Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A intrusão alcalina do Marapicu é uma intrusão localizada no maciço Marapicu-Gericinó-Mendanha situado na região metropolitana do Rio de Janeiro. Este maciço é formado por dois corpos alcalinos: Marapicu e Mendanha que fazem parte do lineamento magmático Poços de Caldas-Cabo Frio. Este lineamento inclui dezenas de corpos ígneos alcalinos de idade Cretácea com uma direção preferencial WNW-ESE. Os litotipos mais abundantes do Maciço Marapicu são representados por nefelina sienitos e sienitos de caráter plutônico, além de, fonolitos caracterizados por intrusões rasas geralmente em forma de diques. Além desses litotipos foram amostradas duas rochas com características químicas de magma parental (lamprófiro e fonolito tefrítico), porém, essas duas amostras não apresentam relação genética com as demais. Também foi amostrado um nefelina sienito que possui sodalita azul como feldspatóide, sendo assim, chamado de nefelina sodalita sienito. Entre os fonolitos coletados para esse trabalho, uma amostra apresenta granada melanita em sua assembleia mineralógica, e esta foi então denominada melanita fonolito. Quimicamente as rochas do Marapicu formam uma série alcalina predominantemente insaturada em sílica, miaskítica e metaluminosa. Dentro desta série se observam duas suítes sendo uma potássica (predominante) e outra sódica. A evolução química do corpo se deu por processo de cristalização fracionada com ou sem assimilação de crosta continental provavelmente dentro de uma fonte mantélica enriquecida. Duas idades de cristalização foram obtidas para o Maciço do Marapicu sendo uma idade 40Ar/39Ar de 80,46 0,58 Ma em hornblenda, e uma idade U-Pb em zircão bastante concordante de 78,0 2,1 Ma. Os dados apresentados aqui em conjunto com dados da literatura apontam para dois modelos geodinâmicos de geração dos corpos alcalinos do sudeste brasileiro, um considera a existência de uma pluma mantélica gerada na astenosfera, o outro tem por base a hipótese de flexura crustal e considera que a carga de sedimentos depositados na plataforma continental exerceria esforços que provocariam fraturas profundas permitindo a ascenção desses magmas. O presente trabalho vem para contribuir no entendimento do alojamento dos corpos alcalinos do sudeste brasileiro através do estudo especifico do Maciço Marapicu em conjunto com dados da literatura / The Marapicu Alkaline intrusion is an intrusion into the Marapicu-Gericinó-Mendanha massif. This massif is formed by two alkaline bodies: Marapicu and Mendanha both making part of the Cretaceous Poços de Caldas-Cabo Frio magmatic lineament located in the Southeastern region of Brazil. This lineament includes tens of Cretaceous alkaline bodies and has a WNW-ESE trend. The most abundant rocks in the massif are plutonic nepheline syenites and syenites and also phonolitic rocks characterized for shallow intrusions as a dike. Besides these rocks were sampling two rocks with chemistry characteristcs of parental magma (basanite tefrite and phonolitic tefrite), nevertheless, this samples have not relationship with the others. There is also a nepheline syenite having blue sodalite as a feldspatoid called nepheline sodalite syenite. Between sampled fonolites to this work there is only sample including melanita garnet in his mineralogy assemblage and them called melanita fonolite. Chemically the Marapicu massif rocks forming an alkaline series SiO2-undersatured predominantly miaskitic and metaluminous. This series presents both potassic and sodic suites being the first one in greater content. Geochemistry data shows that evolution process involved fractional crystallization with or without continental crust assimilation and also indicates that this alkaline magma was generating into the enriched mantle source. Two crystallization age were obtained for Marapicu: 40Ar/39Ar age in hornblende of 80.46 0.58 Ma and U-Pb age in zircon of 78.0 2.1 Ma. The presented data together with literature data pointing for two geodynamic models responsible by the generation of Brazilian alkaline bodies. The first one consider there is a mantellic plume from asthenosphere, the second is based on the hypotheses of crustal flexure and consider that sedimentary charge on the continental platform would make deep fails which the magma ascending. The present work came to contribute on understanding of Brazilian alkaline bodies emplacement through the specific study of Marapicu in conjunct with literature data

