A dissertation submitted to the Faculty of Science, University of the Witwatersrand, in fulfilment of the requirements for the degree of Doctor of Philosophy, Johannesburg 2014 / Namibia is renowned for its abundant mineral resources, a large proportion of which are hosted in the metasedimentary lithologies of the Damara Belt, the northeast-trending inland branch of the Neoproterozoic Pan-African Damara Orogen. Deposit types include late- to post-tectonic (~ 523 – 506 Ma) LCT (Li-Be, Sn-, and miarolitic gem-tourmalinebearing) pegmatites, and uraniferous pegmatitic sheeted leucogranites (SLGs), which have an NYF affinity. Fluid inclusion studies reveal that although mineralization differs between the different types of pegmatites located at different geographic locations, and by extension, different stratigraphic levels, the fluid inclusion assemblages present in these pegmatites are similar; thus different types of pegmatites are indistinguishable from each other based on their fluid inclusion assemblages. Thorough fluid inclusion petrography indicated that although fluid inclusions are abundant in the pegmatites, no primary fluid inclusions could be identified, and rather those studied are pseudosecondary and secondary. Fluid inclusions are aqueo-carbonic (± NaCl), carbonic, and aqueous. It is proposed that all of the pegmatites studied share a similar late-stage evolution, with fluids becoming less carbonic and less saline with the progression of crystallisation. Oxygen isotope ratios allow the discrimination of different pegmatites into two groups, Group A (Sn-, Li-Sn-, and gem-tourmaline-bearing LCT pegmatites), and Group B (Li-Bebearing LCT, and U-bearing NYF pegmatites). Group A pegmatites have O-isotope ratios ranging from 11 to 13 ‰ suggesting that they have an I-type affinity. These values are, however, elevated above those of typical I-type granites (7 - 9 ‰), indicating either a postemplacement low-temperature exchange with meteoric fluid, high-temperature hydrothermal exchange with δ18O country rocks during emplacement, or the derivation of these pegmatites from a non-pelitic/S-type metaigneous source. Group B pegmatites have higher δ18O ratios (δ18O = 15 - 16 ‰), indicative of their S-type affinity, and their derivation from metapelitic source rocks. δD values of all the pegmatites range from -40 ‰ to -90 ‰ indicating that the pegmatitic fluids are primary magmatic with a metamorphic fluid component. Trends in the trace element concentrations of both Group A and Group B pegmatites are very similar to each other, making the two groups indistinguishable from each other on this basis. The Damaran pegmatites also share similar geochemical trends with their country rocks. There is, however, no direct field evidence to suggest that the pegmatites were derived from the in situ anatexis of the country rocks. It is more likely that anatexis occurred some distance away from where the pegmatites were ultimately emplaced, and that the melts migrated and were finally emplaced in pre-existing structures, possibly formed during Damaran deformation. O-isotope and Ti-in-quartz geothermometry indicate that Damaran pegmatites can be subdivided into two groups based on their crystallisation temperatures. LCT pegmatites crystallised at temperatures ranging from ~ 450 - 550 ºC, while the NYF pegmatites crystallised at higher temperatures, ranging from 630 - 670 ºC. It is important to note that the subdivision of pegmatites in Groups A and B based on their O-isotope systematics does not correspond with their subdivision into the LCT and NYF pegmatite families according to their crystallisation temperatures. In addition to clarifying aspects of the emplacement and evolution of the Damaran pegmatites, this study points out that there are several discrepancies in the current classification schemes of pegmatites. It shows that in addition to the problems encountered when trying to distinguish between LCT and NYF pegmatites based on their mineralogy, they also cannot truly be distinguished from each other using their geochemical and isotopic characteristics, or their tectonic settings. It is tentatively proposed that crystallisation temperature be considered as an alternative or additional characteristic in the classification of pegmatites, and that it be considered on a regional scale rather than only in the evaluation of the highly evolved end-members of a pegmatite swarm.

