Chemical models of vitrinite reflectance evolution

A global kinetic model of vitrinite reflectance evolution is developed to illustrate a new approach to vitrinite reflectance modelling. The method utilizes quantitative pyrolysisgas Chromatographic data from isolated vitrinite kerogens to derive the concentrations of structurally specific moieties (alkylphenol precursors) in vitrinite kerogens as a function of rank. This data set is used to calibrate a gaussian distributed activation energy model for phenol-precursor loss from vitrinites using published burial histories. Phenol yield is then correlated with vitrinite reflectance. The predictive vitrinite reflectance model based on this phenol system is tested against a well from the US Gulf Coast area, the results being compared with a Lopatin model of the same well. This type of vitrinite reflectance model is numerically compatible with current generation kinetic models of hydrocarbon production from source rock kerogens, and has a better heating rate independence than Lopatin's method.

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Zusammenfassung Um eine neue Annäherung an das Modellieren der Vitrinit-Reflexion zu demonstrieren, wurde ein global-kinetisches Modell der Entwicklung der Vitrinit-Reflexion erstellt. Die Methode verwendet Daten von quantitativer Pyrolyse-Gas Chromatographie isolierten Vitrinitkerogens, um die Konzentration von strukturspezifischen Moieten (Alkylophenol-Vorläufer) in Vitrinitkerogen als Funktion der Reihenfolge zu erhalten. Verwendet werden diese Daten, um ein nach Gauss verteiltes Aktivierungsenergiemodell zu kalibrieren, das mit Hilfe von veröffentlichten Ablagerungsgeschichten den Phenol-Vorläuferverlust von Vitriniten beschreibt. Die Phenol-Ausbeute wird dann mit der Vitrinit-Reflexion korreliert. Das auf dem Phenolsystem basierende Vitrinit-Reflexionsmodell wird in einem Test einem Bohrloch an der amerikanischen Golfküste gegenübergestellt. Die Ergebnisse werden mit dem Lopatinmodell des selben Bohrlochs verglichen. Diese Art eines Vitrinit-Reflexionsmodells ist numerisch wettbewerbsfähig mit der heutigen Generation kinetischer Modelle der Kohlenwasserstofferzeugung aus Trägergesteinskerogenen. Außerdem ist seine Unabhängigkeit von der Erhitzungsrate größer als mit der Lopatin-Methode.

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Résumé L'auteur présente un modèle cinétique global de l'évaluation du pouvoir réflecteur de la vitrinite, afin d'illuster une approche nouvelle dans la modélisation de ce pourvoir réflecteur. Cette méthode utilise des données quantitatives fournies par la pyrolyse combinée à la Chromatographie en phase gazeuse et relatives à des kérogènes de vitrinite. A partir de ces données, on exprime les concentrations des fractions à structure spécifique dans les kérogènes vitrinitiques en fonction du degré d'évolution. A partir de cet ensemble de données, on établit un modèle de l'énergie d'activation selon une distribution gaussienne, applicable à la perte de phénol-précurseur dans les vitrinites, en se référant à cet effet aux déroulements historiques de l'enfouissement fournis par la littérature. La production de phénol est alors mise en relation avec le pourvoir réflecteur de la vitrinite. Le modèle du pouvoir réflecteur prévisible, basé sur ce système des phénols a été contrôlé dans un forage de la côte du golfe du Mexique (USA), et les résultats comparés à ceux du modèle de Lopatin appliqué au même forage. Le modèle présenté est numériquement compatible avec les modèles cinétiques habituels qui rendent compte de la production d'hydrocarbure à partir des kérogènes des roches-mères; il présente une meilleure indépendance que la méthode de Lopatin par rapport au taux d'échauffement.

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The First Hop: Use of Beaufort Sea Deltas by Hatch-Year Semipalmated Sandpipers

River deltas along Alaska’s Beaufort Sea coast are used by hatch-year semipalmated sandpipers (Calidris pusilla) after leaving their terrestrial natal sites, but the drivers of their use of these stopover sites on the first “hop” of fall migration are unknown. We quantified sandpiper temporal distribution and abundance as related to food resources at three river deltas during the beginning of their fall migration (post-breeding period) to compare the habitat quality among these deltas. We conducted population counts, sampled invertebrates, and captured birds to collect blood samples from individuals for triglyceride and stable isotope analyses to determine fattening rates and diet. Patterns of sandpiper and invertebrate abundance were complex and varied among deltas and within seasons. River deltas were used by sandpipers from late July to late August, and peak sandpiper counts ranged from 1000 to 4000 individuals, of which 98% were hatch-year semipalmated sandpipers. Isotopic signatures from blood plasma samples indicated that birds switched from a diet of upland tundra to delta invertebrate taxa as the migration season progressed, suggesting a dependence on delta invertebrates. Despite differences in diet among deltas, we found no differences in fattening rates of juvenile sandpipers as indicated by triglyceride levels. The number of sandpipers was positively associated with abundance of Amphipoda and Oligochaeta at the Jago and Okpilak-Hulahula deltas; an isotopic mixing model indicated that sandpipers consumed Amphipoda and Oligochaeta at Jago, mostly Chironomidae at Okpilak-Hulahula and Spionidae at Canning. Regardless of the difference in sandpiper diets at the Beaufort Sea deltas, their similar fattening rates throughout the season indicate that all of these stopover sites provide a critical food resource for hatch-year sandpipers beginning their first migration.     

