The EU has set up the target of cutting GHG emissions by at least 55% by 2030 and becoming climateneutral by 2050. Accordingly, the IMO has launched initiatives to reduce CO2 emissions per transportwork by at least 40% by 2030, however the CO2 emissions generated from the ferry operations arecontinuously increasing. Although the research focussing on carbon emission reduction technology isgrowing as well, the emission allocation, the prerequisite for emission measuring and reporting as wellas evaluating emission reduction effects, is still an area that hasn’t been explored in depth especiallyfor the ferry industry. This study explores and evaluates the way of allocating CO2 emissions betweenthe passenger and freight for Ro-Pax ferry. Firstly, the emission allocation methods from differentsectors and modes of transportation have been reviewed, revised and developed into the allocationmethods suitable for Ro-Pax transport. Afterwards, the case study of ferry companies with part or all ofthe routes in the Baltic Sea has been carried out to compare and evaluate the performance of differentemission allocation methods. The study suggests that the weight allocation method has the tendencyto assign large amounts of carbon emissions to the freight, while the passenger accounts for moreemissions when applying area, volume and alternative production methods. Furthermore, the practiceshows that foot passengers could contribute to CO2 emission reduction by choosing ferry travel insteadof the airplane, and the car passengers could generate less CO2 emission by sharing the car withothers. The study provides valuable insights for decision makers, standard setters and ferry companies,and could be the solid groundwork for further research on carbon emission allocation for other transportmodes or deeper exploration of a specific allocation method. / EU har satt upp målet att begränsa ökningen av växthusgasutsläpp till 2030 och IMO har lanseratinitiativ för att leda minskningen av växthusgasutsläpp, men de växthusgasutsläpp som genereras frånfärjetrafiken ökar kontinuerligt. Även om forskningen som fokuserar på teknik och åtgärder för attminska utsläppen av växthusgaser också växer, är utsläppsallokering, grunden för utsläppsminskning,fortfarande ett område som inte har utforskats på djupet, särskilt inte för färjeindustrin. I denna studieundersöks en lämplig metod för att fördela växthusgasutsläpp mellan passagerare och gods för Ro-Pax-färjor. För det första har utsläppsallokeringsmetoder från olika sektorer och transportsätt granskats,reviderats och utvecklats till allokeringsmetoder som är lämpliga för Ro-Pax-transporter. Därefter haren fallstudie av färjerederier med en del av eller alla rutter i Östersjön genomförts för att jämföra ochutvärdera prestandan hos olika utsläppsallokeringsmetoder. Studien visar att viktfördelningsmetodenhar en tendens att tilldela stora mängder koldioxidutsläpp till frakten, medan passagerarna står för merutsläpp när man tillämpar yta, volym och alternativa produktionsmetoder. Dessutom visar praxis attfotpassagerare kan bidra till minskade växthusgasutsläpp genom att välja färja istället för flygplan, ochbilpassagerare kan generera mindre växthusgasutsläpp genom att dela bilen med andra. Studien gervärdefulla insikter för beslutsfattare, standardsättare och färjerederier, och kan utgöra en solid grundför vidare forskning om fördelning av växthusgasutsläpp för andra transportsätt eller djupare utforskningav en specifik fördelningsmetod.

Yes / In order to improve the performance of the reverse osmosis (RO) desalination plant powered by photovoltaic (PV), two cooling systems were proposed in this study to cool the PV and preheating the RO feed water as well. In the cooling design (1), the cooling fluid flows in direct contact with the back surface of the PV through channels of half circular cross-sections. While in the design (2), it flows through channels of squar cross-sections fixed on the PV back surface. Two nano-fluids were also tested as cooling fluid: H2O/CuO and H2O/Al2O3, in addition to distilled water for the purpose of comparison. The effect of changing the weight concentration of the nano-fluid (0.05, 0.1, and 0.15%) on the PV performance was also investigated. The results showed that the PV integrated with the cooling design (1) achieves better performance compared to design (2) at all studied cooling fluids. The improvements in the electric efficiency of the PV integrated with design (1) reached 39.5, 34.8 and 27.3 % when CuO and Al2O3 nano-fluids and distilled water were used as cooling fluid, respectively, compared to the uncooled PV. Based on the obtained experimental results, the PV integrated with design (1) was selected to power the RO with H2O/CuO nano-fluid of weight concentration 0.15% and flow rate 0.15 kg/s being used as the coolant. The RO powered by the improved PV was tested at different salinities of brackish water when the preheating technique was implemented. The results showed that the proposed PV-RO desalination system produces 366 l/day when brackish water of salinity 3000 ppm was used.

