Hydrogen isotopic compositions of individual alkanes as a new approach to petroleum correlation: case studies from the Western Canada Sedimentary Basin

Isotopic compositions of carbon-bound hydrogen in individual n-alkanes and acyclic isoprenoid alkanes, from a number of crude oil samples, were measured using gas chromatography-thermal conversion-isotope ratio mass spectrometry. The precision of this technique is better than 3‰ for most alkanes, compared to the large range of δD variation among the samples (up to 160‰). The oils were selected from major genetic oil families in the Western Canada Sedimentary Basin, with source rocks ranging in age from Ordovician (and possibly Cambrian) to Cretaceous. The hydrogen isotopic composition of alkanes in crude oils is controlled by three factors: isotopic compositions of biosynthetic precursors, source water δD values, and postdepositional processes. The inherited difference in the lipid's biosynthetic origins and/or pathways is reflected by a small hydrogen isotopic variability within n-alkanes, but much larger differences in the δD values between n-alkanes and pristane/phytane. The shift toward lighter hydrogen isotopic compositions from Paleozoic to Upper Cretaceous oils in the WCSB reflects a special depositional setting and/or a minor contribution of terrestrial organic matter. The strong influence of source water δD values is demonstrated by the distinctively lower δD values of lacustrine oils than marine oils, and also by the high values for oils with source rocks deposited in evaporative environments. Thermal maturation may alter the δD values of the alkanes in the oil to some extent, but secondary oil migration does not appear to have had any significant impact. The fact that oils derived from source rocks that could be of Cambrian age still retain a strong signature of the hydrogen isotopic compositions of source organic matter, and source water, indicates that δD values are very useful for oil-source correlation and for paleoenvironmental reconstructions.     

Basic-Level Geographic Categories*

As we experience places, we learn about those places and generalize information into more abstract geographic categories. Rosch's basic-level theory argues that information known about objects is stored in our memories in a three-layered hierarchy. Data that could be used to test this theory in a geographic context was generated by having subjects make lists of activities, characteristics, and parts associated with 11 familiar geographic categories. An analysis of the distribution of information among the geographic categories confirmed two basic predictions of Rosch's theory. Significantly more information was stored in the basic-level geographic categories country, region, state, city, and neighborhood than in the superordinate category place. Significantly more information was not stored in subordinate categories home country, home region, home state, home city, and home neighborhood. The results suggest that geographic information is efficiently stored in memory so that much of what we know about geographic space is stored in basic-level categories that are both distinctive and informative.     

On the integral equation of the continuous-state stochastic reservoir with seasonally varying autocorrelated inflows

The paper deals with continuous-state reservoirs in discrete time, in terms of the (continuous) Moran transform U_t = Z_t + X_t of the (discontinuous) storage levels Z_t. In the non-seasonal case, if the inflows X_t have a first-order Markov structure, the modified storage levels U_t have a second-order Markov structure. It is shown that, for each value of u, the limit p(u,v) as t → ∞ of the joint density p_{t + 1} (u, v) of U_{t+ 1} at u and U_t at v satisfies a certain non-standard first-order linear integral equation of the form

or, equivalently, a standard second-order equation of the form

In the seasonal case, with two seasons, the corresponding bivariate density p(u,v) for consecutive seasons satisfies a second-order integral equation of the form

the kernel being a function of the season-to-season inflow transition densities.     

Tourmaline in a low grade clastic metasedimentary rock: an example of the petrogenetic potential of tourmaline

Detrital tourmaline grains and their associated tourmaline overgrowths provide a means to unravel the provenance and petrogenetic history of low grade clastic metasedimentary rocks. Evidence derives from tourmaline grains found in a lithic wacke metamorphosed to chlorite zone conditions. The detrital tourmaline cores are diagnostic indicators of the source rocks of the sediment whereas the overgrowths record both diagenetic and metamorphic reactions in the rock. Tourmaline grains consist of a detrital core surrounded by asymmetric overgrowths comprised of inner and outer rims. Abrupt chemical discontinuities between each of these zones implies that volume diffusion within tourmaline was minor under the conditions of formation. Compositions of the detrital cores vary widely, yet can be correlated with source rock types that are consistent with lithic fragments recognizable in the metawacke. At either the analogous or antilogous pole, inner rim compositions proximal to the detrital cores converge, despite the substrate tourmaline composition, indicating an approach to chemical equilibrium. However, significant dufferences in Al and X-site vacancies at the expense of Mg, Na and Ti between the analogous and antilogous poles of the inner rims demonstrate the presence of significant amounts of compositional polarity. Outer rim compositions at either pole also converge but compositional polarity between the analogous and antilogous poles persists. The presence of the inner and outer rims separated by a compositional discontinuity suggests punctuated evolution of the overgrowth. This implies that boron was sporadically available during diagenesis and metamorphism. Based on boron contents of minerals, this may correspond to a mechanism such as boron release due to polytypic change of illite or consumption of illite and/or muscovite. As such, tourmaline growth stages may serve as a monitor of chemical reactions in low grade metamorphic rocks.     

