Interaction of cationic water-soluble meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) with ionic and nonionic micelles: aggregation and binding

The equilibrium of meso-tetrakis(4-N-methylpyridiniumyl)porphyrin (TMPyP) in aqueous solution in the presence of surfactants was studied by optical spectroscopic techniques and SAXS (small angle X-ray scattering). Anionic SDS (sodium dodecyl sulfate), zwitterionic HPS (N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate) and nonionic TRITON X-100 (t-octyl-phenoxypolyethoxyethanol), surfactants were used. TMPyP is characterized by a protonation equilibrium with a pK(a) around 1.0, associated with the diacid-free base transition, and a second pK(a) around 12.0 related with the transition between the free base and the monoanion form. Three independent species were observed for TMPyP at pH 6.0 as a function of SDS concentration: free TMPyP, TMPyP-SDS aggregates and porphyrin monomer bound to micelles. For HPS and TRITON X-100, the equilibrium of TMPyP as a function of pH is quite similar to that obtained in pure aqueous solution: no aggregation was observed, suggesting that electrostatic contribution is the major factor in the interaction between TMPyP and surfactants. SAXS data analysis demonstrated a prolate ellipsoidal shape for SDS micelles; no significant changes in shape and size were observed for SDS-TMPyP co-micelles. Moreover, the ionization coefficient, alpha, decreases with the increase of the porphyrin concentration, suggesting the ""screening"" of the anionic charge of SDS by the cationic porphyrin. These results are consistent with optical absorption, fluorescence and RLS (resonance light scattering) spectroscopies data, allowing to conclude that neutral surfactants present a smaller interaction with the cationic porphyrin as compared with an ionic surfactant. Therefore, the interaction of TMPyP with the ionic and nonionic surfactants is predominantly due to the electrostatic contribution. Copyright (c) 2008 Society of Porphyrins & Phthalocyanines.

Benthic foraminiferal assemblages of the South Brazil: Relationship to water masses and nutrient distributions

Using distributions of benthic Foraminifera and bottom-water variables (depth, salinity, temperature, oxygen, suspended matter, organic matter, phosphate, silicate, nitrite, and nitrate), we investigated movements of water masses on the South Brazilian Shelf (27-30 degrees S) and assessed the seasonality of continental runoff on the distribution of shelf water masses. The data were obtained from water and sediment samples collected in the austral winter of 2003 and austral summer of 2004 in three transects. The terrestrial nutrient input was significantly reduced at stations away from the coast, but high values of nutrients were maintained in subsurface waters due the presence of South Atlantic Central Water (SACW) at greater depths. At shallow sampling stations the influence of freshwater runoff was related to (1) the dominance of calcareous benthic Foraminifera, such as lagoon-related Pseudononion atlanticum, Hanzawaia boueana, Bulimina marginata, Bolivina striatula, Elphidium poeyanum, together with several agglutinated species, including Arenoparrella mexicana, Gaudryina exilis, and Trochammina spp., common in coastal environments subject to wide salinity fluctuations. In contrast, smaller forms and higher species diversity characterized the assemblage at offshore stations. In winter, the presence of Buccella peruviana and Uvigerina peregrina at Santa Marta Cape suggest the possible transport of those species of Subantarctic Shelf Waters (SASW) origin. Foraminifera associated to Subtropical Shelf Water (STSW) were dominated by Globocassidulina subglobosa in both seasons. In summer, the occurrence of U. peregrina in the shallower stations suggested the influence of SACW nutrients brought up by upwelling of deeper waters. (C) 2008 Elsevier Ltd. All rights reserved.

A note on a mineralogical analysis of the sediments associated with the Plata River and Patos Lagoon outflows

Riverine waters bring to seas a variety of suspended materials, which are ultimately deposited on the shelf or exported to the deep ocean. Investigation of the mineralogical contents of these continental-borne constituents on seafloors may reveal valuable information about the environmental conditions in the drainage basin. In this note we report results of X-ray diffraction and other analysis of sediments in bottom samples collected on the continental shelf under influence of the Plata River and the Patos Lagoon, in South America. The analysis reveals that non-clay materials are mostly concentrated south of 33 degrees S, while clay sediments are relatively more abundant further north. We propose that such distributions are controlled by the circulation pattern and water mass distribution of the lower and upper layers, respectively. (C) 2008 Elsevier Ltd. All rights reserved.

