Contamination of groundwater by petroleum-hydrocarbons is a widespread environmental problem. Because the petroleum-hydrocarbon resulted plumes could be quite diffuse and widespread, some more economic approaches are desirable for groundwater remediation to provide for long-term control of contaminated groundwater. Monitored natural attenuation (MNA) has been considered as a passive remedial approach to degrade and dissipate contaminants in groundwater. In this study, a full-scale and detailed natural bioremediation investigation was conducted at a petroleum-hydrocarbon spill site in Kaohsiung County, Taiwan. In this natural attenuation study, the following tasks were conducted: (1) groundwater analysis; (2) evaluation of the occurrence of natural attenuation, (3) calculation of biodegradation capacity and natural attenuation rate calculation, (4) evaluation of the percent loss of hydrocarbons due to biodegradation processes by BIOSCREEN model, and (5) application of BIOPLUME III model for the development of remedial strategies. Results show that benzene, toluene, ethylbenzene, and xylene isomers (BTEX) concentrations dropped to below detection limit (BDL) before they reached the downgradient monitor well located 280 m from the spill location. A first-order decay model was applied for the natural attenuation rate calculation. Results reveal that natural biodegradation process was the major cause of the BTEX reduction among the natural attenuation mechanisms. Results from the groundwater analyses indicate that mixed anaerobic biodegradation patterns occurred between the source and mid-plume area, and the aerobic biodegradation dominated the mid and downgradient area. Approximately 74% of the BTEX removal was due to intrinsic biodegradation processes. The calculated natural attenuation rates for BTEX, methyl tert-butyl ether (MTBE), and 1,2,4-trimethylbenzene (1,2,4-TMB) were 0.13, 0.06, and 0.19 1/day, respectively. Evidence for the occurrence of natural attenuation was the decreased contaminant mass flux through the plume cross-sections along the transport path. Evidences for the occurrence of natural BTEX biodegradation included the following: (1) depletion of dissolved oxygen (DO) within the plume; (2) production of biodegradation by-products [Fe(II), CO2, and methane] within the plume; and (3) decreased BTEX concentrations and BTEX as carbon to TOC ratio along the transport path. The calculated biodegradation capacity (45 mg/L) at this site is much higher than the detected concentrations of petroleum-hydrocarbons (1.5 mg/L) within the most contaminated area inside the plume. Thus, natural biodegradation should be able to remove the contaminants effectively. Results suggest that natural attenuation mechanisms can effectively contain the plume and cause the significant removal of petroleum hydrocarbons. Moreover, pump-and-treat and air sparging systems are also feasible technologies to remediate contaminated groundwater at this site.

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Groundwater contamination by petroleum hydrocarbons has become one of the serious environmental problems in many countries. The sources of petroleum-hydrocarbon contaminants may be released from above ground and underground storage tanks, and pipelines. Petroleum hydrocarbons are mainly composed of benzene, toluene, ethyl- benzene, and xylems (BTEX), and other constituents such as methyl-tert-butyl ether (MTBE), naphthalene, 1,3,5-trimethylbenzene (1,3,5-TMB), and 1,2,4-trimethylbenzene (1,2,4-TMB). It is generally recognized that petroleum hydrocarbons have high risks to environmental receptors when hydrocarbon releases occur. Various biological, physical, and chemical remediation technologies (e.g. pump and treat, air sparging, enhanced bioremediation, and chemical oxidation) can be used to remediate petroleum-hydrocarbon contaminated groundwater. However, many of these techniques are typically costly or have limited applications. Permeable reactive barriers (PRBs) are a promising technology for the passive and in situ treatment of contaminated groundwater. A PRB can be defined as ¡§an emplacement of reactive materials in the subsurface designed to intercept a contaminant plume, provide a preferential flow path through the reactive media, and transform the contaminant(s) into environmentally acceptable forms to attain remediation concentration goals at points of compliance.¡¨ The oxygen release materials can be emplaced in the PRBs to passive increase dissolved oxygen (DO) in the subsurface to enhance the intrinsic biodegradation of dissolved hydrocarbons. In the first part of this study, guidelines for PRBs installation have been developed for the remediation of petroleum hydrocarbons, heavy metals, and organic solvents contaminated groundwater. PRB is a cost-effective approach for the remediation of contaminated aquifers. As contaminated groundwater moves through a permeable reactive barrier, the contaminants are scavenged or degraded, and uncontaminated groundwater emerges from the downgradient side of the reactive zone. The permeable reactive barrier concept has several advantages over other remediation technologies currently in use (e.g., pump and treat, air sparging), including absence of mechanical facilities