The main function of a pyroscrubber in petroleum coke calcining process is to oxidize the carbonaceous contents, including hydrocarbon volatiles, of the exhaust gas from the calcination kiln, so as to leave no more than small traces of unburned volatiles, solid carbon, ashes, or emissions (e.g. CO, NOx and SOx) in the flue gas finally discharged. To maximize the energy recovery and reduce pollutant emission from the pyroscrubber, 3-D computational models are developed using FLUENT to simulate the combustion and thermal-flow phenomena inside the pyroscrubber. The results show the 3-D behavior of the flow, the reaction inside the pyroscrubber, effect of different amounts of air injection with respect to combustion efficiency, energy output and NOx emission. A multistage burning strategy is introduced and studied and results show it successfully cuts emission without compromising energy output. A particle combustion model with the homogeneous gas combustion model is also developed and incorporated to investigate CO emission.

Calcined coke is the best material for making carbon anodes for smelting of alumina to aluminum. Calcining is an energy intensive industry and a significant amount of heat is wasted in the calcining process. Efficiently managing this energy resource is tied to the profit margin and survivability of a calcining plant. 3-D computational models are developed using FLUENT to simulate the calcining process inside the long slender kiln. Simplified models are employed to simulate the moving petocke bed with a uniform distribution of moisture evaporation, devolatilization, and coke fines entrainment rate with a conjugate radiation-convection-conduction calculation. The results show the 3-D behavior of the flow, the reaction inside the kiln, heat transfer and the effect of the tertiary air on coke bed heat transfer. The ultimate goals are to reduce energy consumption, recover waste-heat, increase thermal efficiency, and increase the product yield.

The objective of this work was to study the effect of supercritical water on coke formed on ZSM-5 during its use as a dodecane cracking catalyst. ZSM-5 coking was quantified at different reaction times, finding that the presence of supercritical water reduced coke formation by an order of magnitude or more. Coked samples were analyzed using several methods, including temperature programmed oxidation (TPO), attenuated total reflectance infrared (ATR-IR) spectroscopy, carbon-13 nuclear magnetic resonance (13C NMR), diffuse reflectance ultraviolet-visible spectroscopy (DR-UV-vis) and UV-Raman. Coked produced in the absence of SCW was formed by polycyclic aromatic hydrocarbons (PAHs) with more than 4 aromatic rings containing alkyl side chains. Coke produced in the presence of SCW was formed by aromatics with 1 to 3 aromatic rings. The characteristics of coke formed in the absence of water on ZSM-5 that had been pretreated in SCW were intermediate to those of coke formed on fresh ZSM-5 in the presence and absence of water, suggesting that the presence of water influences coke properties. It was also verified that SCW can decrease coke formation due to its effect on Bronsted acidity of the catalyst and ability to promote coke gasification. The effect of coke deposits produced in the presence and absence of SCW on the rate of ethanol dehydration, a model reaction studied under diffusion-controlled conditions, indicated that SCD/SWC coke deactivated less the catalyst than SCD coke.

