Anaerobic digestion is a common process for treatment of wastewater sludge from municipal sewage systems. Volatile sulfur compounds, including volatile organic sulfur compounds (VOSCs) and hydrogen sulfide, have been reported as the most odorous compounds in digestion emissions and impurities which can damage facilities for generation, transportation, storage, and utilization of biogas. There has been no comprehensive study on biological generation and degradation kinetics of VOSC or modeling VOSC behaviors through anaerobic sludge digestion. The goal of the present study was to establish a model for VOSC conversions in anaerobic sludge digestion which could facilitate quantitative analysis of VOSC emissions in anaerobic digestion. VOSCs and methionine were employed in dosed batch tests. VOSC conversion processes in anaerobic methionine digestion have been identified. The kinetics for the identified VOSC degradation and conversion processes were determined at 35 and 55 °C respectively. Mixed-second order kinetics were found to best fit the conversion processes. A model was established based on the identified processes and estimated kinetic constants. To extend the model to VOSC release in anaerobic sludge digestion, mesophilic and thermophilic incubations were conducted with four different sludge samples. The effects of temperature and sludge source on VOSC release patterns were assessed. It was found that an unidentified DMS generation mechanism was triggered in the mesophilic incubation of activated sludge in which iron was dosed. To apply the model which was established based on methionine degradation in sludge digestion, hydrolysis of particulate materials was incorporated. The model simulations for VOSC behavior in thermophilic batch incubation were able to represent the observed VOSC releases. However, the simulations could not well fit the observed VOSC release at 35 ° because the model did not include the unidentified DMS generation mechanism. Application of the model to bench-scale digesters was lack-of-fit. It may have been due to imprecise estimation of the degradable sulfur in the feed sludge. In addition, in the batch tests and digester operation the ratios of the raw and digested sludge were different. This might have resulted in different concentrations of the microorganisms which mediated biotransformations and hence resulted in different kinetic constants.

The need for selective and inexpensive detectors in liquid chromatography is of considerable interest in the determination of sulfur compounds. Of the available-selective sulfur methodologies, flame photometric detector coupled to gas chromatography is the most widely used. It has proven to be a sensitive and selective method for detection of heat stable and volatile sulfur compounds. Fundamentally, this technique is not applicable to high boiling and/or thermolabile sulfur compounds. More recently, hyphenated flame photometric detector has been utilized, with limited success, to monitor sulfur species in liquid chromatography. However, existing HPLC-FPD methodologies have never been applied to real samples, due to the low population of S 2, the emitting species, and the quenching effects of the other species present in the flame. / In this work, two total consumption high-performance liquid chromatography flame photometric (HPLC-FPD) interfaces compatible with either methanolic or aqueous mobile phases are described and optimized for monitoring low volatile and thermally fragile sulfur compounds in biological samples. Each interface was fuelled either by methanol or by hydrogen. The all quartz interfaces enclosed four consecutive thermal processes: (a) thermovaporization of the HPLC effluent; (b) pyrolysis of the organic matrix (including sulfur species) in a kinetic H2/O2 flame; (c) conversion of the oxidized sulfur compounds to H2S in a reducing post-combustion stage fuelled by hydrogen; and (d) transport of the generated hydrides towards a hydrogen radical rich surrounding of an inverted hydrogen-oxygen diffusion flame. Chemiluminescence induced in the last step was integrated as a narrow beam in a light-guide positioned remotely from the analytical cool flame and oriented towards a photomultiplier unit. Radioisotopic assays demonstrated that sulfur (as H235SO4) was transferred quantitatively to the analytical flame. Indirect evidence suggested that sulfur was hydrogenated in the post-combustion step via a thermochemical hydride generation process to mediate the formation of S2. The linearity of calibration graphs (0.9950 < r < 0.9986), where r is the correlation coefficient) and unprecedented HPLC-FPD limits of detection for sulfur compounds (1.5 etag/s for 2-methylthiophene, 2.25 etag/s for carbon disulfide, and 4.5 etag/s for ethanesulfonic acid) allowed for the speciation of sulfur species in garlic extracts. Alternatively, modification of the methanol fuelled interface to a hydrogen fuelled reactor allowed detection of thiosulfinates and high molecular weight sulfur compounds in horse kidney and garlic extracts, respectively.

Thesis (Ph. D.)--Uppsala University, 1983. / Description based on print version record. Bibliography: p. 35-36.

Thesis (Ph.D.) - University of St Andrews, August 2009. / Restricted until 18th August 2010.

Thesis (Ph. D.)--University of Wisconsin, 1967. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliography.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 96-99).

