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.

Compilation of organic carbon distribution and sedimentology in the surface sediments on the continental margin offshore southwestern Africa

In this study we demonstrate the relevance of lateral particle transport in nepheloid layers for organic carbon (OC) accumulation and burial across high-productive continental margins. We present geochemical data from surface sediments and suspended particles in the bottom nepheloid layer (BNL) from the most productive coastal upwelling area of the modern ocean, the Benguela upwelling system offshore southwest Africa. Interpretation of depositional patterns and comparison of downslope trends in OC content, organic matter composition, and 14C age between suspended particles and surface sediments indicate that lateral particle transport is the primary mechanism controlling supply and burial of OC. We propose that effective seaward particle transport primarily along the BNL is a key process that promotes and maintains local high sedimentation rates, ultimately causing high preservation of OC in a depocenter on the upper slope offshore Namibia. As lateral transport efficiently displaces areas of enhanced OC burial from maximum production at highly productive continental margins, vertical particle flux models do not sufficiently explain the relationship between primary production and shallow-marine OC burial. On geologic time scales, the widest distribution and strongest intensity of lateral particle transport is expected during periods of rapid sea-level change. At times in the geologic past, widespread downslope lateral transport of OC thus may have been a primary driver of enhanced OC burial at deeper continental slopes and abyssal basins.

Biomass of large protists from the Infrakingdom Rhizaria in the global ocean

The present data set is a worldwide compilation from 11 oceanographic expeditions during which an underwater vision profiler (UVP) was deployed in situ to determine the vertical distribution (biomass) of 4 taxonomic groups of plankton larger than 600 µm, belonging to the Infrakingdom Rhizaria, including Collodaria, Acantharia, Phaeodaria and other Rhizaria. Vertical distributions are binned in four layers: 0-100, 0-200, 100-500 and 0-500 m.

Oil Flow Rate Measurements Using 198au And Total Count Technique

In industrial plants, oil and oil compounds are usually transported by closed pipelines with circular cross-section. The use of radiotracers in oil transport and processing industrial facilities allows calibrating flowmeters, measuring mean residence time in cracking columns, locate points of obstruction or leak in underground ducts, as well as investigating flow behavior or industrial processes such as in distillation towers. Inspection techniques using radiotracers are non-destructive, simple, economic and highly accurate. Among them, Total Count, which uses a small amount of radiotracer with known activity, is acknowledged as an absolute technique for flow rate measurement. A viscous fluid transport system, composed by four PVC pipelines with 13m length (12m horizontal and 1m vertical) and ½, ¾, 1 and 2-inch gauges, respectively, interconnected by maneuvering valves was designed and assembled in order to conduct the research. This system was used to simulate different flow conditions of petroleum compounds and for experimental studies of flow profile in the horizontal and upward directions. As 198Au presents a single photopeak (411,8 keV), it was the radioisotope chosen for oil labeling, in small amounts (6 ml) or around 200 kBq activity, and it was injected in the oil transport lines. A NaI scintillation detector 2”x 2”, with well-defined geometry, was used to measure total activity, determine the calibration factor F and, positioned after a homogenization distance and interconnected to a standardized electronic set of nuclear instrumentation modules (NIM), to detect the radioactive cloud.

Occupied childhoods: discourses and politics of childhood and their place in Palestinian and Pan-­Arab screen content for children

