O Refinamento de Rietveld como um método para o controle de qualidade de minérios de ferro

O método de Rietveld é uma técnica robusta para a análise quantitativa de fases minerais, através da difração de raios x. A quantificação de minérios de ferro com duas ou mais fases é possível de ser realizada em uma pequena fração de tempo. Esse trabalho apresenta os princípios básicos para a preparação e quantificação de misturas de hematita, magnetita, goethita e quartzo, como constituintes principais de minérios de ferro. Métodos de preparação de amostras especiais são necessários devido a diferenças de variedades de hematita. Diferentes parâmetros de preparação de amostras têm de ser avaliados antes da análise quantitativa. Recomenda-se o preenchimento da amostra, nos porta-amostras, através do método "side loading" ou "back loading". O tempo de moagem depende da variedade de hematita e deve variar entre 4 e 12 minutos. Uma quantificação com misturas de três fases foi realizada e revelou bons resultados, com valores máximos de desvio-padrão relativo de 3%.

Análise do potencial pozolânico da cinza de casca de arroz (CCA) através da técnica de refinamento de Rietveld

É um consenso que a cinza de casca de arroz é um resíduo agrícola com comprovada eficiência pozolânica. Contudo, por se tratar de um resíduo, apresenta problemas de variabilidade decorrente dentre outras coisas de sua origem e dos diferentes processos de geração, fator este que dificulta sua comercialização. Hoje em dia, a determinação da atividade pozolânica do resíduo e determinada pela NBR 5752^[3] (ABNT, 2012) e NBR 5751⁽²⁾(ABNT, 2012). A desvantagem com relação a estes ensaios é o tempo que se leva para ter uma resposta. Nesse sentido, este trabalho visa analisar a eficiência do refinamento de Rietveld para avaliar a pozolanicidade através do parâmetro denominado de índice de amorfismo. Por meio desse refinamento é possível dizer, de forma quantitativa, a porcentagem de elementos reativos que o resíduo apresenta, operadores com conhecimento da técnica de análise levam em torno de dois dias para apresentar os resultados. Para avaliação dessa técnica, as cinzas foram produzidas através da queima em diferentes temperaturas (500, 600, 800, 900 e 1100 ºC). Fixou-se o tempo de queima do material em três horas e a taxa de aquecimento em 5 ºC/min, e resfriamento lento. Posteriormente realizou-se a moagem da cinza e quantificação do índice de amorfismo por meio de refinamento Rietveld. Os resultados demonstraram que o índice de amorfismo pode ser utilizado como parâmetro de controle de cinzas residuais, visto que cinzas com elevado índice de amorfismo apresen-tam uma boa pozolanicidade.

Lattice effects in the quasi-two-dimensional valence-bond-solid Mott insulator EtMe3P[Pd(dmit)(2)](2)

The organic charge-transfer salt EtMe3P[Pd(dmit)(2)](2) is a quasi-two-dimensional Mott insulator with localized spins S = 1/2 residing on a distorted triangular lattice. Here we report measurements of the uniaxial thermal expansion coefficients alpha(i) along the in-plane i = a and c axis as well as along the out-of-plane b axis for temperatures 1.4 K <= T <= 200 K. Particular attention is paid to the lattice effects around the phase transition at T-VBS = 25 K into a low-temperature valence-bond-solid phase and the paramagnetic regime above where effects of short-range antiferromagnetic correlations can be expected. The salient results of our study include (i) the observation of strongly anisotropic lattice distortions accompanying the formation of the valence-bond-solid phase, and (ii) a distinct anomaly in the thermal expansion coefficients in the paramagnetic regime around 40 K. Our results demonstrate that upon cooling through T-VBS the in-plane c axis, along which the valence bonds form, contracts while the second in-plane a axis elongates by the same relative amount. Surprisingly, the dominant effect is observed for the out-of-plane b axis which shrinks significantly upon cooling through T-VBS. The pronounced anomaly in alpha(i) around 40 K is attributed to short-range magnetic correlations. It is argued that the position of this maximum, relative to that in the magnetic susceptibility around 70 K, speaks in favor of a more anisotropic triangular-lattice scenario for this compound than previously thought.

