The hydrodynamic behaviour and mass transfer characteristics of single droplets in a pulsed sieve plate column

The literature relating to the performance of pulsed sieve plate liquid-liquid extraction columns and the relevant hydrodynamic phenomenon have been surveyed. Hydrodynamic behaviour and mass transfer characteristics of droplets in turbulent and non-turbulent conditions have also been reviewed. Hydrodynamic behaviour, i.e. terminal and characteristic velocity of droplets, droplet size and droplet breakup processes, and mass transfer characteristics of single droplets (d≤0.6 cm) were investigated under pulsed (mixer-settler & transitional regimes) and non-pulsed conditions in a 5.0 cm diameter, 100 cm high, pulsed sieve plate column with three different sieve plate types and variable plate spacing. The system used was toluene (displaced) - acetone - distilled water. Existing photographic techniques for following and recording the droplet behaviour, and for observing the parameters of the pulse and the pulse shape were further developed and improved. A unique illumination technique was developed by which a moving droplet could be photographed using cine or video photography with good contrast without using any dye. Droplet size from a given nozzle and droplet velocity for a given droplet diameter are reduced under pulsing condition, and it was noted that this effect is enhanced in the presence of sieve plate. The droplet breakup processes are well explained by reference to an impact-breakup mechanism. New correlations to predict droplet diameter based on this mechanism are given below.vskip 1.0cm or in dimensionless groups as follows:- (We)crit= 3.12 - 1.79 (Eo)crit A correlation based on the isotropic turbulence theory was developed to calculate droplet diameter in the emulsion regime.vskip 1.0cm Experimental results show that in the mixer-settler and transitional regimes, pulsing parameters had little effect on the overall dispersed phase mass transfer coefficient during the droplet formation and unhindered travel periods.

Water detection in jet fuel using a polymer optical fibre Bragg grating

Water is a common impurity of jet fuel, and can exist in three forms: dissolved in the fuel, as a suspension and as a distinct layer at the bottom of the fuel tank. Water cannot practically be eliminated from fuel but must be kept to a minimum as large quantities can cause engine problems, particularly when frozen, and the interface between water and fuel acts as a breeding ground for biological contaminants. The quantities of dissolved or suspended water are quite small, ranging from about 10 ppm to 150 ppm. This makes the measurement task difficult and there is currently a lack of a convenient, electrically passive system for water-in-fuel monitoring; instead the airlines rely on colorimetric spot tests or simply draining liquid from the bottom of fuel tanks. For all these reason, people have explored different ways to detect water in fuel, however all these approaches have problems, e.g. they may not be electrically passive or they may be sensitive to the refractive index of the fuel. In this paper, we present a simple, direct and sensitive approach involving the use of a polymer optical fibre Bragg grating to detect water in fuel. The principle is that poly(methyl methacrylate) (PMMA) can absorb moisture from its surroundings (up to 2% at 23 °C), leading to both a swelling of the material and an increase in refractive index with a consequent increase in the Bragg wavelength of a grating inscribed in the material.

Water detection in jet fuel using a polymer optical fibre Bragg grating

Water is a common impurity of jet fuel, and can exist in three forms: dissolved in the fuel, as a suspension and as a distinct layer at the bottom of the fuel tank. Water cannot practically be eliminated from fuel but must be kept to a minimum as large quantities can cause engine problems, particularly when frozen, and the interface between water and fuel acts as a breeding ground for biological contaminants. The quantities of dissolved or suspended water are quite small, ranging from about 10 ppm to 150 ppm. This makes the measurement task difficult and there is currently a lack of a convenient, electrically passive system for water-in-fuel monitoring; instead the airlines rely on colorimetric spot tests or simply draining liquid from the bottom of fuel tanks. For all these reason, people have explored different ways to detect water in fuel, however all these approaches have problems, e.g. they may not be electrically passive or they may be sensitive to the refractive index of the fuel. In this paper, we present a simple, direct and sensitive approach involving the use of a polymer optical fibre Bragg grating to detect water in fuel. The principle is that poly(methyl methacrylate) (PMMA) can absorb moisture from its surroundings (up to 2% at 23 °C), leading to both a swelling of the material and an increase in refractive index with a consequent increase in the Bragg wavelength of a grating inscribed in the material.

