Phase and partitioning behavior of phenols and polycyclic aromatic hydrocarbons in offshore oil and gas produced water

Produced water constitutes the largest volume of waste from offshore oil and gas operations and is composed of a wide range of organic and inorganic compounds. Although treatment processes have to meet strict oil in water regulations, the definition of “oil” is a function of the analysis process and may include aliphatic hydrocarbons which have limited environmental impact due to degradability whilst ignoring problematic dissolved petroleum species. This thesis presents the partitioning behavior of oil in produced water as a function of temperature and salinity to identify compounds of environmental concern. Phenol, p-cresol, and 4-tert-butylphenol were studied because of their xenoestrogenic power; other compounds studied are polycyclic aromatic hydrocarbon PAHs which include naphthalene, fluorene, phenanthrene, and pyrene. Partitioning experiments were carried out in an Innova incubator for 48 hours, temperature was varied from 4ﾟC to 70ﾟC, and two salinity levels of 46.8‰ and 66.8‰ were studied. Results obtained showed that the dispersed oil concentration in the water reduces with settling time and equilibrium was attained at 48 h settling time. Polycyclic aromatic hydrocarbons (PAHs) partitions based on dispersed oil concentration whereas phenols are not significantly affected by dispersed oil concentration. Higher temperature favors partitioning of PAHs into the water phase. Salinity has negligible effect on partitioning pattern of phenols and PAHs studied. Simulation results obtained from the Aspen HYSYS model shows that temperature and oil droplet distribution greatly influences the efficiency of produced water treatment system.

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.

Preparation of Polymer Nanoparticles by Ring Opening Metathesis Polymerization in Aqueous Dispersed Systems with Water-Soluble Ruthenium-based Catalyst

Ring opening metathesis polymerization (ROMP) is a variant of olefin metathesis used to polymerize strained cyclic olefins. Ruthenium-based Grubbs’ catalysts are widely used in ROMP to produce industrially important products. While highly efficient in organic solvents such as dichloromethane and toluene, these hydrophobic catalysts are not typically applied in aqueous systems. With the advancements in emulsion and miniemulsion polymerization, it is promising to conduct ROMP in an aqueous dispersed phase to generate well-defined latex nanoparticles while improving heat transfer and reducing the use of volatile organic solvents (VOCs). Herein I report the efforts made using a PEGylated ruthenium alkylidene as the catalyst to initiate ROMP in an oil-in-water miniemulsion. 1H NMR revealed that the synthesized PEGylated catalyst was stable and reactive in water. Using 1,5-cyclooctadiene (COD) as monomer, we showed the highly efficient catalyst yielded colloidally stable polymer latexes with ~ 100% conversion at room temperature. Kinetic studies demonstrated first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized with a PEGylated ruthenium alkylidene in miniemulsion to full conversion and with minimal coagulum formation.

Development of An Enhanced Oil Sands Fluid Tailings Generation Model

Bitumen extraction from surface-mined oil sands results in the production of large volumes of Fluid Fine Tailings (FFT). Through Directive 085, the Province of Alberta has signaled that oil sands operators must improve and accelerate the methods by which they deal with FFT production, storage and treatment. This thesis aims to develop an enhanced method to forecast FFT production based on specific ore characteristics. A mass relationship and mathematical model to modify the Forecasting Tailings Model (FTM) by using fines and clay boundaries, as the two main indicators in FFT accumulation, has been developed. The modified FTM has been applied on representative block model data from an operating oil sands mining venture. An attempt has been made to identify order-of-magnitude associated tailings treatment costs, and to improve financial performance by not processing materials that have ultimate ore processing and tailings storage and treatment costs in excess of the value of bitumen they produce. The results on the real case study show that there is a 53% reduction in total tailings accumulations over the mine life by selectively processing only lower tailings generating materials through eliminating 15% of total mined ore materials with higher potential of fluid fines inventory. This significant result will assess the impact of Directive 082 on mining project economic and environmental performance towards the sustainable development of mining projects.

