A chemical and thermodynamic model of oil generation in hydrocarbon source rocks

Thermodynamic calculations and Gibbs free energy minimization computer experiments strongly support the hypothesis that kerogen maturation and oil generation are inevitable consequences of oxidation/reduction disproportionation reactions caused by prograde metamorphism of hydrocarbon source rocks with increasing depth of burial.These experiments indicate that oxygen and hydrogen are conserved in the process.Accordingly, if water is stable and present in the source rock at temperatures ?25 but ?100 °C along a typical US Gulf Coast geotherm, immature (reduced) kerogen with a given atomic hydrogen to carbon ratio (H/C) melts incongruently with increasing temperature and depth of burial to produce a metastable equilibrium phase assemblage consisting of naphthenic/biomarker-rich crude oil, a type-II/III kerogen with an atomic hydrogen/carbon ratio (H/C) of ∼1, and water. Hence, this incongruent melting process promotes diagenetic reaction of detritus in the source rock to form authigenic mineral assemblages.However, in the water-absent region of the system CHO (which is extensive), any water initially present or subsequently entering the source rock is consumed by reaction with the most mature kerogen with the lowest H/C it encounters to form CO₂ gas and a new kerogen with higher H/C and O/C, both of which are in metastable equilibrium with one another.This hydrolytic disproportionation process progressively increases both the concentration of the solute in the aqueous phase, and the oil generation potential of the source rock; i.e., the new kerogen can then produce more crude oil.Petroleum is generated with increasing temperature and depth of burial of hydrocarbon source rocks in which water is not stable in the system CHO by a series of irreversible disproportionation reactions in which kerogens with higher (H/C)s melt incongruently to produce metastable equilibrium assemblages consisting of crude oil, CO₂ gas, and a more mature (oxidized) kerogen with a lower H/C which in turn melts incongruently with further burial to produce more crude oil, CO₂ gas, and a kerogen with a lower H/C and so forth.The petroleum generated in the process progresses from heavy naphthenic crude oils at low temperatures to mature petroleum at ∼150 °C. For example, the results of Computer Experiment 27 (see below) indicate that the overall incongruent melting reaction in the water-absent region of the system C-H-O at 150 °C and a depth of ∼4.3 km of an immature type-II/III kerogen with a bulk composition represented by C₂₉₂H₂₈₈O_12(c) to produce a mature (oxidized) kerogen represented by C₁₂₈H₆₈O_7(c), together with a typical crude oil with an average metastable equilibrium composition corresponding to C_8.8H_16.9 (C_8.8H_16.9(l)) and CO₂ gas (CO_2(g)) can be described by writing

(A)     

Sunken wood habitat for thiotrophic symbiosis in mangrove swamps

Large organic falls to the benthic environment, such as dead wood or whale bones, harbour organisms relying on sulfide-oxidizing symbionts. Nothing is known however, concerning sulfide enrichment at the wood surface and its relation to wood colonization by sulfide-oxidizing symbiotic organisms.In this study we combined in situ hydrogen sulfide and pH measurements on sunken wood, with associated fauna microscopy analyses in a tropical mangrove swamp. This shallow environment is known to harbour thiotrophic symbioses and is also abundantly supplied with sunken wood. A significant sulfide enrichment at the wood surface was revealed. A 72 h sequence of measurements emphasized the wide fluctuation of sulfide levels (0.1–>100 μM) over time with both a tidal influence and rapid fluctuations. Protozoans observed on the wood surface were similar to Zoothamnium niveum and to vorticellids. Our SEM observations revealed their association with ectosymbiotic bacteria, which are likely to be sulfide-oxidizers. These results support the idea that sunken wood surfaces constitute an environment suitable for sulfide-oxidizing symbioses.     

Beerkan multi-runs for characterizing water infiltration and spatial variability of soil hydraulic properties across scales

A method is presented for characterizing the spatial variability of water infiltration and soil hydraulic properties at the transect and field scales. The method involves monitoring a set of 10 Beerkan runs distributed over a 1-m length of soil, and running BEST (Beerkan estimation of soil transfer parameters) methods to derive hydraulic parameters. The Beerkan multi-runs (BMR) method provides a significant amount of data at the transect scale, allowing the determination of correlations between water infiltration variables and hydraulic parameters, and the detection of specific runs affected by preferential flow or water repellence. The realization of several BMRs at several transects on the same site allows comparison of the variation between locations (spatial variability at the field scale) and at the transect scale (spatial variability at the metre scale), using analysis of variance. From the results, we determined the spatial variability of water infiltration and hydraulic parameters as well as its characteristic scale (transect versus field).     

