Actuellement, l’industrialisation de la torréfaction de biomasse se heurte notamment à un manque de connaissances de la nature et de la quantité des matières volatiles produites en fonction des conditions opératoires et de la matière première. L’objectif de ces travaux est donc de mieux comprendre comment s’opère la torréfaction de la biomasse, en se concentrant sur l’étude de la perte de masse du solide et des rendements en matières volatiles. La torréfaction est considérée à partir de bois sec, sous atmosphère inerte et suivant un palier à une température comprise entre 200°C et 300°C. Lors d’une étude expérimentale, du hêtre et ses constituants, à savoir cellulose, xylane et lignine, ont été torréfiés, en régime chimique, dans une thermobalance et dans un pilote de torréfaction à échelle laboratoire. Le bilan matière boucle entre 97% et 104%. Les principales matières volatiles émises par la torréfaction de ce bois sont l’eau, le formaldéhyde, l’acide acétique et le CO2. De l’acide formique, du CO, du méthanol et du furfural sont aussi mesurés en quantité moindre. Certaines de ces espèces ne sont pas produites par tous les constituants du hêtre. Il semble en particulier que l’acide acétique soit produit à partir de la dégradation des acétates contenus dans les hémicelluloses. Par ailleurs, il apparaît en première approximation que la transformation peut être correctement représentée par la loi d’additivité jusqu’à 250°C. Cela n’est plus le cas à 280°C et 300°C, du fait d’interactions entre la cellulose et les deux autres constituants du bois. Celles-ci ralentissent la vitesse de torréfaction de la cellulose. A partir de ces résultats expérimentaux, a été développé dans ces travaux un modèle de torréfaction du bois, basé sur la superposition de « sous-modèles » décrivant chacun la torréfaction d’un constituant du bois. Ce modèle, qui présente comme originalité de prévoir en fonction de la proportion du bois en cellulose/hémicelluloses/lignine à la fois le rendement en solide et en huit espèces volatiles, et de prendre en compte les interactions à l’aide d’un facteur empirique, a été validé sur les expériences de torréfaction du hêtre entre 220°C et 300°C. Son utilisation a mis en évidence l’influence significative des contenus en hémicelluloses et cellulose sur les rendements en produits de la torréfaction. / The industrialization of the biomass torrefaction process requires better knowledge of the volatile species release versus operating conditions and feedstock. In this context, the present work aimed at studying solid mass loss and volatile species yields during biomass torrefaction. This transformation was considered on dry wood, at a temperature plateau between 200°C and 300°C and under inert atmosphere. First, torrefaction experiments were conducted under chemical regime on beechwood and its constituents – cellulose, lignin and hemicelluloses – in a thermobalance and in a lab-scale device. The mass balance closure was achieved with values ranging from 97 and 104%. The main volatile species measured were water, formaldehyde, acetic acid and CO2. Smaller amounts of methanol, CO, formic acid and furfural were also quantified. All those gas species were not produced by the three biomass constituents. In particular acetic acid seems to be produced by the degradation of the acetate groups contained in hemicelluloses. The results showed that in a first approximation torrefaction can be described by the additive law up to 250°C. But this law is not valid at 280°C and 300°C because of interactions between cellulose and the two other wood constituents. These interactions lead to a decrease in the torrefaction rate of cellulose. Based on these experimental results, a model of wood torrefaction was developed. It consists in the superposition of “sub-models” describing the torrefaction of each wood constituent. The originality of this model lies in its ability to predict both solid yield and eight volatile species yields depending on cellulose/hemicellulose/lignin wood composition, and to take into account interactions by means of an empirical factor. It was validated on beechwood torrefaction experiments between 220°C and 300°C. Finally, this model highlighted the significant influence of the proportion of hemicellulose and cellulose on torrefaction product yields.

