Petroleum coke-derived activated carbons were prepared and used for the adsorptive removal of a single-ring naphthenic acid (NA) from synthetic oil sands tailings pond water (TPW). The overall adsorption process was found to be intra-particle diffusion-controlled. The Weber-Morris intra-particle diffusion rate constants decreased from 7.43 to 1.23 mg/g min0.5 after activated carbon was post-oxidized with oxygen, suggesting a hindering effect of oxygen surface groups. The Freundlich model fit of the equilibrium adsorption isotherms and the small negative ΔHo pointed to a physisorption-dominated process and the importance of specific surface area. It was estimated that about 2.7 g/L of basic CO2-activated carbon is needed to reduce NA concentration from 120 mg/L to 2.5 mg/L (~98% removal) in synthetic TPW. However, equilibrium adsorption capacity was found to vary significantly after oxygen or nitrogen groups were introduced onto the surface. Therefore, there is a potential for enhanced adsorption by chemical functionalization of carbon.

Petroleum coke-derived activated carbons were prepared and used for the adsorptive removal of a single-ring naphthenic acid (NA) from synthetic oil sands tailings pond water (TPW). The overall adsorption process was found to be intra-particle diffusion-controlled. The Weber-Morris intra-particle diffusion rate constants decreased from 7.43 to 1.23 mg/g min0.5 after activated carbon was post-oxidized with oxygen, suggesting a hindering effect of oxygen surface groups. The Freundlich model fit of the equilibrium adsorption isotherms and the small negative ΔHo pointed to a physisorption-dominated process and the importance of specific surface area. It was estimated that about 2.7 g/L of basic CO2-activated carbon is needed to reduce NA concentration from 120 mg/L to 2.5 mg/L (~98% removal) in synthetic TPW. However, equilibrium adsorption capacity was found to vary significantly after oxygen or nitrogen groups were introduced onto the surface. Therefore, there is a potential for enhanced adsorption by chemical functionalization of carbon.

Com o aumento do processamento de petróleos mais pesados, torna-se interessante realizar um estudo dos possíveis mecanismos de deterioração que poderão ocorrer em função do aumento do Índice de Acidez Total (IAT). Dessa forma, o presente trabalho teve como objetivo principal avaliar as linhas e equipamentos que compõe a bateria de pré-aquecimento da carga de uma unidade de Hidrotratamento (HDT) de diesel. Esse trecho teoricamente está susceptível a ocorrência de corrosão por ácidos naftênicos devido a dois principais fatores: a presença desses ácidos com teores de neutralização superiores a 0,5 mg KOH/g na composição química da carga e a temperatura de processamento, que se encontra em um intervalo de 200 a 400ºC, adequado para existência de tal mecanismo de deterioração. Os dados obtidos em campo referentes à taxa de corrosão das linhas e dos equipamentos foram parametrizados em suas variáveis operacionais e através de uma análise comparativa com dados encontrados na literatura foram obtidas informações importantes para avaliar a ocorrência de corrosão naftênica. / With the increased processing of heavier oils, it is interesting a study of possible mechanisms of deterioration that may occur due to the increase of the Total Acid Number (TAN). Thus, this study aims to evaluate the main lines and equipment that comprise the battery of preheating of the load of a unit of Hydrotreating (HDT) of diesel. This excerpt is theoretically likely to occur from corrosion by naphthenic acids due to two main factors: the presence of these acids with levels of neutralizing more than 0.5 mg KOH/g in the chemical composition of the load and the temperature of processing, which is in a range from 200 º C to 400 º C, suitable for the existence of such a deterioration mechanism. Data from field concerning to the rate of corrosion of the lines and equipment were parameterized in their operational variables and through a comparative analysis with data found in literature were obtained important information to evaluate the occurrence of naphthenic corrosion.

