979 resultados para air thickness, axial length, Lenstar, partial coherence interferometry, refractive index
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Trough computed tomography (CT), it is possible to evaluate lymph nodes in detail and to detect changes in these structures earlier than with radiographs and ultrasound. Lack of information in the veterinary literature directed the focus of this report to normal aspects of the axillary and mediastinal lymph nodes of adult dogs on CT imaging. A CT scan of 15 normal adult male and female Rottweilers was done. To define them as clinically sound, anamnesis, physical examination, complete blood count, renal and hepatic biochemistry, ECG, and thoracic radiographs were performed. After the intravenous injection of hydrosoluble ionic iodine contrast medium contiguous 10mm in thickness thoracic transverse images were obtained with an axial scanner. In the obtained images mediastinal and axillary lymph nodes were sought and when found measured in their smallest diameter and their attenuation was compared to musculature. Mean and standard deviation of: age, weight, body length and the smallest diameter of the axillary and mediastinal lymph nodes were determined. Mean and standard deviation of parameters: age 3.87±2.03 years, weight 41.13±5.12, and body length 89.61±2.63cm. Axillary lymph nodes were seen in 60% of the animals, mean of the smallest diameter was 3.58mm with a standard deviation of 2.02 and a minimum value of 1mm and a maximum value of 7mm. From 13 observed lymph nodes 61.53% were hypopodense when compared with musculature, and 30.77% were isodense. Mediastinal lymph nodes were identified in 73.33% of the dogs; mean measure of the smallest diameter was 4.71mm with a standard deviation of 2.61mm and a minimum value of 1mm, and a maximum value of 8mm. From 14 observed lymph nodes 85.71% were isodense when compared with musculature and 14.28% were hypodense. The results show that it is possible to visualize axillary and mediastinal lymph nodes in adult clinically sound Rottweilers with CT using a slice thickness and interval of 10mm. The smallest diameter of the axillary and mediastinal lymph nodes not surpassed 7mm and 8mm respectively. Their attenuations were equal or smaller than that of musculature in the post contrast scan.
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The striatum, the largest component of the basal ganglia, is usually subdivided into associative, motor and limbic components. However, the electrophysiological interactions between these three subsystems during behavior remain largely unknown. We hypothesized that the striatum might be particularly active during exploratory behavior, which is presumably associated with increased attention. We investigated the modulation of local field potentials (LFPs) in the striatum during attentive wakefulness in freely moving rats. To this end, we implanted microelectrodes into different parts of the striatum of Wistar rats, as well as into the motor, associative and limbic cortices. We then used electromyograms to identify motor activity and analyzed the instantaneous frequency, power spectra and partial directed coherence during exploratory behavior. We observed fine modulation in the theta frequency range of striatal LFPs in 92.5 ± 2.5% of all epochs of exploratory behavior. Concomitantly, the theta power spectrum increased in all striatal channels (P < 0.001), and coherence analysis revealed strong connectivity (coefficients >0.7) between the primary motor cortex and the rostral part of the caudatoputamen nucleus, as well as among all striatal channels (P < 0.001). Conclusively, we observed a pattern of strong theta band activation in the entire striatum during attentive wakefulness, as well as a strong coherence between the motor cortex and the entire striatum. We suggest that this activation reflects the integration of motor, cognitive and limbic systems during attentive wakefulness.
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Exposure to air pollutants is associated with hospitalizations due to pneumonia in children. We hypothesized the length of hospitalization due to pneumonia may be dependent on air pollutant concentrations. Therefore, we built a computational model using fuzzy logic tools to predict the mean time of hospitalization due to pneumonia in children living in São José dos Campos, SP, Brazil. The model was built with four inputs related to pollutant concentrations and effective temperature, and the output was related to the mean length of hospitalization. Each input had two membership functions and the output had four membership functions, generating 16 rules. The model was validated against real data, and a receiver operating characteristic (ROC) curve was constructed to evaluate model performance. The values predicted by the model were significantly correlated with real data. Sulfur dioxide and particulate matter significantly predicted the mean length of hospitalization in lags 0, 1, and 2. This model can contribute to the care provided to children with pneumonia.