This thesis explores changing discourses of childhood and the ways in which power relations intersect with socio-cultural norms to shape screen-based media for Palestinian children. Situated within the interdisciplinary study of childhood, the research is an institutional and textual analysis that includes discursive and micro-level analysis of the socio-political circumstances within which children consume media in present-day Palestine. The thesis takes a social constructionist view, arguing that ‘childhood’ is not a fixed universal concept and that discourses of childhood are produced at specific historical moments as an effect of power. The study has a three-part research agenda. The first section uses secondary literature to explore theories and philosophies relating to definitions of childhood in Arab societies. The second employs participant observation and semi-structured interviews to understand the history and politics of children’s media in the West Bank. The final part of the research activity focuses on the impact that definitions of childhood and the politics of children’s media have on broadcasting outcomes through an analysis of (a) discourses on children’s media that circulate in Palestinian society, and (b) local and pan-Arab cultural texts consumed by Palestinian children. The analysis demonstrates that complex ideological and political factors are at play, which has led to the marginalisation, politicisation and internationalisation of local production for children. Due to the lack of alternatives, local producers often rely on international funding, and are hence forced to negotiate competing definitions of childhood, which while fitting with an international agenda of normalising the Israeli occupation, conflict culturally and politically with local conceptions of childhood and hopes for the Palestinian nation. While the Palestinian community appreciates the positive potential of local production, discourses and strategies around children’s media show that Palestinian children are constructed as vulnerable, incomplete and in constant need of guidance. Pan-Arab content presents a slightly less didactic approach and in certain cases presents childhood as a dynamic space of empowerment. However, by constructing children as ‘consumercitizens’, it alienates Arab (and Palestinian) children from disadvantaged backgrounds,as the preferred audience is middle-class children living in oil-rich countries of the Gulf.

The importance of improving diet in "Securing Scotland's Health" : progress towards the Scottish dietary goals

Background: In 2013, the Revised Dietary Goals for Scotland (SDGs) were published to “indicate the direction of travel, and assist policy development to reduce the burden of obesity and diet-related disease in Scotland”. They include recommendations for foods (fruit and vegetables, oily fish and red meat) and nutrients (energy, energy density, total fat, saturated fat, trans fatty acids, sugar, salt and fibre). Progress towards the SDGs is monitored using a combination of surveys, principally the secondary analysis of the Living Costs and Food Survey (LCFS). Objective: To obtain estimates of food consumption and nutrient intake for Scotland using LCFS data from 2001 to 2013. Results: For SDGs measured using LCFS data there was little progress towards meeting the goals between 2001 and 2013. This was apparent even amongst least deprived households. Despite evidence of progress for fruit and vegetables up to 2010, consumption subsequently dropped; and there was no change in oil rich fish consumption. Mean total red meat consumption meets the SDG and a significant reduction was found between 2001 and 2013, which was partly accounted for by a fall in red meat products such as sausages and burgers. Energy density increased significantly over time despite a dip in 2012. Saturated fat, total fat and sugar intakes remained considerably higher than the SDGs. Overall there were small but significant decreases in the percentage of food energy from saturated fat and sugars, although intakes appear to have risen since 2011. There was no change in fibre intake. Conclusion: The results presented support work by Food Standards Scotland and the Scottish Government to facilitate improvements to the diet to help prevent obesity. Whilst some very small improvements were observed however, new approaches are required to encourage the population towards a healthier diet to secure Scotland’s health in the future. Funded by Food Standards Scotland, Project Number FS424018. Data provided by DEFRA, Scottish Neighbourhood Statistics, ONS and the UK Data Archive.

Development of variable displacement oil pump for internal combustion engines

In the last years the need to develop more environmentally friendly and efficient cars as led to the development of several technologies to improve the performance of internal combustion engines, a large part of the innovations are focused in the auxiliary systems of the engine, including, the oil pump, this is an element of great importance in the dynamics of the engine as well a considerable energy consumer. Most solutions for oil pumps to this day are fixed displacement, for medium and high speeds, the pump flow rate is higher than the needs of the engine, this excess flow leads to the need for recirculation of the fluid which represents a waste of energy. Recently, technological advances in this area have led to the creation of variable displacement oil pumps, these have become a 'must have' due to the numerous advantages they bring, although the working principle of vane or piston pumps is relatively well known, the application of this technology for the automotive industry is new and brings new challenges. The focus of this dissertation is to develop a new concept of variable displacement system for automotive oil pumps. The main objective is to obtain a concept that is totally adaptable to existing solutions on the market (engines), both dimensionally as in performance specifications, having at the same time an innovative mechanical system for obtaining variable displacement. The developed design is a vane pump with variable displacement going in line with existing commercial solutions, however, the variation of the eccentricity commonly used to provide an variable displacement delivery is not used, the variable displacement is achieved without varying the eccentricity of the system but with a variation of the length of the pumping chamber. The principle of operation of the pump is different to existing solutions while maintaining the ability to integrate standard parts such as control valves and mechanical safety valves, the pump is compatible with commercial solutions in terms of interfaces for connection between engine systems and pump. A concept prototype of the product was obtained in order to better evaluate the validity of the concept. The developed concept represents an innovation in oil pumps design, being unique in its mechanical system for variable displacement delivery.

