Investiga-se a influência de diferentes tratamentos sobre o sistema alumínio com cobertura de óxido de alumínio. A anodização do alumínio em meio de ácido sulfúrico e meio misto de sulfúrico e fosfórico foi empregada para alterar a resistência à corrosão, a espessura, o grau de cobertura e a microdureza do óxido anódico; e a eletrodeposição de ferro no interior óxido anódico em meio de sulfato com tratamento químico de selagem com cério, para alterar a sua condutividade elétrica e a sua resistência à corrosão. Para a eletrodeposição de ferro aplicou-se corrente contínua e pulsada e diversificou-se a composição do eletrólito de Fe(SO4)2(NH4)2.6H2O, com a adição dos ácidos bórico e ascórbico e para o tratamento de selagem, variou-se a concentração do CeCl3. A espectroscopia de energia dispersiva de raios X (EDS), a fluorescência de raios X (FRX) e a análise morfológica por microscopia eletrônica de varredura (MEV) permitiram verificar que, a corrente pulsada eleva o teor de ferro na camada anódica e a presença dos aditivos inibe a oxidação do ferro. As curvas cronopotenciométricas obtidas durante a eletrodeposição de ferro indicaram que a mistura dos ácidos bórico e ascórbico aumentaram a eficiência do processo de eletrodeposição. A espectroscopia de impedância eletroquímica (EIE), medidas de microdureza Vickers (H) e análise morfológica evidenciaram que o tratamento de selagem melhora a resistência à corrosão do filme óxido modificado com ferro. As medidas de impedância elétrica por duas pontas permitiram comprovar o aumento da condutividade elétrica do alumínio anodizado com ferro, mesmo após o tratamento com baixas concentrações de cério. Nanofios de ferro foram preparados utilizando os poros do óxido anódico como matriz. / The influence of different treatments on the aluminum system covered with aluminum oxide is investigated. The aluminum anodization in sulphuric media and in mixed sulphuric and phosphoric media was used to alter the corrosion resistance, thickness, coverage degree and microhardness of the anodic oxide. Iron electrodeposition inside the anodic oxide was used to change its electric conductivity and corrosion resistance. Direct and pulsed current were used for iron electrodeposition and the Fe(SO4)2(NH4)2.6H2O electrolyte composition was changed with the addition of boric and ascorbic acids. To the sealing treatment the CeCl3 composition was varied. The energy dispersive x-ray (EDS), the x-ray fluorescence spectroscopy (FRX) and the morphologic analysis by scanning electronic microscopy (SEM) allowed to verify that, the pulsed current increase the iron content inside the anodic layer and that the use of the additives inhibits the iron oxidation. The chronopotentiometric curves obtained during iron electrodeposition indicated that the boric and ascorbic acids mixture increased the electrodeposition process efficiency. The electrochemical impedance spectroscopy (EIE), the Vickers (H) microhardness measurements and morphologic analysis evidenced that the sealing treatment improves the corrosion resistance of the anodic film modified with iron. The electrical impedance (EI) technique allowed to prove the electric conductivity increase of the anodized aluminum with iron electrodeposited even after the cerium low concentration treatment. Iron nanowires were prepared by using the anodic oxide pores as template.

