Methyl chloride purification for the silicone industry

This study experimentally investigated methyl chloride (MeCl) purification method using an inhouse designed and built volumetric adsorption/desorption rig. MeCl is an essential raw material in the manufacture of silicone however all technical grades of MeCl contain concentrations (0.2 - 1.0 % wt) of dimethyl ether (DME) which poison the process. The project industrial partner had previously exhausted numerous separation methods, which all have been deemed not suitable for various reasons. Therefore, adsorption/desorption separation was proposed in this study as a potential solution with less economic and environmental impact. Pure component adsorption/desorption was carried out for DME and MeCl on six different adsorbents namely: zeolite molecular sieves (types 4 Å and 5 Å); silica gels (35-70 mesh, amorphous precipitated, and 35-60 mesh) and granular activated carbon (type 8-12 mesh). Subsequent binary gas mixture adsorption in batch and continuous mode was carried out on both zeolites and all three silica gels following thermal pre-treatment in vacuum. The adsorbents were tested as received and after being subjected to different thermal and vacuum pre-treatment conditions. The various adsorption studies were carried out at low pressure and temperature ranges of 0.5 - 3.5 atm and 20 - 100 °C. All adsorbents were characterised using Brunauer Emmett Teller (BET), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDXA) to investigate their physical and chemical properties. The well-known helium (He) expansion method was used to determine the empty manifold and adsorption cell (AC) regions and respective void volumes for the different adsorbents. The amounts adsorbed were determined using Ideal gas laws via the differential pressure method. The heat of adsorption for the various adsorbate-adsorbent (A-S) interactions was calculated using a new calorimetric method based on direct temperature measurements inside the AC. Further adsorption analysis included use of various empirical and kinetic models to determine and understand the behaviour of the respective interactions. The gas purification behaviour was investigated using gas chromatography and mass spectroscopy (GC-MC) analysis. Binary gas mixture samples were syringed from the manifold iii and AC outlet before and after adsorption/desorption analysis through manual sample injections into the GC-MS to detect and quantify the presence of DME and ultimately observe for methyl chloride purification. Convincing gas purification behaviour was confirmed using two different GC columns, thus giving more confidence on the measurement reliability. From the single pure component adsorption of DME and MeCl on the as received zeolite 4A subjected to 1 h vacuum pre-treatment, both gases exhibited pseudo second order adsorption kinetics with DME exhibiting a rate constant nearly double that of MeCl thus suggesting a faster rate of adsorption. From the adsorption isotherm classification both DME and MeCl exhibited Type II and I adsorption isotherm classifications, respectively. The strength of bonding was confirmed by the differential heat of adsorption measurement, which was found to be 23.30 and 10.21 kJ mol-1 for DME and MeCl, respectively. The former is believed to adsorb heterogeneously through hydrogen bonding whilst MeCl adsorbs homogenously via van der Waal’s (VDW) forces. Single pure component adsorption on as received zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) resulted in similar adsorption/desorption behaviour in similar quantities (mol kg-1). The adsorption isotherms for DME and MeCl on zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) and activated carbon 8-12 exhibited Type I classifications, respectively. Experiments on zeolite 5A indicated that DME adsorbed stronger, faster and with a slightly stronger strength of interaction than MeCl but in lesser quantities. On the silica gels adsorbents, DME exhibited a slightly greater adsorption capacity whilst adsorbing at a similar rate and strength of interaction compared to MeCl. On the activated carbon adsorbent, MeCl exhibited the greater adsorption capacity at a faster rate but with similar heats of adsorption. The effect of prolonged vacuum (15 h), thermal pre-treatment (150 °C) and extended equilibrium time (15 min) were investigated for the adsorption behaviour of DME and MeCl on both zeolites 4A and 5A, respectively. Compared to adsorption on as received adsorbents subjected to 1 h vacuum the adsorption capacities for DME and MeCl were found to increase by 1.95 % and 20.37 % on zeolite 4A and by 4.52 % and 6.69 % on zeolite 5A, respectively. In addition the empirical and kinetic models and differential heats of adsorption resulted in more definitive fitting curves and trends due to the true equilibrium position of the adsorbate with the adsorbent. Batch binary mixture adsorption on thermally and vacuum pre-treated zeolite 4A demonstrated purification behaviour of all adsorbents used for MeCl streams containing DME impurities, with a concentration as low as 0.66 vol. %. The GC-MS analysis showed no DME detection for the tested concentration mixtures at the AC outlet after 15 or 30 min, whereas MeCl was detectable in measurable amounts. Similar behaviour was also observed when carrying out adsorption in continuous mode. On the other hand, similar studies on the other adsorbents did not show such favourable MeCl purification behaviour. Overall this study investigated a wide range of adsorbents (zeolites, silica gels and activated carbon) and demonstrated for the first time potential to purify MeCl streams containing DME impurities using adsorption/desorption separation under different adsorbent pre-treatment and adsorption operating conditions. The study also revealed for the first time the adsorption isotherms, empirical and kinetic models and heats of adsorption for the respective adsorbentsurface (A-S) interactions. In conclusion, this study has shown strong evidence to propose zeolite 4A for adsorptive purification of MeCl. It is believed that with a technical grade MeCl stream competitive yet simultaneous co-adsorption of DME and MeCl occurs with evidence of molecular sieiving effects whereby the larger DME molecules are unable to penetrate through the adsorbent bed whereas the smaller MeCl molecules diffuse through resulting in a purified MeCl stream at the AC outlet. Ultimately, further studies are recommended for increased adsorption capacities by considering wider operating conditions, e.g. different adsorbent thermal and vacuum pre-treatment and adsorbing at temperatures closer to the boiling point of the gases and different conditions of pressure and temperature.

