Made available in DSpace on 2014-08-20T13:59:04Z (GMT). No. of bitstreams: 1 tese_fabiana_timm.pdf: 864202 bytes, checksum: eb076826201adf7fc6b54e9e5d185d98 (MD5) Previous issue date: 2012-07-31 / The salinity negatively affects crop productivity due to osmotic and toxic effect caused by excess Na+ and Cl- in the soil. The mechanisms used by tolerant species include the control of Na+ uptake, compartmentalization and translocation of Na+ and Cl- by membrane transporters; production of protective osmolytes, increased activity of antioxidant enzymes and cell signaling. Thus, the objective was to evaluate seed germination and early growth of nine white oat genotypes, in order to identify contrasting genotypes for salt tolerance character. For this analysis was performed on the physiological white oat genotypes under different salt concentrations (0; 25; 50; 75 and 100 mM NaCl). The variables analyzed were: germination, first counting germination, index of germination speed, shoot and root length, shoots and roots dry mass of shoots and roots seedling. Based on these results were selected contrasting genotypes in which it was determined the activity of antioxidant enzymes and content of photosynthetic pigments. Seed germination was less affected than the growth of seedlings with increasing concentrations of NaCl, and the root length was most affected. The length of roots and shoots were the variables that best discriminated contrasting genotypes, enabling the identification of a tolerant genotype (URS 22) and sensitive (UPF 16), evidenced by the activity of antioxidant enzymes. The levels of chlorophyll and carotenoid were reduced in accordance with the increase in salt concentration in both genotypes, and lower in genotype UPF 16. Based on the analysis of initial growth was possible to discriminate a sensitive genotype (UPF 16) and a tolerant (URS 22), which showed higher and lower activity of antioxidant enzymes as well as lower and higher pigment contents, respectively. / A salinidade afeta negativamente a produtividade das culturas devido ao efeito osmótico e tóxico causado pelo excesso de íons Na+ e Cl- no solo. Os mecanismos utilizados por espécies tolerantes incluem controle na absorção de Na+; compartimentalização e translocação de Na+ e Cl- pelos transportadores de membrana; produção de osmólitos protetores; aumento na atividade de enzimas antioxidantes e sinalização celular. Assim sendo, o objetivo foi avaliar a germinação das sementes e o crescimento inicial de nove genótipos de aveia branca, identificar genótipos contrastantes para o caráter tolerância à salinidade. Para isso, foram feitas análises fisiológicas dos genótipos de aveia branca submetidos a diferentes concentrações salinas (0,0; 25; 50; 75 e 100 mM de NaCl). As variáveis analisadas foram: porcentagem de germinação, primeira contagem de germinação, índice de velocidade de germinação, comprimento de parte aérea e raiz, massa seca da parte aérea e raízes das plântulas. Com base nestes resultados, foram selecionados genótipos contrastantes nos quais foi determinada a atividade de enzimas antioxidantes e o teor de pigmentos fotossintéticos. A germinação das sementes foi menos afetada que o crescimento das plântulas com o aumento das concentrações de NaCl, sendo que o comprimento de raiz foi mais prejudicado. O comprimento da raiz e parte aérea foram às variáveis que melhor discriminaram os genótipos contrastantes, possibilitando a identificação de um genótipo tolerante (URS 22) e um sensível (UPF 16), comprovado pela atividade das enzimas antioxidantes. Os teores de clorofila e carotenoides reduziram de acordo com o aumento da concentração salina em ambos os genótipos, sendo menores no genótipo UPF 16. Com base nas análises de crescimento inicial foi possível discriminar um genótipo sensível (UPF 16) e um tolerante (URS 22), os quais apresentaram maior e menor atividade das enzimas antioxidantes bem como, menor e maior conteúdo de pigmentos, respectivamente.