Nutrients removed by Kappaphycus alvarezii (Rhodophyta, Solieriaceae) in integrated cultivation with fishes in re-circulating water

The potential of the red alga Kappaphycus alvarezii to remove nutrients was tested to treat effluents of Trachinotus carolinus fish cultivation, and the production of carrageenan in this condition was analyzed. Experiments were conducted in four tanks of 8000 L with approximately 1200 fishes of 30 g each integrated with three tanks of 100 L with 700 g of K. alvarezii, as initial biomass per tank. Seawater was re-circulated between tanks with seaweed and with fish. As a control, three tanks with seawater circulating in an open system were utilized. Seawater samples were collected daily for 10 days and concentrations of nitrate, nitrite, ammonium and phosphate were determined in the inflow and outflow water of the tanks. Significant differences between both collecting points were considered as nutrient removal by the seaweed. Growth rates and carrageenan yields were also analyzed in seaweed cultivated in seawater and in effluents. Growth rates of seaweed cultivated in tanks were lower than those obtained in open sea and in laboratory cultivation. Effluents had concentrations of nitrate and nitrite ca. 100 times higher than in the control. Maximum values of nutrient removal on effluents were: nitrate= 18.2%; nitrite =50.8%; ammonium =70.5% and phosphate =26.8%. All plants survived throughout the experimental period, but some developed ""ice-ice"", a disease associated with physiological stress. After the experimental period, some plants selected and cultivated in open sea presented higher growth rates in 40 days, indicating nutrient storage. No significant differences between carrageenan yields of K alvarezii cultivated in seawater and in the effluents were observed. Our results show that K. alvarezii can be utilized as a biofilter for fish cultivation effluents, reducing the eutrophication process and can also be processed for carrageenan production, which provides an additional benefit to the fisheries. (C) 2008 Elsevier B.V. All rights reserved.

Burrow ventilation and associated porewater irrigation by the polychaete Marenzelleria viridis

Burrow ventilation of benthic infauna generates water currents that irrigate the interstices of the sediments surrounding the burrow walls. Such activities have associated effects on biogeochemical processes affecting ultimately important ecosystem processes. In this study, the ventilation and irrigation behavior of Marenzelleria viridis, an invasive polychaete species in Europe, was analyzed using different approaches. M. viridis showed to perform two types of ventilation: (1) muscular pumping of water out of the burrow and (2) cilia pumping of water into the burrow. Flowmeter measurements presented muscular pumping in time averaged rates of 0.15 ml min(-1). Oxygen needle electrodes positioned above the burrow openings revealed that muscular undulation of the worm body pumps anoxic water out of the burrow. On the other hand, microscope observations of the animal showed that ventilation of oxygen-rich water in the burrow occurs by ciliary action. The volume of water irrigated by M. viridis appears to vary linearly within the first 24 h incubation, with rates ranging from 0.003 to 0.01 ml min(-1). From those rates we could estimate that the time averaged rate of cilia ventilation should be about 0.16 ml min(-1). Since the cilia pumping into the burrow occurs in periods of 24 +/- 12 min and at 50-70% of the measured time, considerable amounts of water from deeper sediments may percolate upwards to the sediment surface. This water is rich in reduced compounds and nutrients and may have important associated ecological implications in the ecosystem (e.g. affecting redox conditions, organic matter degradation, benthic recruitment and primary production). (C) 2010 Elsevier B.V. All rights reserved.

Effects of irrigation on water use and water use efficiency in two fast growing Eucalyptus plantations