P. chrysosporium est un champignon saprophyte capable de dégrader de nombreux xénobiotiques, ce qui le rend particulièrement intéressant pour des applications en bioremédiation. Plusieurs publications mettent en avant l'importance de la maîtrise de l'homéostasie métallique dans la production de certaines enzymes lignolytiques. La présence de manganèse est en effet nécessaire à la production des manganèses peroxydases, alors qu'à l'inverse une carence permettra la production de lignines peroxydases. Cependant, la caractérisation de transporteurs impliqués dans le contrôle de l'homéostasie métallique n'a fait l'objet de recherches poussées que chez le champignon modèle S. cerevisiae. L'analyse des transporteurs putatifs de manganèse de 26 espèces fongiques représentant 20 ordres fongiques a permis de constituer un répertoire de 281 transporteurs de manganèse. L'analyse phylogénétique a permis de mettre en évidence que des processus de duplication, mais également de délétion, avaient eu lieu en particulier chez S. cerevisiae. Cependant ce dernier ne possède pas de transporteurs de manganèse appartenant à la famille des Cation Diffusion Facilitator. Dans le génome de P. chrysosporium, onze transporteurs de manganèse appartenant à différentes familles de gènes ont été identifiés. Le niveau d'expression de ces différents gènes a été étudié notamment en condition lignolytique. Ces transporteurs ont également été clonés afin de vérifier leurs fonctions par complémentation en système hétérologue. Cette étude a permis de mettre en évidence les transporteurs de manganèse putatifs de nombreux organismes fongiques, ainsi que l'absence d'une famille de transporteurs impliquée dans les mouvements de manganèse chez S. cerevisiae / P. chrysosporium is a saprophytic fungus able to degrade many xenobiotics which makes it particularly attractive for applications in bioremediation. Several publications highlight the importance of metal homeostasis in the production of lignolytics enzymes. Indeed the presence of manganese is required for the production of manganese peroxidase. Conversely, deficiency allows the production of lignins peroxidases. Characterization of transporters involved in the control of manganese homeostasis has been only researched in the model S. cerevisiae. Analysis of putative manganese transporters of 26 fungal species representing 20 orders of fungus was used to form a repertory of 281 transporters of manganese. Phylogenetic analysis allowed to highlight that duplication process, but also deletion, had occurred particularly in S. cerevisiae. However this one is devoid of transporters belonging to the manganese Cation Diffusion Facilitator. Eleven transporters belonging to gene families in which manganese transporters have been found were identified in the P. chrysosporium?s genome. Expression level of these genes was examined particularly in ligninolytic condition. Transporters have also been cloned in order to verify their functions by complementation in heterologous system. This study allowed to identify putative manganese transporters of numerous fungal organisms and the lack of a transporters family involved in the manganese transport in S. cerevisiae

Master of Science / Department of Civil Engineering / Dunja Peric / The main objective of this study was to experimentally investigate the Mohr-Coulomb strength parameters of masonry sand mixed with varying amounts of water and lignin. Lignin is a plant-derived biomass, which is a co-product of bio-fuel production. It exhibits binding qualities when mixed with water thus making it an ideal candidate for sustainable non-traditional sand stabilization. An experimental program was devised and carried out to quantify the compaction and early age stress-strain and dilatancy responses of sand-lignin mixes. The program included sieve analysis, Atterberg limit tests, standard Proctor tests, and direct shear tests. The experimental results were used to find the cohesion and the angle of internal friction of the tested material, therefore determining the influence of the amount of lignin and water on the strength of the samples. An extensive data analysis was subsequently completed to gain deeper understanding of the underlying strength gain mechanism. It was found that the normalized cohesion benefit due to lignin is controlled by two variables; water to lignin ratio and void ratio. The lignin and water create a paste, which provides particle bonding at the contacts of sand particles, thus increasing the stress-bearing cross sectional area. Increase in the portion of cross-sectional area occupied by water and lignin normalized by gravimetric lignin content, increases the normalized cohesion up to a point, while the cohesion per gravimetric lignin content decreases with the increasing area ratio. This in turn indicates that cohesion increases only up to 6% of lignin, beyond which it starts to decrease due to the presence of too much fine material within the pores. The presence of lignin in the pores consistently decreases the angle of internal friction. However, for all configurations with lignin tested herein, cohesion was larger than for dry sand, thus indicating strength benefits at low confining pressures or at normal stresses below the so-called limiting normal stress.