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The objective of this study was to investigate the morphology, anatomy and germination behaviour of Phoenix roebelenii seeds. Biometric data were obtained by measuring 100 seeds extracted from recently harvested fruits and air-dried for one day. Four replications of 50 seeds each were previously treated with Vitavax-Thiran and then put to germinate in Sphagnum sp. in plastic trays at room temperature. Morphological details of the seeds were documented with the help of a scanning electronic microscope and then drawings were made with the help of a clear camera coupled to a stereomicroscope. Permanent lamina containing embryo sections were prepared to study its anatomy. The mean dimensions of the seeds were: length of 10.32mm, width of 5.21mm and thickness of 3.91mm. The weight of one thousand seeds was of 151.1g and the mean number of units.kg-1 was 6,600. Germination started between 27 and 58 days after sowing. The seeds are of the albuminous type, the endosperm is hard and the embryo (which is not clearly differentiated) occupies a lateral and peripheral position. During seed germination, seedling protrusion begins with the opening of an operculum, through which the cotyledon petiole is emitted with the embryonic axis at its tip. The portion of the cotyledon petiole that remains inside the seeds acts as a haustorium for the absorption of nutrients from the endosperm. The plumule emerges through a rift in the posterior part of the cotyledon. Secondary roots are observed to grow from the anterior part of the primary root.
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Axial-flux machines tend to have cooling difficulties since it is difficult to arrange continuous heat path between the stator stack and the frame. One important reason for this is that no shrink fitting of the stator is possible in an axial-flux machine. Using of liquid-cooled end shields does not alone solve this issue. Cooling of the rotor and the end windings may also be difficult at least in case of two-stator-single-rotor construction where air circulation in the rotor and in the end-winding areas may be difficult to arrange. If the rotor has significant losses air circulation via the rotor and behind the stator yokes should be arranged which, again, weakens the stator cooling. In this paper we study a novel way of using copper bars as extra heat transfer paths between the stator teeth and liquid cooling pools in the end shields. After this the end windings still suffer of low thermal conductivity and means for improving this by high-heat-conductance material was also studied. The design principle of each cooling system is presented in details. Thermal models based on Computational Fluid Dynamics (CFD) are used to analyse the temperature distribution in the machine. Measurement results are provided from different versions of the machine. The results show that significant improvements in the cooling can be gained by these steps.
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The aim of this thesis was to examine efficiency of freeze crystallization and eutectic freeze crystallization in purification of wastewater by imitating natural freezing. In addition, a mathematic model based on heat transfer to determine ice thickness and ice growth rate was examined. Also, the amount of sodium sulfate crystallized at the eutectic point was under investigation. In literature part, advantages and applications of the freeze crystallization are discussed, and possibility to apply it in Northern hemisphere winter weather conditions is under study. Furthermore, main sources of sodium sulfate from Finnish industries are described. The experiments were carried out in modified chest freezer, where a fan was placed in order to obtain laminar air flow inside. Picolog PT-104 data logger was used to monitor temperature changes in the salt-water solution, and constant temperature was maintained in the crystallizer with Lauda RP 850 thermostat. The impurity of formed ice layer was determined by weighing ice samples after experiment and again after 24 hours drying to full dryness in oven. Volume of salt-water solution was also measured after experiment. The highest purity of formed ice layer was obtained with small temperature difference and with long freezing time. On the other hand, the amount of crystallized sodium sulfate was its greatest with long freezing time and higher temperature difference. The results obtained by the mathematic model and empirical results did not differ significantly in most of the experiments. However, the difference increased when salt-water mixture reached its eutectic point, leading to simultaneous ice and salt crystallization. Eutectic point was reached only with the highest salt concentration with one exception. In these cases, calculated values were in many cases greater than the experimental ones. In winter weather conditions freeze crystallization is cost-effective wastewater treatment method and rather simple. Nonetheless, the efficiency and separation rate are strongly depended on ambient temperature and its changes
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La thérapie par le plein air représente une alternative aux programmes d’intervention conventionnels pour jeunes antisociaux. Elle donne à ses participants l’occasion de modifier leurs pensées et leurs comportements dans un contexte d’expédition, à travers la participation à diverses activités de plein air. Ce faisant, ils développent leur répertoire d’habiletés personnelles et sociales, ce qui pourrait faciliter le désistement d’une conduite antisociale. Un devis expérimental prospectif, avec pré-test et post-tests à trois et six mois, a été utilisé afin d’évaluer l’effet de la durée d’une intervention de thérapie par le plein air sur le niveau d’antisocialité et l’insertion socio-professionnelle de jeunes contrevenants. De plus, l’effet potentiellement médiateur des progrès réalisés au chapitre des habiletés interpersonnelles et de la motivation d’accomplissement a été examiné. Un échantillon de 220 jeunes contrevenants a été observé, divisé aléatoirement selon deux conditions expérimentales, soit un programme de 8 à 10 jours et un programme de 17 à 20 jours. Il apparaît que la durée n’a pas d’effet direct significatif sur le niveau d’antisocialité et l’insertion socio-professionnelle des participants. En revanche, la durée du programme a un effet positif indirect sur le niveau d’antisocialité subséquent des participants, à travers l’amélioration des habiletés interpersonnelles et la motivation d’accomplissement des sujets. Aucune des variables mises en jeu n’a eu un impact significatif sur les progrès observés au niveau de l’insertion socio-professionnelle des sujets. La thérapie par le plein air semble favoriser le désistement d’une conduite antisociale en encourageant le développement de certaines habiletés personnelles qui font habituellement défaut chez les jeunes antisociaux.
