Comparative studies of the kinetic parameters of various algaenans and kerogens via open-system pyrolyses

Kinetic parameters were determined for the first time, via open-system pyrolyses, on algaenans (highly resistant biomacromolecules that are selectively preserved during kerogen formation) isolated from extant microalgae. Parallel studies were also carried out on 10 kerogens exhibiting, with one exception, a low level of maturity. These kerogens included samples chiefly derived from the selective preservation of the above algaenans and samples mainly, or almost exclusively, derived from the “natural vulcanization” pathway. Important differences in activation energy (E_a) distributions were observed between the four algaenans investigated and correlated with their chemical structures. The kerogens predominantly derived from algaenan-selective preservation (Pula alginite, NE 70 and BJ 248 Torbanites, Rundle Oil Shale) also exhibited pronounced differences in E_a distributions. These distributions provided: (i) information on the diversity of the source materials; and (ii) reflected the occurrence of important differences in chemical structures and thermal behaviour between three of the tested kerogens, even though they are all classified as low maturity type I. The Kimmeridge Clay samples and the Lorca Oil Shale showed broad E_a distributions shifted to low energies when compared with the above algaenans and kerogens. Such shifts reflect an important (or even almost exclusive for some of these kerogens) contribution of materials originating from sulphur incorporation into various lipids during early diagenesis. Finally, the kinetic data derived for the nine low maturity fossil samples were extrapolated to a very low, geological heating rate of 3°C Ma⁻¹ and the generation rate curves and cumulative yield curves thus obtained were compared.     

Mineral inclusions in diamonds from the Sputnik kimberlite pipe, Yakutia

The Sputnik kimberlite pipe is a small “satellite” of the larger Mir pipe in central Yakutia (Sakha), Russia. Study of 38 large diamonds (0.7-4.9 carats) showed that nine contain inclusions of the eclogitic paragenesis, while the remainder contain inclusions of the peridotitic paragenesis, or of uncertain paragenesis. The peridotitic inclusion suite comprises olivine, enstatite, Cr-diopside, chromite, Cr-pyrope garnet (both lherzolitic and harzburgitic), ilmenite, Ni-rich sulfide and a Ti-Cr-Fe-Mg-Sr-K phase of the lindsleyite-mathiasite (LIMA) series. The eclogitic inclusion suite comprises omphacite, garnet, Ni-poor sulfide, phlogopite and rutile. Peridotitic ilmenite inclusions have high Mg, Cr and Ni contents and high Nb/Zr ratios; they may be related to metasomatic ilmenites known from peridotite xenoliths in kimberlite. Eclogitic phlogopite is intergrown with omphacite, coexists with garnet, and has an unusually high TiO₂ content. Comparison with inclusions in diamonds from Mir shows general similarities, but differences in details of trace-element patterns. Large compositional variations among inclusions of one phase (olivine, garnet, chromite) within single diamonds indicate that the chemical environment of diamond crystallisation changed rapidly relative to diamond growth rates in many cases. P-T conditions of formation were calculated from multiphase inclusions and from trace element geothermobarometry of single inclusions. The geotherm at the time of diamond formation was near a 35 mW/m² conductive model; that is indistinguishable from the Paleozoic geotherm derived by studies of xenoliths and concentrate minerals from Mir. A range of Ni temperatures between garnet inclusions in single diamonds from both Mir and Sputnik suggests that many of the diamonds grew during thermal events affecting a relatively narrow depth range of the lithosphere, within the diamond stability field. The minor differences between inclusions in Mir and Sputnik may reflect lateral heterogeneity in the upper mantle.     