and the electric power, no groundwater extraction and reinjection, treatment in situ, and cost-effective. The first part of this study presents the designs, applications, and case studies of PRB systems on groundwater remediation. In the second part of this study, oxygen release materials have been constructed and evaluated for the appropriate components in batch experiments. Microbial degradation of petroleum hydrocarbons in groundwater can occur naturally. Since the petroleum-hydrocarbons are generally degraded faster under aerobic conditions, aerobic bioremediation can be applied to enhance the biodegradation of petroleum-hydrocarbons within of the plume if oxygen can be provided to the subsurface economically. Batch experiments were conducted to design and identify the components of the oxygen-releasing materials. Cement and gypsum were used as a binder in this mixtures experments. (1) using cement as the binding material The mixtures of the oxygen release material were prepared by blending cement, peat, sand, ethylene-vinyl acetate copolymer(EVA), calcium peroxide (CaO2), and water together at a ratio of 1.0¡G0.18¡G0.20¡G0.10¡G1.12¡G1.74 by weight. Cement was used as a binder and regular medium filter sand was used to increase the permeability of the mixture. Calcium peroxide releases oxygen upon contact water. The designed material with a density of 1.9 g/cm3 was made of 3.5 cm cube for the batch experiment. Results show that the oxygen release rate of the material is 0.046 mg O2/day/g rock. The oxygen release material was able to remain active in oxygen release for more than three months. (2) using gypsum as the binding material The mixtures of the oxygen release material were prepared by blending gypsum, CaO2, sand, and water together at a ratio of 1¡G0.5¡G0.14¡G0.75 by weight. Gypsum was used as a binder and regular medium filter sand was used to increase the permeability of the mixture. Calcium peroxide releases oxygen upon contact water. The designed material with a density of 1.1 g/cm3 was made of 3.5 cm cube for the batch experiment. Results show that the oxygen release rate of the material is 0.031 mg/day/g. The oxygen release material was able to remain active in oxygen release for more than three months. In the third part of this study, immobilization technology was applied to produce the low permeability wrapping film for the construction of oxygen-releasing granular materials. The mixtures of the oxygen release material were prepared by blending alginate, CaO2, and sand together at a ratio of 8.3¡G1.0¡G1 by weight. The low permeability wrapping film of the oxygen release material was able to remain active in oxygen release for two months. In the fourth part of this study, a laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system on the bioremediation of petroleum-hydrocarbon contaminated groundwater. This system was performed using a series of continuous-flow glass columns including four consecutive soil columns. Simulated petroleum-hydrocarbons contaminated groundwater with a flow rate of 0.263 m/day was pumped into this system. In the column experiment, the samples of column influent and specified sampling ports were collected and analyzed for pH, DO, BTEX, MTBE, and microbial populations. Results show that up to 99% of BTEX removal was observed in this passive system. Results from this study would be useful in designing an efficient and cost-effective passive oxygen-releasing and bioremediation system to remediate petroleum- hydrocarbon contaminated aquifer.

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.

Natural Attenuation can be an effective cleanup option for remediation of Groundwater contamination by BTEX. One of the important aspects of the methodology that has been recognized recently is that mass removal rates, the most important parameters used to determine effectiveness of the methodology, is controlled by groundwater flow regime, which to a large extent controlled by aquifer heterogeneity. Considering this recognition, the primary objective of this research is to quantitatively describe the relationship between natural attenuation rates of BTEX and aquifer heterogeneity using numerical solution techniques. To represent different levels of aquifer heterogeneity, hydraulic conductivity distributions are simulated using Turning Bands Algorithm, changing statistical parameters Coefficient of Variation (CV) and correlation length (h). Visual MODFLOW is used to model the transport of BTEX contamination, at different hydraulic conductivity fields. Degradation rates are calculated by Buscheck&amp / Alcantar and Conservative Tracer Methods. The results show that, for a given h, as CV increases, the plume slows down and stays longer at the domain, so areal extent of plume decreases. For anisotropic field, plumes are more dispersed along x and y-direction, and areal extents of the plumes are greater. During MNA feasibility studies, for the aquifer heterogeneity level of CV and h smaller than 100 % and 10 m, respectively, a minimum recommended biodegradation rate constant of 0.02 d-1 can be used, whereas for the aquifer heterogeneity level of CV and h greater than 100 % and 10 m, respectively, using a minimum biodegradation rate constant of 0.06 d-1 can be recommended.

