Angular dependence of the thermal-lens effect on LiSrAlF(6) and LiSrGaF(6) single crystals

We apply thermal-lens (TL) spectrometry to measure the angular dependence of the TL effect on colquiriite single crystals. The experiments were performed with LiSrAlF(6) and LiSrGaF(6) using a two-beam mode-mismatched configuration. The results show that it is possible to minimize the TL effect by selecting the appropriate crystal orientation. Our data also show that the anisotropy of the linear thermal expansion coefficient drives the amplitude of the TL effect, including the inversion from focusing to defocusing as the crystal orientation angle tends to the c-axis direction. The results may be useful for those working to develop a high-power laser using LiSrAlF(6)(:Cr) and LiSrGaF(6)(:Cr) single crystals, allowing for optimization of the designed laser cavity. (C) 2008 Optical Society of America.

Feature selection environment for genomic applications

Background: Feature selection is a pattern recognition approach to choose important variables according to some criteria in order to distinguish or explain certain phenomena (i.e., for dimensionality reduction). There are many genomic and proteomic applications that rely on feature selection to answer questions such as selecting signature genes which are informative about some biological state, e. g., normal tissues and several types of cancer; or inferring a prediction network among elements such as genes, proteins and external stimuli. In these applications, a recurrent problem is the lack of samples to perform an adequate estimate of the joint probabilities between element states. A myriad of feature selection algorithms and criterion functions have been proposed, although it is difficult to point the best solution for each application. Results: The intent of this work is to provide an open-source multiplataform graphical environment for bioinformatics problems, which supports many feature selection algorithms, criterion functions and graphic visualization tools such as scatterplots, parallel coordinates and graphs. A feature selection approach for growing genetic networks from seed genes ( targets or predictors) is also implemented in the system. Conclusion: The proposed feature selection environment allows data analysis using several algorithms, criterion functions and graphic visualization tools. Our experiments have shown the software effectiveness in two distinct types of biological problems. Besides, the environment can be used in different pattern recognition applications, although the main concern regards bioinformatics tasks.

The impact of the subtropical South Atlantic SST on South American precipitation

The Community Climate Model (CCM3) from the National Center for Atmospheric Research (NCAR) is used to investigate the effect of the South Atlantic sea surface temperature (SST) anomalies on interannual to decadal variability of South American precipitation. Two ensembles composed of multidecadal simulations forced with monthly SST data from the Hadley Centre for the period 1949 to 2001 are analysed. A statistical treatment based on signal-to-noise ratio and Empirical Orthogonal Functions (EOF) is applied to the ensembles in order to reduce the internal variability among the integrations. The ensemble treatment shows a spatial and temporal dependence of reproducibility. High degree of reproducibility is found in the tropics while the extratropics is apparently less reproducible. Austral autumn (MAM) and spring (SON) precipitation appears to be more reproducible over the South America-South Atlantic region than the summer (DJF) and winter (JJA) rainfall. While the Inter-tropical Convergence Zone (ITCZ) region is dominated by external variance, the South Atlantic Convergence Zone (SACZ) over South America is predominantly determined by internal variance, which makes it a difficult phenomenon to predict. Alternatively, the SACZ over western South Atlantic appears to be more sensitive to the subtropical SST anomalies than over the continent. An attempt is made to separate the atmospheric response forced by the South Atlantic SST anomalies from that associated with the El Nino - Southern Oscillation (ENSO). Results show that both the South Atlantic and Pacific SSTs modulate the intensity and position of the SACZ during DJF. Particularly, the subtropical South Atlantic SSTs are more important than ENSO in determining the position of the SACZ over the southeast Brazilian coast during DJF. On the other hand, the ENSO signal seems to influence the intensity of the SACZ not only in DJF but especially its oceanic branch during MAM. Both local and remote influences, however, are confounded by the large internal variance in the region. During MAM and JJA, the South Atlantic SST anomalies affect the magnitude and the meridional displacement of the ITCZ. In JJA, the ENSO has relatively little influence on the interannual variability of the simulated rainfall. During SON, however, the ENSO seems to counteract the effect of the subtropical South Atlantic SST variations on convection over South America.

INTERANNUAL VARIABILITY IN TROPICAL ESTUARINE COPEPOD ASSEMBLAGES OFF NORTHEASTERN BRAZIL

We studied copepod assemblage variability among years, seasons, and tidal states in the Mucuri River estuary (Bahia State, Brazil). Zooplankton samples were collected seasonally through five years (2002-2006) at three sampling stations, one of which was sampled over a complete tidal cycle (two ebb and two flood tides). Temperature, salinity, river flux, and rainfall data were collected. Winter and summer represented dry and wet seasons, respectively. Copepod abundances ranged from 40 to 63% of the total zooplankton assemblage and comprised 46 taxa, among which, common estuarine species such as Temora turbinata (first record for the studied area), Parvocalanus crassirostris, Acartia lilljeborgi, Oithona hebes were the most abundant (euryhaline species). Interannual and seasonal variations were most marked in stenohaline species, e.g.. Notodiaptomus sp. and Thermocyclops minutus; density variations of euryhaline species, which made up the majority of the abundant taxa, were most closely related to tides. Diversity and richness also followed an intertidal pattern of variation.