Made available in DSpace on 2014-06-11T19:35:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-06-30Bitstream added on 2014-06-13T20:26:02Z : No. of bitstreams: 1 martins_dms_dr_araiq.pdf: 866111 bytes, checksum: 704aa80ec2341c65f653eaf5d1f4c8f1 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Os compostos sulfurados no petróleo têm causado diversos problemas como os correlacionados à corrosão de equipamentos, envenenamento de catalisadores em processo de refino, qualidade dos produtos, além de liberação de gases tóxicos diretamente ao meio ambiente. Os compostos sulfurados em especial (enxofre elementar, difenil dissulfeto e 1-butanotiol) podem agravar estes problemas, sendo os principais causadores de corrosão de equipamentos nas refinarias de petróleo. Devido a tais considerações, a proposição deste trabalho é o desenvolvimento de metodologias eletroanalíticas para determinação de compostos sulfurados em gasolina, utilizando os eletrodos de filme de mercúrio, amálgama sólido e hexacianoferrato de cobre. No primeiro trabalho desenvolvido utilizou-se o eletrodo filme de mercúrio juntamente com as técnicas eletroanalíticas de voltametria de varredura linear (VVL), onda quadrada (VOQ) e pulso diferencial (VPD) em solução de acetato de sódio 1,4 mol L-1 e ácido acético 2% em metanol, como eletrólito suporte. O método apresentou limites de detecção na ordem de 10-9 a 10-4 mol L-1 para as técnicas eletroanalíticas de VVL, VOQ e VPD, inferiores aos já relatados na literatura usando método análogo. A quantificação dos compostos de enxofre em amostras de gasolina, a partir do monitoramento do sinal de redução sobre a superfície do eletrodo filme de mercúrio, utilizando a técnica de voltametria de onda quadrada, foi possível sem tratamento prévio da amostra, cujo procedimento mostrou ser bastante eficiente não provocando qualquer interferência associada aos constituintes da matriz, exibindo valores de 3,5x10-8, 3,7x10-7 e 4,2x10-8 mol L-1 para enxofre elementar, difenil dissulfeto e 1-butanotiol, respectivamente. A quantificação nas amostras de gasolina, avaliadas em termos... / The presence of sulfur compounds in petroleum has caused several problems including those related to the corrosion of equipments, and the quality of final products, as well as the emission of toxic gases to the environment. Sulfur compounds (elemental sulfur, diphenyl disulfide and 1-butanethiol), can increase these problems, being the main causes of corrosion of equipments in the refineries of petroleum. Based on these assumptions, the principal proposal of this work is the development of electroanalytical methodology for determination of sulfur compounds in gasoline using the electrodes of mercury film, amalgam solid and copper hexacyanoferrate. In the first developed work the mercury film electrode was used together with the electroanalytical techniques of linear scan voltammetry (LSV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV) in solution of 1.4 mol L-1 sodium acetate and acetic acid 2% in methanol. The method presented detection limits in the order from 10-9 to 10-4 mol L-1 for the electroanalytical techniques of LSV, SWV and DPV. These limits are inferior to the previous related in the literature using similar method. The quantification of the sulfur compounds in gasoline samples, starting from the monitoring of the reduction sign on the mercury film electrode surface using the technique of square wave voltammetry was possible without previous sample treatment, whose procedure showed to be efficient, it not provoking any interference associated to the sample, exhibiting values of 3.5x10-8, 3.7x10-7 and 4.2x10-8 mol L-1 for elemental sulfur, diphenyl disulfide and 1-butanethiol, respectively. The quantification in the samples of gasoline in recovery terms showed that the methodology electroanalytical supplied quite acceptable results with recovery levels and precision compatible to the found by other techniques. In a second... (Complete abstract click electronic access below)

No description available.

No description available.

<p> A series of derivatives of thiazolidine-4-carboxylic acid was prepared from two sulfur containing aminoacids, cysteine and D-penicillamine. Cysteine is very easily oxidized to a disulfide, while penicillamine is less susceptible to oxidation of the sulfhydryl group because of greater steric hindrance. Sulfhydryl aminoacids react readily with aldehydes and ketones to give thiazolidine rings with varying degrees of substitution.</p> <p> Many of the compounds prepared were studied in solution and in the solid state by means of nmr, vibrational spectroscopy, mass spectra and X-ray crystallographic data. Thiazolidine-4-carboxylic acids contain a free carboxyl group and a secondary amino group, both of which can be ionized. Infrared spectra and X-ray crystallography are useful in detecting ionization and hydrogen bonds. An example is given of a compound that can exist in both the zwitterion and the non ionized state depending on the solvent of recrystallization.</p> <p> From previous work in our group we were predicting that increasing steric crowding in the thiazolidine ring in close proximity to the ionizable groups would decrease the tendency of these molecules to ionize. No such simple relationship could be found.</p> / Thesis / Master of Science (MSc)