Materiais bionanocompósitos a base de argilominerais e hidróxidos duplos lamelares como sistemas de liberação de fármacos

Bionanocomposites systems clay base (montmorillonite and sepiolite), layered double hidroxides and biopolymers (carboxymethylcellulose and zein) were evaluated as topical delivery systems with antibacterial activity and as oral delivery systems. For this study, neomycin, a topical antibiotic, indicated mainly for open wound infections. The drug amoxicillin, an antibiotic indicated mainly for throat infections, were also used in this study. Both antibiotics were used as model drugs. Initially, drugs were incorporated directly into the biopolymer matrix, comprising the combination of carboxymethylcellulos and zein, being conformed as movies and balls and evaluated for their antibacterial activity and controlled release simulating gastrointestinal fluids. Moreover, hybrids materials have been prepared where the neomycin drug was incorporated into the lamellar inorganic solids, such as montmorillonite by ion exchange reaction, and the fibrous type, such as sepiolite by adsorption in aqueous solution. But the drug amoxicillin was incorporated into layered double hydroxides by anion exchange and montmorillonite by cation exchange. The resulting hybrids were in turn combined with the biopolymer matrix yielding bionanocomposites shaped materials such as films were tested for their antibacterial activity, and the shaped materials beads were tested for their release in the gastrointestinal fluids. Through the analysis of various physico-chemical techniques, we observed the interactions between the studied materials, the formation of hybrids materials, obtaining the bionanocomposites materials and material efficiency when applied in controlled release of drugs both topical and use oral mainly influenced by the presence of zein, are promising as topical delivery systems and oral drugs.

Alkenone and foraminifera records from sediment samples off Namibia

Radiocarbon stratigraphy is an essential tool for high resolution paleoceanographic studies. Age models based on radiocarbon ages of foraminifera are commonly applied to a wide range of geochemical studies, including the investigation of temporal leads and lags. The critical assumption is that temporal coupling between foraminifera and other sediment constituents, including specific molecular organic compounds (biomarkers) of marine phytoplankton, e.g. alkenones, is maintained in the sediments. To test this critical assumption in the Benguela upwelling area, we have determined radiocarbon ages of total C37-C39 alkenones in 20 samples from two gravity cores and three multicorer cores. The cores were retrieved from the continental shelf and slope off Namibia, and samples were taken from Holocene, deglacial and Last Glacial Maximum core sections. The alkenone radiocarbon ages were compared to those of planktic foraminifera, total organic carbon, fatty acids and fine grained carbonates from the same samples. Interestingly, the ages of alkenones were 1000 to 4500 yr older than those of foraminifera in all samples. Such age differences may be the result of different processes: Bioturbation associated with grain size effects, lateral advection of (recycled) material and redeposition of sediment on upper continental slopes due to currents or tidal movement are examples for such processes. Based on the results of this study, the age offsets between foraminifera and alkenones in sediments from the upper continental slope off Namibia most probably do not result from particle-selective bioturbation processes. Resuspension of organic particles in response to tidal movement of bottom waters with velocities up to 25 cm/s recorded near the core sites is the more likely explanation. Our results imply that age control established using radiocarbon measurements of foraminifera may be inadequate for the interpretation of alkenone-based proxy data. Observed temporal leads and lags between foraminifera based data and data derived from alkenone measurements may therefore be secondary signals, i.e. the result of processes associated with particle settling and biological activity.