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Lamprófiros e diabásios alcalinos afloram no litoral dos estados de São Paulo e Rio de Janeiro e integram o Enxame de Diques da Serra do Mar (EDSM). Essas rochas ocorrem sob a forma de diques e intrudem o Orógeno Ribeira, de idade Neoproterozóica/Cambro-Ordoviciana, inserindo-se no contexto geodinâmico de abertura do Oceano Atlântico Sul durante o Cretáceo Superior. Essas intrusões são subverticais e orientam-se preferencialmente a NE-SW, seguindo a estruturação das rochas encaixantes. Os lamprófiros são classificados como monchiquitos e camptonitos e exibem, respectivamente, textura hipocristalina e holocristalina. Apresentam também textura panidiomórfica, fenocristais de clinopiroxênio e olivina, imersos em matriz formada essencialmente por esses mesmos minerais, além de biotita, kaersutita e minerais opacos. O camptonito apresenta ainda plagioclásio na matriz. Os diabásios alcalinos são hipocristalinos a holocristalinos, equigranulares a inequigranulares, com fenocristais de olivina e/ou clinopiroxênio e/ou plagioclásio, em uma matriz composta essencialmente por esses minerais. As rochas estudadas caracterizam séries alcalinas miaskíticas, com os lamprófiros sendo tanto sódicos, potássicos e ultrapotássicos e os diabásios alcalinos como predominantemente sódicos. Modelagens petrogenéticas envolvendo possíveis processos evolutivos mostram que é improvável que os lamprófiros sejam cogenéticos por processos evolutivos envolvendo tanto cristalização fracionada, com ou sem assimilação concomitante, quanto hibridização. O mesmo ocorre para os diabásios alcalinos. A discriminação de fontes mantélicas foi feita com base nos teores de elementos traços de amostras representativas de líquidos parentais e indica que esse magmatismo alcalino está relacionado a fontes lherzolíticas com fusão parcial na zona de estabilidade do espinélio, isto é, a poucas profundidades. Os dados litogeoquímicos e isotópicos do sistema Sr-Nd das rochas estudadas sugerem tanto o envolvimento de fontes férteis, associadas ao manto sublitosférico, quanto de fontes enriquecidas, relacionadas ao manto litosférico subcontinental. Modelagens de mistura binária revelam que a petrogênese dos lamprófiros e diabásios alcalinos envolveu uma grande participação de um componente fértil misturado com contribuições menores de um componente enriquecido. Idades TDM (760-557 Ma) obtidas sugerem remobilização do manto litosférico no Neoproterozóico, talvez relacionadas à subducção da Placa São Francisco preteritamente à colisão do Orógeno Ribeira. Altas razões CaO/Al2O3 para os líquidos lamprofíricos menos evoluídos, altos teores de Zr, correlações negativas Zr/Hf e Ti/Eu e associação com carbonatitos indicam condições metassomáticas de alto CO2/H2O. Em escala local, modelos geodinâmicos baseados na astenosfera não isotérmica parecem mais aplicáveis. No entanto, modelos geodinâmicos baseados na astenosfera isotérmica (com o envolvimento de plumas) parecem mais indicados num contexto regional, considerando-se outras províncias alcalinas contemporâneas e correlatas. / Alkaline lamprophyres and alkaline diabases of the Serra do Mar Dyke Swarm (SMDS) outcrop along the Southeastern Brazil. These dykes intrude rocks of the so-called Rio Negro Magmatic Arc within the Late Proterozoic-Ordovician Ribeira Orogen and are associated with the opening of South Atlantic Ocean during the Late Cretaceous. Typically, the intrusions are subvertical bearing a NE-SW preferential trend which follows the main lineaments in the area. The lamprophyres are classified as monchiquites and camptonites and show holocrystalline and hypocrystalline textures, respectively. They also have panidiomorphic texture and olivine and clinopyroxene phenocrysts within a matrix composed essentially by these same minerals, kaersutite and biotite. Camptonites still have plagioclase in the matrix. The alkaline diabases are holo- to hypocrystalline, equi- to inequigranular rocks with olivine and/or clinopyroxene and/or plagioclase phenocrysts in a matrix composed essentially by these minerals. These alkaline rocks have miaskitic compositions. Lamprophyres are sodic, potassic and ultrapotassic and alkaline diabases are predominantly sodic. Petrogenetic modeling indicates that lamprophyres are unlikely to be cogenetic by evolutionary processes involving either fractional crystallization, with or without concomitant assimilation, or hybridization. The same applies to the alkaline diabases. Modal-batch partial melting models using samples representing parental liquids indicate that these alkalines mafic rocks are related to lherzolitic sources and that partial melting occurred in the spinel stability field, pointing to a thin continental lithosphere in the region. Lithogeochemical and Sr-Nd isotopic data show that the petrogenesis of these alkaline rocks can be assigned to mixing of mantle sources. Binary mixing models and assimilation tests reveal that the petrogenesis of the lamprophyres and alkaline diabases involve a large amount of participation of a fertile component with small contribution of an enriched component. TDM model ages for the studied rocks suggest remobilization ages of the of the lithospheric mantle during the Neoproterozoic, possibly related to the subduction of the San Francisco plate prior to the collision of the Ribeira Orogen. The high CaO/Al2O3 ratios of less evolved lamprophyric melts, high Zr contents, Zr/Hf and Ti/Eu negative correlations and association with carbonatites point to high CO2/H2O conditions during metassomatism of the subcontinental lithospheric mantle. Geodynamic models based on the non-isothermal asthenospheric mantle seem to apply to the studied mafic alkaline magmatism on a local scale although the isothermal asthenospheric mantle model appears to conceal the petrogenesis of other coeval alkaline provinces in central and southeastern Brazil.