Processing optimized for symmetry in the problem of evasive maneuvers

The increasing number of space debris in operating regions around the earth constitutes a real threat to space missions. The goal of the research is to establish appropriate scientific-technological conditions to prevent the destruction and/or impracticability of spacecraft in imminent collision in these regions. A definitive solution to this problem has not yet been reached with the degree of precision that the dynamics of spatial objects (vehicle and debris) requires mainly due to the fact that collisions occur in chains and fragmentation of these objects in the space environment. This fact threatens the space missions on time and with no prospects for a solution in the near future. We present an optimization process in finding the initial conditions (CIC) to collisions, considering the symmetry of the distributions of maximum relative positions between spatial objects with respect to the spherical angles. For this, we used the equations of the dynamics on the Clohessy-Witshire, representing a limit of validation that is highly computationally costly. We simulate different maximum relative positions values of the corresponding initial conditions given in terms of spherical angles. Our results showed that there are symmetries that significantly reduce operating costs, such that the search of the CIC is advantageously carried out up to 4 times the initial processing routine. Knowledge of CIC allows the propulsion system operating vehicle implement evasive maneuvers before impending collisions with space debris.

Holocenic proxies of sedimentary organic matter and the evolution of Lake Arari-Amazon Region

Four sediment cores were sampled from Lake Arari, located on Marajo Island at the mouth of the Amazon River. The island's vegetation cover is composed mainly of Amazon coastal forest, herbaceous and varzea vegetation. The integration of data on sedimentary structures, pollen, carbon and nitrogen isotope records, C/N ratios and radiocarbon ages allowed the identification of changes in vegetation and the sources of organic matter accumulated in the lake during the Holocene. The data indicate a relatively high flow energy, marine water influence and the presence of mangroves during the lagoon phase between 8990 and 8690 cal yr B.P. and 2310-2230 cal yr B.P. Between 2310 and 2230 cal yr B.P. and similar to 1000 cal yr B.P., the flow energy decreased and the mangroves were replaced by herbaceous vegetation following the decline in marine influence, likely due to the increase in freshwater river discharge. During the last 1000 years, Lake Arari was established in association with the expansion of herbaceous vegetation and the dominance of freshwater algae. (C) 2011 Elsevier BM. All rights reserved.

Electron and photon energy calibration with the ATLAS detector using LHC Run 1 data

This paper presents the electron and photon energy calibration achieved with the ATLAS detector using about 25 fb−1 of LHC proton–proton collision data taken at centre-of-mass energies of √s = 7 and 8 TeV. The reconstruction of electron and photon energies is optimised using multivariate algorithms. The response of the calorimeter layers is equalised in data and simulation, and the longitudinal profile of the electromagnetic showers is exploited to estimate the passive material in front of the calorimeter and reoptimise the detector simulation. After all corrections, the Z resonance is used to set the absolute energy scale. For electrons from Z decays, the achieved calibration is typically accurate to 0.05% in most of the detector acceptance, rising to 0.2% in regions with large amounts of passive material. The remaining inaccuracy is less than 0.2–1% for electrons with a transverse energy of 10 GeV, and is on average 0.3% for photons. The detector resolution is determined with a relative inaccuracy of less than 10% for electrons and photons up to 60 GeV transverse energy, rising to 40% for transverse energies above 500 GeV.

Physicochemical sea ice and water characteristics near Point Barrow 2005-2006

Photosynthetic parameters of phytoplankton and sea ice algae from landfast sea ice of the Chukchi Sea off Point Barrow, Alaska, were assessed in spring 2005 and winter through spring 2006 using Pulse Amplitude Modulated (PAM) fluorometry including estimates of maximum quantum efficiency (Fv/Fm), maximum relative electron transport rate (rETRmax), photosynthetic efficiency (alpha), and the photoadaptive index (Ek). The use of centrifuged brine samples allowed to document vertical gradients in ice algal acclimation with 5 cm vertical resolution for the first time. Bottom ice algae (0-5 cm from ice-water interface) expressed low Fv/Fm (0.331-0.426) and low alpha (0.098-0.130 /(µmol photons/m**2/s)) in December. Fv/Fm and alpha increased in March and May (0.468-0.588 and 0.141-0.438 /(µmol photons/m**2/s), respectively) indicating increased photosynthetic activity. In addition, increases in rETRmax (3.3-16.4 a.u.) and Ek (20-88 µmol photons/m**2/s) from December to May illustrates a higher potential for primary productivity as communities become better acclimated to under-ice light conditions. In conclusion, photosynthetic performance by ice algae (as assessed by PAM fluorometry) was tightly linked to sea ice salinity, temperature, and inorganic nutrient concentrations (mainly nitrogen).