Actuellement, la transformation de la biomasse en bio-carburant ou molécules pour l'industrie chimique fait l'objet de nombreuses recherches. La lignine, en tant que coproduit de l'industrie papetière et de l'éthanol cellulosique, est une ressource des plus disponibles qui pourait être utilisée pour la production d'aromatiques ou de composés phénoliques. Cependant, cette macromolécule constituée d'unités propylphénoliques liées par des liaisons éthers nécessite d'être dépolymérisée. Ce travail porte sur la compréhension des mécanismes de liquéfaction par hydroconversion catalytique d'une lignine de paille de blé extraite par un procédé papetier à la soude. Dans un premier temps, nous avons mené une caractérisation poussée de cette lignine à l'aide de diverses techniques qui nous a permis de proposer une structure modèle. Ensuite, nous avons mis en place un mode opératoire de conversion et un protocole de récupération des produits. La réaction est réalisée en réacteur semi-ouvert à 350°C en présence d'H2 (8MPa), d'un solvant donneur d'hydrogène (tétraline) et d'un catalyseur d'hydrotraitement NiMoP/Al2O3 sulfuré. Les produits se répartissent en une phase liquide (liquéfiat), une phase gaz, une lignine résiduelle et des solides non-solubles dans le THF. Un taux de conversion a été défini comme le rendement en produits non-solides et les valeurs maximales atteintes sont de 81% pds après 28h de réaction avec un excellent bilan matière. Les fractions récupérées ont ensuite été caractérisées en détail avec des techniques d'analyse adaptées. Grâce à ce protocole d'analyse, nous avons pu observer que le solvant permet d'éviter la formation de solides et que le catalyseur intervient principalement sur l'hydrodésoxygénation et l'hydrogénation des molécules issues de la dépolymérisation de la charge. Enfin, nous avons suivis la réaction au cours du temps, ce qui nous a permis de présenter une ébauche de schéma réactionnel. Les premières étapes de conversion sont la décarboxylation, l'hydrogénolyse des OH aliphatiques et la rupture des liaisons éthers entre les unités élémentaires de la lignine, qui entraînent sa dépolymérisation. Puis des processus plus lent se produisent comme l'élimination des groupes méthoxy, principalement par déméthylation suivi de déshydroxylation. Ainsi, les principaux produits obtenus sont des composés phénoliques et des composés désoxygénés / Nowadays, the transformation of lignocellulosic biomass is deeply investigated in order to provide biofuels and chemicals. Lignin, a by-product of pulp and bio-ethanol industry, is an available resource which could be used for the production of aromatic and phenolic compounds. However, this macromolecule mainly made of propylphenolic units linked by ether functions needs to be depolymerized. This work focuses on the study of liquefaction mechanisms by catalytic hydroconversion of wheat straw lignin extracted by a soda pulping. In the first part of this study, an in-depth characterization of this lignin was carried out using techniques. A structure of our lignin was proposed as a result. Then, a procedure was developed to perform the catalytic hydroconversion and recover the products. Catalytic experiments were carried out in a semi-batch reactor at 350°C, using H2 (8 MPa), a hydrogen donor solvent (tetralin) and a sulfide NiMoP/Al2O3 catalyst. The recovered products were separated into a liquid phase, gases, a lignin residue and THF insoluble solids. A conversion of 81 wt% of lignin into non-solid products was reached after 28h of reaction with an excellent mass balance. The characterization of the different fractions was carried out using techniques. Thanks to this protocol, we were able to point out the role of the H-donor solvent for preventing solid formation as well as the role of the catalyst for hydrodeoxygenation and hydrogenation of the depolymerized products. Finally, the catalytic hydroconversion of the lignin was carried out with the different residence times, which helps understanding the transformations occurring during the conversion. At the beginning of the reaction, we observed decarboxylation, hydrogenolysis of aliphatic OH and cleavage of ether linkages between the phenolic units of the lignin. Then, we observed elimination of methoxy groups, mainly by demethylation followed by dehydroxylation. Finally, the main products obtained during the reaction were phenolic and deoxygenated compounds such as aromatics, naphthenes and alkanes

