Mathematical models for petroleum-forming processes: carbon isotope fractionation

A mathematical model has been developed in which carbon isotope fractionation during thermal cracking of n-paraffins can be simulated. The model has been calibrated based on data from laboratory cracking experiments carried out on n-octadecane. Relative rate constants for cleavage of C¹²-C¹², C¹²-C¹³ and C¹³-C¹³ bonds agree with the experimental values obtained by other workers.Application of this model to the process of petroleum formation gives good agreement with some existing experimental data, but suggests that a review of our understanding of isotope fractionation during thermal cracking may be necessary. The relative importance of the degree to which the organic material has been cracked and of the type of the organic material in influencing δC¹³ values is discussed.The present model predicts that cracking of n-paraffin distributions having initial odd or even carbon number predominances can induce isotopic inhomogeneity among the homologs of the resulting distribution. The model exhibits some deficiencies in explaining or predicting the δC¹³ values of ethane and propane in relation to methane in gases and of oils and associated methane. Explanations for these discrepancies may lie in the simplicity of our mathematical model, in our assumption of initial isotopic homogeneity within molecules and in our use of only n-paraffins as the source molecules for the cracking reactions.     

Mathematical models for petroleum-forming processes: n-paraffins and isoprenoid hydrocarbons

Mathematical models have been developed which simulate both random and nonrandom thermal cracking of branched and straight-chain hydrocarbons. Application of these models to n-paraffins suggests that thermal cracking alone cannot be the dominant mechanism in formation of the n-paraffin distributions present in crude oils. Application to isoprenoid hydrocarbons indicates that nonrandom cracking could be important in producing the isoprenoid distributions found in oils.Results of the mathematical modeling show that methane formation should, as predicted from energy considerations, be kinetically disfavored. It therefore is likely that substantial quantities of methane are produced from saturated hydrocarbons only under thermal conditions more severe than those under which oil is produced.The mathematical models employed are adaptable for other geochemical applications, such as isotope fractionation.     

A New Model for Heat Flow in Extensional Basins: Estimating Radiogenic Heat Production

Radiogenic heat production (RHP) represents a significant fraction of surface heat flow, both on cratons and in sedimentary basins. RHP within continental crust—especially the upper crust—is high. RHP at any depth within the crust can be estimated as a function of crustal age. Mantle RHP, in contrast, is always low, contributing at most 1 to 2 mW/m² to total heat flow. Radiogenic heat from any noncrystalline basement that may be present also contributes to total heat flow. RHP from metamorphic rocks is similar to or slightly lower than that from their precursor sedimentary rocks. When extension of the lithosphere occurs—as for example during rifting—the radiogenic contribution of each layer of the lithosphere and noncrystalline basement diminishes in direct proportion to the degree of extension of that layer. Lithospheric RHP today is somewhat less than in the distant past, as a result of radioactive decay. In modeling, RHP can be varied through time by considering the half lives of uranium, thorium, and potassium, and the proportional contribution of each of those elements to total RHP from basement. RHP from sedimentary rocks ranges from low for most evaporites to high for some shales, especially those rich in organic matter. The contribution to total heat flow of radiogenic heat from sediments depends strongly on total sediment thickness, and thus differs through time as subsidence and basin filling occur. RHP can be high for thick clastic sections. RHP in sediments can be calculated using ordinary or spectral gamma-ray logs, or it can be estimated from the lithology.     

Occurrence of a regular C25 isoprenoid hydrocarbon in tertiary sediments representing a lagoonal-type,saline environment

A regular C₂₅ isoprenoid alkane (2,6,10,14,18-pentamethyleicosane) has been isolated from highly saline Tertiary sediments. The isolation utilized elution chromatography, urea adduction and gas chromatography; identification was based on the mass spectrum. This C₂₅ isoprenoid may represent a biological marker, possibly typical for a lagoonal-type, saline environment.     

Measuring low concentrations of Th in water and sediment

²³⁴Th/²³⁸U disequilibria have been used extensively in studies of particle dynamics and the fate and transport of particle-reactive matter in marine environments. Similar work in low salinity, estuarine, and freshwater systems has not occurred primarily because the lower concentrations of both parent and daughter nuclides that are typical of these systems often render established methods for the analysis of ²³⁴Th inadequate. The application of this radionuclide tracer technique to these systems, however, has great potential. To this end, we present a method for measuring low activities of ²³⁴Th in relatively small samples (<200 l) using low background gas-flow proportional counters, a ²²⁹Th yield monitor, and empirical corrections for the interferences from real and apparent betas that are emitted by other thorium isotopes and their progeny. For samples with low ²³⁴Th/²²⁸Th activity ratios, we improve upon current beta counting methodologies that rely on immediate sample counting, weak beta absorption, or multiple beta counts so that, using the analytical approach outlined here, it should be possible to measure ²³⁴Th activities (i) as low as 1.5 dpm/total sample, (ii) up to 2 weeks after radiochemical purification of thorium, and (iii) with only one sample count for alpha and beta activity.     