Application of electron paramagnetic resonance Spectroscopy for validation of the novel (AN plus DN) solvent polarity scale

Based on solvation studies of polymers, the sum (1: 1) of the electron acceptor (AN) and electron donor (DN) values of solvents has been proposed as an alternative polarity scale. To test this, the electron paramagnetic resonance isotropic hyperfine splitting constant, a parameter known to be dependent on the polarity/proticity of the medium, was correlated with the (AN+DN) term using three paramagnetic probes. The linear regression coefficient calculated for 15 different solvents was approximately 0.9, quite similar to those of other well-known polarity parameters, attesting to the validity of the (AN+DN) term as a novel ""two-parameter"" solvent polarity scale.

Polarization effects in molecular dynamics simulations of glass-formers Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8

Thermodynamics, equilibrium structure, and dynamics of glass-forming liquids Ca(NO(3))(2)center dot nH(2)O, n=4, 6, and 8, have been investigated by molecular dynamics (MD) simulations. A polarizable model was considered for H(2)O and NO(3)- on the basis of previous fluctuating charge models for pure water and the molten salt 2Ca(NO(3))(2)center dot 3KNO(3). Similar thermodynamic properties have been obtained with nonpolarizable and polarizable models. The glass transition temperature, T(g), estimated from MD simulations was dependent on polarization, in particular the dependence of T(g) with electrolyte concentration. Significant polarization effects on equilibrium structure were observed in cation-cation, cation-anion, and water-water structures. Polarization increases the diffusion coefficient of H(2)O, but does not change significantly the diffusion coefficients of ions. Viscosity decreases upon inclusion of polarization, but the conductivity calculated with the polarizable model is smaller than the nonpolarizable model because polarization enhances anion-cation interactions.

Gold is not a Faradaic-Efficient Borohydride Oxidation Electrocatalyst: An Online Electrochemical Mass Spectrometry Study

Direct borohydride fuel cells are promising high energy density portable generators. However, their development remains limited by the complexity of the anodic reaction: The borohydride oxidation reaction (BOR) kinetics is slow and occurs at high overvoltages, while it may compete with the heterogeneous hydrolysis of BH(4)(-). Nevertheless, one usually admits that gold is rather inactive toward the heterogeneous hydrolysis of BH(4)(-) and presents some activity regarding the BOR, therefore yielding to the complete eight-electron BOR. In the present paper, by coupling online mass spectrometry to electrochemistry, we in situ monitored the H(2) yield during BOR experiments on sputtered gold electrodes. Our results show non-negligible H(2) generation on Au on the whole BOR potential range (0-0.8 V vs reversible hydrogen electrode), thus revealing that gold cannot be considered as a faradaic-efficient BOR electrocatalyst. We further propose a relevant reaction pathway for the BOR on gold that accounts for these findings.

Temperature effects on the oscillatory electro-oxidation of methanol on platinum

We report in this paper the effect of temperature on the oscillatory electro-oxidation of methanol on polycrystalline platinum in aqueous sulfuric acid media. Potential oscillations were studied under galvanostatic control and at four temperatures ranging from 5 to 35 degrees C. For a given temperature, the departure from thermodynamic equilibrium does not affect the oscillation period and results in a slight increase of the oscillation amplitude. Apparent activation energies were also evaluated in voltammetric and chronoamperometric experiments and were compared to those obtained under oscillatory conditions. In any case, the apparent activation energies values fell into the region between 50 and 70 kJ mol(-1). Specifically under oscillatory conditions an apparent activation energy of 60 +/- 3 kJ mol(-1) and a temperature coefficient q(10) of about 2.3 were observed. The present findings extend our recently published report (J. Phys. Chem. A, 2008, 112, 4617) on the temperature effect on the oscillatory electro-oxidation of formic acid. We found that, despite the fact that both studies were carried out under similar conditions, unlike the case of formic acid, only conventional, Arrhenius, dynamics was observed for methanol.

