Mean and Variability of the Tropical Atlantic Ocean in the CCSM4

This study analyzes important aspects of the tropical Atlantic Ocean from simulations of the fourth version of the Community Climate System Model (CCSM4): the mean sea surface temperature (SST) and wind stress, the Atlantic warm pools, the principal modes of SST variability, and the heat budget in the Benguela region. The main goal was to assess the similarities and differences between the CCSM4 simulations and observations. The results indicate that the tropical Atlantic overall is realistic in CCSM4. However, there are still significant biases in the CCSM4 Atlantic SSTs, with a colder tropical North Atlantic and a hotter tropical South Atlantic, that are related to biases in the wind stress. These are also reflected in the Atlantic warm pools in April and September, with its volume greater than in observations in April and smaller than in observations in September. The variability of SSTs in the tropical Atlantic is well represented in CCSM4. However, in the equatorial and tropical South Atlantic regions, CCSM4 has two distinct modes of variability, in contrast to observed behavior. A model heat budget analysis of the Benguela region indicates that the variability of the upper-ocean temperature is dominated by vertical advection, followed by meridional advection.

Giant magnetofossils and hyperthermal events

Magnetotactic bacteria biomineralize magnetic minerals with precisely controlled size, morphology, and stoichiometry. These cosmopolitan bacteria are widely observed in aquatic environments. If preserved after burial, the inorganic remains of magnetotactic bacteria act as magnetofossils that record ancient geomagnetic field variations. They also have potential to provide paleoenvironmental information. In contrast to conventional magnetofossils, giant magnetofossils (most likely produced by eukaryotic organisms) have only been reported once before from Paleocene-Eocene Thermal Maximum (PETM; 55.8 Ma) sediments on the New Jersey coastal plain. Here, using transmission electron microscopic observations, we present evidence for abundant giant magnetofossils, including previously reported elongated prisms and spindles, and new giant bullet-shaped magnetite crystals, in the Southern Ocean near Antarctica, not only during the PETM, but also shortly before and after the PETM. Moreover, we have discovered giant bullet-shaped magnetite crystals from the equatorial Indian Ocean during the Mid-Eocene Climatic Optimum (similar to 40 Ma). Our results indicate a more widespread geographic, environmental, and temporal distribution of giant magnetofossils in the geological record with a link to "hyperthermal" events. Enhanced global weathering during hyperthermals, and expanded suboxic diagenetic environments, probably provided more bioavailable iron that enabled biomineralization of giant magnetofossils. Our micromagnetic modelling indicates the presence of magnetic multi-domain (i.e., not ideal for navigation) and single domain (i.e., ideal for navigation) structures in the giant magnetite particles depending on their size, morphology and spatial arrangement. Different giant magnetite crystal morphologies appear to have had different biological functions, including magnetotaxis and other non-navigational purposes. Our observations suggest that hyperthermals provided ideal conditions for giant magnetofossils, and that these organisms were globally distributed. Much more work is needed to understand the interplay between magnetofossil morphology, climate, nutrient availability, and environmental variability.

Beyond the diffraction limit of optical/IR interferometers I. Angular diameter and rotation parameters of Achernar from differential phases

Context. Spectrally resolved long-baseline optical/IR interferometry of rotating stars opens perspectives to investigate their fundamental parameters and the physical mechanisms that govern their interior, photosphere, and circumstellar envelope structures. Aims. Based on the signatures of stellar rotation on observed interferometric wavelength-differential phases, we aim to measure angular diameters, rotation velocities, and orientation of stellar rotation axes. Methods. We used the AMBER focal instrument at ESO-VLTI in its high-spectral resolution mode to record interferometric data on the fast rotator Achernar. Differential phases centered on the hydrogen Br gamma line (K band) were obtained during four almost consecutive nights with a continuous Earth-rotation synthesis during similar to 5h/night, corresponding to similar to 60 degrees position angle coverage per baseline. These observations were interpreted with our numerical code dedicated to long-baseline interferometry of rotating stars. Results. By fitting our model to Achernar's differential phases from AMBER, we could measure its equatorial radius R-eq = 11.6 +/- 0.3 R-circle dot, equatorial rotation velocity V-eq = 298 +/- 9 km s(-1), rotation axis inclination angle i = 101.5 +/- 5.2 degrees, and rotation axis position angle (from North to East) PA(rot) = 34.9 +/- 1.6 degrees. From these parameters and the stellar distance, the equatorial angular diameter circle divide(eq) of Achernar is found to be 2.45 +/- 0.09 mas, which is compatible with previous values derived from the commonly used visibility amplitude. In particular, circle divide(eq) and PA(rot) measured in this work with VLTI/AMBER are compatible with the values previously obtained with VLTI/VINCI. Conclusions. The present paper, based on real data, demonstrates the super-resolution potential of differential interferometry for measuring sizes, rotation velocities, and orientation of rotating stars in cases where visibility amplitudes are unavailable and/or when the star is partially or poorly resolved. In particular, we showed that differential phases allow the measurement of sizes up to similar to 4 times smaller than the diffraction-limited angular resolution of the interferometer.

