Biotechnological developments, socio-technical processes and materiality : the affordances and constraints of ‘social innovation'

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Women under the Law in Islamic Spain, 770s-1492

About the Author Daniel Dawson is a senior majoring in History and Political Science at Virginia Commonwealth University. He plans to go on to graduate school to pursue a PhD degree in History with a focus on religious, social and political movements within Latin America and the Caribbean

Stable hydrogen isotope ratios of individual hydrocarbons in sediments and petroleum

Early research into the stable hydrogen isotopic compositions (δD) of petroleum involved bulk deuterium/hydrogen (D/H) measurements which, while providing some useful information, had to contend with the analysis of complex mixtures of hydrocarbons, and alteration resulting from the rapid exchange of nitrogen-, oxygen- and sulphur-bound hydrogen. The use of gas chromatography-isotope ratio mass spectrometry (GC-irMS) overcomes these problems by allowing the analysis of individual compounds containing only the most isotopically conservative aliphatic carbon-bound (C-bound) hydrogen. This project investigates the geochemical utility and reliability of compound-specific δD values, with the aim to better understand and exploit this analytical capability. To demonstrate the source diagnostic potential of compound-specific δD values, normal and branched alkanes extracted from series of immature bog-head coals (torbanites) were analysed. The torbanites contain immature organic matter predominantly from a single, freshwater algal source, i.e. Botryococcus braunii (B. braunii). The δD values of n-alkanes reflect the climate regime at the time of deposition of the torbanites, and vary mainly in response to the δD values of the source meteoric waters in their depositional environments. n-Alkanes from torbanites deposited at high latitude in a glacial climate are depleted in D by up to 70% relative to those from a torbanite deposited at low latitude under a tropical climate regime. Torbanites deposited in a mid-latitude region under cool-temperate conditions contain n-alkanes with δD values falling in between those of n-alkanes from tropical and glacial torbanites.The δD values of the n-alkanes also reflect their multiple source inputs. For example, a saw-toothed profile of n-alkane δD values in Australian torbanites is attributed to a dual-source system: a predominant B. braunii input, with a minor terrestrial plant input to odd-carbon-numbered n-alkanes in the range n-C20 [subscript] to n-C29 [subscript]. The δD values of n-alkanes and isoprenoids (pristane and phytane) differ significantly in two Permian torbanites from Australia, thought to be reflective of the offset between the δD values of their precursors in extant organisms. The torbanite data indicate that a biological δD signal has been preserved for at least 260–280 million years, extending the utility of δD values for palaeoclimate studies. To elucidate the effect of sedimentary processes on the δD values of petroleum hydrocarbons, three sedimentary sequences have been studied. These comprise one from the Perth Basin (Western Australia) and two from the Vulcan Sub-basin (northern Australia) covering a wide range of maturities, i.e. 0.53–1.6% vitrinite reflectance (Ro). The δD values of n-alkanes extracted from immature-early mature sediments (marine shales/siltstones and mudstones) are consistent with that expected of marine-derived n-alkyl lipids. The hydrocarbons become enriched in D with increasing maturity. The large (ca. 115%) biologically-derived offset between the δD values of n-alkanes and acyclic isoprenoids from immature sediments gradually decreases with increasing maturity, as the isoprenoids become enriched in D more rapidly than the n-alkanes. The D-enrichment in isoprenoids correlates strongly with Ro and traditional molecular maturity parameters.This suggests that H/D exchange during maturation occurs via a mechanism involving carbocation-like intermediates, which proceeds more rapidly with compounds containing tertiary carbon centres. Significant epimerisation of pristane and phytane coincides with their D-enrichment, suggesting that hydrogen exchange occurs at their tertiary carbons. A mechanism is proposed which can account for both H/D exchange and the epimerisation of pristane and phytane in the sedimentary environment. Pristane and phytane extracted from a post-mature sediment from the Paqualin-1 sequence are significantly enriched in D (ca. 40%) relative to the n-alkanes, indicating that D-enrichment persists at very high maturity, and is more pronounced for the regular isoprenoids than the n-alkanes. This supports the notion that H/D exchange causes the observed shift in δD values, rather than free-radical hydrogen transfer. The differences between the δD values of pristane and phytane show opposite trends in the Perth Basin and Vulcan Sub-basin sediments. In the Perth Basin, phytane is enriched in D relative to pristane, likely due to a dominant algal source. In the Vulcan Sub-basin, pristane is enriched in D relative to phytane, and thus is attributed to a lower relative input of algal organic matter. The variance of the δD values of pristane and phytane is generally consistent throughout the maturity range and provides evidence that pristane and phytane exchange hydrogen at similar rates. δD analysis of crude oils and condensates reservoired in the Perth Basin and Vulcan Sub-basin has been carried out to evaluate potential applications in oil-source correlation.The n-alkanes from crude oils and condensates are often more enriched in D than n-alkanes extracted from their supposed source rocks, and the oils also show relatively small differences between the δD values of n-alkanes and isoprenoids. These results suggest significant H/D exchange has occurred, implying that the liquids were generated from mature source rocks. A Perth Basin crude oil (Gage Roads-1) thought to be derived from a lacustrine/terrestrial source contains hydrocarbons that are significantly depleted in D relative to Perth Basin oils derived from a marine source, attributed to variability in the isotopic composition of marine and terrestrial source waters. δD values of n-alkanes from Vulcan Sub-basin crude oils and condensates are largely consistent with their prior classification into two groups: Group A, having a marine source affinity; and Group B, having a terrigenous source affinity. Some oils and condensates are suggested to be mixtures of Group A and Group B hydrocarbons, or Group A hydrocarbons and other as yet unknown sources. An exception is a former Group A oil (Tenacious-1) containing n-alkanes that are enriched in D relative to those from other Group A oils and condensates, attributed to mixing with another source of more mature hydrocarbons. The n-alkane δD profile appears to be indicative of source and sedimentary processes. One Perth Basin crude oil (Dongara-14) contains lower-molecular-weight n-alkanes that are depleted in D relative to higher-molecular-weight n-alkanes, attributed to a mixed marine/terrestrial source.Group A crude oils and condensates from the Vulcan Sub-basin display a ‘bowl-shaped’ profile of n-alkane δD values. An upward inflection in the n-alkane δD profile from n-C11 [subscript] to n-C15 [subscript] is suggested to represent the addition of D-enriched lower-molecular-weight n-alkanes from a more mature wet gas/condensate to an initial charge of lower maturity oil. Ultimately, this project has demonstrated that the δD values of individual petroleum hydrocarbons can be used to elucidate the nature of source organic matter and depositional environments. The preservation potential of lipid δD values is greater than previously thought, although it is clear that H/D exchange accompanying maturation can have a significant effect on the δD values of certain hydrocarbons. Thus, great care must be taken when interpreting δD values of individual hydrocarbons, particularly those derived from sediments of high thermal maturity