The non-sustainable nature of fossil fuels as feedstocks for valuable chemicals, combined with the environmental damage caused by their extraction and combustion, increases the need for the development of a bio-based economy. While industry and public opinion are slowly shifting towards acceptance of this change, efficient technologies for the depolymerization and subsequent separation of lignocellulosic biomass fall short of the ever-increasing demand. In particular, there are currently no efficient, sustainable mass scale methods to convert lignin, the most abundant source of aromatic molecules on Earth. The use of oxovanadium(V) catalyst complexes to aerobically cleave C‒C bonds has been demonstrated previously and remains an attractive option for incorporation into a sustainable bio-based economy. Two new triphenoxyamine oxovanadium(V) catalysts with reduced steric bulk and electron density at the metal center (vs. previously reported complexes) have been synthesized for aerobic oxidative diol C‒C bond cleavage. These complexes were found to cleave less activated and more complex substrates than previous generations, including cyclic diols and polyalcohols. Several insights into the reaction pathways of this class of complex were elucidated through a series of kinetic studies. Experimentally, the rate of C‒C bond cleavage of both pinacol and hydrobenzoin was determined to be unaffected by substitution of the O‒H bonds with deuterium, suggesting that currently proposed mechanisms need to be revised. Multiple catalytic regimes were observed during anaerobic reaction, which were not altered significantly by the brief addition of O2. A series of density functional theory calculations revealed a plausible mechanism for the trialkoxy complex that did not involve a proton transfer in the rate determining step, instead suggesting that ligand-arm dissociation-reassociation play a significant role in the reaction. In a second project, new bisphenoxyamine-N-appended base ligand with less steric hindrance and electron density at the metal center, has been synthesized utilizing similar design principles gained from work with triphenoxyamine catalysts. When reacting with lignin model compound 1,2-diphenyl-2-methoxyethanol, this new complex displays a higher selectivity towards aldehydes and esters (relative to previous bisphenoxyamine-N-appended ligands), leading to a higher rate of C‒C bond cleavage. Investigations into the mechanism of bisphenoxy complexes, as well as the role of the N-appended base in reactivity, were performed using substrate pre-complexed bisphenoxy compounds. Thermolysis at 60 and 100 °C produced almost exclusively oxidative C‒H bond cleavage product benzyl methyl ether, with evidence for overoxidation product benzoic acid observed. Thermolysis of labelled substrate pre-complexed revealed that N-appended base may impede C‒C cleavage of 1,2-diphenyl-2-methoxyethanol by forcing the methyl ether away from the oxovanadium(V) center. Through the use of these multidentate phenoxyamine ligands, advances have been made towards sustainable oxovanadium catalysis in the pursuit of efficient and selective lignocellulosic disassembly for a sustainable bio-based economy.

Materialet sly står i centrum i mitt examensprojekt. Som student på Konstfack och i min framtida yrkespraktik har frågor om cirkulär ekonomi och cirkulär design varit närvarande. Det är avgörande för att påverka samtiden och framtiden mot en mer hållbar framtid. Sly är en resurs, ett material som både finns lokalt, regionalt och nationellt. Jag har arbetat med ett material från naturen som av tradition har betraktas ha ett lågt ekonomiskt värde. Syftet var att se om materialet kan förädlas och användas som råvara i produktutveckling och produktdesign. Vidare arbetar jag i en ämnesfråga där begrepp som cirkulär design och biologisk, social och ekologisk hållbarhet är centrala. Projektet rör sig i ämnesfält som bioekonomi, cirkulär design och frågor om lokal produktion.

O presente trabalho avaliou a recalcitrância de diferentes regiões do entrenó de plantas de cana-de-açúcar que apresentavam teores contrastantes de lignina total. As amostras com baixo teor de lignina corresponderam aos híbridos experimentais denominados de H58 e H89, com 18,6% e 16,8% de lignina, respectivamente. As amostras com elevado teor de lignina corresponderam ao híbrido H140 e a um cultivar comercial (CR), com 21,5% e 24,5% de lignina, respectivamente. De cada cana foram obtidas quatro regiões distintas dos entrenós: medula, interface medula-córtex, córtex e fração externa (epiderme mais córtex periférico). Cada uma das amostras foi submetida à hidrólise enzimática com celulases comerciais. Os resultados mostraram uma maior conversão de celulose e hemicelulose na região da medula (celulose: 86%, 78%, 85% e 50%; xilanas: 50%, 36%, 31% e 30% após 72h, para CR, H58, H89 e H140, respectivamente). O córtex e a fração externa foram as regiões mais recalcitrantes, já que as conversões de celulose e xilanas atingiu somente 10% a 38% no córtex e 6% a 10% na fração externa. Embora seja pouco recalcitrante, a medula representou menos do que 10% do volume e da massa do entrenó. Em contraste, o córtex representou 49% do volume do entrenó e 48% a 63% da massa, dependendo do híbrido estudado. A região medular também mostrou a predominância de glucanas (41% - 55%) e menor teor de