Studies on the acid activation of Brazilian smectitic clays

Fuller's earth and acid activated smectitic clays are largely used as bleaching earth for the industrial processing of vegetable, animal and mineral oils and waxes. The paper comments about the nomenclature used for these materials, the nature of the acid activation of smectitic clays (bentonites), activation laboratory procedures and presents a review of the acid activation of bentonites from 20 deposits from several regions of Brazil. The activated clays were tested and show good decolorizing power for soybean, castor, cottonseed, corn and sunflower oils.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Nanoporous materials: pillared clays and regular silicas as an example of synthesis and their porosity characterization by X-ray diffraction

Because of their practical applications, porous materials attract the attention of undergraduate students in a way that can be used to teach techniques and concepts in various chemistry disciplines. Porous materials are studied in various chemistry disciplines, including inorganic, organic, and physical chemistry. In this work, the syntheses of a microporous material and a mesoporous material are presented. The porosity of the synthesized materials is characterized by X-ray diffraction analysis. We show that this technique can be used to determine the pore dimensions of the synthesized materials.

Effect of modified clays on the structure and functional properties of biofilms produced with zein

The purpose of this study was to evaluate changes in the structure and some functional properties of biofilms added with modified clays (Cloisite® 15A and Cloisite® 30B) prepared by the casting method. The analysis of the microstructure of the films, scanning electron microscopy (SEM), Optical microscopy (MO), and Infrared Spectroscopy (FTIR) indicated that the addition of clay in the films resulted in the formation of a heterogeneous microstructure, microcomposite or tactoid. Due to the formation of a microcomposite structure, functional properties of the films added with both clays such as opacity, solubility, and permeability to water vapor (PVA), were not better than those of the control film. Thus, it was concluded that although it is possible to produce a film added with modified clays using the casting method, it was not possible to obtain intercalation or exfoliation in a nanocomposite, which would result in improved functional properties.

Hydraulic conductivity in response to exchangeable sodium percentage and solution salt concentration

Hydraulic conductivity is determined in laboratory assays to estimate the flow of water in saturated soils. However, the results of this analysis, when using distilled or deionized water, may not correspond to field conditions in soils with high concentrations of soluble salts. This study therefore set out to determine the hydraulic conductivity in laboratory conditions using solutions of different electrical conductivities in six soils representative of the State of Pernambuco, with the exchangeable sodium percentage adjusted in the range of 5-30%. The results showed an increase in hydraulic conductivity with both decreasing exchangeable sodium percentage and increasing electrical conductivity in the solution. The response to the treatments was more pronounced in soils with higher proportion of more active clays. Determination of hydraulic conductivity in laboratory is routinely performed with deionized or distilled water. However, in salt affected soils, these determinations should be carried out using solutions of electrical conductivity different from 0 dS m-1, with values close to those determined in the saturation extracts.

Rapid assessment of fruit-color selection by birds using artificial fruits at local scale in Central Amazonia

Modeling clays have been used in several ecological experiments and have proved to be an important tool to variables control. The objective of our study was to determine if fruit color in isolated and grouped displays influences the fruit selection by birds in the field using artificial fruits. Data were collected in six plots distributed homogeneously in 3 km long trails with a minimum distance of 0.5 km. We used a paired experimental design to establish our experiments, so that all treatments were available to the local bird community in each plot. Overall, red was more pecked than brown and white. Isolated red and brown displays were significantly more pecked than others display. Even though our study was conducted in small spatial scales, artificial fruits appeared to be efficient in register fruit consumption attempts by bird. Although inconclusive about selective forces that sharp the dynamics of fruit color polymorphisms and choice by frugivorous birds, our findings corroborate recent studies wherein birds showed preferences by high- over low-contrast fruit signals.

Genesis and classification of Oxisols in a highland toposequence of the upper Jequitinhonha Valley (MG)