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The laser produced plasma from the multi-component target YBa2CU3O7 was analyzed using Michelson interferometry and time resolved emission spectroscopy. The interaction of 10 ns pulses of 1.06 mum radiation from a Q-switched Nd:YAG laser at laser power densities ranging from 0.55 GW cm-2 to 1.5 GW cm-2 has been studied. Time resolved spectral measurements of the plasma evolution show distinct features at different points in its temporal history. For a time duration of less than 55 ns after the laser pulse (for a typical laser power density of 0.8 GW cm-2, the emission spectrum is dominated by black-body radiation. During cooling after 55 ns the spectral emission consists mainly of neutral and ionic species. Line averaged electron densities were deduced from interferometric line intensity measurements at various laser power densities. Plasma electron densities are of the order of 1017 cm-3 and the plasma temperature at the core region is about 1 eV. The measurement of plasma emission line intensities of various ions inside the plasma gave evidence of multiphoton ionization of the elements constituting the target at low laser power densities. At higher laser power densities the ionization mechanism is collision dominated. For elements such as nitrogen present outside the target, ionization is due to collisions only.
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This work aims to study the variation in subduction zone geometry along and across the arc and the fault pattern within the subducting plate. Depth of penetration as well as the dip of the Benioff zone varies considerably along the arc which corresponds to the curvature of the fold- thrust belt which varies from concave to convex in different sectors of the arc. The entire arc is divided into 27 segments and depth sections thus prepared are utilized to investigate the average dip of the Benioff zone in the different parts of the entire arc, penetration depth of the subducting lithosphere, the subduction zone geometry underlying the trench, the arctrench gap, etc.The study also describes how different seismogenic sources are identified in the region, estimation of moment release rate and deformation pattern. The region is divided into broad seismogenic belts. Based on these previous studies and seismicity Pattern, we identified several broad distinct seismogenic belts/sources. These are l) the Outer arc region consisting of Andaman-Nicobar islands 2) the back-arc Andaman Sea 3)The Sumatran fault zone(SFZ)4)Java onshore region termed as Jave Fault Zone(JFZ)5)Sumatran fore arc silver plate consisting of Mentawai fault(MFZ)6) The offshore java fore arc region 7)The Sunda Strait region.As the Seismicity is variable,it is difficult to demarcate individual seismogenic sources.Hence, we employed a moving window method having a window length of 3—4° and with 50% overlapping starting from one end to the other. We succeeded in defining 4 sources each in the Andaman fore arc and Back arc region, 9 such sources (moving windows) in the Sumatran Fault zone (SFZ), 9 sources in the offshore SFZ region and 7 sources in the offshore Java region. Because of the low seismicity along JFZ, it is separated into three seismogenic sources namely West Java, Central Java and East Java. The Sunda strait is considered as a single seismogenic source.The deformation rates for each of the seismogenic zones have been computed. A detailed error analysis of velocity tensors using Monte—Carlo simulation method has been carried out in order to obtain uncertainties. The eigen values and the respective eigen vectors of the velocity tensor are computed to analyze the actual deformation pattem for different zones. The results obtained have been discussed in the light of regional tectonics, and their implications in terms of geodynamics have been enumerated.ln the light of recent major earthquakes (26th December 2004 and 28th March 2005 events) and the ongoing seismic activity, we have recalculated the variation in the crustal deformation rates prior and after these earthquakes in Andaman—Sumatra region including the data up to 2005 and the significant results has been presented.ln this chapter, the down going lithosphere along the subduction zone is modeled using the free air gravity data by taking into consideration the thickness of the crustal layer, the thickness of the subducting slab, sediment thickness, presence of volcanism, the proximity of the continental crust etc. Here a systematic and detailed gravity interpretation constrained by seismicity and seismic data in the Andaman arc and the Andaman Sea region in order to delineate the crustal structure and density heterogeneities a Io nagnd across the arc and its correlation with the seismogenic behaviour is presented.