Progesterone release from a silicone intravaginal ring in pigtailed macaques

Background: Heterosexual HIV transmission continues to spread worldwide. Intravaginal rings (IVRs) formulated with antiretroviral drugs hold great promise for HIV prevention in women. IVRs provide the benefit of being coitally-independent and coitally-covert for an extended period. As a proof-of-concept, we tested the in vivo release of progesterone from a silicone elastomer vaginal ring device. Methods: Six female pig-tailed macaques were treated with a GnRH agonist (Lupron) prior to ring placement. Four macaques received a progesterone-loaded silicone ring, and two macaques received a blank silicone ring. Blood, vaginal swabs, CVL, and/or biopsies were collected during ring placement, and after ring removal. Results: The median plasma progesterone levels for macaques with a progesterone IVR were 13,973 pg/ml (day 3), 12,342 pg/ml (day 7), 10,112 pg/ml (day 14), 8445 pg/ml (day 21) and 8061 pg/ml (day 28), with a significant decrease from day 14 to day 21 (P = 0.0286). The median plasma progesterone levels for macaques with a blank IVR were 221±±± ±±88 pg/ml. Macaques with a progesterone IVR had CVL progesterone levels of 20,935 pg/ml (day 7), 6892 pg/ml (day 21) and 11,515 pg/ml (day 28). Macaques with a blank IVR had CVL progesterone levels of 29 �± 13 pg/ml. There were no disturbances to the normal vaginal microflora, and plasma and CVL cytokine analysis did not indicate a proinflammatory response due to ring placement. The vaginal biopsies did not display any pathology following ring removal. Overall, the IVRs were well tolerated without any indication of inflammation or significant changes in the vaginal compartment.

