(Table A1) Calcium carbonate content of boreholes Kirchrode I and II

The technical details of drilling and coring at the Kirchrode I and II sites are presented. At these sites, a sequence of claystones and marlstones from an Albian shelf basin was recovered. Constraints on the ages of the sediments in the two boreholes are provided by the occurrence of the inoceramid bivalve Actinoceramus sulcatus, the first appearance of which is used to define the Middle/Upper Albian boundary and by observed facies changes that can be correlated to the established lithostratigraphy. The cores from the two boreholes provide a rather complete, 285-m-long sequence of the Upper Albian, with a 155.5-m-long overlap. Analysis of the tectonic structures showed considerable shortening in the Middle and Lower Albian part of the sequence due to normal faulting. Of the Upper Albian, only the lowermost part is affected by faults. The increase in sedimentation rates of terrigenous detritus and of marine biogenic carbonate, which occurs in the basal part of the C. auritus Subzone, is interpreted to reflect a regional change to a more humid climate and regional tectonic movements (uplift of the Rhenish Bohemian massif, subsidence of the Lower Saxony basin intensified locally by halokinetic movements). The further increase in marine productivity in the latest Albian may be related to upwelling of more nutrient-rich deep water along submarine relief in this shelf sea. Identification of Milankovitch cyclicity documented by the fluctuating CaCO3 contents of the sediments is used (i) to constrain the minimum time represented by the Upper Albian deposits, and (ii) to determine the duration of the sea level cycles (Cycle V: >=1.6 Ma, Cycle VI: >=2 Ma), and (iii) to establish the duration of the Late Albian ammonite subzones (e.g. Callihoplites auritus Subzone: 2.1 Ma). Average sedimentation rates determined from the identified 100-ka eccentricity cycles show a stepwise increase in sedimentation rates from 1-2 cm/1000 a in the Lower Albian dark claystones to 7-13 cm/1000 a in the late Late Albian. In addition to the general deepening trend through the Late Albian, two, nearly completely documented 3rd-order sea-level cycles in the Upper Albian of Kirchrode I were recognised, plus another one, cut short by faulting, at the base of the Upper Albian (documented in Kirchrode II). These global sea-level cycles were identified on the basis (a) of the sequence of the abundance maxima of selected benthos and plankton groups, (b) of trends in the fluctuations of the CaCO3 content, and (c) of the abundance of glauconite. The transgression periods in this Upper Albian deep shelf-basin are characterised by intensified circulation. This intensified circulation is found to have affected first the surface-near waters, resulting e.g. in an increase in the abundance of immigrant plankton and nekton species from the Tethys. At a later stage the deep water was affected, supporting then an increased population of suspension-feeding benthos, and causing condensation and erosion in the sediment at the sea floor.

Benthic foraminifera assemblages of the Gulf of Aden

Benthic and selected planktic foraminifera and stable isotope records were determined in a piston core from the Gulf of Aden, NW Arabian Sea that spans the last 530 ka. The benthic foraminifera were grouped into four principal assemblages using Q-mode Principal Component Analyses. Comparison of each of these assemblages with the fauna of the nearby regions enabled us to identify their specific environmental requirements as a function of variability in food supply and strength of the oxygen minimum zone and by that to use them as indicators of surface water productivity. The benthic foraminiferal productivity indicators coupled with the record of Globigerina bulloides, a planktic foraminifer known to be sensitive to productivity changes in the region, all indicate higher productivity during glacial intervals and productivity similar to present or even reduced during interglacial stages. This trend is opposite to the productivity pattern related to the SW summer monsoon of the Arabian Sea and indicates the role of the NE winter monsoon on the productivity of the Gulf of Aden. A period of exceptionally enhanced productivity is recognized in the Gulf of Aden region between ~60 and 13 kyr indicating the intensification of the NE winter monsoon to its maximal activity. Contemporaneous indication of increased productivity in other parts of the Arabian Sea, unexplained so far by the SW summer monsoon variability, might be related to the intensification of the NE winter monsoon. Another prominent event of high productivity, second in its extent to the last glacial productivity event is recognized between 430 and 460 kyr. These two events seem to correspond to periods of similar orbital positioning of rather low precession (and eccentricity) amplitude for a relatively long period. Glacial boundary conditions seem to control to a large extent the NE winter monsoon variability as also indicated by the dominance of the 100 ka cycle in the investigated time series. Secondary in their importance are the 23 and 41 ka cycles which seem also to contribute to the NE monsoonal variability. Following the identification of productivity events related to the NE winter monsoon in the Gulf of Aden, it is possible now to extend this observation to other parts of the Arabian Sea and consider the contribution of this monsoonal system to the productivity fluctuations preserved in the sedimentary records.