Age determination of sediments off western Svalbard

Late Quaternary sediment yields from the Isfjorden drainage area (7327 km**2), a high arctic region on Svalbard characterized by an alpine landscape, have been reconstructed by using seismic stratigraphy supported by sediment core analysis. The sediments that accumulated in the fjord during and since deglaciation can be divided into three stratigraphic units. The volumes of these units were determined and converted into sediment yield rates averaged over the drainage basin. During deglaciation, 13 to 10 ka, the sediment yield was ~860 tons(t)/km**2/yr. In the early Holocene it decreased to 190 t/km**2/yr, and then increased to 390t/km**2/yr during the late Holocene Little Ice Age. When normalized to the approximate glacierized area, these rates correspond to a sediment yield of ~800 t/km**2/yr . Sediment yield from non-glacierized parts of the drainage is estimated to be 35 t/km**2/yr. At times when ice advanced to the shelf edge, sediment was scoured from the fjord and deposited on the outer shelf and in a well-defined deep sea fan. Between 200 ka and 13 ka, 328 km**3 of sediment accumulated here, corresponding to a mean sediment yield rate of 335 t/km**2/yr. This is broadly consistent with calculations based on the above rates of sediment yield in glacierized and non-glacierized areas, and on estimates, based on glacial geology, of the temporal variation in degree of glacierization over the past 200 kyr. These figures indicate that much of the glacigenic sediment on the shelf and slope was eroded from the uplands of Svalbard by small glaciers during interstadials and interglacials. The sediments were temporarily stored in the fjord prior to redeposition on the shelf and slope during ice sheet advance. Taken into consideration, such redisposition of pre-eroded material will reduce estimates of primary ice sheet erosion rate.

O uso da Divergência de Kullback-Leibler e da Divergência Generalizada como medida de similaridade em sistemas CBIR

The content-based image retrieval is important for various purposes like disease diagnoses from computerized tomography, for example. The relevance, social and economic of image retrieval systems has created the necessity of its improvement. Within this context, the content-based image retrieval systems are composed of two stages, the feature extraction and similarity measurement. The stage of similarity is still a challenge due to the wide variety of similarity measurement functions, which can be combined with the different techniques present in the recovery process and return results that aren’t always the most satisfactory. The most common functions used to measure the similarity are the Euclidean and Cosine, but some researchers have noted some limitations in these functions conventional proximity, in the step of search by similarity. For that reason, the Bregman divergences (Kullback Leibler and I-Generalized) have attracted the attention of researchers, due to its flexibility in the similarity analysis. Thus, the aim of this research was to conduct a comparative study over the use of Bregman divergences in relation the Euclidean and Cosine functions, in the step similarity of content-based image retrieval, checking the advantages and disadvantages of each function. For this, it was created a content-based image retrieval system in two stages: offline and online, using approaches BSM, FISM, BoVW and BoVW-SPM. With this system was created three groups of experiments using databases: Caltech101, Oxford and UK-bench. The performance of content-based image retrieval system using the different functions of similarity was tested through of evaluation measures: Mean Average Precision, normalized Discounted Cumulative Gain, precision at k, precision x recall. Finally, this study shows that the use of Bregman divergences (Kullback Leibler and Generalized) obtains better results than the Euclidean and Cosine measures with significant gains for content-based image retrieval.

Late Quaternary deep sea sedimentation off the Niger delta

The oxygen isotopes ratios of benthic foraminifera and detailed radiocarbon ages of the organic matter of an over 15 m long sediment core from the outer Niger delta allow us to date the oxygen isotope stage boundaries 1/2 to 11500 (+/- 650) years BP, 2/3 to approximately 23000 (+/- 2000) years BP. The composition of the predominantly terrigenous clays and accessory pelagic fossils reflects the evolution of the climate over the southwestern Sahel zone and the response of the Eastern Tropical Atlantic to these climatic fluctuations during the Late Quaternary. The dilution of the pelagic fossil concentrations by the terrigenous material and the oxygen isotopes ratios of planktonic foraminifera indicate large fluctuations in the freshwater discharge from the Niger, with high precipitations over the drainage area of this river from 4500 (+/- 300) to 11500 (+/- 650) years BP and from 11800 (+(- 600) to 13000 (+/- 600) years BP while the time intervals in between were as dry as today. Relative increase of kaolinite during wet phases and the association of smectite, chlorite and attapulgite during dry ones characterize the response of the weathering in the Niger drainage basins to the climatic fluctuations. The occurrence of 10-14 A mixed-layers prior to 26000 years BP is correlated with moderate alteration of the crystalline substratum outcrops from the middle-lower part of the Niger Basin. High quartz concentrations are particularly typical for the transition between oxygen isotope stages 1 and 2 at the inception of heavy precipitations in the southern Sahel zone. Sedimentation rates were quite constant, 30-35 cm/1000 years; they became unusually large at the beginning of the Holocene from 10900 (+/- 650) to 11500 (+/- 650) years BP where they reached more than 600 cm/1000 years. Bottom waters around 1100 m depth in the Gulf of Guinea responded to changes in paleo-oceanography of the entire Atlantic Ocean as well as to local influences. Abnormal carbon isotopes ratios and the drastic changes from a highly diversified fauna (during stages 2 and 3. and during the last part of stage 1 after approx. 7000 years BP) to a poorly diversified fauna in the intervenin time span point to the development of a local benthic environment which cannot easily be compared with the corresponding continental and slope environments of the entire Atlantic Ocean.