GIS and optimisation:potential benefits for emergency facility location in humanitarian logistics

Floods are one of the most dangerous and common disasters worldwide, and these disasters are closely linked to the geography of the affected area. As a result, several papers in the academic field of humanitarian logistics have incorporated the use of Geographical Information Systems (GIS) for disaster management. However, most of the contributions in the literature are using these systems for network analysis and display, with just a few papers exploiting the capabilities of GIS to improve planning and preparedness. To show the capabilities of GIS for disaster management, this paper uses raster GIS to analyse potential flooding scenarios and provide input to an optimisation model. The combination is applied to two real-world floods in Mexico to evaluate the value of incorporating GIS for disaster planning. The results provide evidence that including GIS analysis for a decision-making tool in disaster management can improve the outcome of disaster operations by reducing the number of facilities used at risk of flooding. Empirical results imply the importance of the integration of advanced remote sensing images and GIS for future systems in humanitarian logistics.

Spatial ecological complexity measures in GRASS GIS

Good estimates of ecosystem complexity are essential for a number of ecological tasks: from biodiversity estimation, to forest structure variable retrieval, to feature extraction by edge detection and generation of multifractal surface as neutral models for e.g. feature change assessment. Hence, measuring ecological complexity over space becomes crucial in macroecology and geography. Many geospatial tools have been advocated in spatial ecology to estimate ecosystem complexity and its changes over space and time. Among these tools, free and open source options especially offer opportunities to guarantee the robustness of algorithms and reproducibility. In this paper we will summarize the most straightforward measures of spatial complexity available in the Free and Open Source Software GRASS GIS, relating them to key ecological patterns and processes.

A multi-organisational approach for disaster preparedness and response:the use of optimisation and GIS for facility location, stock pre-positioning, resource allocation and relief distribution

From 1992 to 2012 4.4 billion people were affected by disasters with almost 2 trillion USD in damages and 1.3 million people killed worldwide. The increasing threat of disasters stresses the need to provide solutions for the challenges faced by disaster managers, such as the logistical deployment of resources required to provide relief to victims. The location of emergency facilities, stock prepositioning, evacuation, inventory management, resource allocation, and relief distribution have been identified to directly impact the relief provided to victims during the disaster. Managing appropriately these factors is critical to reduce suffering. Disaster management commonly attracts several organisations working alongside each other and sharing resources to cope with the emergency. Coordinating these agencies is a complex task but there is little research considering multiple organisations, and none actually optimising the number of actors required to avoid shortages and convergence. The aim of the this research is to develop a system for disaster management based on a combination of optimisation techniques and geographical information systems (GIS) to aid multi-organisational decision-making. An integrated decision system was created comprising a cartographic model implemented in GIS to discard floodable facilities, combined with two models focused on optimising the decisions regarding location of emergency facilities, stock prepositioning, the allocation of resources and relief distribution, along with the number of actors required to perform these activities. Three in-depth case studies in Mexico were studied gathering information from different organisations. The cartographic model proved to reduce the risk to select unsuitable facilities. The preparedness and response models showed the capacity to optimise the decisions and the number of organisations required for logistical activities, pointing towards an excess of actors involved in all cases. The system as a whole demonstrated its capacity to provide integrated support for disaster preparedness and response, along with the existence of room for improvement for Mexican organisations in flood management.

Estimation of average annual daily traffic (AADT) using geographically weighted regression (GWR) method and geographic information system (GIS)

Annual average daily traffic (AADT) is important information for many transportation planning, design, operation, and maintenance activities, as well as for the allocation of highway funds. Many studies have attempted AADT estimation using factor approach, regression analysis, time series, and artificial neural networks. However, these methods are unable to account for spatially variable influence of independent variables on the dependent variable even though it is well known that to many transportation problems, including AADT estimation, spatial context is important. ^ In this study, applications of geographically weighted regression (GWR) methods to estimating AADT were investigated. The GWR based methods considered the influence of correlations among the variables over space and the spatially non-stationarity of the variables. A GWR model allows different relationships between the dependent and independent variables to exist at different points in space. In other words, model parameters vary from location to location and the locally linear regression parameters at a point are affected more by observations near that point than observations further away. ^ The study area was Broward County, Florida. Broward County lies on the Atlantic coast between Palm Beach and Miami-Dade counties. In this study, a total of 67 variables were considered as potential AADT predictors, and six variables (lanes, speed, regional accessibility, direct access, density of roadway length, and density of seasonal household) were selected to develop the models. ^ To investigate the predictive powers of various AADT predictors over the space, the statistics including local r-square, local parameter estimates, and local errors were examined and mapped. The local variations in relationships among parameters were investigated, measured, and mapped to assess the usefulness of GWR methods. ^ The results indicated that the GWR models were able to better explain the variation in the data and to predict AADT with smaller errors than the ordinary linear regression models for the same dataset. Additionally, GWR was able to model the spatial non-stationarity in the data, i.e., the spatially varying relationship between AADT and predictors, which cannot be modeled in ordinary linear regression. ^