Resource enclavity and corporate social responsibility in Sub-Saharan Africa:the case of oil production in Ghana

Why has Corporate Social Responsibility (CSR) yielded such disappointing outcomes in oil-rich sub-Saharan Africa? Over the past decades, a sizable body of literature has emerged which draws attention to the shortcomings of oil-related development and complementary CSR exercises in the region. Most critiques on the topic, however, assess specific interventions and/or policies but fail to evaluate the complex decision-making processes, dictated heavily by setting, which produce such actions altogether. This thesis attributes CSR outcomes in oil-rich sub-Saharan Africa to the unique context in which the decisions underpinning actions take place. In doing so, the analysis borrows ideas from a diverse body of literature spanning the international development, accounting, management and political science disciplines. To explore these ideas further, the thesis focuses on the case of Ghana. The most recent “addition” to sub-Saharan Africa’s oil club, Ghana provides a rare glimpse of how decisions underpinning CSR have been identified, evolved and reshaped from the outset. To provide a comprehensive picture of CSR in the sector and its impacts at the local level, interviews and focus groups were conducted with a range of stakeholder groups. As is the case throughout sub-Saharan Africa, in Ghana, oil production occurs in offshore “enclaves”, which are disconnected geographically from local communities. This thesis argues that these dynamics have important implications for CSR. Findings point to companies also being disconnected ideologically from local development needs, which, in part explains the questionable CSR that has become such a contentious issue in the debate on oil and development in sub-Saharan Africa in recent years. The enclave-type setting in which oil production occurs appears to have stifled creativity and innovation in the area of CSR. This, along with institutional weaknesses, regulatory deficiencies and the Government of Ghana’s failure to adequately respond to local-level concerns, has produced these outcomes.

Impact of Water Supply and Sanitation on Diarrheal Morbidity among Young Children in the Socioeconomic and Cultural Context of Rwanda (Africa)

This project studied the frequency and of water contamination at the source, during transportation, and at home to determine the causes of contamination and its impact on the health of children aged 0 to 5 years. The methods used were construction of the infrastructure for three sources of potable water, administration of a questionnaire about socioeconomic status and sanitation behavior, anthropometric measurement of children, and analysis of water and feces. The contamination, first thought to be only a function of rainfall, turned out to be a very complex phenomenon. Water in homes was contaminated (43.4%) with more than 1100 total coliforms/100 ml due to the use of unclean utensils to transport and store water. This socio-economic and cultural problem should be ad- dressed with health education about sanitation, The latrines (found in 43.8% of families) presented a double-edged problem. The extremely high population density reduced the surface area of land per family, which resulted in a severe nutritional deficit (15% of the children) affecting mainly young children, rendering them more susceptible to diarrhea (three episodes/child/year).

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.

Seasonal plant water uptake patterns in the saline southeast Everglades ecotone

The purpose of this study was to determine the seasonal water use patterns of dominant macrophytes coexisting in the coastal Everglades ecotone. We measured the stable isotope signatures in plant xylem water of Rhizophora mangle, Cladium jamaicense, and Sesuvium portulacastrum during the dry (DS) and wet (WS) seasons in the estuarine ecotone along Taylor River in Everglades National Park, FL, USA. Shallow soilwater and deeper groundwater salinity was also measured to extrapolate the salinity encountered by plants at their rooting zone. Average soil water oxygen isotope ratios (δ 18O) was enriched (4.8 ± 0.2‰) in the DS relative to the WS (0.0 ± 0.1‰), but groundwater δ 18O remained constant between seasons (DS: 2.2 ± 0.4‰; WS: 2.1 ± 0.1‰). There was an inversion in interstitial salinity patterns across the soil profile between seasons. In the DS, shallow water was euhaline [i.e., 43 practical salinity units (PSU)] while groundwater was less saline (18 PSU). In the WS, however, shallow water was fresh (i.e., 0 PSU) but groundwater remained brackish (14 PSU). All plants utilized 100% (shallow) freshwater during the WS, but in the DS R. mangle switched to a soil–groundwater mix (δ 55% groundwater) while C. jamaicense and S. portulacastrum continued to use euhaline shallow water. In the DS, based on δ 18O data, the roots of R. mangle roots were exposed to salinities of 25.4 ± 1.4 PSU, less saline than either C. jamaicense(39.1 ± 2.2 PSU) or S. portulacastrum (38.6 ± 2.5 PSU). Although the salinity tolerance of C. jamaicense is not known, it is unlikely that long-term exposure to high salinity is conducive to the persistence of this freshwater marsh sedge. This study increases our ecological understanding of how water uptake patterns of individual plants can contribute to ecosystem levels changes, not only in the southeast saline Everglades, but also in estuaries in general in response to global sea level rise and human-induced changes in freshwater flows.