The nature of Ru-NO bonds in ruthenium tetraazamacrocycle nitrosyl complexes-a computational study

Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications.

The last mangroves of Marajo Island - Eastern Amazon: Impact of climate and/or relative sea-level changes

The dynamics, over the last 7500 years, of a mangrove at Marajo Island in northern Brazil were studied by pollen and sedimentary facies analyses using sediment cores. This island, located at the mouth of the Amazon River. is influenced by riverine inflow combined with tidal fluctuations of the equatorial Atlantic Ocean. Herbaceous vegetation intermingled with rainforest dominates the central area of the island, while varzea is the main vegetation type along the littoral. In particular, the modem northeastern coastal zone is covered by a mosaic of dense rainforest, herbaceous vegetation, mangroves, varzea, and restinga. The integration of pollen data and fades descriptions indicates a tidal mud flat colonized by mangroves in the interior of Marajo Island between similar to 7500 cal yr BP and similar to 3200 cal yr BP. During the late Holocene, mangroves retracted to a small area (100-700 m in width) along the northeastern coastal plain. Mangrove expansion during the early and mid Holocene was likely caused by the post-glacial sea-level rise which, combined with tectonic subsidence, led to a rise in tidal water salinity. Salinity must have further increased due to low river discharge resulting from increased aridity during the early and mid Holocene. The shrinking of the area covered by mangrove vegetation during the late Holocene was likely caused by the increase in river discharge during the late Holocene, which has maintained relatively low tidal water salinity in Marajo Island. Tidal water salinity is relatively higher in the northeastern part of the island than in others, due to the southeast-northwest trending current along the littoral. The mixing of marine and riverine freshwater inflows has provided a refuge for mangroves in this area. The increase in flow energy during the last century is related to landward sand migration, which explains the current retraction of mangroves. These changes may indicate an increased exposure to tidal influence driven by the relative sea-level rise, either associated with global fluctuations or tectonic subsidence, and/or by an increase in river water discharge. (C) 2012 Elsevier B.V. All rights reserved.

Conformational preferences for some 3-(4 '-substituted phenylsulfonyl)-1-methyl-2-piperidones through spectroscopic and theoretical studies

The analysis of the infrared (IR) carbonyl band of some 3-(4'-substituted phenylsulfonyl)-1-methyl-2-piperidones 1-5 bearing as substituents: OMe 1, Me 2, H 3, Cl 4 and NO2 5, supported by B3LY13/6-31G(d,p) calculations along with NBO analysis (for 1, 3 and 5) and X-ray diffraction (for 5), indicated the existence of three stable conformations i.e. quasi-axial (q-ax), syn-clinal (s-cl) and quasi-equatorial (q-eq). In the gas phase, the q-ax conformer is calculated as the most stable (ca. 88%) and the least polar, the s-cl conformer is less stable (ca. 12%) but more polar, and the q-eq conformer is the least stable (ca. 1%) and the most polar of the three conformers evaluated. The sum of the most important orbital interactions from NBO analysis and the trend of the electrostatic interactions accounts for the relative populations as well as for the v(CO) frequencies of the q-ax. s-cl and q-eq conformers calculated in the gas phase. The unique IR v(CO) band in CCl4 may be ascribed to the most stable q-ax conformer. The more intense (60%) high frequency doublet component in CHCl3 may be assigned to the summing up of the least stable q-eq and the less stable s-cl conformers, as their frequencies are almost coincident. The occurrence of only a single v(CO) band in both CH2Cl2 and CH3CN supports the fact that the v(CO) band of the two more polar conformers appear as a single band. Additional support to this rationalization is given by the single point PCM method, which showed a progressive increase of the q-eq + s-cl/q-ax population ratio going from the gas phase to CCl4, to CHCl3, to CH2Cl2 and to CN3CN. X-ray single crystal analysis of 5 indicates that this compound displays a quasi-axial geometry with respect to the [O=C-CH-S] moiety, and that the 2-piperidone ring assumes a slightly distorted half-chair conformation. In the crystal packing, molecules of 5 are arranged into supramolecular layers linked through C-H center dot center dot center dot O interactions along with it pi center dot center dot center dot pi interactions between adjacent benzene rings. (C) 2012 Elsevier B.V. All rights reserved.