hemiceluloses (16,8% - 20,5%; exceto H140) e lignina total (12,6% - 18,5%) em relação às demais frações. A determinação de ácidos hidroxicinâmicos nas amostras indicou a predominância de ligações destes ácidos na forma de éster com a hemicelulose e simultaneamente éter com a lignina, independentemente da fração de cana avaliada. Dentre os híbridos, o H89 e o H140 se destacaram por sua baixa e alta recalcitrância, respectivamente. Nas análises microscópicas, o número de feixes vasculares por área foi maior na região do córtex (13 a 22 feixes por 16 mm2) quando comparada com outras regiões, enquanto a fração externa apresentou apenas fibras. A medula se mostrou preenchida, em sua maior parte, por células do parênquima, contendo menos feixes vasculares (5 a 8 feixes por 16 mm2). Dentre os híbridos, o H140 foi o que apresentou menos feixes por área, porém com os maiores diâmetros (entre 390 e 583 ?m, dependendo da região). A presença de feixes vasculares mostrou ser muito importante para explicar a recalcitrância das amostras. Dentre os estudos de correlação realizados, foi possível notar que a recalcitrância das canas estudadas pode ser relacionada não apenas com o teor de lignina total, mas também com a densidade do material, a disponibilidade de celulose e a extensão dos feixes vasculares por área. / This study evaluated the recalcitrance of different regions of the internodes of sugarcane plants which presented contrasting lignin contents. Samples with low lignin content corresponded to the experimental hybrids termed H58 and H89, each one with 18,6% and 16,8% of lignin, respectively. The samples with high lignin content corresponded to the hybrid H140 and a commercial variety of sugarcane (CR), with 21,5% and 24,5%, respectively. Different fractions of the internodes were obtained from each plant: pith, pith-rind interface, rind and outermost rind (epidermis plus peripheral rind). Each sample was submitted to enzymatic hydrolysis with commercial cellulases. Results showed a higher conversion of cellulose and hemicellulose in the pith (cellulose: 86%, 78%, 85% and 50%, xylan: 50%, 36%, 31% and 30% after 72 hours for CR, H58, H89 and H140, respectively). Rind and outermost rind were the most recalcitrant regions, since the cellulose and xylan conversions reached only 10% to 38% in rind and 6% to 10% in the outermost rind. Despite its low recalcitrance, the pith region represented less than 10% of the volume and the dry mass of the internode. In contrast, the rind represented 49% of the internode volume and 48% to 63% of the dry mass, depending on the evaluated hybrid. The pith region also showed the predominance of glucan (41% - 55%) and the lowest contents of hemicellulose (16.8% - 20.5%, except for H140) and total lignin (12.6% - 18.5%). From the hydroxycinnamic acids determination, it was found that these acids were mostly linked to hemicellulose as esters and, simultaneously, to lignin as ether, regardless which fraction was analyzed. Among the hybrids, H89 and H140 stood out for its low and high recalcitrance, respectively. In microscopic analysis, the number of vascular bundles per area was greater in the rind region (13 to 22 bundles per 16 mm2) when compared to other regions, meanwhile the outermost rind showed only fiber cells. The pith showed itself occupied mostly by parenchyma cells, containing less vascular bundles (5 to 8 bundles per 16 mm2). Among the hybrids, H140 showed the smallest number of vascular bundles per area, but with the largest diameters (between 390 and 583 ?m, depending on the region type). The presence of the vascular bundles was found to be very important in order to explain the recalcitrance of the samples. Among the correlation analysis performed, it was noticeable that the recalcitrance of the studied sugarcanes could be related, not only to the total lignin content, but also to the biomass density, the cellulose availability and the extent of vascular bundles per area.

Feed intake assessment is a valuable tool for herd management decisions. The use of markers, either internal or external, is currently the most used technique for estimating feed intake in production animals. Three experiments were conducted with beef and dairy cattle. In dairy cows fed a corn silage based diet with 45% concentrate, the average fecal recovery (FR) of TiO2 was higher than FR of Cr2O3 and both FR were more than unity. The FR was unaffected by the fecal sampling procedure but, estimates for dry-matter digestibility (DMD) and fecal output (FO) were affected. The Cr2O3 + indigestible acid detergent fiber (iADF) marker pair produced accurate dry-matter intake (DMI) estimates. In steers fed diets with different forage sources FR of TiO2 was close to 1 and this marker produced adequate FO estimates. The FR was affected by the forage source that composed the diet and none of the marker pairs produced accurate DMI estimates. In young Nelore bulls