Carbon catalysed hydrogen exchange in petroleum source rocks

Exchange of carbon bound hydrogen has been observed when alkenes, saturated and aromatic hydrocarbons are heated at moderate temperatures on carbonaceous surfaces (activated carbon and coal). Isomerisation of alkenes and the formation of hydrogenated/dehydrogenated products from the saturated and aromatic reactants resulted. A suite of crude oils from the Carnarvon Basin (Western Australia) have been analysed with a view to comparing their relative abundances of structurally similar hydrocarbons. The consistent relationships between hydrocarbons in crude oils that are chemically related via hydrogenation/dehydrogenation reactions suggest that a hydrogen exchange process similar to that demonstrated in laboratory experiments occurs during crude oil formation in sedimentary rocks.     

The El Teniente porphyry Cu–Mo deposit from a hydrothermal rutile perspective

Mineralogical, textural, and chemical analyses (EPMA and PIXE) of hydrothermal rutile in the El Teniente porphyry Cu–Mo deposit help to better constrain ore formation processes. Rutile formed from igneous Ti-rich phases (sphene, biotite, Ti-magnetite, and ilmenite) by re-equilibration and/or breakdown under hydrothermal conditions at temperatures ranging between 400°C and 700°C. Most rutile nucleate and grow at the original textural position of its Ti-rich igneous parent mineral phase. The distribution of Mo content in rutile indicates that low-temperature (∼400–550°C), Mo-poor rutile (5.4 ± 1.1 ppm) is dominantly in the Mo-rich mafic wallrocks (high-grade ore), while high-temperature (∼550-700°C), Mo-rich rutile (186 ± 20 ppm) is found in the Mo-poor felsic porphyries (low-grade ore). Rutile from late dacite ring dikes is a notable exception to this distribution pattern. The Sb content in rutile from the high-temperature potassic core of the deposit to its low-temperature propylitic fringe remains relatively constant (35 ± 3 ppm). Temperature and Mo content of the hydrothermal fluids in addition to Mo/Ti ratio, modal abundance and stability of Ti-rich parental phases are key factors constraining Mo content and provenance in high-temperature (≥550°C) rutile. The initial Mo content of parent mineral phases is controlled by melt composition and oxygen fugacity as well as timing and efficiency of fluid–melt separation. Enhanced reduction of SO₂-rich fluids and sulfide deposition in the Fe-rich mafic wallrocks influences the low-temperature (≤550°C) rutile chemistry. The data are consistent with a model of fluid circulation of hot (>550°C), oxidized (ƒO₂ ≥ NNO + 1.3), SO₂-rich and Mo-bearing fluids, likely exsolved from deeper crystallizing parts of the porphyry system and fluxed through the upper dacite porphyries and related structures, with metal deposition dominantly in the Fe-rich mafic wallrocks.     

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.     

Taconic Orogeny in Pennsylvania: A 15 –20 m.y. Apennine-style Ordovician event viewed from its Martic hinterland

In Pennsylvania, the Taconic Orogeny lasted from 461 to 443 Ma as Cambro-Ordovician slope deposits were deformed into mountains edging the Laurentian craton at the same time that materials from an adjacent deep-water basin were being transported 50 –70 km across a carbonate platform into foreland basins. This paper focuses on shelf-edge hinterland features, mostly the Martic Zone as a folded, stack of imbricate thrust sheets of slope materials that corresponds to Vermont's Taconic Mountains and Southern Quebec's zone of Taconic allochthons. Work of the last century is summarized, corrected, and combined with a new 450 Ma radiometric date and fluid inclusion data from the Pequea Mine within the Martic Zone. These and abundant new graptolite and conodont dates in the foreland paint a revised Pennsylvania picture differing from the northern Taconic areas. Differences are: (1) transport of very large allochthonous masses of deep-water material, the Dauphin Formation, far across the carbonate platform, and (2) deformation migrating progressively across that platform during a 15 –20 m.y. period, incorporating it and its foreland cover into alpine-scale, recumbent folds and thrusts. The scenario has many analogies to Italy's modern Apennine Mountains minus the Latian volcanics.     