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Chemical Engineering, 2016 / In South Africa, the need for water treatment is increasing, especially in the mining sector. As active water treatment technologies are expensive, the mining sector has an increasing need for passive water treatment technology, with low maintenance and operating costs, yet efficient water treatment ability. Literature on passive water treatment suggests that these systems only offer a narrow range of treatment capabilities. Therefore, hybrid water treatment systems could be a solution to low-cost water treatment in South Africa. The Degrading Packed Bed Reactor (DPBR) is one of the units comprising the hybrid treatment group. The DPBR’s main action is to convert sulfates into sulfides and alkalinity. In practice, the main drawback of the DPBR is clogging. Clogging lessens the amount of Acid Mine Drainage (AMD) that comes into contact with Sulfur Reducing Bacteria (SRB) in the DPBR, thereby reducing the efficiency of the bioreactor. In this study, six small-scale DPBRs were constructed. Each was classified according to its unique organic source (manure, straw, vegetable food processing waste, wood shavings, chicken litter and a combined sample with layers of all the carbon sources). Synthetic AMD was fed through the six bioreactors for a period of three months. From the small-scale DPBRs, the permeability, sulfate, iron and pH of the exit samples were measured. On average, the carbon sources removed 50 % of the sulfates and 98 % of the iron from the fed AMD. The different carbon sources showed no significant difference between each other in terms their sulfate and iron removal. The range between the best performing carbon source and the poorest performing carbon source, in terms of sulfate removal, was 17%. For iron removal, the range between the best and poorest performing carbon sources was only 2%. It was found that the permeability of the carbon sources played a larger role in the efficiency of the DPBR than the type of carbon source used. Manure is highly effective in terms of pH improvement, sulfate and iron removal. However, this is at the expense of permeability, as its packing clogs very rapidly. Compost and straw have excellent permeabilities which do not change significantly over long timeframes. This is, however, at the expense of the remedial ability of the packing materials. The combined reactor, in every instance, offers a good compromise between these different behaviours. / GR2016

[pt] A bactéria Rhodococcus opacus foi avaliada como biorreagente para a flotação dos minerais da magnesita calcita e barita. As análises para determinar a conformação de parede o R. opacus estabelecem que é constituída por macromoléculas com características anfipáticas. O balanço entre grupos catiônicos e aniônicos da parede atribui um ponto isoelétrico equivalente de 3,2. Os resultados dos testes de aderência indicam que a bactéria R. opacus tem uma forte afinidade por superfícies de características ácido - base. Medidas dos minerais antes e após da interação com o R. opacus revelaram que embora fossem observadas modificações sobre todas as superfícies dos minerais, a bactéria R. opacus apresentou uma melhor afinidade pela superfície da magnesita. A capacidade de adsorção das células sobre as superfícies foi fortemente dependente dos valores de pH e a velocidade de adsorção atingiu a máxima concentração de células nos primeiros 5 minutos. As isotermas para a adsorção da bactéria sobre os minerais poderiam ser categorizadas do tipo Lagmuir (L) , II. A melhor flotabilidade foi observada em pH 7. Para a magnesita, a porcentagem foi de 92% usando uma concentração de R. opacus de 100 ppm. Para calcita os melhores resultados apresentaram flotabilidade de 55% para uma concentração de 250 ppm. Em relação à barita, os melhores valores de flotabilidade (60%) foram obtidos para uma concentração de R. opacus de 350 ppm. A aproximação termodinâmica determinou que a energia de adesão era negativa para todos os sistemas, sugerindo assim uma adsorção espontânea da bactéria sobre as superfícies minerais. Para magnesita e calcita as teorias DLVO confirmam os resultados experimentais, as atrações eletrostáticas entre as partículas determinaram as forças de interação. Já para barita, a teoria de XDLVO poderia predizer o comportamento das células sobre o mineral. Neste caso as interações ácido-base seriam as responsáveis pela adesão. / [en] Rhodococcus opacus micro-organism was evaluated as a biocollector for flotation of calcite and magnesite and barite. Analyses of R. opacus cell wall indicated the macromolecules configurationl. The IEP value of R. opacus was around 3.2,. The acidic IEP value of R. opacus could be due to the presence of anionic groups on the wall that dominate over the cationic groups. The adherence test showed the R. opacus affinity for acid-base surfaces.The behavior of the minerals, before and after R. opacus interaction, was evaluated and showed that the cells adhesion shifted both the minerals zeta potential curves and the reversal charges in comparison to their original isoelectric points. Adhesion tests suggested a higher affinity of the bacteria for magnesite than calcite and barite. The experiments of the adsorption rate of the R. opacus on the minerals surfaces showed fast behavior, achieving a maximum of cell adsorption after 5 minutes. Adsorption isotherm curves for the minerals could be categorized as Lagmuir (L) type II. The best bioflotability results for the minerals were achieved for pH 7. Magnesite reached values around 93% for a R. opacus concentration of 100 ppm. For calcite the best flotability was of 55% for a R. opacus concentration of 220 ppm. For barite, the best flotability achieved 70% for a bacterial concentration of 350 ppm. Using the thermodynamic approach of the minerals systems, the adhesion energy of R. opacus on the surfaces was negative. The result suggested a spontaneous adsorption of R. opacus on to the all minerals. For magnesite and calcite, the DLVO theory can predict the cell behavior on the minerals surfaces. The electrostatic attractions determine the interaction forces. For barite and pH 7, the X- DLVO theory predicted the R. opacus adhesion on the surface by acid base interactions.