Microstructures layering, mechanisms in the middle waters of the Persian Gulf

Layered structures, known as micro structures in marine environments are common features of which their formation mechanisms are first reviewed. Some methods of measuring such features based on the measurements and theories are presented for the Persian Gulf. This includes determination of layers with temperature inversion (TI) associated with double diffusive convection (DDC). The relevant associated parameters are estimated from ROPME CTD data for late winter and early summer of 1992. Only in certain parts temperature inversion and DDC are observed which seem to produce layered structures. Observations show that the places with TI and DDC are mainly confined to the frontal regions where the water entering the Persian Gulf and water exiting it meet, nearly along the axis of the Gulf. TI and DDC is mainly observer in the northern bound of the front. Typical density ratio for regions with TI and DDC is 0.7 to 0.2 and the mean depth is at about 37 ± 3 m for the Persian Gulf. TI and DDC are also found in the outflow from the Persian Gulf to the Oman Gulf which is found to be at a depth of about 250 m. Horizontal addiction and reduction of solar heating seem to be the main reasons in producing layers with TI and DDC. It is also found that the regime of DDC in the Persian Gulf is more diffusive and the flow associated with intrusion layers with TI is non-isopycnal (more unstable). However for the Oman sea both diffusive and finger regime are observed and the flow is inferred to be isopycnal (more stable statically). Typical heat and salt fluxes due to DDC are found to be 6 W/m2 and 0.36 W/m2 respectively. Effective salinity diffusivity, Ks and heat diffusivity, Kr have been estimated for the places with DDC in the Persian Gulf and Oman Gulf (Ks=1.1 *10-7 m2/s, KT= 1.88*10-6 m2/s). Their values are within the values obtained by others. The buoyancy frequency for the Persian Gulf with typical mean value of 0.05s-1 is much higher than these of the free Oceans. Such large values of N (typically 0.05 s-1) indicate that processes such as tide can produce strong internal waves which may be another factor in producing layered structures. This requires separate study.

Three dimensional models of water flow in the Persian Gulf

Persian Gulf region is globally of great importance due to its economical and political reasons. The importance lies in oil sources and sea exports. Geophysical phenomena dominated in the water circulation affected this region is called Monsoon it stretches from African coasts to the half way of Red Seal affected all coasts of Persian Gulf and goes toward east to the Indian ocean. Other essential factors in the water circulation in this region are net evaporation (several meters in per year), high density and high salinity. In this article the effects of wind stress and evaporation in the water circulation in the region will be considered and model equations for wind forces, density, pressure, gradient, and bottom friction for Persian Gulf will be discussed.

Impacts of oil exploration and exploitation activities on marine environment

Iran possess huge oil reservoir and occupies second place in OPEC. Recent investigation has revealed that reservoir capacity in the country amount to 60 billion barrel of oil. Many measures has been carried out to increase production capacity of oil fields to 4.2 million barrel per day. Thus any distribution in oil exploration may leave adverse effects on social and economic activities. Unfortunately due to absence of a comprehensive CPM on environmental impact assessment, lots of environmental distribution has been occurred in land and off-shore. It is well known that implementation of EIA can reduce environmental hazards. In the present investigation, all major and minor activities associated with oil exploration is identified and subsequently their effects on physical, chemical and biological environment (aquatic) has been brought out. In this context, economical, social and cultural effects of marine oil exploration is also discussed. Subsequently, all methods of EIA were studied and best mitigation plans were drawn up both for exploitation and exploration phases.