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / Nesta dissertação foram estudas rochas máficas dos complexos alcalinos de Morro de São João, Rio Bonito, Tanguá, Gericinó-Mendanha, Morro Redondo, Itatiaia e Passa Quatro. Essas rochas ocorrem na forma de diques e/ou sills. As amostras coletadas foram classificadas como lamprófiros, fonolitos, gabros e diabásios alcalinos. A análise geoquímica permitiu identificar um trend fortemente insaturado e um trend moderadamente alcalino para os complexos estudados. O primeiro é caracterizado por foiditos e fonolitos como membros parentais e mais evoluídos, respectivamente, enquanto o segundo tem basaltos alcalinos como membros parentais e traquitos como os mais evoluídos. Todas as amostras plotam no campo da série alcalina, sendo majoritariamente miaskíticas, sódicas ou potássicas. Adicionalmente, o estudo geoquímico indicou que os complexos alcalinos representam câmaras magmáticas distintas, onde diferentes processos evolutivos tiveram lugar. As modelagens apontaram dois processos de diferenciação distintos nos complexos estudados. Os complexos alcalinos de Morro de São João, Morro Redondo, Gericinó-Mendanha e Itatiaia estariam relacionados a processos de cristalização fracionada. Por outro lado, o Complexo Alcalino de Passa Quatro teria sido diferenciado por processos de cristalização fracionada com esvaziamento e posterior reabastecimento da câmara magmática (RTF). De um modo geral, esses modelos indicaram a presença de mais do que uma série magmática nos complexos estudados e a não cogeneticidade entre as séries agpaíticas e miaskíticas. A discriminação de fontes foi feita com base na análise dos elementos terras raras das amostras parentais de cada um dos complexos (gabro em Morro de São João e lamprófiro nos demais). No entanto, este procedimento não foi aplicado para o Complexo Alcalino de Morro Redondo, uma vez que todas as suas amostras apresentaram valores de MgO muito abaixo do típico para líquidos parentais. O líquido parental do Complexo Alcalino do Gericinó-Mendanha apresentou razões de La/Yb e La/Nb, maior e menor que a unidade, respectivamente, típicas de derivação a partir fontes férteis. Os líquidos parentais dos outros complexos alcalinos tiveram suas razões La/Yb e La/Nb maiores que a unidade, típicas de derivação a partir de fontes enriquecidas. Os modelos desenvolvidos revelaram que os líquidos parentais de cada um dos complexos estudados estariam relacionados a fontes lherzolíticas com granada residual. Além disso, a fusão parcial destas fontes teria ocorrido num intervalo de 1 a 7% dentro da zona da granada. Finalmente, as modelagens petrogenéticas elaboradas permitiram a proposição de um cenário geodinâmico, envolvendo a descompressão adiabática do manto litosférico e sublitosférico anomalamente aquecidos. As características geoquímicas dos líquidos parentais parecem ter sido controladas essencialmente pela mistura desses dois tipos de fontes. / Mafic rocks from the Morro de São João, Rio Bonito, Tanguá, Gericinó-Mendanha, Morro Redondo, Itatiaia and Passa Quatro alkaline complexes were studied based on field, petrographic and lithogeochemical data. The mafic rocks are mostly alkaline lamprophyres and alkaline gabbro (in Morro de São João). The complexes show both strongly undersaturated and mildly alkaline evolutionary trends, having foidites and alkaline basalts as parental compositions. Trachytes and phonolites are the most common evolved rocks. Geochemical modelling has show that miaskitic and agpaitic series are unlikely to be related by fractional crystallization. Enriched mantle sources predominate although a fertile mantle source seems to be related with the Gericinó-Mendanha complex. Parental compositions are related to small amounts of partial melting (1-7%) of garnet lherzolite within the garnet stability field in the mantle. Simple geodynamic models indicate that the alkaline complexes are related to the adiabatic decompression of anomalously hot (~1570C) mantle although unrelated to lithospheric translation over a fixed hotspot or mantle plume. Parental compositions are likely to be strongly controled by mixing of distinctive lithospheric mantle sources and a more homogeneous sublithospheric mantle. The lithospheric components seem to be related with the accreted terranes during the Gondwana amalgamation in Early Proterozoic times.

Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 1979 / Includes bibliographical references. / Ph. D. / Ph. D. Massachusetts Institute of Technology, Department of Chemistry

Phosphoryl transfers are essential chemical reactions in key life processes, including energy production, signal transduction and protein synthesis. They are known for having extremely low reaction rates in aqueous solution, reaching the scale of millions of years. In order to make life possible, enzymes that catalyse phosphoryl transfer, phosphoryl transferases, have evolved to be tremendously proficient catalysts, increasing reaction rates to the millisecond timescale. Due to the nature of the electronic structure of phosphorus atoms, understanding how hydrolysis of phosphate esters occurs is a complex task. Experimental studies on the hydrolysis of phosphate monoesters with acidic leaving groups suggest a concerted mechanism with a loose, metaphosphate-like transition state. Theoretical studies have suggested two possible concerted pathways, either with loose or tight transition state geometries, plus the possibility of a stepwise mechanism with the formation of a phosphorane intermediate. Different pathways were shown to be energetically preferable depending on the acidity of the leaving group. Here we performed computational studies to revisit how this mechanistic shift occurs along a series of aryl phosphate monoesters, suggesting possible factors leading to such change. The fact that distinct pathways can occur in solution could mean that the same is possible for an enzyme active site. We performed simulations on the catalytic activity of β-phosphoglucomutase, suggesting that it is possible for two mechanisms to occur at the same time for the phosphoryl transfer. Curiously, several phosphoryl transferases were shown to be able to catalyse not only phosphate ester hydrolysis, but also the cleavage of other compounds. We modeled the catalytic mechanism of two highly promiscuous members of the alkaline phosphatase superfamily. Our model reproduces key experimental observables and shows that these enzymes are electrostatically flexible, employing the same set of residues to enhance the rates of different reactions, with different electrostatic contributions per residue.

The world stocks of fossil fuels are dwindling and may be all but out before the end of the century. Despite this there is increasing demand for them to be used for transport, and the ever increasing green house gases which their use produces. Renewable and less environmentally damaging forms of fuel are needed. Biofuels, particularly bioethanol, are a possibility to subsidise or replace fossil fuels altogether. Ethanol produced from fermentation of starch sugars from corn are already in wide use. As this bioethanol is currently produced from crops such as corn and sugar cane, that puts fuel crops in direct competition for space and resources with food crops. This has led to increases in food prices and the search for more arable land. Hydrolysis of lignocellulosic biomass, a waste by-product of many industries, to produce the sugars necessary for ethanol production would ease many of the problems with current biofuels. Degradation of lignocellulose is not simple and requires expensive chemical pre-treatments and large quantities of enzymes usually from fungal species making it about 10 times more expensive to produce than corn starch bioethanol. The production of a consolidated bioprocessor, an organism able to degrade, metabolise and ferment cellulosic material to produce ethanol or other useful products would greatly reduce the cost currently associated with lignocellulosic biofuel. Cellulomonas fimi ATCC 484 is an actinomycete soil bacterium able to degrade efficiently cellulosic material. The US Department of Energy (DOE) released the genome sequence at the start of 2012. In this thesis the released genome has been searched, for genes annotated as encoding polysaccharide degrading enzymes as well as for metabolic pathways. Over 100 genes predicted to code for polysaccharide hydrolysing enzymes were identified. Fifteen of these genes have been cloned as BioBricks, the standard synthetic biology functional unit, expressed in E. coli and C. freundii and assayed for endo β-1,4-glucanase activity using RBB-CMC, endo β-1,4-xylanase activity using RBB-xylan, β-D-xylosidase activity using ONPX, β-D-cellobiohydrolase activity using ONPC and α-L-arabinofuranosidase activity using PNPA. Eleven enzymes not previously reported from C. fimi were identified as active on a substrate with the strongest activities being for 2 arabinofuranosidases (AfsA+B), 4 β-xylosidases (BxyC, BxyF, CelE and XynH), an endoglucanase (CelA), and 2 multifunctional enzymes CelD and XynF, active as cellobiohydrolases, xylosidases and endoxylanases. Four enzymes were purified from E. coli cell lysates and characterised. It