O objetivo deste trabalho foi desenvolver métodos para a determinação simultânea de Pb, Si e P em gasolinas por ICP OES em conformidade com a Agência Nacional de Petróleo (ANP). O mercado da gasolina no Brasil é regulado pela Agência Nacional do Petróleo (ANP) e pela Lei Federal 9.478/97 (Lei do Petróleo) e, conforme Resolução ANP n°40, de 25.10.2013, a determinação de chumbo é exigida quando houver suspeita de contaminação. O chumbo era adicionado, desde 1922 para elevar o índice antidetonante da gasolina, mas devido a sua toxicidade foi mundialmente substituído. A determinação do silício passou a ser exigida em 1 de Janeiro de 2014 nas gasolinas, porque frações leves contaminadas com silício, quando usadas como combustíveis, podem gerar problemas aos motores automotivos, uma vez que os aditivos antiespumantes, a base de oligômeros contendo silício, são adicionados durante o processo de refino. O fósforo é um aditivo estimulante da extração do petróleo, sua determinação também é exigida quando houver suspeita de contaminação, pois concentrações acima do limite máximo podem desativar os catalisadores dos carros. No preparo de amostras foram utilizadas duas estratégias, a primeira diluição da gasolina com solventes orgânicos 10% da gasolina e 90% de Premisolv-Constan, com a vantagem da int rodução direta, porém necessita câmara refrigerada e fluxo de O2. E preparo da amostra por emulsão tipo óleo/água (O/W), preparada utilizando 1 mL de gasolina com 3 mL de surfactante Tergitol TMN-6® (20% m v-1), o qual foi escolhido entre 4 surfactantes (TritonTM X-100,TritonTM X-114, TergitolTMTMN-6 e TergitolTM 15-S-9) por ter apresentado melhor desempenho na formação da emulsão e menor branco analítico. Essa segunda estratégia apresentou vantagens em relação a primeira, pois reduz a introdução da matéria orgânica para 10% e dispensa o uso de câmara especial e fluxo de O2. As amostras foram analisadas com a construção de curvas de adição padrão a fim de eliminar os efeitos de matriz. Também foram analisadas amostras dopadas com padrão orgânico nas concentrações dos limites estabelecidos pela Resolução ANP. As recuperações foram de 86% a 98% para Pb, 90% a 106% para Si e 86% a 110% para P. Portanto o método desenvolvido demonstrou a possibilidade da determinação simultânea de Si, Pb e P nos limites estabelecidos pela legislação (Pb = 5 mg LTM-1, P = 1,3 mg L-1 e Si limite máximo ainda não estabelecido) e está de acordo com a Química Verde e Gestão de Saúde Meio Ambiente e Segurança. / The objective of this work was to develop methods for the simultaneous determination of Pb, Si and P in gasoline by ICP-OES in accordance with the National Petroleum Agency (ANP). The Brazilian gasoline market is regulated by the National Petroleum Agency (ANP) and Federal Law 9.478 / 97 (Petroleum Law) and according to ANP Resolution No. 40, dated 10.25.2013, the determination of lead is required when there is suspected contamination. Lead was added since 1922 to raise the antiknock index of gasoline, but because of its toxicity it has been worldwide replaced. The determination of silicon was required on 1 January 2014 in gasoline. Light fractions contaminated with silicon, when used as fuel, can cause problems for automotive engines, since antifoaming additives, based on silicon-containing oligomers, are added during the refining process. Phosphorus is a stimulating additive to petroleum extraction; its determination is also required when contamination is suspected, as concentrations above the upper limit can deactivate the catalysts of the cars. In the preparation of samples, two strategies were used, the first dilution of gasoline with organic solvents 10% of the gasoline and 90% of Premisolv-Constan, with the advantage of direct introduction, however, requires refrigerated chamber and O2 flow. Preparation of the sample by oil / water (O / W) emulsion, using 1 ml of gasoline with 3 ml of Tergitol TMN-6 surf surfactant (20% m v-1), which was chosen among 4 surfactants (TritonTM X-100, TritonTM X-114, TergitolTM TMN-6 e TergitolTM 15-S-9), because it showed better performance in the formation of the emulsion and lower analytical blank. This second strategy presents advantages over the first one because it reduces the introduction of the organic matter to 10% and dispenses