Financial sustainability of cooperatives: a case of portuguese olive oil cooperatives

En Portugal, como en otros países, las cooperativas agrícolas tienen un papel económico importante en el sistema alimentario. Similar a otras organizaciones económicas, las cooperativas agrícolas han sido testigos de cambios estructurales en las últimas décadas en términos de modelos de gobernación y gestión. Las cooperativas agrícolas portuguesas se han visto constreñidas por su contexto a adoptar un modelo tradicional de propiedad y control. El objetivo principal de este estudio era analizar cuestiones relacionadas con la estructura de gestión y desempeño financiero de las cooperativas, basada en los datos recogidos de cooperativas de aceite de oliva situadas en la región interior norte de Portugal. La combinación de un análisis cualitativo de la estructura y toma de decisiones, una evaluación financiera y la aplicación de un enfoque en varios criterios (PROMETHEE II), los resultados están en línea con expectativas (por ejemplo, bajos niveles de participación de los miembros, gestión no profesional, ratios de rentabilidad bajos, bajo apalancamiento y una capacidad para cumplir compromisos financieros), excepto la relación entre la gestión profesional y el desempeño financiero. La existencia de gestión profesional no conduce a mejores resultados financieros. Este resultado refuerza la creencia de que las cooperativas que están estructuradas de diferente manera tienen intereses diferentes y contradictorios a las partes interesadas.

Continuous statistical modelling for rapid detection of adulteration of extra virgin olive oil using mid infrared and Raman spectroscopic data

The main objective of this work was to develop a novel dimensionality reduction technique as a part of an integrated pattern recognition solution capable of identifying adulterants such as hazelnut oil in extra virgin olive oil at low percentages based on spectroscopic chemical fingerprints. A novel Continuous Locality Preserving Projections (CLPP) technique is proposed which allows the modelling of the continuous nature of the produced in-house admixtures as data series instead of discrete points. The maintenance of the continuous structure of the data manifold enables the better visualisation of this examined classification problem and facilitates the more accurate utilisation of the manifold for detecting the adulterants. The performance of the proposed technique is validated with two different spectroscopic techniques (Raman and Fourier transform infrared, FT-IR). In all cases studied, CLPP accompanied by k-Nearest Neighbors (kNN) algorithm was found to outperform any other state-of-the-art pattern recognition techniques.

Methodology for Labeling Oil Products with 123I

The objective was the development a methodology to label organic compounds with radioactive iodine (123I) from the reaction of organic compound with iodine nomochloride (ICL). The process begins with the production of 123ICl from the oxidation of potassium iodate in acid medium. The ICL labeled with 123I is extracted from aqueous phase using diethyl ether and then mixed with the organic compound to be labeled and the process is based on adding the radioactive iodine to the Carbon-Carbon double bonds of the organic compound. To measure the efficiency of the labeling process, in all stages samples were collected and the total activity of 123I was measure. The results show a production yield of 82% for lubricant oil and 85% for gasoline and diesel.

Techno-Economic Assessment of LNG and Diesel Production and Global Trading Based on Hybrid PV-Wind Power Plants and PtG, GtL and PtL Technologies

With growing demand for liquefied natural gas (LNG) and liquid transportation fuels, and concerns about climate change and causes of greenhouse gas emissions, this master’s thesis introduces a new value chain design for LNG and transportation fuels and respective fundamental business cases based on hybrid PV-Wind power plants. The value chains are composed of renewable electricity (RE) converted by power-to-gas (PtG), gas-to-liquids (GtL) or power-to-liquids (PtL) facilities into SNG (which is finally liquefied into LNG) or synthetic liquid fuels, mainly diesel, respectively. The RE-LNG or RE-diesel are drop-in fuels to the current energy system and can be traded everywhere in the world. The calculations for the hybrid PV-Wind power plants, electrolysis, methanation (H2tSNG), hydrogen-to-liquids (H2tL), GtL and LNG value chain are performed based on both annual full load hours (FLh) and hourly analysis. Results show that the proposed RE-LNG produced in Patagonia, as the study case, is competitive with conventional LNG in Japan for crude oil prices within a minimum price range of about 87 - 145 USD/barrel (20 – 26 USD/MBtu of LNG production cost) and the proposed RE-diesel is competitive with conventional diesel in the European Union (EU) for crude oil prices within a minimum price range of about 79 - 135 USD/barrel (0.44 – 0.75 €/l of diesel production cost), depending on the chosen specific value chain and assumptions for cost of capital, available oxygen sales and CO2 emission costs. RE-LNG or RE-diesel could become competitive with conventional fuels from an economic perspective, while removing environmental concerns. The RE-PtX value chain needs to be located at the best complementing solar and wind sites in the world combined with a de-risking strategy. This could be an opportunity for many countries to satisfy their fuel demand locally. It is also a specific business case for countries with excellent solar and wind resources to export carbon-neutral hydrocarbons, when the decrease in production cost is considerably more than the shipping cost. This is a unique opportunity to export carbon-neutral hydrocarbons around the world where the environmental limitations on conventional hydrocarbons are getting tighter.

