Liquid phase benzoylation of arenes over iron promoted sulphated zirconia

The present work undertakes the preparation and physico-chemical characterisation of iron promoted sulphated zirconia (SZ) with different amounts of iron loading and their application to Friedel-Crafts benzoylation of benzene, toluene and xylene under different experimental conditions, XRD and laser Raman techniques reveal the stabilisation of the tetragonal phase of zirconia and the existence of iron in highly dispersed form as Fe203 on the catalyst surface. The surface acidic properties were determined by ammonia temperature programmed desorption (TPD) and perylene adsorption, The results were supported by the TGA studies after adsorption of pyridine and 2,6-dimethylpyridine (2,6-DMP), Strong Lewis acid sites on the surface, which are evident from TPD and perylene adsorption studies. explain the high catalytic activity of the systems towards benzoylation. The experimental results provide evidence for the truly heterogeneous nature of the reaction. The studies also establish the resistance to deactivation in the metal incorporated sulphated systems.

An electrochemical study of 4-aminothiophenol/pt nanoparticle multilayers on gold electrodes

Quartz crystal microbalance (QCM) measurements of the formation of a 4-aminothiophenol (4-ATP)self-assembled monolayer (SAM) at a gold electrode showed that a surface coverage of 118 ng cm(-2) was obtained after a 3 h exposure period, indicating that good surface coverage was achieved. Cyclic voltammetry of the ferricyanide redox couple across this SAM modified surface produced similar results to those of a bare electrode; however, the electroreduction of oxygen was found to be impaired. The 4-ATP SAM layer was not stable to repeated electrochemical oxidation and reduction; it is believed that the 4-ATP SAM layer was first converted to a 4'-mercapto-N-phenylquinone diimine (NPQD) layer followed by subsequent formation of a 4'-mercapto-N-phenylquinone monoimine (NPQM) layer. We also report a quartz crystal microbalance study of the attachment of platinum nanoparticles to such SAM modified electrodes. We show that five times the amount of platinum nanoparticles can be attached to a 4-ATP modified electrode surface (observed frequency change - 187 Hz) compared with an NPQD modified electrode surface (observed frequency change -35 Hz). The presence of the platinum particles was confirmed electrochemically by their surface electrochemical properties, which were different from those of the underlying gold electrode. It is believed that this is the first time that such direct evidence of electrochemical communication between platinum nanoparticles and a SAM modified electrode surface has been obtained. It was also shown to be possible to build up multilayer SAM/nanoparticle modified surfaces while maintaining efficient electrochemical communication. Up to three SAM/nanoparticle sandwich layers were constructed.

The use of elevation map histograms for topographic heterogeneity analysis

Surface defects are extremely important in mechanical characterization of several different materials. Therefore, the analysis of surface finishing is essential for a further simulation of surface mechanical properties in a customized project in materials science and technology. One of the methods commonly employed for such purpose is the statistical mapping of different sample surface regions using the depth from focus technique. The analysis is usually performed directly from the elevation maps which are obtained from the digital image processing. In this paper, the possibility of quantifying the surface heterogeneity of Silicon Carbide porous ceramics by elevation map histograms is presented. The advantage of this technique is that it allows the qualitative or quantitative verification of all surface image fields that cannot be done by using the Surface Plot plugin of image J™ platform commonly used in digital image processing. © 2012 Springer Science+Business Media, LLC.

Nanozeólitas como suportes sólidos para imobilização enzimática: Síntese, caracterização de complexos nanozeólitas/enzimas e sua aplicação como catalisadores heterogêneos para produção de biodiesel via rota etílica

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

The potentially toxic diatom Pseudo-nitzschia H. Peragallo in the Parana and Santa Catarina States, Southern Brazil

A taxonomic survey of the diatom Pseudo-nitzschia H. Peragallo was carried out in the Parana and Santa Catarina coasts, Southern Brazil. Samples were taken in various localities along the coastline using vertical hauls from the bottom to the surface. Electron microscopy revealed five species: the potentially toxic P. australis Frenguelli, P calliantha Lundholm, Moestrup & Has le, P multiseries (Has le) Has le and P pungens (Grunow ex Cleve) Has le (plus P pungens var. cingulata Villac), and the non-toxic P linea Lundholm, Has le & G. A. Fryxell. Southern Brazilian strains of P. calliantha and P multiseries have previously been shown to be toxic, raising concerns about a potential contamination of mussels and oysters being commercially grounded in the region. High morphological variability was observed in valve characters of P calliantha and P pungens, in some cases confirmed in the literature. In P calliantha there was a conspicuous differentiation in two morphotypes separated from each other by the width and the shape of the valve, and the density of the poroids. P linea has not previously been found in Brazilian waters, and P pungens var. cingulata is a new record in Western Atlantic waters. Future investigations using molecular techniques will elucidate whether the genetic variability corresponds to the morphological variation and unveil the possible existence of semicryptic species of Pseudo-nitzschia inhabiting the South Brazilian coast.