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The purpose of this study was to verify the effect of dietary salt (NaCl) supplementation, water hardness and pH on growth, survival and ionoregulation of silver catfish (Rhamdia quelen) juveniles. In the first experiment, juveniles were fed with diets supplemented with 0.0; 0.5; 1.0 e 2.0 % NaCl and exposed to pH 5.5, 7.0 and 9.0 for 35 days. In the second study, fish were maintained for 30 days in three different pH (5.5; 7.0 and 9.0) and four water hardness (30, 60, 120, and 180 mg L-1 CaCO3). The third experiment investigated the effects of the 6.0-8.0 pH range at low water hardness (0, 25 and 50 mg L-1 CaCO3) for 32 days. In the experiments 1 and 2, fish samples were collected at different moments for analyses of Na+, K+ and Cl- net ion fluxes. In all three studies, growth and survival were analyzed. The water utilized was previously adjusted to the appropriate pH and water hardness using NaOH or H2SO4 0.5 M and CaCl2.2H2O, respectively. In the first experiment, fish fed with diet without NaCl supplementation and exposed to pH 7.0 presented significantly higher weight, length, SGR and biomass per tank than those exposed to pH 5.5, and the increase of dietary NaCl protected against the impact of acidic water. Dietary salt supplementation contributed to decrease the osmoregulatory disturbances in the juveniles exposed to acidic or basic pH. In the second study, exposure of juveniles to alkaline or acidic water did not affect survival, but acidic water reduced growth. And, finally, in the third study, juveniles exposed to pH 7.0 and 8.0 at zero water hardness showed significantly higher mortality than those kept at pH 6.0. Survival and growth of juveniles exposed to 25 and 50 mg L-1 CaCO3 was not affected in the 6.0-8.0 pH range. Therefore, the best water hardness for silver catfish juveniles growth and osmoregulation is 30-60 mg L-1 CaCO3 and at low water hardness (next zero) pH must be reduced. It can be concluded that the interaction of dietary salt, pH and water hardness are very important to silver catfish rearing, because they change growth and ionoregulation in this species. / A proposta deste estudo foi verificar o efeito da adição de sal na dieta, dureza da água e pH no crescimento, sobrevivência e ionorregulação de juvenis de jundiá (Rhamdia quelen). No primeiro experimento, juvenis foram alimentados com dietas suplementadas com 0,0; 0,5; 1,0 e 2,0 % NaCl e expostos aos pH 5,5; 7,0 e 9,0 por 35 dias. No segundo estudo, peixes foram mantidos por 30 dias em três pH (5,5; 7,0 e 9,0) e quatro durezas da água (30, 60, 120 e 180 mg L-1 CaCO3). O terceiro experimento investigou os efeitos do pH dentro da faixa de 6.0-8.0 em baixa dureza da água (0, 25 e 50 mg L-1 CaCO3) por 32 dias. Nos experimentos 1 e 2, exemplares foram coletados em diferentes momentos para análise dos fluxos iônicos líquidos de Na+, K+ e Cl. Em todos os três estudos, crescimento e sobrevivência foram analisados. A água utilizada foi previamente ajustada para o pH e dureza da água apropriados usando NaOH ou H2SO4 0,5 M e CaCl2.2H2O, respectivamente. No primeiro experimento, peixes alimentados com dietas sem adição de NaCl e expostos a pH 7,0 apresentaram peso, comprimento, SGR e biomassa por tanque significativamente maiores que aqueles mantidos em pH 5,5, e o aumento de NaCl na dieta protegeu contra o impacto da água ácida. A inclusão de sal na dieta reduziu os distúrbios osmorregulatórios nos juvenis expostos a pH ácido ou básico. No segundo trabalho, juvenis expostos a águas alcalinas ou ácidas não tiveram sua sobrevivência afetada, mas o crescimento foi reduzido em água ácida. E finalmente, no terceiro estudo, juvenis expostos a pH 7,0 e 8,0 em dureza zero da água apresentaram mortalidade significativamente maior que aqueles mantidos em pH 6.0. Nos juvenis expostos a 25 e 50 mg L-1 CaCO3 a sobrevivência e o crescimento não foram afetados na faixa de pH 6,0-8,0. Portanto, a melhor dureza da água para crescimento e osmorregulação de juvenis de jundiá se encontra entre 30-60 mg L-1 CaCO3, e em dureza baixa (próxima de zero) deve-se reduzir o pH da água. Pode-se concluir que a interação de parâmetros como sal na dieta, pH e dureza da água são deveras importantes no cultivo do jundiá, uma vez que alteram o crescimento e a ionorregulação desta espécie.