Intimate Distance: The Unconscious Dimensions of the Rapport Between Researcher and Researched

To explore how psychoanalysis might contribute to the methodology of human geography, this article returns to Freud's experiences of psycho-logical analysis before he develops psychoanalysis as a distinct understanding of the mind, identity formation, and subjectivity. Going back over the early history of psychoanalysis, Freud's psychoanalysis can be seen as an attempt to solve a set of problems inherent in late nineteenth-century psycho-logical analysis. Thus, it is possible to cast his methodological solutions in a new light. In particular, this article explores the problems associated with the unconscious rapport that developed in the therapeutic use of hypnotism in the cure of hysterical symptoms, for both doctor and patient. Freud's techniques can be seen as a way to produce an appropriate detachment—or intimate distance—between himself and his clients. This intimate distance is instructive. As a corrective to certain trajectories within human geography, this article identifies five methodological propositions that might inform future research.     

Benthic meiofauna community composition at polluted and non-polluted sites in New Zealand intertidal environments

Meiofauna composition was investigated for six field sites, including polluted and non-polluted sites, within two regions (Auckland and Bay of Plenty) during winter (July-August 2004) in the North Island of New Zealand. Physico-chemical parameters were measured during the sampling period and meiofauna distribution and abundance were compared with these measured parameters. Analysis of meiofauna abundance indicated that foraminiferans, nematodes and ostracods were the taxa that contributed to the variability between field sites within the Auckland region. However, no clear taxa dominance was seen in the Bay of Plenty region. Comparison of meiofauna abundance and physico-chemical parameters was done using multivariate analysis (PRIMER). However, no clear relationships between the parameters were observed in any field site in either region. The Shannon-Weiner index of diversity did not show any clear differentiation between polluted and non-polluted field sites. Therefore, from the present study, the taxa or physico-chemical parameters used could not effectively characterise pollution at the investigated field sites.     

Environmental changes on Yugorski Peninsula, Kara Sea, Russia, during the last 12,800 radiocarbon years

New pollen and radiocarbon data from an 8.6-m coastal section, Cape Shpindler (69°43′N; 62°48′E), Yugorski Peninsula, document the latest Pleistocene and Holocene environmental history of this low Arctic region. Twelve AMS ¹⁴C dates indicate that the deposits accumulated since about 13,000 until 2000 radiocarbon years BP. A thermokarst lake formed ca. 13,000–12,800 years BP, when scarce arctic tundra vegetation dominated the area. By 12,500 years BP, a shallow lake existed at the site, and Arctic tundra with Poaceae, Cyperaceae, Salix, Saxifraga, and Artemisia dominated nearby vegetation. Climate was colder than today. Betula nana became dominant during the Early Preboreal period about 9500 years BP, responding to a warm event, which was one of the warmest during the Holocene. Decline in B. nana and Salix after 9500 years BP reflects a brief event of Preboreal cooling. A subsequent increase in Betula and Alnus fruticosa pollen percentages reflects amelioration of environmental conditions at the end of Preboreal period (ca. 9300 years BP). A decline in arboreal taxa later, with a dramatic increase in herb taxa, reflects a short cold event at about 9200 years BP. The pollen data reflect a northward movement of tree birch, peaking at the middle Boreal period, around 8500 years BP. Open Betula forest existed on the Kara Sea coast of the Yugorski Peninsula during the Atlantic period (8000–4500 years BP), indicating that climate was significantly warmer than today. Deteriorating climate around the Atlantic–Subboreal boundary (ca. 4500 years BP) is recorded by a decline in Betula percentages. Sedimentation slowed at the site, and processes of denudation and/or soil formation started at the beginning of the Subatlantic period, when vegetation cover on Yugorski Peninsula shifted to near-modern assemblages.     