Thermodynamics of Axial Substitution and Kinetics of Reactions with Amino Acids for the Paddlewheel Complex Tetrakis(acetato)chloridodiruthenium(II,III)

The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru-2(CH3COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters Delta H degrees, Delta S degrees, and Delta V degrees were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru-2 substituted species. The results revealed that the [Ru-2(CH3COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

Spatial-temporal variations in phytoplankton size and colored detrital matter absorption at global and regional scales, as derived from twelve years of SeaWiFS data (1998-2009)

A procedure has been proposed by Ciotti and Bricaud (2006) to retrieve spectral absorption coefficients of phytoplankton and colored detrital matter (CDM) from satellite radiance measurements. This was also the first procedure to estimate a size factor for phytoplankton, based on the shape of the retrieved algal absorption spectrum, and the spectral slope of CDM absorption. Applying this method to the global ocean color data set acquired by SeaWiFS over twelve years (1998-2009), allowed for a comparison of the spatial variations of chlorophyll concentration ([Chl]), algal size factor (S-f), CDM absorption coefficient (a(cdm)) at 443 nm, and spectral slope of CDM absorption (S-cdm). As expected, correlations between the derived parameters were characterized by a large scatter at the global scale. We compared temporal variability of the spatially averaged parameters over the twelve-year period for three oceanic areas of biogeochemical importance: the Eastern Equatorial Pacific, the North Atlantic and the Mediterranean Sea. In all areas, both S-f and a(cdm)(443) showed large seasonal and interannual variations, generally correlated to those of algal biomass. The CDM maxima appeared in some occasions to last longer than those of [Chl]. The spectral slope of CDM absorption showed very large seasonal cycles consistent with photobleaching, challenging the assumption of a constant slope commonly used in bio-optical models. In the Equatorial Pacific, the seasonal cycles of [Chl], S-f, a(cdm)(443) and S-cdm, as well as the relationships between these parameters, were strongly affected by the 1997-98 El Ni o/La Ni a event.

Phylogenetic identification of marine bacteria isolated from deep-sea sediments of the eastern South Atlantic Ocean

The deep-sea environments of the South Atlantic Ocean are less studied in comparison to the North Atlantic and Pacific Oceans. With the aim of identifying the deep-sea bacteria in this less known ocean, 70 strains were isolated from eight sediment samples (depth range between 1905 to 5560 m) collected in the eastern part of the South Atlantic, from the equatorial region to the Cape Abyssal Plain, using three different culture media. The strains were classified into three phylogenetic groups, Gammaproteobacteria, Firmicutes and Actinobacteria, by the analysis of 16s rRNA gene sequences. Gammaproteobacteria and Firmicutes were the most frequently identified groups, with Halomonas the most frequent genus among the strains. Microorganisms belonging to Firmicutes were the only ones observed in all samples. Sixteen of the 41 identified operational taxonomic units probably represent new species. The presence of potentially new species reinforces the need for new studies in the deep-sea environments of the South Atlantic.

Effectiveness of the Brazilian influenza vaccination policy, a systematic review

Since 1999, Brazil has undertaken annual influenza vaccine campaigns, free of charge, targeting the elderly population, health professionals, and immune-deficient patients. We conducted a systematic review of literature in order to evaluate the effectiveness of the initiative. We used the keywords influenza, vaccine, Brazil and effectiveness to search the main databases. Thirty-one studies matched our inclusion and exclusion criteria. Influenza vaccine coverage among the elderly is high, though not as high as suggested by the official figures. Estimates on effectiveness are scarce. The majority come from ecological studies that show a modest reduction in mortality and hospital admissions due to influenza-related causes. Such reduction is not evident in the North and Northeastern states of Brazil, a finding that is probably related to the different seasonal pattern of influenza in equatorial and tropical regions. Brazilian epidemiologists still owe society better-designed studies addressing the effectiveness of influenza vaccine campaigns.

What drives the seasonality of photosynthesis across the Amazon basin? A cross-site analysis of eddy flux tower measurements from the Brasil flux network

We investigated the seasonal patterns of Amazonian forest photosynthetic activity, and the effects thereon of variations in climate and land-use, by integrating data from a network of ground-based eddy flux towers in Brazil established as part of the ‘Large-Scale Biosphere Atmosphere Experiment in Amazonia’ project. We found that degree of water limitation, as indicated by the seasonality of the ratio of sensible to latent heat flux (Bowen ratio) predicts seasonal patterns of photosynthesis. In equatorial Amazonian forests (5◦ N–5◦ S), water limitation is absent, and photosynthetic fluxes (or gross ecosystem productivity, GEP) exhibit high or increasing levels of photosynthetic activity as the dry season progresses, likely a consequence of allocation to growth of new leaves. In contrast, forests along the southern flank of the Amazon, pastures converted from forest, and mixed forest-grass savanna, exhibit dry-season declines in GEP, consistent with increasing degrees of water limitation. Although previous work showed tropical ecosystem evapotranspiration (ET) is driven by incoming radiation, GEP observations reported here surprisingly show no or negative relationships with photosynthetically active radiation (PAR). Instead, GEP fluxes largely followed the phenology of canopy photosynthetic capacity (Pc), with only deviations from this primary pattern driven by variations in PAR. Estimates of leaf flush at three

