Theoretical study on the reactivity of sulfate species with hydrocarbons

The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions () and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive.Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of relative to . However, in formation waters typically encountered in petroleum reservoirs, the concentration of is likely to be significantly lower than the levels used in the laboratory, with most of the dissolved sulfate occurring as , aqueous calcium sulfate ([CaSO₄]_(aq)), and aqueous magnesium sulfate ([MgSO₄]_(aq)). Our calculations indicate that TSR reactions that occur in natural environments are most likely to involve bisulfate ions () and/or magnesium sulfate contact ion-pairs ([MgSO₄]_CIP) rather than ‘free’ sulfate ions () or solvated sulfate ion-pairs, and that water chemistry likely plays a significant role in controlling the rate of TSR.     

Mechanisms of sulfur introduction chemically controlled: δS imprint

Organic sulfur in marine sediment is ³⁴S enriched relative to the co-existing pyrite. This phenomenon is still enigmatic. Timing of the sulfur incorporation, immobilization and different sulfur species involved are part of the explanations. The reduced sulfur species incorporation into organic matter (OM) is generally assumed to have negligible δ³⁴S fractionation. This assumption has never been confirmed by laboratory experimental data. The present study measures the δ³⁴S changes resulting from reduced sulfur species (sulfides and polysulfide anions) incorporation into organic model compounds in an aquatic and low temperature (25 °C) system that simulates diagenetic marine environment. In addition, we also investigate the δ³⁴S fractionation and the isotope chemical mixing in the formation of polysulfide anions produced from elemental sulfur and sulfide anions. The results showed total isotope mixing between the two species in the formation of polysulfides. Acidification of the polysulfides solution caused δ³⁴S fractionation between the released elemental sulfur and H₂S. The incorporation of polysulfides and sulfides into carbonyl groups, caused ³⁴S enrichment relative to the starting polysulfides and sulfide of 4–5‰. The ³⁴S enrichment of the sulfurized carbonyl groups showed a minimal effect by temperature (0–70 °C) and is not affected by salinity, polysulfides composition, reaction time or solubility in water. The incorporation of polysulfides and sulfides into brominated organic compounds was negligibly ³⁴S enriched. The chemical mechanisms controlling the polysulfides incorporation into OM depend mostly on the functional groups and determine the ³⁴S enrichment of the sulfurized OM. The results presented in this study can explain part of the difference between pyrite δ³⁴S and sulfurized OM δ³⁴S in natural marine sediments.     

The earthquake swarm of December 2007 in the Mila region of northeastern Algeria

In December 2007, the Mila region of northeastern Algeria experienced thousands of microearthquakes (0.8????Md????3.9) recorded by eight temporary stations, in addition to permanent stations. Most of the events were too small to be located precisely, but a set of 122 precisely located events shows an alignment of epicenters, extending mainly in a horizontal band at about 1?C2?km depth in a NNW?CSSE direction and concentrated in a small area, 3?km southeast of Jebel Akhal, a small rocky hill between the Beni Haroun dam/reservoir and the Oued Athmania reservoir. The reservoirs are connected by pipelines, and a pumping station ensures water can be transferred between them at transient pressures of up to 80?bars. During the pumping in 2007, only 45?% of the transferred water (~600,000?m³ per day) was recovered at the Oued Athmania reservoir, and a large amount of the slightly pressurized water leaked through defective joints in a tunnel that passes through the Jebel. This water penetrated deeply into the soil with the assistance of preexisting fractures, faults, and karsts. Nine days after the first pumping started, a local increase in pore fluid pressures at shallow depths triggered seismicity southeast of Jebel Akhal, where the faults were probably close to failure. The focal mechanisms show a near vertical N?CS strike-slip fault plane under regional NW?CSE tectonic compression. One of the fault plane solutions is consistent with the NNW?CSSE direction along which the seismic events are aligned. Furthermore, a long-term comparison of the seismic activity in the region versus water levels behind the dam and the pumping of water shows that the earthquake swarm was a one-off event related to the pumping operation.     