Um grande passivo ambiental da atualidade refere-se à contaminação dos recursos hídricos por hidrocarbonetos. Os atuais sistemas de remediação buscam a utilização de adsorventes alternativos para remoção destes poluentes. O objetivo desta tese de doutorado foi avaliar o uso da cinza de casca de arroz (CCA) e de carvão ativado (CA) na adsorção de BTEX – benzeno, tolueno, etilbenzeno e xileno em soluções aquosas. A CCA foi gerada a partir do processo de queima de casca de arroz para aproveitamento energético e o CA obtido comercialmente. As propriedades físicas, químicas e microestruturais da CCA e do CA foram caracterizadas através de análises de distribuição granulométrica, área superficial, porosidade, massa específica, capacidade de hidratação, pH, ponto de carga zero, perda ao fogo, carbono total, composição química elementar, determinação de fases cristalinas, determinação de grupos funcionais e análise de imagem. Estudos de adsorção cinéticos e de equilíbrio (isotermas) foram efetuados com soluções padrões de benzeno, tolueno, xileno e etilbenzeno em sistemas monocompostos e em misturas BTEX. A quantificação foi realizada por por cromatografia gasosa com detector de ionização de chama. Na cinética de adsorção, foram avaliadas as variáveis: tempo de contato adsorvente-adsorbato (15, 30, 60, 120 e 240 minutos); concentração inicial do adsorbato (1, 5, 10 e 20 mg/L) e dosagem do adsorvente (10 e 20 g/L). Os modelos cinéticos de Pseudo-primeira ordem, Pseudo-segunda ordem e Difusão intrapartícula foram ajustados aos dados experimentais. Isotermas experimentais foram obtidas para cada composto e para a mistura BTEX. Os modelos de Langmuir, Freundlich e Sips foram ajustados aos resultados experimentais para os sistemas com monocompostos. A caracterização das amostras indicou que o CA apresenta microestrutura uniforme com grande área superficial formada por micro e mesoporos e alto teor de carbono. Já a CCA apresenta uma microestrutura heterogênea formada por macroporos e com alto teor de sílica. Os estudos cinéticos demonstraram que a CCA e o CA apresentam capacidades de adsorção altas e semelhantes no tempo de equilíbrio de 120 minutos. De forma geral, a remoção de cada composto na mistura foi menor que a remoção obtida quando em sistemas de monocompostos, onde a capacidade de adsorção se deu na seguinte ordem (em massa de adsorbato por massa de adsorvente): etilbenzeno > xileno > tolueno > benzeno. O modelo cinético de Pseudo-segunda ordem apresentou a melhor correlação para todos os ensaios. As isotermas experimentais obtidas para os monocompostos caracterizam a adsorção em superfícies porosas com formação de monocamada. Os ajustes aos modelos teóricos não apresentaram unanimidade, observando em algumas situações uma correlação adequada para Langmuir e Freundlich. Nas misturas BTEX, as isotermas experimentais para a CCA indicam uma competição pelos sítios ativos do adsorvente entre benzeno/tolueno e entre etilbenzeno/xileno. Os resultados obtidos sugerem que a adsorção de BTEX ocorre preferencialmente através de efeito hidrofóbico já que o CA é um material carbonoso e a CCA configura-se como uma matriz de sílica com fração carbonosa. Os valores de remoção ficaram entre 78,8 e 100%, demonstrando que a CCA apresenta-se como um material alternativo para a adsorção de benzeno, tolueno, etilbenzeno e xileno presente em solução aquosas. / The contamination of water resources by hydrocarbons is considered a significant environmental impact. The remediation systems currently search alternative adsorbents to remove this pollutants. The aim of this work was to investigate the use of rice husk ash (RHA) and activated carbon (AC) in the removal of BTEX (benzene, toluene, ethylbenzene, and xylene) from aqueous solutions. The RHA used was generated as a byproduct of the combustion of rice husk for energy generation, while AC was purchased from the market. Samples of both materials were characterized based on physical, chemical, and microstructural standards (grain size distribution, surface area, porosity, specific weight, hydration capacity, pH, zero load test, loss on ignition, total carbon, chemical composition, crystalline phases, functional groups, and image analysis). The adsorption assays were carried out using standard benzene, toluene, xylene, and ethylbenzene individually and mixed. Quantification of compounds was conducted by gas chromatography with Flame Ionization Detector. Adsorption kinetics was evaluated based on the variables contact time between adsorbent and adsorbate (15, 30, 60, 