Models for the estimation of thermodynamic properties of layered double hydroxides: application to the study of their anion exchange characteristics

Several models for the estimation of thermodynamic properties of layered double hydroxides (LDHs) are presented. The predicted thermodynamic quantities calculated by the proposed models agree with experimental thermodynamic data. A thermodynamic study of the anion exchange process on LDHs is also made using the described models. Tables for the prediction of monovalent anion exchange selectivities on LDHs are provided. Reasonable agreement is found between the predicted and the experimental monovalent anion exchange selectivities.

Flow injection spectrophotometric determination of adrenaline using a solid-phase reactor containing triiodide ions immobilized in an anion-exchange resin

A flow injection spectrophotometric procedure with on-line solid-phase reactor containing ion triiodide immobilized in an anion-exchange resin is proposed for the determination of adrenaline (epinephrine) in pharmaceutical products. Adrenaline is oxidized by triiodide ion immobilized in an anionic-exchange resin yielding adrenochrome which is transported by the carrier solution and detected at a wavelength of 488 nm. Adrenaline was determined in three pharmaceutical products in the 6.4 x 10-6 to 3.0 x 10-4 mol L-1 concentration range with a detection limit of 4.8 x 10-7 mol L-1. The recovery of this analyte in three samples ranged from 96.0 to 105 %. The analytical frequency was 80 determinations per hour and the RSDs were less than 1 % for adrenaline concentrations of 6.4 x 10-5 and 2.0 x 10-4 mol L-1 (n=10). A paired t-test showed that all results obtained for adrenaline in commercial formulations using the proposed flow injection procedure and a spectrophotometric batch procedure agree at the 95% confidence level.

Estimating subsoil resistance to nitrate leaching from easily measurable pedological properties

Leaching of nitrate (NO3-) can increase the groundwater concentration of this anion and reduce the agronomical effectiveness of nitrogen fertilizers. The main soil property inversely related to NO3- leaching is the anion exchange capacity (AEC), whose determination is however too time-consuming for being carried out in soil testing laboratories. For this reason, this study evaluated if more easily measurable soil properties could be used to estimate the resistance of subsoils to NO3- leaching. Samples from the subsurface layer (20-40 cm) of 24 representative soils of São Paulo State were characterized for particle-size distribution and for chemical and electrochemical properties. The subsoil content of adsorbed NO3- was calculated from the difference between the NO3- contents extracted with 1 mol L-1 KCl and with water; furthermore, NO3- leaching was studied in miscible displacement experiments. The results of both adsorption and leaching experiments were consistent with the well-known role exerted by AEC on the nitrate behavior in weathered soils. Multiple regression analysis indicated that in subsoils with (i) low values of remaining phosphorus (Prem), (ii) low soil pH values measured in water (pH H2O), and (iii) high pH values measured in 1 moL L-1 KCl (pH KCl), the amounts of surface positive charges tend to be greater. For this reason, NO3- leaching tends to be slower in these subsoils, even under saturated flow condition.

Hidróxidos duplos lamelares: nanopartículas inorgânicas para armazenamento e liberação de espécies de interesse biológico e terapêutico

Studies about the inorganic nanoparticles applying for non-viral release of biological and therapeutic species have been intensified nowadays. This work reviews the preparation strategies and application of layered double hydroxides (LDH) as carriers for storing, carrying and control delivery of intercalated species as drugs and DNA for gene therapy. LDH show low toxicity, biocompatibility, high anion exchange capacity, surface sites for functionalization, and a suitable equilibrium between chemical stability and biodegradability. LDH can increase the intercalated species stability and promote its sub-cellular uptake for biomedical purposes. Concerning the healthy field, LDH have been evaluated for clinical diagnosis as a biosensor component.

Serum factors inhibitory for in vitro development of Plasmodium falciparum blood-stage parasites

Sera from 29 individuals residing in a malaria-endemic region of Colombia were evaluated by an inhibition assay for their capacity to retard the growth of Plasmodium falciparum in vitro. The inhibitory activity was found to be independent of antibody activity. Furthermore, the degree of inhibition of parasite development was variable, depending on the parasite isolate used for the assay and the season of malaria transmission. We selected sera with high inhibitory activity and carried out partial analytical characterization by anion exchange fast protein liquid chromatography (FPLC) to identify the chemical nature of the inhibitory factor(s). The results suggested that the in vitro inhibitory activity might result from the additive effect of different molecules. It appears that these molecules could be non-specifically induced by stimulation of the immune system, they seem to play a role in the immunity to malaria.