was found that AfsB has an optimum activity at pH 6.5 and 45ºC, BxyF has optimum activity at pH 6.0 and 45ºC and XynH has optimum activity at pH 9.0 and 80ºC. XynF exhibited different optima for the 3 substrates with pH 6.0 and 60ºC for ONPC, pH 4.5 and 50ºC for ONPX and pH 5.5 and 40ºC for RBB-xylan. Searching the genome and screening genes for activities will help genome annotation in the future by increasing the number of positively annotated genes in the databases. The BioBrick format is well suited for rapid cloning and expression of genes to be classified. Searching and screening the genome has also given insights into the complex and large network of enzymes required to fully hydrolyse and metabolise the sugars released from lignocellulose. These enzymes are spread across many different glycosyl hydrolase families conferring different catalytic activities. The characterisation of these novel enzymes points towards a system adapted to not only a broad specificity of substrate but also environmental factors such as high temperature and pH. Genomic analysis revealed gene clusters and traits which could be used in the design of a synthetic cellulolytic network, or for the conversion of C. fimi into a consolidated bioprocessor itself.

This thesis reports on the research outcome of corrosion mechanism and corrosion rate of mild steel in different environments (saline, alkaline solutions and concrete media) using potentiodynamic polarization technique. The study also included the effect of corrosion on bond strength between reinforcing steel and concrete using pull-out test. Corrosion of mild steel and 316L stainless steel with different surface conditions in 1, 3 and 5% saline (NaCl + Distilled water) was investigated. Specimens ground with 200 and 600 grit silicon carbide grinding paper as well as 1μm surface finish (polished with 1μm diamond paste) were tested. In case of mild steel specimens, reduction in surface roughness caused increase in corrosion rate, while in 316L stainless steel corrosion rate decreased as the surface roughness improved. Metallographic examination of corroded specimens confirmed breakdown of passive region due to pitting corrosion. Corrosion of mild steel was also investigated in alkaline solution (saturated calcium hydroxide, pH =12.5) contaminated with 1, 3 and 5% saline. A series of corrosion experiments were also conducted to examine the efficiency of various concentrations of calcium nitrite (CN) on corrosion behaviour of both as-received and polished mild steel in alkaline solution containing 3% saline after 1 hour and 28 days of exposure. Corrosion rate was higher for the as-received than polished mild steel surface under the same testing conditions in NaCl alkaline solution with and without nitrites due to the effect of surface roughness. Morphology investigation of mild steel specimens in alkaline solution ii containing chlorides and nitrites showed localized pits even at nitrite concentration equal to chloride concentration. Corrosion of steel bars embedded in concrete having compressive strengths of 20, 30 and 46MPa was also investigated. The effect of 2 and 4% CN by weight of cement on corrosion behaviour of steel bar in low and high concrete strengths specimens were also studied. All reinforced concrete specimens were immersed in 3% saline solution for three different periods of 1, 7 and 15 days. In order to accelerate the chemical reactions, an external current of 0.4A was applied. Corrosion rate was measured by retrieving electrochemical information from polarization tests. Pull-out tests of reinforced concrete specimens were then conducted to assess the corroded steel/concrete bond characteristics. Experimental results showed that corrosion rate of steel bars and bond strength were dependent on concrete strength, amount of CN and acceleration corrosion period. As concrete strength increased from 20 to 46MPa, corrosion rate of embedded steel decreased. First day of corrosion acceleration showed a slight increase in steel/concrete bond strength, whereas severe corrosion due to 7 and 15 days corrosion acceleration significantly reduced steel/concrete bond strength. Addition of only 2% CN did not give corrosion protection for steel reinforcement in concrete with 20MPa strength at long time of exposure. However, the combination of good quality concrete and addition of CN appear to be a desirable approach to reduce the effect of chloride induced corrosion of steel reinforcement. At less time of exposure, specimens without CN showed higher bond strength in both concrete mixes than those with CN. After 7 days of corrosion acceleration, the higher concentration of CN gave higher bond strength in both concrete mixes. The same trend was observed at 15 days of corrosion acceleration except for the specimen with 20MPa compressive strength and 2% CN which recorded the highest deterioration in bond strength.