North Sea Oil and Genuine Saving in the Scottish Economy

The World Bank has published estimates of sustainability of consumption paths by adjusting saving rates to take account of the depletion of non-renewable resources. During the period of North Sea oil production Scotland has been in a fiscal union with the rest of the UK. The present paper adjusts the World Bank data to produce separate genuine saving estimates for Scotland and the rest of the UK for 1970-2009, based on a ‘derivation’ principle for oil revenues. The calculations indicate that Scotland has had a negative genuine saving rate for most of the period of exploitation of North Sea oil resources, with genuine saving being positive in the rest of the UK during this period.

FPGA-based architecture for hyperspectral endmember extraction

Hyperspectral instruments have been incorporated in satellite missions, providing data of high spectral resolution of the Earth. This data can be used in remote sensing applications, such as, target detection, hazard prevention, and monitoring oil spills, among others. In most of these applications, one of the requirements of paramount importance is the ability to give real-time or near real-time response. Recently, onboard processing systems have emerged, in order to overcome the huge amount of data to transfer from the satellite to the ground station, and thus, avoiding delays between hyperspectral image acquisition and its interpretation. For this purpose, compact reconfigurable hardware modules, such as field programmable gate arrays (FPGAs) are widely used. This paper proposes a parallel FPGA-based architecture for endmember’s signature extraction. This method based on the Vertex Component Analysis (VCA) has several advantages, namely it is unsupervised, fully automatic, and it works without dimensionality reduction (DR) pre-processing step. The architecture has been designed for a low cost Xilinx Zynq board with a Zynq-7020 SoC FPGA based on the Artix-7 FPGA programmable logic and tested using real hyperspectral data sets collected by the NASA’s Airborne Visible Infra-Red Imaging Spectrometer (AVIRIS) over the Cuprite mining district in Nevada. Experimental results indicate that the proposed implementation can achieve real-time processing, while maintaining the methods accuracy, which indicate the potential of the proposed platform to implement high-performance, low cost embedded systems, opening new perspectives for onboard hyperspectral image processing.

A Study of Environmental Disclosures in the European Oil and Gas Industry : With Reference to the Global Reporting Initiative

Background and Problem: Sustainability reporting is a growing trend in the society. One of the most exposed industries to environmental matters is the oil and gas industry, which commit to sustainability reporting in order to deal with the industry’s destructive operations. The Global Reporting Initiative (GRI) provides voluntary guidelines in sustainability reporting, which increase transparency for the company’s stakeholders. However, it is controversial that the oil and gas industry put a great effort into sustainability reporting even though the industry is environmentally destructive. This gap is interesting to investigate and will contribute to the academic discussion. Therefore, this thesis will focus on the sustainability reporting in the oil and gas industry and to what extent the industry actually discloses material environmental information about their operations. Purpose: The purpose of this thesis is to examine how the sustainability reporting has changed in the oil and gas industry in Europe. This is performed from a stakeholder perspective. Further, it aims to investigate how oil and gas companies have followed the GRI guidelines and how the reporting has changed over time. Method: A quantitative method is used in order to answer the research questions. The data sample is based on oil and gas companies reporting according to the GRI framework during year 2012 to year 2014. The empirical data is gathered from the studied companies’ environmental category in their sustainability reports. Further, a content analysis technique, with a coding scheme, was set up to interpret and analyse the information. To enable an easy overview of the findings, the relevant data is presented in tables and diagrams. Empirical Findings and Conclusion: The majority of the studied companies have increased their level of compliance in the environmental category. Although, the majority of the companies have increased their reporting, the compliance level differs between the companies. The most reported sectors are the; “Water”, “Biodiversity”, “Emissions”, “Effluents and Waste”, “Compliance”, and “Overall”. Further, the empirical findings show that there is an overall increase in the amount of disclosed information per indicator. The conclusion of this thesis is that the environmental disclosures have increased in the oil and gas industry from year 2012 to 2014.

Effects of IFRS adoption on the financial statements of Nigerian listed entities: the case of oil and gas companies