Vegetation:environment relationships and water management in Shark Slough, Everglades National Park

The hydrologic regime of Shark Slough, the most extensive long hydroperiod marsh in Everglades National Park, is largely controlled by the location, volume, and timing of water delivered to it through several control structures from Water Conservation Areas north of the Park. Where natural or anthropogenic barriers to water flow are present, water management practices in this highly regulated system may result in an uneven distribution of water in the marsh, which may impact regional vegetation patterns. In this paper, we use data from 569 sampling locations along five cross-Slough transects to examine regional vegetation distribution, and to test and describe the association of marsh vegetation with several hydrologic and edaphic parameters. Analysis of vegetation:environment relationships yielded estimates of both mean and variance in soil depth, as well as annual hydroperiod, mean water depth, and 30-day maximum water depth within each cover type during the 1990’s. We found that rank abundances of the three major marsh cover types (Tall Sawgrass, Sparse Sawgrass, and Spikerush Marsh) were identical in all portions of Shark Slough, but regional trends in the relative abundance of individual communities were present. Analysis also indicated clear and consistent differences in the hydrologic regime of three marsh cover types, with hydroperiod and water depths increasing in the order Tall Sawgrass , Sparse Sawgrass , Spikerush Marsh. In contrast, soil depth decreased in the same order. Locally, these differences were quite subtle; within a management unit of Shark Slough, mean annual values for the two water depth parameters varied less than 15 cm among types, and hydroperiods varied by 65 days or less. More significantly, regional variation in hydrology equaled or exceeded the variation attributable to cover type within a small area. For instance, estimated hydroperiods for Tall Sawgrass in Northern Shark Slough were longer than for Spikerush Marsh in any of the other regions. Although some of this regional variation may reflect a natural gradient within the Slough, a large proportion is the result of compartmentalization due to current water management practices within the marsh.We conclude that hydroperiod or water depth are the most important influences on vegetation within management units, and attribute larger scale differences in vegetation pattern to the interactions among soil development, hydrology and fire regime in this pivotal portion of Everglades.

Water source utilization and foliar nutrient status differs between upland and flooded plant communities in wetland tree islands

Tree islands in the Everglades wetlands are centers of biodiversity and targets of restoration, yet little is known about the pattern of water source utilization by the constituent woody plant communities: upland hammocks and flooded swamp forests. Two potential water sources exist: (1) entrapped rainwater in the vadose zone of the organic soil (referred to as upland soil water), that becomes enriched in phosphorus, and (2) phosphorus-poor groundwater/surface water (referred to as regional water). Using natural stable isotope abundance as a tracer, we observed that hammock plants used upland soil water in the wet season and shifted to regional water uptake in the dry season, while swamp forest plants used regional water throughout the year. Consistent with the previously observed phosphorus concentrations of the two water sources, hammock plants had a greater annual mean foliar phosphorus concentration over swamp forest plants, thereby supporting the idea that tree island hammocks are islands of high phosphorus concentrations in the oligotrophic Everglades. Foliar nitrogen levels in swamp forest plants were higher than those of hammock plants. Linking water sources with foliar nutrient concentrations can indicate nutrient sources and periods of nutrient uptake, thereby linking hydrology with the nutrient regimes of different plant communities in wetland ecosystems. Our results are consistent with the hypotheses that (1) over long periods, upland tree island communities incrementally increase their nutrient concentration by incorporating marsh nutrients through transpiration seasonally, and (2) small differences in micro-topography in a wetland ecosystem can lead to large differences in water and nutrient cycles.