120, and 240 min), initial adsorbate concentration (1, 5, 10, and 20 mg/L), and adsorbent dose (10 and 20 g/L). The kinetic models pseudo 1st order, pseudo 2nd order, and intra-particle diffusion were adjusted to experimental data. Experimental isotherms were obtained for each compound and for the BTEX mixture. The Langmuir, Freundlich, and Sips models were adjusted to the experimental results for the systems that used one compound at a time. Sample characterization revealed the differences in composition, microstructure, surface area, and pore size between RHA and AC. Kinetic studies showed that RHA and AC have high and similar adsorption capacities at the equilibrium time of 120 min. Generally, the amount of each hydrocarbon removed from the mixture was lower than the removal achieved in the single-compound systems, for which removal rate followed the sequence (adsorbate mass/ adsorbent mass) ethylbenzene > xylene > toluene > benzene. The pseudo 2nd order kinetics model presented the best correlation for all assays. The experimental isotherms obtained for single-compound systems characterized the adsorption on porous surfaces, forming monolayers. No overall concordance was observed in the adjustment of the theoretical models, and in some situations the Langmiur and Freundlich models presented appropriate correlation coefficients. Considering the BTEX mixtures, the experimental isotherms constructed for RHA indicated the existence of competition for active sites of the adsorbent material between benzene and toluene and between ethylbenzene and xylene. The results obtained suggest that BTEX adsorption occurs preferentially through the hydrophobic effect, since AC is a carbonaceous material, while RHA is composed mainly of silica, with a carbonaceous fraction. Removal rates were between 78.8% and 100%, indicating that RHA is an interesting alternative in the removal of benzene, toluene, ethylbenzene, and xylene from aqueous solutions.

O objetivo desta tese foi o desenvolvimento de um equipamento compacto para o tratamento de águas subterrâneas contaminadas por BTEX e TPH em postos de combustíveis. Esta questão ambiental é uma preocupação mundial devido ao nível de contaminação e a quantidade de vazamentos existentes, toxicidade dos poluentes e a necessidade de uso de aquíferos para consumo humano. O equipamento é composto por unidades que contemplam as seguintes etapas: (a) sucção e volatilização de compostos orgânicos voláteis; (b) injeção de ar (“air sparging”) para remoção de substâncias orgânicas voláteis; e (c) filtro de adsorção com recheio composto por mistura de 50% de carvão ativado e 50% de cinza de casca de arroz para a remoção de TPH. A parte experimental envolveu a caracterização de águas subterrâneas contaminadas e estudos em escala piloto e real. Os resultados obtidos demostraram que o equipamento de remediação desenvolvido é altamente eficiente para o tratamento de águas subterrâneas contaminadas. Com um tempo de detenção de 8 horas, obtiveram-se decréscimos superiores a 96% de BTEX e TPH. Nesta situação, a água contaminada tratada alcança valores que atendem aos critérios de lançamento estabelecidos pelas legislação nacional vigente. / This study describes the development of a compact device to treat groundwater contaminated with BTEX and TPH in gas stations. This environmental issue raises concerns worldwide, due to the level of contamination, the high occurrence of leaks, the toxicity of contaminants, and the importance of aquifers for human consumption. The equipment was formed by: a) a suction and treatment stage using vacuum and aeration with injectors (to replace the suction system based on a conventional vacuum pump and the air stripping and/or air sparging system); b) small-scale surface aerators (to replace the air stripping and/or air sparging system); c) an adsorption filter using a mixture of activated carbon (50%) and rice husk ash (50%) (to replace the activated carbon system). The experiment was conducted in four stages: a) characterization of groundwaters; b) presentation of the adsorbents used in the filter; c) pilot test (under controlled conditions to measure the efficiency to remove BTEX and TPH); and d) the full-scale tests (observation and confirmation of equipment efficiency). The results show that the remediation equipment developed is highly efficient to treat contaminated groundwater. An 8-h retention time afforded to reduce BTEX and TPH levels by over 96%. In this scenario, the treated water parameters meet the current legal requirements for discharge.