O sistema de plantio direto (SPD) é extensivamente utilizado no Brasil por tratar-se de prática conservacionista, capaz de melhorar a qualidade do solo e diminuir os custos da produção em relação ao plantio convencional. Neste sistema as condições edafoclimáticas distintas e a adoção de diferentes culturas na entressafra sugerem diferenças na distribuição e na qualidade da matéria orgânica de solos (MOS), devido ao tempo de resiliência da palha em cobertura. A interação entre a MOS e os pesticidas já foi bastante estudada, mas apenas parcialmente esclarecida uma vez que a maioria dos estudos considera a MOS como um compartimento homogêneo, ignorando o papel de seus diferentes componentes moleculares. Assim sendo, o objetivo principal deste trabalho é avaliar o efeito da composição, distribuição e interação com a fase mineral da MOS na sorção de herbicidas aplicados às culturas de soja e milho, sob sistema plantio direto em diferentes condições edafoclimáticas: tropical (Região Centro-Oeste) e subtropical (Região Sul). Os herbicidas alaclor, bentazon e imazetapir foram selecionados devido às suas importâncias junto a essas culturas e suas propriedades físico-químicas distintas. Para tal, soram amostrados 12 Latossolos, na camada de 0 a 5 cm excluindo a palha de superfície, sendo seis representativos do Estado do Paraná (clima subtropical) e seis representativos do Estado do Mato Grosso do Sul (clima tropical). A determinação dos atributos físico e químicos, formas de ferro e alumínio, estudo da qualidade da MOS por espectroscopia de Ressonância Nuclear Magnética do 13C e fracionamento físico dos solos foram os métodos utilizados. Foi observado maior acúmulo de carbono orgânico (C.O) nos solos subtropicais devido ao maior teor de óxidos de alumínio de baixa cristalinindade, além da maior precipitação. Para os solos de ambas as regiões, a estabilização da MOS ocorre através da formação de complexos nos agregados tamanho argila ( ~ 50% do teor de C.O). Em relação às interações com a fase mineral, observou-se que os óxidos de alumínio estão relacionados à proteção física da MOS enquanto que os óxidos de ferro parecem participar das reações de decomposição e humificação através da formação de complexos com grupos carboxílicos. Para o alaclor, a presença de formas de alumínio de baixa cristalinidade diminuiu a sua sorção a MOS, entretanto a sorção deste herbicida não foi correlacionada a nenhum grupo funcional. Para o bentazon, foi observada correlação positiva entre a sorção e materiais orgânicos mais decompostos e também, com o alumínio complexado a MOS. Para o imazetapir, houve correlações positivas com as formas de ferro e alumínio e o grupo funcional carboxil. Para os três herbicidas a maior sorção foi observada nos agregados de tamanho silte (53 a 2 ?m) e, de maneira geral, a sorção nos solos tropicais foi maior que nos subtropicais. O efeito da exposição de sítios de carga após o fracionamento físico dos solos foi evidente para o imazetapir incrementando sua sorção em comparação a sorção no solo inteiro o que evidencia a maior quantidade de sítios bloqueados nos solos tropicais. / No-tillage System (NT) is widely used in Brazil due to improve soil quality and reduce production costs compared to conventional tillage. Different climatic conditions and the adoption of different cultures in the offseason suggest differences in the distribution and quality of soil organic matter (SOM) due to the resilience time of straw in coverage in NT. Interactions between SOM and pesticides has been widely studied, but only partially elucidated. In most of studies, the MOS as a homogeneous compartment and there is not the knowledge about the role of its various molecular components. Therefore, the aim of this work is to evaluate the effect of the composition, distribution and interaction with the mineral phase of SOM on sorption of herbicides applied to soybean and corn under no-tillage in tropical (Central-west) and subtropical (South Region) soils. Alachlor, bentazon and imazethapyr herbicides were selected because of its large use in these cultures and different physicochemical properties. For this, it was sampled 12 soils at 0-5 cm layer excluding the straw surface, six representing the Paraná State (subtropical) and six representative of Mato Grosso de Sul State (tropical). Physical and chemical attributes, iron and aluminum forms, study of quality of SOM by Nuclear Magnetic Resonance Spectroscopy of 13C and soil physical fractionation methods were used for this purpose. Greater accumulation of organic carbon (OC) was observed in subtropical soils due to higher low crystalline aluminum oxides contents, in addition to lower temperatures and higher moisture in this region. For soils of both regions, the SOM stabilization occurs through the formation of complexes in the clay fraction (~ 50 % of the OC content). Regarding interactions with the mineral phase, it was observed that aluminum oxides are related to physical protection of SOM while iron oxides appear to participate in the decomposition and humification reactions by forming complexes with carboxylic groups. For alachlor, low crystallinity aluminum forms decreased its MOS sorption but sorption of this herbicide was not correlated with any functional group. For bentazon, positive correlation was observed between sorption and more decomposed organic material and with the complexed aluminum in MOS. For imazethapyr, there were positive correlations with iron and aluminum forms and carboxyl functional group. For the three herbicides better sorption was observed in the silt size fractions (53-2 ?m) and in general, sorption in tropical was higher than in subtropical soils. The effect of charge sites exposure after soil physical fractionation was evident for imazethapyr increasing its sorption compared to the whole soil which shows the greatest amount of blocked sites in tropical soils.