Three dimensional circulation of water with variable wind in the Caspian Sea

This research is based on a numerical model for forecasting the three-dimensional behavior of (sea) water motion due to the effect of a variable wind velocity. The results obtained are then analyzed and compared with observation. This model is based on the equations that overcome the current and distribution of temperature by applying the method of finite difference with assuming Δx, Δy as constant and Δz, variable. The model is based on the momentum equation, continuity equation and thermodynamic energy equation and tension at the surface and middle layers and bottom stress. The horizontal and vertical eddy viscosity and thermal diffusivity coefficients we used in accordance with that of the Bennet on Outario Lake (1977). Considering the Caspian Sea dimension in numerical model the Coriolis parameter used with β effects and the approximation Boussines have been used. For the program controlling some simple experiment with boundary condition similar to that of the Caspian Sea have been done. For modeling the Caspian Sea the grid of the field was done as follows: At horizontal surface grid size is 10×10km extension and at vertical in 10 layers with varying thickness from surface to bed respectively as: 5, 10, 20, 3, 50, 100, 150, 200, 25, 500 and higher. The data of wind as velocity، direction and temperature of water related to 15th September 1995 at 6،12 and 18 o’clock were obtained from synoptic station at the Caspian Sea shore and the research marine of Haji Alief. The information concerning shore wind was measured and by the method of SPM (shore protection manual) was transferred to far shore winds through interpolation and by use of inverse square distance of position distribution of the wind velocity at the Caspian surface field was obtained. The model has been evaluated according to the reports and observations. Through studying the position of the current in different layers، the velocity in the cross section in the northern، southern and the middle layers، will be discussed. The results reveal the presence of the circulation cells in the three above mentioned areas. The circulation with depth is reduced too. The results obtained through the numerical solution of the temperature equation have been compared with the observation. The temperature change in different layers in cross section illustrates the relative accordance of the model mentioned.

Quantitative characterization of physico-chemical properties of the active layers of reverse osmosis and nanofiltration membranes, and their relation to membrane performance

The main objectives of this dissertation were: (i) to develop experimental and analytical procedures to quantify different physico-chemical properties of the ultra-thin (~ 100 nm) active layers of reverse osmosis (RO) and nanofiltration (NF) membranes and their interactions with contaminants; (ii) to use such procedures to evaluate the similarities and differences between the active layers of different RO/NF membranes; and (iii) to relate characterization results to membrane performance. Such objectives were motivated by the current limited understanding of the physico-chemical properties of active layers as a result of traditional characterization techniques having limitations associated with the nanometer-scale spatial resolution required to study these ultra-thin films. Functional groups were chosen as the main active layer property of interest. Specific accomplishments of this study include the development of procedures to quantify in active layers as a function of pH: (1) the concentration of both negatively and positively ionized functional groups; (2) the stoichiometry of association between ions (i.e., barium) and ionized functional groups (i.e., carboxylate and sulfonate); and (3) the steric effects experienced by ions (i.e., barium). Conceptual and mathematical models were developed to describe experimental results. The depth heterogeneity of the active layer physico-chemical properties and interactions with contaminants studied in this dissertation was also characterized. Additionally, measured concentrations of ionized functional groups in the polyamide active layers of several commercial RO/NF membranes were used as input in a simplified RO/NF transport model to predict the rejection of a strong electrolyte (i.e., potassium iodide) and a weak acid (i.e., arsenious acid) at different pH values based on rejection results at one pH condition. The good agreement between predicted and experimental results showed that the characterization procedures developed in this study serve as useful tools in the advancement of the understanding of the properties and structure of the active layers of RO/NF membranes, and the mechanisms of contaminant transport through them.