The effect of magnesium, strontium, and other alkaline earths on the formation and persistence of metastable carbonates in the natural environment was investigated to determine the nature of the controlling mechanism. Barium and beryllium were studied to evaluate the effect of ionic radius; magnesium and strontium, in order to determine if the results correlate with the usual order of stability for complexes and adsorbed species. Known weights of aragonite were placed in contact with solutions of beryllium, magnesium, calcium, strontium, and barium. Samples were covered and periodically both pH and percent composition of aragonite determined; supernatant liquids and precipitates were analyzed for cation concentrations by atomic absorption spectroscopy and titrimetric methods. Results indicated that the order of effectiveness of alkaline earth metals in inhibiting recrystallization is : Be > Mg > Sr > Ba. This is the expected order of effectiveness for both surface and solution effects. A solution effect (i.e., sequestration of bicarbonate ions) is strongly suggested by the chemical behavior of each cation.

Wastewater activated sludge is produced during the biological treatment of wastewater. After treating the sewage, the sludge is allowed to settle. Part of the settled material is returned to the treatment process as return activated sludge (RAS) and the excess is removed as waste activated sludge (WAS). The handling and disposal of the sludge are energy and capital-intensive treatments, with a significant environmental impact. This work studies the possibility to utilize RAS (an example of wastewater sludge) as a source of surface active agents. The results indicate that higly surface active materials can be extracted from RAS, and that the RAS extract has potential applications as a detergent and wood adhesive. The results also suggest that recovering a suite of products from RAS, a biological heterogenous source, can be technically feasible. An effective alkaline treatment was developed (at pH>12) that can extract up to 75% of the sludge’s organic matter, a yield higher than previously reported. Increasing the extraction pH increased the extract surface activity, which is linked to increasing the amount of higher molecular weight molecules and the presence of phospholipids. Increasing the extraction pH beyond 11 was also related to extensive cell lysis, increasing significantly the amount of recovered material and the surface activity of the extract. The alkaline extract has properties comparable to commercial detergents. Without further purification, the extract has a low surface tension (37 mN/m on average) and performs similarly to synthetic detergents. Further assessment of the RAS extract (insensitivity to pH, surface tension, interfacial tension) suggests that it may be suitable for commercial applications. The RAS extract can also be formulated into wood adhesives using glutaraldehyde as a crosslinker. The extract fraction with 10-50 kDa constituents at pH 9 achieves high adhesive shear strengths (4.5 MPa on average, at 30% relative humidity and 25°C) with 40% of wood failure. The adhesive strength of RAS-based adhesives is strongly correlated to its protein content.

Up to 30% by mass of plant cell walls are comprised of hemicelluloses. The remainder is comprised of cellulose, lignin and extractives. Potential economic uses of hemicellulose include hydrogels, fibre additives in pulp mill paper-making and as a substrate for fermentation processes. Development of a fermentation process with sugars from hemicellulose has become of increasing interest due to their potential as a feedstock for fermentation-based liquid fuels and other bio-based chemicals. These can be incorporated into existing processes, in particular alkaline chemical pulping mills, where up to 50% of the hemicelluloses are today degraded and eventually combusted. The main objective of this project is to examine the solubility and aggregation properties of xylans (the predominant hemicellulose), as this will hopefully lead to better solubility-based separations for their recovery. This was done at Michigan State University by alkaline extraction at 85°C on milled birch wood, and at 130 and 170°C (both time-dependent) on birch chips, with 50 g/L sodium hydroxide. This was then followed by precipitation/aggregation experiments with ethanol, polyDADMAC (a polycationic flocculant) and by acidification. Characterisation was done by performing dynamic light scattering (DLS) and size exclusion chromatography (SEC) analysis on resolubilised recovered material from the different extraction conditions. From these, size distributions, molecular weights and degrees of polymerization (DP) could be estimated. The DP values for the extracted polymers were higher than the expected values for hardwood xylans, owing to the incoherent SEC chromatograms. This may be due to aggregate formation with other polymers or re-solubilisation issues of the hemicellulose precipitates. The estimated size range for model xylan was between 100 to 300 nm and the ethanol precipitates seemed to also lie around this region, as detected by DLS. One of the major factors contributing to the difficulty of analysing the results was the issue of re-solubilisation of the hemicellulose precipitates and flocculates. / <p>Validerat; 20120827 (anonymous); 2017-02-08 Nedladdad 414 gånger t.o.m. september 2016. Downloaded 414 times up until september 2016 (marisr)</p>