Atmospheric corrosion takes place on most metals as they interact with thesurrounding environment. A degradation of the metal is the common result,which often leads to a shortened lifespan of the material. Hence, knowledge onthe fundamental interaction between a gas containing corrosive constituentsand a metal surface, which is the starting point of atmospheric corrosion, isimportant in many contexts. As the nature of atmospheric corrosion is inherentlycomplex, it imposes demands on the analytical studies that are neededin order to understand the fundamentals on a molecular level. Consequently,in-situ vibrational techniques, providing molecular information, have beenutilized in this work to study atmospheric corrosion by targeting the initialstages of the interaction between corrosive air and a metal surface. The initialstages (from minutes until days of exposure) were studied as these havea large influence on the atmospheric corrosion for prolonged exposure times. More specifically, the interaction between humidified air to which organicacids were added, and zinc was targeted in order to address a situation inindoor atmospheric corrosion, where organic acids are of importance. Zinc isa constituent in e.g. brass, which is an alloy used in many indoor applications. A systematic investigation utilizing complementary acting vibrational techniquesthus enabled detailed information on the mechanisms of the onsetof atmospheric corrosion of zinc induced by acetic and formic acid. Corrosionproducts of both two dimensional and three dimensional character couldbe separately studied by combining VSFS (interface sensitive), IRAS (nearsurfacesensitive), and CRM (bulk sensitive). The Zn surface was found to be heterogeneous with different hydroxylgroups present on the surface. As this surface was exposed to formic or aceticacid, the OH groups on the surface were rapidly displaced in a ligand exchangewith formate or acetate. These ligands, organised in two dimensionalstructures, promoted corrosion by weakening the bonds of the Zn atoms totheir surrounding matrix. The subsequent growth of three dimensional corrosion products, Zn hydroxyacetate and formate, observed within short exposure times of Zn exposedto acetic and formic acid, was found to be electrochemical in nature.Cathodic areas consisting of more crystalline ZnO were observed. The potentialdifference between these more noble areas on the surface and those of lessnoble character created an electrochemical cell, initiating release of Zn ionsinto the aqueous adlayer in the anodic reactions. These Zn ions precipitatedas localised corrosion products. The cathodic areas increased the local pHon the surface, thereby promoting precipitation in their vicinity. The resultson initial stages of this type of corrosion were found to have similarities withprevious field studies of Zn exposed to real indoor environments. One way to decrease the corrosion rate of zinc is by adsorbing a corrosioninhibitor to the metal surface in order to protect it. As a model for sucha corrosion inhibitor, octadecanethiol (CH3(CH2)17SH) was seen to provideincreased corrosion protection of both reduced and oxidised Zn substrates byforming an adsorbed surface layer with an ordered structure. / QC 20100719

In the work, photocatalytical treatment of acetic acid wastewater by nanostructured film of TiO2 under ultra-violet ¡]UV¡^ light illumination was studied. Nanosized TiO2 suspension was prepared by the sol-gel process. Then it was dip-coated on indium tin-oxide¡]ITO¡^glass, which could be used as the anode if applicable. Effects the UV light intensity, UV light wavelength, reactive area of TiO2 film, solution pH, and applied bias voltage on photocatalysis efficiency of acetic acid in term of COD removal were studied in this work. Experimental results have shown that a pseudo first-order kinetics was obeyed in all tests. In this study UV light of 312nm outperformed that of 365nm ¡]15.3¢H vs. 11.0¢H¡^. UV light intensity of 20W was also found to be superior to 10W with COD removal of 11.0¢H against 6.7¢H. COD removal at pH¡×3.18 was about 3.6 times greater as compared with that of at pH=9.98. When the reactive area of TiO2 film was increased to three times, the COD removal was almost doubled. An applied external voltage was found to enhance the removal of COD. When an external voltage of 15V was applied, the COD removal was increased to 84.6¢H. It is ascribed to an external voltage would prevent or lower the extent of electron-hole recombination. In this work, the pseudo first-order reaction rate equation K¡¬=1.7679(COD)-0.7547 was obtained for various concentrations of acetic acid tested.