[pt] A redução por hidrogênio e a decomposição térmica de um minério laterítico saprolítico foram estudadas utilizando a técnica de termogravimetria (TGA). A identificação das fases minerais formadas após o processamento foi feita utilizando as técnicas de difração de raios X (DRX) e microscopia eletrônica de varredura acoplada a espectrômetro de energia dispersiva (MEV/EDS). O produto obtido manteve o níquel aprisionado na estrutura do material e forneceu um baixo índice de extração desse metal (em torno de 3 porcento) na etapa de lixiviação amoniacal. Desta forma, novos experimentos de redução foram conduzidos na presença de diferentes reagentes químicos (Na2CO3, S8 e NaCl) visando a aumentar a solubilidade do níquel. Observou-se que todos os reagentes químicos utilizados viabilizaram o aumento da extração de Ni, sendo o maior deles para os testes utilizando 10 porcento de NaCl. Então, experimentos de redução por hidrogênio e decomposição térmica, do mesmo minério, na presença de NaCl, foram feitos utilizando a técnica de termogravimetria, com as fases minerais e alguns produtos gasosos formados sendo identificados utilizando as técnicas de DRX e MEV/EDS. Tais experimentos e caracterizações sugerem que a presença do NaCl no sistema promove a segregação do níquel, e a sua consequente solubilização posterior, em função da ocorrência das seguintes reações: (1o) Redução do óxido de níquel pelo hidrogênio: NiO + H2(g) → Ni + H2O(g); (2o) Formação de HCl: Al2SiO5 + 2NaCl + SiO2 + H2O(g) à 2HCl(g) + 2NaAlSiO4; (3o) Cloração do níquel metálico pelo HCl: Ni + 2HCl(g) → NiCl2 + H2(g);(4o) Redução do cloreto de níquel pelo hidrogênio: NiCl2 + H2(g) → Ni + 2HCl(g). A influência da temperatura e da porcentagem de NaCl no forno de redução no rendimento da etapa de lixiviação amoniacal foram avaliadas e os resultados mostraram que a presença de apenas 1 porcento de NaCl aumentou os valores de extração para níveis próximos de 90 porcento, quando os experimentos de redução foram conduzidos à temperatura de 850°C. / [en] The reduction by hydrogen and the thermal decomposition of a lateritic saprolite nickel ore were studied using the thermogravimetric technique (TGA). The identification of the mineral phases generated after the processing was carried out using X-ray diffraction (XRD) and scanning electron microscopy coupled to a dispersive energy spectrometer (SEM/EDS) techniques. The reduced ore was leached in amoniacal solution and the low value of nickel extraction (≈3 percent) were attributed to the formation of forsterite and enstatite. Thus reduction test were carried out in the presence of chemicals (Na2CO3, NaCl and S8) and the highest extractions values were found for the tests using 10 percent NaCl. Finally, reduction tests on H2 atmosphere in rotary kiln were performed in the presence of NaCl and the product of the reaction was leached in ammoniacal solution. The presence of only 1 percent of NaCl in the furnace increased the nickel extraction values from ≈3 percent to ≈ 90 percent when the experiment was carried out at 850°C. According to the results of X ray diffractometry (XRD) and thermogravimetric analysis (TGA) the presence of NaCl in the system and the reducing atmosphere of H2 promote the segregation of nickel according to the following steps: 1).. Nickel oxide reduction by hydrogen: NiO + H2(g) → Ni + H2O(g). 2) Formation of HCl: Al2SiO5 + 2NaCl + SiO2 + H2O à 2HCl(g) + 2NaAlSiO4. 3). Chlorination of metallic nickel by HCl: Ni + 2HCl(g) → NiCl2 + H2(g). 4). Reduction of nickel chloride by hydrogen: NiCl2 + H2(g) → Ni + 2HCl(g).