Orientador: Maria Margarita Torres Moreno / Banca: Antenor Zanardo / Banca: André Sampaio Mexias / Banca: Viviane Carillo Ferrari / Banca: Sérgio Ricardo Christofoletti / Resumo: As rochas sedimentares da Formação Corumbataí (Neopermiano) afloram próximas à borda leste da Bacia do Paraná e na região de Rio Claro (SP) constituem importante fonte de matéria-prima para a indústria cerâmica regional. O objetivo deste trabalho foi estudar a gênese e a evolução dos argilominerais presentes nos litotipos de dois perfis posicionados estratigraficamente na porção basal da Formação Corumbataí. As amostras foram coletadas nas frentes de lavra das minerações Pieroni e Estrela Dalva, localizadas no Distrito de Assistência, município de Rio Claro (SP) e analisadas através de difração de raios X, espectrometria de fluorescência de raios X, microscopia ótica e granulometria por absorção de raios X. A aplicação de técnicas complementares na interpretação dos difratogramas, como decomposição de picos e elaboração de difratogramas calculados, permititu a identificação dos argilominerais individualizados e interestratificados e associá-los aos processos deposicional, diagenético, hidrotermal e intempérico que atuaram ao longo da evolução geológica da Bacia do Paraná. A assembléia dos argilominerais é constituída por illita 2M1, illita 1Md, clorita, illita/clorita, clorita/esmectita e esmectita. O politipo illita 2M1 dioctaédrico é predominante e constitui o único argilomineral detrítico. Os argilominerais illita 1Md, clorita e illita/clorita resultam de transformações provocadas pela atuação de fluidos termais originados a partir da intrusão dos magmas básicos na forma de diques e sills correlatos à Formação Serra Geral, de idade Eocretácea. O interestratificado clorita/esmectita constitui o registro do início da fase pós-hidrotermal. / Abstract: Corumbataí Formation (Neopermian) sedimentary rocks arise near of the East edge of Parana Basin and in Rio Claro region (SP) constitute important raw material source for the regional ceramic industry. The aim of this work is to show genesis and evolution of clay minerals of the litotypes of two minings stratigraphycally located in Corumbatai Formation basal zone. The samples were collected from Pieroni and Estrela Dalva minings, in Assistencia District, Rio Claro city (SP) and analysed by techniques of X-ray diffraction, chemical analysis, optical microscopy and grain-size distribution. Aplicattion of complementary techniques in difratograms analysis as peak decomposition and calculated patterns difratograms allowed individualized and interstratified clay minerals identification and associate them with deposicional, diagenetic, hidrothermal and weathering processes during Parana Basin geological evolution. Clay minerals assemblage includes illite 2M1, illite 1Md, chlorite, illite/chlorite, chlorite/smectite and smectite. The polytipe illite 2M1dioctahedral is the predominant detritic clay mineral. Illite 1Md, chorite and illite/chlorite are the result of transformation due to basic magmas intrusions as sills and dykes associated to Serra Geral Formation (Eocretaceous). The presence of smectite at the top litotypes is due to weathering processes, conditioned for Cenozoic sediments that recover Corumbatai Formation rocks. The results suggest that the superimposed hidrothermalism on these pelitic rocks from the eocretaceous intrusions related to Serra Geral Formation constitutes the main geologic process during pelitic rocks evolution, changing the previous features and preparing all the posterior mechanisms, including the weathering alteration. / Doutor

This paper presents the comparison of shrinkage and corrosion characteristics of optimized hybrid Rice Husk Ash (RHA)/Fly Ash (FA)-modified Concrete, with those of normal concrete in the marine environment. Uses of both FA and RHA have numerous environmental benefits. Shrinkage performance was determined by subjecting the mixes to restrained shrinkage testing per ASTM C1581. The time to cracking of the specimens improved an average of 18% with the hybrid mixes. Corrosion testing of reinforced columns was performed in a simulated tidal cycle Marine Environment. Corrosion potential improved by as much as 35% for the mix with the highest FA/RHA replacement, and corrosion activity as measured with potentiostat equipment improved by an average of 34% . These results indicate a clear performance improvement of the modified concrete that is proportional to the percent replacement of cement. / by Diana Arboleda. / Thesis (M.S.C.S.)--Florida Atlantic University, 2010 / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2010. Mode of access: World Wide Web.