No presente trabalho foi estudado o efeito da adição de cálcio, bário e estrôncio (0%-5% em massa) em catalisadores Ni/Al2O3, contendo 5% de níquel em massa, frente à reação de reforma a vapor do etanol com o objetivo de inibir a reação de desidratação do etanol, precursor do carbono. Os catalisadores foram preparados por dois métodos: impregnação (I) e co-precipitação (C). Inicialmente todos os catalisadores obtidos foram submetidos a analise de espectroscopia dispersiva em emissão de raios X (EDX), para confirmação de suas composições químicas, em seguida foram aplicados na reação de reforma a vapor do etanol, dentre os catalisadores estudados os que apresentaram a menor formação de eteno foram, 5%Ca-5%Ni/Al (I) e 5%Ca-5%Ni/Al (C) dentre os que continham cálcio; 0,5%Ba-5%Ni/Al (I) e 5%Ba-5%Ni/Al (C) dentre os que continham bário e 5%Sr-5%Ni/Al (I) e 5%Sr-5%Ni/Al (C) dentre os que continham estrôncio, sendo então submetidos as etapas de caracterização, difração de raios X (DRX), redução a temperatura programada (RTP), área superficial específica pelo método BET e reação de decomposição do isopropanol. O desempenho destes catalisadores foi comparado com o obtido para os catalisadores sem aditivos 5Ni/Al(I) e 5Ni/Al(C). O método da impregnação demonstrou ser mais eficiente do que o método da co-precipitação para o alcance dos objetivos do trabalho e o catalisador 5Ca-5Ni/Al (I) foi o mais efetivo na redução da acidez da alumina e consequentemente mostrou menor deposição de carbono. / Catalysts of Ni/Al2O3 containing 5wt% of nickel and modified by calcium, barium and strontium addition (0wt% - 5wt%) were tested in the ethanol steam reforming with the goal of reduce the reaction of dehydratation of ethanol, a carbon precursor. The catalysts were prepared by two methods: impregnation (I) and co-precipitation (C). Initially, all catalysts were subjected to analysis by Energy-dispersive X-ray spectroscopy (EDX), to confirm their chemical compositions, then they were applied in the steam reforming of ethanol, Among the catalysts studied those with lower ethene production were: 5%Ca-5%Ni/Al (I), 5%Ca-5%Ni/Al (C) among those containing calcium; 0,5%Ba-5%Ni/Al (I), 5%Ba-5%Ni/Al (C) among those containing barium and 5%Sr-5%Ni/Al (I), 5%Sr-5%Ni/Al (C) among those containing strontium, being submitted to the characterization by X-ray diffraction (XRD), temperature programmed reduction (TPR), specific surface area by BET method and reaction of isopropanol decomposition. The performance of these catalysts was compared to with the catalysts without additives 5(wt%)Ni/Al(I) and 5(wt%)Ni/Al(C). The impregnation method was more effective than the method co-precipitation for achieving the objectives of this work and the catalyst 5Ni-5Ca/Al (I) was the more effective in the reduction of alumina acidity and also showed the lower carbon deposition.

Neste trabalho foi desenvolvido um procedimento analítico empregando o processo de multicomutação para determinação de íons cloreto com detecção fotométrica para aplicação em amostras de coque de petróleo. O procedimento foi baseado no método espectrofotométrico descrito no Standard Methods, onde a reação entre tiocianato de mercúrio (II) e cloreto leva ao deslocamento dos íons tiocianato e à formação de um complexo de coloração vermelha com o Fe (III), que foi monitorado em 455 nm. Foram construídos dois módulos de análise empregando válvulas solenóide de três vias no primeiro e válvulas de estrangulamento no outro. Com os parâmetros analíticos otimizados para o primeiro módulo, obteve-se uma curva analítica linear para o intervalo de 0,25 a 4,0 mg L-1 de cloreto (R= 0,997), com um limite de detecção de 0,12 mg L-1 (3xbranco/inclinação); RSD de 1,7% (n=15) e uma freqüência de amostragem de 50 det h-1. O segundo módulo de análise foi proposto a fim de eliminar a etapa de acidificação das soluções de referência e amostras. Esta etapa era efetuada off line para liberar as bolhas formadas na reação. A curva analítica obtida para este módulo foi linear para o intervalo de 0,25 a 6,0 mg L-1 de cloreto (R= 0,999), com um limite de detecção de 0,04 mg L-1 (3xbranco/inclinação); RSD de 0,8% (n=15) e uma frequência de amostragem de 50 det h-1. O módulo foi aplicado em amostras de coque de petróleo e também no material de referência certificado. / In this work was developed an analytical procedure employing multicommutation for the photometric determination of chloride in petroleum coke. The procedure was based on the photometric method described on Stand Method, where the reaction between mercury(II) thyocyanate and chloride causes the displacement of the thyocyanate ions, which reacted with iron(III) forming a compound that monitored at 472 nm. Two analysis modules were designed employing three-way and pinch solenoid valves. After the optimizing of the analytical parameters related to analysis module that employed three-way solenoid valves, the analytical curve presented a linear response in the concentration range of 0.25 to 4.0 mg L-1 (R = 0.997). A detection limit of 0.12 mg L-1 chloride, a relative standard deviation of 1.7 % (n = 15) and a sampling frequency of 50 determination per hour were also achieved. The second analysis module was designed to avoid acidification step of sample and reference solutions that was carried out off line to prevent bubbled delivering. The analytical curve presented a linear response within the concentration range of 0.25 up to 6.0 mg L-1 chloride (R=0.999). Detection limit of 0.04 mg L-1, standard deviation of 0.8 % (n=15), and sampling frequency of 50 determination per hours were of achieved. The proposed system was used for the determination of chloride in petroleum coke and also in certified material.

