Oil-generation kinetics for organic facies with Type-II and -IIS kerogen in the Menilite Shales of the Polish Carpathians

The Menilite Shales (Oligocene) of the Polish Carpathians are the source of low-sulfur oils in the thrust belt and some high-sulfur oils in the Carpathian Foredeep. These oil occurrences indicate that the high-sulfur oils in the Foredeep were generated and expelled before major thrusting and the low-sulfur oils in the thrust belt were generated and expelled during or after major thrusting. Two distinct organic facies have been observed in the Menilite Shales. One organic facies has a high clastic sediment input and contains Type-II kerogen. The other organic facies has a lower clastic sediment input and contains Type-IIS kerogen. Representative samples of both organic facies were used to determine kinetic parameters for immiscible oil generation by isothermal hydrous pyrolysis and S₂ generation by non-isothermal open-system pyrolysis. The derived kinetic parameters showed that timing of S₂ generation was not as different between the Type-IIS and -II kerogen based on open-system pyrolysis as compared with immiscible oil generation based on hydrous pyrolysis. Applying these kinetic parameters to a burial history in the Skole unit showed that some expelled oil would have been generated from the organic facies with Type-IIS kerogen before major thrusting with the hydrous-pyrolysis kinetic parameters but not with the open-system pyrolysis kinetic parameters. The inability of open-system pyrolysis to determine earlier petroleum generation from Type-IIS kerogen is attributed to the large polar-rich bitumen component in S₂ generation, rapid loss of sulfur free-radical initiators in the open system, and diminished radical selectivity and rate constant differences at higher temperatures. Hydrous-pyrolysis kinetic parameters are determined in the presence of water at lower temperatures in a closed system, which allows differentiation of bitumen and oil generation, interaction of free-radical initiators, greater radical selectivity, and more distinguishable rate constants as would occur during natural maturation. Kinetic parameters derived from hydrous pyrolysis show good correlations with one another (compensation effect) and kerogen organic-sulfur contents. These correlations allow for indirect determination of hydrous-pyrolysis kinetic parameters on the basis of the organic-sulfur mole fraction of an immature Type-II or -IIS kerogen.     

Early Carboniferous (Viséan) emplacement of the collisional Kłodzko–Złoty Stok granitoids (Sudetes, SW Poland): constraints from geochemical data and zircon U–Pb ages

Sensitive high-resolution ion microprobe zircon U–Pb dating and geochemical data of igneous rocks from the composite K?odzko–Z?oty Stok (KZS) Granite Pluton, Sudetic Block, indicate that the granitoids represent an Early Carboniferous Viséan phase of Variscan metaluminous, high-K, I-type, syn-collisional granite magmatism within the Saxothuringian Zone of the Central European Variscides. Igneous zircon records hypabyssal magmatism that produced various granitoids and lamprophyre (spessartite) emplaced from ca. 340 to 331 Ma. The KZS granitoids have compositions ranging from granodiorite to monzonite, low A/CNK ratios (<1), and are associated with abundant mafic members. Most of them are alkaline, highly potassic, and moderately evolved. The major and trace element contents of the KZS granitoids suggest geochemical heterogeneity, and the hybrid nature of magmas derived from a range of sources in the middle crust, with a strong input of material from the upper mantle. Mixing of magmas of mantle origin with high-K material from partly melted continental crust was probably a more important factor than fractional crystallization, in controlling the evolution of the magmas. The mean Pb–U ages of the main population of igneous zircon from a quartz monzodiorite (?elazno) and hornblende monzonite (Droszków) are 340.2 ± 2.5 Ma and 339.5 ± 3.1 Ma, respectively. A slightly younger biotite-hornblende granodiorite from Chwalis?aw, 336.7 ± 2.5 Ma, was cut by a spessartite dyke at 333.1 ± 3.1 Ma. This indicates that mafic magmas were immediately intruded into fractured, probably incompletely solidified, granodiorites. The lamprophyric dyke also contains igneous zircon of Neoproterozoic age, 566.3 ± 6.4 Ma, typical of the crust in the Saxothuringian Zone. Tonalite from Ptasznik Hill near Droszków is of similar age to the spessartite, 331.5 ± 2.6 Ma. High REE contents in the tonalite and its igneous zircon indicate advanced differentiation of granitic magma, producing a more leucocratic melt associated with post-magmatic activity including abundant late crosscutting pegmatites and quartz veins, and contact metasomatic mineralization. The KZS granitoids have rather similar petrographic and geochemical characteristics to granitoids from other parts of the Central European Variscides, where a thickened orogenic root caused a substantial rise in crustal temperatures, producing granitoid magmas closely correlated with regional tectonic activity between the Saxothuringian and Brunovistulia Terranes at the NE margin of the Bohemian Massif.     

