were observed indicating the beginning of hydrocarbon oxidation in the anomalous holes. The anomalous 10-m holes also had high concentrations of isotopically enriched CO₂, indicating the oxidation of hydrocarbons. Concentrations of the gases decreased upward, as expected, indicating oxidation and transport into the atmosphere. The ancient source of the gases was confirmed by ¹⁴C determinations on CO₂, with radiocarbon ages approaching 38 ka within 5 m of the surface.Modeling was used to analyze the distribution of hydrocarbons in the anomalous and background 10-m holes. Diffusion alone was not sufficient to account for the hydrocarbon concentration distributions, however the data could be fit with the addition of a consumptive reaction. First-order rate constants for methanotrophic oxidation were obtained by inverse modeling. High rates of oxidation were found, particularly near the surface in the anomalous 10-m holes, demonstrating the effectiveness of the process in the attenuation of CH₄ microseepage. The results also demonstrate the importance of CH₄ measurements in the planning of a monitoring and verification program for geological CO₂ sequestration in sites with significant remaining hydrocarbons (i.e. spent oil reservoirs).     

Experiments on Methane Displacement by Carbon Dioxide in Large Coal Specimens

Carbon dioxide (CO₂) is considered to be the most important greenhouse gas in terms of overall effect. CO₂ geological storage in coal beds is of academic and industrial interest because of economic synergies between greenhouse gas sequestration and coal bed methane (CH₄) recovery by displacement/adsorption. Previously, most work focused on either theoretical analyses and mathematical simulations or gas adsorption?Cdesorption experiments using coal particles of millimeter size or smaller. Those studies provided basic understanding of CH₄ recovery by CO₂ displacement in coal fragments, but more relevant and realistic investigations are still rare. To study the processes more realistically, we conducted experimental CH₄ displacement by CO₂ and CO₂ sequestration with intact 100?×?100?×?200?mm coal specimens. The coal specimen permeability was measured first, and results show that the permeability of the specimen is different for CH₄ and CO₂; the CO₂ permeability was found to be at least two orders of magnitude greater than that for CH₄. Simultaneously, a negative exponential relationship between the permeability and the applied mean stress on the specimen was found. Under the experimental stress conditions, 17.5?C28.0 volumes CO₂ can be stored in one volume of coal, and the displacement ratio CO₂?CCH₄ is as much as 7.0?C13.9. The process of injection, adsorption and desorption, displacement, and output of gases proceeds smoothly under an applied constant pressure differential, and the CH₄ content in the output gas amounted to 20?C50% at early stages, persisting to 10?C16% during the last stage of the experiments. Production rate and CH₄ fraction are governed by complex factors including initial CH₄ content, the pore and fissure fabric of the coal, the changes in this fabric as the result of differential adsorption of CO₂, the applied stress, and so on. During CO₂ injection and CH₄ displacement, the coal can swell from effects of gas adsorption and desorption, leading to changes in the microstructure of the coal itself. Artificial stimulation (e.g. hydraulic fracturing) to improve coalbed transport properties for either CO₂ sequestration or enhanced coal bed methane recovery will be necessary. The interactions of large-scale induced fractures with the fabric at the scale of observable fissures and fractures in the laboratory specimens, as well as to the pore scale processes associated with adsorption and desorption, remain of profound interest and a great challenge.     

Cuticles and Spores in Situ of Coniopteris hymenophylloides from the Middle Jurassic in Gansu,Northwestern China

Coniopteris was a ubiquitous plant of the Jurassic and Cretaceous periods and played an important role in the flora of the time. However, its anatomical structure is relatively poorly known. The specimens of Coniopteris hymenophylloides(Brongniart) Seward described here were collected from the Yaojie Formation in Gansu Province, northwestern China. The sterile fronds are characterized as being at least bipinnate with alternate arranged linear pinnae covered by thin cuticles. Fertile fronds are linear-lanceolate, with single sorus at the margin of each fertile pinnule. In situ spores are typically trilete, triangle to subcircular in polar view, cap-shaped in equatorial view, and 37 μm in average diameter. The trilete marking is straight and narrow, generally extends to 4/5 of the spore radius. The spore surface is smooth, and parts of the exine are granulated. The epidermal cells of cuticles are irregular in shape, approximately 40-60μm long and 10-20 μm wide. The elliptical stomatal complexes are paracytic,approximately 30 μm long and 19 μm wide,and irregularly distributed. On the basis of its epidermal structures and comparisons with extant ferns, we consider that Coniopteris displays combined features of the related extant genera.     

