Quaternary ammonium compounds (QACs) are ubiquitous contaminants found worldwide in both engineered and natural systems. QACs are toxic to aquatic organisms and cause co-selection for antibiotic resistance, thus providing a reservoir of antibiotic-resistant bacteria, as well as antibiotic resistance genes in QAC-polluted environments. The objectives of the research presented here were to: a) systematically assess the fate and toxicity of QACs using quantitative structure-activity relationships (QSAR); b) evaluate the biotransformation potential of QACs under aerobic, anoxic and anaerobic conditions; and c) assess the potential toxicity of QACs biotransformation products. Nine QACs, belonging to three homologous groups -- monoalkonium, dialkonium and benzalkonium chlorides -- were the target QACs. The QACs critical micelle concentration (CMC) was determined. Then, the CMC was used as a descriptor to derive relationships between QAC structure and partitioning to biosolids as well as acute Microtox® toxicity. QACs with low CMCs had a relatively high adsorption affinity for biosolids and a lower toxicity than QACs with higher CMCs, which suggests that QACs that are more mobile and more (bio)available are more toxic. The biotransformation potential of benzalkonium chlorides (BAC) -- the most commonly used QACs found in engineered and natural biological systems -- under aerobic, methanogenic, nitrate reducing, and fermentative conditions was evaluated using bioenergetics and batch bioassays. The aerobic BAC biotransformation involved sequential dealkylation and debenzylation steps resulting in the formation of benzyl dimethyl amine, and dimethyl amine, respectively. The bacterial community involved in the aerobic BAC degradation was mainly composed of species belonging to the Pseudomonas genus. All QACs tested were recalcitrant under methanogenic conditions and inhibited methanogenesis at and above 25 mg QAC/L. Under nitrate reducing and fermentative conditions, BAC was transformed to alkyldimethyl amines via an abiotic reaction known as modified Hofmann degradation and a biotic reaction known as fumarate addition, respectively. Both reactions are based on a mechanism known as nucleophilic substitution. The discovery of BAC transformation by the above mentioned two reactions is the first ever report to document QAC transformation under anoxic/anaerobic conditions and delineate the transformation pathway.

Thesis (M.S.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on April 15, 2008) Vita. Includes bibliographical references.

Thesis (Ph. D.)--Chemical and Biomolecular Engineering, Georgia Institute of Technology, 2007. / Kohl, Paul, Committee Chair ; Bottomley, Lawrence, Committee Member ; Eckert, Charles, Committee Member ; Fuller, Tom, Committee Member ; Teja, Amyn, Committee Member.

Quaternary ammonium salts are surface active bactericides. A mechanism of their biological activity has been well studied experimentally, and it encompasses two stages. The first stage involves electrostatic interactions of polar functional groups of the salts with oppositely charged functional groups on a bacterial cell surface, and the second stage includes incorporation of their lipophilic groups into a bacterial cell membrane. However, despite numerous experimental studies, computational modelling of this mechanism with the aim to support experimental observations with theoretical conclusions, to the author's knowledge, has not yet been reported. In the current study, linear regression models correlating theoretical descriptors of lipophilicity and electronic properties of mono- and disubstituted imidazolium carboxylates with their biological activity towards Escherichia coli have been developed. These models established that biological activity of these salts is governed by the chemical structures of imidazolium cations, and that the centre of this biological activity is located in the long alkyl side chains of the cations. It was also found that these side chains have an intrinsic electronic potential to form internal C-H- -H-C electrostatic interactions when their lengths reach seven carbon atoms. Additionally, the nature of the C-H- -O-C inter-ionic electrostatic interactions in imidazolium carboxylates has been explored via a topological analysis of these interactions in 1-ethyl-3-methylimidazolium acetate. Thus, it was established that these electrostatic interactions are hydrogen bonds.

This report discusses research involving the reactions of 2-arylprop-1-en-3-yltrimethyl ammonium iodides with sulfur nucleophiles and the useful synthetic applications of the adducts formed. The present work may be subdivided into four sections: 1) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with benzenethiol; 2) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with the sodium salt of benzenesulfinic acid; 3) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with 2-mercapto-1-methyl imidazole; and 4) oxidation of 2-aryl-3-phenylthio-1-propenes and 2-aryl-3-phenylsulfonyl-1-propenes using sodium perborate. This report outlines the experimental conditions and procedures responsible for the synthesis of these products; in addition, this report describes the physical properties, NMR and IR spectra of the compounds synthesized, as well as offers a possible mechanism for their formation. The classes of compounds synthesized include: 2-aryl-3-phenylthio-1-propenes; 2-aryl3-phenylsulfonyl-1-propenes; 3-(2-aryl-l-propenyl)2-(1-methylimidazoyl)thioethers; and 2-aryl-2-acetoxy-3-phenylsulfonyl-1-propanols. Recommendations are listed to suggest future research in this area.