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: Desalination, by means of reverse osmosis (RO), in combination with other processes, can produce potable water at high recoveries. Antiscalants are generally used to reduce scaling on equipment surfaces and to improve water recovery during RO by slowing down the precipitation kinetics of sparingly soluble salts in the RO feed, thereby allowing concentration levels in the RO brine at several times the solubility limit of these salts. In addition, a fraction of the concentrate may be recycled back to the feed of the RO-membrane to improve the overall recovery, but only after the super saturated salts in the concentrate have been precipitated. The inhibitory character of the antiscalants (which are rejected into the concentrate stream) complicates the removal of salt from the concentrate and therefore prohibits such recycling. The focus of this study is aimed at properly understanding some of the parameters that influence the functionality or effectiveness of antiscalants used in high sulphate waters, with the purpose to override the effect of the antiscalant in the concentrate stream and force precipitation of the super saturated salts in solution. A batch crystallization technique, which considers the precipitation of calcium sulphate dehydrate (gypsum) from a solution of changing super saturation, was used to perform precipitation tests 1) on synthetically prepared solutions, super saturated with gypsum and 2) industrial concentrate, rich in sulphate (produced by concentrating acid mine drainage (AMD) by means of a lab scale RO unit). During batch crystallization, the precipitation process was observed by means of monitoring the depletion of calcium, using a calcium selective electrode (ISE). Deductions concerning the kinetics of precipitation were made from observing two kinetic variables (response variables) e.g. the induction time and the growth rate (tC80 – inferential variable). Two antiscalants have been evaluated in this study: a phosphonate based antiscalant (HYDREX) and a polyacrylate antiscalant (BULAB), at concentrations of 4 mg/l and 12 mg/l. The objective was to chemically and physically manipulate the antiscalant effectiveness, override its effect and force precipitation of gypsum by means of changing parameters in the system, such as the temperature (15°C- 25°C), pH (4-10), ferric chloride concentration (2-10 mg/l) or seeding the solution with gypsum seed at a concentration of 0-2000 mg/l. In addition, lime and a combination of gypsum and lime were also used for seeding at concentrations of 2000 mg/l. The induction time, prior to precipitation, was found to be most strongly affected by the change in seed concentration and pH at a given antiscalant concentration. Seed at a concentration of 2000 mg/l was sufficient in most cases to immediately override the effect of HYDREX and BULAB (at 4-12 mg/l) and produce ~ 0 minutes induction time. A pH of 10 increased the adsorption capacity of HYDREX and BULAB, leading to longer induction times (exceeding 24 hours in some cases). At a pH of 4 the adsorption capacity was very low for both HYDREX and BULAB (lower) leading to shorter induction times (zero to 100 minutes). It was especially in the ‘no-seed’ cases that the effect of pH on the induction time was prominent. The rate of precipitation (crystal growth rate) was increased at a temperature of 25°C, compared to 15°C (the rate increased two fold for an increase in 10°C). The addition of lime-seed, instead of gypsum, (at 2000 mg/l) produced growth rates, two times higher compared to when gypsum was used at the same conditions. In Addition, seeding with lime produced induction times (150 minutes for HYDREX and 50 minutes for BULAB) prior to precipitation, compared to zero induction time when gypsum was used at the same conditions. It was proven that an induction time could be eliminated by adding a combination of gypsum and lime both at a concentration of 2000 mg/l. with the added benefit of the higher growth rate. An increase in the calcium concentration increased the crystal growth rate in the presence of HYDREX. The presence of a high pH, however caused the effect of calcium on the growth (in the presence of BULAB) to be overshadowed. At a higher pH the growth rate of gypsum slowed down as a result of the increase in adsorption capacity of the polymer onto the crystal surface. The interaction of the antiscalant with FeCl3 seemed to be important with regard to crystal growth. Higher ferric concentrations (10 mg/l) were sufficient to limit the inhibitory effect of 12 mg/l antiscalant (HYDREX and BULAB) on the crystal growth rate. Conversely, low ferric concentration resulted in slower growth rates in the presence of an antiscalant. The best conditions (within the scope of the current study), sufficient 1) to override the inhibitory effect of antiscalants (HYDREX and BULAB) and 2) to produce rapid precipitation of gypsum, lie in the use of seeding with gypsum and lime (2000 mg/l), adding ferric chloride (10 mg/l), lowering the pH to 4 or lower (which can only be obtained when lime is not added) and setting the solution temperature to a moderate value of 25°C or higher. These ‘best’ conditions were subsequently applied to a concentrate, produced from concentrating AMD in a RO unit, and proved to be even more successful in overriding the effect of HYDREX and BULAB than in synthetic aqueous solutions. The induction times of precipitation of AMD in all cases were ~ 0 minutes, whereas the growth rate increased threefold compared to the synthetic tests. The presence of additional foreign precipitates of aluminum, calcium and magnesium as well as an increased [SO4ª-] x [Caª+] product of 3.73 (AMD concentrate) vs. 3.46 (synthetic solutions) is thought to be responsible for the increase in precipitation kinetics when only gypsum seed was used. The addition of lime caused an increase in the precipitation potential of the brine by increasing the calcium concentration. Although the addition of lime caused an increase in the pH to 12.3 (at which point the antiscalant was most effective), the increase in pH is likely to cause an increase in the natural carbonate in the water, which would stimulate CaCO3 precipitation. The CaCO3 precipitate would be responsible for the adsorption of antiscalants, reducing their efficiency. / AFRIKAANSE OPSOMMING: Ontsouting by wyse van tru-osmose (TO), in samewerking met ander prosesse, kan help om drinkwater te lewer teen verhoogte herwinning. Tipies word antiskaalmiddels gebruik om bevuiling op die oppervlak van toerusting te verminder en terselfdetyd herwinning te verhoog deurdat dit die presipitasiekinetika van superversadigde soute in die TO voerwater vertraag. Dit lei daartoe dat water (superversadig met soute) deur die membraansisteem kan beweeg, sonder om bevuiling te veroorsaak. ‘n Breukdeel van die konsentraat kan herwin word na die TO voer om sodoende die algehele waterherwinning te verhoog. Dit kan egter eers gebeur nadat die soute in die konsentraat neergeslaan en verwyder is. Die inhirente ‘vertragingskarakter’ van antiskaalmiddels (wat ook in die konsentraat stroom beland) kompliseer die verwydering van sout vanuit die konsentraat en verhoed so herwinning. Die fokus van hierdie studie is daarop gemik om die parameters wat die funksionaliteit of effektiwiteit van antiskaalmiddels (wat in sulfaatryke waters gebruik word), beter te verstaan. Die doel is daarop gemik om die betrokke antiskaalmiddel se effek te kanselleer asook presipitasie van die superversadigde soute in oplossing aan te help. ‘n Lot (‘batch’) kristallisasietegniek wat die presipitasie van kalsiumsulfaatdehidraat (gips) beskou vanuit ‘n oplossing waar die konsentrasie verander soos presipitasie plaasvind, is gebruik om presipitasietoetse uit te voer 1) op oplossings wat sinteties versadig is met gips en 2) op sulfaatryke AMD (gekonsentreer met behulp van ‘n laboratoriumskaal TO eenheid). Die presipitasie proses is in elke geval waargeneem, deur die vermindering van die kalsium konsentrasie in die oplossing dop te hou, met die gebruik van ‘n kalsiumselektiewe elektrode. Afleidings rakende die kinetika van presipitasie is gemaak deur twee responsveranderlikes dop te hou: die induksietyd en die kristal groeitempo (tC80). Twee antiskaalmiddels by ‘n konsentrasies van 4 dpm (deetjies per miljoen) en 12 dpm is evalueer: ‘n fosfonaat (HYDREX) and poliakrilaat (BULAB). Die doel was om die antiskaalmiddel se werking chemies en fisies te manipuleer, hul werking teen te werk en presipitasie van gips te forseer. Die manipulasie het geskied deur die volgende parameters te verander: temperatuur (15°C-25°C), pH (4-10), FeCl3 (2-10 mg/l) of saad byvoeging (gips: 2000 mg/l). Kalsiumhidroksied (gebuste kalk) en ‘n kombinasie van gips en gebluste kalk is ook gebruik by konsentrasies van 2000 mg/l. Die induksietyd (by ‘n spesifieke antiskaalmiddel konsentrasie) is die sterkste beïnvloed deur ‘n verandering in saad konsentrasie en pH verandering. In die meeste gevalle was ‘n saad konsentrasie van 2000 mg/l voldoende om die induksie effek van beide HYDREX en BULAB te vernietig en nulminute induksietyd is verkry. ‘n pH van 10 het gelei tot die verhoging van die adsorpsiekapasiteit van HYDREX en BULAB wat gelei het tot langer induksietye (in sommige gevalle het dit 24 uur oorskry). By ‘n pH van 4 was die adsorpsie kapasiteit van beide antiskaalmiddels baie laag (laer vir BULAB) en induksie-tye is beperk tot 100 minute. Dit is veral wanneer geen saad toegevoeg is nie wat die effek van pH prominent was. Die tempo van presipitasie was verhoog by ‘n temperatuur van 25°C (2 keer hoër as by 15°C). Die byvoeging van gebluste kalk teen 2000 mg/l het ‘n kristal groeitempo, 2 keer hoër as in die