Effects of low-salinity and high-turbidity waters one mpirical ocean colour algorithms: an example for Southwestern Atlantic waters

The spectral reflectance of the sea surface recorded using ocean colour satellite sensors has been used to estimate chlorophyll-a concentrations for decades. However, in bio-optically complex coastal waters, these estimates are compromised by the presence of several other coloured components besides chlorophyll, especially in regions affected by low-salinity waters. The present work aims to (a) describe the influence of the freshwater plume from the La Plata River on the variability of in situ remote sensing reflectance and (b) evaluate the performance of operational ocean colour chlorophyll algorithms applied to Southwestern Atlantic waters, which receive a remarkable seasonal contribution from La Plata River discharges. Data from three oceanographic cruises are used, in addition to a historical regional bio-optical dataset. Deviations found between measured and estimated concentrations of chlorophyll-a are examined in relation to surface water salinity and turbidity gradients to investigate the source of errors in satellite estimates of pigment concentrations. We observed significant seasonal variability in surface reflectance properties that are strongly driven by La Plata River plume dynamics and arise from the presence of high levels of inorganic suspended solids and coloured dissolved materials. As expected, existing operational algorithms overestimate the concentration of chlorophyll-a, especially in waters of low salinity (S<33.5) and high turbidity (Rrs(670)>0.0012 sr−1). Additionally, an updated version of the regional algorithm is presented, which clearly improves the chlorophyll estimation in those types of coastal environment. In general, the techniques presented here allow us to directly distinguish the bio-optical types of waters to be considered in algorithm studies by the ocean colour community.

Three-dimensional Vortex Structures on Heated Micro-lattice in a Gas

This paper addresses the microscale heat transfer problem from heated lattice to the gas. A micro-device for enhanced heat transfer is presented and numerically investigated. Thermal creep induces 3-D vortex structures in the vicinity of the lattice. The gas flow is in the slip flow regime (Knudsen number Kn⩽0.1Kn⩽0.1). The simulations are performed using slip flow Navier–Stokes equations with boundary condition formulations proposed by Maxwell and Smoluchowski. In this study the wire thicknesses and distances of the heated lattice are varied. The surface geometrical properties alter significantly heat flux through the surface.

Redistribution of particles across the nucleus of comet 67P/Churyumov-Gerasimenko

Context. We present an investigation of the surface properties of areas on the nucleus of comet 67P/Churyumov-Gerasimenko. Aims. We aim to show that transport of material from one part of the cometary nucleus to another is a significant mechanism that influences the appearance of the nucleus and the surface thermal properties. Methods. We used data from the OSIRIS imaging system onboard the Rosetta spacecraft to identify surface features on the nucleus that can be produced by various transport mechanisms. We used simple calculations based on previous works to establish the plausibility of dust transport from one part of the nucleus to another. Results. We show by observation and modeling that "airfall" as a consequence of non-escaping large particles emitted from the neck region of the nucleus is a plausible explanation for the smooth thin deposits in the northern hemisphere of the nucleus. The consequences are also discussed. We also present observations of aeolian ripples and ventifacts. We show by numerical modeling that a type of saltation is plausible even under the rarified gas densities seen at the surface of the nucleus. However, interparticle cohesive forces present difficulties for this model, and an alternative mechanism for the initiation of reptation and creep may result from the airfall mechanism. The requirements on gas density and other parameters of this alternative make it a more attractive explanation for the observations. The uncertainties and implications are discussed.