Geochemistry of sediment cores of the Southern Ocean

We examine the possibility that glacial increase in the areal extent of reducing sediments might have changed the oceanic Cd inventory, thereby decoupling Cd from PO4. We suggest that the precipitation of Cd-sulfide in suboxic sediments is the single largest sink in the oceanic Cd budget and that the accumulation of authigenic Cd and U is tightly coupled to the organic carbon flux into the seafloor. Sediments from the Subantarctic Ocean and the Cape Basin (South Atlantic), where oxic conditions currently prevail, show high accumulation rates of authigenic Cd and U during glacial intervals associated with increased accumulation of organic carbon. These elemental enrichments attest to more reducing conditions in glacial sediments in response to an increased flux of organic carbon. A third core, overlain by Circumpolar Deep Water (CPDW) as are the other two cores but located south of the Antarctic Polar Front, shows an approximately inverse pattern to the Subantarctic record. The contrasting patterns to the north and south of the Antarctic Polar Front suggest that higher accumulation rates of Cd and U in Subantarctic sediments were driven primarily by increased productivity. This proposal is consistent with the hypothesis of glacial stage northward migration of the Antarctic Polar Front and its associated belt of high siliceous productivity. However, the increase in authigenic Cd and U glacial accumulation rates is higher than expected simply from a northward shift of the polar fronts, suggesting greater partitioning of organic carbon into the sediments during glacial intervals. Lower oxygen content of CPDW and higher organic carbon to biogenic silica rain rate ratio during glacial stages are possible causes. Higher glacial productivity in the Cape Basin record very likely reflects enhanced coastal up-welling in response to increased wind speeds. We suggest that higher productivity might have doubled the areal extent of suboxic sediments during the last glacial maximum. However, our calculations suggest low sensitivity of seawater Cd concentrations to glacial doubling of the extent of reducing sediments. The model suggests that during the last 250 kyr seawater Cd concentrations fluctuated only slightly, between high levels (about 0.66 nmol/kg) on glacial initiations and reaching lowest values (about 0.57 nmol/kg) during glacial maxima. The estimated 5% lower Cd content at the last glacial maximum relative to modern levels (0.60 nmol/kg) cannot explain the discordance between Cd and delta13C, such as observed in the Southern Ocean. This low sensitivity is consistent with foraminiferal data, suggesting minimal change in the glacial Cd mean oceanic content.

Biogenic and lithogenic silica, silicic acid, production of biogenic silica, and irradiance measurements during the Ross Sea Bloom Project 1994-1996

The development of the seasonal phytoplankton bloom in the Ross Sea was studied during two cruises. The first, conducted in November-December 1994, investigated the initiation and rapid growth of the bloom, whereas the second (December 1995-January 1996) concentrated on the bloom's maximum biomass period and the subsequent decline in biomass. Central to the understanding of the controls of growth and the summer decline of the bloom is a quantitative assessment of the growth rate of phytoplankton. Growth rates were estimated over two time scales with different methods. The first estimated daily growth rates from isotropic incorporation under simulated in situ conditions, including 14C, 15N and 32Si uptake measurements combined with estimates of standing stocks of particulate organic carbon, nitrogen and biogenic silica. The second method used daily to weekly changes in biomass at selected locations, with net growth rates being estimated from changes in standing stocks of phytoplankton. In addition, growth rates were estimated in large-volume experiments under optimal irradiances. Growth rates showed distinct temporal patterns. Early in the growing season, short-term estimates suggested that growth rates of in situ assemblages were less than maximum (relative to the temperature-limited maximum) and were likely reduced due to low irradiance regimes encountered under the ice. Growth rates increased thereafter and appeared to reach their maximum as biomass approached the seasonal peak, but decreased markedly in late December. Differences between the major taxonomic groups present were also noted, especially from the isotopic tracer experiments. The haplophyte Phaeocystic antarctica was dominant in 1994 throughout the growing season, and it exhibited the greatest growth rates (mean 0.41/day) during spring. Diatom standing stocks were low early in the growing season, and growth rates averaged 0.100/day. In summer diatoms were more abundant, but their growth rates remained much lower (mean of 0.08/day) than the potential maximum. Understanding growth rate controls is essential to the development of predictive models of the carbon cycle and food webs in Antarctic waters.