Phosphorus accumulation and pollution potential in a hapludult fertilized with pig manure

Successive applications of pig litter to the soil surface can increase the phosphorus (P) content and alter its adsorption, promoting P transfer to surface or subsurface waters. The purpose of this study was to evaluate P accumulation and the pollution potential of a soil after application of pig litter. In March 2010, eight years after the installation of an experiment in Braço do Norte, Santa Catarina, SC, Brazil, on a Typic Hapludult, soil was sampled (layers 0-2.5, 2.5-5, 5-10, 10-15, 15-20 and 20-30 cm) after the following fertilization treatments: no pig litter fertilization, pig slurry application and pig manure application. In this period, 694 and 1,890 kg P2O5 ha-1 were applied in the treatments with pig slurry and pig manure, respectively. The P content was determined, based on Mehlich-1, anion exchange resin (AER), 0.01 mol L-1 CaCl2 and total P in the samples. The adsorption isotherm parameters were also determined by the Langmuir and Koski-Vähälä & Hartikainem models in the layers 0-2.5 and 20-30 cm. The application of 1,890 kg P2O5 ha-1 in the form of pig manure led to P accumulation, as evidenced by Mehlich-1, down to a depth of 15 cm, by AER and 0.01 mol L-1 CaCl2 down to 20 cm and by total P to 30 cm. After application of 1,890 kg P2O5 ha-1 in the form of pig manure, the values of maximum P adsorption capacity were lowest in the deepest layer (20-30 cm), indicating the occupation of part of the adsorption sites of the particles. The application of swine manure to the soil over eight years increased the P quantity in the soil solution of the surface layer, indicating environmental contamination risk for surface and subsurface waters.

Accumulation of phosphorus fractions and contamination potential in vineyard soils in the southern region of the state of Santa Catarina, Brazil

In vineyards, if phosphate is applied both before planting and at intervals during growth without consideration of technical criteria, the soil P fractions may be increased and their proportions altered. This study was carried out to evaluate the accumulation of P fractions and the parameters of the adsorption isotherm in a sandy Typic Hapludalf soil in vineyards with a history of successive and excessive phosphate fertilization. In December 2010, two vineyards were selected, one 4 and the other 15 years old, in Urussanga, State of Santa Catarina (Brazil). Three trenches were dug in each area and soil was collected from the 0-5, 5-10 and 10-20 cm depth ranges. The soil samples were dried in a forced-air oven, sieved and subjected to chemical analyses, P chemical fractionation and P adsorption isotherms. Excessive phosphate fertilization, before and during cultivation, particularly in the older vineyard and, consequently, with a longer history of phosphate fertilization, increased the inorganic P concentrations to the depth of 20 cm, especially in labile fractions extracted by anion exchange resin and NaHCO3 in the non-labile fraction, as well as in the non-labile fraction extracted by 1.0 mol L-1 HCl. The application of phosphate fertilizers and the long cultivation period increased the P levels in the organic labile fraction extracted by 0.5 mol L-1 NaHCO3, and especially in the moderately labile fraction extracted by 0.1 and 0.5 mol L-1 NaOH. Phosphate fertilization of older vineyards, i.e., cultivated for 15 years, increased the amounts of P desorbed in water, indicating a risk of contamination of surface waters and groundwater. The phosphate fertilization before planting, without considering the results of soil analysis, and during cultivation, disregarding the results of soil analysis, leaf analysis and expected yield, led to a reduction in the maximum P adsorption capacity in the 0-5 cm layer of vineyard 2, indicating saturation of part of the reactive particle adsorption sites.

Modificação do polímero condutor polianilina para uso como trocador catiônico

This article reports the use of polyaniline (PAni), chemically and electrochemically synthesized, for copper removal from aqueous solutions. PAni films were electrodeposited on reticulated vitreous carbon (RVC). In all cases, p-toluenesulfonate anion (PTS-) was used as the dopant to obtain cation exchange properties. RVC/PAni showed no expressive copper removal due to the small amount of polymer in the film. Chemically synthesized PAni-PTS- was obtained in its reduced form (leucoesmeraldine). PAni degraded at neutral pH but remained stable at low pH, showing a very high ion-exchange capacity, which is superior to those observed for commercial resins.