The Cenozoic Ailaoshan – Red River shear zone marks the present day western margin of the South China Block. Along this margin are well preserved late Paleoproterozoic to early Neoproterozoic sedimentary and volcanic successions. This work examines the ages and tectonic environments for the formation of the successions, as well as significance of the regional tectono-magmatic events on the formation of widespread iron oxide-copper deposits. The oldest succession is the Paleoproterozoic Dahongshan Group. A new SHRIMP UPb age of 1675 ± 8 Ma for a tuffaceous schist unit confirms its Paleoproterozoic age. Detrital zircon ages of the Dahongshan Group range between Archean to Paleoproterozoic (ca. 2780 – 1860 Ma). They include a population of ca. 2400 – 2100 Ma grains, which have no known source region on the exposed Yangtze Block. Previous geochemical studies of metavolcanic rocks from the Dahongshan Group have suggested that these rocks were erupted in an oceanic setting. However, this study shows that the metavolcanics are extremely altered and cannot be used for reliable tectonic discrimination. Based on the characteristics of sedimentary rocks in the Dahongshan Group, it is suggested that these rocks were deposited in a continental setting. Overlying the Dahongshan Group is a thick sedimentary sequence which has been variably termed the Kunyang, Dongchuan, Huili or Xide Groups. In the past, these rocks have been considered as a Mesoproterozoic rift succession. However, no precise age constraints were available for the succession. In this study, this sequence is found to contain at least two separate tectonostratigraphic units. The oldest (ca.1140 Ma) is comprised of alkaline basalt with a geochemical and isotopic character similar to that of modern intracontinental rift basalts. The presence of Cathaysia-derived sediments in this unit indicates sedimentary transportation from the southerly Cathaysia Block to the northerly Yangtze Block (in present coordinates) in South China at that time, which suggests an “impactogen” scenario. The thick sedimentary sequence of what has traditionally been defined as the Kunyang Group has been found to have significantly younger depositional age of ca.1000 – 960 Ma. The composition of sedimentary rocks and the provenance of detrital zircons from the Kunyang Group are consistent with a foreland basin setting. The depositional age of this sequence coincides with the timing of Sibao Orogeny as determined elsewhere in the South China Block. Summary Page ii Numerous iron oxide - copper (gold) deposits occur within the rocks of the Dahongshan and Kunyang Groups. Previous studies have classified these deposits into two deposit styles: the Dahongshan-type Paleoproterozoic VMS mineralisation hosted within the Dahongshan Group, and the Dongchuan-type diagenetic carbonate and shale-hosted deposits hosted within the Kunyang Group. However, both deposit types share similarities with the iron oxide – copper (gold) deposit class, such as stratabound disseminated and massive copper ores, abundance of iron oxide occurring mostly as low Ti - magnetite and haematite, and variable enrichments in Au, Ag, Co, F, Mo, P and REE. 40Ar/39Ar data from both deposit types indicate mineralisation ages of ca. 850 – 830 Ma and 780 – 740 Ma.

Several studies on small animals have shown that MRI enhanced with nanoparticles of iron oxide (USPIO) is able to detect the neuroinflammation. However, to our knowledge, no team had yet investigated the potential of this approach for monitoring an anti-inflammatory treatment. In this context, we have demonstrated the feasibility of this approach to monitor the effects of minocycline after cerebral ischemia in mice. MRI is a very sensitive technique for the detection of iron, but the precise location of USPIO as well as their quantification is difficult. We therefore propsed to complete the MRI approach by a new technique to our knowledge in the field of USPIO imaging in the brain : Synchrotron radiation tomography. We here present the first results showing the feasibility of this approach and a comparative study of the sensitivity of two techniques used for the detection of USPIO in the brain. In the last part of our work, we report our results on the biotransformation of USPIOs in the spleen of the mouse during the first 40 days after intravenous injection obtained by transmission electron microscopy (TEM).