Late Holocene lake level dynamics inferred from magnetic susceptibility and stable oxygen isotope data: Lake Elsinore, southern California (USA)

Southern California faces an imminent freshwater shortage. To better assess the future impact of this water crisis, it is essential that we develop continental archives of past hydrological variability. Using four sediment cores from Lake Elsinore in Southern California, we reconstruct late Holocene (3800 calendar years B.P.) hydrological change using a twentieth-century calibrated, proxy methodology. We compared magnetic susceptibility from Lake Elsinore deep basin sediments, lake level from Lake Elsinore, and regional winter precipitation data over the twentieth century to calibrate the late Holocene lake sediment record. The comparison revealed a strong positive, first-order relationship between the three variables. As a working hypothesis, we suggest that periods of greater precipitation produce higher lake levels. Greater precipitation also increases the supply of detritus (i.e., magnetic-rich minerals) from the lake's surrounding drainage basin into the lake environment. As a result, magnetic susceptibility values increase during periods of high lake level. We apply this modern calibration to late Holocene sediments from the lake's littoral zone. As an independent verification of this hypothesis, we analyzed ¹⁸O_(calcite), interpreted as a proxy for variations in the precipitation:evaporation ratio, which reflect first order hydrological variability. The results of this verification support our hypothesis that magnetic susceptibility records regional hydrological change as related to precipitation and lake level. Using both proxy data, we analyzed the past 3800 calendar years of hydrological variability. Our analyses indicate a long period of dry, less variable climate between 3800 and 2000 calendar years B.P. followed by a wet, more variable climate to the present. These results suggest that droughts of greater magnitude and duration than those observed in the modern record have occurred in the recent geological past. This conclusion presents insight to the potential impact of future droughts on the over-populated, water-poor region of Southern California.     

Predicted changes in fire weather suggest increases in lightning fire initiation and future area burned in the mixedwood boreal forest

Forecasting future fire activity as a function of climate change is a step towards understanding the future state of the western mixedwood boreal ecosystem. We developed five annual weather indices based on the Daily Severity Rating (DSR) of the Canadian Forest Fire Weather Index System and estimated their relationship with annual, empirical counts of lightning fire initiation for 588 landscapes in the mixedwood boreal forest in central-eastern Alberta, Canada from data collected between 1983 and 2001 using zero-inflated negative binomial regression models. Two indices contributed to a parsimonious model of initiation; these were Seasonal Severity Rating (SSR), and DSR-sequence count. We used parameter estimates from this model to predict lightning fire initiation under weather conditions predicted in 1 × CO₂ (1975–1985), 2 × CO₂ (2040–2049) and 3 × CO₂ (2080–2089) conditions simulated by the Canadian Regional Climate Model (CRCM). We combined predicted initiation rates for these conditions with existing empirical estimates of the number of fire initiations that grow to be large fires (fire escapes) and the fire size distribution for the region, to predict the annual area burned by lightning-caused fires in each of the three climate conditions. We illustrated a 1.5-fold and 1.8-fold increase of lightning fire initiation by 2040–2049 and 2080–2089 relative to 1975–1985 conditions due to changes in fire weather predicted by the CRCM; these increases were calculated independent of changes in lightning activity. Our simulations suggested that weather-mediated increases in initiation frequency could correspond to a substantial increase in future area burned with 1.9-fold and 2.6-fold increases in area burned in 2040–2049 and 2080–2089 relative to 1975–1985 conditions, respectively. We did not include any biotic effects in these estimates, though future patterns of initiation and fire growth will be regulated not only by weather, but also by vegetation and fire management.     

Supercritical gas sorption on moist coals

The effect of moisture on the CO₂ and CH₄ sorption capacity of three bituminous coals from Australia and China was investigated at 55 °C and at pressures up to 20 MPa. A gravimetric apparatus was used to measure the gas adsorption isotherms of coal with moisture contents ranging from 0 to about 8%. A modified Dubinin–Radushkevich (DR) adsorption model was found to fit the experimental data under all conditions. Moisture adsorption isotherms of these coals were measured at 21 °C. The Guggenheim–Anderson–de Boer (GAB) model was capable of accurately representing the moisture isotherms over the full range of relative pressures.Moist coal had a significantly lower maximum sorption capacity for both CO₂ and CH₄ than dry coal. However, the extent to which the capacity was reduced was dependent upon the rank of the coal. Higher rank coals were less affected by the presence of moisture than low rank coals. All coals exhibited a certain moisture content beyond which further moisture did not affect the sorption capacity. This limiting moisture content was dependent on the rank of the coal and the sorbate gas and, for these coals, corresponded approximately to the equilibrium moisture content that would be attained by exposing the coal to about 40–80% relative humidity. The experimental results indicate that the loss of sorption capacity by the coal in the presence of water can be simply explained by volumetric displacement of the CO₂ and CH₄ by the water. Below the limiting moisture content, the CO₂ sorption capacity reduced by about 7.3 kg t^− 1 for each 1% increase in moisture. For CH₄, sorption capacity was reduced by about 1.8 kg t^− 1 for each 1% increase in moisture.The heat of sorption calculated from the DR model decreased slightly on addition of moisture. One explanation is that water is preferentially attracted to high energy adsorption sites (that have high energy by virtue of their electrostatic nature), expelling CO₂ and CH₄ molecules.