Eucalyptus plantations occupy almost 20 million ha worldwide and exceed 3.7 million ha in Brazil alone. Improved genetics and silviculture have led to as much as a three-fold increase in productivity in Eucalyptus plantations in Brazil and the large land area occupied by these highly productive ecosystems raises concern over their effect on local water supplies. As part of the Brazil Potential Productivity Project, we measured water use of Eucalyptus grandis x urophylla clones in rainfed and irrigated stands in two plantations differing in productivity. The Aracruz (lower productivity) site is located in the state of Espirito Santo and the Veracel (higher productivity) site in Bahia state. At each plantation, we measured stand water use using homemade sap flow sensors and a calibration curve using the clones and probes we utilized in the study. We also quantified changes in growth, leaf area and water use efficiency (the amount of wood produced per unit of water transpired). Measurements were conducted for 1 year during 2005 at Aracruz and from August through December 2005 at Veracel. Transpiration at both sites was high compared to other studies but annual estimates at Aracruz for the rainfed treatment compared well with a process model calibrated for the Aracruz site (within 10%). Annual water use at Aracruz was 1394 mm in rainfed treatments versus 1779 mm in irrigated treatments and accounted for approximately 67% and 58% of annual precipitation and irrigation inputs respectively. Increased water use in the irrigated stands at Aracruz was associated with higher sapwood area, leaf area index and transpiration per unit leaf area but there was no difference in the response of canopy conductance with air saturation deficit between treatments. Water use efficiency at the Aracruz site was also not influenced by irrigation and was similar to the rainfed treatment. During the period of overlapping measurements, the response to irrigation treatments at the more productive Veracel site was similar to Aracruz. Stand water use at the Veracel site totaled 975 mm and 1102 mm in rainfed and irrigated treatments during the 5-month measurement period respectively. Irrigated stands at Veracel also had higher leaf area with no difference in the response of canopy conductance with air saturation deficit between treatments. Water use efficiency was also unaffected by irrigation at Veracel. Results from this and other studies suggest that improved resource availability does not negatively impact water use efficiency but increased productivity of these plantations is associated with higher water use and should be given consideration during plantation management decision making processes aimed at increasing productivity. Published by Elsevier B.V.

In Situ Effect of Dentifrices Associated to CO2 Laser in the Permeability of Eroded Root Dentin

Objective: The aim of this study was to evaluate, through a crossover 2 x 2 in situ trial, the effect of a desensitizing dentifrice associated with CO2 laser irradiation to control the permeability of eroded root dentin. Background data: Facing the increased prevalence of erosive lesion and the need for preventive means to control painful symptoms related to them. Methods: Eighty slabs of bovine root dentin were subjected to initial erosive challenge (citric acid 0.3%, 2 h), followed by a remineralizing period in artificial saliva (24 h). Specimens were then divided according to dentin treatment: desensitizing dentifrice, desensitizing dentifrice + CO2 laser, fluoride anticavity dentifrice. and fluoride anticavity dentifrice + CO2 laser. After a 2-day lead-in period, 10 volunteers wore an intraoral palatal appliance containing four root dentin slabs, in two phases of 5 days each. During the intraoral phase, one side of the appliance was immersed in 0.3% citric acid, and the opposite side was immersed in deionized water, four times a day. One hour after the immersions, all specimens were brushed with dentifrice slurry provided by the researcher. After a 7-day washout period, volunteers were crossed over on the different dentifrice group. Each phase having been completed, the specimens were evaluated for permeability through an optical microscope. Results: Data were analyzed using ANOVA and no significant difference (p = 0.272) was found between the surface treatments performed on bovine root dentin. Conclusions: It can be concluded that fluoride anticavity or desensitizing dentifrice, regardless of the association with the CO2 laser irradiation, was able to control the permeability of eroded root dentin.

Factors controlling water-column respiration in rivers of the central and southwestern Amazon Basin

We examined the factors controlling the variability in water-column respiration rates in Amazonian rivers. Our objectives were to determine the relationship between respiration rates and the in situ concentrations of the size classes of organic carbon (OC), and the biological source (C-3 and C-4 plants and phytoplankton) of organic matter (OM) supporting respiration. Respiration was measured along with OC size fractions and dissolved oxygen isotopes (delta O-18-O-2) in rivers of the central and southwestern Amazon Basin. Rates ranged from 0.034 mu mol O-2 L-1 h(-1) to 1.78 mu mol O-2 L-1 h(-1), and were four-fold higher in rivers with evidence of photosynthetic production (demonstrated by delta O-18-O-2<24.2 parts per thousand) as compared to rivers lacking such evidence (delta O-18-O-2>24.2 parts per thousand; 1.35 +/- 0.22 vs. 0.30 +/- 0.29 mu mol L-1 h(-1)). Rates were likely elevated in the former rivers, which were all sampled during low water, due to the stimulation of heterotrophic respiration via the supply of a labile, algal-derived substrate and/or the occurrence of autotrophic respiration. The organic composition of fine particulate OM (FPOM) of these rivers is consistent with a phytoplankton origin. Multiple linear regression analysis indicates that [FPOC], C:N-FPOC ratios, and [O-2] account for a high amount of the variability in respiration rates (r(2) = 0.80). Accordingly, FPOC derived from algal sources is associated with elevated respiration rates. The delta C-13 of respiration-derived CO2 indicates that the role of phytoplankton, C-3 plants, and C-4 grasses in supporting respiration is temporally and spatially variable. Future scaling work is needed to evaluate the significance of phytoplankton production to basin-wide carbon cycling.