A 12 V Substrate-Integrated PbO2-Activated Carbon Asymmetric Hybrid Ultracapacitor with Silica-Gel-Based Inorganic-Polymer Electrolyte

A 12 V Substrate-Integrated PbO2-Activated Carbon hybrid ultracapacitor (SI-PbO2-AC HUCs) with silica-gel sulfuric acid electrolyte is developed and performance tested. The performance of the silica-gel based hybrid ultracapacitor is compared with flooded and AGM-based HUCs. These HUCs comprise substrate-integrated PbO2 (SI-PbO2) as positive electrodes and high surface-area activated carbon with dense graphite-sheet substrate as negative electrodes. 12 V SI-PbO2-AC HUCs with flooded, AGM and gel electrolytes are found to have capacitance values of 308 F, 184 F, and 269 F at C-rate and can be pulse charged and discharged for 100,000 cycles with only a nominal decrease in their capacitance values. The best performance is exhibited by gel-electrolyte HUCs.

Studies on 12 V substrate-integrated lead-carbon hybrid ultracapacitors

A cost-effective 12 V substrate-integrated lead-carbon hybrid ultracapacitor is developed and performance tested. These hybrid ultracapacitors employ flexible-graphite sheets as negative plate current-collectors that are coated amperometrically with a thin layer of conducting polymer, namely poly-aniline to provide good adhesivity to activated-carbon layer. The positive plate of the hybrid ultracapacitors comprise conventional lead-sheet that is converted electrochemically into a substrate-integrated lead-dioxide electrode. 12 V substrate-integrated lead-carbon hybrid ultracapacitors both in absorbent-glass-mat and polymeric silica-gel electrolyte configurations are fabricated and characterized. It is possible to realize 12 V configurations with capacitance values of similar to 200 F and similar to 300 F, energy densities of similar to 1.9 Wh kg(-1) and similar to 2.5 Wh kg(-1) and power densities of similar to 2 kW kg(-1) and similar to 0.8 kW kg(-1), respectively, having faradaic-efficiency values of similar to 90 % with cycle-life in excess of 100,000 cycles. The effective cost of the mentioned hybrid ultracapacitors is estimated to be about similar to 4 US$/Wh as compared to similar to 20 US$/Wh for commercially available ultracapacitors.

Electrochemiluminescence sensor using tris(2,2 '-bipyridyl)ruthenium(II) immobilized in Eastman-AQ55D-silica composite thin-films

An electrochemiluminescence (ECL) sensor with good long-term stability and fast response time has been developed. The sensor was based on the immobilization of tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)(3)(2+)) into the Eastman-AQ55D-silica composite thin films on a glassy carbon electrode. The ECL and electrochemistry of Ru(bpy)(3)(2+) immobilized in the composite thin films have been investigated, and the modified electrode was used for the ECL detection of oxalate, tripropylamine (TPA) and chlorpromazine (CPZ) in a flow injection analysis system and showed high sensitivity. Because of the strong electrostatic interaction and low hydrophobicity of Eastman-AQ55D, the sensor showed no loss of response over 2 months of dry storage. In use, the electrode showed only a 5% decrease in response over 100 potential cycles. The detection limit was 1 mumol l(-1) for oxalate and 0.1 mumol l(-1) for both TPA and CPZ (S/N = 3), respectively. The linear range extended from 50 mumol l(-1) to 5 mmol l(-1) for oxalate, from 20 mumol l(-1) to 1 mmol l(-1) for TPA, and from 1 mumol l(-1) to 200 mumol l(-1) for CPZ.