Basés sur la bio-oxidation de la matière organique, le compostage et le vermicompostage émettent des quantités non négligeables de CO2. Ainsi, ce travail s’intéresse (1) à la stabilisation potentielle du carbone de la matière organique compostable due à l’ajout de minéraux, avec et sans vers, et (2) l’influence des minéraux sur la maturité et la qualité du compost final. La première expérience consista en une incubation de matière organique, permettant d’obtenir différents composts et vermicomposts, avec et sans minéraux, de suivre les émissions de carbone et d’analyser les produits obtenus. Une deuxième incubation a été menée pour étudier l’effet de ces produits en tant qu’amendement sur un sol. Enfin, le suivi de la croissance de A.Thaliana en présence de co-composts et co-vermicomposts en tant que fertilisant fut réalisé. La présence de minéraux lors du compostage induit une baisse des émissions de carbone, probablement due à la formation d’associations organo-minérales ou bien par un changement des communautés microbiennes. De plus, les co-composts, en tant qu’amendement semblent augmenter les stocks de carbone du sol, comparé à un compost classique. Enfin, bien que l’aspect fertilisant des co-composts obtenus soit optimum, ils n’ont pas amélioré la croissance d’A.Thaliana. La présence de vers lors du co-compostage a augmenté les émissions de carbone mais l’effet positif des minéraux sur la minéralisation était toujours observable. De plus, les vers ont augmenté la biodisponibilité des nutriments et le co-vermicompost a permis d’améliorer les propriétés du sol ainsi que la croissance des végétaux comparé à un (vermi)compost classique et un co-compost. / Due to bio-oxidative mechanisms, composting and vermicomposting produce a large amount of CO2 emissions. Therefore, in this study we aimed to assess (1) the potential stabilization of carbon of fresh organic matter due to mineral presence, with and without worms, and (2) the influence of minerals on maturity and quality of the finished products. The first experiment was based on a laboratory incubation of fresh organic matter, which allowed to obtain composts and vermicomposts, with and without minerals, to monitor carbon emissions and to analyse the final products. A second incubation was carried out to investigate the effect of these products as organic amendment on an arenic cambisol. Finally, the last experiment was carried out to assess the use of co-composts and co-vermicomposts as potting media, by following the growth of. A.Thaliana. The presence of minerals during composting induced a decrease of carbon emission, likely due to the formation of organo-mineral associations or shift of microbial communities. Moreover, the use of co-compost as soil conditioner may allow to increase soil carbon storage, compared to a regular compost. Although the physico-chemical characteristics of the end-products were optimum for its use as potting media, no beneficial aspects on A.Thaliana growth has been observed. In presence of worms during co-composting, the carbon emissions were increased due to worm activities but the positive effect of minerals was still observed. In addition, worms improved the nutrient availability in the end products. Therefore, co-vermicompost tended to improve soil properties and to enhance plant growth compared to a regular (vermi)compost.

Os minerais sáo essenciais para a saúde e para reprodução de vacas leiteiras. O objetivo desse trabalho foi avaliar o efeito da utilização de um suplemento de microminerais injetável contendo cobre, manganês, selênio e zinco, 20 dias antes da inseminação artificial, sobre a saúde uterina, perfil de progesterona, desenvolvimento do embrião e fertilidade de vacas Holandesas. O experimento doi dividido em duas fases. Na primeira fase foram usados 306 vacas, entre 2 a 8 anos de idade, foram divididas em um grupo que recebeu suplemento de microminerais injetável (SIM)contendo cobre, manganês, selênio e zinco, 20 dias antes da inseminação artificial (IA) e um grupo controle, que não recebeu nenhum tratamento. Esses animais foram bloqueados por pariedade (primíparas e multíparas), período voluntário de espera (pequeno período de espera PPE e longo período de espera - LPE) e por fazenda (fazenda 1 e 2). Nessa etapa foi avaliada saúde uterina, atraves do corrimento vaginal uterino e pela endometrite citológica. Na segunda fase foram separados 130 animais, divididos em um grupo que recebeu suplemento de microminerais injetável contendo cobre, manganês, selênio e zinco, 20 dias antes da inseminação artificial e um grupo controle, que não recebeu nenhum tratamento, esse animais foram bloqueados por pariedade (primíparas e multíparas). Foi avaliada a concentração de progesterona, o diagnóstico de gestação e a morfometria da vesícula amniótica e do embrião/feto. Não foi encontrado diferença estatística entre grupos experimentais nas avaliações do corrimento vaginal purulento e na endometrite citológica, quando foi bloqueado por pariedade, período voluntário de espera e fazenda, também não foi encontrado diferença estatística. Não houve diferença entre os grupos no ferfil de progesterona, mas quando foi analisada a porcentagem de animais que estava púberes, encontrou-se diferença estatística dentre os grupos no dia 4 (dias após IA), onde a porcentagem de animais púberes no grupo que recebeu SIM foi maior que o grupo tratamento (P = 0,0319). Não foi encontrada diferença no diagnostico de gestação e na perda de prenhez. Na avaliação da morfometria do embrião, os animais que receberam SIM, a vesícula amniótica (longitudinal) e o comprimento do embrião (cabeça-nádega e abdominal) foram maiores que o grupo controle com 36 dias. Em conclusão o emprego com o tratamento com Sim 20 dias antes da IA, não tem efeito sobre a saúde uterina, prenhez e na perda de prenhez, mas melhorou a porcentagem de animais púberes e o tamanho do embrião. / Minerals are essentials to the health and reproduction of dairy cattle. The aim of this study was to evaluate the effect of the use of na injectable trace element supplement containing copper, manganese, selenium and zinc 20 days before the artificial insemination, on the uterine health, progesterone profile, embryo development and fertility of Hostein dairy cows. The trial was divided in two steps. In the first step, 306 cows, between 2 and 8 years old were divided in two groups. The first group received injectable trace element supplement (ITES) containing copper, manganese, selenium and zinc 20 days before the artificial insemination (AI). The second group did not receive the treatment, constituting the control group. These animals were blocked by parity (primiparous and multiparous), voluntary waiting period (short voluntary waiting period SVWP and long voluntary waiting period - LVWP) and farm (farm 1 and 2).In this step, uterine healthy was evaluated by checking the uterine vaginal discharge and by cytological endimetritis. In the second step, 130 cows were divided in two groups, which cows received same treatments used in the first step. These cows were blocked by parity (primiparous and multiparous) and progesterone concentration, pregnancy diagnosis, and amniotic vesicle and embryo/fetus morfology were evaluated. The evaluation of purulent vaginal discharge and cytological endometritis showed no statistical significance between treatment groups. When cows were blocked by parity, the voluntary waiting period and farm did not show any difference. While no differences were detected between groups when progesterone proflile was evaluated, the percentage of pubescent animais on day 4 after showed diferences. In the ITES group, the percentage of pubescent animals was increased compared to the treatment group (P = 0.0319). No differences were detected to pregnancy diagnosis and pregnancy loss. Studying embryo morphometry, the amniotic vesicle (longitudinal) and embryo length (head-buttock) were higher in ITES group compared to treatment group at 36 days. In conclusion, although the use of ITES 20 days before AI did not show any effect on the uterine healthy, pregnancy and pregnancy loss, the percentage of pubescent animais and embryo length was increased.