Com o aumento do processamento de petróleos mais pesados, torna-se interessante realizar um estudo dos possíveis mecanismos de deterioração que poderão ocorrer em função do aumento do Índice de Acidez Total (IAT). Dessa forma, o presente trabalho teve como objetivo principal avaliar as linhas e equipamentos que compõe a bateria de pré-aquecimento da carga de uma unidade de Hidrotratamento (HDT) de diesel. Esse trecho teoricamente está susceptível a ocorrência de corrosão por ácidos naftênicos devido a dois principais fatores: a presença desses ácidos com teores de neutralização superiores a 0,5 mg KOH/g na composição química da carga e a temperatura de processamento, que se encontra em um intervalo de 200 a 400ºC, adequado para existência de tal mecanismo de deterioração. Os dados obtidos em campo referentes à taxa de corrosão das linhas e dos equipamentos foram parametrizados em suas variáveis operacionais e através de uma análise comparativa com dados encontrados na literatura foram obtidas informações importantes para avaliar a ocorrência de corrosão naftênica. / With the increased processing of heavier oils, it is interesting a study of possible mechanisms of deterioration that may occur due to the increase of the Total Acid Number (TAN). Thus, this study aims to evaluate the main lines and equipment that comprise the battery of preheating of the load of a unit of Hydrotreating (HDT) of diesel. This excerpt is theoretically likely to occur from corrosion by naphthenic acids due to two main factors: the presence of these acids with levels of neutralizing more than 0.5 mg KOH/g in the chemical composition of the load and the temperature of processing, which is in a range from 200 º C to 400 º C, suitable for the existence of such a deterioration mechanism. Data from field concerning to the rate of corrosion of the lines and equipment were parameterized in their operational variables and through a comparative analysis with data found in literature were obtained important information to evaluate the occurrence of naphthenic corrosion.

Ácidos naftênicos correspondem à complexa mistura de ácidos carboxílicos presentes no petróleo, responsáveis diretamente pela sua acidez e pela sua corrosividade em fase líquida durante o refino. Tais compostos também estão presentes nas frações destiladas do petróleo, causando diversos problemas na qualidade final do produto. Uma possível forma de remover esses ácidos das frações destiladas é através da adsorção em materiais porosos. Contudo, os resultados até então apresentados indicam que resinas trocadoras de íons seriam os melhores adsorventes destes compostos, o que poderia aumentar o custo do processo e diminuir sua viabilidade. Neste trabalho, dois adsorventes comerciais (argila e alumina ativada) foram caracterizados por diversas técnicas físico-químicas e avaliados quanto à sua capacidade de remover os ácidos naftênicos de frações médias e pesadas de petróleo. Avaliou-se, ainda, para fins de comparação, o comportamento de ácidos naftênicos comerciais em óleos sintéticos preparados com óleo mineral. Em complementação, a corrosividade do aço carbono nos meios estudados foi também verificada. A argila apresentou maior afinidade com os ácidos naftênicos, tendo capacidade de adsorção superior e cinética de processo ligeiramente mais rápida às da alumina para as cargas sintéticas. No entanto, em virtude da maior concorrência pelos sítios de adsorção, apresentada pelos outros componentes presentes em óleos reais, observou-se uma perda na eficiência para estas amostras. Neste caso, a alumina apresentou melhores resultados. Embora ambos adsorventes tenham apresentado boa capacidade de remoção do soluto, a resina trocadora de íons ainda apresentou resultado mais eficaz para as amostras reais. Nas condições desse estudo, a taxa de corrosão do aço nas amostras sintéticas e em duas das reais não foi significativa e apenas uma delas apresentou-se corrosiva (Óleo 1). No entanto, a remoção dos ácidos naftênicos por