The Li+, Na+ and K+ ion exchange reaction process on the surface of mixed oxide SiO2/TiO2/Sb2O5 surface prepared by the sol-gel processing method

The porous mixed oxide SiO2/TiO2/Sb2O5 obtained by the sol-gel processing method presented a good ion exchange property and a high exchange capacity towards the Li+, Na+ and K+ ions. In the H+/M+ ion exchange process, the H+ / Na+ could be described as presenting an ideal character. The ion exchange equilibria of Li+ and K+ were quantitatively described with the help of the model of fixed tetradentate centers. The results of simulation evidence that for the H+ / Li+ exchange the usual situation takes place: the affinity of the material to the Li+ ions is decreased with increasing the degree of ion exchange. On the contrary, for K+ the effects of positive cooperativity, that facilitate the H+ / K+ exchange, were revealed.

Soil chemical properties affected by cover crops under no-tillage system

The use of cover crops in no-tillage systems (NTS) can significantly improve the soil's fertility. Thus, a study was performed to evaluate changes in chemical properties of soil caused by cover crops in a no-tillage system. The field experiment consisted of the following crop rotation: cover crops/rice/cover crops/rice. The experimental design was in randomized blocks with three replications. Treatments consisted of four cover crops (Brachiaria brizantha(Hochst. ex A. Rich.) Stapf. cv. Marandu, Brachiaria ruziziensis R. Germ. and C.M. Evrard, Panicum maximum Jacq. cv. Colonião, and Pennisetum glaucum(L.) R. Br. cv. BN-2) and fallow (control treatment). Soil samples were collected at the beginning of the summer crop in Oct 2007, Oct 2008 and Oct 2009 at 0-5 cm soil depth. The use of cover crops provided for a significant increase in the level of nutrients, soil organic matter, cation exchange capacity, and base saturation in the soil. Soil fertility improved from the first to second year with the growing of cover crops. The soil under cover crops P. glaucum, B. ruziziensis, and B. brizantha showed higher fertility than the area under fallow.

Gradual correction of phosphorus availability in the no-tillage system

ABSTRACT In areas cultivated under no-tillage system, the availability of phosphorus (P) can be raised by means of the gradual corrective fertilization, applying phosphorus into sowing furrows at doses higher than those required by the crops. The objective of this work was to establish the amount of P to be applied in soybean crop to increase content of P to pre-established values at the depth of 0.0 to 0.10 m. An experiment was carried out on a clayey Haplorthox soil with a randomized block experimental design distributed in split-split plot, with four replications. Two soybean crop systems (single or intercropped with Panicum maximum Jaca cv. Aruana) were evaluated in the plots. In addition, it was evaluated four P levels (0, 60, 120 and 180 kg ha-1 P2O5) applied in the first year in the split plots; and four P levels (0, 30, 60 and 90 kg ha-1 P2O5) applied in the two subsequent crops in the split-split plot. Contents of P were extracted by Mehlich-1 and Anion Exchange Resin methods from soil samples collected in the split-split plot. It was found that it is necessary to apply 19.4 or 11.1 kg ha-1 of P2O5, via triple superphosphate as source, to increase 1 mg dm-3 of P extracted by Mehlich-1 or Resin, respectively, in the 0.0 to 0.10 m layer of depth. The soil drain P character decreases as the amount of this nutrient supplied in the previous crops is increased.

Environmental determinants for natural regeneration of gallery forest at the Cerrado/Amazonia boundaries in Brazil

Natural regeneration and structure and their relationship to environmental variables were studied in three sections of a gallery forest, in Eastern Mato Grosso, Brazil (14º43′S and 52º21′W). The assumption was that natural regeneration is constrained by environmental determinants at all stages of development of the tree community. The objective was to analyse the forest structure and to verify the relationship between species distribution and abundance at different stages of regeneration and environmental variables. In each section, 47 contiguous (10x10m) permanent plots were established to sample trees (gbh≥15cm), following a systematic design. Seedlings (0.01 to 1m height), saplings (1.01 to 2m) and poles (from 2.01m height to gbh<15cm) were sampled in sub-plots of 1x1m, 2x2m and 5x5m, respectively. In each plot, soil properties, gaps projection, bamboos, rocky cover, declivity and depth of ground watertable were determined. The relationships between the environmental variables with trees and seedling communities were assessed by canonical correspondence analysis. In spite of the sections being near to each other, they presented large differences in floristics, structure and site conditions. The forest soil presented a low cation exchange capacity and a high level of Al saturation. The occurrence of bamboos and gaps and the depth of ground watertable limited the occurrence of poles and trees. The high degree of structural heterogeneity for each regeneration category was related primarily to a humidity gradient; but soil fertility (Ca+Mg) was also a determinant of seedling and sapling communities.