A Review and Evaluation of Specific Heat Capacities of Rocks,Minerals, and Subsurface Fluids. Part 2: Fluids and Porous Rocks

Heat capacities of solid sediments and pore fluids within a basin can influence geothermal gradients when sedimentation or erosion is rapid. This paper provides data on specific heat capacities of pore fluids and porous rocks. It includes data on specific heat capacities of water, ice, and gas hydrates at reference temperatures, as well as equations for calculating the specific heat capacity of those substances as a function of temperature. It also provides values for specific heat capacities of oil and natural gases at low temperatures, as well as equations describing the temperature and pressure dependence of the specific heat capacities of those substances. Finally, it shows how to calculate the specific heat capacity of mixtures of solid materials, or of mixtures of solids and pore fluids. The data and equations provided herein can be incorporated directly into existing modeling software by users and software developers.     

A New Model for Heat Flow in Extensional Basins: Radiogenic Heat,Asthenospheric Heat,and the McKenzie Model

The McKenzie model proposed in 1978, which is widely used in calculating the thermal history of rift basins and other extensional basins, incorrectly assumes that all heat passing through the lithosphere originates below the lithosphere. In reality, heat from radiogenic sources within the lithosphere, especially in the upper crust, may represent more than half the heat flow at the top of basement. Thinning of the lithosphere during extension does indeed result in an increase of heat flowing from the asthenosphere, but this thinning also reduces the radiogenic heat from within the lithosphere. Because these two effects cancel to a large degree, the direct effects of lithospheric extension on heat flow at the top of basement are smaller than those predicted by the McKenzie model. Because of permanent loss of radiogenic material by lithospheric thinning, the heat flow at the top of basement long after rifting will be lower than the pre-rift heat flow.The McKenzie model predicts an instantaneous increase in heat flow during rifting. The Morgan model proposed in 1983, however, predicts a substantial time delay in the arrival of the higher heat flow from the asthenosphere at the top of basement or within sediments. Using the Morgan model, heat flow during the early stages of rifting will actually be lower than prior to rifting, because the time delay in the loss of radiogenic heat is less than the time delay in arrival of new heat from the asthenosphere.     

Phosphate-rich sedimentary rocks: Significance for organic facies and petroleum exploration

Phosphorus-bearing rocks and sediments can be divided into two genetically distinct classes: phosphatic shales or limestones and phosphorites. Phosphatic shales are primary sediments in which phosphate nodules or micronodules have formed diagenetically by precipitation of calcium phosphates derived mainly from organic phosphorus. The nodules form in reducing environments at shallow depths within the sediments, where loss of phosphate by diffusion to the overlying water column is minimized. Highly biogenic sediments containing large amounts of organic matter and some fine clastic debris provide ideal environments for the formation of phosphate nodules.Phosphorites, in contrast, represent concentrated accumulations of reworked phosphate nodules which originated in phosphatic shales or limestones. Currents, wave action, recrystallization, and erosion and resedimentation are important mechanisms in the concentration process.Phosphatic shales and limestones may become excellent oil source rocks if thermal maturity is achieved. They are useful facies indicators for anoxic or nearly anoxic depositional environments, and are often associated with restricted basins, or, during certain geologic periods, with broad shelves developed during transgressions. Phosphorites, in contrast, are often correlated with sea-level regressions or uplifts. They are modest source rocks because of their low organic carbon contents and the fact that they were reworked under oxidizing conditions. Nevertheless, because phosphorites are derived from, and often grade into, phosphatic shales, they also are of potential utility in the search for oil source beds.     

A Review and Evaluation of Specific Heat Capacities of Rocks,Minerals, and Subsurface Fluids. Part 1: Minerals and Nonporous Rocks

Heat capacities of the rocks within a sedimentary basin can significantly influence geothermal gradients if sedimentation or erosion is rapid. This paper provides data on specific heat capacities of minerals and nonporous rocks at 20°C, derives equations for calculating specific heat capacities of minerals and nonporous rocks at temperatures between 0°C and 1200°C, and shows that pressure effects on heat capacities of solids can be neglected. It derives an equation for estimating specific heat capacity of any mineral or nonporous rock as a function of density. Finally, it shows how to calculate the specific heat capacity of any mixture of solid materials. A companion paper discusses specific heat capacities of the fluids in pore spaces of rocks and of fluid-filled porous rocks. The data for minerals and rocks provided herein can be incorporated directly into existing modeling software by users. However, the temperature-dependent equations would have to be incorporated by software developers.     

Evolution of Sandstone Porosity Through Time. The Modified Scherer Model: A Calculation Method Applicable to 1-D Maturity Modeling and Perhaps to Reservoir Prediction

Scherer's model of 1987 successfully predicted present-day porosities of sandstones using four factors: burial depth, stratigraphic age, quartz content, and degree of sorting. This model now has been modified to predict sandstone porosity through time in order to provide a better way to model sandstone porosity for 1-D basin modeling. The Modified Scherer Model (MSM) has many advantages over the depth-dependent Sclater-Christie (Athy) and Falvey-Middleton equations used for calculating porosity in 1-D modeling, because it predicts major differences resulting from age, sedimentation rate, sandstone composition, and pressure that are not considered in depth-dependent models. The only additional information required by the MSM is quartz content and Trask sorting coefficient. If these are not known, they may be estimated with reasonable confidence. The Modified Scherer Method could be added easily to existing software packages for 1-D modeling. It also may prove useful for making preliminary estimates of reservoir porosity (including timing of porosity loss), especially in early stages of exploration.