(Table 1) Temperature and foraminiferal Mg/Ca ratios of samples off Japan

We studied Mg/Ca in high-Mg, shallow-water benthic foraminifera in culture and in samples from natural environments, in order to evaluate the expression of latitudinal and seasonal temperature variability in Mg/Ca in their tests. We cultured Planoglabratella opercularis (d'Orbigny) and Quinqueloculina yabei Asano under controlled temperature (10°-25°C) and salinity (30-38) conditions. Both species show a linear correlation between Mg/Ca and temperature, but they differ in temperature sensitivity. Salinity does not significantly influence Mg/Ca. In the samples collected in nature, Mg/Ca and seawater temperatures are positively correlated, but there are more complexities than in the records for cultured specimens due to such factors as seasonal fluctuations in temperature. We conclude that Mg/Ca ratios in monospecific benthic foraminiferal samples may be used as a reliable temperature proxy, if the lifetime of the species is taken into account.

Relative abundance of anaerobic methanotrophic archaea in bacterial mat Cascadia margin off Oregon

The microbially mediated anaerobic oxidation of methane (AOM) is the major biological sink of the greenhouse gas methane in marine sediments (doi:10.1007/978-94-009-0213-8_44) and serves as an important control for emission of methane into the hydrosphere. The AOM metabolic process is assumed to be a reversal of methanogenesis coupled to the reduction of sulfate to sulfide involving methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB) as syntrophic partners which were describes amongst others in Boetius et al. (2000; doi:10.1038/35036572). In this study, 16S rRNA-based methods were used to investigate the distribution and biomass of archaea in samples from sediments above outcropping methane hydrate at Hydrate Ridge (Cascadia margin off Oregon) and (ii) massive microbial mats enclosing carbonate reefs (Crimea area, Black Sea). Sediment samples from Hydrate Ridge were obtained during R/V SONNE cruises SO143-2 in August 1999 and SO148-1 in August 2000 at the crest of southern Hydrate Ridge at the Cascadia convergent margin off the coast of Oregon. The second study area is located in the Black Sea and represents a field in which there is active seepage of free gas on the slope of the northwestern Crimea area. Here, a field of conspicuous microbial reefs forming chimney-like structures was discovered at a water depth of 230 m in anoxic waters. The microbial mats were sampled by using the manned submersible JAGO during the R/V Prof. LOGACHEV cruise in July 2001. At Hydrate Ridge the surface sediments were dominated by aggregates consisting of ANME-2 and members of the Desulfosarcina-Desulfococcus branch (DSS) (ANME-2/DSS aggregates), which accounted for >90% of the total cell biomass. The numbers of ANME-1 cells increased strongly with depth; these cells accounted 1% of all single cells at the surface and more than 30% of all single cells (5% of the total cells) in 7- to 10-cm sediment horizons that were directly above layers of gas hydrate. In the Black Sea microbial mats ANME-1 accounted for about 50% of all cells. ANME-2/DSS aggregates occurred in microenvironments within the mat but accounted for only 1% of the total cells. FISH probes for the ANME-2a and ANME-2c subclusters were designed based on a comparative 16S rRNA analysis. In Hydrate Ridge sediments ANME-2a/DSS and ANME-2c/DSS aggregates differed significantly in morphology and abundance. The relative abundance values for these subgroups were remarkably different at Beggiatoa sites (80% ANME-2a, 20% ANME-2c) and Calyptogena sites (20% ANME-2a, 80% ANME-2c), indicating that there was preferential selection of the groups in the two habitats.

