Dissertation (Ph.D.)--Auburn University, 2007. / Abstract. Includes bibliographic references (p.111-131).

The labelling of methyl tertiary butyl ether (MTBE), an oxygenate additive used extensively in gasoline blending, as an environmentally harmful chemical has led to the banning and subsequent phasing-out of this additive in California (USA). In response, the global petroleum industry is currently considering replacement strategies, which include the use of tertiary amyl methyl ether (TAME) or ethanol. Subsequently, SASOL (South African Coal and Oil Limited), a local petrochemical company, in its capacity as an environmentally responsible player in the global petroleum and aligned chemical markets, has commissioned this investigation into the environmental fate of the fuel oxygenates: TAME, ethanol and MTBE. In order to evaluate the environmental fate of the oxygenates, this dissertation has formed a three-tiered approach, using MTBE as a benchmark. The first tier assessed the general fate behaviour of the oxygenates using an evaluative model. A generic evaluative model, developed by Mackay et al. (l996a), called the Equilibrium Criterion (EQc) model was used for this purpose. This fugacity based multimedia model showed MTBE and TAME to have similar affinities for the water compartment. Ethanol was demonstrated to have a pre-disposition for the air compartment. Parameterisation of the EQC model to South African conditions resulted in the development of ChemSA, which reiterated the EQC findings. The second tier quantified the persistence (P), bioaccumulation (B) and long-range transport (LRT) potential of the additives. This tier also included a brief toxicity (T) review. MTBE and ethanol were demonstrated to be persistent and non-persistent, respectively, according to three threshold limit protocols (Convention on the Long Range Trans-boundary Air Pollution Persistent Organic Chemical Protocol; the United Nations Environment Programme Global Initiative; and the Track 1 criteria as defined by the Canadian Toxic Substances Management Policy, as referred to by the Canadian Environmental Protection Act 1999). These protocols were not unanimous in the persistence classification of TAME. Further investigation of persistence was conducted using a persistence and long-range transport multimedia model, called TaPL3, developed by Webster et al. (1998) and extended by Beyer et al. (2000). TaPL3 reiterated the conclusions drawn from the threshold limit protocols, indicating that TAME's classification worsened from non-persistent to persistent on moving from an air emission to a water emission scenario. This served to emphasise the negative water compartment affinity associated with TAME. Using classification intervals defined by Beyer et al. (2000), TaPL3 demonstrated that the long-range transport potential of the oxygenates increased in the order of TAME, ethanol and MTBE; however, it was concluded that none of the oxygenates were expected to pose a serious long-range transport threat. Bioaccumulation was not expected to be a pertinent environmental hazard. As expected, the oxygenates were dismissed as potential bioaccumulators by the first level of a screening method developed by Mackay and Fraser (2000); as well as by the threshold limit protocols listed above. Simulation of biomagnification, using an equilibrium food chain model developed by Thomann (1989), demonstrated that none of the oxygenates posed a biomagnification threat. A review of toxicity data confirmed that none of the three oxygenates are considered particularly toxic. LDso values indicated the following order of increasing toxicity: ethanol, MTBE and TAME. The third tier focussed on oxygenate aqueous behaviour. A simple equilibrium groundwater model was used to analyse the mobility of the oxygenates in groundwater. TAME was found to be 21 % less mobile than MTBE. Ethanol was shown to be very mobile; however, the applicability of the equilibrium model to this biodegradable alcohol was limited. An analysis of liquid-liquid equilibria comprised of oxygenate, water and a fuel substitution chemical was performed to investigate fuel-aqueous phase partitioning and the co-solvency effects of the oxygenates. Ethanol was shown to partition appreciably into an associated water phase from a fuel-phase. Moreover, this alcohol was shown to act as a co-solvent drawing fuel chemicals into the water phase. MTBE was found to partition sparingly into the water phase from a fuel-phase, with TAME partitioning less than MTBE. Neither ether was shown to act as a co-solvent. It was concluded that TAME and ethanol pose less of a burden to the environment than MTBE. Ethanol was assessed to be environmentally benign; however, it was concluded that ethanol's air compartment affinity and the extent of its co-influence on secondary solutes justified the need for further investigation before its adoption as a fuel additive. This project showed sufficient variation in the environmental behaviour of TAME and MTBE to justify the abandonment of the axiom that MTBE and TAME behave similarly in the environment. However, as MTBE is a significant water pollutant, and TAME has been shown to share a similar water affinity, it is cautiously recommended that the assumption of environmental similarity be discarded, except for the water compartment. / Thesis (M.Sc.Eng.)-University of Natal, Durban, 2002.