Stable isotope record and lithic fragments distribution in sediments of MIS9-14 of the North Atlantic

Stable isotope and ice-rafted debris records from three core sites in the mid-latitude North Atlantic (IODP Site U1313, MD01-2446, MD03-2699) are combined with records of ODP Sites 1056/1058 and 980 to reconstruct hydrographic conditions during the middle Pleistocene spanning Marine Isotope Stages (MIS) 9-14 (300-540 ka). Core MD03-2699 is the first high-resolution mid-Brunhes record from the North Atlantic's eastern boundary upwelling system covering the complete MIS 11c interval and MIS 13. The array of sites reflect western and eastern basin boundary current as well as north to south transect sampling of subpolar and transitional water masses and allow the reconstruction of transport pathways in the upper limb of the North Atlantic's circulation. Hydrographic conditions in the surface and deep ocean during peak interglacial MIS 9 and 11 were similar among all the sites with relative stable conditions and confirm prolonged warmth during MIS 11c also for the mid-latitudes. Sea surface temperature (SST) reconstructions further reveal that in the mid-latitude North Atlantic MIS 11c is associated with two plateaus, the younger one of which is slightly warmer. Enhanced subsurface northward heat transport in the eastern boundary current system, especially during early MIS 11c, is denoted by the presence of tropical planktic foraminifer species and raises the question how strongly it impacted the Portuguese upwelling system. Deep water ventilation at the onset of MIS 11c significantly preceded surface water ventilation. Although MIS 13 was generally colder and more variable than the younger interglacials the surface water circulation scheme was the same. The greatest differences between the sites existed during the glacial inceptions and glacials. Then a north - south trending hydrographic front separated the nearshore and offshore waters off Portugal. While offshore waters originated from the North Atlantic Current as indicated by the similarities between the records of IODP Site U1313, ODP Site 980 and MD01-2446, nearshore waters as recorded in core MD03-2699 derived from the Azores Current and thus the subtropical gyre. Except for MIS 12, Azores Current influence seems to be related to eastern boundary system dynamics and not to changes in the Atlantic overturning circulation.

Age determination, foraminiferal abundance and stable isotope ratios of sediment core CH82-20

A core from the Mid-Atlantic Ridge at 43.5°N and ~3 km water depth shows distinct evidence of the deglacial events known as Heinrich event 1 (probably the marine equivalent of Oldest Dryas cooling in Europe) and the Younger Dryas. The Heinrich event, dated at three levels to between 14.3 and 15.0 ka, is marked by a minimum in foraminifera per gram, by maxima in rates of sedimentation, ice rafted debris per gram, and relative abundance of N. pachyderma (s.), and by a delta18O minimum in planktonic foraminifera. The Younger Dryas event is marked by peak abundance of N. pachyderma (s.) and a planktonic delta18O maximum. Benthic foraminiferal delta13C reaches minimum values during both the Heinrich event and the Younger Dryas. Our data indicate pronounced changes in surface water properties were coupled with reduced production of North Atlantic Deep Water at each of these times.

Stable isotope ratios and foraminiferal abundance of sediment cores from the Western Iberian Margin

Rapid climate changes at the onset of the last deglaciation and during Heinrich Event H4 were studied in detail at IMAGES cores MD95-2039 and MD95-2040 from the Western Iberian margin. A major reorganisation of surface water hydrography, benthic foraminiferal community structure, and deepwater isotopic composition commenced already 540 years before the Last Isotopic Maximum (LIM) at 17.43 cal. ka and within 670 years affected all environments. Changes were initiated by meltwater spill in the Nordic Seas and northern North Atlantic that commenced 100 years before concomitant changes were felt off western Iberia. Benthic foraminiferal associations record the drawdown of deepwater oxygenation during meltwater and subsequent Heinrich Events H1 and H4 with a bloom of dysoxic species. At a water depth of 3380 m, benthic oxygen isotopes depict the influence of brines from sea ice formation during ice-rafting pulses and meltwater spill. The brines conceivably were a source of ventilation and provided oxygen to the deeper water masses. Some if not most of the lower deep water came from the South Atlantic. Benthic foraminiferal assemblages display a multi-centennial, approximately 300-year periodicity of oxygen supply at 2470-m water depth. This pattern suggests a probable influence of atmospheric oscillations on the thermohaline convection with frequencies similar to Holocene climate variations. For Heinrich Events H1 and H4, response times of surface water properties off western Iberia to meltwater injection to the Nordic Seas were extremely short, in the range of a few decades only. The ensuing reduction of deepwater ventilation commenced within 500-600 years after the first onset of meltwater spill. These fast temporal responses lend credence to numerical simulations that indicate ocean-climate responses on similar and even faster time scales.