Data partitioning and replication management in distributed geographic information system (GIS) database

This research presents several components encompassing the scope of the objective of Data Partitioning and Replication Management in Distributed GIS Database. Modern Geographic Information Systems (GIS) databases are often large and complicated. Therefore data partitioning and replication management problems need to be addresses in development of an efficient and scalable solution. ^ Part of the research is to study the patterns of geographical raster data processing and to propose the algorithms to improve availability of such data. These algorithms and approaches are targeting granularity of geographic data objects as well as data partitioning in geographic databases to achieve high data availability and Quality of Service(QoS) considering distributed data delivery and processing. To achieve this goal a dynamic, real-time approach for mosaicking digital images of different temporal and spatial characteristics into tiles is proposed. This dynamic approach reuses digital images upon demand and generates mosaicked tiles only for the required region according to user's requirements such as resolution, temporal range, and target bands to reduce redundancy in storage and to utilize available computing and storage resources more efficiently. ^ Another part of the research pursued methods for efficient acquiring of GIS data from external heterogeneous databases and Web services as well as end-user GIS data delivery enhancements, automation and 3D virtual reality presentation. ^ There are vast numbers of computing, network, and storage resources idling or not fully utilized available on the Internet. Proposed "Crawling Distributed Operating System "(CDOS) approach employs such resources and creates benefits for the hosts that lend their CPU, network, and storage resources to be used in GIS database context. ^ The results of this dissertation demonstrate effective ways to develop a highly scalable GIS database. The approach developed in this dissertation has resulted in creation of TerraFly GIS database that is used by US government, researchers, and general public to facilitate Web access to remotely-sensed imagery and GIS vector information. ^

Water resources assessment and geographic information system (GIS)-based stormwater runoff estimates for artificial recharge of freshwater aquifers in New Providence, Bahamas

The Bahamas is a small island nation that is dealing with the problem of freshwater shortage. All of the country’s freshwater is contained in shallow lens aquifers that are recharged solely by rainfall. The country has been struggling to meet the water demands by employing a combination of over-pumping of aquifers, transport of water by barge between islands, and desalination of sea water. In recent decades, new development on New Providence, where the capital city of Nassau is located, has created a large area of impervious surfaces and thereby a substantial amount of runoff with the result that several of the aquifers are not being recharged. A geodatabase was assembled to assess and estimate the quantity of runoff from these impervious surfaces and potential recharge locations were identified using a combination of Geographic Information Systems (GIS) and remote sensing. This study showed that runoff from impervious surfaces in New Providence represents a large freshwater resource that could potentially be used to recharge the lens aquifers on New Providence.

The Role of GIS in DRR: Classifying and Improving GIS Capabilities in Small Towns and Rural Areas

Optimizing GIS capability does not always require that the municipality obtain cutting edge professionals and resources. This paper offers a disaster risk reduction (DRR) design methodology for small towns and rural areas that employs a multi-variable classification system, enabling customization for effective DRR. Determining appropriate GIS capacity requires that a community first be evaluated in order to identify its disaster risk reduction/disaster management (DRR/DM) requirements. These requirements are then considered in conjunction with the municipality's resources to establish the desired capability. Qualification levels for major aspects of GIS capability with respect to DRR/DM are provided along with descriptions of each level and suggested procedures for advancement to the next level. It should be noted that a municipality can be classified at a different level with respect to different variables. Needs vary according to the community, thus attainment of a uniform capability level may not be necessary.