A sinterização de finos de minério de ferro é utilizada já há mais de 5 decênios , embora o maior impulso tenha-se verificado na década de 1950-1960. No Brasil, a Companhia Siderúrgica Belgo Mineira foi a pioneira nesses estudos, já em 1938. A literatura cita trabalhos analisando inúmeros fatores no estudo da sinterização, seja quanto aos tipos de equipamentos, às variáveis do processo, às variáveis da mistura a sinterizar, às variáveis do sínter produzido, até recente estudo sobre sinterização semi-redutora . Na presente tese o autor propõe-se a analisar o efeito das variações de algumas características dos combustíveis na sinterização de minério de ferro. Com o levantamento das curvas térmicas (curvas de evolução da temperatura com o tempo, num determinado ponto do interior da carga) o autor pretende analisar certos efeitos das matérias voláteis, da cinza e da reatividade dos combustíveis. Serão, também, verificados os efeitos de pequenas variações de unidade na sinterização, tendo em vista que, em unidades de operação contínua de sinterização, os recentes métodos adotados para controle da umidade da mistura a sinterizar (tais como por sonda de nêutrons e baseado na resistividade elétrica da carga) permitem avaliar o teor de umidade com sensibilidade dentro da faixa de 1%, isto é, com desvio de mais ou menos 0,5% (3), (4). Além do coque, que é o combustível normalmente empregado na sinterização, foram utilizados o carvão metalúrgico de Santa Catarina e o carvão vegetal (de eucalipto). Ênfase maior foi dada ao carvão metalúrgico, por razões que são justificadas logo adiante.O \"carvão metalúrgico\" de Santa Catarina, é o principal produto do beneficiamento do carvão mineral betuminoso das jazidas desse Estado, para emprego na produção de coque, geralmente em mistura com outro carvão importado da mesma categoria. Julgou-se que a possibilidade de aproveitamento desse carvão metalúrgico (não coqueificado) na sinterização, mormente com o encarecimento do carvão importado, ora verificado, poderá representar uma nova solução aos problemas siderúrgicos nacionais, tanto sob ponto de vista econômico, como estratégico e social. Além disso, o desvio de uma parcela do carvão metalúrgico nacional para a sinterização, dentro do critério da mistura com determinada quota de carvão importado, permitirá a operação dos altos fornos com coque de melhor qualidade. / Sem abstracts

A presente pesquisa objetivou estudar a remoção dos poluentes presentes em uma água residuária de coqueria, através do processo biológico de nitritação/desnitritação operando um reator de lodo ativado em bateladas seqüenciais em duas etapas sucessivas. Durante a primeira, o reator foi alimentado com um efluente sintético composto por dois poluentes abundantes em despejos de coqueria: nitrogênio amoniacal (500 mg N/L) e fenol (1.000 mg C6H5OH/L). Na segunda, o reator foi alimentado com o despejo gerado na unidade de coqueria de uma indústria siderúrgica integrada. Ao longo da primeira etapa, ao final da fase aeróbia dos 28 ciclos de tratamento, foi possível alcançar eficiências de remoção de N-NH3 superiores a 90% com predominância do N-NO2 - na massa líquida do reator evidenciado pelas relações N-NO2 -/ (N-NO2 - + N-NO3 -) superiores a 86%. O principal mecanismo de inibição das bactérias oxidantes