Partial melting of metagreywackes, Part II. Compositions of minerals and melts

A series of experiments on the fluid-absent melting of a quartz-rich aluminous metagreywacke has been carried out. In this paper, we report the chemical composition of the phases present in the experimental charges as determined by electron microprobe. This analytical work includes biotite, plagioclase, orthopyroxene, garnet, cordierite, hercynite, staurolite, gedrite, oxide, and glass, over the range 100–1000 MPa, 780–1025 °C. Biotites are Na- and Mg-rich, with Ti contents increasing with temperature. The compositions of plagioclase range from An₁₇ to An₃₅, with a significant orthoclase component, and are always different from the starting minerals. At high temperature, plagioclase crystals correspond to ternary feldspars with Or contents in the range 11–20 mol%. Garnets are almandine pyrope grossular spessartine solid solutions, with a regular and significant increase of the grossular content with pressure. All glasses are silicic (SiO₂ = 67.6–74.4 wt%), peraluminous, and leucocratic (FeO + MgO = 0.9–2.9 wt%), with a bulk composition close to that of peraluminous leucogranites, even for degrees of melting as high as 60 vol.%. With increasing pressure, SiO₂ contents decrease while K₂O increases. At any pressure, the melt compositions are more potassic than the water-saturated granitic minima. The H₂O contents estimated by mass balance are in the range 2.5–5.6 wt%. These values are higher than those predicted by thermodynamic models. Modal compositions were estimated by mass balance calculations and by image processing of the SEM photographs. The positions of the 20 to 70% isotects (curves of equal proportion of melt) have been located in the pressure-temperature space between 100 MPa and 1000 MPa. With increasing pressure, the isotects shift toward lower temperature between 100 and 200 MPa, then bend back toward higher temperature. The melting interval increases with pressure; the difference in temperature between the 20% and the 70% isotects is 40 °C at 100 MPa, and 150 °C at 800 MPa. The position of the isotects is interpreted in terms of both the solubility of water in the melt and the nature of the reactions involved in the melting process. A comparison with other partial melting experiments suggests that pelites are the most fertile source rocks above 800 MPa. The difference in fertility between pelites and greywackes decreases with decreasing pressure. A review of the glass compositions obtained in experimental studies demonstrates that partial melting of fertile rock types in the crust (greywackes, pelites, or orthogneisses) produces only peraluminous leucogranites. More mafic granitic compositions such as the various types of calk-alkaline rocks, or mafic S-type rocks, have never been obtained during partial melting experiments. Thus, only peraluminous leucogranites may correspond to liquids directly formed by partial melting of metasediments. Other types of granites involve other components or processes, such as restite unmixing from the source region, and/or interaction with mafic mantle-derived materials. Received: 11 July 1995 / Accepted: 27 February 1997     

Harmonic Analysis of Sedimentary Cyclic Sequences in Kansas, Midcontinent, USA

Several stratigraphic sequences in the Upper Carboniferous (Pennsylvanian) in Kansas (Midcontinent, USA) were analyzed quantitatively for periodic repetitions. The sequences were coded by lithologic type into strings of datasets. The strings then were analyzed by an adaptation of a one-dimensional Fourier transform analysis and examined for evidence of periodicity. The method was tested using different states in coding to determine the robustness of the method and data. The most persistent response is in multiples of 8–10 ft (2.5–3.0 m) and probably is dependent on the depositional thickness of the original lithologic units. Other cyclicities occurred in multiples of the basic frequency of 8–10 with persistent ones at 22 and 30 feet (6.5–9.0 m) and large ones at 80 and 160 feet (25–50 m). These levels of thickness relate well to the basic cyclothem and megacyclothem as measured on outcrop. We propose that this approach is a suitable one for analyzing cyclic events in the stratigraphic record.     

Arrays of Unpumped Wells for Plume Migration Control by Semi-Passive In Situ Remediation

Arrays of unpumped wells can be used as discontinuous permeable walls in which each well serves both as a means to focus ground water flow into the well for treatment and as a container either for permeable reactive media which directly destroy dissolved ground water contaminants or for devices or materials which release amendments that support in situ degradation of contaminants within the aquifer downgradient of the wells. This paper addresses the use of wells for amendment delivery, recognizing the potential utility of amendments such as electron acceptors (e.g., oxygen nitrate), electron donors (primary substrates), and microbial nutrients for stimulating bioremediation, and the potential utility of oxidizers, reducers, etc., for controlled abiotic degradation. Depending on its rate and constraints, the remedial reaction may occur within the well and/or downgradient. For complete remediation of ground water passing through the well array, the total flux of amendment released must meet or exceed the total flux demand imposed by the plume. When there are constraints on the released concentration of amendment (relative to the demand), close spacing of the wells may be required. If the flux balance allows wider spacing, it is likely that limited downgradient spreading of the released amendment will then be the primary constraint on interwell spacing. Divergent flow from the wells, roughly two times the well diameter, provides the bulk of downgradient spreading and constrains maximum well spacing in the absence of significant lateral dispersion. Stronger lateral dispersion enhances the spreading of amendment, thereby increasing the lateral impact of each well, which allows for wider well spacing.     

Estimating the seismic displacement of friction pendulum isolators based on non‐linear response history analysis

A procedure for developing equations that estimate the isolator displacement due to strong ground motion is applied to buildings isolated with the friction pendulum system. The resulting design equations, based on rigorous non‐linear analysis, offer an alternative to the iterative equivalent‐linear methods used by current U.S. building codes. The governing equations of the system are reduced to a form such that the median normalized displacement of the system due to an ensemble of ground motions is found to depend on only the isolation period—a function of the curvature of the isolator—and the friction force at incipient slip normalized by peak ground velocity. The normalization is effective in minimizing the dispersion of the normalized displacement for an ensemble of ground motions, implying that the median normalized displacement is a reliable estimate of response. The design equations reflect the significant (20 to 38%) increase in displacement when the excitation includes two lateral components of ground motion instead of just one component. Equivalent‐linear methods are shown to underestimate by up to 30% the exact median displacement determined by non‐linear response history analysis for one component of ground motion, and building codes include at most a 4.4% increase for a second component. Copyright © 2003 John Wiley & Sons, Ltd.     