fed corn silage or Tifton-85 hay based diets with varying F:C ratios, the average FR of internal markers acetyl bromide lignin (ABL), indigestible neutral detergent fiber (iNDF), iADF and cutin was different from 100%. Markers Cr2O3 and TiO2 had FR lower and higher than 100%, respectively. The combination of internal and external markers to estimate DMI produced satisfactory and accurate results, particularly Cr2O3 based pairs with iNDF and iADF. Internal markers ABL and cutin deserve more attention. The GRAB sampling procedures yielded accurate DMD, FO and DMI estimates, which were as good as or better than BULK sampling procedures. Regardless of the fecal sampling method and the composition of the diet, it is necessary to establish the FR of the markers to be used in each experiment, in order to obtain correct estimates. None of the markers had complete FR consistent throughout the 3 experiments. Cutin and ABL had lower than unity FR on all diets and failed to produce accurate DMD estimates. When either one was paired with Cr2O3 or TiO2, DMI estimates were also not accurate. Of the indigestible fibers, iNDF and iADF, the later was more accurate in estimating DMI when paired with Cr2O3. Consistently throughout the experiments, FR was lower than and higher than unity for internal and external markers, respectively. Corrected FO estimates were accurate for Cr2O3 on various diets under GRAB sampling. The same was not true for TiO2, which even after FR correction was applied failed to produce accurate FO estimates consistently. The method of dosing the external markers is extremely important and greatly affects and determines results. Whichever the method, it must allow the animals to display normal feeding behavior and not affect performance. The GRAB sampling procedures can replace TFC (once FR is established) which may open new possibilities for pasture based or collectively housed animals. / A determinação do consumo de alimentos é uma valiosa ferramenta na hora da tomada de decisões de manejo do rebanho. O uso de marcadores, sejam internos ou externos, é atualmente a técnica mais utilizada para estimar o consumo em animais de produção. Três experimentos foram conduzidos. Em vacas de leite alimentadas com silagem de milho com 45% de concentrado, a recuperação fecal (RF) média de TiO2 foi maior do que a RF de Cr2O3 e ambas foram maiores do que a unidade. A RF não foi afetada pelo método de coleta de fezes, mas, as estimativas de digestibilidade da matéria seca e produção fecal (PF) foram. A dupla de marcadores Cr2O3+i fibra detergente ácido indigestível (iADF) produziu estimativas de consumo de matéria seca (CMS) acuradas. Em novilhos alimentados com diferentes fontes de forragem, a RF do TiO2 foi próxima a 1 e este marcador produziu estimativas de PF adequadas. A RF foi afetada pela fonte de forragem que compunha a dieta e nenhum dos marcadores produziu estimativas de CMS acuradas. Em tourinhos Nelore alimentados com dietas compostas de silagem de milho ou feno de Tifton-85 e diferentes relações de volumoso:concentrado, a RF média dos marcadores internos lignina brometo de acetila (LBA), fibra detergente ácido indigestível (iFDN), (iFDA) e cutina foi diferente de 100%. Os marcadores Cr2O3 e TiO2 tiveram RF menor e maior que 100%, respectivamente. A combinação de marcadores internos e externos para estimar o CMS produziu resultados acurados e satisfatórios, principalmente as duplas Cr2O3 e iFDN ou iFDA. Os marcadores internos LBA e cutina merecem mais estudos. O método de coleta GRAB produziu estimativas de DMS, PF e CMS acuradas, as quais foram iguais ou melhores que as produzidas pelo método de coleta BULK. Independentemente do método de coleta de fezes e da composição da dieta, é necessário estabelecer a RF real dos marcadores que serão usados em experimento para obter estimativas corretas. Nenhum dos marcadores teve RF completa e consistente nos 3 experimentos. A cutina e LBA tiveram RF menor do que a unidade em todas as dietas e falharam em produzir estimativas acuradas de DMS. Quando qualquer dos dois foi pareado com Cr2O3 ou TiO2 as estimativas de CMS também não foram acuradas. Das fibras indigestíveis, iFDN e iFDA, a segunda foi mais acurada em estimar o CMS quando pareada com Cr2O3. As estimativas de PF corrigida foram acuradas para Cr2O3 em diferentes dietas sob metodologia de coleta GRAB. O mesmo não foi observado para o TiO2, que produziu estimativas enviesadas inclusive após a correção. O método de dosagem dos marcadores externos é extremadamente importante já que afeta e determina em grande medida os resultados. Qualquer que seja o método, este deve permitir ao animal comportar-se e alimentar-se normalmente sem comprometer seu desempenho. Os métodos de coleta GRAB podem substituir a coleta total de fezes (CTF) (após determinação da RF) o que poderá abrir novas possibilidades para estudos com animais em pastagem ou alojados em baias coletivas.