adsorção conseguiu reduzir a taxa de corrosão neste meio em até 99% / Naphthenic acids comprise a complex mixture of carboxylic acids that are present in petroleum. They are directly responsible for the oil acidity and its corrosiveness in liquid phase during the refining process. Such compounds are also presents in the derivatives, causing several problems to product quality. A possible way of removing these acids from those oil fractions is using the adsorption process in porous solids. Nevertheless, results presented so far show that ion exchange resins would be the best adsorbent for these acids, which could make this process very expensive. In this work, two commercial adsorbents (clay and activated alumina) were characterized by several physical-chemistry techniques and evaluated concerning their capacity of removing naphthenic acids from average and heavy fractions of crude oil. For comparison the behavior of commercial naphthenic acids in synthetic commercial samples prepared with mineral oil was also evaluated. In addition, the carbon steel corrosiveness in the studied systems was verified. Clay adsorbent presented better affinity with the acids, showing a greater capacity and a faster kinetics than alumina for synthetic oils. However, because of the higher competition with the other components present in real oils for the adsorption sites, a loss of efficiency for these samples was observed. In that case, alumina showed better results. Although both adsorbents have showed good capacity of removal of acids, the ion exchange resin still presented the best results for real samples. At the conditions of this study, the steel corrosiveness in the synthetic oils, as well as the data obtained for two of the real ones, was not significant, and only one of the real samples (Oil 1) corroded the carbon steel coupon. However, the naphthenic acid removal was able to reduce the corrosiveness in this medium up to 99%

Com o aumento do processamento de petróleos mais pesados, torna-se interessante realizar um estudo dos possíveis mecanismos de deterioração que poderão ocorrer em função do aumento do Índice de Acidez Total (IAT). Dessa forma, o presente trabalho teve como objetivo principal avaliar as linhas e equipamentos que compõe a bateria de pré-aquecimento da carga de uma unidade de Hidrotratamento (HDT) de diesel. Esse trecho teoricamente está susceptível a ocorrência de corrosão por ácidos naftênicos devido a dois principais fatores: a presença desses ácidos com teores de neutralização superiores a 0,5 mg KOH/g na composição química da carga e a temperatura de processamento, que se encontra em um intervalo de 200 a 400ºC, adequado para existência de tal mecanismo de deterioração. Os dados obtidos em campo referentes à taxa de corrosão das linhas e dos equipamentos foram parametrizados em suas variáveis operacionais e através de uma análise comparativa com dados encontrados na literatura foram obtidas informações importantes para avaliar a ocorrência de corrosão naftênica. / With the increased processing of heavier oils, it is interesting a study of possible mechanisms of deterioration that may occur due to the increase of the Total Acid Number (TAN). Thus, this study aims to evaluate the main lines and equipment that comprise the battery of preheating of the load of a unit of Hydrotreating (HDT) of diesel. This excerpt is theoretically likely to occur from corrosion by naphthenic acids due to two main factors: the presence of these acids with levels of neutralizing more than 0.5 mg KOH/g in the chemical composition of the load and the temperature of processing, which is in a range from 200 º C to 400 º C, suitable for the existence of such a deterioration mechanism. Data from field concerning to the rate of corrosion of the lines and equipment were parameterized in their operational variables and through a comparative analysis with data found in literature were obtained important information to evaluate the occurrence of naphthenic corrosion.

