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.     

Chasing a 'loose and baggy monster': almshouses and the geography of charity

This paper goes some way towards redressing the lack of geographical literature on charity through exploring the geography of the British domestic charitable sector. The size and geography of the third sector is outlined, followed by an analysis of how almshouses can be understood as inherently geographical and deeply embedded in local social networks of inclusion as well as exclusion.     

Nonlinear Rate Dependent Model of High Damping Rubber Bearing

The accurate analysis of the response of isolated structures requires the application of appropriate models of isolation devices. The purpose of this paper is to analyse a nonlinear strain rate dependent model of a high damping rubber bearing which simulates the horizontal behaviour of the device under specified vertical load using a nonlinear elastic spring-dashpot element. The effectiveness of the model is checked by fitting the experimental data concerning three different rubber bearings. The results of the study show that the model can simulate the bearing behaviour over a wide shear strain range with small simulation errors. This revised version was published online in July 2006 with corrections to the Cover Date.     

Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

The Darwin Rise demise: the western Pacific guyot heights trace the trans-Pacific Mendocino fracture zone

The Darwin Rise has been proposed so many times and in so many forms and places that the time has come to make a more comprehensive examination of the region. Lying on the NW Pacific Plate between the Geisha Guyots, the Mid-Pacific Mountains, the equator, and the trenches, the region is roughly bounded by magnetic anomaly M20 (147 Ma). It was subjected to a massive outpouring of lava about 105 to 120 Ma, which created the guyots and seamounts in that region. Guyots are excellent tools for studying events of long ago because they eroded in the same lowstand in the Cretaceous and guyot relief, therefore, is a surrogate for paleo-sealevel. The relief is derived by subtracting the break depth of the summit plateau of a guyot from the regional depth. Guyot relief would necessarily be less in the center than to the periphery if the feature formed on a pre-existing rise, as has been postulated. The existence of a paleo-Darwin Rise would give concentric contours for the region in question. Of the sixty guyots used in this study, thirty-seven of these guyots were surveyed using SASS multibeam in the Marcus-Wake seamount group. Twenty-three guyots were surveyed using random track single-beam sonar surveys. An entirely different scenario is shown. Data revealed a major fracture passing through the area coevally or after the guyots formed. Because the depths to the summit are not the same now, vertical tectonics occurred after subaerial erosion. This means the fracture formed during and after the erosion (roughly 105 Ma) and influenced the normal sequence of events in guyot formation. Depending on how one deciphers trends through the Hess Rise morass, SASS bathymetry shows a continuation of the Surveyor/Mendocino fracture zone swarm inside the M20 region to the NE of these data. The fracture swarm continues to the western Pacific trench system. Based on this information, if the Darwin Rise ever existed, it had to have done so elsewhere.