No description available.

Para aumentar os volumes de extração de petróleo, resolver e prevenir problemas nas operações de produção são utilizados diversos produtos químicos, dentre os quais se destacam os inibidores de corrosão, que são utilizados em toda cadeia produtiva do petróleo visando proteger o sistema da deterioração por corrosão. Os sais de amônio quaternário são uma das classes de inibidores mais utilizadas pela indústria do petróleo devido a sua grande eficiência. Entretanto, sua solubilidade em água faz com que estejam presentes na água produzida representando um risco para contaminação ambiental, visto que possuem baixa biodegrabilidade e potencial de bioacumulação. Como se encontram misturados a outros produtos químicos e sob efeitos das variações do ambiente em que são aplicados, definir um método de análise confiável e viável para monitoramento em linha representa um desafio para os laboratórios de campos de produção. Neste trabalho, foi estudado o emprego da fluorescência de ultravioleta na quantificação de um inibidor de corrosão do tipo sal de amônio quaternário em água. Foram obtidos espectros de emissão do produto comercial em água, além do estudo de variáveis instrumentais e interferentes presentes na água produzida. A comparação com padrões de sal de amônio quaternário permitiu identificar como principal fluorófilo, um sal alquil-aril de amônio quaternário. Estudos de estabilidade revelaram que a adsorção do inibidor de corrosão nas superfícies dos frascos plásticos provoca a queda do sinal fluorescente e que a adição de isopropanol reduz este efeito de 40 para 24%. Foram obtidas curvas de calibração com a formulação comercial e com o cloreto de 2-metil-4-dodecil-benzil-trimetil amônio com uma boa correlação. Amostras sintéticas do inibidor foram determinadas com um erro relativo de 2,70 a 13,32%. O método de adição padrão foi avaliado usando uma amostra de água produzida, e os resultados não foram satisfatórios, devido à interferência, principalmente, de compostos orgânicos aromáticos presentes / In order to increase the volume of oil extraction, solve and prevent problems in oil production, several chemical products are used. Corrosion inhibitors are the main chemical products used in the whole oil production chain, whose objective is to protect the system from deterioration caused by corrosion. The quaternary ammonium salts are the kind of inhibitor which is more frequently used by the oil industry due to its great efficiency. However, its solubility in water allows them to remain in the produced water representing a risk of environmental contamination, since they have low biodegrability and tendency to bioaccumulation. Once they are mixed to other chemical products and affected by the variations of the environment where they are applied, it becomes a challenge to production field laboratories to select a reliable and viable analysis method for on-line monitoring. This essay tends to focus on the use of the ultraviolet fluorescence in the quantification of an inhibitor of corrosion of the quaternary ammonium salt type in water. There has been obtained emission spectra of the commercial product in water besides the study of instrumental variables and interference of chemical substances in the produced water. The comparison with quaternary ammonium salt standards allow identifying an alkyl-aryl quaternary ammonium salt as the main fluorophore. Tests of stability have demonstrated that the addition of isopropyl alcohol reduces the fall of the fluorescent signal from 40 to 24% in three days time. This fall is caused by the adsorption of corrosion inhibitor in the surface of plastic containers. Good correlation curves of calibration have been obtained with commercial formularization and methyldodecylbenzyl trimethyl ammonium chloride. Synthetic samples of inhibitor have been determined with a relative error from 2,70 to 13,32%. One produced water sample from a production field has been used to evaluate the standard addition method. Satisfactory results have not been successfully achieved, principally, due to the interference of aromatics organic compounds found in the water sample