de nitrito (BON) foram concentrações de amônia livre no conteúdo do reator entre 3,2 e 19,5 mg NH3/L. As taxas específicas de nitritação variaram entre 0,03 e 0,11 kg N-NH3/ kg SSV.dia, para temperaturas no conteúdo do reator entre 15 e 34°C. Durante a fase anóxica, o fenol mostrou-se adequado como fonte de carbono para a biomassa desnitritante, desde que as taxas de aplicação volumétricas fossem inferiores a 0,02 kg fenol/m³.hora. Respeitando essa condição, foi possível alcançar: eficiências de remoção de fenol entre 45 e 56%; taxas específicas de remoção de fenol entre 0,03 e 0,09 kg C6H5OH / kg SSV.dia; taxas específicas de desnitritação entre 0,03 e 0,06 kg N-NO2 -/ kg SSV.dia e eficiências de remoção de (N-NO2 - + N-NO3 -) superiores a 95%. Ao longo da fase anóxica foram retiradas amostras do conteúdo do reator para a realização de análises de nitrofenóis (NF). Os resultados acusaram a presença de 2 nitrofenol e 4 nitrofenol em concentrações proporcionais à taxa de aplicação volumétrica do fenol na massa líquida do reator. A presença desses compostos em concentrações inferiores a 0,5 mg/L não causou impacto sobre a desnitritação biológica. As análises realizadas em amostras coletadas ao final da reação anóxica, não acusaram a presença de 2 e 4 NF, demonstrando que esses compostos podem ser biodegradados por uma biomassa bem adaptada ao fenol. A concepção do sistema para tratamento da água residuária de coqueria via nitritação/desnitritação envolveu a operação de dois reatores (principal e reator de polimento) operados em bateladas seqüenciais. As condições de operação do reator principal eram manipuladas para viabilizar o acúmulo de NNO2 - ao final da fase aeróbia e promover a desnitritação durante a fase anóxica, utilizando como fonte de carbono a própria matéria orgânica presente no despejo. Como o sobrenadante do reator principal apresentava concentrações elevadas de N-NO2 -, esse efluente era aplicado no reator de polimento, juntamente com etanol como fonte de carbono para redução do NNO2 -. Ao final da fase aeróbia dos ciclos de tratamento conduzidos no reator principal alcançaram-se: relações NO2 -/ (N-NO2 - + N-NO3 -) superiores a 88%; eficiências de remoções de nitrogênio total superiores a 60%; remoções de N-NH3 superiores a 90%, para valores de pH na massa líquida do reator entre 7,8 e 8,5 e, temperatura entre 23 e 31°C. Tal qual ocorrido durante a primeira etapa da investigação, o principal mecanismo de inibição da atividade das bactérias oxidantes de nitrito foi a toxicidade conferida pelas concentrações de amônia livre (3,7 a 15,7 mg NH3/L) no conteúdo do reator. Durante a fase anóxica, as eficiências de remoção de (N-NO2 - foram limitadas pela disponibilidade de matéria orgânica biodegradável no despejo da coqueria, razões DBO/DQOafluente superiores a 80% resultaram em remoções de N-NO2 - próximas de 100%. Quanto ao reator de polimento, pode-se afirmar que o etanol teve um efeito positivo sobre a remoção de matéria orgânica da água residuária da coqueria, considerando a configuração (dois lodos) utilizada. / The present research aimed to study the coke-oven wastewater treatment over nitritation/denitritation in an activated sludge sequencing batch reactor in two successive phases. During the first one, the reactor was fed with a synthetic