Submitted by Irene Nascimento (irene.kessia@ufpe.br) on 2016-06-20T18:14:17Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE COMPLETA FINAL - GRAZIELE NASCIMENTO.pdf: 1640569 bytes, checksum: b37271f18a2ccb0018a4524168b48c7a (MD5) / Made available in DSpace on 2016-06-20T18:14:17Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) TESE COMPLETA FINAL - GRAZIELE NASCIMENTO.pdf: 1640569 bytes, checksum: b37271f18a2ccb0018a4524168b48c7a (MD5) Previous issue date: 2016-01-15 / PRH-28 ANP / A presença de ácidos naftênicos no querosene de aviação (QAV) implica em um aumento de sua acidez com efeito corrosivo elevado, diminuição da estabilidade térmica, formação de sais insolúveis e depósitos de carbono. A remoção desses compostos por adsorção é considerada uma alternativa eficiente, uma vez que podem ser recuperados, purificados e comercializados para outros fins. A síntese e caracterização de peneiras moleculares mesoporosas do tipo MCM-41 com potencial aplicação em adsorção e catálise vêm sendo bastante estudada em função de suas características, como elevada área superficial, diâmetro e volume de poros. Neste contexto, este trabalho propôs a síntese de adsorventes do tipo MCM-41 modificados, visando à remoção de ácidos naftênicos em mistura modelo de QAV (ácido n-dodecanóico em n-dodecano). Os adsorventes MCM-41, Sr-MCM-41, La- MCM-41, Ce-MCM-41, Sr-La-MCM-41, Sr-Ce-MCM-41 foram sintetizados pelo método hidrotérmico e caracterizados pelas técnicas de análise termogravimétrica (TG), difração de raios-X (DRX), adsorção/dessorção de N2 através dos métodos Brunauer, Emmett e Teller (BET) e Barrett, Joyner e Halenda (BJH), espectroscopia na região do infravermelho por transformada de Fourier (FT-IR), microscopia eletrônica de varredura com espectroscopia de energia dispersiva por raios-X (MEV/EDS) e pH do ponto de carga zero (pHpzc). Foi realizado um estudo para seleção do adsorvente a ser utilizado nos estudos de adsorção. Com o adsorvente selecionado, foram realizados estudos cinéticos e equilíbrio de adsorção em sistema de banho finito. A partir dos dados obtidos, foi avaliado o sistema continuo de leito fixo e os ciclos de adsorção/dessorção. O método hidrotérmico foi eficiente, conforme os resultados obtidos pelas análises de caracterização, uma vez que após a incorporação dos metais, os materiais mantiveram a estrutura padrão da MCM-41. A partir do estudo do pHpzc verificou-se que a incorporação do metal alcalino terroso Sr aumentou a basicidade de todos os materiais. O adsorvente Sr-Ce-MCM-41 apresentou maior estabilidade térmica, bem como maiores volume e diâmetro de poros, apresentando também uma maior capacidade adsortiva. O estudo cinético permitiu verificar que o equilíbrio foi atingido após 420 minutos, com capacidade de 0,64 gác.g-1 ads e % de remoção de 82,5%. A isoterma de adsorção apresentou comportamento do tipo IV e a maior capacidade adsortiva quantificada na faixa de concentração estudada foi de 0,8 gác.g-1 ads. O modelo cinético de Langmuir- Freundlich e o modelo de Brunauer, Emmett e Teller (BET) representaram de forma satisfatória os dados experimentais da cinética e equilíbrio de adsorção em sistema de banho finito. No sistema de leito fixo, os tempos de ruptura e saturação da curva foram afetados pela variação da vazão e da concentração de alimentação do leito. Os dados experimentais foram ajustados ao modelo de Langmuir-Freundlich, uma vez que foram desprezados os efeitos de resistência à transferência de massa e de difusão. Os estudos de adsorção/dessorção indicaram a possibilidade de recuperação de ácidos naftênicos visando seu posterior aproveitamento e aplicação. O adsorvente estudado Sr-Ce-MCM-41 apresentou potencial para a remoção de ácidos naftênicos presentes em QAV modelo nas condições estudadas. / The presence of naphthenic acids in the