O licor negro, cuja composição majoritária é de lignina, é o principal subproduto gerado após a obtenção de polpa celulósica. Este polímero natural é caracterizado pela elevada massa molecular (MM) e composição aromática. Processos físico-químicos são empregados na fragmentação da lignina com o objetivo de obter compostos aromáticos, cuja fonte não renovável é oriunda de derivados do petróleo. A biodegradação da lignina, causada pela ação de enzimas ligninolíticas fúngicas pode prover compostos aromáticos de baixo peso molecular, como fenóis e antioxidantes, utilizados em diversos segmentos industriais. O objetivo deste trabalho foi estudar a modificação estrutural da lignina causada por fungos basidiomicetos coletados de mata nativa e campos de reflorestamento de eucalipto. Os ensaios de biodegradação foram inicialmente conduzidos utilizando-se 10 espécies de fungos, cultivados em duas concentrações de licor negro (10% e 15%, v/v). No ensaio com licor menos concentrado, utilizaram-se 10 espécies, e no ensaio com licor 15% utilizou-se somente a espécie Pycnoporus sanguineus. As análises realizadas para o estudo da modificação estrutural da lignina foram: espectroscopia na região do infravermelho (FTIR/ATR), cromatografia líquida de gel filtração e espalhamento de raios-X a baixo ângulo (SAXS). P. sanguineus e espécies de fungos do gênero Trametes possuem elevada capacidade de consumir a lignina presente no licor 10%, após 14 dias. A atividade de enzimas ligninolíticas de P. sanguineus foi investigada nas duas concentrações de licor. No licor 10%, observou-se elevada atividade das enzimas ligninolíticas manganês peroxidase (MnP), lacase e peroxidases; somente a MnP foi detectada com maior atividade no licor 15%. Análises de Demanda Bioquímica de Oxigênio (DBO) indicaram que o licor negro 10% biodegradado por P. sanguineus possui elevada carga de DBO, sendo tóxico a Daphia magna e Hydra attenuatta. Análises de metabólitos produzidos pelos fungos no licor negro 10% por cromatografia gasosa acoplada à espectrometria de massas (GC-MS) indicaram, principalmente, a produção de açúcares e álcoois em concentrações não muito diferentes dos seus respectivos controles. Embora os fungos sejam capazes de reduzir a massa molecular da lignina presente no licor negro, compostos derivados da sua fragmentação podem sofrer reações de condensação ou repolimerização, contribuindo, eventualmente, para elevar sua massa molecular / Black liquor which the bulk content is lignin, is the main product generated after obtaining cellulose pulp. This natural polymer is characterized by high molecular weight (MW) and aromatic compounds. Physical-chemical processes can be employed to fragment lignin and to produce aromatic compounds to replace those from non-renewable sources such as petroleum. Biodegradation of lignin can provide low molecular weight compounds, such as phenols and antioxidants, which may be employed in various industrial processes. The aim of this work was to investigate the structural modification of lignin caused by basidiomycetes fungi, obtained from native forest and Eucalyptus fields. The biodegradation assay was done with10 fungi species cultivated with two concentrations of black licor (10% and 15%, v/v). The assay with 10% liquor, 10 species of basidiomycete fungi were used, and in the assay with 15% liquor, it was used only Pycnoporus sanguineus. The analyses carried out to determine the structural modification of lignin were: infrared spectroscopy (FTIR/ATR), liquid chromatography gel filtration and small angle X-ray scattering (SAXS). P. sanguineus and fungi of Trametes genera had high capacity to consume the lignin content in the 10% liquor, after 14 days of cultivation. After that, P. sanguineus was selected for assays of ligninolytic enzymes activities in the two liquor concentrations. High activities of manganese peroxidase (MnP), laccase and peroxidase were detected in the 10% liquor, whereas in the concentration of 15% only high MnP activity was detected. Biochemical Oxygen Demand, analysis (BOD) indicated that the biodegraded liquor had high BOD load, and it was toxic to Daphia magna and Hydra attenuata. Metabolites produced by the fungi in the liquor 10% were analysed by gas chromatography-mass spectrometry (GC-MS), which indicated mainly the production of sugars and alcohols in concentrations not far from their respective controls. Although the fungus is able to decrease molecular weight of lignin, its fragments derivatives can undergo condensation or repolymerization reactions, contributing, eventually, to increase its molecular weight