with the use of special chamber and O2 flow. Samples were analyzed by constructing standard addition curves to eliminate matrix effects. We also analyzed doped samples with organic standards in the concentrations of the limits established by ANP Resolution. The recoveries were 86% to 98% for Pb, 90% to 106% for Si and 86% to 110% for P. Therefore, the method developed demonstrated the possibility of simultaneous determination of Si, Pb and P within the limits established by the legislation (Pb = 5 mg L-1, P = 1,3 mg L-1 and Si maximum limit not yet established) and is in accordance with the Green Chemistry and Health Management Environment and Safety.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. Johannesburg, August 2015. / Petrol and diesel fumes are known to be anthropogenic sources of air pollutants that have a negative impact on both environmental and human health. In developing countries, attendants are still employed to pump fuel for customers. In South Africa gas pump attendants refuel vehicles with various octane unleaded petrol, lead replacement petrol (LRP) and diesel on a daily basis. Attendants are particularly at risk to adverse health effects associated with inhalation of hazardous air pollutants (HAPs). Of increasing concern in recent years are the volatile organic compounds (VOCs), with particular reference to the six aromatic hydrocarbons (benzene, toluene, ethyl benzene and three isomeric xylenes), namely the BTEX.

This thesis consists of four self-contained papers related to energydemand and household cooking energy.Paper [I] examine the impact of price, income and non-economicfactors on gasoline demand using a structural time series model. Theresults indicated that non-economic factors did have an impact ongasoline demand and also one of the largest contributors to changes ingasoline demand in both countries, especially after the 1990s. Theresults from the time varying parameter model (TVP) indicated thatboth price and income elasticities were varying over time, but thevariations were insignificant for both Sweden and the UK. Theestimated gasoline trend also showed a similar pattern for the twocountries, increasing continuously up to 1990 and taking a downturnthereafter.Paper [II] studies whether the commonly used linear parametricmodel for estimating aggregate energy demand is the correctfunctional specification for the data generating process. Parametricand nonparametric econometric approaches to analyzing aggregateenergy demand data for 17 OECD countries are used. The resultsfrom the nonparametric correct model specification test for theparametric model rejects the linear, log-linear and translogspecifications. The nonparametric results indicate that the effect of theincome variable is nonlinear, while that of the price variable is linearbut not constant. The nonparametric estimates for the price variable isrelatively low, approximately −0.2.Paper [III] relaxed the weak separability assumption betweengasoline demand and labor supply by examining the effect of laborsupply, measured by male and female working hours on gasolinedemand. I used a flexible semiparametric model that allowed fordifferences in response to income, age and labor supply, respectively.Using Swedish household survey data, the results indicated that therelationship between gasoline demand and income, age and laborsupply were non-linear. The formal separability test rejects the null ofseparability between gasoline demand and labor supply. Furthermore,there was evidence indicating small bias in the estimates when oneignored labor supply in the model.Paper [IV] investigated the key factors influencing the choice ofcooking fuels in Ghana. Results from the study indicated thateducation, income, urban location and access to infrastructure werethe key factors influencing household’s choice of the main cookingfuels (fuelwood, charcoal and liquefied petroleum gas). The study alsofound that, in addition to household demographics and urbanization,the supply (availability) of the fuels influenced household choice forthe various fuels. Increase in household income was likely to increasethe probability of choosing modern fuel (liquefied petroleum gas andelectricity) relative to solid (crop residue and fuelwood) and transitionfuel (kerosene and charcoal).