effluent composed by two abundant pollutants present in coke-oven wastewaters: total ammonia nitrogen (500 mg TAN.l-1) and phenol (1,000 mg C6H5OH.l-1). During the second phase, the reactor was fed with the wastewater produced in an integrated steel industrys coke-plant. The results of the first phase (28 cycles) showed that was possible to achieve TAN removal efficiencies higher than 90% with NO2 --N predominance in the reactor content, evidenced by the rates NO2 --N/ (NO2 --N + NO3 --N) higher than 86%. The main mechanism of the nitrite oxidizer bacteria (NOB) inhibition was free ammonia concentrations between 3.2 and 19.5 mg NH3.l-1. The specific nitritation rates varied between 0.03 and 0.11 kg TAN. kg VSS-1.d-1, for temperatures between 15 and 34oC. Phenol showed to be suitable as carbon source for denitrifying biomass, once the volumetric application rates were lower than 0.02 kg phenol.m-3.h-1. Obeying this condition, it was possible to achieve: phenol removal efficiencies between 45 and 56%; specific phenol removal rates between 0.03 and 0.09 kg C6H5OH. kg VSS-1.d-1; specific denitritation rates between 0.03 and 0.06 kg NO2 --N . kg VSS-1.d-1 and removal efficiencies of (NO2 --N + NO3 --N) higher than 95%. During the anoxic phase, samples were collected from the reactor content for nitrophenols analyses. The results showed the presence of 2- nitrophenol (2-NP) and 4-nitrophenol (4-NP) in concentrations proportional to phenol volumetric application rate in the reactor liquid mass. The presence of those compounds in concentrations lower than 0.5 mg/L does not cause impact over the biological denitritation. The analyses accomplished in samples collected at the end of the anoxic reaction do not show the presence of 2 and 4-NP, demonstrating that these compounds can be biodegraded by a well-adapted biomass. The arrangement of the system for the treatment of coke-oven wastewater (Phase 02) over nitritation/denitritation involved the operation of two sequencing batch reactors (the main reactor and the polishing one). The operational conditions of the main reactor were manipulated to make feasible the NO2 --N accumulation at the end of the aerobic stage and promote the denitritation using the own organic matter present in the cokeoven wastewater as carbon source. As the supernatant of the main reactor presented high nitrite concentrations, this effluent was conducted to a biological denitrifying polishing reactor with ethanol as carbon source. At the end of the aerobic stage of the treatment cycles conducted in the main reactor, it was achieved: NO2 --N/ (NO2 --N + NO3 --N) higher than 88%; total nitrogen removal efficiencies higher than 60%; ammonia nitrogen removal higher than 90%. As occurred during the first phase of the investigation, the main NOB activity inhibition was the toxicity of the free ammonia concentrations (3.7 to 15.7 mg NH3.l-1) in the reactor content. At the end of anoxic stage, the NO2 --N removal efficiencies were limited by the availability of the biodegradable organic matter in the coke-oven wastewater but BOD/CODinfluent higher than 80% resulted in NO2 --N removals next to 100%. Regarding to the polishing reactor, it can be stated that the ethanol had a positive effect over the organic matter removal of the coke-oven wastewater.