O branqueamento de polpa quimiotermomecânica (CTMP) normalmente é realizado empregando peróxido de hidrogênio (H2O2) em meio alcalino. Esta etapa produz elevados volumes de efluentes, que por necessitarem de tratamento adequado, favorecem o aumento dos gastos no processo industrial. A utilização de dióxido de carbono (CO2) líquido em condições sub/supercríticas pode contribuir para a redução na quantidade de efluentes líquidos, gerados nas etapas de branqueamento, devido à volatilização do dióxido de carbono ao final da reação, minimizando gastos e possíveis impactos ambientais. O presente trabalho foi realizado visando melhorias na etapa de branqueamento de polpa CTMP de Eucalyptus, tendo por objetivo principal o estudo exploratório do comportamento da polpa, ao empregar soluções aquosas de H2O2, na presença de CO2 em estado sub/supercrítico, em pH ácido. Este sistema de reação foi denominado pela sigla P(SC/CO2-ácido). Foram estudados os efeitos das variáveis: pressão, temperatura, tempo de reação, consistência da polpa e porcentagem de H2O2 sobre a eficiência do branqueamento. Os resultados foram comparados com métodos convencionais de branqueamento, realizados em banho termostatizado, em pH alcalino. Verificou-se também o efeito da pressão, substituindo o fluido CO2 por N2 (nitrogênio) a 150 bar em condições sub/supercríticas, utilizando tanto pH alcalino (sistema P(SC/N2-alcalino)) quanto pH ácido (sistema P(SC/N2-ácido)). As condições mais adequadas ao branqueamento P(SC/CO2-ácido) foram: 16% de H2O2, 180 minutos, 20% de consistência, 70°C e 73 bar. Além disso, foi realizado um estudo com modelos de lignina para verificar a ocorrência de reação na presença de H2O2 e CO2 e quais produtos são obtidos nestas condições. O método de branqueamento convencional, desenvolvido em meio alcalino, possibilitou a obtenção de alvuras mais elevadas (80°GE) em relação ao método realizado em condições sub/supercríticas, na presença de CO2 (61°GE). Apesar disso, o branqueamento empregando o sistema P(SC/CO2-ácido) revelou resultados interessantes: possibilitou acréscimo no valor de alvura da polpa, sem causar degradação acentuada das fibras, mesmo em condições de elevadas pressões e concentração de H2O2; e permitiu redução no volume de água consumido, o que levou à produção de menor volume de efluentes líquidos. O método utilizando o sistema P(SC/N2-alcalino) apresentou valores de alvuras (79°GE) comparáveis ao método convencional. Os estudos empregando modelos de lignina apresentaram resultados que fornecem suporte para confirmar a ocorrência de oxidação. / The bleaching of chemithermomechanical pulp (CTMP) is usually performed using hydrogen peroxide (H2O2) in alkaline medium. This stage produces high quantity of effluent to be treated, increasing the costs of the industrial process. The usage of liquid carbon dioxide (CO2) under sub/supercritical conditions can help in reducing the amount of liquid effluents generated in the bleaching stages, due to the carbon dioxide volatilization at the end of the reaction, minimizing costs and possible environmental impacts. This work aimed at improving the bleaching stage of Eucalyptus CTMP, being the main objective the exploratory study of the pulp behavior, by using aqueous solutions of H2O2 in the presence of CO2 under sub/supercritical conditions in acid pH. This reaction system was named as P (SC/CO2-acid) symbol. It was studied the effects of the variables: pressure, temperature, pulp consistency and percentage of H2O2 on the bleaching efficiency. The results were compared with conventional bleaching carried out in polyethylene bags in a heated water bath in alkaline pH. It was also verified the pressure effects by replacing the use of CO2 by N2 at 150 bar in sub/supercritical conditions, in alkaline pH (P(SC/N2-alkaline) system) and acid pH (P(SC/N2-acid) system). The most appropriate P (SC/CO2-acid) bleaching conditions were: 16% H2O2, 180 minutes, 20% pulp consistency, 70°C and 73 bar. Furthermore, a study was conducted with lignin models to verify the occurrence of reaction with H2O2 and CO2, and the products obtained in these conditions. The cellulosic substrate, in general, showed a low deterioration, even considering the conditions of high pressures and peroxide concentrations. The conventional bleaching method, performed in alkaline medium, gave higher brightness (80°GE) than the method carried out under CO2 in sub/supercritical conditions (61°GE). However, the bleaching using the P(SC/CO2-acid) system showed interesting results: increasing of the pulp brightness, without causing severe degradation of the fibers, even in conditions of high pressure and peroxide concentration; and it reduced the volume of water consumed, leading to lower production of liquid effluents. The P(SC/N2-alkaline) method showed brightness values (79°GE) comparables with the conventional method. Studies using lignin models showed results that support the confirmation of occurrence of oxidation reactions.