Carbonyl products of the gas phase reaction of ozone with 1,1-disubstituted alkenes

Carbonyl products have been identified and their formation yields measured in experiments involving the gas phase reaction of ozone with 1,1-disubstituted alkenes at ambient T and p=1 atm. of air. Sufficient cyclohexane was added to scavenge the hydroxyl radical in order to minimize OH-alkene and OH-carbonyl reactions. Formation yields (carbonyl formed/ozone reacted) of primary carbonyls were close to the value of 1.0 that is consistent with the mechanism: O₃+R₁R₂C=CH₂ (HCHO+R₁R₂COO)+(1–)(R₁COR₂+H₂COO) where formaldehyde and the ketone R₁ COR₂ are the primary carbonyls and R₁R₂COO and H₂COO are the corresponding biradicals. Measured values of were 0.58–0.82 and indicate modest preferential formation of formaldehyde and the disubstituted biradical as compared to the ketone and the biradical H₂COO. Carbonyls other than the primary carbonyls were identified. Their formation is discussed in terms of subsequent reactions of the disubstituted biradicals R₁R₂COO. Similarities and differences between disubstituted and monosubstituted biradicals are outlined.     

Study of geothermal water intrusion due to groundwater exploitation in the Puebla Valley aquifer system, Mexico

Significant intrusion of geothermal water into fresh groundwater takes place in the Puebla Valley aquifer system, Mexico. The decline in the potentiometric surface due to the overexploitation of the groundwater induces this intrusion. This hydrological system comprises three aquifers located in Plio-Quaternary volcanic sediments and Mesozoic calcareous rocks. The hydraulic balance of the aquifer shows that the annual output exceeds the natural inputs by 12 million m³. Between 1973 and 2002, a drop in the potentiometric surface, with an 80 m cone of depression, was identified in a 5-km-wide area located southwest of the city of Puebla. Chemical analyses performed on water samples since 1990 have shown an increase in total dissolved solids (TDS) of more than 500 mg/L, coinciding with the region showing a cone of depression in the potentiometric surface. A three-dimensional flow and transport model, based on the hydrogeological and geophysical studies, was computed by using the MODFLOW and MT3D software. This model reproduces the evolution of the aquifer system during the last 30 years and predicts for 2010 an additional drawdown in the potentiometric surface of 15 m, and an increase in the geothermal water intrusion.     

Spatial process and data models: Toward integration of agent-based models and GIS

The use of object-orientation for both spatial data and spatial process models facilitates their integration, which can allow exploration and explanation of spatial-temporal phenomena. In order to better understand how tight coupling might proceed and to evaluate the possible functional and efficiency gains from such a tight coupling, we identify four key relationships affecting how geographic data (fields and objects) and agent-based process models can interact: identity, causal, temporal and topological. We discuss approaches to implementing tight integration, focusing on a middleware approach that links existing GIS and ABM development platforms, and illustrate the need and approaches with example agent-based models.     

Up to what temperature is petroleum stable? New insights from a 5200 free radical reactions model

The discovery of crude oils and condensates at ever higher temperatures casts doubt on the validity of the usual geochemical modelling approach, that uses empirical reactions and rate constants. The solution used to account for such a high thermal stability is presently to adjust the rate parameters, but the physical meaning and scientific value of such a strategy can be questioned. We have developed a mechanistic model consisting of 5200 lumped free radical reactions to describe the thermal evolution of a mixture of 52 organic species meant to represent light petroleum. Rate constants used are those available in the literature or estimated using well established thermochemistry-reactivity correlations. Chemical structures included in the model are linear, branched and cyclic hydrocarbons, hydro- and alkyl-aromatics, PAHs, and three heteroatomic compounds. Reactions include cracking and alkylation chains and inhibiting and accelerating reactions from the various reactants. This model has been applied to several mixtures with various proportions of reaction inhibitors and accelerators, and to a composition representing a light mature oil. From the results obtained, we conclude that mature oils will be stable up to 240–260 °C, depending on their composition, and that the thermal cracking of oil to gas is not possible under reasonable basin conditions. The kinetics of petroleum cracking are thus much slower than generally recognized.     