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-05T15:09:29Z No. of bitstreams: 1 DISSERTAÇÃO FINAL.pdf: 3240794 bytes, checksum: fce90db127264d620f42a924b9d61224 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-04-15T12:34:56Z (GMT) No. of bitstreams: 1 DISSERTAÇÃO FINAL.pdf: 3240794 bytes, checksum: fce90db127264d620f42a924b9d61224 (MD5) / Made available in DSpace on 2013-04-15T12:34:56Z (GMT). No. of bitstreams: 1 DISSERTAÇÃO FINAL.pdf: 3240794 bytes, checksum: fce90db127264d620f42a924b9d61224 (MD5) / CAPES / Este estudo teve como principal objetivo caracterizar a atmosfera da principal área de influência industrial do Recôncavo Baiano, através da análise da especiação dos compostos inorgânicos de S, N e Cl na fase gasosa e particulada < 2 μm. O estudo foi realizado em seis estações de monitoramento: Barra do Jacuípe, Camaçari (Estação Gravatá), Lamarão do Passé, Candeias, São Francisco do Conde e Madre de Deus em outubro de 2010. As amostragens das espécies químicas estudadas foram feitas com: amostradores passivos (AP) para as espécies NO2 e SO2, tubos de difusão (denuder) revestidos com solução de ácido cítrico 1,0 x 10-2 para amônia e 1,0 x 10 -2 mol L-1 NaF para ácidos fortes (HCl, HNO3 e H2SO4), este último em um sistema de termodifusão, também capaz de coletar em um denuder aquecido a 140°C sais de amônio termicamente instáveis (NH4Cl e NH4NO3) e sobre uma membrana de policarbonato, partículas < 2 μm, estável àquela temperatura. A metodologia analítica utilizada para determinação das espécies foi cromatografia iônica (Cl-, NO3-, SO42- como representantes dos compostos de SO2, dos ácidos fortes, de sais de amônio na fase gasosa e particulada < 2 μm) e espectrofotometria molecular usando o método Griess-Saltzman ( = 540 nm) e o método Azul de indofenol ( = 630 nm) para determinação de NO2 e NH3, respectivamente. Os dados coletados em 2010 permitiram concluir que as massas de ar vindas do Atlântico (13 nmol m-3 HCl, 2,9 nmol m-3 HNO3, 1,6 nmol m-3 H2SO4, 9,8 nmol m-3 SO2, 16 nmol m-3 de NO2 e 84 nmol m-3 NH3) não são muito enriquecidas na fase gasosa e fase particulada com relação a HNO3 e H2SO4, pelas emissões do complexo industrial. No entanto, o enriquecimento é acentuado no caso de HCl, SO2, NO2 e NH3. Entre os ácidos fortes determinados na atmosfera na área de influência do complexo industrial, ácido clorídrico predomina, como esperado, de acordo com suas emissões locais como um poluente primário. Em relação à fase particulada < 2 μm como produtos de transformações de ácidos fortes na atmosfera, NH4Cl foi a espécie predominante. / Salvador

Para aumentar os volumes de extração de petróleo, resolver e prevenir problemas nas operações de produção são utilizados diversos produtos químicos, dentre os quais se destacam os inibidores de corrosão, que são utilizados em toda cadeia produtiva do petróleo visando proteger o sistema da deterioração por corrosão. Os sais de amônio quaternário são uma das classes de inibidores mais utilizadas pela indústria do petróleo devido a sua grande eficiência. Entretanto, sua solubilidade em água faz com que estejam presentes na água produzida representando um risco para contaminação ambiental, visto que possuem baixa biodegrabilidade e potencial de bioacumulação. Como se encontram misturados a outros produtos químicos e sob efeitos das variações do ambiente em que são aplicados, definir um método de análise confiável e viável para monitoramento em linha representa um desafio para os laboratórios de campos de produção. Neste trabalho, foi estudado o emprego da fluorescência de ultravioleta na quantificação de um inibidor de corrosão do tipo sal de amônio quaternário em água. Foram obtidos espectros de emissão do produto comercial em água, além do estudo de variáveis instrumentais e interferentes presentes na água produzida. A comparação com padrões de sal de amônio quaternário permitiu identificar como principal fluorófilo, um sal alquil-aril de amônio quaternário. Estudos de estabilidade revelaram que a adsorção do inibidor de corrosão nas superfícies dos frascos plásticos provoca a queda do sinal fluorescente e que a adição de isopropanol reduz este efeito de 40 para 24%. Foram obtidas curvas de calibração com a formulação comercial e com o cloreto de 2-metil-4-dodecil-benzil-trimetil amônio com uma boa correlação. Amostras sintéticas do inibidor foram determinadas com um erro relativo de 2,70 a 13,32%. O método de adição padrão foi avaliado usando uma amostra de água produzida, e os resultados não foram satisfatórios, devido à interferência, principalmente, de compostos orgânicos aromáticos presentes / In order to increase the volume of oil extraction, solve and prevent problems in oil production, several chemical products are used. Corrosion inhibitors are the main chemical products used in the whole oil production chain, whose objective is to protect the system from deterioration caused by corrosion. The quaternary ammonium salts are the kind of inhibitor which is more frequently used by the oil industry due to its great efficiency. However, its solubility in water allows them to remain in the produced water representing a risk of environmental contamination, since they have low biodegrability and tendency to bioaccumulation. Once they are mixed to other chemical products and affected by the variations of the environment where they are applied, it becomes a challenge to production field laboratories to select a reliable and viable analysis method for on-line monitoring. This essay tends to focus on the use of the ultraviolet fluorescence in the quantification of an inhibitor of corrosion of the quaternary ammonium salt type in water. There has been obtained emission spectra of the commercial product in water besides the study of instrumental variables and interference of chemical substances in the produced water. The comparison with quaternary ammonium salt standards allow identifying an alkyl-aryl quaternary ammonium salt as the main fluorophore. Tests of stability have demonstrated that the addition of isopropyl alcohol reduces the fall of the fluorescent signal from 40 to 24% in three days time. This fall is caused by the adsorption of corrosion inhibitor in the surface of plastic containers. Good correlation curves of calibration have been obtained with commercial formularization and methyldodecylbenzyl trimethyl ammonium chloride. Synthetic samples of inhibitor have been determined with a relative error from 2,70 to 13,32%. One produced water sample from a production field has been used to evaluate the standard addition method. Satisfactory results have not been successfully achieved, principally, due to the interference of aromatics organic compounds found in the water sample