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Inthis paper,we define partial moments for a univariate continuous random variable. A recurrence relationship for the Pearson curve using the partial moments is established. The interrelationship between the partial moments and other reliability measures such as failure rate, mean residual life function are proved. We also prove some characterization theorems using the partial moments in the context of length biased models and equilibrium distributions
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The present study investigates the systematics and evolution of the Neotropical genus Deuterocohnia Mez (Bromeliaceae). It provides a comprehensive taxonomic revision as well as phylogenetic analyses based on chloroplast and nuclear DNA sequences and presents a hypothesis on the evolution of the genus. A broad morphological, anatomical, biogeographical and ecological overview of the genus is given in the first part of the study. For morphological character assessment more than 700 herbarium specimens from 39 herbaria as well as living plant material in the field and in the living collections of botanical gardens were carefully examined. The arid habitats, in which the species of Deuterocohnia grow, are reflected by the morphological and anatomical characters of the species. Important characters for species delimitation were identified, like the length of the inflorescence, the branching order, the density of flowers on partial inflorescences, the relation of the length of the primary bracts to that of the partial inflorescence, the sizes of floral bracts, sepals and petals, flower colour, the presence or absence of a pedicel, the curvature of the stamina and the petals during anthesis. After scrutinizing the nomenclatural history of the taxa belonging to Deuterocohnia – including the 1992 syonymized genus Abromeitiella – 17 species, 4 subspecies and 4 varieties are accepted in the present revision. Taxonomic changes were made in the following cases: (I) New combinations: A. abstrusa (A. Cast.) N. Schütz is re-established – as defined by Castellanos (1931) – and transfered to D. abstrusa; D. brevifolia (Griseb.) M.A. Spencer & L.B. Sm. includes accessions of the former D. lorentziana (Mez) M.A. Spencer & L.B. Sm., which are not assigned to D. abstrusa; D. bracteosa W. Till is synonymized to D. strobilifera Mez; D. meziana Kuntze ex Mez var. carmineo-viridiflora Rauh is classified as a subspecies of D. meziana (ssp. carmineo-viridiflora (Rauh) N. Schütz); D. pedicellata W. Till is classified as a subspecies of D. meziana (ssp. pedicellata (W. Till) N. Schütz); D. scapigera (Rauh & L. Hrom.) M.A. Spencer & L.B. Sm ssp. sanctae-crucis R. Vásquez & Ibisch is classified as a species (D. sanctae-crucis (R. Vásquez & Ibisch) N. Schütz); (II) New taxa: a new subspecies of D. meziana Kuntze ex Mez is established; a new variety of D. scapigera is established; (the new taxa will be validly published elsewhere); (III) New type: an epitype for D. longipetala was chosen. All other species were kept according to Spencer and Smith (1992) or – in the case of more recently described species – according to the protologue. Beside the nomenclatural notes and the detailed descriptions, information on distribution, habitat and ecology, etymology and taxonomic delimitation is provided for the genus and for each of its species. An key was constructed for the identification of currently accepted species, subspecies and varieties. The key is based on easily detectable morphological characters. The former synonymization of the genus Abromeitiella into Deuterocohnia (Spencer and Smith 1992) is re-evalutated in the present study. Morphological as well as molecular investigations revealed Deuterocohnia incl. Abromeitiella as being monophyletic, with some indications that a monophyletic Abromeitiella lineage arose from within Deuterocohnia. Thus the union of both genera is confirmed. The second part of the present thesis describes and discusses the molecular phylogenies and networks. Molecular analyses of three chloroplast intergenic spacers (rpl32-trnL, rps16-trnK, trnS-ycf3) were conducted with a sample set of 119 taxa. This set included 103 Deuterocohnia accessions from all 17 described species of the genus and 16 outgroup taxa from the remainder of Pitcairnioideae s.str. (Dyckia (8 sp.), Encholirium (2 sp.), Fosterella (4 sp.) and Pitcairnia (2 sp.)). With its high sampling density, the present investigation by far represents