Numerical modeling of reservoirs or pipes in groundwater seepage

In groundwater studies, the numerical modeling of complex boundary conditions can be made easier by considering reservoirs and pipes as “reservoir” finite elements, which can store or release large volumes of water at almost constant hydraulic head. The numerical code to be used must solve the complete conservation equation with unlinked functions for the water retention curve and the unsaturated hydraulic conductivity, and the ability to describe these as step functions. Four examples illustrate the performance of the “reservoir” element: reservoir pumping, laboratory variable-head permeability test, vertical flow in an open borehole, and pumping test with well storage.     

Physical properties and petrologic description of rock samples from an IOCG mineralized area in the northern Fennoscandian Shield, Sweden

The Tjårrojåkka Fe–Cu-prospect in northern Sweden is considered an example of a Fe-oxide Cu–Au (IOCG) deposit and is hosted in metamorphosed Paleoproterozoic volcanic and intrusive rocks. Rock samples from 24 outcrops were collected for petrophysical analysis (magnetic susceptibility, remanent magnetization, variation of magnetic susceptibility with temperature, Curie temperature and density). The major Cu-prospect in the area has been studied by magnetic and electron microprobe analyses of four selected rock samples. The samples are from an exploration well that intersects the main Cu-mineralized body.The magnetic analyses show that magnetite is the dominant magnetic mineral, while hematite and other Fe-minerals are present in minor amounts. The electron microprobe observations confirm the presence of magnetite and further indicate that hematite is an alteration product of magnetite. Moreover, microprobe observations indicate that Fe-sulfides are present in negligible amounts in the samples from the Tjårrojåkka area. The strong spatial relationship of Cu-minerals (e.g., chalcopyrite) and the oxidation of magnetite to hematite suggest that the presence of rocks with low magnetic susceptibility in areas dominated by high susceptibility rocks may be a signal of related Cu-prospects.     

Impact of mining activities on soils and sediments at the historical mining area in Podljubelj,NW Slovenia

The abandoned Hg mine in Podljubelj was in operation with interceptions from 1557 to 1902. The entire operating period yielded about 110 000 tons of ore, from which 360 tons of Hg was produced. The objective of the research project was to establish the contents and spatial distribution of Hg in soils and stream sediments in the vicinity of the mine. On an area of 88 ha the soil was sampled in a 100 × 100 m grid. Two soil horizons (0–5 cm and 20–30 cm) were sampled in order to distinguish between geogenic and anthropogenic Hg sources. It was established that on an area of about 9 ha Hg content in soil exceeds The New Dutchlist action value for Hg (10 mg/kg). Total Hg concentrations in soil samples vary between 0.17 and 719 mg/kg, with a mean of 3.0 mg/kg. Mercury contents in stream sediments range from 0.065 to 1.4 mg/kg, with a mean of 0.64 mg/kg. The highest determined value in soils was found in the area around the former roasting furnace, where the ore was processed. Increased Hg concentrations were also found on the mine waste dump (108 mg/kg). Mercury contents in soils generally decrease with soil profile depth and with the distance from the mine and from the roasting furnace location. Mercury also appears in higher concentrations along the road that runs through the valley, which results from the use of Hg-bearing ore residues in road construction. The average enrichment factor (EF) of Hg in topsoil with respect to subsoil is 3.3. Calculated enrichment factors show higher values also for Cd (3.2), Pb (2.7), Ca (2.4) and P (1.9). The average enrichment factor of Hg in topsoil with regard to the established Slovenian soil averages (EF_slo) is 19. EF_slo of other determined chemical elements do not exceed 3.0.     

