Quantification of permanent and variable charges in reference soils of the State of Pernambuco, Brazil

The electrical charges in soil particles are divided into structural or permanent charges and variable charges. Permanent charges develop on the soil particle surface by isomorphic substitution. Variable charges arise from dissociation and association of protons (H+), protonation or deprotonation, and specific adsorption of cations and anions. The aim of this study was to quantify the permanent charges and variable charges of Reference Soils of the State of Pernambuco, Brazil. To do so, 24 subsurface profiles from different regions (nine in the Zona da Mata, eight in the Agreste, and seven in the Sertão) were sampled, representing approximately 80 % of the total area of the state. Measurements were performed using cesium chloride solution. Determination was made of the permanent charges and the charges in regard to the hydroxyl functional groups through selective ion exchange of Cs+ by Li+ and Cs+ by NH4+, respectively. All the soils analyzed exhibited variable cation exchange capacity, with proportions from 0.16 to 0.60 and an average of 0.40 when related to total cation exchange capacity.

Surface Complexation Modeling in Variable Charge Soils: Charge Characterization by Potentiometric Titration

ABSTRACT Intrinsic equilibrium constants of 17 representative Brazilian Oxisols were estimated from potentiometric titration measuring the adsorption of H+ and OH− on amphoteric surfaces in suspensions of varying ionic strength. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. The former was fitted by calculating total site concentration from curve fitting estimates and pH-extrapolation of the intrinsic equilibrium constants to the PZNPC (hand calculation), considering one and two reactive sites, and by the FITEQL software. The latter was fitted only by FITEQL, with one reactive site. Soil chemical and physical properties were correlated to the intrinsic equilibrium constants. Both surface complexation models satisfactorily fit our experimental data, but for results at low ionic strength, optimization did not converge in FITEQL. Data were incorporated in Visual MINTEQ and they provide a modeling system that can predict protonation-dissociation reactions in the soil surface under changing environmental conditions.

Surface Complexation Modeling in Variable Charge Soils: Prediction of Cadmium Adsorption

ABSTRACT Intrinsic equilibrium constants for 22 representative Brazilian Oxisols were estimated from a cadmium adsorption experiment. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. Intrinsic equilibrium constants were optimized by FITEQL and by hand calculation using Visual MINTEQ in sweep mode, and Excel spreadsheets. Data from both models were incorporated into Visual MINTEQ. Constants estimated by FITEQL and incorporated in Visual MINTEQ software failed to predict observed data accurately. However, FITEQL raw output data rendered good results when predicted values were directly compared with observed values, instead of incorporating the estimated constants into Visual MINTEQ. Intrinsic equilibrium constants optimized by hand calculation and incorporated in Visual MINTEQ reliably predicted Cd adsorption reactions on soil surfaces under changing environmental conditions.

Water-Stable Aggregates and Associated Carbon in a Subtropical Rice Soil Under Variable Tillage

ABSTRACT Tillage systems can influence C sequestration by changing aggregate formation and C distribution within the aggregate. This study was undertaken to explore the impact of no-tillage without straw (NT-S) and with straw (NT+S), and moldboard plow without straw (MP-S) and with straw (MP+S), on soil aggregation and aggregate-associated C after six years of double rice planting in a Hydragric Anthrosol in Guangxi, southwest of China. Soil samples of 0.00-0.05, 0.05-0.20 and 0.20-0.30 m layers were wet-sieved and divided into four aggregate-size classes, >2 mm, 2.00-0.25 mm, 0.25-0.053 and <0.053 mm, respectively, for measuring aggregate associated C and humic and fulvic acids. Results showed that the soil organic carbon (SOC) stock in bulk soil was 40.2-51.1 % higher in the 0.00-0.05 m layer and 11.3-17.0 % lower in the 0.05-0.20 m layer in NT system (NT+S and NT-S) compared to the MP system (MP+S and MP-S), respectively. However, no statistical difference was found across the whole 0.00-0.30 m layer. The NT system increased the proportion of >2 mm aggregate fraction and reduced the proportion of <0.053 mm aggregates in both 0.00-0.05 and 0.05-0.20 m layers. The SOC concentration, SOC stock and humic and fulvic acids within the >0.25 mm macroaggregate fraction also significantly increased in the 0.00-0.5 m layer in NT system. However, those within the 2.00-0.25 mm aggregate fraction were significantly reduced in the 0.05-0.200 m layer under NT system. Straw incorporation increased not only the SOC stock in bulk soil, but also the proportion of macroaggregate, aggregate associated with SOC and humic and fulvic acids concentration within the aggregate. The effect of straw on C sequestration might be dependent on the location of straw incorporation. In conclusion, the NT system increased the total SOC accumulation and humic and fulvic acids within macroaggregates, thus contributing to C sequestration in the 0.00-0.05 m layer.