In this study, production of organic acids from cheese-whey was studied. Optimization of organic acids production was performed in semi-batch and batch reactors. Two sets of experiments were performed. First set of experiments were performed in semi-batch reactors for the optimization of organic loading rate (OLR) and hydraulic retention time (HRT). As a result of Set 1 experiments optimum OLR was found to be 15 g COD l-1. Second set of experiments were performed in batch reactors by using the optimum OLR found in Set 1 experiments. Set 2 experiments were conducted to study the effect of using different seed cultures and Basal Media (BM) on Volatile fatty avid (VFA) production. Main acidogenesis products were acetic acid (Hac), butyric acid (Buty) and propionic acid (HPr) with smaller quantities of i-butyric acid (i-Buty), valeric acid (Val) and caproic acid (Cap). It was seen that BM had a suppressive effect on ethanol (EtOH) production while it stimulated the VFA production. Higher VFA productions and variety of VFA types were observed in Test Reactors seeded with acidogenic culture (R3 and R6).

Today, numerous studies indicate the presence of synthetic organics such as nonylphenol (NP) compounds in wastewater. NP compounds are a group of chemicals including nonylphenol, nonylphenol polyethoxylates (NPnEO) and nonylphenoxy polyethoxy acetic acids (NPnEC). Since NP compounds have significant industrial, commercial and domestic use, they enter environmental systems and reach human beings from various pathways. Their presence is of concern because they are toxic, carcinogenic and endocrine disrupting due to their ability to mimic oestrogen hormone. The information available on the degradation of NPnEOs, is such that degradation starts with the reduction of ethylene oxide units, resulting in the formation of nonylphenol, nonylphenol mono- or diethoxylate (NP1EO and NP2EO) and nonylphenoxy acetic acid (NP1EC). Although their fate during wastewater treatment was investigated in the past, not many research investigating their fate in sludge treatment can be found. Therefore, the objective of this study is first to come up with reliable extraction and measurement methods for NP compounds and then to investigate the fate of NP2EO in aerobic digesters. After the development of techniques for the extraction and measurement of NP compounds, aerobic reactors spiked with NP2EO were operated. The samples were analyzed for solids content, COD, pH and NP compounds. The results showed that NP2EO degrades rapidly under aerobic conditions. As time proceeded, NP1EC formation was observed with the degradation of NP2EO, and NP1EC became the dominant specie. The solids concentration measurements showed that concentration of NP compounds did not affect the efficiency of aerobic digesters.

Thesis (M.S.)--Mississippi State University. Department of Chemistry. / Title from title screen. Includes bibliographical references.

Thesis (M.S.) -- Mississippi State University. Dave C. Swalm School of Chemical Engineering. / Title from title screen. Includes bibliographical references.

Thesis (M.S.)--Ohio University, March, 2007. / Title from PDF t.p. Includes bibliographical references.

Thesis (MScAgric)--University of Stellenbosch, 2000. / ENGLISH ABSTRACT: The quality of wine is influenced by numerous factors. These factors include the quality of the grapes, winemaking techniques and quality control throughout the winemaking process. It is thus very important that any process leading to the lowering of the quality of the wine be prevented. Evidence in the wine industry shows that bacterial spoilage is still very much a common problem in many wineries. The spoilage of wine by bacteria can lead to amongst other problems, elevated volatile acidity levels, of which only a certain concentration limit in wine is permitted. Usually more than 90% of the volatile acidity of wine consists of acetic acid. Different yeast strains, heterofermentative lactic acid bacteria and acetic acid bacteria (which can