Seepage of methane at Jaco Scar,a slide caused by seamount subduction offshore Costa Rica

Methane (CH₄) concentrations and CH₄ stable carbon isotopic composition ( \( \delta^{13} {\text{C}}_{{{\text{CH}}_{4} }} \) ) were investigated in the water column within Jaco Scar. It is one of several scars formed by massive slides resulting from the subduction of seamounts offshore Costa Rica, a process that can open up structural and stratigraphical pathways for migrating CH₄. The release of large amounts of CH₄ into the adjacent water column was discovered at the outcropping lowermost sedimentary sequence of the hanging wall in the northwest corner of Jaco Scar, where concentrations reached up to 1,500 nmol L^?1. There CH₄-rich fluids seeping from the sedimentary sequence stimulate both growth and activity of a dense chemosynthetic community. Additional point sources supplying CH₄ at lower concentrations were identified in density layers above and below the main plume from light carbon isotope ratios. The injected CH₄ is most likely a mixture of microbial and thermogenic CH₄ as suggested by \( \delta^{13} {\text{C}}_{{{\text{CH}}_{4} }} \) values between ?50 and ?62 ‰ Vienna Pee Dee Belemnite. This CH₄ spreads along isopycnal surfaces throughout the whole area of the scar, and the concentrations decrease due to mixing with ocean water and microbial oxidation. The supply of CH₄ appears to be persistent as repeatedly high CH₄ concentrations were found within the scar over 6 years. The maximum CH₄ concentration and average excess CH₄ concentration at Jaco Scar indicate that CH₄ seepage from scars might be as significant as seepage from other tectonic structures in the marine realm. Hence, taking into account the global abundance of scars, such structures might constitute a substantial, hitherto unconsidered contribution to natural CH₄ sources at the seafloor.     

Methane-rich fluid inclusions in skarn near the giant REE–Nb–Fe deposit at Bayan Obo, Northern China

We report fluid inclusion data for skarn, formed at the contact between Hercynian granitoids and dolomite of the Proterozoic Bayan Obo Group, in the vicinity of Bayan Obo REE–Nb–Fe deposit, Inner Mongolia, China. Three types of fluid inclusions are identified: two-phase CH₄-rich, three-phase liquid–vapour–solid and two-phase aqueous inclusions. Using microthermometry and laser Raman microprobe analysis to calculate isochores for CH₄-bearing inclusions, we estimate fluid trapping conditions at T=280 to 344 °C and P<1 to 2.3 kbar. Such conditions are compatible with formation of CH₄ inclusions as a result of reaction between graphite in the country rocks (black slate sequence) and fluids derived from magma. The lack of carbonaceous material in the inclusions supports the hypothesis that CH₄ was generated during fluid migration rather than by in situ reaction. In contrast to the skarn, and despite the fact that similar graphite-bearing slates are found in the host rocks, no CH₄-bearing inclusions have been so far reported from Bayan Obo REE ores. We therefore conclude that the skarn-forming fluids in the contact aureole of the Hercynian granitoids were not involved at any stage in the formation of the Bayan Obo deposit.     

Insights into preservation of fossil plant cuticles using thermally assisted hydrolysis methylation

The chemical composition of Cretaceous leaf remains showing exceptionally well preserved cuticles was investigated using pyrolysis gas chromatography–mass spectrometry (Py-GC–MS) and thermally assisted hydrolysis methylation (THM)-GC–MS. Samples of Coniferales (Frenelopsis) and Ginkgoales (Nehvizdya penalveri) leaf remains were collected from freshwater and coastal marine depositional environments. Material for pyrolysis included (i) untreated leaves and cuticles obtained after extraction from mineral rock matrix and bleaching, (ii) kerogen fraction from both materials, (iii) non-hydrolysable fraction from kerogen. The THM-GC–MS data from untreated leaves and bleached cuticles show that the fossil cuticle geopolymer essentially released aliphatic components upon thermal treatment, with a dominance of fatty acids (FAs) and n-alkanes/n-alkenes. The FAs are essentially resistant to bleaching and remain after solvent extraction. They occur mainly as short chain compounds ranging from C₆ to C₁₆ and with maximum abundance at C₈–C₉. The n-alkanes/n-alkenes from kerogen and the non-hydrolysable residue occur mainly as short chain compounds in the range C₁₀–C₁₆, with the highest abundance at C₉–C₁₂. The THM-GC–MS pyrograms of the fossil cuticles differ from those of cutan from fresh living plants. They support the preservation model via polymerization of monomers derived from cutin or from unsaturated cell FAs.     