Thermochemical redox equilibria of ZoBell's solution

The redox potential of ZoBell's solution, consisting of $\text{3.33 × 10}{}^{\mathrm{?3}}$ molar K₄Fe(CN)₆, $\text{3.33 × 10}{}^{\mathrm{?3}}$ molar K₃Fe(CN)₆ and 0.10 molar KCl, has been measured by a polished platinum electrode vs a saturated KCl, Ag/AgCl reference electrode. Measurements in the temperature range 8–85°C fit the equation $\text{E(}\text{volts}\text{) = 0.23145 ? 1.5220 × 10}{}^{\mathrm{?3}}\text{(t ? 25) ? 2.2449 × 10}{}^{\mathrm{?6}}\text{(t ? 25)}{}^2$ where $\text{t}$ is in degrees Celsius. Evaluation of literature data was necessary to obtain a reliable value for the Ag/AgCl half-cell reference potential as a function of temperature. Combining the measurements from this study with the literature evaluation of the Ag/AgCl reference potential yields the temperature dependent potential for ZoBell's solution: $\text{E(}\text{volts}\text{) = 0.43028 ? 2.5157 × 10}{}^{\mathrm{?3}}\text{(t ? 25) ? 3.7979 × 10}{}^{\mathrm{?6}}\text{(t ? 25)}{}^2$ relative to the standard hydrogen potential. From these data the enthalpy, entropy, free energy and heat capacity for the ferro-ferricyanide redox couple have been calculated. The temperature equation for the potential of ZoBell's solution may be used for checking potentiometric equipment in the determination of the redox potential of natural waters.     

The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K

While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al₂(SO₄)₃ · 17H₂O, alunite, KAl₃(SO₄)₂(OH)₆, jurbanite, Al(SO₄)(OH) · 5H₂O, and basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O. An examination of literature values shows that the log $\text{K}{}_{\mathrm{sp}}\text{= ?85.4}$ for alunite and log $\text{K}{}_{\mathrm{sp}}\text{= ?117.7}$ for basaluminite. In this report the log $\text{K}{}_{\mathrm{sp}}\text{= ?7.0}$ is estimated for alunogen and log $\text{K}{}_{\mathrm{sp}}\text{= ?17.8}$ is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from $\text{pH < 0}$ up to the range of 3–5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4–7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals.Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption.     

A stress-transfer model for the development of extension fracture boudinage

The term boudinage is used to describe a wide variety of extensional structures in deformed rocks. This paper is mainly concerned with boudinage resulting from through-layer extension fractures followed by separation of the layer segments, thus forming boudins with more or less rectangular cross-sections. In principle, this process is similar to the break up of fibres in fibre-reinforced composite materials extended parallel to the fibre direction. Both processes are controlled by the transfer of stress from the matrix to the fibre (or layer) and a mathematical model for fibre-matrix stress transfer (the ‘fibre-loading’ model) is well established. We have used this as a basis for developing a stress transfer model for boudinage. The only difference in the basic mathematical formulation results from geometric differences between the two systems; the geometric expressions in the fibre-loading model have, therefore, been rederived for the layer-matrix case.Stress-transfer theory predicts that the tensile stress in a layer segment rises from a minimum at the end of a segment to a maximum at the centre. This behaviour, which is clearly shown by finite-element models of boudinage structure, suggests that extension fracture boudinage develops by successive ‘mid-point’ fracturing. According to stress-transfer theory, the process will continue until a layer is reduced to segments (boudins) all of which are shorter than some critical length (for which the tensile fracture strength of the layer is equal to the tensile stress at the mid-point). In practice, successive fracturing will be influenced by two other factors: (1) in nature the controlling material properties (tensile fracture strength, elastic moduli) will not be single-valued but will have a distribution reflecting local variations in lithology and microstructure and (2) major pre-deformation flaws may be present in a layer which will control the ‘starting length’ of layer segments. These factors are incorporated with the stress-transfer theory into a statistical (Monte Carlo) model for extension fracture boudinage which results in a prediction of boudin aspect ratios. The predicted distribution compares very closely with the observed distribution of 91 quartzite boudins within Lower Carboniferous slates at Tintagel, Cornwall.The stress-transfer model implies that boudin-defining fractures occur sequentially so that inter-boudin gap lengths will be unequal. Strain estimates based on boudinage structure will vary according to which part and how much of a layer is sampled. A much improved strain estimate is possible based on sequentially closing the inter-boudin gaps. The stress-transfer theory also leads to the possibility of estimating palaeostress from boudinage structure and is the only model available which predicts an aspect ratio distribution of boudins formed by extension fracture. Other than our own, we know of no published data on boudin aspect ratio distributions. Hence, further elaboration of the model is not possible until more field data is available. We hope that our work will encourage the systematic measurement of boudinage as well as the development of alternative models.