Fraile Detection of Solar $$-Modes by Fossat et al.

The internal gravity modes of the Sun are notoriously difficult to detect, and the claimed detection of gravity modes presented by Fossat et al. (Astron. Astrophys.604, A40, 2017) is thus very exciting. Given the importance of these modes for understanding solar structure and dynamics, the results must be robust. While Fossat et al. described their method and parameter choices in detail, the sensitivity of their results to several parameters was not presented. Therefore, we test the sensitivity of the results to a selection of the parameters. The most concerning result is that the detection vanishes when we adjust the start time of the 16.5-year velocity time-series by a few hours. We conclude that this reported detection of gravity modes is extremely fragile and should be treated with utmost caution.     

Molecular evidence for life in the 3.5 billion year old Warrawoona chert

The biological origin of organic matter in the oldest siliceous sediments (cherts) is still debated. To address this issue, the insoluble organic matter (kerogen) was isolated from a chert of the Warrawoona group. The chemical structure of the kerogen was investigated through a combination of analytical techniques including solid-state ¹³C nuclear magnetic resonance and pyrolysis. Although dominated by aromatic hydrocarbons, the pyrolysate comprises a homologous series of long chain aliphatic hydrocarbons characterized by odd-over-even carbon number predominance. This distribution is only consistent with a biological origin. As kerogen must be contemporaneous of the solidification of the chert, this observation should be regarded as an evidence for the presence of life on Earth, 3.5 By ago.     

Les Dépots Fumerolliens Terrestres et Marins de l’Ile Vulcano (Italie)

Many hydrothermal deposits are formed around the marine and terrestrial fumarolic vents of Vulcano island (Italy). Their genesis is related to the recombination of the elements brougth by the fumaroles and those liberated by the destruction of pre-existing minerals.     

Modeling flocculation in a hypertidal estuary

When fine particles are involved, cohesive properties of sediment can result in flocculation and significantly complicate sediment process studies. We combine data from field observations and state-of-the-art modeling to investigate and predict flocculation processes within a hypertidal estuary. The study site is the Welsh Channel located at the entrance of the Dee Estuary in Liverpool Bay. Field data consist of measurements from a fixed site deployment during 12–22 February 2008. Grain size, suspended sediment volume concentration, and current velocity were obtained hourly from moored instruments at 1.5 m above bed. Near-bottom water samples taken every hour from a research vessel are used to convert volume concentrations to mass concentrations for the moored measurements. We use the hydrodynamic model Proudman Oceanographic Laboratory Coastal Ocean Modelling System (POLCOMS) coupled with the turbulence model General Ocean Turbulence Model (GOTM) and a sediment module to obtain three-dimensional distributions of suspended particulate matter (SPM). Flocculation is identified by changes in grain size. Small flocs were found during flood and ebb periods—and correlate with strong currents—due to breakup, while coarse flocs were present during slack waters because of aggregation. A fractal number of 2.4 is found for the study site. Turbulent stresses and particle settling velocities are estimated and are found to be related via an exponential function. The result is a simple semiempirical formulation for the fall velocity of the particles solely depending on turbulent stresses. The formula is implemented in the full three-dimensional model to represent changes in particle size due to flocculation processes. Predictions from the model are in agreement with observations for both settling velocity and SPM. The SPM fortnight variability was reproduced by the model and the concentration peaks are almost in phase with those from field data.     

Microstructural Inhomogeneity and Mechanical Anisotropy Associated with Bedding in Rothbach Sandstone

This study present the result of conventional triaxial tests conducted on samples of Rothbach sandstone cored parallel, oblique (at 45 degrees) and perpendicular to the bedding at effective pressures ranging from 5 to 250 MPa. Mechanical and microstructural data were used to determine the role of the bedding on mechanical strength and failure mode. We find that samples cored at 45 degrees to the bedding yield at intermediate level of differential stress between the ones for parallel and perpendicular samples at all effective pressures. Strain localization at high confining pressure (i.e., in the compactive domain) is observed in samples perpendicular and oblique to the bedding but not in samples cored parallel to the bedding. However, porosity reduction is comparable whether compactive shear bands, compaction bands or homogeneous cataclastic flow develop. Microstructural data suggest that (1) mechanical anisotropy is controlled by a preferred intergranular contact alignment parallel to the bedding and that (2) localization of compaction is controlled by bedding laminations and grain scale heterogeneity, which both prevent the development of well localized compaction features.