O presente estudo avaliou o efeito da suplementação mineral injetável de cobre (Cu) e zinco (Zn) sobre a resposta imunológica e o desempenho de bovinos de corte a pasto, foram avaliadas vacas no período pré-parto (experimento I) e seus bezerros até pós desmama (experimento II). O experimento foi realizado na Faculdade de Zootecnia e Engenharia de Alimentos da USP, Campus de Pirassununga-SP. No experimento I, foram avaliadas sessenta vacas prenhas por inseminação, distribuídas aleatoriamente em delineamento inteiramente casualizado com dois tratamentos (T e S). No tratamento testemunha (T), as vacas receberam soro fisiológico como placebo, e no tratamento suplementado (S) receberam mineral injetável via subcutânea (75 mg de cobre e 250 mg de zinco), com aproximadamente 75 dias antes do parto. Foram avaliados os teores de Cu e Zn séricos, IgG e IgM, ceruloplasmina e a atividade fagocitária. Os dados experimentais foram analisados utilizando-se o PROC MIXED do SAS (SAS, 2009), com o nível de significância de 5% para interpretação estatística de todos os testes. Os teores de cobre, zinco, IgM, IgG, ceruloplasmina e a atividade fagocitária das vacas não apresentaram diferença (p>0,05) entre os tratamentos. Da mesma forma, não houve influencia (p>0,05) das vacas nos teores de Cu e Zn séricos, na resposta imunológica e no desempenho dos bezerros aos 70 dias de idade (primeira coleta de sangue). O fornecimento de Cu e Zn injetável aos 75 dias antes do parto não alterou os teores de zinco, cobre e ceruloplasmina sérica, bem como a resposta imunológica até 30 dias após o parto. Como não houve diferença significativa entre as mães, foi considerado que os bezerros eram provenientes de vacas homogêneas. Assim, no experimento II, cinquenta e quatro bezerros filhos destas vacas, foram distribuídos aleatoriamente em delineamento inteiramente casualizado em 2 tratamentos: (T) - bezerros não suplementados, que receberam soro fisiológico como placebo; (S) - bezerros suplementados com cobre (15 mg aos 70 dias, 45 mg aos 140 dias e 60 mg aos 210 dias) e zinco (50 mg aos 70 dias, 150 mg aos 140 dias e 200 mg aos 210 dias). Foram realizadas colheitas de sangue com aproximadamente 70, 140, 170, 210 e 240 dias de idade, para avaliação dos teores de Cu e Zn sérico, ceruloplasmina, IgG e IgM e a atividade fagocitária. A suplementação parenteral de Cu e Zn aos 70, 140 e 210 dias não alteraram (p>0,05) os teores de Cu e Zn séricos, a resposta imunológica, o desempenho, a atividade da enzima superóxido dismutase e a atividade fagocitária de bezerros Nelore. A falta de resposta ao suplemento mineral injetável deveu-se possivelmente ao fato dos bezerros já estarem recebendo as quantidades adequadas de cobre e de zinco nas suas dietas. / This study evaluated the effect of injectable Cu and Zn on the immune response and performance of beef cattle on pasture, cows were evaluated in the antepartum period (experiment I) and their calves to post weaning (experiment II). The experiment was perfomed at the Faculty of Animal Science and Food Engineering, University of São Paulo, Campus Pirassununga. In experiment I, sixty pregnant Nelore cows by insemination were divided in a completely randomized design in two treatments. In the control treatment (T), the 30 cows received saline as placebo, the supplemented (S) received mineral injection subcutaneously (75 mg of copper and 250 mg of zinc), 75 days prior to parturition, when also received clostridiosis vaccine. It were evaluated the serum levels of Cu and Zn, IgG, and IgM, ceruloplasmin, SOD and phagocytic activity. Experimental data were analyzed using PROC MIXED of SAS (SAS, 2009), with 5% significance level for statistical interpretation of all tests. The levels of copper, zinc, IgM, IgG, ceruloplasmin and the phagocytic activity of the cows had no statistical difference (p>0.05) between treatments. Similarly, there wasn\'t influence (p>0.05) of cows for Cu and Zn serum, immune response and performance of calves at 70 days of age (first blood sample). The supply of Cu and Zn injection at 75 days before delivery did not change the levels of zinc, copper and serum ceruloplasmin and the immune response 30 days after delivery. Since there was no significant difference between the mothers, it was considered that the calves were from homogeneous cows. In experiment II, fifty four calves born from these cows were distributed completely randomized design with 2 treatments: (T) - calves not supplemented that receive solution saline as placebo and (S) - calves supplemented with injectable mineral applied subcutaneously containing copper (15 mg at 70 days, 45 mg at 140 days and 60 mg at 210 days) and zinc (50 mg at 70 days, 150 mg at 140 days and 200 mg at 210 days. Blood samples were realized with approximately 70, 140, 170, 210 and 240 days of age. Were assessed levels of serum Cu and Zn, ceruloplasmin, IgG and IgM and the phagocytic activity. Parenteral supplementation of Cu and Zn at 70, 140 and 210 days didn\'t alter (p>0.05) the contents of Cu and Zn serum, the immune response, performance, activity of superoxide dismutase and the phagocytic activity of Nelore calves. The lack of response to injectable mineral supplement possibly was due to the fact that the calves were already taking adequate amounts of copper and zinc in their diets.