aviation kerosene (jet fuel) implies an increase in its acidity with high corrosive effect, decreased thermal stability, formation of insoluble salts and carbon deposits. The removal of these compounds by adsorption is considered to be an effective alternative, since they can be recovered, purified and sold for other purposes. The synthesis and characterization of mesoporous molecular sieves MCM-41 type with potential application in adsorption and catalysis have been extensively studied due to their characteristics, such as high surface area, diameter and pore volume. In this context, this paper proposed the adsorbent synthesis of MCM-41 modified type, aimed at removing naphthenic acid mixed model of jet fuel (n-dodecanoic acid in n-dodecane). The MCM-41, Sr-MCM- 41, La-MCM-41, Ce-MCM-41, Sr-La-MCM-41, Sr-Ce-MCM-41 adsorbents were synthesized by hydrothermal method and characterized by techniques thermogravimetric analysis (TGA), X-ray diffraction (XRD), N2 adsorption/desorption using the Brunauer, Emmett and Teller (BET) and Barrett, Joyner and Halenda (BJH) methods, spectroscopy in the infrared Fourier transform (FT-IR), scanning electron microscopy with energy dispersive spectroscopy X-ray (SEM/EDS) and pH of zero charge point (pHpzc). A study was conducted to check the adsorbent for use in adsorption studies. With the selected adsorbent, kinetic studies were performed and adsorption equilibrium finite bath system. From the data obtained, we evaluated the system continuous fixed bed and the cycles of adsorption/desorption. The hydrothermal method was effective as the results of the characterization analyzes, since after the incorporation of metals, materials maintained the pattern structure of MCM-41. From the PHpzc study it was found that the incorporation of the alkaline earth metal Sr increased basicity of all materials. The Sr-Ce-MCM-41 adsorbent has higher thermal stability and higher pore volume and pore diameter, also having a greater adsorption capacity. The kinetic study showed that equilibrium is reached after 420 minutes, with a capacity of 0.64 gac.g-1 ads and % removal of 82.5%. The adsorption isotherm presented type IV behavior and higher adsorptive capacity quantified in the studied concentration range was 0.8 gac.g-1 ads. The kinetic model of Langmuir-Freundlich and model of Brunauer, Emmett and Teller (BET) were satisfactory experimental data of adsorption kinetics and equilibrium in finite bath system. In the fixed bed system, the breakthrough time and saturation curve were affected by varying the flow rate and the bed of the feed concentration. The experimental data were fitted to the model of Langmuir-Freundlich, since the effects of mass transfer resistance and diffusion were discarded. Studies of adsorption/desorption indicated the possibility of naphthenic acid recovery aiming their subsequent use and application. The adsorbent studied Sr-Ce-MCM-41 has potential for the removal of naphthenic acids present in jet fuel model in the conditions studied.

nÃo hà / O elevado Ãndice de acidez presente no petrÃleo processado na indÃstria do setor PetrÃleo e GÃs Natural exige dos diversos equipamentos, uma elevada resistÃncia à corrosÃo. Dentre os materiais empregados nos equipamentos destacam-se os aÃos Cr-Mo e os aÃos inoxidÃveis austenÃticos com adiÃÃo de molibdÃnio. Estes aÃos nÃo tem apresentado rendimento satisfatÃrio quando em operaÃÃo nestes equipamentos. A utilizaÃÃo de aÃos inoxidÃveis ferrÃticos vem crescendo significativamente com o avanÃo tecnolÃgico e com a adiÃÃo de elementos de liga tem-se obtido aÃos com maiores resistÃncia mecÃnica e a corrosÃo, aliado a uma boa soldabilidade. Desta forma o objetivo deste trabalho à estudar o efeito do teor de molibdÃnio na resistÃncia a corrosÃo naftÃnica, nas alteraÃÃes microestruturais, propriedades mecÃnicas e