Increasingly stringent emission requirements and dwindling petroleum reserves have generated interest in expanding the role of synthesis gas (syngas) fuels in power generation applications. Syngas fuels are the product of gasifying organic-based feedstock such as coal and biomass and are composed of mainly H₂ and CO. However, the use of syngas fuels in lean premixed gas turbine systems has been limited in part because the behavior of turbulent flames in these mixtures at practical gas turbine operating conditions are not well understood. This thesis presents an investigation of the influence of fuel composition and pressure on the turbulent consumption speed, ST,GC, and the turbulent flame brush thickness, FBT, for these mixtures. ST,GC and FBT are global parameters which represent the average rate of conversion of reactants to products and the average heat release distribution of the turbulent flame respectively. A comprehensive database of turbulent consumption speed measurements obtained at pressures up to 20 atm and H₂/CO ratios of 30/70 to 90/10 by volume is presented. There are two key findings from this database. First, mixtures of different H₂/CO ratios but with the same un-stretched laminar flame speeds, SL,0, exposed to the same turbulence intensities, u'rms , have different turbulent consumption speeds. Second, higher pressures augment the turbulent consumption speed when SL,0 is held constant across pressures and H₂/CO ratios. These observations are attributed to the mixture stretch sensitivities, which are incorporated into a physics-based model for the turbulent consumption speed using quasi-steady leading points concepts. The derived scaling law closely resembles Damkhler's classical turbulent flame speed scaling, except that the maximum stretched laminar flame speed, SL,max, arises as the normalizing parameter. Scaling the ST,GC data by SL,max shows good collapse of the data at fixed pressures, but systematic differences between data taken at different pressures are observed. These differences are attributed to non-quasi-steady chemistry effects, which are quantified with a Damkhler number defined as the ratio of the chemical time scale associated with SL,max and a fluid mechanic time scale. The observed scatter in the normalized turbulent consumption speed data correlates very well with this Damkhler number, suggesting that ST,GC can be parameterized by u'rms/SL,max and the leading point Damkhler number. Finally, a systematic investigation of the influence of pressure and fuel composition on the flame brush thickness is presented. The flame brush thickness is shown to be independent of the H₂/CO ratio if SL,0 is held constant across the mixtures. However, increasing the equivalence ratio for lean mixtures at a constant H₂/CO ratio, results in a thicker flame brush. Increasing the pressure is shown to augment the flame brush thickness, a result which has not been previously reported in the literature. Classical correlations based on turbulent diffusion concepts collapse the flame brush thickness data obtained at fixed u'rms/U₀ and pressure reasonably well, but systematic differences exist between the data at different u'rms/U₀ and pressures.

A controlled column experiment was conducted to investigate the geophysical response of gasoline spills into the partially saturated sand column. The column was 0.61 diameter (ID) and 2 m high cylindrical polyvinyl chloride, which was packed with the Borden sand to a height of 1.95 m, flushed with CO2, saturated, and drained to a height of 0.73 m. The monitoring techniques used for this experiment was DC resistivity and time domain reflectometry (TDR) methods. The column was equipped with resistivity electrodes and TDR probes, which were placed on the column wall vertically with 3 cm intervals, on opposite sides, two monitoring wells, an injection well, a manometer, an outlet/inlet system, and a vent. A total amount of 5 liters of standard API 91-01 gasoline was added to the system in steps of 1, 2, and 2 liters to examine the geophysical response to different amounts of gasoline. Measurements were taken before and after each injection and also during subsequent fluctuation of the water table. Both monitoring techniques were able to record even the minor changes in the trend of conductivity and permittivity profiles due to the addition of the small amount of gasoline during the first spill. The conductivity and permittivity profiles obtained before lowering the water level below the original level and those obtained after the water level reached to the original level do not match, which is an indication of entrapped gasoline inside the pores. Two core samples was taken from the sand symmetrically after each water table fluctuation and analyzed for total petroleum hydrocarbon (TPH) analysis and the results were compared to the conductivity and permittivity results. The conductivity profile obtained using DC resistivity method was compared to that of obtained using TDR method. The profiles match in the saturated zone where all of the pores are connected with water and therefore electrolytic conduction is predominant. In the unsaturated zone, where there is low pore water connectivity, TDR measured conductivity values are higher than those measured using the resistivity method. Water saturation values were calculated using conductivity and permittivity values before and after each injection. Different values of saturation exponent (n) were tested for Archie’s law until an appropriate value was found which gave the best water saturation from conductivity data for clean Borden sand. Then, the water saturation obtained from permittivity values using Topp’s equations for different materials were compared to that of obtained from conductivity values using Archie’s equation. Topp’s equation for 30 µm glass beads provided the best match. Furthermore, other equations developed by other researchers were examined to obtain water saturation profiles from the permittivity values; all of them overestimate the water saturation for Borden sand. The water saturation profiles after the gasoline spills obtained using both Archie’s law and Topp’s equation do not match, perhaps because both equations were developed for three-phase (water-solid-air) systems.