Este trabalho teve por objetivo avaliar os efeitos do uso de dietas com diferentes balanço cátion-aniônico dietético (BCAD) na produção e na qualidade do leite de búfala, nas características fermentativas através da técnica de produção de gás in vitro, além de traçar perfil nutricional de búfalas em lactação em propriedades de bubalinocultura da região central do Estado de São Paulo. Dessa forma, a tese está apresentada na forma de 11 capítulos, sendo que os capítulos 1, 2 e 11 descrevem a introdução, revisão de literatura e considerações finais, respectivamente. Os demais descrevem diferentes experimentos realizados sob a temática geral de 2012 a 2014. O capítulo 3 contém a avaliação de quatro dietas catiônicas com alto BCAD (+362, +370, +379 e +390 mEq/kg/MS) formuladas conforme rendimento do queijo muçarela para 350 búfalas, divididas em dois grupos (búfalas com menos e acima de 100 dias de lactação no início do experimento) durante período experimental de 120 dias. Dez tratamentos foram designados adotando-se diferentes formas de sistema de alimentação durante todo o experimento. A covarivavel idade não influenciou na produção e qualidade do leite das búfalas, exceto na contagem de células somáticas (CCS) e condutividade elétrica nas búfalas ≤100 dias de lactação. Houve diferenças significativas entre os tratamentos para a produção de leite diária em ambos os grupos de búfalas. Somente a lactose apresentou diferenças entre os tratamentos em búfalas no início da lactação. A forma do sistema de alimentação com alteração das dietas contendo diferentes BCAD a cada 30 dias não produz efeitos na produção e qualidade do leite em búfalas no estágio inicial da lactação, porém aumenta a produção de leite em búfalas acima de 100 dias de lactação. No capítulo 4 a produção diária e a qualidade do leite foram avaliadas em 297 búfalas, divididas em dois grupos, um com menos de 100 e outro de 100 a 220 dias de lactação recebendo duas dietas catiônicas com baixo BCAD: D121 (+121 mEq/kg/MS) e D164 (+164 mEq/kg/MS) em dois sistema de alimentação, definindo quatro tratamentos. O BCAD influenciou na produção de leite das búfalas, entretanto, o menor BCAD produziu melhoria na produção de leite. O BCAD mais elevado promoveu aumentos nos teores de proteína, sólidos totais (ST), extrato seco desengordurado (ESD) e CCS nas búfalas de 100 a 200 dias de lactação. No capítulo 5 quatro dietas aniônicas com BCAD de -61, -67, -73 e -100 mEq/kg/MS foram avaliadas em 259 búfalas, divididas em dois grupos, com 100 a 200 dias e acima de 200 dias de lactação. O BCAD negativo não interferiu na produção de leite diária e na qualidade do leite das búfalas, porém, influenciou no teor de gordura e lactose do leite em ambos os grupos de lactação e ainda nos teores de proteína, sólidos totais e CSS nas búfalas acima de 200 dias de lactação. No capítulo 6, foram avaliados três níveis crescentes de BCAD de +40, +120 e +190 mEq/kg/MS na produção, qualidade e minerais no leite de búfalas, não observando alterações significantes na produção, qualidade e minerais no leite de búfala, exceto na condutividade elétrica, acidez titulável e nos teores de Na e Cl. No capítulo 7 realizou-se a caracterização da produção, qualidade e minerais do leite na curva de lactação de búfalas em dietas catiônicas com baixo BCAD. Os dados mostraram que a curva da lactação iniciou-se ascendente, com pico no 2°. e 3°. mês e posterior declínio com maior produção de leite nos primeiros 90 dias da lactação (40%). As búfalas paridas no segundo semestre apresentaram média diária de produção de leite ao longo da lactação superior que as paridas no primeiro semestre com a qualidade do leite semelhante em ambas os grupos. Os teores de gordura, proteína, ST e ESD ao longo da lactação aumentaram no leite e depois se mantiveram constantes, enquanto que a lactose diminuiu e a CCS não se alterou ao longo do experimento. Os níveis de macrominerais no leite de búfala foram constantes durante a lactação, exceto o cloro que sofreu queda. O Ca e o K apresentaram-se em maior concentração. No capítulo 8 é descrita a caracterização da produção acumulada e diária do leite de búfala na curva de lactação em função da duração da lactação, número da lactação e faixa etária dos animais, recebendo dieta com BCAD médio de +83 mEq/kg/MS. A curva da lactação em búfalas caracterizou-se pelo crescimento da produção de leite até os primeiros 90 dias, seguida de um declínio gradativo até o final da lactação, não existindo influência da duração da lactação, número da lactação e da faixa etária dos animais. Foram identificadas quatro fases com diferentes níveis de queda mensal de produção em relação ao mês anterior (aumento; leve, médio e forte declínios). Búfalas mais velhas acima de 11 anos de idade apresentam declínio mais acentuado que búfalas mais jovens. No início da lactação até 90 dias, búfalas com maior número de lactações e faixa etária produziram mais leite que as mais jovens. No capítulo 9 compararam-se dietas com BCAD de +110, +220 e +440 mEq/kg/MS na cinética de fermentação ruminal, por