Les hydrates de gaz sont une façon non conventionnelle de piéger et de stocker des molécules de gaz par cristallisation d’eau à haute pression et à basse température. Les sels d'ammonium quaternaire forment des semiclathrates hydrates à pression atmosphérique et des hydrates mixtes en présence de gaz. Il est important de connaître leurs propriétés thermodynamiques, afin d'évaluer leurs applications potentielles : une des ces-ci est la capture du dioxyde de carbone à partir des gaz de combustion. Dans nos expériences, les semiclathrates ont été fabriqués à partir de sels de peralkylammonium (TBAB, TBACl, TBAF), et de bromure de tétra-butylphosphonium (TBPB) en combinaison avec plusieurs gaz : CO2, N2, CH4. La pression de formation a été fortement réduite par rapport aux hydrates de gaz respectifs.Afin de déterminer les coefficients d'activité des hydrates en présence de sels, un modèle eNRTL a été conçue. Des systèmes comportant un sel ou deux sels ont été modélisés en présence d’hydrate de CH4 et sont en accord avec la littérature. Un système en présence de TBAB et de CH4 a été également étudié : la modélisation diffère des données expérimentales de la littérature, probablement en raison d’une structure différente. Cependant, les résultats sont prometteurs, et le modèle donne une bonne prédiction. Sur la base des résultats expérimentaux, un procédé à l'échelle pilote a été conçu. Ce nouveau procédé consiste à former des hydrates mixtes de TBAB et de CO2 dans une colonne à bulles. Les hydrates sont ensuite retirés de la colonne et après dépressurisation, les hydrates mixtes se transforment en hydrates de TBAB, libérant du CO2, qui est renvoyé à la colonne à bulles. / Gas hydrates are a non conventional way of trapping and storing gas molecules trough the crystallization of water under the high pressure and low temperature conditions. Quaternary ammonium salts form hydrates at atmospheric pressure and can also form mixed hydrates in the presence of gas. It’s important to know their thermodynamic properties in order to evaluate their potential applications: one of these applications is the capture of carbon dioxide from flue gas. The semiclathrates studied were made from peralkylamonium salts (TBAB, TBACl, TBAF) and tetrabutyl phosphonium bromide (TBPB) plus several gases: CO2, N2, and CH4. The formation pressure was greatly reduced with regards to the respective gas hydrates. An eNRTL model for determining the activity coefficients of hydrate forming systems with salts has been used. Single and double salts systems were analyzed in the presence of CH4 and the data obtained is in a good agreement with the literature. The TBAB and CH4 semiclathrates system was also investigated with the results being different of those of the literature probably due to a difference on the structure of the semiclathrate. However, the results are promising, and the model gives a good predictionBased on the experimental results, a pilot plant scale process was designed. This new process consists in forming mixed hydrates of TBAB and CO2 in a bubble column. The hydrates are then removed from the column and after expansion, the mixed hydrates transform into TBAB hydrates releasing CO2, which can be returned to the bubble column.