Litosol: suas características e provável gênese

Some of the characteristics peculiar to Litosois are discussed based on data published on Litosois occurring in the States of São Paulo and Paraná. Litosois are the first stages of development of a soil. Litosois probably originate through the exposure of the rockbed caused by an excessive relief. Rock weathering processes are intensive, prevailing those of chemical nature rather than those processes in which physical phenomena dominate. The A horizon has a high organic matter content (2% to 10%). Silt and clay amount to approximately 50% of the fine earth in the A horizon, with the exception of Litosois originated from sandstone and granite. The SiO2/Al2O3 relationship of the soil's colloidal complex and the clay's cation exchange capacity indicate that it is quite probable the presence of 2:1 type clay in Litosois derived from basic rocks.

Sampling strategies for tropical forest nutrient cycling studies: a case study in São Paulo, Brazil

The precise sampling of soil, biological or micro climatic attributes in tropical forests, which are characterized by a high diversity of species and complex spatial variability, is a difficult task. We found few basic studies to guide sampling procedures. The objective of this study was to define a sampling strategy and data analysis for some parameters frequently used in nutrient cycling studies, i. e., litter amount, total nutrient amounts in litter and its composition (Ca, Mg, Κ, Ν and P), and soil attributes at three depths (organic matter, Ρ content, cation exchange capacity and base saturation). A natural remnant forest in the West of São Paulo State (Brazil) was selected as study area and samples were collected in July, 1989. The total amount of litter and its total nutrient amounts had a high spatial independent variance. Conversely, the variance of litter composition was lower and the spatial dependency was peculiar to each nutrient. The sampling strategy for the estimation of litter amounts and the amount of nutrient in litter should be different than the sampling strategy for nutrient composition. For the estimation of litter amounts and the amount of nutrients in litter (related to quantity) a large number of randomly distributed determinations are needed. Otherwise, for the estimation of litter nutrient composition (related to quality) a smaller amount of spatially located samples should be analyzed. The determination of sampling for soil attributes differed according to the depth. Overall, surface samples (0-5 cm) showed high short distance spatial dependent variance, whereas, subsurface samples exhibited spatial dependency in longer distances. Short transects with sampling interval of 5-10 m are recommended for surface sampling. Subsurface samples must also be spatially located, but with transects or grids with longer distances between sampling points over the entire area. Composite soil samples would not provide a complete understanding of the relation between soil properties and surface dynamic processes or landscape aspects. Precise distribution of Ρ was difficult to estimate.

Variability of apparently homogeneous soilscapes in São Paulo state, Brazil: I. spatial analysis

The spatial variability of strongly weathered soils under sugarcane and soybean/wheat rotation was quantitatively assessed on 33 fields in two regions in São Paulo State, Brazil: Araras (15 fields with sugarcane) and Assis (11 fields with sugarcane and seven fields with soybean/wheat rotation). Statistical methods used were: nested analysis of variance (for 11 fields), semivariance analysis and analysis of variance within and between fields. Spatial levels from 50 m to several km were analyzed. Results are discussed with reference to a previously published study carried out in the surroundings of Passo Fundo (RS). Similar variability patterns were found for clay content, organic C content and cation exchange capacity. The fields studied are quite homogeneous with respect to these relatively stable soil characteristics. Spatial variability of other characteristics (resin extractable P, pH, base- and Al-saturation and also soil colour), varies with region and, or land use management. Soil management for sugarcane seems to have induced modifications to greater depths than for soybean/wheat rotation. Surface layers of soils under soybean/wheat present relatively little variation, apparently as a result of very intensive soil management. The major part of within-field variation occurs at short distances (< 50 m) in all study areas. Hence, little extra information would be gained by increasing sampling density from, say, 1/km² to 1/50 m². For many purposes, the soils in the study regions can be mapped with the same observation density, but residual variance will not be the same in all areas. Bulk sampling may help to reveal spatial patterns between 50 and 1.000 m.