Analysis of steranes and triterpanes in geolipid extracts by automatic classification of mass spectra

A computer method is described for the automatic classification of triterpanes and steranes into gross structural type from their mass spectral characteristics. The method has been applied to the spectra obtained by GC-MS analysis of two mixtures of standards and of hydrocarbon fractions isolated from the Green River and Messel oil shales. Almost all of the steranes and triterpanes identified previously in both shales were classified, in addition to a number of new components. The results indicate that classification of such alkanes is possible with a laboratory computer system. The method has application to diagenesis and maturation studies, and to oil/oil and oil/source rock correlations, in which rapid screening of large numbers of samples is required.     

Evaluation of fractionation effects during the early stages of primary migration

A stepwise extraction technique, based on that of Beletskaya (1972), has been aplied to sedimentary rock samples of variable grain size and maturity from a Neogene sequence in the Pannonian Basin (S.E. Hungary). The resulting chloroform extracts, claimed by Beletskaya (1978) to sample “open” and mineralogically “closed” pores, have been analysed by gas chromatography and gas chromatography-mass spectrometry. Differences in the concentrations of the two extracts and the concentrations of their hydrocarbon fractions, and in the distributions of $\text{n}$-alkanes and steroid hydrocarbons suggest that either the “open” pores are impregnated with mature oil which has migrated from depth, or that movement of organic material from the “closed” to “open” pores occurs with considerable fractionation based on both polarity and molecular size. The implications of these differences for source rock-oil correlation studies are discussed and an assessment of mechanisms for primary migration is given.     

Release of sulfur- and oxygen-bound components from a sulfur-rich kerogen during simulated maturation by hydrous pyrolysis

An immature sulfur-rich marl from the Gessosso-solfifera Formation of the Vena del Gesso Basin (Messinian, Italy) has been subjected to hydrous pyrolysis (160 to 330°C) to simulate maturation under natural conditions. The kerogen of the unheated and heated samples was isolated and the hydrocarbons released by selective chemical degradation (Li/EtNH₂ and HI/LiAlH₄) were analysed to allow a study of the fate of sulfur- and oxygen-bound species with increasing temperature. The residues from the chemical treatments were also subjected to pyrolysis–GC to follow structural changes in the kerogens. In general, with increasing hydrous pyrolysis temperature, the amounts of sulfide- and ether-bound components in the kerogen decreased significantly. At the temperature at which the generation of expelled oil began (260°C), almost all of the bound components initially present in the unheated sample were released from the kerogen. Comparison with an earlier study of the extractable organic matter using a similar approach and the same samples provides molecular evidence that, with increasing maturation, solvent-soluble macromolecular material was initially released from the kerogen, notably as a result of thermal cleavage of weak carbon–heteroatom bonds (sulfide, ester, ether) even at temperatures as low as 220°C. This solvent-soluble macromolecular material then underwent thermal cleavage to generate hydrocarbons at higher temperatures. This early generation of bitumen may explain the presence of unusually high amounts of extractable organic matter of macromolecular nature in very immature S-rich sediments.     

Kinetics of the aromatisation of rearranged ring-C monoaromatic steroid hydrocarbons

The kinetics of the aromatisation of both rearranged and non-rearranged monoaromatics have been investigated in the laboratory under free radical conditions. These studies have indicated that the aromatisation rate constant for the non-rearranged is greater than that for the rearranged isomers at any one particular temperature. Since the members of the rearranged series coelute with their non-rearranged counterparts when both series are present in geological extracts, these results suggest that care needs to be exercised when assessing extents of maturation using monoaromatic and triaromatic steroid hydrocarbons.     

Deep structure of the Longling–Ruili fault underneath Ruili basin near the eastern Himalayan syntaxis: insights from magnetotelluric imaging