all be spoilage microorganisms) can produce acetic acid in high concentrations. It is thus important to be able to prevent the formation of this acid by controling the unwanted growth of these spoilage microorganisms. Acetic acid and other medium chain fatty acids, octanoic- and decanoic acid, can also lead to stuck or sluggish fermentations. A stuck or sluggish fermentation can also lead to wine spoilage, due to sugar remaining in the fermentation which can be utilized by spoilage microorganisms. Acetic- and other fatty acids enter the yeast cell by passive diffussion and releases its proton in the cytoplasm, thereby acidifying the cytoplasm and inhibiting some enzymes. These acids can also work synergistically with ethanol and its inhibitory effect is also dependent on the temperature. Yeast strains can also differ in their resistance to acetic and other medium chain fatty acids and these acids can also influence the growth of lactic acid bacteria. How acetic acid bacteria influence the winemaking process and the used measures to keep these bacteria from spoiling wine have been the subject of very little attention in the past. This was due to the belief that the anaerobic conditions prevailing in wine and the use of sulfur dioxide are enough to control these bacteria, since acetic acid bacteria were always described as being strictly aerobic microorganisms. Recently, some evidence showed that acetic acid bacteria can survive and even overcome the limits that the winemaking process places on its growth. These bacteria are also known to inhibit the yeasts growth and fermentation ability due to the production of acetic acid and other factors. A research programme on the origin of volatile acidity in South African wines had been initiated at the Department of Viticulture and Enology and at the Institute for Wine Biotechnology at the University of Stellenbosch after increases in volatile acidity in different South African wines had been reported. This spurred us to investigate the occurrence of acetic acid bacteria in South African red wine fermentations, which forms part of this study, and to identify the dominant acetic acid bacterial strains. The sulfur dioxide resistance of five representative strains were also determined, as well as the effect of metabolites which were produced by these bacteria on yeast growth and fermentation ability. Our results indicate that acetic acid bacteria can occur in high concentrations in the fresh must and during alcoholic fermentation. In the 1998 harvesting season acetic acid bacteria occurred at 106-107 cfu per ml in the fresh must. In 1999 these numbers were 104-105 cfu/ml. Acetic acid bacteria numbers decreased in 1998 to 102-103 cfulml during fermentation. The survival of these bacteria in 1999 correlated with the pH of the must, as well as sulfur dioxide dosages in the must. In must with a low pH and higher sulfur dioxide the number of acetic acid bacterial numbers decreased more drastically than in the high pH, low sulfur dioxide musts. This was also true for acetic acid bacterial counts during cold soaking of musts, with the number of acetic acid bacteria increasing during the cold soaking period in musts with a high pH. In musts with a low pH and higher S02 dosages acetic acid bacterial counts did not, however, increase during cold soaking. Gluconobacter oxydans dominated in the fresh must with Acetobacter liquefaciens and especially Acetobacter pasteurianus dominating during the fermentation. Different biochemical and physiological tests revealed that 52% of the 115 isolates tested belong to A. pasteurianus. The high occurrence of A. liquefaciens with A. pasteurianus during fermentation showed that the dominant acetic acid bacterial species in South Africa differed from reports from other wine producing countries. The sulfur dioxide resistance of the acetic acid bacteria tested also differed in white grape juice, with a molecular sulfur dioxide concentration of 0.64 mg/I being necessary to eliminate all the acetic acid bacterial