Independent Monitoring the Cuban Economic Zone Oil Development

The extensive impact and consequences of the 2010 Deep Water Horizon oil drilling rig failure in the Gulf of Mexico, together with expanding drilling activities in the Cuban Exclusive Economic zone, have cast a spotlight on Cuban oil development. The threat of a drilling rig failure has evolved from being only hypothetical to a potential reality with the commencement of active drilling in Cuban waters. The disastrous consequences of a drilling rig failure in Cuban waters will spread over a number of vital interests of the US and of nations in the Caribbean in the general environs of Cuba. The US fishing and tourist industries will take major blows from a significant oil spill in Cuban waters. Substantial ecological damage and damage to beaches could occur for the US, Mexico, Haiti and other countries as well. The need exists for the US to have the ability to independently monitor the reality of Cuban oceanic oil development. The advantages of having an independent US early warning system providing essential real-time data on the possible failure of a drilling rig in Cuban waters are numerous. An ideal early warning system would timely inform the US that an event has occurred or is likely to occur in, essentially, real-time. Presently operating monitoring systems that could provide early warning information are satellite-based. Such systems can indicate the locations of both drilling rigs and operational drilling platforms. The system discussed/proposed in this paper relies upon low-frequency underwater sound. The proposed system can complement existing monitoring systems, which offer ocean-surface information, by providing sub-ocean surface, near-real time, information. This “integrated system” utilizes and combines (integrates) many different forms of information, some gathered through sub-ocean surface systems, and some through electromagnetic-based remote sensing (satellites, aircraft, unmanned arial vehicles), and other methods as well. Although the proposed integrated system is in the developmental stage, it is based upon well-established technologies.

Multifunctional nanoparticles in cancer: In vitro characterization, in vivo distribution, and cellular response after laser-NIR dye-induced heating

A novel biocompatible and biodegradable polymer, termed poly(Glycerol malate co-dodecanedioate) (PGMD), was prepared by thermal condensation method and used for fabrication of nanoparticles (NPs). PGMD NPs were prepared using the single oil emulsion technique and loaded with an imaging/hyperthermia agent (IR820) and a chemotherapeutic agent (doxorubicin, DOX). The size of the void PGMD NPs, IR820-PGMD NPs and DOX-IR820-PGMD NPs were approximately 90 nm, 110 nm, and 125 nm respectively. An acidic environment (pH=5.0) induced higher DOX and IR820 release compared to pH=7.4. DOX release was also enhanced by exposure to laser, which increased the temperature to 42°C. Cytotoxicity of DOX-IR820-PGMD NPs was comparable in MES-SA but was higher in Dx5 cells compared to free DOX plus IR820 (p<0.05). The combination of hyperthermia (HT) and chemotherapy improved cytotoxicity in both cell lines. We also explored the cellular response after rapid, short-term and low thermal dose (laser/Dye/NP) induced-heating, and compared it to slow, long-term and high thermal dose cell incubator heating by investigating the reactive oxygen species (ROS) level, hypoxia-inducible factor-1&agr; (HIF-1&agr;) and vascular endothelial growth factor (VEGF) expression. The cytotoxicity of IR820-PGMD NPs after laser/Dye/NP HT resulted in higher cancer cell killing compared to incubator HT. ROS level, HIF-1&agr; and VEGF expression were elevated under incubator HT, while maintained at the baseline level under the laser/Dye/NP HT. In vivo mouse studies showed that NP formulation significantly improved the plasma half-life of IR820 after tail vein injection. Significant lower IR820 content was observed in kidney in DOX-IR820-PGMD NP treatment as compared to free IR820 treatment in our biodistribution studies (p<0.05). In conclusion, both IR820-PGMD NPs and DOX-IR820-PGMD NPs were successfully developed and used for both imaging and therapeutic purposes. Rapid and short-term laser/Dye/NP HT, with a low thermal dose, did not up-regulate HIF-1&agr; and VEGF expression, whereas slow and long-term incubator HT, with a high thermal dose, can enhance expression of both HIF-1&agr; and VEGF.^