Light hydrocarbons geochemistry of surface sediments from Pranhita-Godavari Basin,Andhra Pradesh

A geochemical study of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh, India was carried out using light hydrocarbon compounds to assess the hydrocarbon potential of the basin. Suite of 80 soil samples were collected from the depth of 2.5 m and analyzed for adsorbed light gaseous hydrocarbons namely methane (CH₄), ethane (C₂H₆) and propane (C₃H₈) in Gas chromatograph. Compound specific Carbon isotope ratios for CH₄ and C₂H₆ were also determined using GC-C IRMS (Gas Chromatograph Combustion Isotope Mass Spectrometer). The presence of moderate to low concentrations of methane (C_CH4 C_{CH_4 } : 1 to 138 ppb), ethane (H₄{H_4 }: 1 to 35 ppb) and propane (C_{C3 H8} C_{C_3 H_8 } : 1 to 20 ppb) was measured in the soil samples. Carbon isotopic composition of d¹³ C_CH4 \delta ^{13} C_{CH_4 } ranges between −27.9 to −47.1 ‰ and d¹³ C_{C2 H6} \delta ^{13} C_{C_2 H_6 } ranged between −36.9 to −37.2 ‰ (V-PDB) indicating that these gases are of thermogenic origin. Study of soil samples suggests the area has good potential for hydrocarbon.     

Multiple magnetization events in the Red River carbonates, Williston Basin, Canada: Evidence for fluid-flow?

Samples collected from the Upper Ordovician Red River carbonates in a well at the centre of the Williston Basin revealed two paleomagnetic components with different inclinations, 60.3 ± 3.9° (k = 70.7, N = 12) and 20.4 ± 3.3° (k = 141.2, N = 8), but similar declination values in individual specimens. Inclination-only analysis indicates two possible scenarios for the age of these two magnetizations: in scenario (a) the timing of magnetization happened sometime between Late Ordovician to Devonian; and in scenario (b) there are two different remagnetizations, one that overlaps Pennsylvanian to Permian time while the other can have either a Late Jurassic or a Tertiary age. Whereas dolomitization and some isotopic data tend to support scenario (a), previous paleomagnetic data from the Williston Basin and from younger units in the same well, the tectonic evolution of the basin, and the hydrocarbon maturation pattern in the Red River carbonates all favour chemical remagnetization(s) driven by orogenic fluids during the Alleghenian and Laramide orogenies.     

Graphite precipitation in C—O—H fluid inclusions: closed system compositional and density changes,and thermobarometric implications

 Equilibrium C–O–H fluid speciation calculations predict that graphite will precipitate from initially graphite saturated fluid inclusions during cooling and exhumation of metamorphic rocks. In the case that no mass is gained or lost by the inclusions, the original X _O ratio [O/(O+H)] of the fluid phase must be maintained. Given this closed system constraint, the down-temperature progress of graphite precipitation can easily be monitored as a function of the varible X _O, and produces some effects that are of significance to fluid inclusion studies: 1. Variation of the H₂O : CO₂ : CH₄ relationship in the graphite-saturated COH fluid, namely increase of X _H2 ^O and decrease of the carbonic fraction; 2. Decrease of fluid density due to precipitation of graphite, which is denser than the residual fluid; 3. Alteration of the CO₂ : CH₄ ratio of the fluid, depending on the initial O : H ratio of the fluid: for X _O>1/3, fluids increase their CO₂ : CH₄ ratio with decreasing temperature, and vice-versa. This implies that the CO₂ : CH₄ ratio measured at room T will not represent the trapping value, which is in any case closer to unity. As a consequence of density reduction, isochores extrapolated from densities observed at room temperature do not pass through the pressure-temperature conditions at which the inclusion was trapped, with pressure underestimates of up to 2 kbar. Actual P-T trapping conditions are located along the equilibrium “bulk isochore” (curve of constant-X _O, constant-volume) of the fluid. Alteration of the CO₂ : CH₄ ratio is a mechanism by which a CO₂-rich or CH₄-rich carbonic phase can be formed from aqueous fluids that are slightly off the neutral X _O=1/3 value. Subsequent segregation of this phase from the aqueous counterpart may account for the formation of pure CO₂ and CH₄ fluids in the upper crust. Received: 15 March 1995 / Accepted: 1 June 1995