Developing Emergency Preparedness Plans For Orlando International Airport (MCO) Using Microscopic Simulator WATSim

Emergency preparedness typically involves the preparation of detailed plans that can be implemented in response to a variety of possible emergencies or disruptions to the transportation system. One shortcoming of past response plans was that they were based on only rudimentary traffic analysis or in many cases none at all. With the advances in traffic simulation during the last decade, it is now possible to model many traffic problems, such as emergency management, signal control and testing of Intelligent Transportation System technologies. These problems are difficult to solve using the traditional tools, which are based on analytical methods. Therefore, emergency preparedness planning can greatly benefit from the use of micro-simulation models to evaluate the impacts of natural and man-made incidents and assess the effectiveness of various responses. This simulation based study assessed hypothetical emergency preparedness plans and what geometric and/or operational improvements need to be done in response to emergency incidents. A detailed framework outlining the model building, calibration and validation of the model using microscopic traffic simulation model WATSim (academic version) is provided. The Roadway network data consists of geometric layout of the network, number of lanes, intersection description which include the turning bays, signal timings, phasing sequence, turning movement information etc. The network in and around the OIA region is coded into WATSim with 3 main signalized intersections, 180 nodes and 235 links. The travel demand data includes the vehicle counts in each link of the network and was modeled as percentage turning count movements. After the OIA network was coded into WATSim, the road network was calibrated and validated for the peak hour mostly obtained from ADT with 8% K factor by comparing the simulated and actual link counts at 15 different key locations in the network and visual verification done. Ranges of scenarios were tested that includes security checkpoint, route diversion incase of incident in or near the airport and increasing demand on the network. Travel time, maximum queue length and delay were used as measures of effectiveness and the results tabulated. This research demonstrates the potential benefits of using microscopic simulation models when developing emergency preparedness strategies. In all 4 main Events were modeled and analyzed. In Event 1, occurrence of 15 minutes traffic incident on a section of South Access road was simulated and its impact on the network operations was studied. The averaged travel time under the incident duration to Side A was more than doubled (29 minutes, more than a 100% increase) compared to the base case and similarly that of Side B two and a half times more (23 minutes, also more than a 100% increase). The overall network performance in terms of delay was found to be 231.09 sec/veh. and baseline 198.9 sec/veh. In Event 2, two cases with and without traffic diversions were assumed and evaluated under 15 minutes traffic incident modeled at the same link and spot as in Event 1. It was assumed that information about the traffic incident was disseminated upstream of the incident 2 minutes after the incident had occurred. This scenario study demonstrated that on the average, 17% (4 minutes) to 41% (12 minutes) per vehicle of travel time savings are achieved when real-time traffic information was provided to 26% percent of the drivers diverted. The overall network performance in delay for this event was also found to improve significantly (166.92 sec/veh). These findings led to the conclusion that investment in ITS technologies that support dissemination of traffic information (such as Changeable Message Signs, Highway Advisory Radio, etc) would provide a great advantage in traffic management under emergency situations and road diversion strategies. Event 3 simulated a Security Check point. It was observed that on the average, travel times to Sides A and B was 3 and 5 minutes more respectively compared to its baseline. Averaged queue length of 650 feet and 890 feet worst case was observed. Event 4 determined when and where the network breaks down when loaded. Among 10 sets of demand created, the network appeared to be breaking down at 30% increase based on the network-wide delay and at 15% based on Level of Service (LOS). The 90% increase appeared to have the most effect on the network with a total network-wide delay close to 620 seconds per vehicle which is 3 and a half times compared to the baseline. Conclusions and future scope were provided to ensure continued safe and efficient traffic operations inside and outside the Orlando International Airport region and to support efficient and informed decision making in the face of emergency situations