teenwoordigheid van gips gelewer. Gebluste kalk saad byvoeging het egter gelei tot ‘n indukisetyd (150 minute vir HYDREX en 50 minute vir BULAB). Hierdie probleem is oorkom deur ‘n kombinasie van gips en gebluste kalk te gebuik teen ‘n konsentrasie van 2000 mg/l. Geen induksie tyd is waargeneem met die voordeel van ‘n hoër presipitasietempo (kristal groei). ‘n Verhoging van kalsium konsentrasie verhoog die kristal groei tempo in die teenwoordigheid van HYDREX. Nietemin, die invloed van pH oorskadu die invloed van kalsium op die groei tempo (in die teenwoordigheid van BULAB). By ‘n hoë pH word die kristal groei tempo vertraag as gevolg van die verhoging van die adsorpsiekapasiteit van die antiskaalmiddel. Die interaksie van FeCl3 met die antiskaalmiddel blyk van belang te wees. By hoë FeCl3 konsentrasies (10 dpm), is die werking van beide HYDREX en BULAB (12 dpm) beperk. Die ‘beste’ kondisies (verkry binne die konteks van hierdie studie), 1) om die vertragingseffek van HYDREX en BULAB teen te werk en 2) spoedige presipitasie van gips te bewerk, lê in die gebruik van saad (gips en gebluste kalk teen 2000 mg/l), die byvoeging van FeCl3 (10 mg/l), ‘n lae pH (4 of laer, wat natuurlik net tersprake is wanneer slegs gips as saad gebruik word aangesien geluste kalk die pH sal lig) asook ‘n relatiewe hoë temperatuur (25°C). Hierdie ‘beste’ kondisies is toegepas in AMD konsentraat om die effek van HYDREX en BULAB te vernietg en gips te presipiteer en die gevolg was dat dit selfs meer suksesvol was as in sintetiese oplossings. In elke geval is die induksietyd na nul minute toe verminder, terwyl die kristal groei tempo 3 maal verhoog het in vergelyking met die sintetiese toetse. Die teenwoordigheid van onsuiwerhede insluitende aluminium, kalsium, magnesium sowel as ‘n verhoging in die [SO4ª-]x[Caª+] produk (3.73 teenoor 3.46 vir sintetiese toetse), blyk verantwoordelik te wees vir die versnelling van die kinetika. Met die byvoeging van gebluste kalk is dit waarskynlik dat die verhoging van die pH (12.3) lei tot die verhoging van natuurlike karbonate in die water wat weer CaCO3 stimlueer. Die teenwoordigheid van CaCO3 kan verantwoordelik gehou word vir bykomende nukleasie en groei, sowel as die deaktivering van antiskaal effektiwiteit.

Orientador: Gilda Carneiro Ferreira / Banca: Ene Glória da Silveira / Banca: Job Jesus Batista / Banca: José Ricardo Sturaro / Banca: Wanderley Rodrigues Bastos / Resumo: Neste estudo, através de uso de ferramentas geoestatísticas, foi estabelecido e analisado o padrão de dispersão do mercúrio total em solos da sub-bacia do rio Corumbiara, estado de Rondônia, nas profundidades de 0 a 10 cm e 10 a 30 cm, considerando-se ainda a geologia e a geomorfologia da área na sua interpretação. Os resultados obtidos através de espectrofotometria de absorção atômica, indicam um valor médio de mercúrio para os solos da sub-bacia de 74,54 μg.kg-1, sendo 72,91 μg.kg-1 na profundidade de 0 a 10 cm e 76,18 μg.kg-1 na profundidade de 10 a 30 cm, em geral inferiores aos de outras regiões da Amazônia. O padrão de dispersão em ambas as profundidades mostra-se semelhante. Os Neossolos Quartzarênicos apresentaram as maiores concentrações médias de mercúrio total, da ordem de 112,61 μg.kg-1, seguido pelos Latossolos com 100,92 μg.kg-1, Argissolos com 88,60 μg.kg-1, Neossolos Flúvicos com 63,09 μg.kg-1 e Gleissolos com 32,96 μg.kg-1. A análise do padrão de dispersão permitiu identificar que o rio Corumbiara tem suas nascentes e a de seus principais tributários posicionadas na parte alta da sub-bacia, onde se encontram os solos com as maiores concentrações relativas de mercúrio total, em unidades geomorfológicas de natureza erosiva e sob impacto da ocupação antrópica. O médio curso e foz do rio Corumbiara se localizam na parte baixa da sub-bacia, dominada por unidade geomorfológica de natureza deposicional, com solos com as menores concentrações relativas de mercúrio. O aparente paradoxo entre a elevada concentração relativa de mercúrio total nos solos erodidos pelo rio Corumbiara e as concentrações relativamente baixas nos solos da área de deposição, pode ser explicado pela natureza pantanosa do ambiente de deposição, o qual favorece a metilação e a remoção do mercúrio destes sedimentos. / Abstract: Using geostatistical tools, this study analysed and identified the dispersal pattern of total mercury in soils from the Corumbiara River sub-basin, Rondônia. The samples were taken from depths of 0 to 10 cm and 10 to 30 cm. This interpretation took into consideration the geology and geomorphology of the region. The results obtained through Atomic Absorption Spectrofotometry (AAS) indicate an average value of mercury in the sub-basin soils of 74.54 μg.kg-1. The shallower sample horizon averaged 72.91 μg.kg-1 while the deeper averaged 76.18 μg.kg-1. These values are generally lower than those in other regions of the Amazon. The dispersion