strains tested. The A. hansenii strain was found to be the most resistant to sulfur dioxide and G. oxydans the least resistant. The latter strain was eliminated by only 0.05 mg/I molecular sulfur dioxide, while A. hansenii was only eliminated by 0.64 mg/I molecular sulfur dioxide. The A. pasteurianus, A. liquefaciens and A. aceti strains tested displayed varying degrees of resistance to sulfur dioxide. The volatile acidity produced by these bacteria profoundly influenced the growth and fermentation ability of yeast, which led to slow/stuck fermentation. The A. hansenii and A. pasteurianus strains produced the most volatile acidity in grape juice, with up to 4.02 g/I for A. hansenii within 4 days, which led to a stuck alcoholic fermentation. This was, however, prevented by inhibiting or eliminating the acetic acid bacteria with sufficient sulfur dioxide additions prior to yeast inoculation. Compounds produced by acetic acid bacteria can also influence wine quality. Certain organic acids were produced and metabolized by acetic acid bacteria, as well as acetoin. We could not, however, detect any other fatty acids that are inhibitory to yeast (produced by these bacteria). This study clearly showed that acetic acid bacteria could occur during fermentation and that certain winemaking techniques, like the maintenance of a low pH in the must and sulfur dioxide additions can influence the growth and survival of acetic acid bacteria. Acetic acid bacteria also influence both the winemaking process by inhibiting yeast as well as the quality of the wine by producing acetic acid and/or other compounds. This study also shed some light on the occurrence of acetic acid bacterial species in the South African context and could be important in assisting the winemaker, as well as the scientific reseacher, in finding ways to inhibit acetic acid bacteria in the ongoing battle against these spoilage microorganisms of wine. / AFRIKAANSE OPSOMMING: Wynkwaliteit word deur verskillende faktore beinvloed. Dit sluit die druifkwaliteit, wynmaak tegnieke en kwaliteitsbeheer deur die wynmaakproses in. Enige prosesse en faktore wat tot die verlaging in wynkwaliteit kan lei moet dus ten alle koste voorkom word. Die bederf van wyn deur bakterieë kan en is 'n algemene probleem in enige kelder. Bakteriese bederf kan, onder andere, lei tot verhoogte vlugtige suurheid, waarvan 'n sekere konsentrasie limiet in wyn toegelaat word. Asynsuur maak gewoonlik 90% van die vlugtige suurheid uit. Asynsuur kan deur verskillende gisrasse, heterofermantatiewe melksuurbakterieë en asynsuurbakterieë (wat almal wyn kan bederf) gevorm word. Die vorming van asynsuur in wyn kan dus voorkom word deur die ongewenste groei van dié organismes te voorkom. Asynsuur en ander medium ketting vetsure, soos oktanoë- en dekanoësuur, kan ook tot slepende of gestaakte gistings lei. Suiker wat in die wyn agterbly wat In slepende/gestaakte fermentasie ondergaan kan deur bederf bakterieë gebruik word om die wyn te bederf. Ongedissosieerde asynsuur en ander vetsure dring die gissel binne deur passiewe diffussie en stel 'n proton vry in die sitoplasma wat sitoplasma versuur en sekere ensieme inhibeer. Hierdie sure werk ook sinergisties met etanol en hul inhiberede effek is ook temperatuur afhanklik. Gisrasse verskil in hul weerstandbiedendheid teen asynsuur- en ander mediumketting vetsure en dié vetsure kan ook melksuurbakterieë se groei beïnvloed. Hoe asynsuurbakterieë wyn bederf en die aksies wat geneem kan word om dit te verhoed is in die verlede nie baie ondrsoek nie. Dit is hoofsaaklik daaraan toe te skryf dat geglo is dat die anaerobiese kondisies in wyn en die gebruik van swaweidioksied die groei van asynsuurbakterieë, wat altyd beskryf is as streng aerobe mikroorganismes, kan beheer. Daar is onlangs aangetoon dat asynsuurbakterieë kan oorleef in wyn en selfs die ongunstige kondisies daarin kan oorkom. Hierdie bakterieë is ook in staat om gisgroei en fermentasie vermoë te inhibeer deur die produksie van asynsuur en ander faktore. In