Combined theoretical and experimental investigations of porous crystalline materials

This thesis combines solid-state nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), chemical synthesis, isotopic enrichment and density-functional theory (DFT) calculations to provide insight into a number of microporous materials. The first class of materials studied is metal-organic frameworks (MOFs), where the presence of paramagnetic ions has a range of effects on the ¹³C NMR spectra, depending on the nature of the ligand-metal interactions. For the Cu²⁺-based MOFs, HKUST-1 and STAM-1, the assignment of the NMR spectra is non-intuitive, and unambiguous assignment requires specific ¹³C labelling of the organic linker species. It is shown that ¹³C NMR spectra of these two MOFs could act as a sensitive probe of the nature of “guest” molecules bound to the Cu²⁺. The second class of materials is aluminophosphates (AlPOs). It is shown that, using a series of relatively simple linear relationships with the crystal structure, the NMR parameters calculated by DFT (with calculation times of several hours) can be predicted, often with experimentally-useful accuracy, in a matter of seconds using the DIStortion analysis COde (DISCO), which is introduced here. The ambient hydration of the AlPO, JDF-2, to AlPO-53(A) is shown to occur slowly, with incomplete hydration after ~3 months. The resulting AlPO-53(A) is disordered and some possible models for this disorder are investigated by DFT. The final class of materials is gallophosphates (GaPOs), particularly GaPO-34 and related materials. The two as-prepared forms of GaPO-34 are characterised by solid-state NMR, and their calcination investigated by TGA and in-situ powder XRD. An unusual dehydrofluorinated intermediate phase is isolated and characterised for the first time by solid-state NMR. The fully calcined material is shown to be stable under anhydrous conditions, but hydrates rapidly in air. The hydrated material is stable under ambient conditions, but collapses upon heating. Partial dehydration without collapse is achieved by gentle heating or room-temperature evacuation. The impurity phases, GaPO₄ berlinite and GaPO-X are investigated by solid-state NMR and, while the structure of GaPO-X remains unknown, much structural information is obtained

The Devil in Cartagena: Slavery, religion and resistance in seventeenth-century Caribbean Colombia