Size exclusion chromatography (SEC) separates molecules based on their actual size rather than their molecular weight. This indicates that the smaller a molecule is, the longer it will be held in the column since it can penetrate the pores more effectively than a bigger molecule, resulting in a longer retention time, whereas the larger molecule has a shorter retention time. In order to achieve reliable and accurate results the asymmetry factor of the packed columns should be between 0.6-1.4. The aim for this project was to examine whether or not the batch variations of the base matrix used to derive WorkBeads™ 40S and 40Q displayed either hydrophobic or hydrophilic interactions by running different types of proteins through columns packed with the base matrices. The project was performed using an ÄKTA explorer equipped with an ultraviolet (UV) detector and a refractive index detector (RID). The data was gathered and analyzed with the Unicorn™ by Cytiva. The results from the first experiments showed that lysozyme did not elute as expected or not at all, thus leading to a concern that the there might be some hydrophobic interactions in the base matrix, which is a porous media in the form of spherical particles that have been selected for their physical stability and inertness (lack of reactivity and adsorptive properties), and lysozyme. With this suspicion in mind, the different batches of the base matrix underwent hydrophobic interaction chromatography (HIC), where the results may be interpreted in a way that there might electrostatic interactions instead of hydrophobic interactions. However, due to the gel not being suitable for HIC the results were unreliable. By subsequently running lysozyme and other proteins through the columns at different NaCl concentrations the results showed consistent elution at NaCl concentrations > 150 mM, yet inconsistent at a concentration of 150 mM for lysozyme. The elution order by size showed that although lysozyme has a larger hydrodynamic radius (Rh) than cytochrome c it eluted later, which is theoretically incorrect, but it might be owing to some of the base matrix's characteristics or the lysozyme's dual nature of expressing both hydrophobic and hydrophilic interactions on the base matrix. Because of the inconsistent results from lysozyme, another experiment just at 150 mM was conducted where lysozyme did elute consistently with a KD value < 1.  Lastly, a titration was performed on the base matrix where some of it was brominated and some of it was not, which was the reference. The results showed that there could be hydrophobic interactions on the brominated sample and hydrophilic interactions on the reference sample. However, what is more likely is that lysozyme is an unreliable protein to use to determine hydrophobicity on this type of gel. / Size exclusion chromatography (SEC) separerar molekyler baserat på deras faktiska storlek snarare än deras molekylvikt. Detta indikerar att ju mindre en molekyl är, desto längre kommer den att hållas i kolonnen eftersom den kan tränga sig in i porerna mer effektivt än en större molekyl, vilket resulterar i en längre retentionstid, medan den större molekylen har en kortare retentionstid. För att uppnå tillförlitliga och nogranna resultat bör asymmetrifaktorn hos de packade kolonnerna vara mellan 0.6-1.4. Syftet med detta projekt var att undersöka huruvida batchvariationerna av basmatrisen som användes för att ta fram WorkBeads™ 40S och 40Q uppvisade antingen hydrofoba eller hydrofila interaktioner genom att köra olika typer av proteiner genom kolumner packade med basmatriserna. Projektet utfördes med en ÄKTA explorer utrustad med en ultraviolett (UV) detektor och en refractive index detector (RID). Data samlades in och analyserades med Unicorn™ av Cytiva. Resultaten från de första experimenten visade att lysozym inte eluerade som förväntat eller inte alls, vilket ledde till en oro för att det kan finnas vissa hydrofoba interaktioner i basmatrisen, som är ett poröst medium i form av sfäriska partiklar som har har valts ut för deras fysikaliska stabilitet och inerthet (brist på reaktivitet och adsorptiva egenskaper), och lysozym. Med denna misstanke i åtanke genomgick de olika bactherna av basmatrisen hydrofob