Navorsingsprogram om die oorsprong van verhoogde vlugtige suurheid in Suid-Afrikaanse wyne te bepaal is deur die Departement Wingerd- en Wynkunde en die Instituut vir Wynbiotegnologie van die Universiteit van Stellenbosch geinisieer. Dit het ons aangemoedig om die voorkoms van asynsuurbakterieë in Suid-Afrikaanse rooiwyngistings, wat deel vorm van hierdie ondersoek, en ook die dominante asynsuurbakterie rasse te identifiseer. Die swaweidioksied bestandheid van vyf verteenwoordegende rasse en die effek wat metaboliete wat deur dié bakterieë geproduseer is op gisgroei en gisitingsvermoë is bepaal. Ons resultate bewys dat asynsuurbakterieë teen hoë getalle in vars mos en gedurende alkoholiese gisting kan voorkom. Asynsuurbakterieë het gedurende die 1998 seisoen teen 106-107 kve/ml en in 1999 teen 104-105 kve/ml in die vars mos voorgekom. Gedurende fermentasie het hierdie getalle in die 1998 seisoen gedaal na 102-103 kve/ml. Die oorlewing van hierdie bakterieë het gedurende die 1999 seisoen gekorrelleer met die pH en swaweidioksied konsentrasies van die mos. In die lae pH, hoë swaweidioksied moste het asynsuurbakterie getalle vinniger en meer dramaties gedaal as in die hoë pH, lae swaweidioksied moste. Asynsuurbakterie getalle het dieselfde tendens getoon in moste gedurende dopkontak by lae temperature. In moste met 'n hoë pH het asynsuurbakterie getalle toegeneem gedurende koue dopkontak, terwyl dit nie gebeur het nie in moste met 'n lae pH en hoë swaweidioksied konsentrasies. In die vars mos het Gluconobacter oxydans en gedurende die fermentasie Acetobacter liquefaciens en veral Acetobacter pasteurianus oorheers. Verskillende biochemiese en fisiologiese toetse het bepaal dat 52% van die 115 isolate A. pasteurianus is. Die hoë voorkoms van A. liquefaciens saam met A. pasteurianus gedurende gisting bewys dat die voorkoms en dominansie van asynsuurbakterieë in Suid- Afrika verskil van ander wynproduserende lande. Die swaweidioksied weerstandbiedendheid van die asynsuurbakterieë wat getoets het, het ook verskil, met 0.64 mg/I molekulêre swaweIdioksied nodig om hul almal te elimineer in wit druiwesap. Die A. hansenii en G. oxydans rasse was die mees weerstandbiedend en sensitiefste onderskeidelik ten opsigte van swaweidioksied. Slegs 0.05 mg/I molekulêre swaweidioksied was voldoende om G. oxydans te elimineer, terwyl A. hansenii deur 0.64 mg/I molekulêre swaweidioksied geëlimineer is. Die A. pasteurianus, A. liquefaciens en A. aceti rasse het verskillende swaweidioksied weerstandbiedendheid getoon. Die vlugtige suurheid wat deur dié bakterieë geproduseer is het die groei en gistingvermoë van gis drasties beinvloed, wat tot slepende/gestaakte fermentasies gelei het. Die A. hansenii en A. pasteurianus rasse het die meeste vlugtige suurheid geproduseer, met tot 4.02 g/I geproduseer deur A. hansenii na vier dae se groei, wat tot 'n gestaakte fermentasie gelei het. Dit is egter voorkom deur die asynsuurbakterieë te elimineer deur genoegsame swaweidioksied toevoegings tot die mos voor gisinokulasie te doen. Verbindings wat deur asynsuurbakterieë geproduseer word kan ook wynkwaliteit beinvloed. Sekere anorganiese sure is deur hierdie bakterieë geproduseer, terwyl ander gemetaboliseer is. Asetoïen is geproduseer deur die getoetse asynsuurbakterieë. Ons kon egter nie ander vetsure wat gis inhibeer opspoor nie. (Geproduseer deur die bakterieë). Hierdie studie bewys dat asynsuurbakterieë gedurende alkoholiese fermentasie kan voorkom en dat sekere wynmaaktegnieke, soos die verkryging van moste met 'n lae pH en genoegsame swaweidioksied toevoegings die groei en oorlewing van asynsuurbakterieë kan beivloed. Asynsuurbakterieë kan ook beide die wynmaakproses, deur giste te inhibeer, en die wynkwaliteit beivloed deur die produksie van asynsuur en/of ander verbindings. Hierdie studie het ook kennis oor die voorkoms van asynsuurbakterieë in Suid-Afrikaanse moste verbeter en kan ook as 'n nuttige hulpmiddel dien vir die wynmaker en navorser in die stryd om hierdie bederf organismes van wyn te elimineer.