the most comprehensive molecular study of Deuterocohnia up till now. All data sets were analyzed separately as well as in combination, and various optimality criteria for phylogenetic tree construction were applied (Maximum Parsimony, Maximum Likelihood, Bayesian inferences and the distance method Neighbour Joining). Congruent topologies were generally obtained with different algorithms and optimality criteria, but individual clades received different degrees of statistical support in some analyses. The rps16-trnK locus was the most informative among the three spacer regions examined. The results of the chloroplast DNA analyses revealed a highly supported paraphyly of Deuterocohnia. Thus, the cpDNA trees divide the genus into two subclades (A and B), of which Deuterocohnia subclade B is sister to the included Dyckia and Encholirium accessions, and both together are sister to Deuterocohnia subclade A. To further examine the relationship between Deuterocohnia and Dyckia/Encholirium at the generic level, two nuclear low copy markers (PRK exon2-5 and PHYC exon1) were analysed with a reduced taxon set. This set included 22 Deuterocohnia accessions (including members of both cpDNA subclades), 2 Dyckia, 2 Encholirium and 2 Fosterella species. Phylogenetic trees were constructed as described above, and for comparison the same reduced taxon set was also analysed at the three cpDNA data loci. In contrast to the cpDNA results, the nuclear DNA data strongly supported the monophyly of Deuterocohnia, which takes a sister position to a clade of Dyckia and Encholirium samples. As morphology as well as nuclear DNA data generated in the present study and in a former AFLP analysis (Horres 2003) all corroborate the monophyly of Deuterocohnia, the apparent paraphyly displayed in cpDNA analyses is interpreted to be the consequence of a chloroplast capture event. This involves the introgression of the chloroplast genome from the common ancestor of the Dyckia/ Encholirium lineage into the ancestor of Deuterocohnia subclade B species. The chloroplast haplotypes are not species-specific in Deuterocohnia. Thus, one haplotype was sometimes shared by several species, where the same species may harbour different haplotypes. The arrangement of haplotypes followed geographical patterns rather than taxonomic boundaries, which may indicate some residual gene flow among populations from different Deuteroccohnia species. Phenotypic species coherence on the background of ongoing gene flow may then be maintained by sets of co-adapted alleles, as was suggested by the porous genome concept (Wu 2001, Palma-Silva et al. 2011). The results of the present study suggest the following scenario for the evolution of Deuterocohnia and its species. Deuterocohnia longipetala may be envisaged as a representative of the ancestral state within the genus. This is supported by (1) the wide distribution of this species; (2) the overlap in distribution area with species of Dyckia; (3) the laxly flowered inflorescences, which are also typical for Dyckia; (4) the yellow petals with a greenish tip, present in most other Deuterocohnia species. The following six extant lineages within Deuterocohnia might have independently been derived from this ancestral state with a few changes each: (I) D. meziana, D. brevispicata and D. seramisiana (Bolivia, lowland to montane areas, mostly reddish-greenish coloured, very laxly to very densely flowered); (II) D. strobilifera (Bolivia, high Andean mountains, yellow flowers, densely flowered); (III) D. glandulosa (Bolivia, montane areas, yellow-greenish flowers, densely flowered); (IV) D. haumanii, D. schreiteri, D. digitata, and D. chrysantha (Argentina, Chile, E Andean mountains and Atacama desert, yellow-greenish flowers, densely flowered); (V) D. recurvipetala (Argentina, foothills of the Andes, recurved yellow flowers, laxly flowered); (VI) D. gableana, D. scapigera, D. sanctae-crucis, D. abstrusa, D. brevifolia, D. lotteae (former Abromeitiella species, Bolivia, Argentina, higher Andean mountains, greenish-yellow flowers, inflorescence usually simple). Originating from the lower montane Andean regions, at least four lineages of the genus (I, II, IV, VI) adapted in part to higher altitudes by developing densely flowered partial inflorescences, shorter flowers and – in at least three lineages (II, IV, VI) – smaller rosettes, whereas species spreading into the lowlands (I, V) developed larger plants, laxly flowered, amply branched inflorescences and in part larger flowers (I).