The Influence of Hydrologic Restoration on Groundwater-Surface Water Interactions in a Karst Wetland, the Everglades (FL, USA)

Efforts to rehydrate and restore surface water flow in karst wetlands can have unintended consequences, as these highly conductive and heterogeneous aquifers create a close connection between groundwater and surface water. Recently, hydrologic restoration efforts in the karstic Taylor Slough portion of the Everglades has changed from point source delivery of canal water (direct restoration), to the use of a series of surface water recharge retention basins (diffuse restoration). To determine the influence of restoration on groundwater-surface water interactions in the Taylor Slough headwaters, a water budget was constructed for 1997–2011 using 70 hydro-meteorological stations. With diffuse restoration, groundwater seepage from the Everglades toward the urban boundary increased, while the downstream delivery of surface water to the main portion of the slough declined. The combined influence of diffuse restoration and climate led to increased intra-annual variability in the volume of groundwater and surface water in storage but supported a more seasonally hydrated wetland compared to the earlier direct tactics. The data further indicated that hydrologic engineering in karst wetland landscapes enhances groundwater-surface water interactions, even those designed for restoration purposes.

Volume averaging of multiphase flows with hydrate formation in subsea pipelines

In oil and gas pipeline operations, the gas, oil, and water phases simultaneously move through pipe systems. The mixture cools as it flows through subsea pipelines, and forms a hydrate formation region, where the hydrate crystals start to grow and may eventually block the pipeline. The potential of pipe blockage due to hydrate formation is one of the most significant flow-assurance problems in deep-water subsea operations. Due to the catastrophic safety and economic implications of hydrate blockage, it is important to accurately predict the simultaneous flow of gas, water, and hydrate particles in flowlines. Currently, there are few or no studies that account for the simultaneous effects of hydrate growth and heat transfer on flow characteristics within pipelines. This thesis presents new and more accurate predictive models of multiphase flows in undersea pipelines to describe the simultaneous flow of gas, water, and hydrate particles through a pipeline. A growth rate model for the hydrate phase is presented and then used in the development of a new three-phase model. The conservation equations of mass, momentum, and energy are formulated to describe the physical phenomena of momentum and heat transfer between the fluid and the wall. The governing equations are solved based on an analytical-numerical approach using a Newton-Raphson method for the nonlinear equations. An algorithm was developed in Matlab software to solve the equations from the inlet to the outlet of the pipeline. The developed models are validated against a single-phase model with mixture properties, and the results of comparative studies show close agreement. The new model predicts the volume fraction and velocity of each phase, as well as the mixture pressure and temperature profiles along the length of the pipeline. The results from the hydrate growth model reveal the growth rate and location where the initial hydrates start to form. Finally, to assess the impact of certain parameters on the flow characteristics, parametric studies have been conducted. The results show the effect of a variation in the pipe diameter, mass flow rate, inlet pressure, and inlet temperature on the flow characteristics and hydrate growth rates.

Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance.

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) has been demonstrated as an alternative technique to deposit conjugated polymer films for photovoltaic applications; yet, a fundamental understanding of how the emulsion target characteristics translate into film properties and solar cell performance is unclear. Such understanding is crucial to enable the rational improvement of organic solar cell (OSC) efficiency and to realize the expected advantages of emulsion-based RIR-MAPLE for OSC fabrication. In this paper, the effect of the primary solvent used in the emulsion target is studied, both experimentally and theoretically, and it is found to determine the conjugated polymer cluster size in the emulsion as well as surface roughness and internal morphology of resulting polymer films. By using a primary solvent with low solubility-in-water and low vapor pressure, the surface roughness of deposited P3HT and PCPDTBT polymer films was reduced to 10 nm, and the efficiency of P3HT:PC61BM OSCs was increased to 3.2% (∼100 times higher compared to the first MAPLE OSC demonstration [ Caricato , A. P. ; Appl. Phys. Lett. 2012 , 100 , 073306 ]). This work unveils the mechanism of polymer film formation using emulsion-based RIR-MAPLE and provides insight and direction to determine the best ways to take advantage of the emulsion target approach to control film properties for different applications.