Gamma Emitters on Micro-Becquerel Activity Level in Air at Kraków (Poland)

The Petryanov air filters combined into half-year sets were analyzed for the presence of ⁴⁰K, ¹³⁷Cs and ²²Na by means of low-background gamma rays spectrometry. Each sample contains aerosols from more than 1 Mm³ of air. Samples were collected in ground level air at Kraków (Southern Poland) from 1996 to 2002. Activity concentrations of ⁴⁰K are almost constant with the mean of 14.7± 4.5 Bq m^–3. Activity concentrations of ¹³⁷Cs, which are on the level of single Bq m^{– 3} show exponential decrease with effective half-life time of 7.07± 0.77 years. The cosmogenic ²²Na shows a strong seasonal variation with significant different mean values activity concentration between 0.333± 0.095 Bq m^–3 and 0.137± 0.045 Bq m^–3, for summer and winter, respectively. Moreover, the activity ratio for two cosmogenic radionuclides: ²²Na and measured previously ⁷Be show also changes with statistically significant seasonal differences. The lower values were found during winters. The mechanisms which might govern this ratio are discussed. The conclusion is that transport of ²²Na during summer seems to be so much effective, that results in kind of relative depletion of stratosphere of this nuclide.     

The urban heat island in the city of Poznań as derived from Landsat 5 TM

Deforestation is expanding and accelerating into the remaining areas of undisturbed forest, and the quality of the remaining forests is declining today. Assessing the climatic impacts of deforestation can help to rectify this alarming situation. In this paper, how historical deforestation may affect global climate through interactive ocean and surface albedo is examined using an Earth system model of intermediate complexity (EMIC). Control and anomaly integrations are performed for 1000 years. In the anomaly case, cropland is significantly expanded since AD 1700. The response of climate in deforested areas is not uniform between the regions. In the background of a global cooling of 0.08 °C occurring with cooler surface air above 0.4 °C across 30° N to 75° N from March to September, the surface albedo increase has a global cooling effect in response to global-scale replacement of forests by cropland, especially over northern mid-high latitudes. The northern mid-latitude (30° N–60° N) suffers a prominent cooling in June, suggesting that this area is most sensitive to cropland expansion through surface albedo. Most regions show a consistent trend between the overall cooling in response to historical deforestation and its resulting cooling due to surface albedo anomaly. Furthermore, the effect of the interactive ocean on shaping the climate response to deforestation is greater than that of prescribed SSTs in most years with a maximum spread of 0.05 °C. This difference is more prominent after year 1800 than that before due to the more marked deforestation. These findings show the importance of the land cover change and the land surface albedo, stressing the necessity to analyze other biogeophysical processes of deforestation using interactive ocean.     

Simulation of an uncertain emission market for greenhouse gases using agent-based methods

The paper presents the problem of a simulation of the greenhouse gases emission permits market where only low accuracy emission amounts are known. An organization of the market with uncertain emissions is proposed and trading rules for individual market participants are discussed. Simulation of the market is based on a multi-agent system. Negotiation of purchase/sale prices between the parties are introduced, where the trading parties adopt one of two options: (i) bilateral negotiations, and (ii) sealed bid reverse auctions. Results of simulation runs show trajectories of transaction prices, as well as probability distributions of learning agents’ bidding prices.     

Nondimensionalization of the Atmospheric Boundary-Layer System: Obukhov Length and Monin–Obukhov Similarity Theory

Boundary-Layer Meteorology - The Obukhov length, although often adopted as a characteristic scale of the atmospheric boundary layer, has been introduced purely based on a dimensional argument...     

CO 2 emission trading model with trading prices

In this paper we consider the buying/selling prices of carbon dioxide (CO₂) emission permits in trading models with uncertainty. Permission prices, although usually omitted from standard models, may significantly influence the trading market. We thus undertook to construct a more realistic trade model and to compare it with the standard one. To do this, we introduced several important changes to the standard model, namely, (1) a new optimized quality function; and (2) transactions with price negotiations between regions. We also enhanced the model using methods described in the literature to allow it to deal with reported emissions uncertainty. Additionally, we used an original method of simulating this kind of market based on a specialized evolutionary algorithm (EA).     

Temporal variations in heat fluxes over a central European city centre

Summary Energy fluxes have been measured over an area near the centre of the city of Łódź, Poland, since November 2000. The site was selected because the building style (surface cover and morphology) is typical of European cities, yet distinct from the majority of cities where energy balance observations have been studied thus far. The multi-year dataset permits consideration of temporal changes in energy balance partitioning over a wide range of seasonal and synoptic conditions and of the role of heat storage and anthropogenic fluxes in the energy balance. Partitioning of net radiation into the turbulent fluxes is consistent in the two years, with the largest differences occurring due to differing precipitation. The monthly ensemble diurnal cycles of the turbulent fluxes over the two years are similar. The largest differences occur during the July–September period, and are attributable to greater net radiation and lower rainfall in 2002. The latent heat flux accounts for approximately 40% of the turbulent heat transfer on an annual basis. The average daily daytime Bowen ratio and its variability are slightly reduced during the summer (growing) season. Anthropogenic heat is a significant input to the urban energy balance in the winter. The fluxes observed in this study are consistent with results from other urban sites.     

Early stage of critical clusters growth in phenomenological and molecular dynamics simulation models

The growth of critical clusters is discussed in the paper according to the classical and molecular dynamics (MD) approaches. A new formula for molecule numbers in critical clusters has been derived within the framework of the classical approach. A set of equations controlling the early stage of growth in a neighborhood of a critical size is presented. As far as molecular dynamics simulation is concerned, a computational technique based on the DL_POLY code is described in brief. Computation results are presented concerning cluster formation of H₂O vapor, distribution of clusters versus time, cluster growth and radial density distribution of isolated clusters. A comparison with the classical results is made for a case of dense vapor, where the mechanism of strong condensation is predominant. The Hertz–Knudsen formula seems to be verified by the molecular dynamics results.