D. Tech. Mechanical Engineering. / Discusses how to reduce the negative impacts of petroleum oil based fuels in reciprocating engines on the environment through the use of oxygenated (alcohol) blends, while not deteriorating engine performance. The specific objectives are as follows: To evaluate the performance characteristics of n-butanol-diesel blends: B5, B10 and B20, in a direct-injection turbo-charged diesel engine and to compare findings with a study that was carried out by others (Sayin, 2010). To compare the performance, combustion and emission characteristics of dual alcohol-gasoline with single alcohol-gasoline blends fired in a naturally-aspirated (NA) spark ignition (SI) engine. To compare the combustion and emission characteristics of dual alcohol (methanol-n-butanol-gasoline) blends with single alcohol (methanol-gasoline) blends in a single-cylinder SI engine. To evaluate the combustion and regulated emission characteristics of DF and n-butanol/diesel blends (B5, B10, and B20 where B5 represents 5 % shared volume of n-butanol to 95 % diesel fuel) fired in a high load turbo-charged diesel engine and to compare the findings with a study that was conducted by Raslavicius & Bazaras, (2010).

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.

Em muitos países e principalmente no Brasil, compostos oxigenados tais como etanol e metil terta-butil-éter (MTBE) têm sido adicionados à gasolina em cerca de 26% do seu volume para aumentar a octanagem do motor e diminuir a emissão de monóxido de carbono e os níveis de ozônio na atmosfera. O derramamento de tais gasolinas, referidas como gasolina oxigenada tem um efeito cosolvente, provocando um aumento da concentração dos hidrocarbonetos na água subterrânea. A taxa de dissolução em água da gasolina oxigenada, que é dependente das propriedades químicas dos compostos orgânicos, determinam o grau e a severidade de contaminação da água subterrânea nas vizinhanças do derramamento. O objetivo do trabalho foi analisar e quantificar o potencial de contaminação da água subterrânea e de solos arenosos residuais dos arenitos da Formação Botucatu por derramamento de gasolina oxigenada. As análises realizadas buscam fornecer dados para a modelagem numérica em casos envolvendo derramamento de gasolina. Ensaios de equilíbrio em lote e de dissolução em colunas foram realizados objetivando a determinação da concentração aquosa de hidrocarbonetos da gasolina em equilíbrio de fases e a avaliação do tempo estimado para total dissolução em água dos hidrocarbonetos da gasolina pura. Ambos os ensaios analisaram também o efeito cosolvente do etanol na mistura. Verificou-se a validade da lei de Raoult e do modelo log-linear na determinação da concentração aquosa da gasolina pura e oxigenada. Em colunas de solos não saturados avaliou-se a difusão na fase vapor dos compostos orgânicos da gasolina em função do tempo. Finalizando as análises, fez-se uma simulação numérica do transporte da gasolina em zonas não saturadas fazendo-se uso do programa R-UNSAT. / In many countries and mainly in Brazil oxygenated compounds such as ethanol and MTBE have been added to gasoline up to 26% to increase the octane level and to reduce carbon monoxide and ozone levels in the air. The spill of such gasolines, referred as oxygenated gasoline has a potential cosolvent effect, resulting in an increased groundwater concentration of hydrocarbons. The rate of oxygenated gasoline dissolution, which is dependent of the chemical properties of the compounds, determines the degree and severity of groundwater contamination in the vicinity of the spill. The goal of this research was to analyze and to quantify the potential of contamination of the groundwater and of the residual sandy soils from Botucatu sandstone due to the spill of oxigenated gasoline. The performed analysis supply data to the numerical model in case of gasoline spills. Laboratory batch and column leaching tests were carried out in order to determine the equilibrium aqueous concentration of the hydrocarbons compounds of gasoline and to evaluate the time scale for aqueous dissolution of the hydrocarbons compounds. Both tests have analyzed the cosolvent effect of ethanol in the mixture. It was verified the validity of the Raoult's law and the log-linear cosolvency model to estimate the solubility of the hydrocarbons compounds from unamended gasoline and from oxygenated gasoline. Column tests with unsaturated undisturbed soil samples were carried out to investigate the vapor-phase diffusion of aromatic hydrocarbons compounds with time. Finally the transport of gasoline in unsaturated zones was simulated with the R-UNSAT model.