patterns are similar for both sample sets. The Arenosols had the highest average concentrations of total mercury, of the order of 112,61 μg.kg-1, followed by Oxisols with 100,92 μg.kg-1, Argisols with 88,60 μg.kg-1, Fluvisols with 63,09 μg.kg-1 and Gleysols with 32,96 μg.kg-1. Analysis of the dispersion patterns identified that the highest concentrations of mercury are found in soils located in the upper sub-basin, which are dominated by erosive geomorphological units and under impact of human occupation. The average course and mouth of the Corumbiara River is located in the lower part of the subbasin. This is dominated by geomorphological units of a depositional nature and with soils with lower concentrations of mercury. The apparent paradox between the high concentration of total mercury in sediments eroded by the Corumbiara River and the relatively low concentrations in sediments in the deposition area can be explained by the nature of the wetland environment of deposition. This wetland environment promotes the methylation of mercury and the removal of these sediments. / Doutor

Intrusões de afinidade kimberlítica (E1 e Es1) ocorrem associadas a mica xistos da Sequência Metavulcano-sedimentar Nova Brasilândia, a sudeste do estado de Rondônia. Os corpos foram estudados por meio de geofísica e as amostras analisadas do ponto de vista mineralógico, petrográfico e geoquímico. Os dados obtidos possibilitam classificar essas ocorrências, respectivamente, como brecha kimberlítica da fácies diatrema e brecha kimberlítica da fácies cratera. Mineralogicamente, as rochas contêm olivina (pseudomorfos), piroxênio, granada, ilmenita e mica como principais constituintes; perovskita acha-se restrita à intrusão E1 enquanto que anfibólio aparece como produto de alteração do piroxênio em Es1. Além disso, elas são portadoras de xenólitos de natureza diversa (eclogíticos e peridotíticos em E1; eclogíticos em Es1). Ainda que afetadas por processos de contaminação e de alteração, como sugerido pelos valores dos índices de contaminação e de ilmenita, as amostras analisadas se distinguem por suas características químicas principais, como natureza ultrabásica, riqueza em MgO (\'mg POT.#\' = 0,81-0,86) e baixa concentração em álcalis, notadamente em \'Na IND.2\'O. O padrão de distribuição dos elementos hidromagmatófilos é muito similar para as duas intrusões, com pronunciadas anomalias positivas em Ba e Nb e negativas em K e Nd. Já as terras raras exibem comportamento também concordante, linear, e com visível fracionamento das leves em relação às pesadas. Isotopicamente, os valores para as razões iniciais de Sr são muito diferentes para as duas intrusões, com a E1 se caracterizando por mostrar valores mais baixos para a razão \'ANTPOT.87 Sr\'/\'ANTPOT.86 Sr\' (0,705133-0,705240). Ao contrário, a Es1 tem valores consideravelmente mais altos (0,712479-0,712848), a indicar a ação de processos de contaminação. Determinações Sm/Nd em concentrados de minerais (granada e piroxênio) e em rocha total levaram à elaboração de isócronas indicando uma idade de 293 \'+ OU -\'18 Ma para E1, e de 317 \'+ OU -\' 45 Ma para Es1, assim como a possível correlação dessas intrusões com as ocorrências kimberlíticas do Grupo Mitu, no Peru. À vista das informações obtidas, e com base na definição de Mitchell (1986), é também aqui sugerido que as intrusões investigadas, ao lado de outras mais reconhecidas na área, sejam partes integrantes de um novo campo kimberlítico, o de Colorado do Oeste, no estado de Rondônia, mais velho que o não muito distante campo de Paranatinga, MT, com idade em torno de 85 Ma. / Kimberlitic affinity intrusions (E1 and Es1) are found associated with mica schists belonging to the Nova Brasilândia Metavolcano-sedimentary Sequence, at southeastern Rondônia state. They have been investigated by geophysics methods and the rock samples studied from the mineralogical, petrographic and geochemical point of view. The available data allow to classify the above intrusions as a kimberlitic breccia of diatreme facies and a kimberlitic breccia of cratera facies, respectively. Mineralogically, the rocks contain olivine (pseudomorphs), pyroxene, garnet, ilmenite and mica as main constituents; perovskite is only found in the E1 intrusion, whereas amphibole is a typical alteration product from pyroxene in Es1. Furthermore, they carry xenoliths of different natures (eclogitic and peridotitic in E1; eclogitic in Es1). Although the rocks have been affected by contamination and alteration processes, as suggested by the values of contamination and ilmenite indexes, the analyzed samples can be distinguished by their main chemical characteristics, such as ultrabasics nature, MgO richness (\'mg POT.