meio de parâmetros da produção de gases totais e metano, degradabilidade da matéria seca e orgânica e produção de ácidos graxos de cadeia curta e nitrogênio amoniacal em 24 e 96 horas de inoculação, com a técnica de produção de gases in vitro, usando inóculo de conteúdo ruminal de bubalinos. Não foram observadas diferenças entre os tratamentos em qualquer variável avaliada. As ausências de efeitos sugerem ações outras do BCAD sobre o metabolismo animal do que sobre o metabolismo ruminal na produção de efeitos sobre o desempenho produtivo dos animais. Concluindo esses estudos, o capítulo 10 descreve a avaliação do sistema de exploração de leite de búfalas de quatro propriedades rurais, compreendendo um total de 794 búfalas, com caracterização da composição de 11 tipos de dietas e composição químico-bromatológica de ingredientes das dietas utilizadas. As búfalas apresentaram ingestão de matéria seca média diária de 17,8 kg por animal (2,6% do peso vivo e 91 g MS/kg0,75) e produção de leite média de 8,1 kg/animal/dia com conversão alimentar de 2,2 kg de MS por kg de leite produzido/animal/dia. / This study aimed to evaluate the effects of feeding diets with different dietary cation-anion difference (DCAD) in the production and quality of buffalo milk, in the fermentation characteristics by in vitro gas production technique, and in addition to showing nutritional profile lactating buffalo on farms located in the central region of São Paulo state, Brazil. Thus, this thesis is presented in the form of eleven sections, where the Chapters 1, 2 and 11 describe the introduction, literature review, and final considerations, respectively. The others describe different experiments performed under the general theme from 2012 to 2014. The Chapter 3 contains the evaluation of four cationic diets with high DCAD (+362, +370, +379 and +390 mEq / kg / MS) formulated as mozzarella cheese yield basis in 350 buffaloes, divided into two groups (buffaloes less and above 100 days of lactation at beginning of the experiment) during the experimental period of 120 days. Ten treatments were assigned adopting different ways feeding system throughout the experiment. The covariate age did not influence the production and quality of milk, except in somatic cell counting (SCC) and electrical conductivity in buffaloes ≤100 days of lactation. Significant differences were observed between treatments for daily milk production in both groups buffaloes. Only lactose has differed between treatments in buffaloes in early lactation. The feeding system with changing diets containing different DCAD every 30 days has no effect on production and quality of milk in buffalo in the early stage of lactation, but it increases milk production in buffalo over 100 days of lactation. In chapter 4, the daily production and milk quality were evaluated in 297 buffaloes, divided into two groups, one with less than 100 and another 100-220 days of lactation receiving two cationic diets with low DCAD: D121 (+121 mEq / kg / DM) and D164 (+164 meq / Kg / MS) to two feeding systems, defining four treatments. DCAD has influenced the milk production of buffaloes. Lower DCAD has produced higher milk production. The highest DCAD has promoted increases in protein, total solids (TS), solid no fat (SNF) and SCC in buffaloes with 100-200 days of lactation. In Chapter 5, four anionic diets with DCAD of -61, -67, -73 and -100 mEq / kg / DM were evaluated in 259 buffaloes, divided into two groups: between 100 - 200 days and over 200 days of lactation. The negative DCAD has not interfered in daily milk production and milk quality in buffaloes, however, has influenced the fat and lactose contents of milk in buffalo in both groups of lactation and also in protein levels, and total solid and SCC of buffalo over 200 days of lactation. In Chapter 6, were evaluated three increasing levels of DCAD: +40, +120 and +190 mEq / kg / DM in production, quality and minerals in buffalo milk. No significant differences were observed in production, quality and minerals in buffalo milk except in electrical conductivity, acidity and levels of Na and Cl. In Chapter 7, the characterization of production, quality and minerals of milk along the lactation curve were evaluated in buffaloes on cationic diets with low DCAD. The data showed that the lactation curve started rising, peaking on the 2nd. and 3rd. month and subsequent decline with higher milk production in the first 90 days of lactation (40%). The calved buffaloes in the second half of the year had higher average daily milk production along the lactation than that calved in the first half with the quality of milk similar in both groups. The fat, protein, TS and SNF increased in milk throughout the lactation and, then remained constant, while lactose decreased and the SCC did not change. The buffalo milk macrominerals have maintained the same levels along lactation, except chlorine that dropped. Ca and K showed up in higher concentration. In Chapter 8 describes the characterization of accumulated and daily production of buffalo milk during lactation