Evolution and variability of the East Asian summer monsoon during the Pliocene: Evidence from clay mineral records of the South China Sea

The Late Pliocene is thought to be characterized by the simultaneous intensification of both the East Asian winter monsoon (EAWM) and East Asian summer monsoon (EASM). However, the evolution of the EASM during the Pliocene remains still controversial and only little is known about the dynamics of the EASM during the Pliocene on orbital time scales. Here we use clay mineral assemblages in sediments from Ocean Drilling Program (ODP) Site 1143 in the southern South China Sea (SCS) to obtain proxy records of past changes in the EASM climate during the Pliocene. Provenance analysis suggests that illite, chlorite and kaolinite originated mainly from the Mekong River drainage area. Smectite was derived mainly from the Indonesian islands. The kaolinite/illite ratio and the chemical index of alteration (CIA) of siliciclastic sediments allowed us to reconstruct the history of chemical weathering and physical erosion of the Mekong River drainage area and thus, the evolution of,the EASM during the Pliocene. Our clay minerals proxy data suggests a stronger EASM during the Early Pliocene than during the Late Pliocene. We propose that the long-term evolution of the EASM has been driven by global cooling rather than the uplift of the Tibetan Plateau. Spectral analysis of kaolinite/ illite ratio displays a set of strong periodicities at 100 ka, 30 ka, 28 ka, 25 ka, and 22 ka. with no clear obliquityrelated signal. Our study suggests that the Pliocene EASM intensity on orbital time scales is not only controlled by the Northern Hemisphere summer insolation, but also strongly influenced by equatorial Pacific ENSO-like ocean atmosphere dynamics. (C) 2010 Elsevier B.V. All rights reserved.

The Mid-Brunhes Event and West Antarctic ice sheet stability

The complex cyclical nature of Pleistocene climate, driven by the evolving orbital configuration of the Earth, is well known but not well understood. A major climatic transition took place at the Mid-Brunhes Event (MBE), ca. 430 ka ago after which the amplitude of the ca.100 ka climate oscillations increased, with substantially warmer interglacials, including periods warmer than present. Recent modelling has indicated that while the timing of these warmer-than-present transient (WPT) events is consistent with southern warming due to a deglaciation-forced slowdown of the Atlantic Meridional Overturning Circulation, the magnitude of warming requires a local amplification, for which a candidate is the feedback of significant West Antarctic Ice Sheet (WAIS) retreat. We here extend this argument, based on the absence of WPTs in the early ice core record (450–800 ka ago), to hypothesize that the MBE could be a manifestation of decreased WAIS stability, triggered by ongoing subglacial erosion.

Middle and Late Pleistocene humid periods recorded in palaeolake deposits of the Nafud desert, Saudi Arabia

Present climate in the Nafud desert of northern Saudi Arabia is hyper-arid and moisture brought by north-westerly winds scarcely reaches the region. The existence of abundant palaeolake sediments provides evidence for a considerably wetter climate in the past. However, the existing chronological framework of these deposits is solely based on radiocarbon dating of questionable reliability, due to potential post-depositional contamination with younger 14C. By using luminescence dating, we show that the lake deposits were not formed between 40 and 20 ka as suggested previously, but approximately ca 410 ka, 320 ka, 200 ka, 125 ka, and 100 ka ago. All of these humid phases are in good agreement with those recorded in lake sediments and speleothems from southern Arabia. Surprisingly, no Holocene lake deposits were identified. Geological characteristics of the deposits and diatom analysis suggest that a single, perennial lake covered the entire south-western Nafud ca 320 ka ago. In contrast, lakes of the 200 ka, 125 ka, and 100 ka humid intervals were smaller and restricted to interdune depressions of a pre-existing dune relief. The concurrent occurrence of humid phases in the Nafud, southern Arabia and the eastern Mediterranean suggests that moisture in northern Arabia originated either from the Mediterranean due to more frequent frontal depression systems or from stronger Indian monsoon circulation, respectively. However, based on previously published climate model simulations and palaecolimate evidence from central Arabia and the Negev desert, we argue that humid climate conditions in the Nafud were probably caused by a stronger African monsoon and a distinct change in zonal atmospheric circulation.