A vibrational spectroscopic study of the oxidation of pyrite by molecular oxygen

In situ flow-through attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to investigate the formation, and step-wise oxidation, of sulfoxyanions at the pyrite surface during oxidation by molecular oxygen. The surface was studied under two different pH regimes (pH 2.5 and pH 5.6) and under two light conditions (dark and ultraviolet light). It was experimentally observed that multiple sulfoxyanions were present at the pyrite surface during oxidation by molecular oxygen, spectroscopically illustrating the concept of sulfur step-wise oxidation. The results from photochemical experiments were complex and suggest a dependence on both pH and surface speciation.     

Are isolated stable rigid clasts in shear zones equivalent to voids?

Particles in shear enclose important information about a rock's past and can potentially be used to decipher the kinematic history and mechanical behavior of a certain outcrop or region. Isolated rigid clasts in shear zones often exhibit systematic inclinations with respect to the shear-plane at small angles, tending towards the instantaneous stretching direction of the shear zone. This shape preferred orientation cannot be easily explained by any of the analytical theories used in geology. It was recently recognized that a weak mantle surrounding the clast or a slipping clast–matrix interface might be responsible for the development of the observed inclinations. Physical considerations lead us to conjecture that such mantled, rigid clasts can be effectively treated as voids that are not allowed to change their shape. The resulting equivalent void conjecture agrees well with numerical and field data and has the following important geological implications. (i) Clasts in shear zones can have stable positions in simple shear without the requirement of an additional pure shear component. (ii) The stable orientation can be approached either syn- or antithetically; hence, the clast can rotate against the applied shear sense. (iii) The strain needed to develop a strong shape preferred orientation is small (γ≈1) and therefore evaluations based on other theories may overestimate strain by orders of magnitude. (iv) The reconstruction of far-field shear flow conditions and kinematic vorticity analysis must be modified to incorporate these new findings.     

Torngat ultramafic lamprophyres and their relation to the North Atlantic Alkaline Province

Geological mapping and diamond exploration in northern Quebec and Labrador has revealed an undeformed ultramafic dyke swarm in the northern Torngat Mountains. The dyke rocks are dominated by an olivine-phlogopite mineralogy and contain varying amounts of primary carbonate. Their mineralogy, mineral compositional trends and the presence of typomorphic minerals (e.g. kimzeyitic garnet), indicate that these dykes comprise an ultramafic lamprophyre suite grading into carbonatite. Recognized rock varieties are aillikite, mela-aillikite and subordinate carbonatite. Carbonatite and aillikite have in common high carbonate content and a lack of clinopyroxene. In contrast, mela-aillikites are richer in mafic silicate minerals, in particular clinopyroxene and amphibole, and contain only small amounts of primary carbonate. The modal mineralogy and textures of the dyke varieties are gradational, indicating that they represent end-members in a compositional continuum.

The Torngat ultramafic lamprophyres are characterized by high but variable MgO (10–25 wt.%), CaO (5–20 wt.%), TiO₂ (3–10 wt.%) and K₂O (1–4 wt.%), but low SiO₂ (22–37 wt.%) and Al₂O₃ (2–6 wt.%). Higher SiO₂, Al₂O₃, Na₂O and lower CO₂ content distinguish the mela-aillikites from the aillikites. Whereas the bulk rock major and trace element concentrations of the aillikites and mela-aillikites overlap, there is no fractional crystallization relation between them. The major and trace element characteristics imply related parental magmas, with minor olivine and Cr-spinel fractionation accounting for intra-group variation.

The Torngat ultramafic lamprophyres have a Neoproterozoic age and are spatially and compositionally closely related with the Neoproterozoic ultramafic lamprophyres from central West Greenland. Ultramafic potassic-to-carbonatitic magmatism occurred in both eastern Laurentia and western Baltica during the Late Neoproterozoic. It can be inferred from the emplacement ages of the alkaline complexes and timing of Late Proterozoic processes in the North Atlantic region that this volatile-rich, deep-seated igneous activity was a distal effect of the breakup of Rodinia. This occurred during and/or after the rift-to-drift transition that led to the opening of the Iapetus Ocean.