Water use in a sugarcane plantation

The evapotranspiration (E) from a sugarcane plantation in the southeast Brazil was measured by the eddy-covariance method during two consecutive cycles. These represented the second (393 similar to days) and third year (374 similar to days) re-growth (ratoon). The total E in the first cycle was 829 similar to mm, accounting for 69% of rainfall, whereas in the second cycle, it was 690 similar to mm, despite the total rainfall (1353 similar to mm) being 13% greater. The ratio of E to available energy, the evaporative fraction, exhibited a smaller variation between the first and second cycles: 0.58 and 0.51, respectively. The estimated interception losses were 88 and 90 similar to mm, respectively, accounting for approximately 7% of the total rainfall. The sugarcane yield in the second cycle (61.5 similar to +/-similar to 4.0 similar to t similar to ha-1) was 26% lower than the first cycle, as well as lower than the regional average for the third ratoon (76 similar to t similar to ha-1). The below average yield was associated with less available soil water at the beginning of the cycle, with the amount of rainfall recorded during the first 120 similar to days of re-growth in the second cycle being 16% of that recorded in the first (203 similar to mm).

Interannual variation in commercial oyster (Crassostrea gigas) farming in the sea (Florianopolis, Brazil, 27 degrees 44 ' S; 48 degrees 33 ' W) in relation to temperature, chlorophyll a and associated oceanographic conditions

Aquaculture of filter-feeding bivalve mollusks involves the fruitful conversion of marine particulate organic matter into premium protein of high nutritive value. Culture performance of bivalves is largely dependent on hydrological conditions and directly affected by e. g. temperature and chlorophyll levels. Accordingly, these parameters may be related with seasonality but also with oceanographic features combined with climate events. Yields of Pacific cupped oyster (Crassostrea gigas) reared at commercial procedures in suspended structures (long-lines) in a sheltered bay in Southern Brazil (Santa Catarina State, 27S 43'; 48 W 30') were evaluated in relation to local environmental conditions: sea surface temperature, chlorophyll a concentration, and associate effects of cold fronts events and El Nino and La Nina periods. Outputs from four consecutive commercial crop years were analyzed (2005/06, 2006/07, 2007/08, 2008/09) in terms of oyster survival and development time during the following grow-out phases of the culture cycle: seed to juvenile, juvenile to adult, adult to marketable. Since culture management and genetics were standardized significant differences verified among crop performance could be mostly related to environmental effects. Time series of temperature and chlorophyll a (remote sensing data) from crop periods displayed significant seasonal and interannual variation. As expected, performance during initial grow-out stages (seed to juvenile) was critical for final crop yield. Temperature was the main factor affecting survival in these initial stages with a trend of negative correlation, though not statistically significant. On the other hand, oyster development rate was significantly and positively affected by chlorophyll a concentration. Chlorophyll a values could be increased by upwelled cold nutrient-rich South Atlantic Central Water (SACW, related to predominant Northern winds) though further dependent on occurrence of Southern winds (cold fronts) to assist seawater penetration into the sheltered farming area. Lower salinity nutrient-rich northward drifted waters from La Plata River discharge may also result in chlorophyll a rise in the farming area. The El Nino period (July 2006 to February 2007) coincided with lower chlorophyll a levels in the farming site that may be related to both decreased number of cold fronts as well as predominance of Northern winds that retain northward spreading of La Plata River discharge waters. In contrast, the La Nina period (August 2007 to June 2008) corresponded to higher chlorophyll a values in the farming area by both upwelling of SACW and penetration of La Plata River discharge water assisted by increased occurrence of Southern winds and cold fronts. The recognition of the potentially changing climate and effects upon the environment will be an important step in planning future development of bivalve aquaculture.

