Hydrous pyrolysis of a Type III source: fractionation effects during primary migration in natural and artificially matured samples

A core from the Cambay Shale Formation of the Cambay Basin, containing immature Type III organic matter, was pyrolysed at 300°C for different durations of time to different maturation levels. Fractionation effects were studied employing a three-step extraction technique after removal of the expelled pyrolysate. The extractable organic matter (EOM) obtained on extraction of the whole core is assumed to be that present in open pores, while that obtained on finely crushing the sample is assumed to be that present in closed pores. The EOM obtained from 1 cm chips is termed EOM from semi-open pores. The gross composition of the pyrolysates expelled during pyrolysis is not similar to the oils reservoired in the area, and there is no significant fractionation observed between expelled pyrolysates and unexpelled EOM. Our study indicates movement of fluids between closed, semi-open and open pores. In both systems, there is a higher concentration of EOM in open pores than in semi-open and closed pores, and the fraction of EOM in open pores is much greater in the artificial system than in the natural system. Fractionation effects on n-alkane and isoprenoid hydrocarbon-based parameters were also studied. n-Alkenes are present in semi-open and closed pores of the immature core and in the core after it was pyrolysed to 300°C for 6 and 48 h, but are absent in the open pores. n-Alkenes are present in closed pores in the naturally matured core. Presence of n-alkenes in the pyrolysates expelled during the 6 and 48 h experiments, but their absence in the open pores of the core, indicates that expulsion also occurs through temporary microfractures during laboratory pyrolysis, whereas in the natural system expulsion from closed pores seems to be only via semi-open and open pores.     

Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

Benchmarking the thermomechanical behaviour of clays — a progress report — the CEC interclay project

In 1989 a small-scale exercise conducted by the CEC as part of its research programme into the underground storage of radioactive waste highlighted the difficulty of making accurate predictions a priori, of the geomechanical behaviour of clay. Given source data about the Boom clay from the underground research facility at Mol, three organisations independently performed f.e. analyses of two somewhat hypothetical problems. While the results were very broadly in agreement, they were shown to be sensitive to both the type of constitutive model used and the way data was fitted to the model.

Subsequently, the CEC sponsored a more comprehensive benchmark exercise called INTERCLAY II. This involves eleven organisations from various member states of the EC in a project encompassing the three aspects of software development for predictive modelling: verification, validation on the laboratory scale and the treatment of in-situ tests. The paper briefly describes the exercise currently in progress and presents the main results achieved to date concentrating on validation aspects.     

Effects of temperature on strength and compressibility of sand-bentonite buffer

Dense sand-bentonite buffer (γ_d = 1.67Mg/m³) has been proposed in Canada as one of several barriers for isolating nuclear fuel waste. The buffer will be required to function under conditions of high total pressures and elevated temperatures approaching 100°C. Summary results are presented from two test programs: (1) isothermal consolidated undrained triaxial (CIU¯) tests; and (2) isothermal drained constant-p′ (CID) triaxial tests. Specimens were consolidated at effective stresses up to 9.0 MPa and temperatures up to 100°C.

The results indicate parallel hardening lines at systematically lower values of specific volume at elevated temperatures. In shear, increased temperatures produced lower values of maximum deviator stressq_f, and higher pore water pressure changesΔu_f. The net result is curved peak strength envelops in plots ofq_f versusp_f′ that are higher at elevated temperatures, even though the strengths,q_f of individual specimens are lower. The critical state strength envelope is curved inq, p′-planes.

The effect of drained heating on buffer to 100°C is not marked. Compressibilities, stiffnesses, strengths, and pore water pressure generation are all affected, but none of the changes are great.     

The mean and turbulence structure simulation of the monsoon trough boundary layer using a one-dimensional model withe-l ande-ε closures