#\' = 0,81-0,86) and low alkalis content. The distribution pattern of the hydromagmatophile elements is very similar for the rocks of both instrusions, showing pronounced positive anomalies of Ba and Nd and negative ones of K and Nd. The rare earth elements behavior is also identical for the both occurrences; it is linear and displays marked fractionation of light elements in to the heavy ones. Isotopically, Sr initial ratio values are quite different for both instrusions: E1 shows low values for the \'ANTPOT.87 Sr\'/\'ANTPOT.86 Sr\' (0,705133-0,705240); on contrary, they are higher for Es1 (0.712479-0.712848), indicating that these rocks have been subjected to contamination processes. Sm/Nd determinations on mineral concentrates (garnet and pyroxene) and whole rock samples provided isochron ages of 293 \'+ OU -\' 18 and 317 \'+ OU -\' 45 Ma for the E1 and Es1 intrusions, respectively, allowing their correlation with kimberlitic occurrences of the Mitu Group in Peru. On the basis of the available data and accord to Mitchell (1986), it is here suggested that the investigated intrusions, in addition to some other bodies already recognized in the area, may represented a new kimberlitic field, the Colorado do Oeste one, older than the Paranatinga field not so far away and showing an age around 85 Ma.

Made available in DSpace on 2014-06-11T19:30:59Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-12-13Bitstream added on 2014-06-13T19:40:38Z : No. of bitstreams: 1 000741383.pdf: 4661010 bytes, checksum: cea0b65f99a47eb077f2cdaa817049d0 (MD5) / Neste trabalho, buscou-se identificar proteínas responsáveis pelo transporte de mercúrio em amostras de leite materno coletadas da população ribeirinha do rio Madeira. Para isso, inicialmente, foi obtido o proteoma das amostras de leite por eletroforese bidimensional (2D PAGE) após precipitação das proteínas em meio acetônico. Nos spots proteicos obtidos no processo de fracionamento das proteínas, nas amostras de cabelo e de leite das lactantes foram feitas determinações de mercúrio por espectrometria de absorção atômica de vapor frio (CVAAS) e espectrofotometria de fluorescência atômica de vapor frio (CVAFS). As determinações por CVAFS indicaram a presença de mercúrio em dois spots proteicos (spot 1, spot 2), os quais foram caracterizados por espectrometria de massas em sequência com ionização por electrospray (ESI MS MS) e por meio de busca no banco de dados Uniprot. A análise por ESI MS MS identificaram o spot 1 como sendo a proteína b caseína (pI = 5,52 e MM = 26,01 kDa) e o spot 2 como sendo a proteína Lisozima C (pI = 9,30 e MM = 16,50 kDa). Os resultados obtidos nas determinações de mercúrio nos spots 1 e 2 permitiram estabelecer relação estequiométrica de um átomo de mercúrio por quatro moléculas de b caseína e de um átomo de mercúrio por molécula de lisozima C. Com base nos dados obtidos é possível inferir, no caso da b caseína, que a ligação do mercúrio não é específica, tratando-se de uma proteína metal-binding, não configurando o mercúrio como um cofator metálico, o que não desqualifica a b caseína como possível biomarcadora de mercúrio. Em relação a Lisozima C, a presença de metionina (base mole) na sequência peptídica pode estabelecer ligações com íons metálicos com características de ácido mole, como o Hg2+, configurando uma ligação mais estável desse íon com grupos sulfidrilas da Lisozima C e, caracterizando essa proteína como possível biomarcador de... / In this study, we aimed to identify proteins responsible for the mercury transport in breast milk samples collected from the lactating of Madeira River region, Rondônia - Brazil. For this, we first obtained the proteome of milk samples by two-dimensional electrophoresis (2D PAGE) after proteins precipitation in acetone medium. In the protein spots obtained from proteins fractionation, in hair and milk samples of lactating mercury determinations were carried out by cold vapor atomic absorption spectrometry (CVAAS) and by cold vapor atomic fluorescence spectrophotometry (CVAFS). CVAFS determinations indicated the presence of mercury in two protein spots (spot 1, spot 2), which were characterized by electrospray ionization tandem mass spectrometry (ESI MS MS) and by searching in the Uniprot database. The ESI MS MS analysis identified the spot 1 as the b casein protein (pI = 5.52 and MM = 26.01 kDa) and spot 2 as the lysozyme C protein (pI = 9.30 and MW = 16, 50 kDa). The results obtained in the mercury determinations in the spots 1 and 2 allowed to establish a stoichiometric ratio of one mercury atom per four molecules of b casein and one mercury atom per of lysozyme C molecule. Based on the obtained data it can be inferred, in the case of b casein, that mercury binding is not specific, treating yourself of a metal-binding protein, not configuring the mercury as a metal cofactor what does not disqualify the b casein as a possible mercury biomarker. Regarding lysozyme C, the presence of methionine (soft base) in the peptide sequence can establish links with metal ions with features of soft acid, such as Hg2+, configuring a stable binding of this metal ion with sulfhydryl groups of lysozyme C and, characterizing this protein as a possible mercury biomarker