soldabilidade em novas ligas Fe-Cr-Mo. Com base nos teores de elementos presentes foram levantados diagramas pseudo-binÃrios para identificar as fases e os tratamentos tÃrmicos afim de determinar as melhores combinaÃÃes de cromo e molibdÃnio. Amostras das ligas solubilizadas foram retiradas para a caracterizaÃÃo por microscopia Ãtica e microscopia eletrÃnica de varredura a fim de verificar se o tratamento de solubilizaÃÃo foi capaz de promover a obtenÃÃo de uma microestrutura completamente ferrÃtica. AtravÃs da realizaÃÃo de ensaios dureza, traÃÃo e impacto foram determinadas as propriedades mecÃnicas das ligas experimentais. Foram realizadas soldagens sem e com adiÃÃo de material empregando os processos TIG e MIG. Foi feita anÃlise de tamanho de grÃo da ZAC das ligas, caracterizaÃÃo microestrutural das regiÃes da solda e levantamento da microdureza. Os resultados obtidos mostraram que as ligas Fe-Cr-Mo apresentaram uma microestrutura ferrÃtica na condiÃÃo solubilizada, com grÃos grandes e propriedades mecÃnicas superiores ao de ligas comerciais, onde o molibdÃnio apresenta uma efeito mais significativo no aumento das propriedades mecÃnicas. O teores de cromo e molibdÃnio favoreceram a um comportamento frÃgil das ligas a temperatura ambiente, contudo para uma temperatura superior a 60 oC, as ligas tendem a apresentar um comportamento do tipo dÃctil. O tamanho de grÃo e as propriedades das ligas indicam que as mesmas seriam de dificil soldabilidade. Contudo, foi possÃvel realizar a soldagem das ligas empregando os processos TIG e MIG. AlÃm da microestrutura ferrÃtica, as ligas apresentaram a formaÃÃo de carbonetos do tipo M6C e M23C6 apÃs a realizaÃÃo das soldagens. / The high level of naphthenic acidity present in oils processed in refineries requires a high corrosion resistance of equipment and ducts. Among materials used in the Petroleum industry we highlight the Cr-Mo steels and austenitic stainless steel with molybdenum in their composition. These steels have not shown satisfactory performance when in contact with Petroleum rich in naphthenic acid. Iron-Chromium steels with Mo in their composition have become an alternative to this application. The main objective of this work was to study the effect the increasing of molybdenum content on the naphthenic corrosion resistance, microstructural changes, mechanical properties and weldability of Fe-Cr-Mo with Mo content higher than used in commercial alloys. Pseudo-binary diagrams for different compositions of Fe-Cr-Mo alloys were made to identify, phases and possible heat treatments. Solubilized samples of different alloy compositions were characterized by optical microscopy and scanning electron microscopy. Mechanical properties of experimental alloys were determined the through hardness, tensile and impact tests. Welds were carried out with and without addition of material using TIG and MIG processes. HAZ grain size of alloys and microstructural characterization of welded regions and the microhardness survey were performed. The results showed that the alloys Fe-Cr-Mo showed a ferritic microstructure in the solubilized condition, with large grains and mechanical properties superior to commercial alloys. The molybdenum increases naphthenic corrosion resistance and has a significant effect in the mechanical properties. The increase of chromium and molybdenum contents favored a brittle behavior of alloys at room temperature. The studied alloys tend to exhibit a ductile behavior when tested at temperatures exceeding 60 ÂC. At a first glance, grain size and mechanical properties of the alloys indicated that it would be difficult to weld these alloys. However, it was possible to perform the welding of alloys using TIG and MIG processes. This work deals with phases and carbides that precipitate when welding with different parameters.