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OBJETIVOS: Determinar los factores pronóstico, cambios maculares morfológicos y de capa de fibras nerviosas ganglionares posterior a vitrectomÃa pars plana, en la Fundación Oftalmológica Nacional. MATERIALES Y MÉTODOS: Estudio longitudinal de antes y después (3y6 meses) de la vitrectomÃa pars plana (VPP) en pacientes con membrana epirretiniana, agujero macular, sÃndrome de tracción vÃtreo macular y opacidades vÃtreas no-inflamatorias. Se realizó seguimiento clÃnico y con tomografÃa de coherencia óptica. RESULTADOS: Grupo de 60 pacientes (mujeres 65.0%), edad promedio 65.45+9.49años y tiempo de enfermedad promedio 23+29.79meses. Las indicaciones de VPP (n=60ojos) fueron agujero macular (38.3%) y membrana epirretiniana (36.7%). Se encontró diferencia significativa entre grosor del complejo capa de células ganglionares (CCG)+capa plexiforme interna (CPI) inicial y 3 meses (p=0.039), correlación entre grosor del complejo CCG+CPI al tercer y sexto mes (r=0.704,p<0.001) y grosor del complejo CCG+CPI al tercer mes con grosor foveal central (CFT) al tercer y sexto mes (r=–0.594,p<0.001 y r=–0.595,p=0.001). Mayores de 65años tenÃan menor grosor de CFNG a 6meses (r=-0.528,p=0.007). El grosor de CFNG promedio y la presencia de la zona elipsoide inicial fueron factores pronósticos de buena agudeza visual al tercer mes de VPP (r2=0.414,p=0.018, y r2=0.414,p=0.010). CONCLUSIÓN: El grosor de CFNG y la presencia de la zona elipsoide inicial tienen alta capacidad predictiva de buena agudeza visual al tercer mes de VPP, y, correlación inversa entre grosor del complejo CCG+CPI con CFT al tercer y sexto mes de VPP.
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We have developed an ensemble Kalman Filter (EnKF) to estimate 8-day regional surface fluxes of CO2 from space-borne CO2 dry-air mole fraction observations (XCO2) and evaluate the approach using a series of synthetic experiments, in preparation for data from the NASA Orbiting Carbon Observatory (OCO). The 32-day duty cycle of OCO alternates every 16 days between nadir and glint measurements of backscattered solar radiation at short-wave infrared wavelengths. The EnKF uses an ensemble of states to represent the error covariances to estimate 8-day CO2 surface fluxes over 144 geographical regions. We use a 12×8-day lag window, recognising that XCO2 measurements include surface flux information from prior time windows. The observation operator that relates surface CO2 fluxes to atmospheric distributions of XCO2 includes: a) the GEOS-Chem transport model that relates surface fluxes to global 3-D distributions of CO2 concentrations, which are sampled at the time and location of OCO measurements that are cloud-free and have aerosol optical depths <0.3; and b) scene-dependent averaging kernels that relate the CO2 profiles to XCO2, accounting for differences between nadir and glint measurements, and the associated scene-dependent observation errors. We show that OCO XCO2 measurements significantly reduce the uncertainties of surface CO2 flux estimates. Glint measurements are generally better at constraining ocean CO2 flux estimates. Nadir XCO2 measurements over the terrestrial tropics are sparse throughout the year because of either clouds or smoke. Glint measurements provide the most effective constraint for estimating tropical terrestrial CO2 fluxes by accurately sampling fresh continental outflow over neighbouring oceans. We also present results from sensitivity experiments that investigate how flux estimates change with 1) bias and unbiased errors, 2) alternative duty cycles, 3) measurement density and correlations, 4) the spatial resolution of estimated flux estimates, and 5) reducing the length of the lag window and the size of the ensemble. At the revision stage of this manuscript, the OCO instrument failed to reach its orbit after it was launched on 24 February 2009. The EnKF formulation presented here is also applicable to GOSAT measurements of CO2 and CH4.
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X-ray reflectivity (XR) and grazing incidence X-ray diffraction (GIXD) have been used to examine an oxyethylene-b-oxybutylene (E23B8) copolymer film at the air-water interface. The XR data were fitted using both a one- and a two-layer model that outputted the film thickness, roughness, and electron density. The best fit to the experimental data was obtained using a two-layer model (representing the oxyethylene and oxybutylene blocks, respectively), which showed a rapid thickening of the copolymer film at pressures above 7 mN/m. The large roughness values found indicate a significant degree of intermixing between the blocks and back up the GIXD data, which showed no long range lateral ordering within the layer. It was found from the electron density model results that there is a large film densification at 7 mN/m, possibly suggesting conformational changes within the film, even though no such change occurs on the pressure-area isotherm at the same surface pressure.
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One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reponed for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO2 using the principle of micellar catalysis. [CF3(CF2)(8)COO](2)Co.xH(2)O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co2+ cations in scCO(2)) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water-CO2 mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 degreesC. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF3(CF2)(8)COO](2)Mg.yH(2)O/Co(II) acetate is as effective as the [CF3(CF2)(8)COO](2)Co.xH(2)O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO(2) can be easily separated via CO2 depressurisation and be reused without noticeable deactivation. (C) 2003 Elsevier B.V. All rights reserved.