Microbialites and lipid biomarker from coral reefs off the volcanic islands Tahiti and Vanuatu and from the nonvolcanic sites Belize and the Maldives

The occurrence of microbialites in post-glacial coral reefs has been interpreted to reflect an ecosystem response to environmental change. The greater thickness of microbialites in reefs with a volcanic hinterland compared to thinner microbial crusts in reefs with a non-volcanic hinterland led to the suggestion that fertilization of the reefal environment by chemical weathering of volcanic rocks stimulated primary productivity and microbialite formation. Using a molecular and isotopic approach on reef-microbialites from Tahiti (Pacific Ocean), it was recently shown that sulfate-reducing bacteria favored the formation of microbial carbonates. To test if similar mechanisms induced microbialite formation in other reefs as well, the Tahitian microbialites are compared with similar microbialites from coral reefs off Vanuatu (Pacific Ocean), Belize (Caribbean Sea, Atlantic Ocean), and the Maldives (Indian Ocean) in this study. The selected study sites cover a wide range of geological settings, reflecting variable input and composition of detritus. The new lipid biomarker data and stable sulfur isotope results confirm that sulfate-reducing bacteria played an intrinsic role in the precipitation of microbial carbonate at all study sites, irrespective of the geological setting. Abundant biomarkers indicative of sulfate reducers include a variety of terminally-branched and mid chain-branched fatty acids as well as mono-O-alkyl glycerol ethers. Isotope evidence for bacterial sulfate reduction is represented by low d34S values of pyrite (-43 to -42 per mill) enclosed in the microbialites and, compared to seawater sulfate, slightly elevated d34S and d18O values of carbonate-associated sulfate (21.9 to 22.2 per mill and 11.3 to 12.4 per mill, respectively). Microbialite formation took place in anoxic micro-environments, which presumably developed through the fertilization of the reef environment and the resultant accumulation of organic matter including bacterial extracellular polymeric substances (EPS), coral mucus, and marine snow in cavities within the coral framework. ToF-SIMS analysis reveals that the dark layers of laminated microbialites are enriched in carbohydrates, which are common constituents of EPS and coral mucus. These results support the hypothesis that bacterial degradation of EPS and coral mucus within microbial mats favored carbonate precipitation. Because reefal microbialites formed by similar processes in very different geological settings, this comparative study suggests that a volcanic hinterland is not required for microbialite growth. Yet, detrital input derived from the weathering of volcanic rocks appears to be a natural fertilizer, being conductive for the growth of microbial mats, which fosters the development of particularly abundant and thick microbial crusts.

Siliceous phytoplankton fluxes off northwest Africa

Four years of observations (1988-1991) of downward fluxes of diatoms and silicoflagellates at a trap site off Cape Blanc (ca. 20°N, 20°W), northwest Africa, are presented. Significant variations in flux and species composition were observed as well as a marked drop in the export of biogenic opal (and diatoms) from 1988 to 1989; fluxes remained low thereafter. We hypothesize that this diminution might be related to decreased coastal upwelling intensity and offshore spreading of the typical chlorophyll filament, and/or a lesser silicate content of upwelling waters off Cape Blanc. In addition, the more seaward positioning of the mooring may have influenced the fluxes. At all times, diatoms were the most prominent contributors to the biogenic opal flux, and diatom fluxes closely paralleled total mass flux fluctuations. Although species composition varied seasonally, no significant qualitative variations were observed from year to year. In general, the dominance of neritic diatoms, such as Thalassionema nitzschioides var. nitzschioides, resting spores of Chaetoceros and Cyclotella litoralis, reflected the continuous offshore influence of coastal upwelling at the Cape Blanc trap site, with stronger intensity in spring/summer. In contrast, the occurrence of pelagic diatoms (e.g. Nitzschia bicapitata, N. interruptestriata, T. nitzschioides var. parva and Fragilariopsis doliolus), and high silicoflagellate fluxes (mainly Dictyocha messanensis) were linked to inshore transport of oceanic waters, generally in winter. With the exception of some fragile, pelagic diatoms, dominant species found in the settled material also occurred in the underlying sediments, suggesting that diatom thanatocoenosis downcore (Organisms preserved from the top to the bottom in sediment core) can be used as a reliable indicator of the intensity and persistence of the offshore spreading of coastal upwelling.