interaktionskromatografi (HIC), där resultaten kan tolkas på ett sätt att det kan förekomma elektrostatiska interaktioner istället för hydrofoba interaktioner. Men på grund av att gelen inte var lämplig för HIC var resultaten opålitliga. Genom att efteråt köra lysozym och andra proteiner genom kolonnerna vid olika NaCl-koncentrationer visade resultaten konsekvent eluering vid NaCl-koncentrationer > 150 mM, men ändå inkonsekventa vid en koncentration av 150 mM för lysozym. Elueringsordningen efter storlek visade att även om lysozym har en större hydrodynamisk radie (Rh) än cytokrom c, eluerade det senare, vilket är teoretiskt inkorrekt, men det kan bero på några av basmatrisens egenskaper eller lysozymets dubbla natur att uttrycka både hydrofoba och hydrofila interaktioner på basmatrisen. På grund av de inkonsekventa resultaten från lysozym, utfördes ett annat experiment enbart vid 150 mM där lysozym eluerade konsekvent med ett KD-värde < 1. Slutligen utfördes en titrering på basmatrisen där en del av den var bromerad och en del av den inte, vilket var referensen. Resultaten visade att det kunde finnas hydrofoba interaktioner på det bromerade provet och hydrofila interaktioner på referensprovet. Men vad som är mer troligt är att lysozym är ett opålitligt protein att använda för att bestämma hydrofobicitet på denna typ av gel.

The role of sodium chloride (NaCl) particles and ammonium sulfate ((NH4)2SO4) particles on the initial atmospheric corrosion of copper and zinc was investigated under in situ and ex situ conditions using microgravimetry, FTIR spectroscopy, ion chromatography, scanning electron microscopy with x-ray microanalysis and the scanning Kelvin probe. For the first time, in situ infrared spectra were collected on a micron level during particle induced atmospheric corrosion using a recently developed experimental set-up for in situ FTIR microspectroscopy. Lateral distribution of corrosion and reaction products on copper and zinc surfaces was determined and could be connected with the mechanisms of the initial particle induced corrosion. The recently discovered secondary spreading effect from NaCl electrolyte droplets on metal surfaces was studied under in situ conditions and the effect of CO2 on the spreading process was elaborated. The ambient level of CO2 (350 ppm, 1 ppm = 10-6 volume parts) results in a relatively low secondary spreading effect, whereas the lower level of CO2 (<5 ppm) causes a much faster secondary spreading effect over a large area. At low CO2 concentration alkaline conditions will prevail in the cathodic area, leading to large changes in the surface tension at the oxide/electrolyte interface in the peripherical parts of the droplet. This induces a surface tension driven convective flow of electrolyte from the NaCl droplet. The continuous growth of the secondary spreading area at low CO2 concentration is possible due to the galvanic coupling with the droplet leading to transport of sodium ions to this region and maintenance of the alkaline conditions. At 350 ppm CO2, carbonate formation in the secondary spreading area results in lowering of the pH, increasing the surface tension of the oxide/electrolyte interface and inhibiting the secondary spreading. CO2 strongly affects the NaCl-induced atmospheric corrosion rate of copper. The overall influence of CO2 and NaCl depends on at least three identified mechanisms. At low NaCl particle density, CO2 affects the secondary spreading effect from the electrolyte droplet. This leads to a larger effective cathodic area at low CO2 concentration and a higher corrosion rate. The more alkaline surface electrolyte present at low CO2 concentration also affects the formation of corrosion products and the amount of soluble copper chloride. Whereas the presence of larger amounts of soluble chloride tends to increase the corrosion rate, the formation of CuO results in a more protective surface film which decreases the corrosion rate. This effect was observed at higher NaCl particle densities, where the secondary spreading areas overlapped with adjacent NaCl particle clusters. The formation of CuO leads to lower corrosion rates compared to ambient CO2 concentration in which this phase was not formed. For zinc, the formation of a more