Magnetotelluric (MT) geophysical profiling has been applied to the determination of the deep structure of the Longling–Ruili fault (LRF), part of a convergent strike-slip fault system, underneath thick Caenozoic cover in Ruili basin in southwestern Yunnan, China. The recorded MT data have been inverted using a two-dimensional (2-D) nonlinear conjugate gradients scheme with a variety of smooth starting models, and the resulting models show common subsurface conductivity structures that are deemed geological significant. The models show the presence of a conductive (5–60 Ω m) cover sequence that is thickest (1–1.5 km) in the centre of the basin and rapidly pinches out towards the margins. A half-graben structure is interpreted for the Ruili basin. This is underlain by about 7–10 km thick upper crustal layer of high resistivity (>200–4000 Ω m) that is dissected by steep faults, which we interpret to flatten at depth and root into an underlying mid-crustal conductive layer at about 10 km depth. The mid-crustal layer does not appear to have been severely affected by faulting; we interpret it as a zone of partial melt or intracrustal detachment. The MT models suggest SE directed thrusting of basement rocks in the area. The Longling–Ruili fault is interpreted as a NW-dipping feature bounding one of the identified upper crustal fragments underneath Ruili city. We suggest that MT imaging is a potent tool for deep subsurface mapping in this terrain.     

Temporal aspects of the abrasion of microphytic crusts under grain impact

Wind‐tunnel simulations of the response of two moss crusts to grain impact indicate that, given sufficient time, these surfaces will deteriorate under very low wind velocities only slightly above u_*t for the loose, saltating grains. In parallel with these experiments, the frequency distributions of ultimate strength and penetration energy were determined for each of the two crust types via penetrometry. Pohlia was found to be stronger than Tortula; but, even so, both of these crusts had ultimate strengths 20–350 times higher than the force delivered by a single grain impacting each surface at a velocity of 1 ms^?1. In comparison, the modulus of deformation and penetration energy data were very similar for the two surface types, especially for the weakest areas of crust development. This observation is in accord with the wind‐tunnel simulations that also found no consistent difference in the response of these two crust types to impact. In comparison with crusts formed by clay and salt, fibrous microphytic crusts are morphologically complex and typically weak. The notable elasticity of these surfaces does reduce the force of grain impact, and thereby provides some protection against rupture. One of the central conclusions of this study suggests that not only is the particle kinetic energy at impact important in crust breakdown, but also tiny fractures at points of localized stress concentration contribute to a progressive reduction in the integrity of the filament net. In some of the experiments conducted as part of this study, up to 50 or more minutes of constant bombardment was required to produce small abrasion marks on selected areas of the microphytic crust. This study prepares a foundation for future experiments needed to examine the breakdown of complex crusts formed in nature. Copyright © 2002 John Wiley & Sons, Ltd.     

Simulating Groundwater-Streamflow Connections in the Upper Colorado River Basin

In mountain, snow driven catchments, snowmelt is supposed to be the primary contribution to river streamflows during spring. In these catchments the contribution of groundwater is not well documented because of the difficulty to monitor groundwater in such complex environment with deep aquifers. In this study we use an integrated hydrologic model to conduct numerical experiments that help quantify the effect of lateral groundwater flow on total annual and peak streamflow in predevelopment conditions. Our simulations focus on the Upper Colorado River Basin (UCRB; 2.8 × 10⁵ km²) a well-documented mountain catchment for which both streamflow and water table measurements are available for several important sub-basins. For the simulated water year, our results suggest an increase in peak flow of up to 57% when lateral groundwater flow processes are included—an unexpected result for flood conditions generally assumed independent of groundwater. Additionally, inclusion of lateral groundwater flow moderately improved the model match to observations. The correlation coefficient for mean annual flows improved from 0.84 for the no lateral groundwater flow simulation to 0.98 for the lateral groundwater flow one. Spatially we see more pronounced differences between lateral and no lateral groundwater flow cases in areas of the domain with steeper topography. We also found distinct differences in the magnitude and spatial distribution of streamflow changes with and without lateral groundwater flow between Upper Colorado River Sub-basins. A sensitivity test that scaled hydraulic conductivity over two orders of magnitude was conducted for the lateral groundwater flow simulations. These results show that the impact of lateral groundwater flow is as large or larger than an order of magnitude change in hydraulic conductivity. While our results focus on the UCRB, we feel that these simulations have relevance to other headwaters systems worldwide.     

Patuxent Landscape Model: 4. Model application

Using the LHEM/SME the Patuxent Landscape Model (PLM) was built to simulate fundamental ecological processes in the watershed scale driven by temporal (nutrient loadings, climatic conditions) and spatial (land use patterns) forcings. The model addresses the effects of both the magnitude and spatial patterns of land use change and agricultural practices on hydrology, plant productivity, and nutrient cycling in the landscape.