Dynamical aspects of atmospheric data assimilation in the tropics

A faithful depiction of the tropical atmosphere requires three-dimensional sets of observations. Despite the increasing amount of observations presently available, these will hardly ever encompass the entire atmosphere and, in addition, observations have errors. Additional (background) information will always be required to complete the picture. Valuable added information comes from the physical laws governing the flow, usually mediated via a numerical weather prediction (NWP) model. These models are, however, never going to be error-free, why a reliable estimate of their errors poses a real challenge since the whole truth will never be within our grasp. The present thesis addresses the question of improving the analysis procedures for NWP in the tropics. Improvements are sought by addressing the following issues: - the efficiency of the internal model adjustment, - the potential of the reliable background-error information, as compared to observations, - the impact of a new, space-borne line-of-sight wind measurements, and - the usefulness of multivariate relationships for data assimilation in the tropics. Most NWP assimilation schemes are effectively univariate near the equator. In this thesis, a multivariate formulation of the variational data assimilation in the tropics has been developed. The proposed background-error model supports the mass-wind coupling based on convectively-coupled equatorial waves. The resulting assimilation model produces balanced analysis increments and hereby increases the efficiency of all types of observations. Idealized adjustment and multivariate analysis experiments highlight the importance of direct wind measurements in the tropics. In particular, the presented results confirm the superiority of wind observations compared to mass data, in spite of the exact multivariate relationships available from the background information. The internal model adjustment is also more efficient for wind observations than for mass data. In accordance with these findings, new satellite wind observations are expected to contribute towards the improvement of NWP and climate modeling in the tropics. Although incomplete, the new wind-field information has the potential to reduce uncertainties in the tropical dynamical fields, if used together with the existing satellite mass-field measurements. The results obtained by applying the new background-error representation to the tropical short-range forecast errors of a state-of-art NWP model suggest that achieving useful tropical multivariate relationships may be feasible within an operational NWP environment.

Oxygen and Chlorophyll Distribution in the Eastern Atlantic Ocean from 0º to 35ºS.

Programa de doctorado en Oceanografía. Trabajo presentado para la obtención del Diploma de Estudios Avanzados.

Zooplankton, micronekton and biological pump: Beyond the mesopelagic zone

[EN] Migrant biota transports carbon to the mesopelagic zone due to their feeding at the shallower layers and their defecation, respiration, excretion and mortality at depth. The so-called active flux has been considered a small number compared to gravitational sinking. Recent assessments in subtropical waters show an important effect due to predation by interzonal diel vertical migrants (DVMs). The consumption and subsequent transport of epipelagic zooplankton by DVMs (mainly micronekton) to the mesopelagic zone seemed similar to the mean gravitational export. However, the consequences of this active transport to the bathypelagic zone are almost unknown. Here, we show the effect of the Atlantic and Pacific equatorial upwelling systems on the vertical distribution of acoustic backscatter from the surface to bathypelagic depths. The enhancement of the acoustic signal below the upwelling zone was observed to reach 4000 m depth, coinciding with high abundances and activity of bacteria at those depths. The results suggest an active carbon transport from the epipelagic driven by zooplankton and micronekton, enhancing the efficiency of the biological pump and giving an insight about the fate of an increased productivity at the shallower layers of the ocean

Meridional changes in water mass distributions off NW Africa during November 2007/2008

[EN] An optimum multiparameter analysis was applied to a data set for the eastern boundary of the North Atlantic subtropical gyre, gathered during November of two consecutive years and spanning from 16 to 36º N. This data set covers over 20º of latitude with good meridional and zonal resolution over the whole coastal transition zone. The contribution from six water types in the depth range between 100 and 2000 m is solved. In the 100 to 700 m depth range the central waters of southern and northern origin meet abruptly at the Cape Verde Frontal Zone. This front traditionally has been reported to stretch from Cape Blanc, at about 21.5º N, to the Cape Verde Islands, but in our case it penetrates as far as 24º N over the continental slope. South of 21º N latitude we actually find a less saline and more oxygenated variety of South Atlantic Central Water, which we ascribe to less diluted equatorial waters. In the 700 to 1500 m depth range the dominant water type is a diluted form of Antarctic Intermediate Water (AAIW), whose influence smoothly disappears north of the Canary Islands as it is replaced by Mediterranean Water (MW); at latitudes where both water masses coexist, we observe MW offshore while AAIW is found near-shore. North Atlantic Deep Water is the dominating water type below about 1300/1700 m depth south/north of the Canary Islands; this abrupt change in depth suggests the existence of different paths for the deep waters reaching both sides of the archipelago.