A controlled column experiment was conducted to investigate the geophysical response of gasoline spills into the partially saturated sand column. The column was 0.61 diameter (ID) and 2 m high cylindrical polyvinyl chloride, which was packed with the Borden sand to a height of 1.95 m, flushed with CO2, saturated, and drained to a height of 0.73 m. The monitoring techniques used for this experiment was DC resistivity and time domain reflectometry (TDR) methods. The column was equipped with resistivity electrodes and TDR probes, which were placed on the column wall vertically with 3 cm intervals, on opposite sides, two monitoring wells, an injection well, a manometer, an outlet/inlet system, and a vent. A total amount of 5 liters of standard API 91-01 gasoline was added to the system in steps of 1, 2, and 2 liters to examine the geophysical response to different amounts of gasoline. Measurements were taken before and after each injection and also during subsequent fluctuation of the water table. Both monitoring techniques were able to record even the minor changes in the trend of conductivity and permittivity profiles due to the addition of the small amount of gasoline during the first spill. The conductivity and permittivity profiles obtained before lowering the water level below the original level and those obtained after the water level reached to the original level do not match, which is an indication of entrapped gasoline inside the pores. Two core samples was taken from the sand symmetrically after each water table fluctuation and analyzed for total petroleum hydrocarbon (TPH) analysis and the results were compared to the conductivity and permittivity results. The conductivity profile obtained using DC resistivity method was compared to that of obtained using TDR method. The profiles match in the saturated zone where all of the pores are connected with water and therefore electrolytic conduction is predominant. In the unsaturated zone, where there is low pore water connectivity, TDR measured conductivity values are higher than those measured using the resistivity method. Water saturation values were calculated using conductivity and permittivity values before and after each injection. Different values of saturation exponent (n) were tested for Archie’s law until an appropriate value was found which gave the best water saturation from conductivity data for clean Borden sand. Then, the water saturation obtained from permittivity values using Topp’s equations for different materials were compared to that of obtained from conductivity values using Archie’s equation. Topp’s equation for 30 µm glass beads provided the best match. Furthermore, other equations developed by other researchers were examined to obtain water saturation profiles from the permittivity values; all of them overestimate the water saturation for Borden sand. The water saturation profiles after the gasoline spills obtained using both Archie’s law and Topp’s equation do not match, perhaps because both equations were developed for three-phase (water-solid-air) systems.

Petroleum hydrocarbons (PHCs) such as gasoline are ubiquitous organic compounds present at contaminated sites throughout the world. Accidental spills and leakage from underground storage tanks results in the formation of PHC source zones that release hundreds of organic compounds, including the high impact, acutely toxic and highly persistent aromatics (e.g., benzene, toluene, ethylbenzene, xylenes, trimethylbenzenes and naphthalene) into groundwater. Contamination by these compounds continues to persist until the PHC source zone is treated in place or removed. In situ chemical oxidation (ISCO) employing persulfate was identified as a potentially viable technology for the treatment of PHC source zones. The effectiveness and efficiency and, therefore, the overall economic feasibility of a persulfate-based ISCO treatment system depend upon the reactivity of the target organic compounds and the interaction of persulfate with aquifer media. The objective of this research was to investigate the persistence of unactivated and activated persulfate in the presence of aquifer materials, and to examine persulfate oxidation of PHC compounds at both the bench- and pilot-scales. A series of bench-scale studies were performed to estimate persulfate degradation kinetic parameters in the presence of seven well-characterized, uncontaminated aquifer materials and to quantify the changes in specific properties of these materials. Batch experiments were conducted in an experimental system containing 100 g of solids and 100 