Peat as a natural solid-phase for copper preconcentration and determination in a multicommuted flow system coupled to flame atomic absorption spectrometry

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 mol L(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 mu g L(-1), with a detection limit estimated as 3 mu g L(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n = 20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111 % range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level. (C) 2009 Elsevier B.V. All rights reserved.

Modelação da interacção entre um plasma de arco de alta pressão e cátodos refractários

Nesta dissertação apresento um estudo detalhado de vários aspectos da interacção entre um plasma de arco de alta pressão e cátodos refractários. Um modelo da camada de plasma junto ao cátodo num plasma sujeito a uma pressão da ordem de uma ou várias atmosferas é reconsiderado com base em recentes resultados teóricos. A física da camada de plasma junto ao cátodo é analisada para valores da queda de tensão na camada de plasma junto ao cátodo até 50V, de acordo com recentes resultados experimentais que mostram que a queda de tensão na camada de plasma junto ao cátodo numa descarga de arco de alta pressão pode atingir valores tão elevados. São identificados os mecanismos que originam a não monotonia da dependência da densidade de fluxo de energia (proveniente do plasma para a superfície do cátodo) em relação à temperatura da superfície do cátodo, para um valor fixo da queda de tensão junto ao cátodo. Uma descrição fechada da interacção plasma-cátodo é obtida por meio da resolução numérica do problema não linear com condições de fronteira para a distribuição da temperatura no interior do corpo do cátodo. São apresentados resultados da modelação numérica da descarga difusa nas condições de funcionamento de uma lâmpada de descarga experimental, sendo bom o acordo entre os resultados numéricos e os dados experimentais. Manchas solitárias num cátodo plano infinito e modos difuso e mancha axialmente simétricos em cátodos finitos de descargas de arco de alta pressão são estudados num grande intervalo de corrente. São analisados aspectos gerais e apresentados resultados numéricos referentes a cátodos de tungsténio planos e de forma cilíndrica a operar num plasma de argon à pressão atmosférica para correntes de arco até 100 kA. Émostrado, em particular, que a temperatura da superfície do cátodo no interior de uma mancha solitária varia relativamente pouco, podendo ser estimada com uma precisão de cerca de 200 − 300K sem ser necesário resolver a equação da condução térmica no corpo do cátodo. O comportamento assimptótico das soluções para um cátodo finito no caso limite de altas correntes é encontrado e confirmado pelos resultados numéricos. É confirmado um padrão geral das características tensão-corrente de vários modos de transferência de corrente em cátodos finitos sugerido previamente com base numa análise de bifurcações. É estudada a transição de modos mancha num cátodo finito no limite de cátodos de grandes dimensões para o modo mancha solitária num cátodo plano infinito. É estabelecido que o modo mancha solitária representa uma forma limite do modo mancha de alta tensão num cátodo finito. É considerada a questão da distinção entre modo difuso e modo mancha num cátodo finito. É desenvolvida uma abordagem para o cálculo de pontos de bifurcação nos quais soluções mancha tridimensionais bifurcam-se a partir de soluções que descrevem o modo difuso e modos mancha axialmente simétricos. Em particular, é calculado o primeiro ponto de bifurcação posicionado na solução que descreve o modo difuso e, por conseguinte, o seu limite de estabilidade, isto é, a corrente abaixo da qual o modo difuso torna-se instável. São apresentados os resultados da modelação numérica efectuada para o caso de um cátodo de tungsténio de forma cilíndrica a operar num plasma de alta pressão. É estudado o efeito produzido no limite de estabilidade pelas variações dos parâmetros de controle (dimensões do cátodo, função de trabalho do material do cátodo, tipo e pressão do gás que produz o plasma). Foi encontrado que o comportamento do limite de estabilidade sujeito a estas variações está em conformidade com as tendências observadas experimentalmente. Foi encontrado que o limite de estabilidade é muito mais sensível às variações dos parâmetros de controle do que as características tensão-corrente do modo difuso, sendo o efeito mais forte produzido pelas variações das dimensões do cátodo e da função de trabalho do material do cátodo. Este resultado está em conformidade com o facto experimental de que a transição difuso-mancha é de difícil reprodução.