Assessment of silicone polymer composites for the trace extraction of herbicides : a tool for environmental forensics

Passive samplers are not only a versatile tool to integrate environmental concentrations of pollutants, but also to avoid the use of live sentinel organisms for environmental monitoring. This study introduced the use of magnetic silicone polymer composites (Fe-PDMS) as passive sampling media to pre-concentrate a wide range of analytes from environmental settings. The composite samplers were assessed for their accumulation properties by performing lab experiments with two model herbicides (Atrazine and Irgarol 1051) and evaluated for their uptake properties from environmental settings (waters and sediments). The Fe-PDMS composites showed good accumulation of herbicides and pesticides from both freshwater and saltwater settings and the accumulation mechanism was positively correlated with the log Kow value of individual analytes. Results from the studies show that these composites could be easily used for a wide number of applications such as monitoring, cleanup, and/or bioaccumulation modeling, and as a non-intrusive and nondestructive monitoring tool for environmental forensic purposes.

Context-Based Customization of Routing Functions for Web GIS Applications

This poster presentation features three route planning applications developed by the Florida International University GIS Center and the Geomatics program at the University of Florida, and outlines their context based differences. The first route planner has been developed for cyclists in three Florida counties, i.e. Miami Dade County, Broward County, and Palm Beach County. The second route planner computes safe pedestrian routes to schools and has been developed for Miami Dade County. The third route planner combines pre-compiled cultural/eco routes and point-to-point route planning for the City of Coral Gables. This poster highlights the differences in design (user interface) and implementation (routing options) between the three route planners as a result of a different application context and target audience.

Design and Development of Geographical Information System (GIS) Map for Nuclear Waste Streams

A nuclear waste stream is the complete flow of waste material from origin to treatment facility to final disposal. The objective of this study was to design and develop a Geographic Information Systems (GIS) module using Google Application Programming Interface (API) for better visualization of nuclear waste streams that will identify and display various nuclear waste stream parameters. A proper display of parameters would enable managers at Department of Energy waste sites to visualize information for proper planning of waste transport. The study also developed an algorithm using quadratic Bézier curve to make the map more understandable and usable. Microsoft Visual Studio 2012 and Microsoft SQL Server 2012 were used for the implementation of the project. The study has shown that the combination of several technologies can successfully provide dynamic mapping functionality. Future work should explore various Google Maps API functionalities to further enhance the visualization of nuclear waste streams.

GIS layers of seafloor characteristics in the Azores region (North Atlantic), links to files in ArcGIS format

Inventory of some important datasets related to the physical characteristics of the seafloor surrounding the Azores Archipelago. The objective is to ensure that our compilation is readily available for any researchers interested in this type information but also to support institutions responsible for the management and conservation of local resources.

Aplicação de géis de goma guar no processo de clarificação de salmouras e águas produzidas

Produced water is considered the main effluent of the oil industry, due to their increased volume in mature fields and its varied composition. The oil and grease content (TOG) is the main parameter for the final disposal of produced water. In this context, it is of great significance to develop an alternative method based on guar gum gel for the treatment of synthetic produced water, and using as the differential a polymer having high hydrophilicity for clarifying waters contaminated with oil. Thus, this study aims to evaluate the efficiency of guar gum gels in the remotion of oil from produced water. Guar gum is a natural polymer that, under specific conditions, forms three-dimensional structures, with important physical and chemical properties. By crosslinking the polymer chains by borate ions in the presence of salts, the effect salting out occurs, reducing the solubility of the polymer gel in water. As a result, there is phase separation with the oil trapped in the collapsed gel. The TOG was quantified from the spectroscopy in the ultraviolet and visible region. The system was proven to be highly efficient in the removal of dispersed oil from water produced synthetically, reaching removal percentages above 90%.