Um grande passivo ambiental da atualidade refere-se à contaminação dos recursos hídricos por hidrocarbonetos. Os atuais sistemas de remediação buscam a utilização de adsorventes alternativos para remoção destes poluentes. O objetivo desta tese de doutorado foi avaliar o uso da cinza de casca de arroz (CCA) e de carvão ativado (CA) na adsorção de BTEX – benzeno, tolueno, etilbenzeno e xileno em soluções aquosas. A CCA foi gerada a partir do processo de queima de casca de arroz para aproveitamento energético e o CA obtido comercialmente. As propriedades físicas, químicas e microestruturais da CCA e do CA foram caracterizadas através de análises de distribuição granulométrica, área superficial, porosidade, massa específica, capacidade de hidratação, pH, ponto de carga zero, perda ao fogo, carbono total, composição química elementar, determinação de fases cristalinas, determinação de grupos funcionais e análise de imagem. Estudos de adsorção cinéticos e de equilíbrio (isotermas) foram efetuados com soluções padrões de benzeno, tolueno, xileno e etilbenzeno em sistemas monocompostos e em misturas BTEX. A quantificação foi realizada por por cromatografia gasosa com detector de ionização de chama. Na cinética de adsorção, foram avaliadas as variáveis: tempo de contato adsorvente-adsorbato (15, 30, 60, 120 e 240 minutos); concentração inicial do adsorbato (1, 5, 10 e 20 mg/L) e dosagem do adsorvente (10 e 20 g/L). Os modelos cinéticos de Pseudo-primeira ordem, Pseudo-segunda ordem e Difusão intrapartícula foram ajustados aos dados experimentais. Isotermas experimentais foram obtidas para cada composto e para a mistura BTEX. Os modelos de Langmuir, Freundlich e Sips foram ajustados aos resultados experimentais para os sistemas com monocompostos. A caracterização das amostras indicou que o CA apresenta microestrutura uniforme com grande área superficial formada por micro e mesoporos e alto teor de carbono. Já a CCA apresenta uma microestrutura heterogênea formada por macroporos e com alto teor de sílica. Os estudos cinéticos demonstraram que a CCA e o CA apresentam capacidades de adsorção altas e semelhantes no tempo de equilíbrio de 120 minutos. De forma geral, a remoção de cada composto na mistura foi menor que a remoção obtida quando em sistemas de monocompostos, onde a capacidade de adsorção se deu na seguinte ordem (em massa de adsorbato por massa de adsorvente): etilbenzeno > xileno > tolueno > benzeno. O modelo cinético de Pseudo-segunda ordem apresentou a melhor correlação para todos os ensaios. As isotermas experimentais obtidas para os monocompostos caracterizam a adsorção em superfícies porosas com formação de monocamada. Os ajustes aos modelos teóricos não apresentaram unanimidade, observando em algumas situações uma correlação adequada para Langmuir e Freundlich. Nas misturas BTEX, as isotermas experimentais para a CCA indicam uma competição pelos sítios ativos do adsorvente entre benzeno/tolueno e entre etilbenzeno/xileno. Os resultados obtidos sugerem que a adsorção de BTEX ocorre preferencialmente através de efeito hidrofóbico já que o CA é um material carbonoso e a CCA configura-se como uma matriz de sílica com fração carbonosa. Os valores de remoção ficaram entre 78,8 e 100%, demonstrando que a CCA apresenta-se como um material alternativo para a adsorção de benzeno, tolueno, etilbenzeno e xileno presente em solução aquosas. / The contamination of water resources by hydrocarbons is considered a significant environmental impact. The remediation systems currently search alternative adsorbents to remove this pollutants. The aim of this work was to investigate the use of rice husk ash (RHA) and activated carbon (AC) in the removal of BTEX (benzene, toluene, ethylbenzene, and xylene) from aqueous solutions. The RHA used was generated as a byproduct of the combustion of rice husk for energy generation, while AC was purchased from the market. Samples of both materials were characterized based on physical, chemical, and microstructural standards (grain size distribution, surface area, porosity, specific weight, hydration capacity, pH, zero load test, loss on ignition, total carbon, chemical composition, crystalline phases, functional groups, and image analysis). The adsorption assays were carried out using standard benzene, toluene, xylene, and ethylbenzene individually and mixed. Quantification of compounds was conducted by gas chromatography with Flame Ionization Detector. Adsorption kinetics was evaluated based on the variables contact time between adsorbent and adsorbate (15, 30, 60, 