protective corrosion product layer was not observed and the corrosion rate is generally higher for low than for ambient CO2 concentration. The presence of NaCl particles on the metal surfaces strongly affects the SO2 interaction with the metal surfaces. The oxidation of S(IV) turned out to be fast at the area of the NaCl-containing electrolyte droplet, both for copper and zinc. On copper surfaces, both sulphate (SO4 2-) and dithionate (S2O6 2-) ions formed which is consistent with a copper catalysed reaction route for sulfite oxidation including the formation of a Cu(II)–sulfito complex as an important step. For zinc, a surface mediated sulfite oxidation process leads to rapid formation of sulphate in the electrolyte droplet area. The presence of SO2 strongly inhibits the secondary spreading due to the decrease in pH induced by absorption of SO2 in the cathodic areas. The presence of gaseous oxidants, such as NO2 and O3, has previously been considered as an important prerequisite for the oxidation of sulfite on copper. The results obtained here suggest that the formation of local electrochemical cells induced by deposited NaCl particles could be another important route for S(IV)- oxidation to sulfate formation. On copper, SO2 was also found to promote the formation of less soluble copper chlorides, such as paratacamite (Cu2(OH)3Cl) and nantokite (CuCl). The electrolyte droplet was dried after 24 hours of exposure due to the formation of less soluble paratacamite (Cu2(OH)3Cl) and nantokite (CuCl) and led to a decrease in the corrosion rate. Thus, SO2 alone promotes the corrosion rate of copper, whereas in the presence of NaCl particles the corrosion rate of copper may slow down due to the formation of insoluble copper chloride compounds. The lateral distribution of corrosion products after exposure of NaCl contaminated copper and zinc surfaces to humid air with gaseous pollutants is a result of the formation of local electrochemical cells at the particles and concomitant differences in chemical composition and pH. For (NH4)2SO4 deposited copper and zinc surfaces the corrosion effects increase with the amount of pre-deposited particles and with the exposure time. On copper, the size of the particles affects the corrosion rate, smaller particles resulting in a higher corrosion rate than larger particles at equal amount of deposition. The formation of Cu2O was the dominant corrosion product after exposure longer than 10 days. (NH4)2SO4 particles result in enhanced Cu2O formation on copper due to a reaction sequence involving catalysis by NH3. The corrosion of copper by (NH4)2SO4 particles was much larger than that induced by NaCl particles. However, for zinc, the (NH4)2SO4 particles lead to smaller corrosion effects than those of NaCl particles. For both particles, significant corrosion attack was observed at relative humidity (RH) lower than the deliquescence point of the salts. / QC 20101001

Aquest treball tracta dels diferents comportaments que ha tingut l'aigua subterrània a la vall Salada de Cardona i en el seu aiguabarreig amb el riu Cardener. Aquest riu, ha arribat a ser problemàtic per les seves conseqüències ambientals i de potabilitat en les xarxes públiques de Barcelona i l'àrea metropolitana.La vall Salada és un impressionant aflorament de materials salins en forma de diapir, en el qual hi ha diferents aportacions d'aigua superficial i subterrània. La dissolució dels materials salins per l'aigua dolça és el primer motor que altera la fisonomia de la Muntanya de Sal i també la morfologia de la vall. Tant l'aigua superficial com la interna han provocat esfondraments dels materials superiors a manera de bòfies. En tota aquesta dinàmica de dissolució dels materials salins, hi ha un procés de protecció natural amb la salmorra resultant, que actua sempre que no hi ha un flux exterior prou important per retirar-la. D'aquesta manera, en les zones amb materials salins, propenses a la dissolució per l'aigua, es forma una capa de salmorra a les parts baixes, a manera de cubeta autoprotegida en la base. Els fets més importants pel que fa al comportament de l'aigua subterrània a la vall Salada han estat les entrades d'aigua a la mina. En la darrera i més greu entrada d'aigua a la mina Las Salinas (14 