(Table 2) Distribution of alkenone unsaturation index UK37 of the eastern North Atlantic

This paper reports the concentrations and within-class distributions of long-chain alkenones and alkyl alkenoates in the surface waters (0-50 m) of the eastern North Atlantic, and correlates their abundance and distribution with those of source organisms and with water temperature and other environmental variables. We collected these samples of >0.8 µm particulate material from the euphotic zone along the JGOFS 20°W longitude transect, from 61°N to 24°N, during seven cruises of the UK-JGOFS Biogeochemical Ocean Flux Study (BOFS) in 1989-1991; the biogeographical range of our 53 samples extends from the cold (<10°C), nutrient-rich and highly productive subarctic waters of the Iceland Basin to the warm (>25°C) oligotrophic subtropical waters off Africa. Surface water concentrations of total alkenone and alkenoates ranged from <50 ng/l in oligotrophic waters below 40°N to 2000-4500 ng/l in high latitude E. huxleyi blooms, and were well correlated with E. huxleyi cell densities, supporting the assumption that E. huxleyi is the predominant source of these compounds in the present day North Atlantic. The within-class distribution of the C37 and C38 alkenones and C36 alkenoates varied strongly as a function of temperature, and was largely unaffected by nutrient concentration, bloom status and other surface water properties. The biosynthetic response of the source organisms to growth temperature differed between the cold (<16°C) waters above 47°N and the warmer waters to the south. In cold (<16°C) waters above 47°N, the relative amounts of alkenoates and C38 alkenones synthesized was a strong function of growth temperature, while the unsaturation ratio of the alkenones (C37 and C38) was uncorrelated with temperature. Conversely, in warm (>16°C) waters below 47°N, the relative proportions of alkenoates and alkenones synthesized remained constant with increasing temperature while the unsaturation ratios of the C37 and C38 methyl alkenones (Uk37 and Uk38Me, respectively) increased linearly. The fitted regressions of Uk37 and Uk38Me versus temperature for waters >16°C were both highly significant (r**2 > 0.96) and had identical slopes (0.057) that were 50% higher than the slope (0.034) of the temperature calibration of Uk37 reported by Prahl and Wakeham (1987; doi:10.1038/330367a0) over the same temperature range. These observations suggest either a physiological adjustment in biochemical response to growth temperature above a 16-17°C threshold and/or variation between different E. huxleyi strains and/or related species inhabiting the cold and warm water regions of the eastern North Atlantic. Using our North Atlantic data set, we have produced multivariate temperature calibrations incorporating all major features of the alkenone and alkenoate data set. Predicted temperatures using multivariate calibrations are largely unbiased, with a standard error of approximately ±1°C over the entire data range. In contrast, simpler calibration models cannot adequately incorporate regional diversity and nonlinear trends with temperature. Our results indicate that calibrations based upon single variables, such as Uk37, can be strongly biased by unknown systematic errors arising from natural variability in the biosynthetic response of the source organisms to growth temperature. Multivariate temperature calibration can be expected to give more precise estimates of Integrated Production Temperatures (IPT) in the sedimentary record over a wider range of paleoenvironmental conditions, when derived using a calibration data set incorporating a similar range of natural variability in biosynthetic response.

Investigation of time series stations along a productivity gradient north of the Canary Islands

Three stations along a productivity gradient north of the Canary Islands were investigated for surface-water properties, particle flux, and composition (biogenic and lithogenic components, and stable nitrogen isotope composition, delta15N) and export production. Investigation sites along the east-west transect off the NW African upwelling margin included the European Station for Time-Series in the Ocean, Canary Islands (ESTOC), one location contiguous to the NW African upwelling zone in the Eastern Boundary Current (EBC) and one station north of the island La Palma (LP). The seasonality of surface-water properties along the transect was mainly influenced by the winter cooling and simultaneous phytoplankton maximum and, in addition at EBC, by nearby upwelling. Accordingly, particle flux and composition along the transect were closely linked to the winter bloom sedimentation and upwelling related enhanced plankton biomass stemming from the primary upwelling and the Cape Yubi filament at EBC. During all seasons, particle flux was highest at EBC and had the highest contribution of biogenic opal and lithogenic components, and the lowest delta15N compared to the offshore stations. But contrary to what would be expected from the productivity gradient, particle flux did not decrease from ESTOC to LP. Below the upper several hundred meters, particle flux was enhanced by additional particle input along the entire transect, manifested by an increase of flux with depth and lower delta15N values. We offer a scenario in which intermediate nepheloid layers originating from the primary upwelling as well as particle dispersion from upwelling filaments, mainly the Cape Ghir filament, impact on the trap stations as far as 700 km into the open ocean. This study contributes to our understanding of the poorly resolved biogeochemical transition between the productive shelf and subtropical gyre provinces.