Chemical composition of altered volcanic rocks from ODP Sites 193-1188 and 193-1189

The conventional model of leaching volcanic rocks as a source of metals in a seafloor hydrothermal systems has been tested by examining the behavior of Pb and other trace elements during hydrothermal alteration. ODP Leg 193 drill sites 1188 (Snowcap) and 1189 (Roman Ruins) on Pual Ridge in the eastern Manus Basin offshore eastern Papua New Guinea provide a unique three-dimensional window into an active back-arc hydrothermal system. We investigate by means of a LA-ICP-MS microbeam technique the capacity of Pb to be leached from a host volcanic rock exposed to various types and intensities of alteration. Our results are in general agreement with previous studies that utilized bulk analytical techniques but provide a more detailed explanation of the processes. Fresh representative dacitic lavas from the Pual Ridge have an average whole rock Pb content of 5.2 ppm, an average interstitial glass Pb content of 5.6 ppm and an average plagioclase Pb content of 1.0 ppm. Altered matrix samples have highly variable Pb values ranging from 0 to 52.4 ppm. High Pb values in altered samples are associated with a low temperature chlorite and clay mineral assemblage, in some cases overprinted by a high temperature (up to 350°C) silica-rich "bleaching" alteration. Only the most highly altered matrix samples have REE patterns that differ from the fresh Pual Ridge dacite. This may represent either different lava histories or alteration characteristics that have affected normally immobile REEs. Altered samples with the highest Pb values have similar REE patterns to those of the local unaltered lavas. They are compositionally similar to typical Pual Ridge dacites indicating a genetic relationship between the main regional volcanic suite and the subseafloor hydrothermally altered, Pb-enriched material. Relative loss/gain for Pb between the analyzed altered samples and a calculated precursor show a maximum relative gain of 901%. Samples with relative Pb gain from both drill sites are associated with lower temperature alteration mineral assemblages characterized by pervasive chloritization. The related lower temperature (220-250°C) neutral to slightly acidic fluids have been ascribed by others to return circulation of hydrothermal fluids that did not interact with seawater. Because altered samples have a higher Pb content than the fresh precursor, leaching of fresh volcanic rocks cannot be the source of Pb in the hydrothermal systems.

Physical oceanography during five ECOMARGE cruises

The first experiment of the ECOMARGE programme (ECOsystèmes de MARGE continentale) was initiated in 1983-1984, in the Gulf of Lions (northwestern Mediterranean Sea). The objectives of the ECOMARGE-I experiment were: to quantify the transfer of particulate matter, in general, and of organic carbon, in particular, from its introduction to and formation in the waters of the continental shelf-to its consumption or sedimentation on the shelf or its transfer to the slope and deep sea; and to understand the processes involved in that transfer, consumption and sedimentation together with their variability in space and time. The results of that experiment, from 1983 to 1988, are presented in this Special Issue. The highlights of the results are summarised in this paper. These results indicate that, of the particles formed in the waters of the continental shelf and those introduced by rivers, some are deposited as sediments on the shelf. A portion is transported offshore, however, to the slope and deep sea. The Rho^ne River, in the northeastern part of the study area, is the major source of continental material; this is transported to sea in a benthic nepheloid layer and, mostly, alongshore to the southwest. Here, it largely leaves the shelf through the canyons, especially the Lacaze-Duthiers Canyon. In the offshore waters, particle concentrations and distributions show surficial, intermediate and benthic nepheloid layers. These turbid structures increase towards the southwest, corresponding to the seaward shift of the front between the coastal waters and the Liguro-Provençal cyclonic gyre, a major forcing function in the Gulf of Lions. Considering the source and fate of particles (largely biogenic from the euphotic zone and abiogenic from deeper waters) a layered system is described, which is emphasized by the concentrations of natural and artificial elements and compounds. Of the flux of particles to the Lacaze-Duthiers Canyon, on a decadal scale, about 30% (as a minimum) is estimated to be stored as sediment; the remainder is transported down-canyon, towards the deep sea. The temporal variability of processes affecting this net seaward transport, of both biogenic and abiogenic material, is from hours, days to seasonal, and probably interannual, time scales. The response of the system to these variations is rapid, with pulses of increased discharge of particles from the adjacent shelf being detected in sediment traps in the Lacaze-Duthiers Canyon in less than 16 days (the temporal resolution of the traps). Based upon the study of tracers of particulate matter and environmental factors (i.e. river discharge and climatic conditions), it appears that the contribution from the Rho^ne River and its adjacent area is maximal during the winter; at this time, the flow of the Liguro-Provençal Current also increases. In contrast, the maximum relative contribution of the adjacent southwesterly area to the flux in the Lacaze-Duthiers Canyon occurs in summer, during storm events.