Bulk 15N, and 13Corg ratios, and calculation of unutilized nitrate of surface samples off the southwest coast of Africa (Table 1)

Bulk delta15N values in surface sediment samples off the southwestern coast of Africa were measured to investigate the biogeochemical processes occurring in the water column. Nitrate concentrations and the degree of utilization of the nitrate pool are the predominant controls on sedimentary delta15N in the Benguela Current region. Denitrification does not appear to have had an important effect on the delta15N signal of these sediments and, based on delta15N and delta13C, there is little terrestrial input.

(Table 1, Page 94) Elemental abundances in ferromanganese nodules and crusts from the Pernambuco Plateau and guyots off northeast Brazil

Ferromanganese deposits, mostly manganese crusts, are common in elevations along the northeastern Brazilian continental margin. Association of the deposits with more or less altered basaltic rock can be observed. On the Pernambuco Plateau and Ceara Guyot, ferromanganese deposits occur associated with phosphatic material and nodules. The mineralogical composition of the ferromanganese deposits indicates a predominance of the manganese oxide phase dMnO2. Low contents of Mn and Cu are characteristic of their chemical composition. Fe and Mn in the deposits probably precipitated from the sea water.

(Table 1) Water column silicic acid concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Silicon isotopic signatures (d30Si) of water column silicic acid (Si(OH)4) were measured in the Southern Ocean, along a meridional transect from South Africa (Subtropical Zone) down to 57° S (northern Weddell Gyre). This provides the first reported data of a summer transect across the whole Antarctic Circumpolar Current (ACC). d30Si variations are large in the upper 1000 m, reflecting the effect of the silica pump superimposed upon meridional water transfer across the ACC: the transport of Antarctic surface waters northward by a net Ekman drift and their convergence and mixing with warmer upper-ocean Si-depleted waters to the north. Using Si isotopic signatures, we determine different mixing interfaces: the Antarctic Surface Water (AASW), the Antarctic Intermediate Water (AAIW), and thermoclines in the low latitude areas. The residual silicic acid concentrations of end-members control the d30Si alteration of the mixing products and with the exception of AASW, all mixing interfaces have a highly Si-depleted mixed layer end-member. These processes deplete the silicic acid AASW concentration northward, across the different interfaces, without significantly changing the AASW d30Si composition. By comparing our new results with a previous study in the Australian sector we show that during the circumpolar transport of the ACC eastward, the d30Si composition of the silicic acid pools is getting slightly, but significantly lighter from the Atlantic to the Australian sectors. This results either from the dissolution of biogenic silica in the deeper layers and/or from an isopycnal mixing with the deep water masses in the different oceanic basins: North Atlantic Deep Water in the Atlantic, and Indian Ocean deep water in the Indo-Australian sector. This isotopic trend is further transmitted to the subsurface waters, representing mixing interfaces between the surface and deeper layers. Through the use of d30Si constraints, net biogenic silica production (representative of annual export), at the Greenwich Meridian is estimated to be 5.2 ± 1.3 and 1.1 ± 0.3 mol Si/m**2 for the Antarctic Zone and Polar Front Zone, respectively. This is in good agreement with previous estimations. Furthermore, summertime Si-supply into the mixed layer of both zones, via vertical mixing, is estimated to be 1.6 ± 0.4 and 0.1 ± 0.5 mol Si/m**2, respectively.

Grain-size analysis of surface sediments, continental margin off NW Africa

The terrigenous fraction of seabed sediments recovered along the north-west African continental margin illustrates spatial variability in grain size attributed to different transport mechanisms. Three subpopulations are determined from the grain-size analyses (n = 78) of the carbonate-free silt fraction applying an end-member modelling algorithm (G. J. Weltje, 1997). The two coarsest end-members are interpreted as representing aeolian dust, and the fine-grained end-member is related to fluvial supply. The end-member model thus allows aeolian fallout to be distinguished from fluvial-sourced mud in this area. The relative contributions of the end-members show distinct regional variations that can be related to different transport processes and pathways. Understanding present-day sediment dispersal and mixing is important for a better understanding of older sedimentary records and palaeoclimate reconstructions in the region.