mL of persulfate solution at 1 or 20 g/L. Column experiments were designed to mimic in situ conditions with respect to oxidant to solids mass ratio and were performed in a stop-flow mode using a 1 g/L persulfate solution. The degradation of persulfate followed a first-order rate law for all aquifer materials investigated. An order of magnitude decrease in reaction rate coefficients was observed for systems that used a persulfate concentration of 20 g/L as compared to those that used 1 g/L due to ionic strength effects. As expected, the column experiments yielded higher reaction rate coefficients than batch experiments for the same persulfate concentration due to the lower oxidant to solids mass ratio. Bench-scale data was used to develop a kinetic model to estimate the kinetic response of persulfate degradation during these tests. The push-pull tests involved the injection of persulfate (1 or 20 g/L) and a conservative tracer into a hydraulically isolated portion of the sandy aquifer at CFB Borden, Canada. The kinetic model developed from the bench-scale data was able to reproduce the observed persulfate temporal profiles from these push-pull tests. This implies that persulfate degradation kinetics is scalable from bench-scale to in situ scale, and bench tests can be employed to anticipate in situ degradation. The estimated reaction rate coefficients indicate that persulfate is a persistent oxidant for the range of aquifer materials explored with half lives ranging from 2 to 600 days, and therefore in situ longevity of persulfate will permit advective and diffusive transport in the subsurface. This is critical for successful delivery of oxidant to dispersed residuals in the subsurface. Activation of persulfate is generally recommended to enhance its oxidation potential and reactivity towards organic compounds. This approach may influence the stability of persulfate-activator system in the presence of aquifer materials. A series of batch tests were performed to investigate persistence of persulfate at two concentrations (1 or 20 g/L) using three contemporary activation strategies (citric acid chelated-ferrous, peroxide and high pH ) in the presence of 4 well-characterized, uncontaminated aquifer materials. Chelation by citric acid was ineffective in controlling the interaction between persulfate and Fe(II) and a rapid loss in persulfate concentration was observed. Higher Fe(II) concentration (600 mg/L) led to greater destabilization of persulfate than lower Fe(II) concentration (150 mg/L) and the persulfate loss was stoichiometrically equivalent to the Fe(II) concentration employed. Subsequent to this rapid loss of persulfate, first-order degradation rate coefficients (kobs) were estimated which were up to 4 times higher than the unactivated case due to the interaction with Fe(III) and CA. Total oxidation strength (TOS) was measured for peroxide activation experiments and was observed to decrease rapidly at early time due peroxide degradation. This was followed by slow degradation kinetics similar to that of unactivated persulfate implying that the initial TOS degradation was peroxide dominated and the long-term kinetics were dominated by persulfate degradation. The kobs used to capture TOS degradation for later time were shown to depend upon unactivated persulfate and peroxide degradation rate coefficients, and peroxide concentration. Either a slow peroxide degradation rate and/or higher peroxide concentration allow a longer time for peroxide and persulfate to interact which led to kobs ~1 to 100 times higher than kobs for unactivated persulfate. For alkaline activation, kobs were only 1 to 4 times higher than unactivated persulfate and therefore alkaline conditions demonstrated the least impact on persulfate degradation among the various activation strategies used. For all activation trials, lower stability of persulfate was observed at 1 g/L as compared to 20 g/L due to insufficient persulfate and/or ionic strength effects. A series of batch reactor trials were designed to observe the behavior of the nine high impact gasoline compounds and the bulk PHC fraction measures subjected to various persulfate activation strategies over a 28-day period. This bench-scale treatability used unactivated persulfate (1 or 20 g/L) and activated persulfate (20 g/L). Activation employed chelated-Fe(II), peroxide, high pH or two aquifer materials as activators. No significant oxidation of the monitored compounds was observed for unactivated persulfate at 1 g/L, but 20 g/L persulfate concentration resulted in their near-complete oxidation. Oxidation