On 28 July 2010, the Nigerian Federal Executive Council approved January 1, 2012 as the effective date for the convergence of Nigerian Statement of Accounting Standards (SAS) or Nigerian GAAP (NG-GAAP) with International Financial Reporting Standards (IFRS). By this pronouncement, all publicly listed companies and significant public interest entities in Nigeria were statutorily required to issue IFRS based financial statements for the year ended December, 2012. This study investigates the impact of the adoption of IFRS on the financial statements of Nigerian listed Oil and Gas entities using six years of data which covers three years before and three years after IFRS adoption in Nigeria and other African countries. First, the study evaluates the impact of IFRS adoption on the Exploration and Evaluation (E&E) expenditures of listed Oil and Gas companies. Second, it examines the impact of IFRS adoption on the provision for decommissioning of Oil and Gas installations and environmental rehabilitation expenditures. Third, the study analyses the impact of the adoption of IFRS on the average daily Crude Oil production cost per Barrel. Fourth, it examines the extent to which the adoption and implementation of IFRS affects the Key Performance Indicators (KPIs) of listed Oil and Gas companies. The study further explores the impact of IFRS adoption on the contractual relationships between Nigerian Government and Oil and Gas companies in terms of Joint Ventures (JVs) and Production Sharing Contracts (PSCs) as it relates to taxes, royalties, bonuses and Profit Oil Split. A Paired Samples t-test, Wilcoxon Signed Rank test and Gray’s (Gray, 1980) Index of Conservatism analyses were conducted simultaneously where the accounting numbers, financial ratios and industry specific performance measures of GAAP and IFRS were computed and analysed and the significance of the differences of the mean, median and Conservatism Index values were compared before and after IFRS adoption. Questionnaires were then administered to the key stakeholders in the adoption and implementation of IFRS and the responses collated and analysed. The results of the analyses reveal that most of the accounting numbers, financial ratios and industry specific performance measures examined changed significantly as a result of the transition from GAAP to IFRS. The E&E expenditures and the mean cost of Crude Oil production per barrel of Oil and Gas companies increased significantly. The GAAP values of inventories, GPM, ROA, Equity and TA were also significantly different from the IFRS values. However, the differences in the provision for decommissioning expenditures were not statistically significant. Gray’s (Gray, 1980) Conservatism Index shows that Oil and Gas companies were more conservative under GAAP when compared to the IFRS regime. The Questionnaire analyses reveal that IFRS based financial statements are of higher quality, easier to prepare and present to management and easier to compare among competitors across the Oil and Gas sector but slightly more difficult to audit compared to GAAP based financial statements. To my knowledge, this is the first empirical research to investigate the impact of IFRS adoption on the financial statements of listed Oil and Gas companies. The study will therefore make an enormous contribution to academic literature and body of knowledge and void the existing knowledge gap regarding the impact and implications of IFRS adoption on the financial statements of Oil and Gas companies.

The development of a photoacoustic Instrument for the monitoring of oil and other hydrocarbons in water.

The present methods for the detection of oil in discharge water are based either on chemical analysis of intermittent samples or bypass pipelines with instrumentation to detect either dissolved or dispersed hydrocarbons by a variety of optical techniques including absorption, scattering and fluorescence. However, test have shown that no single instruments entirely meets either present needs or satisfies the requirements of the future more stringent legislation which may limit total hydrocarbon content to 30 ppm or even less. Hence, in this paper, a detector is devised which can detect both dissolved and dispersed oil products, has a high immunity to scattering and can operate in-line and harsh environments with a detection sensitivity of a few ppm throughout a wide range of operations.

A numerical model for prediction of oil, trajectory due to extraction activity in the north coasts of the Persian Gulf

This thesis considers a three- dimensional numerical model based on 3-D Navier— Stokes and continuity equations involving various wind speeds (North west), water surface levels, horizontal shier stresses, eddy viscosity, densities of oil and gas condensate- water mixture flows. The model is used to simulate the prediction of the surface movement of oil and gas condensate slicks from spill accident in the north coasts of Persian Gulf.

Interactions between drugs and drug-nutrient in enteral nutrition: a review based on evidences

Introduction: Enteral nutrition (EN) provides calories, macronutrients and micronutrients in adequate quantity and quality to meet the patient's needs. Some drugs when crushed and diluted may have their properties altered, including the reduction of bioavailability causing the reduction of the serum concentration of the drug; tube obstruction; drug-drug interaction or drug-nutrient interaction. Methods: The study was conducted through review of submitted articles in the databases of the Virtual Health Library (VHL): MEDLINE (National Library of Medicine, USA), Lilacs (Latin American and Caribbean Literature on Health Sciences) PUBMED - NCBI (National Center for Biotechnology Information) and COCHRANE. Results: For this survey, 42 articles were identified during database searching. After applying the inclusion and exclusion criteria, 08 articles were selected, obtained from the MEDLINE and Lilacs. Discussion: Some interactions were found such as the aluminium hydroxide and lactulose with the enteral nutrition, which may result in a precipitation and reduction of drug bioavailability. Mineral oil will alter the absorption of fat-soluble vitamins and reduces the tube light. Others results were found as phenytoin, warfarin, captopril and furosemide with enteral nutrition may reduce the maximum serum concentration. Conclusion: Drug interactions are more common in day-to-day activities than health professionals may suppose. Knowledge on the matter may also assist in reducing cases of obstruction of tubes, through which enteral nutrition and medications are administered. Thus, the multidisciplinary team, acting together, may have more beneficial effects to the patient.