Numerical simulations of the Mediterranean sea outflow: impact of the entrainment parameterization in an isopycnic coordinate ocean model

Gravity current entrainment is essential in determining the properties of the interior ocean water masses that result from marginal sea overflows. Although the individual entraining billows will be unresolvable in large-scale ocean models for the foreseeable future, some large-scale simulations are now being carried out that do resolve the intermediate scale environment which may control the rate of entrainment. Hallberg [Mon. Wea. Rev. 128 (2000) 1402] has recently developed an implicit diapycnal mixing scheme for isopycnic coordinate ocean models that includes the Richardson number dependent entrainment parameterization of Turner [J. Fluid Mech. 173 (1986) 431], and which may be capable of representing the gravity current evolution in large-scale ocean models. The present work uses realistic regional simulations with the Miami Isopycnic Coordinate Ocean Model (MICOM) to evaluate ability of this scheme to simulate the entrainment that is observed to occur in the bottom boundary currents downstream of the Mediterranean outflow. These simulations are strikingly similar to the observations, indicating that this scheme does produce realistic mixing between the Mediterranean outflow and the North Atlantic Central Water. Sensitivity studies identify the critical Richardson number below which vigorous entrainment occurs as a particularly important parameter. Some of these experiments also show meddies detaching from the Mediterranean undercurrent at locations that appear to be highly influenced by topographic features.     

MaxEnt power spectrum estimation using the Fourier transform for irregularly sampled data applied to a record of stellar luminosity

The principle of maximum entropy is applied to the spectral analysis of a data signal with general variance matrix and containing gaps in the record. The role of the entropic regularizer is to prevent one from overestimating structure in the spectrum when faced with imperfect data. Several arguments are presented suggesting that the arbitrary prefactor should not be introduced to the entropy term. The introduction of that factor is not required when a continuous Poisson distribution is used for the amplitude coefficients. We compare the formalism for when the variance of the data is known explicitly to that for when the variance is known only to lie in some finite range. The result of including the entropic measure factor is to suggest a spectrum consistent with the variance of the data which has less structure than that given by the forward transform. An application of the methodology to example data is demonstrated.     

Aerial electromagnetic sounding of the lithosphere of Venus

Electromagnetic (EM) investigation depths are larger on Venus than Earth due to the dearth of water in rocks, in spite of higher temperatures. Whistlers detected by Venus Express proved that lightning is present, so the Schumann resonances ～10–40 Hz may provide a global source of electromagnetic energy that penetrates ～10–100 km. Electrical conductivity will be sensitive at these depths to temperature structure and hence thermal lithospheric thickness. Using 1D analytic and 2D numerical models, we demonstrate that the Schumann resonances—transverse EM waves in the ground-ionosphere waveguide—remain sensitive at all altitudes to the properties of the boundaries. This is in marked contrast to other EM methods in which sensitivity to the ground falls off sharply with altitude. We develop a 1D analytical model for aerial EM sounding that treats the electrical properties of the subsurface (thermal gradient, water content, and presence of conductive crust) and ionosphere, and the effects of both random errors and biases that can influence the measurements. We initially consider specified 1D lithospheric thicknesses 100–500 km, but we turn to 2D convection models with Newtonian temperature-dependent viscosity to provide representative vertical and lateral temperature variations. We invert for the conductivity-depth structure and then temperature gradient. For a dry Venus, we find that the error on temperature gradient obtained from any single local measurement is ～100%—perhaps enough to distinguish “thick” vs. “thin” lithospheres. When averaging over thousands of kilometers, however, the standard deviation of the recovered thermal gradient is within the natural variability of the convection models, <25%. A “wet” interior (hundreds of ppm H₂O) limits EM sounding depths using the Schumann resonances to <20 km, and errors are too large to estimate lithospheric properties. A 30-km conductive crust has little influence on the dry-interior models because the Schumann penetration depths are significantly larger. We conclude that EM sounding of the interior of Venus is feasible from a 55-km high balloon. Lithospheric thickness can be measured if the upper-mantle water content is low. If H₂O at hundreds of ppm is present, the deeper, temperature-sensitive structure is screened, but the “wet” nature of the upper mantle, as well as structure of the upper crust, is revealed.