Mosquito (Diptera: Culicidae) assemblages associated with Nidularium and Vriesea bromeliads in Serra do Mar, Atlantic Forest, Brazil

Background: The most substantial and best preserved area of Atlantic Forest is within the biogeographical sub-region of Serra do Mar. The topographic complexity of the region creates a diverse array of microclimates, which can affect species distribution and diversity inside the forest. Given that Atlantic Forest includes highly heterogeneous environments, a diverse and medically important Culicidae assemblage, and possible species co-occurrence, we evaluated mosquito assemblages from bromeliad phytotelmata in Serra do Mar (southeastern Brazil). Methods: Larvae and pupae were collected monthly from Nidularium and Vriesea bromeliads between July 2008 and June 2009. Collection sites were divided into landscape categories (lowland, hillslope and hilltop) based on elevation and slope. Correlations between bromeliad mosquito assemblage and environmental variables were assessed using multivariate redundancy analysis. Differences in species diversity between bromeliads within each category of elevation were explored using the Renyi diversity index. Univariate binary logistic regression analyses were used to assess species co-occurrence. Results: A total of 2,024 mosquitoes belonging to 22 species were collected. Landscape categories (pseudo-F value = 1.89, p = 0.04), bromeliad water volume (pseudo-F = 2.99, p = 0.03) and bromeliad fullness (Pseudo-F = 4.47, p < 0.01) influenced mosquito assemblage structure. Renyi diversity index show that lowland possesses the highest diversity indices. The presence of An. homunculus was associated with Cx. ocellatus and the presence of An. cruzii was associated with Cx. neglectus, Cx. inimitabilis fuscatus and Cx. worontzowi. Anopheles cruzii and An. homunculus were taken from the same bromeliad, however, the co-occurrence between those two species was not statistically significant. Conclusions: One of the main findings of our study was that differences in species among mosquito assemblages were influenced by landscape characteristics. The bromeliad factor that influenced mosquito abundance and assemblage structure was fullness. The findings of the current study raise important questions about the role of An. homunculus in the transmission of Plasmodium in Serra do Mar, southeastern Atlantic Forest.

Enhancing spiral-wound ultrafiltration performance for direct drinking water treatment through operational procedures improvement: A feasible option for the Sao Paulo Metropolitan Region

This work aimed to evaluate the influence of specific operational conditions on the performance of a spiral-wound ultrafiltration pilot plant for direct drinking water treatment, installed at the Guarapiranga's reservoir, in the Sao Paulo Metropolitan Region. Results from operational tests showed that the volume of permeate produced in the combination of periodic relaxation with flushing and chlorine dosage procedures was 49% higher than the volume obtained when these procedures were not used. Two years of continuous operation demonstrated that the ultrafiltration pilot plant performed better during fall and winter seasons, higher permeate flow production and reduced chemical cleanings frequency. Observed behavior seems to be associated with the algae bloom events in the reservoir, which are more frequent during spring and summer seasons, confirmed by chlorophyll-a analysis results. Concentrate clarification using ferric chloride was quite effective in removing NOM and turbidity, allowing its recirculation to the ultrafiltration feed tank. This procedure made it possible to reach almost 99% water recovery considering a single 54-hour recirculation cycle. Water quality monitoring demonstrated that the ultrafiltration pilot plant was quite efficient, and that potential pathogenic organisms, Escherichia coil and total coliforms, turbidity and apparent color removals were 100%, 95.1%, and 91.5%, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Study of La2-xCaxCuO4 perovskites for the low temperature water gas shift reaction

The effects of small fractions of calcium (x = 0, 0.05, 0.1, 0.15, and 0.20) on the structure and the catalytic properties of La2-xCaxCuO4 peroviskites have been investigated. The samples have been synthesized using the co-precipitation method. Perovskite-type oxides were characterized by XRD, TPR, XPS, XANES, SEM, and TEM. Catalytic tests for the water gas shift reaction (WGSR) were carried out in a tubular reactor at 290 degrees C. All samples showed a well-defined perovskite structure with surface areas between 6 and 18 m(2) g(-1). The partial substitution of La by Ca enhanced the stability of the perovskites and increased their reduction temperature. All catalysts were actives for WGSR, and the best catalytic performance was obtained for the La1.85Ca0.15CuO4 catalyst, but the samples with 5 and 10% of Ca had the best TOF values for reaction. These results can be associated to promoter effect of calcium, the high surface area, and the reducible species Cu-0 and Cu1+. (C) 2011 Elsevier B.V. All rights reserved.