The identification of petroleum acids, also known as ‘naphthenic’ acids (NA), has been an analytical challenge for over 140 years. However, most recent interest in NA has arisen due to concerns over their presence and apparent associated toxic effect in oil platform produced waters and oil sands process waters (OSPW), respectively. Understanding the toxicity, transformations during biodegradation and remediation treatments and predicting the fate of NA in the environment will be aided by the identification of individual NA. However the elucidation of individual acid structures by standard chromatographic techniques, such as GC-MS, has so far been limited by the extreme complexity of the NA mixtures. Recent analysis of NA as the methyl ester derivatives, by multidimensional gas chromatography-mass spectrometry (GC×GC-MS), has resulted in the identification of several tri- to pentacyclic, aromatic and sulphur-containing acids as well as tricyclic diacids. Therefore the current investigation focused on the identification of the abundant bicyclic acids in petroleum and OSPW acid extracts, utilising the unparalleled chromatographic separation and mass spectrometric detection offered by GC×GC-MS. Analysis of fractionated NA as methyl esters, resulted in the first identification of several bicyclic acids in OSPW including several novel bridged bicyclic acids, several fused bicyclic acids, as well as some terpenoid-derived drimane and labdane acids. However, identifications were limited somewhat by a lack of reference mass spectra and lack of availability of reference compounds for co-chromatography. A complementary method, based on an historical approach, involving reduction of NA esters to hydrocarbons, was modified and substantially improved. Analysis of the hydrocarbons resulting from the reduced acids, by GC×GC-MS, and comparison of the hydrocarbon mass spectra with the more abundant reference spectra available for petroleum hydrocarbons, resulted in the identification of over 40 individual bicyclic acids including fused, bridged and terpenoid-derived acids. The study provides the most comprehensive analysis of one of the major classes of NA (the bicyclic acids) to date. The methods developed were applied to the structural elucidation of NA in commercial NA and OSPW NA and resulted in the identification of numerous alicyclic, aromatic and sulphur-containing acids, supporting and extending previous identifications. There is clear potential for this method to be used for the identification of other unknown acids and functionalised biomarkers in complex matrices. The new knowledge of the acid structures in petroleum and OSPW NA can now be used to inform future research into the environmental monitoring and toxicity of NA.

Naphthenic acids (NAs) are oil-derived mixtures of carboxylic acids and are aquatic contaminants of emerging concern. The objective of the research presented in this thesis was to investigate the toxicity of NAs in tadpoles of the frog Silurana (Xenopus) tropicalis. Using electrospray ionization high-resolution mass spectrometry (ESI-HRMS), I determined that the proportions of O2 (presumably carboxylic acid moiety) species were 98.8, 98.9 and 58.6% respectively, for two commercial extracts (S1 and S2), and acid extractable organics (AEOs) from oil sands process-affected water (OSPW). The rank order potency based on the lethal concentration fifty (LC50) and effect concentration fifty (EC50) with and without normalization for the quantity of O2 species was S1 > S2 > AEO. The main effects observed were reduced body size, edema, and cranial, cardiac, gut and ocular abnormalities. Oligonucleotide microarray technology was used to determine the transcriptomic responses in developing S. tropicalis embryos following exposure to S1 and S2 at a sub-lethal concentration of 2 mg/L. Some of the significantly enriched pathways (p < 0.05) included metabolism and cell membrane depolarization, and some were related to observed abnormalities including edema, gastrointestinal system, and cartilage differentiation. I established and validated a derivatization method for NAs using pentafluorobenzyl bromide (PFBBr) prior to gas chromatography-electron impact mass spectrometry (GC-EIMS) to increase chromatographic resolution, and sensitivity, compared to boron trifluoride-methanol (BF3/MeOH) and N-tert-Butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA). Solid-phase microextraction of volatiles originating from S1, S2, Merichem NAs and an AEO mixture led to the identification of 54, 56, 40 and 4 compounds, respectively. The compounds identified in the mixtures included aliphatic and cyclic hydrocarbons, carboxylic acids, alkyl-benzenes, phenols, naphthalene and alkyl-naphthalene, and decalin compounds. To determine the chemical nature of the toxic compounds in NA mixtures, the S2 and AEOs preparations were fractionated using open column chromatography. A non-polar and a polar fraction were obtained from S2. Overall, the toxicity of the polar fraction was not significantly different from whole S2 (p > 0.05). Six fractions of AEOs were obtained, however because of limited material, only the toxicities of F3 and F4 were assessed. The toxicity of F3 was significantly lower than AEOs (p < 0.05) and F4 was not toxic for S. tropicalis (p > 0.05). These results suggest that during fractionation, toxic compounds were lost or that the toxicity of AEOs results from the combined effects of the compounds present in the whole extract. The toxicological dose descriptors, morphometric, transcriptomic and chemical analysis herein presented may contribute to the development of environmental guidelines for NAs and AEOs.