Made available in DSpace on 2014-06-11T19:32:54Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-02-06Bitstream added on 2014-06-13T21:05:11Z : No. of bitstreams: 1 pedrinho_ean_dr_jabo.pdf: 618876 bytes, checksum: 1ad857ab1fbea921a5b1a0748c8aaa28 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Estudos sobre a atividade microbiológica que ocorre na rizosfera de diversos vegetais levaram ao descobrimento de grupos de microrganismos importantes para o desenvolvimento vegetal. Dentre eles estão as rizobactérias que são capazes de colonizar as raízes, estimulando-a diretamente ou beneficiando o crescimento e o desenvolvimento de diversas plantas, essas bactérias são chamadas Rizobactérias Promotoras de Crescimento em Plantas ou RPCP. Este trabalho teve o objetivo de isolar, identificar, testar a capacidade da solubilização de fosfato, produção de ácido indol- acético (AIA) e fixação de nitrogênio de alguns isolados obtidos de quatro regiões diferentes do Brasil, assim como o efeito da inoculação destes em sementes de milho (híbrido Imapcto) testados na casa de vegetação. As metodologias utilizadas neste trabalho propiciaram a seleção de isolados que se destacaram positivamente. A análise parcial do gene 16S rRNA dos 87 isolados possibilitou a identificação dos gêneros, Bacillus, Burkholderia e Azospirillum, sendo os mais freqüentes totalizando 78% dos isolados, seguidos de Sphingomonas, Pseudomonas, Herbaspirillum, Pantoea e Bosea. Desses, 42 foram positivos no teste colorimétrico para detecção de produção do AIA e somente 24 apresentaram a capacidade de solubilização do fosfato. A partir destes resultados selecionou-se um organismo pertencente ao gênero Sphingomonas para ser testado em casa de vegetação como promotor de crescimento em conjunto com as estirpes de Azospirillum brasilense (AbV5 e AbV6). As plantas foram avaliadas quanto à altura, aos vinte e setenta dias após a germinação, e a massa seca da parte aérea e radicular foram quantificadas após setenta dias, no encerramento do experimento. Já a capacidade de redução do acetileno a etileno in vitro foi positiva somente para quatro organismos pertencentes aos gêneros Pseudomonas... / Studies on the microbial activity that occurs in the rhizosphere of different plants have led to the discovery of groups of important microorganisms to plant development. Among them are the rhizobacteria that are able to colonize the roots, stimulating it directly or benefiting the growth and development of many plants, these bacteria are called Plant Growth Promotion Rhizobacteria in plants or RPCP. This study aimed to isolate, identify, test the ability of phosphate solubilization, production of indoleacetic acid (IAA) and nitrogen fixation of some isolates from four different regions of Brazil, as well as the effect of inoculation in these maize seeds (hybrid Imapcto) tested in the greenhouse. The methods used in this study enabled the selection of isolates that stood out positively. The analysis of partial 16S rRNA gene of the 87 isolates allowed the identification of genera, Bacillus, Azospirillum and Burkholderia, with the most frequent totaling 78% of isolates, followed by Sphingomonas, Pseudomonas, Herbaspirillum, Pantoea and Bosea. Of these, 42 were positive in the colorimetric test for detection of production of the EIA and only 24 had the capacity of phosphate solubilization. From these results picked up a body belonging to the genus Sphingomonas to be tested in the greenhouse as promoter of growth together with the strains of Azospirillum brasilense (AbV5 and AbV6). The plants were then evaluated for the twenty and seventy days after germination and dry weight of shoot and root were quantified after seventy days, at the end of the experiment. The capacity of reduction of acetylene to ethylene in vitro were positive for only four bodies belonging to the genera Pseudomonas, Burkholderia, Sphingomonas and Herbaspirillum amid NFb. With these isolates tested was the ability to fix nitrogen evaluating the development of maize seedlings in a greenhouse for thirty days... (Complete abstract click electronic access below)

The thesis describes the synthesis and application of various alkynones derived from the bis-Weinreb amide of tartaric acid in the total synthesis of macrolactone natural products. The thesis is divided into three sections. First section of the thesis describes the optimization and generalization of the procedure for the addition of alkynyl Grignard / lithium reagents to the bis-Weinreb amide derived from tartaric acid to yield the mono alkynyl ketones was developed. Application of the formed γ-oxo amides was demonstrated in the synthesis of polyols with varied substitutions particularly the synthesis of 1,2,4-triols was accomplished using Ley’s dithianylation as the key step. Scheme 1: Synthesis of polyols from the bis-weinreb amide of tartaric acid. Application of the strategy to the total synthesis of decanolactone natural products achaetolide and (Z)-isomer of (6S,7R,9R)-6,7-dihydroxy-9-propylnon-4-eno-9-lactone was featured. Section B of the thesis deals with the enantiospecific total synthesis of 14-membered macrolactone Sch 725674. Key reactions in the synthesis include the synthesis of the 1,2,4-triol unit from tartaric acid, olefin cross metathesis and ring closing metathesis. Scheme 4: Enantiospecific total synthesis of Sch 725674. Section C of the thesis describes the enantiospecific synthesis of the C9-C22 fragment of the 28-membered polyene polyol macrolide pentamycin. Although isolated in 1958, total synthesis of this antifungal compound was not reported. In application of the methodology developed, the alkynone prepared from the bis-Weinreb amide was elaborated to the required fragment.