δC of low-molecular-weight organic acids generated by the hydrous pyrolysis of oil-prone source rocks

Low-molecular-weight (LMW) aqueous organic acids were generated from six oil-prone source rocks under hydrous-pyrolysis conditions. Differences in total organic carbon-normalized acid generation are a function of the initial thermal maturity of the source rock and the oxygen content of the kerogen (OI). Carbon-isotope analyses were used to identify potential generation mechanisms and other chemical reactions that might influence the occurrence of LMW organic acids. The generated LMW acids display increasing ¹³C content as a function of decreasing molecular weight and increasing thermal maturity. The magnitudes of observed isotope fractionations are source-rock dependent. These data are consistent with δ¹³C values of organic acids presented in a field study of the San Joaquin Basin and likely reflect the contributions from alkyl-carbons and carboxyl-carbons with distinct δ¹³C values. The data do not support any particular organic acid generation mechanism. The isotopic trends observed as a function of molecular weight, thermal maturity, and rock type are not supported by either generation mechanisms or destructive decarboxylation. It is therefore proposed that organic acids experience isotopic fractionation during generation consistent with a primary kinetic isotope effect and subsequently undergo an exchange reaction between the carboxyl carbon and dissolved inorganic carbon that significantly influences the carbon isotope composition observed for the entire molecule. Although generation and decarboxylation may influence the δ¹³C values of organic acids, in the hydrous pyrolysis system described, the nondestructive, pH-dependent exchange of carboxyl carbon with inorganic carbon appears to be the most important reaction mechanism controlling the δ¹³C values of the organic acids.     

Using DC resistivity tomography to detect and characterize mountain permafrost

Direct-current (DC) resistivity tomography has been applied to different mountain permafrost regions. Despite problems with the very high resistivities of the frozen material, plausible results were obtained. Inversions with synthetic data revealed that an appropriate choice of regularization constraints was important, and that a joint analysis of several tomograms computed with different constraints was required to judge the reliability of individual features. The theoretical results were verified with three field experiments conducted in the Swiss and the Italian Alps. At the first site, near Zermatt, Switzerland, the location and the approximate lateral and vertical extent of an ice core within a moraine could be delineated. On the Murtel rock glacier, eastern Swiss Alps, a steeply dipping boundary at its frontal part was observed, and extremely high resistivities of several MΩ indicated a high ice content. The base of the rock glacier remained unresolved by the DC resistivity measurements, but it could be constrained with transient EM soundings. On another rock glacier near the Stelvio Pass, eastern Italian Alps, DC resistivity tomography allowed delineation of the rock glacier base, and the only moderately high resistivities within the rock glacier body indicated that the ice content must be lower compared with the Murtel rock glacier.     

Comparative study of the inelastic response of base isolated buildings

This article presents a numeric comparative study of the inelastic structural response of base isolated buildings. The comparative study includes the following isolation systems: laminated rubber bearings, New Zealand one, pure friction and the frictional pendulum ones. The study is based on obtaining non‐linear response spectra for various design parameters using six earthquake records. Usually the base isolation of a new building seeks to maintain the structure in the linear elastic range. The response of old weak buildings or the response of new ones subjected to extreme earthquakes may not be, necessarily, in the aforementioned ideal elastic range. Consequently, it is important to characterize the response of isolated buildings responding inelastically. A conclusion from this research is that the isolators affect significantly the structural response of weak systems. Rubber isolators seem slightly less sensitive to plastification that may occur in the structure compared to friction isolators. Ductility demands in the structure are affected significantly by friction and neoprene protected systems, in particular sliding ones where larger demands are obtained. Copyright © 2002 John Wiley & Sons, Ltd.     

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.