120, and 240 min), initial adsorbate concentration (1, 5, 10, and 20 mg/L), and adsorbent dose (10 and 20 g/L). The kinetic models pseudo 1st order, pseudo 2nd order, and intra-particle diffusion were adjusted to experimental data. Experimental isotherms were obtained for each compound and for the BTEX mixture. The Langmuir, Freundlich, and Sips models were adjusted to the experimental results for the systems that used one compound at a time. Sample characterization revealed the differences in composition, microstructure, surface area, and pore size between RHA and AC. Kinetic studies showed that RHA and AC have high and similar adsorption capacities at the equilibrium time of 120 min. Generally, the amount of each hydrocarbon removed from the mixture was lower than the removal achieved in the single-compound systems, for which removal rate followed the sequence (adsorbate mass/ adsorbent mass) ethylbenzene > xylene > toluene > benzene. The pseudo 2nd order kinetics model presented the best correlation for all assays. The experimental isotherms obtained for single-compound systems characterized the adsorption on porous surfaces, forming monolayers. No overall concordance was observed in the adjustment of the theoretical models, and in some situations the Langmiur and Freundlich models presented appropriate correlation coefficients. Considering the BTEX mixtures, the experimental isotherms constructed for RHA indicated the existence of competition for active sites of the adsorbent material between benzene and toluene and between ethylbenzene and xylene. The results obtained suggest that BTEX adsorption occurs preferentially through the hydrophobic effect, since AC is a carbonaceous material, while RHA is composed mainly of silica, with a carbonaceous fraction. Removal rates were between 78.8% and 100%, indicating that RHA is an interesting alternative in the removal of benzene, toluene, ethylbenzene, and xylene from aqueous solutions.

O objetivo desta tese foi o desenvolvimento de um equipamento compacto para o tratamento de águas subterrâneas contaminadas por BTEX e TPH em postos de combustíveis. Esta questão ambiental é uma preocupação mundial devido ao nível de contaminação e a quantidade de vazamentos existentes, toxicidade dos poluentes e a necessidade de uso de aquíferos para consumo humano. O equipamento é composto por unidades que contemplam as seguintes etapas: (a) sucção e volatilização de compostos orgânicos voláteis; (b) injeção de ar (“air sparging”) para remoção de substâncias orgânicas voláteis; e (c) filtro de adsorção com recheio composto por mistura de 50% de carvão ativado e 50% de cinza de casca de arroz para a remoção de TPH. A parte experimental envolveu a caracterização de águas subterrâneas contaminadas e estudos em escala piloto e real. Os resultados obtidos demostraram que o equipamento de remediação desenvolvido é altamente eficiente para o tratamento de águas subterrâneas contaminadas. Com um tempo de detenção de 8 horas, obtiveram-se decréscimos superiores a 96% de BTEX e TPH. Nesta situação, a água contaminada tratada alcança valores que atendem aos critérios de lançamento estabelecidos pelas legislação nacional vigente. / This study describes the development of a compact device to treat groundwater contaminated with BTEX and TPH in gas stations. This environmental issue raises concerns worldwide, due to the level of contamination, the high occurrence of leaks, the toxicity of contaminants, and the importance of aquifers for human consumption. The equipment was formed by: a) a suction and treatment stage using vacuum and aeration with injectors (to replace the suction system based on a conventional vacuum pump and the air stripping and/or air sparging system); b) small-scale surface aerators (to replace the air stripping and/or air sparging system); c) an adsorption filter using a mixture of activated carbon (50%) and rice husk ash (50%) (to replace the activated carbon system). The experiment was conducted in four stages: a) characterization of groundwaters; b) presentation of the adsorbents used in the filter; c) pilot test (under controlled conditions to measure the efficiency to remove BTEX and TPH); and d) the full-scale tests (observation and confirmation of equipment efficiency). The results show that the remediation equipment developed is highly efficient to treat contaminated groundwater. An 8-h retention time afforded to reduce BTEX and TPH levels by over 96%. In this scenario, the treated water parameters meet the current legal requirements for discharge.