de març de 1998), l'alteració dels materials salins situats sobre la mina es va anar estenent i aprofundint fins a interceptar el sostre de la cavitat subterrània a uns 50 metres de la superfície. Però hi havia un lleuger llindar entre les cubetes d'alteració i la del riu Cardener. Una vegada desprotegit aquest llindar per l'escolament de les salmorres residuals, les aigües dolces dissolen aquesta barrera natural i arriba un moment (a principis de gener del 1999) que les aigües del riu Cardener es desplacen cap a l'interior de la mina seguint el gradient més favorable. Afortunadament, durant els darrers mesos l'Administració s'afanyà a construir un túnel pel riu, de manera que s'anul·là el meandre del Cardener al seu pas pels materials salins de la vall Salada.Posteriorment a la construcció del túnel de derivació del Cardener, i amb el consegüent bombeig cap al col·lector, sembla que s'hagi trobat la solució gairebé definitiva a la salinització de l'aigua del riu. Però el cabal que recull la bomba al fons de la mina, més aviat sembla que augmenta. Es fan hipòtesis d'altres possibilitats de recàrrega a l'aqüífer pels laterals del diapir. S'han fet mesures de georesistivitat elèctrica i es poden obtenir dades de pous als laterals del diapir i dins la llera antiga del riu;això permet demostrar que encara entren cabals similars als que es bombegen a l'interior de la mina. A partir d'aquestes dades es reconstrueix el futur hidrogeològic de la vall Salada. Així doncs, es creuque aquest cabal residual que entra a la vall serà cada vegada més gran, pel fet que l'aigua dolça dissoldrà cada vegada més el llindar dels laterals. Llavors s'esdevindrà un gradient més accentuat, cosa que produirà esfondraments per falta de material als laterals. D'altra banda, si algun dia deixa de funcionar la bomba, el nivell de salmorra de l'interior de la mina pujarà fins al nivell natural de la antiga llera del riu. En aquesta zona es podrà formar per dissolució un llac d'aigua salada. Segurament, a més llarg termini, a escala geològica, la pujadadiapírica dels materials salins més el sobrepès de la salmorra frenaran progressivament l'avenç d'aquest procés i es podrà tornar a tenir unes condicions similars a les que la vall Salada havia tingut.

A nanofilm rotation method is developed to study the rotation of nanograins and the formation of various low energy interfaces. Epitaxial NiO and Ag nanofilms are prepared by ion beam sputtering onto the (100), (110), (111) and (112) surfaces of NaCl single crystal. By overlapping of the above films with an angle difference, and annealing at relatively low temperatures the nanograins are induced to rotate till a stable interface is reached. The rotation process and the stable interfaces are determined by transmission electron microscopy. Many new interfaces between mixed planes are found, and their orientation relationships and structures are analyzed. The rotation speed increase with temperature and is fast above 200oC.

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The influence of pH (3.0, 5.0 and 7.0) and ionic strength (0, 50 and 100 mM NaCl) on the physicochemical and emulsifying properties of cruciferin-rich (CPI) and napin-rich (NPI) protein isolates were examined. Specifically, the surface characteristics (charge and hydrophobicity), solubility, interfacial tension and emulsifying activity (EAI) and stability (ESI) indices were measured. In the case of the cruciferin-rich protein isolate, surface charge was found to be negatively and positively charged at pHs above and below its isoelectric point (~4.6-4.8), respectively, ranging in potential from -33 mV at pH 8.0 to +33 mV at pH 3.0. In the presence of NaCl, the overall magnitude of charge became reduced at all pHs. In contrast, hydrophobicity, solubility and the ability for CPI to reduce interfacial tension all were found to be dependent upon both pH and NaCl concentration. Solubility was found to be lowest at pH 5.0 (~11%) and 7.0 (16%) for CPI without salt, but was significantly improved with the addition of NaCl (>80%). Interfacial tension was found to be lowest (10-11 mN/m) for pH 5.0 – 0 mM NaCl and pH 7.0 – 50/100 mM NaCl. Overall, the presence of salt reduced EAI with increasing levels of NaCl at pH 