Corrected ICESat altimetry data, surface mass balance, and firn elevation change on Antarctic ice shelves

Accurate prediction of global sea-level rise requires that we understand the cause of recent, widespread and intensifying glacier acceleration along Antarctic ice-sheet coastal margins. Floating ice shelves buttress the flow of grounded tributary glaciers and their thickness and extent are particularly susceptible to changes in both climate and ocean forcing. Recent ice-shelf collapse led to retreat and acceleration of several glaciers on the Antarctic Peninsula. However, the extent and magnitude of ice-shelf thickness change, its causes and its link to glacier flow rate are so poorly understood that its influence on the future of the ice sheets cannot yet be predicted. Here we use satellite laser altimetry and modelling of the surface firn layer to reveal for the first time the circum-Antarctic pattern of ice-shelf thinning through increased basal melt. We deduce that this increased melt is the primary driver of Antarctic ice-sheet loss, through a reduction in buttressing of the adjacent ice sheet that has led to accelerated glacier flow. The highest thinning rates (~7 m/a) occur where warm water at depth can access thick ice shelves via submarine troughs crossing the continental shelf. Wind forcing could explain the dominant patterns of both basal melting and the surface melting and collapse of Antarctic ice shelves, through ocean upwelling in the Amundsen and Bellingshausen Seas and atmospheric warming on the Antarctic Peninsula. This implies that climate forcing through changing winds influences Antarctic Ice Sheet mass balance, and hence global sea-level, on annual to decadal timescales.

Neutron spectra and dosimetric assessment around a neutron Howitzer container

The neutron Howitzer container at the Neutron Measurements Laboratory of the Nuclear Engineering Department of the Polytechnic University of Madrid (UPM), is equipped with a 241Am-Be neutron source of 74 GBq in its center. The container allows the source to be in either the irradiation or the storage position. To measure the neutron fluence rate spectra around the Howitzer container, measurements were performed using a Bonner spheres spectrometer and the spectra were unfolded using the NSDann program. A calibrated neutron area monitor LB6411 was used to measure the ambient dose equivalent rates, H*(10). Detailed Monte-Carlo simulations were performed to calculate the measured quantities at the same positions. The maximum relative deviation between simulations and measurements was 19.53%. After validation, the simulated model was used to calculate the equivalent dose rate in several key organs of a voxel phantom. The computed doses in the skin and lenses of the eyes are within the ICRP recommended dose limits, as is the H*(10) value for the storage position.

Grain size analysis of ODP Site 162-984

Past changes in the freshwater balance of the surface North Atlantic Ocean are thought to have influenced the rate of deep-water formation, and consequently climate (Broecker and Denton, 1989, doi:10.1016/0016-7037(89)90123-3; Manabe and Stouffer, 1996; doi:10.1038/378165a0). Although water-mass proxies are generally consistent with an impact of freshwater input on meridional overturning circulation (Boyle and Keigwin, 1987, doi:10.1038/330035a0), there has been little dynamic evidence to support this linkage. Here we present a 25,000 year record of variations in sediment grain size from south of Iceland, which indicates vigorous bottom-water currents during both the last glacial maximum and the Holocene period. Together with reconstructions of North Atlantic water-mass distribution, vigorous bottom currents suggest a shorter residence time of northern-source waters during the last glacial maximum, relative to the Holocene period. The most significant reductions in flow strength occur during periods that have been associated with freshening of the surface North Atlantic. The short-term deglacial oscillations in bottom current strength are closely coupled to changes in Greenland air temperature, with a minimum during the Younger Dryas cold reversal and a maximum at the time of rapid warming at the onset of the Holocene. Our results support a strong connection between ocean circulation and rapid climate change.

Green-Ampt approximations

The solution to the Green and Ampt infiltration equation is expressible in terms of the Lambert W-1 function. Approximations for Green and Ampt infiltration are thus derivable from approximations for the W-1 function and vice versa. An infinite family of asymptotic expansions to W-1 is presented. Although these expansions do not converge near the branch point of the W function (corresponds to Green-Ampt infiltration with immediate ponding), a method is presented for approximating W-1 that is exact at the branch point and asymptotically, with interpolation between these limits. Some existing and several new simple and compact yet robust approximations applicable to Green-Ampt infiltration and flux are presented, the most accurate of which has a maximum relative error of 5 x 10(-5)%. This error is orders of magnitude lower than any existing analytical approximations. (c) 2005 Elsevier Ltd. All rights reserved.