An attempt has been made here to study the sensitivity of the mean and the turbulence structure of the monsoon trough boundary layer to the choice of the constants in the dissipation equation for two stations Delhi and Calcutta, using one-dimensional atmospheric boundary layer model withe-ε turbulence closure. An analytical discussion of the problems associated with the constants of the dissipation equation is presented. It is shown here that the choice of the constants in the dissipation equation is quite crucial and the turbulence structure is very sensitive to these constants. The modification of the dissipation equation adopted by earlier studies, that is, approximating the Tke generation (due to shear and buoyancy production) in theε-equation by max (shear production, shear + buoyancy production), can be avoided by a suitable choice of the constants suggested here. The observed turbulence structure is better simulated with these constants. The turbulence structure simulation with the constants recommended by Aupoixet al (1989) (which are interactive in time) for the monsoon region is shown to be qualitatively similar to the simulation obtained with the constants suggested here, thus implying that no universal constants exist to regulate dissipation rate. Simulations of the mean structure show little sensitivity to the type of the closure parameterization betweene-l ande-ε closures. However the turbulence structure simulation withe-ε. closure is far better compared to thee-l model simulations. The model simulations of temperature profiles compare quite well with the observations whenever the boundary layer is well mixed (neutral) or unstable. However the models are not able to simulate the nocturnal boundary layer (stable) temperature profiles. Moisture profiles are simulated reasonably better. With one-dimensional models, capturing observed wind variations is not up to the mark.     

Thorium and uranium isotopes in a manganese nodule from the Peru basin determined by alpha spectrometry and thermal ionization mass spectrometry (TIMS): Are manganese supply and growth related to climate?

Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution²³⁰Th_excess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (²³⁰Th), 0.43–1.40 ppm (²³²Th), 0.09–0.49 ppb (²³⁴U) and 1.66–8.24 ppm (²³⁸U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the²³⁰Th_excess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant²³⁰Th_excess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.     

Field assessment of acid mine drainage contamination in surface and ground water

Both sulfate and conductivity are useful indicators of acid mine drainage (AMD) contamination. Unlike pH, they are both extremely sensitive to AMD even where large dilutions have occurred. The advantage of using sulfate to trace AMD is that unlike other ions it is not removed to any great extent by sorption or precipitation processes, being unaffected by fluctuations in pH. These two parameters are also closely associated as would be expected, as conductivity is especially sensitive to sulfate ions. Therefore, as sulfate analysis is difficult in the field, conductivity can be used to predict sulfate concentration in both AMD and contaminated surface waters using regression analysis. Most accurate predictions are achieved by using equations given for specific conductivity ranges or AMD sources. There is also potential to use conductivity to predict approximate concentrations of key metals when the pH of the water is within their respective solubility ranges.     

Subduction,mega-shear systems and Late Palaeozoic basin development in the African segment of Gondwana

 Basins within the African sector of Gondwana contain a Late Palaeozoic to Early Mesozoic Gondwana sequence unconformably overlying Precambrian basement in the interior and mid-Palaeozoic strata along the palaeo-Pacific margin. Small sea-board Pacific basins form an exception in having a Carboniferous to Early Permian fill overlying Devonian metasediments and intrusives. The Late Palaeozoic geographic and tectonic changes in the region followed four well-defined consecutive events which can also be traced outside the study area. During the Late Devonian to Early Carboniferous period (up to 330 Ma) accretion of microplates along the Patagonian margin of Gondwana resulted in the evolution of the Pacific basins. Thermal uplift of the Gondwana crust and extensive erosion causing a break in the stratigraphic record characterised the period between 300 and 330 Ma. At the end of this period the Gondwana Ice Sheet was well established over the uplands. The period 260–300 Ma evidenced the release of the Gondwana heat and thermal subsidence caused widespread basin formation. Late Carboniferous transpressive strike-slip basins (e.g. Sierra Australes/Colorado, Karoo-Falklands, Ellsworth-Central Transantarctic Mountains) in which thick glacial deposits accumulated, formed inboard of the palaeo-Pacific margin. In the continental interior the formation of Zambesi-type rift and extensional strike-slip basins were controlled by large mega-shear systems, whereas rare intracratonic thermal subsidence basins formed locally. In the Late Permian the tectonic regime changed to compressional largely due to northwest-directed subduction along the palaeo-Pacific margin. The orogenic cycle between 240 and 260 Ma resulted in the formation of the Gondwana fold belt and overall north–south crustal shortening with strike-slip motions and regional uplift within the interior. The Gondwana fold belt developed along a probable weak crustal zone wedged in between the cratons and an overthickened marginal crustal belt subject to dextral transpressive motions. Associated with the orogenic cycle was the formation of mega-shear systems one of which (Falklands-East Africa-Tethys shear) split the supercontinent in the Permo-Triassic into a West and an East Gondwana. By a slight clockwise rotation of East Gondwana a supradetachment basin formed along the Tethyan margin and northward displacement of Madagascar, West Falkland and the Gondwana fold belt occurred relative to a southward motion of Africa. Received: 2 October 1995 / Accepted: 28 May 1996