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.

Estudo de algumas reações oxoacidobásicas no solvente NaCl fundido entre 1100K e 1200K

Equilibrium constants (K) of some oxoacidbasic reactions in molten NaCl in the temperature range of 1100K to 1200K, have been measured potentiometrically with a calcia stabilized zirconia oxide ion (O2-) indicator electrode. In molten NaCl at 1100K the pKs values (in molality scale) for HCl/H2O and HO-/H2O are respectively 11.0 ± 0.3; 1.6 ± 0.3 and the pKs for CaO is 4.3 ± 0.3. The results have been compared with those determined previously by Combes for the molten equimolar NaCl-KCl mixture and are in good agreement with literature data and gives some qualitative explanation of the comparison of oxoacidbasic properties between molten NaCl and NaCl-KCl.

Método de estudo da adsorção de triadimenol com micro-colunas de solo e centrifugação

Normally, the determination of equilibrium constants (k d) in batch experiments uses a high solution to soil ratio, which does not represent field conditions. In this study we present an alternative method to evaluate adsorption constants, using micro-columns of soil at higher soil to solution ratios. The centrifugation force and equilibration time were investigated. The triadimenol distribution along the column profile is controlled by diffusion and equilibration times greater than 24 h are needed to achieve reproducibility. The centrifugation force must be superior to 670 g in order to guarantee enough extraction of the liquid solution from the soil columns.

The interaction between sulfathiazole and cobalt(II): potentiometric studies

Potentiometric studies of sulfathiazole (HST) in the presence and absence of cobalt(II) were performed. Equilibrium constants for the formation of the detected species, [Co(ST)]+ and [Co(ST)(OH)], are reported. UV-Vis spectrophotometric measurements suggest that the coordination Co(II)-sulfathiazole might be through a N atom, which, in agreement with MO calculations, could be a thiazolic one. In spite of sulfonamides being better ligands at pH >7, [Co(ST)]+ was found at pH » 3.

Cat's claw oxindole alkaloid isomerization induced by common extraction methods

Cat's claw oxindole alkaloids are prone to isomerization in aqueous solution. However, studies on their behavior in extraction processes are scarce. This paper addressed the issue by considering five commonly used extraction processes. Unlike dynamic maceration (DM) and ultrasound-assisted extraction, substantial isomerization was induced by static maceration, turbo-extraction and reflux extraction. After heating under reflux in DM, the kinetic order of isomerization was established and equations were fitted successfully using a four-parameter Weibull model (R² > 0.999). Different isomerization rates and equilibrium constants were verified, revealing a possible matrix effect on alkaloid isomerization.

Propriedades relacionadas à acidez e basicidade a partir da abordagem em química computacional

Analytical Chemistry books lack a clear link between thermodynamic and equilibrium approaches involving acids and bases. In this work, theoretical calculations were performed to search for these relations. An excellent relationship was found between difference in Gibbs free energy, ∆G of acid dissociation reaction and ∆G of hydrolysis reaction of the corresponding conjugate base. A relationship between ∆G of hydrolysis reaction of conjugate acids and their corresponding atomic radius was also identified, showing that stability plays an important role in hydrolysis reactions. Finally, the importance of solvation in acid/base behavior was demonstrated when comparing the corresponding theoretical and experimental ∆G´s.

Potentiometric quantification and speciation of oxygenated groups in humic substances using BEST7 software

In this study the BEST7 software was employed to quantify different classes of functional groups and to model the proton titration behavior of humic substances. To illustrate the process, the Suwannee River fulvic acid of the IHSS (International Humic Substances Society) was used. Five categories - two classes of phenolic groups (phenol and cathecol), two classes of carboxylic groups (benzoic and phtalic) and the combination between them (salicylic) - of oxygenated groups were considered as being responsible for the potentiometric behavior of the sample and were quantitatively determined. The most and the least abundant groups were cathecol (3.300 ± 0.010 mmol g-1) and phenol (1.225 ± 0.070 mmol g-1), respectively. The estimated equilibrium constants were also determined and were in good agreement with the literature values for phenol and cathecol groups and for benzoic, phtalic and salicylic acids. Distribution diagrams of the species were generated with the software SPE and SPEPLOT.

Seed viability constants for Eucalyptus grandis

This work aimed to analyse Eucalyptus grandis W.Hill ex Maiden seed behaviour, under controlled deterioration, and to estimate viability equation constants for the species. Seeds were harvested in the growing season of 1999, and the moisture contents were adjusted from 11.3% to a range between 1.2 and 18.1% at 25ºC. The subsamples were sealed into laminate aluminium-foil packets, for storage in incubators at 40, 50 and 65±0.5ºC. The seeds presented orthodox performance, in which the constants for predicting seed longevity of E. grandis were K E = 9.661, C W = 6.467, C H = 0.03498 and C Q = 0.0002330. The usual and inverse relationship between water content and seed longevity was also observed. The lowest moisture content limit for application of the viability equation at 65ºC was 4.9%, estimated under hygroscopic equilibrium with 23% of relative humidity in the storage environment.

Equilibrium studies of 2,2'-(5-bromo-6-methylpyrimidine-2,4-diyl)bis(azanediyl)dipropanoic acid with some transition-metal ions in aqueous solution

The stability constants of the 1:1 complexes formed between M2+ (M2+: Mn2+, Ni2+, Cu2+, or Cd2+) and BMADA2- (BMADA: 2,2'-(5-bromo-6-methylpyrimidine-2,4 diyl)bis(azanediyl)dipropanoic acid) were determined by potentiometric pH titration in aqueous solution (I = 0.1 mol L-1, NaNO3, 25 °C). The stability of the binary M - BMADA complexes is determined by the basicity of the carboxyl or amino groups. All the stability constants reported in this work exhibit the usual trend, and the order obtained was Mn2+< Ni2+ < Cu2+ > Cd2+. The observed stability order for BMADA approximately follows the Irving - Williams sequence. In the M - BMADA complexes, the M ion is able to form a macrochelate via the pyrimidine group of BMADA.