Submitted by Fernanda Rodrigues de Lima (fernanda.rlima@ufpe.br) on 2018-07-23T22:00:44Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO José Luiz Lima Silva.pdf: 1419285 bytes, checksum: 89b1ec229690ad6fe71dbc714f805505 (MD5) / Approved for entry into archive by Alice Araujo (alice.caraujo@ufpe.br) on 2018-07-24T18:35:47Z (GMT) No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO José Luiz Lima Silva.pdf: 1419285 bytes, checksum: 89b1ec229690ad6fe71dbc714f805505 (MD5) / Made available in DSpace on 2018-07-24T18:35:47Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO José Luiz Lima Silva.pdf: 1419285 bytes, checksum: 89b1ec229690ad6fe71dbc714f805505 (MD5) Previous issue date: 2017-01-31 / A utilização de poços é uma boa alternativa para a Região Metropolitana de Recife (RMR), por causa da existência de mananciais subterrâneos de boa qualidade e devido à crescente escassez de fontes hídricas superficiais nas bacias hidrográficas próximas. Contudo, certos problemas como a falta de saneamento e a presença de empreendimentos potencialmente poluidores, dentre eles os postos de combustíveis, que oferecem risco de acidentes envolvendo vazamentos, aumentam consideravelmente a consequente contaminação do lençol freático. Nesse contexto, o presente trabalho partiu do interesse de saber como se comportaram as plumas de contaminação no entorno de três postos de abastecimento, localizados na RMR. No passado, há aproximadamente quinze anos atrás, estes foram alvo de denúncias sobre vazamentos de combustíveis. Certos compostos em combustíveis como óleo diesel e gasolina, respectivamente os hidrocarbonetos poliaromáticos (HPA) e benzeno, tolueno, etilbenzeno e xileno (BTEX), quando presentes, revelam que a água foi contaminada por petroderivados. Para esta pesquisa foram coletadas amostras de água e dados de campo de poços próximos aos três postos de combustíveis suspeitos. Foram determinadas as concentrações dos referidos hidrocarbonetos via cromatografia gasosa com espectrômetro de massa, e de parâmetros de potabilidade. Os resultados encontrados sugerem atenuação natural em todos os locais próximos dos poços analisados, uma vez que as concentrações foram mínimas ou nenhuma. De qualquer maneira, sugere-se a necessidade de trabalhos semelhantes para avaliação dos hidrocarbonetos em solos ao longo do tempo, caracterização da microbiota no processo de biodegradação anaeróbia nos poços e elaboração de textos normativos fixando exigências de monitoramento desses contaminantes para a qualidade da água consumida pela população que utiliza poços em áreas potencialmente sujeitas à contaminação por combustíveis. / The use of wells is a good alternative for the Metropolitan Region of Recife (RMR), due to the existence of good quality underground springs and due to the increasing scarcity of surface water sources in the nearby river basins. However, certain problems such as lack of sanitation and the presence of potentially polluting undertakings, including fuel stations, which pose a risk of accidents involving leaks, considerably increase the consequent contamination of the water table. In this context, the present study started from the interest of knowing how the contamination feathers behaved in the surroundings of three filling stations, located in the RMR. In the past, about fifteen years ago, these were the subject of complaints about fuel leaks. Certain compounds in fuels such as diesel and petrol, respectively the polyaromatic hydrocarbons (HPA) and benzene, toluene, ethylbenzene and xylene (BTEX), when present, reveal that the water has been contaminated by petroderivatives. For this research, water samples and field data were collected from wells near the three suspect fuel stations. The concentrations of said hydrocarbons were determined by gas chromatography with mass spectrometer, and by potability parameters. The results suggest natural attenuation at all sites near the analyzed wells, since the concentrations were minimal or none at all. Nevertheless, it is suggested the need for similar studies to evaluate hydrocarbons in soils over time, characterization of the microbiota in the process of anaerobic biodegradation in the wells and elaboration of normative texts setting the monitoring requirements of these contaminants for the quality of the water consumed By the population using wells in areas potentially subject to fuel contamination.