rates were enhanced by 2 to 18 times by activation with peroxide or chelated-Fe(II). For alkaline activation, pH 11 trials demonstrated ~2 times higher oxidation rates than the unactivated results. For pH 13 activation the oxidation rates of benzene, toluene and ethylbenzene were reduced by 50% while for the remaining monitored compounds they were enhanced by 5 to 100%. Natural activation by both aquifer materials produced oxidation rates similar to the unactivated results, implying that either activation by minerals associated with aquifer material was not significant or that any potential activation was offset by radical scavenging from aquifer material constituents. Acid-catalyzation at pH <3 may enhance oxidation rates in weakly buffered systems. Oxidation of the monitored compounds followed first-order reaction kinetics and rate coefficients were estimated for all the trials. Overall, activated and unactivated persulfate appear to be suitable for in situ treatment of gasoline. Persulfate under unactivated or naturally activated conditions demonstrated significant destruction of gasoline compounds and showed higher persulfate persistence when in contact with aquifer solids as compared to chelated-Fe(II) or peroxide-activated persulfate systems. This observation was used as the basis for selecting unactivated sodium persulfate for a pilot-scale treatment of gasoline-contaminated source zone at CFB Borden, Canada where a ~2000 L solution of persulfate (20 g/L) was injected into a PHC source zone. Concentration of organics and inorganics were frequently monitored over a 4 month period across a 90 point monitoring fence line installed down-gradient. Treatment performance was measured by estimating organic and inorganic mass loading across the monitoring fence. Increased mass loading for sodium was observed over time as the treatment volume moved across the fence-line indicating transport of the inorganic slug created upon oxidant injection. The mass loading also increased for sulfate which is a by-product generated either due to persulfate degradation during oxidation of organic compounds or during its interaction with aquifer materials. Oxidation of organic compounds was evident from the enhanced mass loading of dissolved carbon dioxide. More importantly, a significant (45 to 86%) decrease in mass loading of monitored compounds was observed due to oxidation by injected persulfate. The cumulative mass crossing the monitoring fence-line was 20 to 50% lower than that expected without persulfate treatment. As the inorganic slug was flushed through the source zone and beyond the monitoring fence, the mass loading rate of sodium, sulfate and carbon dioxide decreased and approached background condition. Mass loading of the monitored compounds increased to within 40 to 80% of the pre-treatment conditions, suggesting partial rebound. These investigations assessed the impact of activation on persulfate persistence and treatability of gasoline and served to establish guidelines for anticipating field-scale persulfate behavior under similar conditions. In summary, unactivated persulfate is a stable oxidant in the presence of aquifer materials and its persistence depends upon TOC and Fe(Am) content of the materials, ionic strength, and aquifer to solids mass ratio. Persulfate exhibits significant destruction of gasoline compounds and can be employed for the remediation of gasoline-contaminated sites. Peroxide and chelated-Fe(II) enhance oxidation rates of these compounds, but reduce stability of the persulfate-activator system. Persulfate activation using high pH conditions does not significantly impact persulfate persistence but reduces the overall destruction of gasoline compounds. Therefore, activation imposes a trade-off between enhanced oxidation rates and reduced persulfate persistence. Kinetic model is representative of persulfate degradation at bench- and pilot-scales and can be used for estimation of in situ degradation. The quantification of oxidation rates for gasoline compounds under activated and unactivated persulfate conditions will assist decision-making for identification of appropriate remediation options when targeting contamination by gasoline or by specific high impact gasoline compounds. While persulfate oxidation resulted in partial treatment of a small gasoline source zone, aggressive persulfate load will be required during injection for a complete clean-up. Overall, persulfate-based in situ chemical oxidation was demonstrated to be an effective and a viable technology for the remediation of contaminated soil and groundwater.