Adição de vermiculita expandida mícron em pastas de baixa densidade para cimentação de poços de petróleo

The northeastern region of Brazil has a large number of wells producing oil using a method of secondary recovery steam injection, since the oil produced in this region is essentially viscous. This recovery method puts the cement / coating on thermal cycling, due to the difference in coefficient of thermal expansion between cement and metal coating causes the appearance of cracks at this interface, allowing the passage of the annular fluid, which is associated with serious risk socioeconomic and environmental. In view of these cracks, a correction operation is required, resulting in more costs and temporary halt of production of the well. Alternatively, the oil industry has developed technology for adding new materials in cement pastes, oil well, providing high ductility and low density in order to withstand the thermo-mechanical loads generated by the injection of water vapor. In this context, vermiculite, a clay mineral found in abundance in Brazil has been applied in its expanded form in the construction industry for the manufacture of lightweight concrete with excellent insulation and noise due to its high melting point and the presence of air in their layers lamellar. Therefore, the vermiculite is used for the purpose of providing low-density cement paste and withstand high temperatures caused by steam injection. Thus, the present study compared the default folder containing cement and water with the folders with 6%, 8% and 10% vermiculite micron conducting tests of free water, rheology and compressive strength where it obtained the concentration of 8 % with the best results. Subsequently, the selected concentration, was compared with the results recommended by the API standard tests of filtered and stability. And finally, analyzed the results from tests of specific gravity and time of thickening. Before the study we were able to make a folder with a low density that can be used in cementing oil well in order to withstand the thermo-mechanical loads generated by steam injection

Avaliação da influência do nacl em pastas de cimento portland para cimentação de poços de petróleo em zonas evaporíticas

One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate

Nutrients limiting the Algal Growth Potential (AGP) in the Gulf of Riga, eastern Baltic Sea, in spring and early summer 1996

In May, June and July 1996, samples wcre collected along one transect greatly influenced by river discharge (eastern side of the gulf), along one transect slightly influence by river discharge (western side), at one station Iocated in the mouth of the main river (River Daugava), at one station located in the center of the Gulf and at several nearshore locations of the western side. Ratios of rnolecular concentrations of in situ dissolved ioorganic nitrogen, phosphorus and silicon, as weIl as enrichment bioassays were llsed to dctcrrnine which nutrient (s) lirnited the potential biomass of phytoplankton. Both comparison of (NO.d-N02+NJ.L): P04 (DIN: DIP) values with Redfic1d's ratio and bioassay inspection led to the sarne conclusions. Phosphorus was clearly the nutrient most limiting for the potcntial biornass of test species in nitrogen- rich waters, which occurred in mid spring, in the upper layer of the southern-eastern part of the Gulf which is greatly influenced by river discharge. In late spring, with the decrease of the total DIN reserve, nitrogen and phosphorus showed an equallimiting role. In deeper layers of this area and out of the river plume (western side and central part of the gulf), nitrogen was the limiting nutrient. In summer, whcn river discharge was the lowest, a11 DIN concentrations but one ranged between 1.6 and 2.6 µM, and the whole area was nitrogen-limited for both the cyanobacterial and the algal test strains. In 74% of the samples for which nitrogen was the limiting nutrient, phosphorus was recorded to be the second potentially limiting nutrient. In contrast, silicon never appeared as limiting the growth potential of either Microcystis aeruginosa or Phaeodactylum tricornutum; phosphorus was the limiting nutrient when DIN: Si03 values were >1 (in May), but DIN: Si03 was <1 when nitrogen was limiting (June and July). The authors conclude that the recently reported decrease of silicon loading in coastal waters and its subsequent enhanced importance in pushing the outcome of species competition towards harmful species may not yet be the most important factor for the Gulf of Riga. Iron appeared for 12% of the tests in the list of nutrients limiting the potential biomass. Tentative results also indicated that a significant fraction of the nitrogen (~,4 µg-atom N 1(-1) taken up by Microcystis aeruginosa may have been in the form of dissolved organic nitrogen (DON). It is thus also suggested tentatively that more attention be paid to these nitrients during further research in the Gulf of Riga.