Avaliação genética de características de escores visuais de bovinos da raça Nelore da desmama até a maturidade

Os objetivos neste estudo foram estimar parâmetros genéticos das características categóricas musculosidade, estrutura física, aspectos raciais, conformação, ônfalo, pigmentação e sacro e predizer os valores genéticos utilizando-se a estatística bayesiana sob modelo animal de limiar, considerando diferentes idades de bovinos da raça Nelore. As informações de escores visuais foram obtidas nos anos de 2000 a 2005 de bovinos provenientes de 13 fazendas participantes do Programa Nelore Brasil. Nas análises bicaracterísticas, foram utilizados 500.000 até 1.100.000 ciclos para alcançar a convergência da cadeia de Gibbs. O descarte inicial e o intervalo amostral foram de 100.000 e 1.000 ciclos, respectivamente. As características de escores visuais avaliadas aos 8 e 22 meses de idade apresentaram estimativas de herdabilidades moderadas, indicando resposta rápida à seleção direta. Os escores visuais indicaram possibilidade de resposta rápida à seleção direta e, portanto, devem ser incorporados em programas de melhoramento genético como critérios de seleção. As estimativas de correlações genéticas entre musculosidade, estrutura física e conformação também indicam que a seleção direta para uma destas características trará progresso genético às outras. Recomenda-se utilizar os escores visuais como critérios de seleção em pelo menos duas fases de vida do animal, na desmama e ao sobreano.

Evaluation of the Effect of Retightening and Mechanical Cycling on Preload Maintenance of Retention Screws

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Inferência bayesiana aplicada à estimação de herdabilidades dos parâmetros da curva de crescimento de fêmeas da raça Nelore

Objetivou-se estimar parâmetros genéticos, utilizando inferência Bayesiana, para as estimativas dos parâmetros individuais de peso à maturidade (Â) e taxa de crescimento, obtidos pela função de crescimento Brody. O arquivo estava constituído de 14.563 registros de pesos e idades referentes a 1.158 fêmeas da raça Nelore, participantes do Programa de Melhoramento Genético da Raça Nelore. Para a análise das estimativas dos parâmetros da curva, via inferência bayesiana, foi proposto um modelo animal unicaráter, que incluiu como fixo o efeito de grupo contemporâneo (animais nascidos no mesmo estado, no mesmo trimestre do ano, mesmo ano e mesmo regime alimentar) e como aleatórios os efeitos genético direto e residual. Nessa análise, foram utilizados dois diferentes tamanhos para as cadeias geradas pelo algoritmo de amostragem de Gibbs, de 550 e 1.100 mil ciclos, com períodos de descarte amostral de 50 e 100 mil ciclos, respectivamente, e amostragens a cada 500 e 1.000 ciclos, respectivamente. As médias posteriores da variância genética aditiva e residual foram próximas, tanto para  quanto para a, mesmo quando implementados diferentes tamanhos para as cadeias geradas pelo algoritmo de amostragem de Gibbs. Os coeficientes de herdabilidade estimados para Â, variaram de 0,44 a 0,46, amplitude semelhante aos 0,46 a 0,48 obtidos para as estimativas de. Essas magnitudes indicam que a seleção pode ser usada como instrumento para alterar a forma da curva de crescimento desses animais. Entretanto, o uso das informações obtidas, visando à alteração da curva de crescimento dos animais, deve ser feito com grande cautela, uma vez que as características a serem trabalhadas na modificação do formato da curva de crescimento, de acordo com resultados da literatura especializada, são negativamente correlacionadas.