This study presents a simple way of obtaining hydrogen gas (H2) from various ranks of coal, coke, and graphite using nanosecond laser pulses. Powder samples of coal and graphite with and without water were irradiated with 1064 nm and 532 nm pulses from an Nd: YAG laser for 45 minutes under air and argon atmospheres. It was observed that 532 nm laser pulses were more effective than 1064 nm pulses in gas generation and both were nonlinearly correlated with respect to the laser energy density. Mainly hydrogen (H2) and carbon monoxide (CO) were observed. The H2 to CO ratio shows that the highest efficiency rank was the anthracite coal, with an average ratio of 1.4 due to its high fixedcarbon content and relatively high hydrocarbon amount. Coal samples were characterized by scanning electron microscope (SEM), Fourier transform infrared (FTIR) spectroscopy, Thermogravimetric analyzer (TGA), and calorimeter. Graphite was used as a pure carbon source to study the possible reactions of gas yielded during irradiation process. The amount of H2 produced was negligible when graphite powder was exposed under the air and argon atmospheres. On the other hand, H2 was obtained from irradiation of graphite powder in the presence of water due to a possible carbon-water reaction. When coal powders were irradiated under air and argon atmosphere, the amount of produced H2 increased drastically compared to graphite due to the presence of hydrocarbons in coal. In addition, theoretical simulations by a standard finite difference method supported experimental observations.

The oil sands operations in northeast Alberta, Canada, employ unconventional processes to produce synthetic crude oil (SCO). Because the extracted bitumen, ¡®the form of oil in oil sands¡¯, is highly viscous, it requires thermal upgrading to produce SCO. Coking technology is used to convert heavy bitumen fractions to lighter volatile fractions. During this process, an enormous volume of solid coke is produced and the metal impurities (e.g. Al, Fe, Mn, Ni, Ti and V) present in bitumen fractions end-up in the coke particles. As coke demands significant space for storage, oil sands companies are exploring options for placing coke into reclamation landscapes for long term storage and recovery. However, coke holds appreciable amounts of potentially leachable metals that may impede the performance of reclamation landscapes. Although two previous coke leaching studies had showed that coke released metals into water at concentrations exceeding the Canadian guidelines for the protection of aquatic life, the ecotoxicological hazard and risk of these metals were not well characterized. Therefore, the overall goal of this research was to characterize the fate and toxicity of metals associated with coke. In this research, the toxicity of coke leachates collected from oil sands field sites and those artificially generated in the laboratory were evaluated using a standard three-brood Ceriodaphnia dubia tests. Coke leachates (CLs) collected over a period of 20 months from two field lysimeters were found to be acutely toxic to C. dubia. Vanadium concentrations were significantly higher (p¡Ü0.05) than concentrations of all other metals in CLs from both lysimeters, and also in leachates from a laboratory batch renewal leaching study. Furthermore, toxic unit (TU) calculations suggested that Ni and V were likely the cause of CL toxicity, but this was not explicitly proven. Therefore, a chronic toxicity identification and evaluation (TIE) approach was adopted to identify and confirm the cause(s) of CL toxicity. Coke was subjected to a 15 day batch leaching process in the laboratory at pH 5.5 and 9.5 in order to characterize the effect of pH on metals release from coke, and to generate CLs for use in TIE tests. The 7-day LC50 estimates for C. dubia survival were 6.3% and 28.7% (v/v) for CLs generated at pH 5.5 and 9.5, respectively. The dissolved concentrations of Mn, Ni and Zn were high (p¡Ü0.05) in pH 5.5 CL, whereas Al, Mo and V were high (p¡Ü0.05) in pH 9.5 CL. Evidence gathered from a series of chronic TIE tests revealed that Ni and V were the cause of toxicity in pH 5.5 CL, whereas V was the primary cause of toxicity in pH 9.5 CL. Further, the influence of bicarbonate, chloride and sulfate ions on metals release, speciation and Ni and V toxicity was investigated. The type and amount of metals released from coke was significantly influenced by the ion type elevated in the leaching solution. Specifically, sulfate influenced mobilization of Ni, Fe, Mn and Zn from coke, whereas bicarbonate enhanced Al, Mo and V releases from coke. With respect to toxicity, increasing bicarbonate decreased the 7-day Ni2+ IC50 from 6.3 to 2.3 ¦Ìg Ni2+/L suggesting enhanced Ni toxicity at high pH or alkalinity. Conversely, sulfate showed a protective effect against V toxicity to C. dubia. The research presented in this thesis suggests that coke will not be inert when stored in reclamation landscapes and that metals, particularly Ni and V, could reach ecotoxicologically relevant levels in surface waters or substrate porewaters, under favourable leaching conditions. Operationally, efforts should focus on remediation and monitoring of metals released from coke, particularly Ni and V, in impacted wetlands, especially before discharging water into natural wetlands and/or local streams and rivers.