Influence of land-use change on near-surface hydrological processes: Undisturbed forest to pasture

Soil compaction that follows the clearing of tropical forest for cattle pasture is associated with lower soil hydraulic conductivity and increased frequency and volume of overland flow. We investigated the frequency of perched water tables, overland flow and stormflow in an Amazon forest and in an adjacent 25-year-old pasture cleared from the same forest. We compared the results with the frequencies of these phenomena estimated from comparisons of rainfall intensity and soil hydraulic conductivity. The frequency of perched water tables based on rainfall intensity and soil hydraulic conductivity was expected to double in pasture compared with forest. This corresponded closely with an approximate doubling of the frequency of stormflow and overland flow in pasture. In contrast, the stormflow volume in pasture increased 17-fold. This disproportional increase of stormflow resulted from overland flow generation over large areas of pasture, while overland flow generation in the forest was spatially limited and was observed only very near the stream channel. In both catchments, stormflow was generated by saturation excess because of perched water tables and near-surface groundwater levels. Stormflow was occasionally generated in the forest by rapid return flow from macropores, while slow return flow from a continuous perched water table was more common in the pasture. These results suggest that deforestation for pasture alters fundamental mechanisms of stormflow generation and may increase runoff volumes over wide regions of Amazonia. (C) 2009 Elsevier B.V. All rights reserved.

Near infrared spectroscopy for soil bulk density assessment

P>Soil bulk density values are needed to convert organic carbon content to mass of organic carbon per unit area. However, field sampling and measurement of soil bulk density are labour-intensive, costly and tedious. Near-infrared reflectance spectroscopy (NIRS) is a physically non-destructive, rapid, reproducible and low-cost method that characterizes materials according to their reflectance in the near-infrared spectral region. The aim of this paper was to investigate the ability of NIRS to predict soil bulk density and to compare its performance with published pedotransfer functions. The study was carried out on a dataset of 1184 soil samples originating from a reforestation area in the Brazilian Amazon basin, and conventional soil bulk density values were obtained with metallic ""core cylinders"". The results indicate that the modified partial least squares regression used on spectral data is an alternative method for soil bulk density predictions to the published pedotransfer functions tested in this study. The NIRS method presented the closest-to-zero accuracy error (-0.002 g cm-3) and the lowest prediction error (0.13 g cm-3) and the coefficient of variation of the validation sets ranged from 8.1 to 8.9% of the mean reference values. Nevertheless, further research is required to assess the limits and specificities of the NIRS method, but it may have advantages for soil bulk density predictions, especially in environments such as the Amazon forest.

Gaseous and fluvial carbon export from an Amazon forest watershed

The transfer of carbon (C) from Amazon forests to aquatic ecosystems as CO(2) supersaturated in groundwater that outgases to the atmosphere after it reaches small streams has been postulated to be an important component of terrestrial ecosystem C budgets. We measured C losses as soil respiration and methane (CH(4)) flux, direct CO(2) and CH(4) fluxes from the stream surface and fluvial export of dissolved inorganic C (DIC), dissolved organic C (DOC), and particulate C over an annual hydrologic cycle from a 1,319-ha forested Amazon perennial first-order headwater watershed at Tanguro Ranch in the southern Amazon state of Mato Grosso. Stream pCO(2) concentrations ranged from 6,491 to 14,976 mu atm and directly-measured stream CO(2) outgassing flux was 5,994 +/- A 677 g C m(-2) y(-1) of stream surface. Stream pCH(4) concentrations ranged from 291 to 438 mu atm and measured stream CH(4) outgassing flux was 987 +/- A 221 g C m(-2) y(-1). Despite high flux rates from the stream surface, the small area of stream itself (970 m(2), or 0.007% of watershed area) led to small directly-measured annual fluxes of CO(2) (0.44 +/- A 0.05 g C m(2) y(-1)) and CH(4) (0.07 +/- A 0.02 g C m(2) y(-1)) per unit watershed land area. Measured fluvial export of DIC (0.78 +/- A 0.04 g C m(-2) y(-1)), DOC (0.16 +/- A 0.03 g C m(-2) y(-1)) and coarse plus fine particulate C (0.001 +/- A 0.001 g C m(-2) y(-1)) per unit watershed land area were also small. However, stream discharge accounted for only 12% of the modeled annual watershed water output because deep groundwater flows dominated total runoff from the watershed. When C in this bypassing groundwater was included, total watershed export was 10.83 g C m(-2) y(-1) as CO(2) outgassing, 11.29 g C m(-2) y(-1) as fluvial DIC and 0.64 g C m(-2) y(-1) as fluvial DOC. Outgassing fluxes were somewhat lower than the 40-50 g C m(-2) y(-1) reported from other Amazon watersheds and may result in part from lower annual rainfall at Tanguro. Total stream-associated gaseous C losses were two orders of magnitude less than soil respiration (696 +/- A 147 g C m(-2) y(-1)), but total losses of C transported by water comprised up to about 20% of the +/- A 150 g C m(-2) (+/- 1.5 Mg C ha(-1)) that is exchanged annually across Amazon tropical forest canopies.