Compressive fatigue in titanium dental implants submitted to fluoride ions action

The aim of this study was to assess the influence of a fluoridated medium on the mechanical properties of an internal hexagon implant-abutment set, by means of compression, mechanical cycling and metallographic characterization by scanning electronic microscopy. Five years of regular use of oral hygiene with a sodium fluoride solution content of 1500 ppm were simulated, immersing the samples in this medium for 184 hours, with the solutions being changed every 12 hours. Data were analyzed at a 95% confidence level with Fisher's exact test. After the action of fluoride ions, a negative influence occurred in the mechanical cycling test performed in a servohydraulic machine (Material Test System-810) set to a frequency of 15 Hz with 100,000 cycles and programmed to 60% of the maximum resistance of static compression test. The sets tended to fracture by compression on the screw, characterized by mixed ruptures with predominance of fragile fracture, as observed by microscopy. An evidence of corrosion by pitting on sample surfaces was found after the fluoride ions action. It may be concluded that prolonged contact with fluoride ions is harmful to the mechanical properties of commercially pure titanium structures.

Air-particle abrasion on zirconia ceramic using different protocols: Effects on biaxial flexural strength after cyclic loading, phase transformation and surface topography

This study evaluated the effect of different air-particle abrasion protocols on the biaxial flexural strength and structural stability of zirconia ceramics. Zirconia ceramic specimens (ISO 6872) (Lava, 3M ESPE) were obtained (N=336). The specimens (N=118, n=20 per group) were randomly assigned to one of the air-abrasion protocols: Gr1: Control (as-sintered); Gr2: 50 μm Al2O3 (2.5 bar); Gr3: 50 μm Al2O3 (3.5 bar); Gr4: 110 μm Al2O3(2.5 bar); Gr5: 110 μm Al2O3 (3.5 bar); Gr6: 30 μm SiO2 (2.5 bar) (CoJet); Gr7: 30 μm SiO2(3.5 bar); Gr8: 110 μm SiO2 (2.5 bar) (Rocatec Plus); and Gr9: 110 μm SiO2 (3.5 bar) (duration: 20 s, distance: 10 mm). While half of the specimens were tested immediately, the other half was subjected to cyclic loading in water (100,000 cycles; 50 N, 4 Hz, 37 °°C) prior to biaxial flexural strength test (ISO 6872). Phase transformation (t→m), relative amount of transformed monoclinic zirconia (FM), transformed zone depth (TZD) and surface roughness were measured. Particle type (p=0.2746), pressure (p=0.5084) and cyclic loading (p=0.1610) did not influence the flexural strength. Except for the air-abraded group with 110 μm Al2O3 at 3.5 bar, all air-abrasion protocols increased the biaxial flexural strength (MPa) (Controlnon-aged: 1030±153, Controlaged: 1138±138; Experimentalnon-aged: 1307±184-1554±124; Experimentalaged: 1308±118-1451±135) in both non-aged and aged conditions, respectively. Surface roughness (Ra) was the highest with 110 μm Al2O3(0.84 μm. FM values ranged from 0% to 27.21%, higher value for the Rocatec Plus (110 μm SiO2) and 110 μm Al2O3 groups at 3.5 bar pressure. TZD ranged between 0 and 1.43 μm, with the highest values for Rocatec Plus and 110 μm Al2O3 groups at 3.5 bar pressure. © 2013 Elsevier Ltd.