The contamination of aquifer systems by petroleum hydrocarbons is a global problem. Underground storage tanks used for storing these hydrocarbons often leak, resulting in subsurface contamination. The hazards associated with petroleum hydrocarbon contamination are mainly attributable to the BTEX compounds, namely benzene, toluene, ethylbenzene and xylenes together with trimethylbenzenes (TMBs) and naphthalene due to their potential to impact human health and the ease with which they can enter the groundwater system. In situ chemical oxidation (ISCO) is the delivery of strong chemical oxidants to the subsurface for the purpose of treating organic contaminants. ISCO can be an effective way to remediate organic contaminants from the soil and groundwater. Sodium persulphate is one of the newer oxidants to gain widespread use in treating petroleum hydrocarbon contamination, though without being fully understood. This investigation tested the ability of unactivated sodium persulphate in treating dissolved phase and residual BTEX contamination through bench-scale laboratory tests and a pilot-scale field study. A degradation potential batch reactor test was carried out to assess the efficacy of unactivated sodium persulphate in oxidizing petroleum hydrocarbons present in contaminated groundwater as well as its effect on aquifer material from a field site. This test was carried out at a sodium persulphate concentration of 20 g/L. Results from this test did not follow the expected first-order degradation, and so subsequent experiments were carried out using a sodium persulphate concentration of 100 g/L. A test to determine the degree of interaction between the oxidant and aquifer material was also conducted. It was found that the degree of natural oxidant interaction for the field site in question was very low. 1000 kg of sodium persulphate was dissolved in nearly 10,000 L of water and injected into the subsurface. Electrical conductivity (EC), pH, sodium, persulphate, sulphate and BTEX were all monitored during the subsequent 152-day post-injection monitoring period. An empirical relationship was determined between EC and the concentration of sodium in groundwater. This enabled the use of EC as a real-time tracer to track the progress of the injectate. Field results supported predictions based on a simulation model that density-driven flow would play an important role in the delivery of the injectate. A portion of the injectate was believed to have been missed by the monitoring network. Areas that did show elevated tracer results in some cases showed a decrease in BTEX concentrations. Results were categorized in four ways. The first category had wells that showed strong evidence of injectate presence but little to no change in BTEX levels. The second category was comprised of wells that showed a reduction in BTEX levels along with the presence of injectate. BTEX levels in some wells rebounded towards the end of the study period. The third category consisted of wells that showed the presence of dilute injectate but did not show any reduction in BTEX concentrations. The fourth and final category was of wells that showed no evidence of having been affected by the injectate in any way. BTEX levels were the same as background. The oxidation of BTEX by unactivated sodium persulphate was found to be successful, though the vagaries of oxidant delivery and field sampling made difficult the accurate determination of the degree of success.

The rapid growth of gasoline consumption in the USA for the last decades brings much concern to scientists and politicians. Therefore many researchers investigated the influence of the main factors that have an impact on gasoline demand. In our study we tried to estimate gasoline demand in the USA, using national time series data for the period 1984-2010. Gasoline demand function considered in this paper includes price, income, fuel efficiency and gasoline consumption in previous year, as the main explanatory variables. The model is estimated using simultaneous equations and cointegration and error correction model (ECM). The results of both methods show a significant price and income effect on gasoline demand. The price is found inelastic and its impact on gasoline demand is very small, however when we correct for endogeneity of price variable, we obtain higher price elasticity. The results on income elasticities obtained from two methods are dubious, since the two methods gave us the different results. In whole, an income raise will lead to an increase of consumption, gasoline demand is inelastic with respect to income in the short-run, while in the long-run it is found to be elastic according to 2SLS method, while the results of cointegration method indicate that gasoline response to income changes is higher in the short-run than in the long-run. Lag of error term suggests that around 57% of adjustment between short-run and long-run occurs during the first year.

Understanding the physics governing primary atomization of high pressure fuel sprays is of paramount importance to accurately model combustion in direct injection engines. The small length and time scales of features that characterize this process falls below the resolution power of typical grids in CFD simulations, which necessitates the inclusion of physical models (sub-models) to account for unresolved physics. Unfortunately current physical models for fuel spray atomization used in engine CFD simulations are based on significant empirical scaling because there is a lack of experimental data to understand the governing physics. The most widely employed atomization sub-model used in current CFD simulations assumes the spray atomization process to be dominated by aerodynamically-driven surface instabilities, but there has been no quantitative experimental validation of this theory to date. The lack of experimental validation is due to the high spatial and temporal resolutions required to simultaneously to image these instabilities, which is difficult to achieve. The present work entails the development of a diagnostic technique to obtain high spatial and temporal resolution images of jet breakup and atomization in the near nozzle region of Gasoline Direct Injection (GDI) sprays. It focuses on the optical setup required to achieve maximum illumination, image contrast, sharp feature detection, and temporal tracking of interface instabilities for long-range microscopic imaging with a high-speed camera. The resolution and performance of the imaging system is characterized by evaluating its modulation transfer function (MTF). The setup enabled imaging of GDI sprays for the entire duration of an injection event (several milliseconds) at significantly improved spatial and temporal resolutions compared to historical spray atomization imaging data. The images show that low to moderate injection pressure sprays can be visualized with a high level of detail and also enable the tracking of features across frames within the field of view (FOV)