Dynamics of experimental populations of native and introduced blowflies (Diptera: Calliphoridae): mathematical modelling and the transition from asymptotic equilibrium to bounded oscillations

The equilibrium dynamics of native and introduced blowflies is modelled using a density-dependent model of population growth that takes into account important features of the life-history in these flies. A theoretical analysis indicates that the product of maximum fecundity and survival is the primary determinant of the dynamics. Cochliomyia macellaria, a blowfly native to the Americas and the introduced Chrysomya megacephala and Chrysomya putoria, differ in their dynamics in that the first species shows a damping oscillatory behavior leading to a one-point equilibrium, whereas in the last two species population numbers show a two-point limit cycle. Simulations showed that variation in fecundity has a marked effect on the dynamics and indicates the possibility of transitions from one-point equilibrium to bounded oscillations and aperiodic behavior. Variation in survival has much less influence on the dynamics.

Spatio-temporal dynamics and transition from asymptotic equilibrium to bounded oscillations in Chrysomya albiceps (Diptera, Calliphoridae)

The sensitivity of parameters that govern the stability of population size in Chrysomya albiceps and describe its spatial dynamics was evaluated in this study. The dynamics was modeled using a density-dependent model of population growth. Our simulations show that variation in fecundity and mainly in survival has marked effect on the dynamics and indicates the possibility of transitions from one-point equilibrium to bounded oscillations. C. albiceps exhibits a two-point limit cycle, but the introduction of diffusive dispersal induces an evident qualitative shift from two-point limit cycle to a one fixed-point dynamics. Population dynamics of C. albiceps is here compared to dynamics of Cochliomyia macellaria, C. megacephala and C. putoria.

In vitro chloroquine resistance modulation study on fresh isolates of Brazilian Plasmodium falciparum: intrinsic antimalarial activity of phenothiazine drugs

Phenothiazine drugs - fluphenazine, chlorpromazine, methotrimeprazine and trifluoperazine - were evaluated as modulating agents against Brazilian chloroquine-resistant fresh isolates of Plasmodium falciparum. Aiming to simulate therapeutic schedules, chloroquine was employed at the concentration used for sensitive falciparum malaria treatment and anti-psychotic therapeutic concentrations of the phenothiazine drugs were adopted in two-fold serial dilutions. The in vitro microtechnique for drug susceptibility was employed. Unlike earlier reported data, the phenothiazine modulating effect was not observed. However, all the drugs demonstrated intrinsic antiplasmodial activity in concentrations lower than those described in the literature. In addition, IC50 estimates have been shown to be inferior to the usual anti-psychotic therapeutic concentrations. Statistical analysis also suggested an increase in the parasitaemia rate or, even, a predominant antiparasitic effect of phenothiazine over chloroquine when used in combination.

Carbon balance and crop residue management in dynamic equilibrium under a no-till system in Campos Gerais

The adoption of no-tillage systems (NT) and the maintenance of crop residues on the soil surface result in the long-term increase of carbon (C) in the system, promoting C sequestration and reducing C-CO2 emissions to the atmosphere. The purpose of this study was to evaluate the C sequestration rate and the minimum amount of crop residues required to maintain the dynamic C equilibrium (dC/dt = 0) of two soils (Typic Hapludox) with different textural classes. The experiment was arranged in a 2 x 2 x 2 randomized block factorial design. The following factors were analyzed: (a) two soil types: Typic Hapludox (Oxisol) with medium texture (LVTM) and Oxisol with clay texture (LVTA), (b) two sampling layers (0-5 and 5-20 cm), and (c) two sampling periods (P1 - October 2007; P2 - September 2008). Samples were collected from fields under a long-term (20 years) NT system with the following crop rotations: wheat/soybean/black oat + vetch/maize (LVTM) and wheat/maize/black oat + vetch/soybean (LVTA). The annual C sequestration rates were 0.83 and 0.76 Mg ha-1 for LVTM and LVTA, respectively. The estimates of the minimum amount of crop residues required to maintain a dynamic equilibrium (dC/dt = 0) were 7.13 and 6.53 Mg ha-1 year-1 for LVTM and LVTA, respectively. The C conversion rate in both studied soils was lower than that reported in other studies in the region, resulting in a greater amount of crop residues left on the soil surface.

The effect of intrinsic soil properties on soil quality assessments

The assessment of soil quality is based on indicators and indices derived from soil properties. However, intrinsic soil properties may interfere with other soil properties that vary under different land uses and are used to calculate the indices. The aim of this study was to assess the extent to which intrinsic soil properties (clay and iron oxide contents) explain variable soil properties (sum of bases, potential acidity, organic carbon, total porosity, and bulk density) under different land uses (native forest, no-tillage and conventional agriculture) on small family farms in Southern Brazil. The results showed that the five properties evaluated can be included in soil quality assessments and are not influenced by the clay and iron oxide contents. It was concluded that for little weathered 1:1 and 2:1 phyllosilicate rich-soils, if the difference between the maximum and the minimum clay content under the different land uses is less than about 200 g kg-1 and the iron oxide content less than about 15 g kg-1, the physico-chemical soil properties in the surface layer are determined mostly by the land use.