Orientador: Pedro de Magalhães Padilha / Banca: Gustavo Rocha de Castro / Banca: Paulo dos Santos Roldan / Banca: Amauri Antonio Menegário / Banca: Lincoln Carlos Silva de Oliveira / Resumo: Neste trabalho, buscou-se identificar proteínas responsáveis pelo transporte de mercúrio em amostras de leite materno coletadas da população ribeirinha do rio Madeira. Para isso, inicialmente, foi obtido o proteoma das amostras de leite por eletroforese bidimensional (2D PAGE) após precipitação das proteínas em meio acetônico. Nos spots proteicos obtidos no processo de fracionamento das proteínas, nas amostras de cabelo e de leite das lactantes foram feitas determinações de mercúrio por espectrometria de absorção atômica de vapor frio (CVAAS) e espectrofotometria de fluorescência atômica de vapor frio (CVAFS). As determinações por CVAFS indicaram a presença de mercúrio em dois spots proteicos (spot 1, spot 2), os quais foram caracterizados por espectrometria de massas em sequência com ionização por electrospray (ESI MS MS) e por meio de busca no banco de dados Uniprot. A análise por ESI MS MS identificaram o spot 1 como sendo a proteína b caseína (pI = 5,52 e MM = 26,01 kDa) e o spot 2 como sendo a proteína Lisozima C (pI = 9,30 e MM = 16,50 kDa). Os resultados obtidos nas determinações de mercúrio nos spots 1 e 2 permitiram estabelecer relação estequiométrica de um átomo de mercúrio por quatro moléculas de b caseína e de um átomo de mercúrio por molécula de lisozima C. Com base nos dados obtidos é possível inferir, no caso da b caseína, que a ligação do mercúrio não é específica, tratando-se de uma proteína metal-binding, não configurando o mercúrio como um cofator metálico, o que não desqualifica a b caseína como possível biomarcadora de mercúrio. Em relação a Lisozima C, a presença de metionina (base mole) na sequência peptídica pode estabelecer ligações com íons metálicos com características de ácido mole, como o Hg2+, configurando uma ligação mais estável desse íon com grupos sulfidrilas da Lisozima C e, caracterizando essa proteína como possível biomarcador de ... / Abstract: In this study, we aimed to identify proteins responsible for the mercury transport in breast milk samples collected from the lactating of Madeira River region, Rondônia - Brazil. For this, we first obtained the proteome of milk samples by two-dimensional electrophoresis (2D PAGE) after proteins precipitation in acetone medium. In the protein spots obtained from proteins fractionation, in hair and milk samples of lactating mercury determinations were carried out by cold vapor atomic absorption spectrometry (CVAAS) and by cold vapor atomic fluorescence spectrophotometry (CVAFS). CVAFS determinations indicated the presence of mercury in two protein spots (spot 1, spot 2), which were characterized by electrospray ionization tandem mass spectrometry (ESI MS MS) and by searching in the Uniprot database. The ESI MS MS analysis identified the spot 1 as the b casein protein (pI = 5.52 and MM = 26.01 kDa) and spot 2 as the lysozyme C protein (pI = 9.30 and MW = 16, 50 kDa). The results obtained in the mercury determinations in the spots 1 and 2 allowed to establish a stoichiometric ratio of one mercury atom per four molecules of b casein and one mercury atom per of lysozyme C molecule. Based on the obtained data it can be inferred, in the case of b casein, that mercury binding is not specific, treating yourself of a metal-binding protein, not configuring the mercury as a metal cofactor what does not disqualify the b casein as a possible mercury biomarker. Regarding lysozyme C, the presence of methionine (soft base) in the peptide sequence can establish links with metal ions with features of soft acid, such as Hg2+, configuring a stable binding of this metal ion with sulfhydryl groups of lysozyme C and, characterizing this protein as a possible mercury biomarker / Doutor

This dissertation investigates the importance of diffusional and convective fluxes for salts in reverse osmosis (RO) and nanofiltration (NF) membranes. Moreover, the physical and thermodynamic factors controlling the salt permeability are analyzed. The study utilizes direct osmosis (DO) experiments and RO experiments, the later using both flat sheet and spiral wound membrane configurations. The salts considered are chlorides and acetates of alkali metals and alkaline earth metals. The equation governing the salt transport in DO experiments is derived and a phenomenon inverse to concentration polarization in RO is observed. The salt permeability in DO is equal to the salt permeability calculated for the valid cases of the used RO models. DO is suggested as an alternative method in characterizing the salt transport