Simulating maize phenology as a function of air temperature with a linear and a nonlinear model

The objective of this study was to adapt a nonlinear model (Wang and Engel - WE) for simulating the phenology of maize (Zea mays L.), and to evaluate this model and a linear one (thermal time), in order to predict developmental stages of a field-grown maize variety. A field experiment, during 2005/2006 and 2006/2007 was conducted in Santa Maria, RS, Brazil, in two growing seasons, with seven sowing dates each. Dates of emergence, silking, and physiological maturity of the maize variety BRS Missões were recorded in six replications in each sowing date. Data collected in 2005/2006 growing season were used to estimate the coefficients of the two models, and data collected in the 2006/2007 growing season were used as independent data set for model evaluations. The nonlinear WE model accurately predicted the date of silking and physiological maturity, and had a lower root mean square error (RMSE) than the linear (thermal time) model. The overall RMSE for silking and physiological maturity was 2.7 and 4.8 days with WE model, and 5.6 and 8.3 days with thermal time model, respectively.

Análise genética de escores de avaliação visual de bovinos com modelos bayesianos de limiar e linear

O objetivo deste trabalho foi comparar as estimativas de parâmetros genéticos obtidas em análises bayesianas uni-característica e bi-característica, em modelo animal linear e de limiar, considerando-se as características categóricas morfológicas de bovinos da raça Nelore. Os dados de musculosidade, estrutura física e conformação foram obtidos entre 2000 e 2005, em 3.864 animais de 13 fazendas participantes do Programa Nelore Brasil. Foram realizadas análises bayesianas uni e bi-características, em modelos de limiar e linear. De modo geral, os modelos de limiar e linear foram eficientes na estimação dos parâmetros genéticos para escores visuais em análises bayesianas uni-características. Nas análises bi-características, observou-se que: com utilização de dados contínuos e categóricos, o modelo de limiar proporcionou estimativas de correlação genética de maior magnitude do que aquelas do modelo linear; e com o uso de dados categóricos, as estimativas de herdabilidade foram semelhantes. A vantagem do modelo linear foi o menor tempo gasto no processamento das análises. Na avaliação genética de animais para escores visuais, o uso do modelo de limiar ou linear não influenciou a classificação dos animais, quanto aos valores genéticos preditos, o que indica que ambos os modelos podem ser utilizados em programas de melhoramento genético.

Tamanho de amostra para estimação do coeficiente de correlação linear de Pearson entre caracteres de milho

O objetivo deste trabalho foi determinar o tamanho de amostra para a estimação do coeficiente de correlação linear de Pearson entre caracteres de três híbridos de milho. Para as análises, foram tomadas aleatoriamente 361, 373 e 416 plantas, respectivamente, de híbridos simples, triplo e duplo. Para cada planta, os seguintes caracteres foram mensurados: diâmetro maior e menor do colmo, altura da planta e altura, peso, comprimento e diâmetro da espiga, número de fileiras por espiga, peso e diâmetro de sabugo, massa de cem grãos, número de grãos por espiga, comprimento e produtividade de grãos. Para cada um dos 91 pares de caracteres e híbridos, foi determinado o tamanho de amostra a partir de "bootstrap", com reposição de 1.000 amostras, de cada tamanho de amostra simulado. Na estimação do coeficiente de correlação linear de Pearson com a mesma precisão, o tamanho de amostra (número de plantas) aumenta na direção de pares de caracteres com menor intensidade de relação linear, independentemente do tipo de híbrido. Para os 91 pares de caracteres estudados, 252 plantas são suficientes para a estimação do coeficiente de correlação linear de Pearson, no intervalo de confiança de "bootstrap" de 95%, igual a 0,30

Degree of multicollinearity and variables involved in linear dependence in additive-dominant models

The objective of this work was to assess the degree of multicollinearity and to identify the variables involved in linear dependence relations in additive-dominant models. Data of birth weight (n=141,567), yearling weight (n=58,124), and scrotal circumference (n=20,371) of Montana Tropical composite cattle were used. Diagnosis of multicollinearity was based on the variance inflation factor (VIF) and on the evaluation of the condition indexes and eigenvalues from the correlation matrix among explanatory variables. The first model studied (RM) included the fixed effect of dam age class at calving and the covariates associated to the direct and maternal additive and non-additive effects. The second model (R) included all the effects of the RM model except the maternal additive effects. Multicollinearity was detected in both models for all traits considered, with VIF values of 1.03 - 70.20 for RM and 1.03 - 60.70 for R. Collinearity increased with the increase of variables in the model and the decrease in the number of observations, and it was classified as weak, with condition index values between 10.00 and 26.77. In general, the variables associated with additive and non-additive effects were involved in multicollinearity, partially due to the natural connection between these covariables as fractions of the biological types in breed composition.