5.0 and 7.0, but not at pH 3.0. In contrast, ESI became reduced with the addition of NaCl (regardless of the concentration) from ~15.7 min at 0 mM NaCl to ~12 min with 50/100 mM NaCl, from ~14.7 min at 0 mM NaCl to ~11.5 min with 50/100 mM NaCl and from 15.1 min at 0 mM NaCl to ~11.7 min with 50/100 mM NaCl for pH 3.0, 5.0 and 7.0, respectively. ESI also was found to be unaffected by pH. In the case of a napin-rich protein isolate, surface charge for the NPI in the absence of NaCl ranged between ~ +10 mV to ~ -5 mV depending on the pH, becoming electrically neutral at pH 6.6. The addition of NaCl acted to reduce the surface charge on the NPI and caused a shift in its isoelectric point to pH 3.5 and 3.9 for the 50 and 100 mM NaCl levels, respectively. Overall, surface hydrophobicity for the NPI was reduced as the pH increased, whereas as NaCl levels were raised the hydrophobicity declined. In contrast, NPI solubility was found to be high (~93-100%) regardless of the solvent conditions. The ability of NPI to reduce interfacial tension was enhanced at higher pHs, however the effect of NaCl was pH dependent. Overall, EAI values were similar in magnitude at pH 3.0 and 5.0, and lower at pH 7.0. The effect of NaCl on EAI was similar at pH 3.0 and 7.0, where EAI at the 0 mM and 100 mM NaCl levels were similar in magnitude, but increased significantly at 50 mM NaCl. However, the EAI values at pH 5.0 were reduced as the level of NaCl increased. Overall, the stability of NPI-stabilized emulsions degraded rapidly and the addition of salt induced faster emulsion instability. In summary, CPI and NPI were very different in terms of their physicochemical properties. However, the emulsifying properties were similar in magnitude indicating that they had similar emulsifying potential under the solvent conditions examined.

This research work is aimed at understanding the electronic properties of Bi(110) nanostructures. This study chiefly uses Scanning Tunneling Microscopy (STM), Scanning Tunneling Spectroscopy (STS) and Non Contact Atomic Force Microscope (NCAFM) to investigate the geometric and electronic structure of Bi(110) islands on highly oriented pyrolytic graphite (HOPG) substrate. STM measurements are the primary focus of the thesis which involves imaging the bismuth islands and study of its atomic structure. STM images of the Bi(110) islands reveal a ‘wedding cake’ profile of the bismuth islands that show paired layers on top of a base. I(V) (Current vs voltage) data was acquired via STS techniques and its first derivative was compared to DFT calculations. The comparison implied the presence of a dead wetting layer which was present only underneath the bismuth islands. We observed bilayer damped oscillations in the surface energy that were responsible for the stability of paired layers in Bi(110) islands. Interesting Moiré pattern arising out of misorientation between the substrate and the overlayer are also observed in STM images on some bismuth islands. Bright features pertaining to enhanced LDOS (local density of states) were observed on the perimeter of the bismuth islands and stripes in the STM images and STS dI/dV maps which appear at energies around the Fermi level. The bright features which we termed as ‘bright beaches (BB)’ are also observed on grain boundaries and defects that suggest that they are related to termination of the chain of bismuth atoms. The Bi(110) islands and stripes were observed to form preferred widths with a well defined periodicity. This peculiar phenomenon was attributed to a lateral quantum size effect (QSE) that results from a Fermi wave vector with appropriate shifts in Fermi energy. The widths of the islands prefer to adjust themselves at the nodes of this in-plane Fermi wavelength. NaCl deposited on a HOPG substrate forms cross shaped islands which were used as spacers to limit the interaction between the bismuth films and the underlying HOPG substrate. The NaCl islands are transparent to the flow of tunneling current and allow STS measurements. The LDOS of Bi/HOPG was very similar to the LDOS of Bi deposited on NaCl/HOPG which suggests that the wetting layer underneath the bismuth islands plays an important role in decoupling the film from the underlying substrate.