Periglaziale Deckschichten auf carbonatreichen Gesteinen der geologischen Formation des Muschelkalks sind bisher nur peripher Gegenstand wissenschaftlicher Untersuchungen innerhalb der Deckschichtenfor-schung. Um diese Lücke zu schließen, widmet sich die vorliegende Arbeit dem Aufbau des oberflächenna-hen Untergrundes im Muschelkalk in einem Teilgebiet in der ostthüringischen Triaslandschaft. Die Ergebnisse zeigen, dass die periglazialen Deckschichten in Abhängigkeit von lithologischen Gesteins-merkmalen und Relieffaktoren (Exposition, Neigung) eine hohe räumliche Heterogenität hinsichtlich der stoff-lichen Zusammensetzung, der vertikalen Gliederung und Gründigkeit aufweisen. Sie sind in Basislagen (LB), Mittellagen (LM) und Hauptlagen (LH) gegliedert, die ihrerseits eigenständige Schichten beinhalten können. Die Lagenbildungen über carbonatreichen Gesteinen des Muschelkalks weisen Besonderheiten im Aufbau, in den stofflichen Eigenschaften und in ihrer Genese auf. Die Basislagen sind in der Regel mehrgliedrig entwickelt und können bis zu drei, faziell zu unterscheidende Substratkomplexe enthalten. Dies sind i) eine skelettfreie Kalksteinbraunlehm-Fließerde (LB-F), ii) ein Kalk-steinbraunlehmschutt (LB-1) und iii) ein Kalksteinschutt (LB-2). Die Zweiteilung der Basislagenschutte sowie die Abfolge LB-1/ LB-2 (LB-1 über LB-2) können als charakteristische Merkmale der Basislagenbildung über Muschelkalk herausgestellt werden. Skelettfreie Kalksteinbraunlehme (LB-F) stellen eine Besonderheit auf Carbonatgesteinen dar, da vergleichbare Bildungen auf quarz- und silikatreichen Standorten fehlen. Die Hauptlagen werden in eine schluffreiche (LH) und tonreiche (LHT) Fazies unterschieden. Beide zeichnen sich durch eine vollständige Skelettfreiheit aus, die ebenfalls als übergreifendes Merkmal über Muschelkalk gelten kann. Zwei Mittellagentypen sind mit skelettfreier Mittellage (LM) und skeletthaltiger Mittellage (LMs) vertreten. Die Genese der Basislagenabfolge LB-F/ LB-1/ LB-2 fand vollständig im Weichselglazial statt und schließt eine periglaziale Genese der Kalksteinbraunlehme ein. Die Beteiligung von Spülprozessen an der (Geli-) Solifluktion hat die Akkumulation von Lösungsrückständen (= Kalksteinbraunlehm) gefördert. Die Zweiteilung der Basisschutte kann ebenfalls durch die Mitwirkung ablualer Prozesse erklärt werden. Die Kalksteinbraun-lehm-Fließerde entstand synsedimentär zur Bildung der Basislagenschutte durch laterale Ausspülung. Die Variabilität der Lössedimente wird neben Luv-/Lee-Effekten und präsedimentäre karstartige Hohlformen vor allem auch über eine differenzierte periglaziale Bodenfeuchte- und Vegetationsverteilung gesteuert. In der Arbeit wurden u.a. der gU/fU-Quotient, pedogene Eisenoxide (Feo, Fed), Gesamteisengehalt (Fet), Fet/Ton-Quotient und (Fed-Feo/(Fet/Ton)-Quotient (nach GÜNSTER et al. 2001) sowie die Korrelation von Tongehalt und pedogenem Eisen für alle oben genannten Substrate ermittelt. Eine integrative Betrachtung dieser Parameter ist grundsätzlich geeignet, primäre Sedimenteigenschaften der Substrate herauszustellen und eine pedogenetische Überprägung abzugrenzen. Darüber hinaus erlauben sie Aussagen zur Genese. Der Tongehalt der Mittellagen konnte neben der Überformung durch Tonverlagerung als sedimentogene Ei-genschaft belegt werden. Kalksteinbraunlehme mit weniger als 65% Tongehalt müssen nicht grundsätzlich lösslehmbeeinflusst sein. Rezente Lösungsprozesse und eine rezente Weiterbildung der Kalksteinbraunleh-me konnten auch im Liegenden mächtigerer Lösssedimente nachgewiesen werden. Es wird gezeigt, wie die periglazialen Decksedimente in ihrer räumlichen, vertikalen und stofflichen Variabilität Einfluss auf die Heterogenität der Bodendecke nehmen.

This work details the synthesis and growth mechanisms of 1D magnetic and semiconducting nanostructures. Specifically, magnetic iron oxide and ZnS-SiO2 nanowires are examined. These materials are chosen due to their promise for biomedical and electronic applications and the perceived need to both create these structures as tools for these applications and to understand their formation processes so that they can be manufactured at a scale and efficiency suitable for commercialization. The current state and impact of nanotechnology is discussed through the lens of continuing technological advances and environmental factors, and the term is defined according to a specific set of criterion involving size, utility, and uniqueness. Details of synthesis and characterization of Fe3O4, ε-Fe2O3, and ZnS-SiO2 core-shell nanowires are presented. Observations regarding the growth of these structures are paired with additional experiments, simple simulations, and other literature to discuss the classical VLS growth process in general, and its applicability to these structures in particular. Finally, some exciting future applications are discussed, with details for initial experimental work presented in the appendix.

Thesis (Ph.D.); Submitted to The University of California at Berkeley, Berkeley, CA (US); 1 Sep 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "LBNL--55022" Prilliman, Gerald Stephen. USDOE Director. Office of Science. Office of Basic Energy Sciences (US) 09/01/2003. Report is also available in paper and microfiche from NTIS.

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