Dosimetria dos cones radiocirúrgicos Radionics de diâmetros de 5 mm a 50 mm para um feixe de 6 MV de um acelerador linear Mevatron MD digital

Os parâmetros dosimétricos de um feixe de raios X de pequeno diâmetro para um sistema de radiocirurgia comercial foram medidos em água com um detector de diodo de Si do tipo p. As razões tecido-máximo, o fator de espalhamento total e os perfis dos feixes a profundidades de 5 e 10 cm foram medidos para 17 feixes de diâmetros circulares de 5 mm a 50 mm, em incrementos de 2,5 mm. Os fatores de espalhamento totais caíram lentamente, de 0,947 para 0,888 entre os cones de 50 mm e 12,5 mm de diâmetro (variação de 7%); para os cones entre 10 mm e 5 mm de diâmetro, esta queda foi bem maior, de 0,854 para 0,666 (variação de 28%). Os valores obtidos para a relação tecido-máximo são consistentes com dados publicados. Os perfis dos feixes foram medidos nas direções x e y, e estão dentro de 0,2 mm para todos os cones entre as duas direções. A medida da largura à meia-altura se encontra dentro de 1 mm com o diâmetro nominal dos cones.

Implantação de um programa de controle de qualidade de um acelerador linear de 6 MeV de fótons

Este trabalho apresenta a parte operacional do processo final envolvido na implantação de um programa de controle de qualidade por meio de testes rotineiros mecânicos e de radiação. O programa de controle de qualidade, durante 35 meses, mostrou a estabilidade excelente deste acelerador.

Análise das isotermas de adsorção de Cu(II), Cd(II), Ni(II) e Zn(II) pela N-(3,4-dihidroxibenzil) quitosana empregando o método da regressão não linear

Adsorption of Cu(II), Ni(II), Pb(II) and Zn(II) ions from aqueous solutions by N-(3,4-dihydroxybenzyl) chitosan have been carried out. The Langmuir (L), Freundlich (F), Langmuir - Freundlich (LF), Redlich-Peterson (RP) and Tóth (T) adsorption isotherms models have been applied to fit the experimental data. Nonlinear regression computational program "Enzefitte", which is a library of the more commonly used adsorption isotherm equations for obtaining tabular outuput suitable for plotting theoretical of fitted isotherms, has been used to estimate the adsorption parameters. These parameters were used to calculate the amount adsorbed q calc., a function of concentration (C).

Aplicação de algoritmos genéticos na seleção de variáveis em espectroscopia no infravermelho médio: determinação simultânea de glicose, maltose e frutose

Genetic algorithm was used for variable selection in simultaneous determination of mixtures of glucose, maltose and fructose by mid infrared spectroscopy. Different models, using partial least squares (PLS) and multiple linear regression (MLR) with and without data pre-processing, were used. Based on the results obtained, it was verified that a simpler model (multiple linear regression with variable selection by genetic algorithm) produces results comparable to more complex methods (partial least squares). The relative errors obtained for the best model was around 3% for the sugar determination, which is acceptable for this kind of determination.

Cálculo ab initio de intensidades Raman dinâmicas utilizando a teoria da resposta linear

In this paper a methodology for the computation of Raman scattering cross-sections and depolarization ratios within the Placzek Polarizability Theory is described. The polarizability gradients are derived from the values of the dynamic polarizabilities computed at the excitation frequencies using ab initio Linear Response Theory. A sample application of the computational program, at the HF, MP2 and CCSD levels of theory, is presented for H2O and NH3. The results show that high correlated levels of theory are needed to achieve good agreement with experimental data.

Alquilbenzeno sulfonato linear: uma abordagem ambiental e analítica

The environmental impact of detergents and other consumer products is behind the continued interest in the chemistry of the surfactants used. Of these, linear alkylbenzene sulfonates (LASs) are most widely employed in detergent formulations. The precursors to LASs are linear alkylbenzenes (LABs). There is also interest in the chemistry of these hydrocarbons, because they are usually present in commercial LASs (due to incomplete sulfonation), or form as one of their degradation products. Additionally, they may be employed as molecular tracers of domestic waste in the aquatic environment. The following aspects are covered in the present review: The chemistry of surfactants, in particular LAS; environmental impact of the production of LAS; environmental and toxicological effects of LAS; mechanisms of removal of LAS in the environment, and methods for monitoring LAS and LAB, the latter in domestic wastes. Classical and novel analytical methods employed for the determination of LAS and LAB are discussed in detail, and a brief comment on detergents in Brazil is given.