Implications of long-term land-use change for the hydrology and solute budgets of small catchments in Amazonia

The replacement of undisturbed tropical forest with cattle pasture has the potential to greatly modify the hydrology of small watersheds and the fluxes of solutes. We examined the fluxes of water, Cl(-), NO(3)(-)-N: SO(4)(2--)-S, NH(4)(+)-N, Na(+), K(+), Mg(2+) and Ca(2+) in different flow paths in similar to 1 ha catchments of undisturbed open tropical rainforest and a 20 year-old pasture established from forest in the southwestern Brazilian Amazon state of Rondonia. Storm flow discharge was 18% of incident rainfall in pasture, but only 1% in forest. Quickflow predominated over baseflow in both catchments and in both wet and dry seasons. In the pasture, groundwater and quickflow were important flow paths for the export of all solutes. In the forest, quickflow was important for NO(3)(-)-N export, but all other solutes were exported primarily by groundwater outflow. Both catchments were sinks for SO(4)(2-)-S and Ca(2+), and sources of Na(+). The pasture catchment also lost K(+) and Mg(2+) because of higher overland flow frequency and volume and to cattle excrement. These results show that forest clearing dramatically influences small watershed hydrology by increasing quickflow and water export to streams. They also indicate that tropical forest watersheds are highly conservative for most solutes but that pastures continue to lose important cations even decades after deforestation and pasture establishment. (c) 2008 Elsevier B.V. All rights reserved.

Understanding the Influences of Spatial Patterns on N Availability Within the Brazilian Amazon Forest

Nitrogen variations at different spatial scales and integrated across functional groups were addressed for lowland tropical forests in the Brazilian Amazon as follows: (1) how does N availability vary across the region over different spatial scales (regional x landscape scale); ( 2) how are these variations in N availability integrated across plant functional groups ( legume 9 non-legume trees). Leaf N, P, and Ca concentrations as well the leaf N isotope ratios (delta(15)N) from a large set of legume and non-legume tree species were measured. Legumes had higher foliar N/Ca ratios than non-legumes, consistent with the high energetic costs in plant growth associated with higher foliar P/Ca ratios found in legumes than in non-legumes. At the regional level, foliar delta(15)N decreased with increasing rainfall. At the landscape level, N availability was higher in the forests on clayey soils on the plateau than in forests on sandier soils. The isotope as well as the non-isotope data relationships here documented, explain to a large extent the variation in delta(15)N signatures across gradients of rainfall and soil. Although at the regional level, the precipitation regime is a major determinant of differences in N availability, at the landscape level, under the same precipitation regime, soil type seems to be a major factor influencing the availability of N in the Brazilian Amazon forest.

A flow injection procedure based on solenoid micro-pumps for spectrophotometric determination of free glycerol in biodiesel

A flow system designed with solenoid micro-pumps is proposed for fast and greener spectrophotometric determination of free glycerol in biodiesel. Glycerol was extracted from samples without using organic solvents. The determination involves glycerol oxidation by periodate, yielding formaldehyde followed by formation of the colored (3,5-diacetil-1,4-dihidrolutidine) product upon reaction with acetylacetone. The coefficient of variation, sampling rate and detection limit were estimated as 1.5% (20.0 mg L(-1) glycerol, n =10), 34 h(-1), and 1.0 mg L(-1) (99.7% confidence level), respectively. A linear response was observed from 5 to 50 mg L(-1), with reagent consumption estimated as 345 mu g of KIO(4) and 15 mg of acetylacetone per determination. The procedure was successfully applied to the analysis of biodiesel samples and the results agreed with the batch reference method at the 95% confidence level. (C) 2010 Elsevier B.V. All rights reserved.

An environmentally friendly flow system for high-sensitivity spectrophotometric determination of free chlorine in natural waters

A green and highly sensitive analytical procedure was developed for the determination of free chlorine in natural waters, based on the reaction with N,N-diethyl-p-phenylenediamine (DPD). The flow system was designed with solenoid micro-pumps in order to improve mixing conditions by pulsed flows and to minimize reagent consumption as well as waste generation. A 100-cm optical path flow cell based on a liquid core waveguide was employed to increase sensitivity. A linear response was observed within the range 10.0 to 100.0 mu g L(-1), with the detection limit, coefficient of variation and sampling rate estimated as 6.8 mu g (99.7% confidence level), 0.9% (n = 20) and 60 determinations per hour, respectively. The consumption of the most toxic reagent (DPD) was reduced 20,000-fold and 30-fold in comparison to the batch method and flow injection with continuous reagent addition, respectively. The results for natural and tap water samples agreed with those obtained by the reference batch spectrophotometric procedure at the 95% confidence level. (C) 2010 Elsevier By. All rights reserved.