This thesis examines the role of religion in African communities in seventeenth-century Caribbean Colombia, and the tensions between the system of racial and religious hierarchy imposed by the Catholic Church and Spanish authorities and the everyday religious life of free and enslaved Africans and their descendants. It will examine interactions between African religion and Christianity and African resistance to Spanish Catholic authority. It will examine Spanish-Catholic thought on African spirituality, and investigate the relationship between African subjects and Catholic authorities in the Spanish Atlantic. It explores the goals of Catholic authorities in relation to African subjects, and the various methods they employed in order to Christianize Africans living under Spanish rule. Drawing on trial transcripts from the Cartagena Office of the Inquisition, it will examine everyday African religious life and the relationship between Africans and Christianity in Colombia and the Spanish Caribbean. It will use the Inquisition trials of African religious practitioners to demonstrate how African ritual knowledge spread throughout the Spanish Atlantic world, and the role that the Inquisition played in inadvertently promoting this spread. It will also examine the ways in which African defendants drew on both their own religious traditions and Christian ideas to subvert authority and work within Spanish society. Furthermore, it will examine Spanish anxieties about African religious practices, and the connection between such practices and a general fear of African insurrection connected to the Spanish wars against palenques, cities of free Africans who had escaped slavery. Ultimately, this thesis seeks to examine the relationship between everyday African religious life and Spanish-Catholic authority and hierarchy in early colonial Caribbean Colombia. As a result, it seeks to provide a thorough understanding of power dynamics between Spanish and African communities in the Americas, and the role that African communities in Caribbean Colombia played in the social and cultural development of the Atlantic World

A study of subsurface vapor intrusion from exploration & production waste

Expanding city growth is causing the inhabitants of Louisiana to move further into rural areas. Abandoned oil and gas production sites are being used for residential and light commercial purposes. This thesis will attempt to determine if known benzene levels in Exploration and Production (E&P) waste will be harmful to human health via subsurface vapor intrusion into the newly developed residential and light commercial structures. Louisiana does not currently regulate benzene during the closure of pits that contained E&P waste. Current pit closure techniques warrant testing for benzene Based on current Louisiana legislation, benzene contamination of groundwater is currently the most protected human exposure route to benzene from E&P waste. Indoor air emissions from benzene in E&P waste in the soil must be studied to determine the risks associated to developing residential properties on abandoned exploration and production sites. Exploration and Production waste is described in Louisiana Administrative Code (LAC) 43:Part XIX. Section 129.B as “drilling wastes, salt water, and other wastes associated with the exploration, development, or production of crude oil or natural gas wells and which is not regulated by the provisions of, and, therefore, exempt from the Louisiana Hazardous Waste Regulations and the Federal Resource Conservation and Recovery Act.†The constituents of concern tested in soil and groundwater, which are currently regulated by Statewide Order 29-B for pit closures are chlorides, petroleum hydrocarbons, and metals. Previous studies of E&P waste are used to determine the characteristics, concentration, and potential harm from benzene to human health found in E&P wastes. These studies were funded by the State and are used in this thesis to provide Louisiana related data. These previous studies of E&P waste are also used as baseline references for known benzene concentrations in E&P waste. A risk assessment outline established by F.B. Thomas in combination with the calculations provided by the Johnson and Ettinger Model (1991) for Subsurface Vapor Intrusion into Buildings are used to estimate the risk of the indoor air exposure to benzene vapors remaining in the soil from closed E&P waste pits

Calculating NMR parameters in aluminophosphates : evaluation of dispersion correction schemes

Periodic density functional theory (DFT) calculations have recently emerged as a popular tool for assigning solid-state nuclear magnetic resonance (NMR) spectra. However, in order for the calculations to yield accurate results, accurate structural models are also required. In many cases the structural model (often derived from crystallographic diffraction) must be optimised (i.e., to an energy minimum) using DFT prior to the calculation of NMR parameters. However, DFT does not reproduce weak long-range "dispersion'' interactions well, and optimisation using some functionals can expand the crystallographic unit cell, particularly when dispersion interactions are important in defining the structure. Recently, dispersion-corrected DFT (DFT-D) has been extended to periodic calculations, to compensate for these missing interactions. Here, we investigate whether dispersion corrections are important for aluminophosphate zeolites (AlPOs) by comparing the structures optimised by DFT and DFT-D (using the PBE functional). For as-made AlPOs (containing cationic structure-directing agents (SDAs) and framework-bound anions) dispersion interactions appear to be important, with significant changes between the DFT and DFT-D unit cells. However, for calcined AlPOs, where the SDA-anion pairs are removed, dispersion interactions appear much less important, and the DFT and DFT-D unit cells are similar. We show that, while the different optimisation strategies yield similar calculated NMR parameters (providing that the atomic positions are optimised), the DFT-D optimisations provide structures in better agreement with the experimental diffraction measurements. Therefore, it appears that DFT-D calculations can, and should, be used for the optimisation of calcined and as-made AlPOs, in order to provide the closest agreement with all experimental measurements.PostprintPeer reviewe