The oil sands operations in northeast Alberta, Canada, employ unconventional processes to produce synthetic crude oil (SCO). Because the extracted bitumen, ¡®the form of oil in oil sands¡¯, is highly viscous, it requires thermal upgrading to produce SCO. Coking technology is used to convert heavy bitumen fractions to lighter volatile fractions. During this process, an enormous volume of solid coke is produced and the metal impurities (e.g. Al, Fe, Mn, Ni, Ti and V) present in bitumen fractions end-up in the coke particles. As coke demands significant space for storage, oil sands companies are exploring options for placing coke into reclamation landscapes for long term storage and recovery. However, coke holds appreciable amounts of potentially leachable metals that may impede the performance of reclamation landscapes. Although two previous coke leaching studies had showed that coke released metals into water at concentrations exceeding the Canadian guidelines for the protection of aquatic life, the ecotoxicological hazard and risk of these metals were not well characterized. Therefore, the overall goal of this research was to characterize the fate and toxicity of metals associated with coke. In this research, the toxicity of coke leachates collected from oil sands field sites and those artificially generated in the laboratory were evaluated using a standard three-brood Ceriodaphnia dubia tests. Coke leachates (CLs) collected over a period of 20 months from two field lysimeters were found to be acutely toxic to C. dubia. Vanadium concentrations were significantly higher (p¡Ü0.05) than concentrations of all other metals in CLs from both lysimeters, and also in leachates from a laboratory batch renewal leaching study. Furthermore, toxic unit (TU) calculations suggested that Ni and V were likely the cause of CL toxicity, but this was not explicitly proven. Therefore, a chronic toxicity identification and evaluation (TIE) approach was adopted to identify and confirm the cause(s) of CL toxicity. Coke was subjected to a 15 day batch leaching process in the laboratory at pH 5.5 and 9.5 in order to characterize the effect of pH on metals release from coke, and to generate CLs for use in TIE tests. The 7-day LC50 estimates for C. dubia survival were 6.3% and 28.7% (v/v) for CLs generated at pH 5.5 and 9.5, respectively. The dissolved concentrations of Mn, Ni and Zn were high (p¡Ü0.05) in pH 5.5 CL, whereas Al, Mo and V were high (p¡Ü0.05) in pH 9.5 CL. Evidence gathered from a series of chronic TIE tests revealed that Ni and V were the cause of toxicity in pH 5.5 CL, whereas V was the primary cause of toxicity in pH 9.5 CL. Further, the influence of bicarbonate, chloride and sulfate ions on metals release, speciation and Ni and V toxicity was investigated. The type and amount of metals released from coke was significantly influenced by the ion type elevated in the leaching solution. Specifically, sulfate influenced mobilization of Ni, Fe, Mn and Zn from coke, whereas bicarbonate enhanced Al, Mo and V releases from coke. With respect to toxicity, increasing bicarbonate decreased the 7-day Ni2+ IC50 from 6.3 to 2.3 ¦Ìg Ni2+/L suggesting enhanced Ni toxicity at high pH or alkalinity. Conversely, sulfate showed a protective effect against V toxicity to C. dubia. The research presented in this thesis suggests that coke will not be inert when stored in reclamation landscapes and that metals, particularly Ni and V, could reach ecotoxicologically relevant levels in surface waters or substrate porewaters, under favourable leaching conditions. Operationally, efforts should focus on remediation and monitoring of metals released from coke, particularly Ni and V, in impacted wetlands, especially before discharging water into natural wetlands and/or local streams and rivers.