Advanced Aerogel Composites for Oil Remediation and Recovery

Oil spills in marine environments often damage marine and coastal life if not remediated rapidly and efficiently. In spite of the strict enforcement of environmental legislations (i.e., Oil Pollution Act 1990) following the Exxon Valdez oil spill (June 1989; the second biggest oil spill in U.S. history), the Macondo well blowout disaster (April 2010) released 18 times more oil. Strikingly, the response methods used to contain and capture spilled oil after both accidents were nearly identical, note that more than two decades separate Exxon Valdez (1989) and Macondo well (2010) accidents.

The goal of this dissertation was to investigate new advanced materials (mechanically strong aerogel composite blankets-Cabot® Thermal Wrap™ (TW) and Aspen Aerogels® Spaceloft® (SL)), and their applications for oil capture and recovery to overcome the current material limitations in oil spill response methods. First, uptake of different solvents and oils were studied to answer the following question: do these blanket aerogel composites have competitive oil uptake compared to state-of-the-art oil sorbents (i.e., polyurethane foam-PUF)? In addition to their competitive mechanical strength (766, 380, 92 kPa for Spaceloft, Thermal Wrap, and PUF, respectively), our results showed that aerogel composites have three critical advantages over PUF: rapid (3-5 min.) and high (more than two times of PUF’s uptake) oil uptake, reusability (over 10 cycles), and oil recoverability (up to 60%) via mechanical extraction. Chemical-specific sorption experiments showed that the dominant uptake mechanism of aerogels is adsorption to the internal surface, with some contribution of absorption into the pore space.

Second, we investigated the potential environmental impacts (energy and chemical burdens) associated with manufacturing, use, and disposal of SL aerogel and PUF to remove the oil (i.e., 1 m3 oil) from a location (i.e., Macondo well). Different use (single and multiple use) and end of life (landfill, incinerator, and waste-to-energy) scenarios were assessed, and our results demonstrated that multiple use, and waste-to-energy choices minimize the energy and material use of SL aerogel. Nevertheless, using SL once and disposing via landfill still offers environmental and cost savings benefits relative to PUF, and so these benefits are preserved irrespective of the oil-spill-response operator choices.

To inform future aerogel manufacture, we investigated the different laboratory-scale aerogel fabrication technologies (rapid supercritical extraction (RSCE), CO2 supercritical extraction (CSCE), alcohol supercritical extraction (ASCE)). Our results from anticipatory LCA for laboratory-scaled aerogel fabrication demonstrated that RSCE method offers lower cumulative energy and ecotoxicity impacts compared to conventional aerogel fabrication methods (CSCE and ASCE).

The final objective of this study was to investigate different surface coating techniques to enhance oil recovery by modifying the existing aerogel surface chemistries to develop chemically responsive materials (switchable hydrophobicity in response to a CO2 stimulus). Our results showed that studied surface coating methods (drop casting, dip coating, and physical vapor deposition) were partially successful to modify surface with CO2 switchable chemical (tributylpentanamidine), likely because of the heterogeneous fiber structure of the aerogel blankets. A possible solution to these non-uniform coatings would be to include switchable chemical as a precursor during the gel preparation to chemically attach the switchable chemical to the pores of the aerogel.

Taken as a whole, the implications of this work are that mechanical deployment and recovery of aerogel composite blankets is a viable oil spill response strategy that can be deployed today. This will ultimately enable better oil uptake without the uptake of water, potential reuse of the collected oil, reduced material and energy burdens compared to competitive sorbents (e.g., PUF), and reduced occupational exposure to oiled sorbents. In addition, sorbent blankets and booms could be deployed in coastal and open-ocean settings, respectively, which was previously impossible.