Photometric Evolution of the Orbital Light Curves of the Slow Nova V723 Cas

UBVRI photoelectric and CCD photometry of the slow nova V723 Cas obtained in the years 1995–2003 is presented. The evolution of light curves in 1-year intervals, folded with the orbital period 0.69326 days, shows an increase of the amplitude of the wave-like variations from 0.07 to 1.3 mag during the years 1997–2003. The fact that the shape and amplitude of the orbital light curves does not depend on wavelength is most probably related to the geometry of eclipses combined with the distribution of circumstellar matter in the system.     

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H₂S_(gas). Up to 70% of this organic sulfur is released as H₂S_(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in ³⁴S during thermal maturation compared with the initial δ³⁴S values. The δ³⁴S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most ³⁴S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H₂S is a result of the system not being in equilibrium. As partial pressure of H₂S_(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ³⁴S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ³⁴S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H₂S-pyrite correlations. In particular, the use of pyrite-kerogen δ³⁴S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ³⁴S of each phase including the H₂S_(gas). H₂S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.     

Physical Controls on Spatial Variability in Decomposition of Organic Matter in Lake Kinneret,Israel

High resolution chemical data collected during summer 2003 indicate that the lower water mass (LWM) of the thermally stratified Lake Kinneret (LK) can be subdivided into three layers: a benthic boundary layer (BBL), overlain by the hypolimnion (HYP), and on top, the lower part of the metalimnion (ME-L). After onset of thermal stratification, the BBL is the first layer that turns anoxic, followed shortly afterward by the ME-L, while the HYP remains oxic and has relatively higher pH until later in summer. Thus, during the early summer, the HYP forms an oxygen-containing layer in-between two DO-deficient layers. Somewhat later, the HYP is characterized by still having significant levels of nitrate NO₃, while in both adjacent layers nitrate is already removed through denitrification. The mechanisms controlling the gradual decline of dissolved oxygen (DO) in the HYP during the summer were studied. The seasonal mean lake-wide vertical eddy diffusion coefficient in this layer, evaluated from heat flux measurements, is approximately 4 × 10⁻⁶ m² s⁻¹. The vertical oxygen flux due to diffusion from within the HYP toward its oxygen-deficient upper and lower boundaries accounts for most of the slow summer decline in DO in this layer. A smaller portion of this decline can be attributed to in-layer respiratory processes. The low turbidity, relatively high pH, and slow accumulation rate of NH₄ in the HYP support the notion that the slower mineralization processes occurring in this layer result from relatively low ambient concentrations of biodegradable organic matter, most probably due to the short residence time of the particles settling through this layer.     

Reconditioning fault slip inversions via InSAR data discretization

A major difficulty in inverting geodetic data for fault slip distribution is that measurement errors are mapped from the data space onto the solution space. The amplitude of this mapping is sensitive to the condition number of the inverse problem, i.e., the ratio between the largest and smallest singular value of the forward matrix. Thus, unless the problem is well-conditioned, slip inversions cannot reveal the actual fault slip distribution. In this study, we describe a new iterative algorithm that optimizes the condition of the slip inversion through discretization of InSAR data. We present a numerical example that demonstrates the effectiveness of our approach. We show that the condition number of the reconditioned data sets are not only much smaller than those of uniformly spaced data sets with the same dimension but are also much smaller than non-uniformly spaced data sets, with data density that increases towards the model fault.     

Expected planets in globular clusters

We argue that all transient searches for planets in globular clusters have a very low detection probability. Planets of low-metallicity stars typically do not reside at small orbital separations. The dependence of planetary system properties on metallicity is clearly seen when the quantity   I _e ≡ M _p[ a (1 − e )]²  is considered;   M _p, a   and e are the planet mass, semimajor axis and eccentricity, respectively. In high-metallicity systems, there is a concentration of systems at high and low values of I _e , with a low-populated gap near   I _e ∼ 0.3 M _J au²  , where M _J is Jupiter's mass. In low-metallicity systems, the concentration is only at the higher range of I _e , with a tail to low values of I _e . Therefore, it is still possible that planets exist around main-sequence stars in globular clusters, although at small numbers because of the low metallicity, and at orbital periods of ≳10 d. We discuss the implications of our conclusions on the role that companions can play in the evolution of their parent stars in globular clusters, for example, influencing the distribution of horizontal branch stars on the Hertzsprung–Russell diagram of some globular clusters, and in forming low-mass white dwarfs.