in membranes. The method can be more advantageous than RO due to the lower costs and simplicity of the apparatus. The models used to calculate the salt transport parameters in RO experiments are Spiegler-Kedem model, which considers both diffusion and convection of salt, and Kimura-Sourirajan model, which considers only diffusion of salt. It is found that diffusion is the dominant mechanism of transport in both RO and NF membranes. The percentage of the salt diffusional flux of the total flux is highest for seawater membranes and it is approximately equal for brackish water and nanofiltration membranes. The salt diffusive flux contribute more to the total flux for the 1:2 salts than for 1:1 salts. The two RO models are found equivalent in determining the salt permeability for only the seawater membranes. The Kimura-Sourirajan model overestimates the salt permeability coefficient for salts with rejection coefficient lower than 86%. The permeation rates for studied salts follow the lyotropic series regardless the membrane type (RO or NF), the membrane configuration (flat sheet or spiral wound), the process (DO or RO), or the models used for the calculations. This order of salt permeability is explained by the hydration of the cations, which is quantified by the enthalpy and entropy of hydration. The relative free energy theory can also be used to predict the salt permeability in a membrane based on preliminary data.

Les prolinols peuvent être tranformés en 3-hydroxypipéridines par une réaction stéréospécifique d'agrandissement de cycle initiée par l'anhydride trifluoroacétique. Ce réarrangement peut être expliqué par la formation d'un intermédiaire aziridinium. Cette réaction a été mise à profit dans la synthèse formelle du composé Ro 67-8867 qui a été réalisée à partir de la (R)-(+)-α-méthylbenzylamine en utilisant comme étape-clé une réaction de cyclisation d'énolate de zinc et la réaction d'agrandissement de cycle. Deux synthèses formelles de la (-)-swainsonine ont également été développées à partir de la L-proline en utilisant une addition diastéréosélective d'organomagnésien sur un prolinal, une réaction de métathèse cyclisante, une dihydroxylation diastéréosélective et un agrandissement de cycle de prolinols. Par analogie avec le réarrangement précédent, l'expansion de cycle de prolinols en présence de DAST a été étudiée: dans le cas général, un mélange de 3-fluoropipéridines et de fluorométhylpyrrolidines est obtenu. Dans certains cas, un réarrangement sélectif a pu être observé. Des cas de réarrangements très sélectifs ont été observés lorsque les prolinols sont substitués par un groupement encombrant soit en C4 (éther silylé), soit en C2 (centre quaternaire) soit sur l'azote (Tr).

Anesthesia-induced spatial learning impairments in aged rats model postoperative cognitive dysfunction (POCD) in the elderly surgical population. Mechanisms underlying both normal age-related cognitive decline and anesthesia-induced spatial learning deficits in aged rats were investigated. With respect to the involvement of inflammasome activation and age-related cognitive decline, I hypothesized that the aged hippocampus exhibits an elevated activation of inflammasome components contributing to elevated levels of IL-1β in the aged brain. Age-related cognitive decline was identified in a subpopulation of male Fischer 344 rats. Activation of the NLRP1 inflammasome was elevated in the aged brain, contributing to spatial learning deficits in aged rats. With respect to anesthesia-induced spatial learning impairment in aged rats, I hypothesized that an increase in NR2B subunit in the hippocampus and cortex during and following isoflurane anesthesia exposure resulting in spatial learning impairment in aged rats via disruption of downstream signaling molecule, extracellular-signal regulated protein kinase (ERK). Anesthesia exposure resulted in chronic spatial learning impairment in aged rats that were previously unimpaired in spatial learning tasks. Additionally, anesthesia induced elevated levels of N-methyl-D-aspartate (NMDA) receptor NR2B subunit protein expression in aged. It was concluded that various factors contribute to age-related spatial impairment including: NLRP1 inflammasome activation and NMDA receptor NR2B protein expression elevation. It was also concluded that anesthesia exposure exacerbates the elevation in NR2B protein expression in the aged brain, with subsequent disruption of ERK activation leading to chronic spatial learning deficits in aged rats. In the final chapter, a relationship for the interplay between inflammation and NMDA receptor function in the aged brain is discussed. In addition, a novel mechanism for anesthesia-induced cognitive deficits is presented. Therapeutic treatments for cognitive decline and anesthesia-induced cognitive deficits are explored. Finally, future lines of research are proposed.