curve as a function of lactation period, number of lactation and age of the animals fed diet with medium DCAD of +83 mEq/kg/DM. The lactation curve in buffaloes characterized by the growth of milk production until the first 90 days, followed by a gradual decline until the end of lactation, with no influence of lactation period, lactation number and age of the animals. Four phases have been identified with different monthly decline levels of production compared to the previous month (increase; slight, medium and, strong declines). Older buffaloes above 11 years of age had steeper decline than younger buffaloes. In early lactation up to 90 days, buffaloes with more lactations and age have produced more milk than younger. In Chapter 9, three diets of DCAD +110, +220 and +440 mEq/kg DM were evaluated by ruminal fermentation kinetics, involving total production and methane gases, degradability of dry matter and organic matter and fatty acids of short chain and ammonia nitrogen productions in 24 and 96 hours of inoculation, by using in vitro gas production technique with inoculum of rumen contents of buffalo. No differences were observed between treatments. No observed effects suggest other actions of DCAD on animal metabolism than on ruminal metabolism in producing productive performance of the animals. Completing these studies, Chapter 10 describes the evaluation of buffalo milk operating system of four rural properties, comprising a total of 794 buffaloes, with characterization of the composition of 11 types of diets and chemical composition of the diet ingredients used. The buffaloes had dry matter intake daily average of 17.8 kg per animal (2.6% of body weight and 91 g DM / kg0.75) and average milk production of 8.1 kg / animal / day with feed conversion 2.2 kg of dry matter per kg of produced milk / animal / day.

As cargas minerais têm sido utilizadas em misturas com os mais variados tipos de polímeros, misturas estas chamadas compósitos, com a finalidade de barateamento de custos e, mais particularmente, porque agregam melhorias das características físicas e químicas das peças fabricadas. As indústrias químicas fabricantes de polímeros têm procurado desenvolver novos tipos de polímeros. A disputa torna-se acirrada pelo grande mercado consumidor que existe. As empresas tentam, então, atender as mais diversas necessidades de tipos e características físicas e químicas dos materiais e peças fabricados pelas indústrias consumidoras. No Brasil as cargas minerais ainda são utilizadas pelas indústrias, na sua maioria, de forma empírica, em misturas com os polímeros. O entendimento das propriedades intrínsecas das cargas minerais e dos polímeros, da influência da tensão superficial na interação entre eles, o desenvolvimento de novos equipamentos de medida da tensão superficial, o desenvolvimento de agentes de tratamento superficial visando melhorar a compatibilidade de energia entre a carga mineral e o polímero, tudo isso tem contribuído para uma melhor compreensão e previsão das propriedades de compósitos e nanocompósitos. Várias pesquisas têm sido desenvolvidas nesta direção, cujo intuito principal é o de comparar o efeito do uso, em polímeros, de cargas minerais diversas, tratadas e não tratadas superficialmente com agentes químicos como silanos e ácidos graxos. As características físicas e químicas dos produtos destas misturas, como elongamento, tensão de ruptura à flexão, deformações ao calor, etc, são medidas e definidas, constatando-se modificações nestas propriedades quando comparadas com as mesmas propriedades para os polímeros puros. / The mineral fillers have been used in admixtures with a large variety of polymers called composites with the purpose not only of reducing their prices but mainly due to the improvements of their physical and chemical characteristics. The polymer manufacturers have been looking for the development of new types of polymers and composites in a battle driven by the great existing market as well as the consumers needs for products with distinct physical and chemical properties and lower prices. In Brazil the mineral fillers are still mainly used in empirical admixtures with polymers. The understanding of the intrinsic properties of mineral fillers and polymers, the influence of the surface tensions in the mineral/polymer interactions, the development of new equipments for measuring the surface tension, as well as chemical agents to promote the surface compatibility between mineral and polymer, has contributed for a better understanding and foreseeing the properties of composites and nanocomposites. Many researches have been developed under this direction with the goal of comparing the effect of using mineral fillers with and without superficial treatment by by chemical agents in admixed with polymers. The physical and chemical properties of these composites, such as elongation, flexural tensile strength, heating behavior and many others are measured and defined, supporting the properties enhancement when compared with the same properties for the stand alone polymers.