The Brazilian System of Soil Classification (SiBCS) is a taxonomic system, open and in permanent construction, as new knowledge on Brazilian soils is obtained. The objective of this study was to characterize the chemical, physical, morphological, micro-morphological and mineralogical properties of four pedons of Oxisols in a highland toposequence in the upper Jequitinhonha Valley, emphasizing aspects of their genesis, classification and landscape development. The pedons occupy the following slope positions: summit - Red Oxisol (LV), mid slope (upper third) - Yellow-Red Oxisol (LVA), lower slope (middle third)- Yellow Oxisol (LA) and bottom of the valley (lowest third) - "Gray Oxisol" ("LAC"). These pedons were described and sampled for characterization in chemical and physical routine analyses. The total Fe, Al and Mn contents were determined by sulfuric attack and the Fe, Al and Mn oxides in dithionite-citrate-bicarbonate and oxalate extraction. The mineralogy of silicate clays was identified by X ray diffraction and the Fe oxides were detected by differential X ray diffraction. Total Ti, Ga and Zr contents were determined by X ray fluorescence spectrometry. The "LAC" is gray-colored and contains significant fragments of structure units in the form of a dense paste, characteristic of a gleysoil, in the horizons A and BA. All pedons are very clayey, dystrophic and have low contents of available P and a pH of around 5. The soil color was related to the Fe oxide content, which decreased along the slope. The decrease of crystalline and low- crystalline Fe along the slope confirmed the loss of Fe from the "LAC". Total Si increased along the slope and total Al remained constant. The clay fraction in all pedons was dominated by kaolinite and gibbsite. Hematite and goethite were identified in LV, low-intensity hematite and goethite in LVA, goethite in LA. In the "LAC", no hematite peaks and goethite were detected by differential X ray diffraction. The micro-morphology indicated prevalence of granular microstructure and porosity with complex stacking patterns.. The soil properties in the toposequence converged to a single soil class, the Oxisols, derived from the same source material. The landscape evolution and genesis of Oxisols of the highlands in the upper Jequitinhonha Valley are related to the evolution of the drainage system and the activity of excavating fauna.

Redox index of soil carbon stability

As an alternative to the relatively complex and expensive spectroscopic methods, the redox properties of humic acids, determined by potentiometric titrations, have been used to evaluate the stability of soil organic C. The objective of the present study was to establish a Redox Index of C Stability (RICS) and to correlate it with some properties of the humic acids extracted from different modal soils in Brazil (distinct weathering stages or management) to facilitate system comparison. The RICS was efficient for soil comparison and variations were comparable to those of the chemical and spectroscopic methods used for humic acid characterization. The values of soil pH, point of zero salt effect, sum of bases, exchangeable Ca content, weathering index, as well as the humic acid O/C ratio, quinone and semiquinone free radical contents, aromatic C and fluorescence intensity were closely related with the RICS. The RICS was higher in less weathered soils, with more active clays and higher fertility. The RICS values of soils under long-term sugarcane management were ranked in decreasing order: unburned, burned with vinasse, burned without vinasse.

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.

Effect of soil interacting herbicides on soybean nodulation in Balcarce, Argentina

Two trials were performed in Balcarce, Argentina (37° 45' LS; 58° 18' LW) during 1993-94, to assess the effect of eight herbicides applied individually or in tank mixtures, on nodule number, nodule dry weight, seed yield and N percent in seed in soybean Asgrow 3205, inoculated with Bradyrhizobium japonicum CB 1809. Individual herbicides and doses in kg ha-1 of a.i. were metribuzin (0.48), acetochlor (0.90), metolachlor (1), flumioxazin (0.075), trifluralin (0.96), imazaquin (0.20), imazethapyr (0.10) and chlorimuron ethyl (0.0125). The mixtures were metribuzin+acetochlor (0.48+0.9), flumioxazin+acetochlor (0.075+0.9), imazaquin+acetochlor (0.2+0.9), metribuzin+metolachlor (0.48+1.92), and flumioxazin+ metolachlor (0.075+1.92). A control treatment without herbicides was included. Both trials were laid out as randomized complete blocks with four replicates, on a loam illitic thermic petrocalcic Paleudoll, 5.7% organic matter (OM), 25% clay, 30.4 cmol kg-1 CEC. Nodules were sampled at V2 (second node), V6 (sixth node) and R5 (beginning seed) growth stages. Herbicides did not significantly affect the beginning of nodulation or nodule number and mass at R5, not either grain yield or N accumulation. This indicates lack of interference between soil interacting herbicides and N fixation in the high organic matter, loam soils of SE Buenos Aires province, even though a tendency in less number and dry weight of nodules was evident at the two latter growth stages.

Migration of dissolved organic carbon in biochars and biochar-mineral complexes

The objective of this work was to determine the contribution of dissolved organic carbon (DOC) from a biochar mineral complex (BMC), so as to better understand the interactions between DOC, biochar, clay, and minerals during thermal treatment, and the effects of BMC on amended soils. The BMC was prepared by heating a mixture of a H3PO4-treated saligna biochar from Acacia saligna, clays, other minerals, and chicken manure. The BMC was applied to a sandy loam soil in Western Australia, where wheat was grown. Liquid chromatography-organic carbon detection (LC-OCD) tests were carried out on water extracts from the untreated biochar, the BMC, the BMC-amended soil, and on a control soil to measure the DOC concentration. LC-OCD tests provide a fingerprint of the DOC, which allows the fractions of DOC to be determined. Thermal processing enhanced the reaction of the A. saligna biochar with manure, clays and minerals, and affected the distribution of the DOC fractions. Notably, the process leads to immobilization of hydrophobic DOC and to an increase in the concentration of low-molecular-weight neutrals in the BMC. The application of the BMC to soil increases the DOC in the amended soil, especially the biopolymer fraction.

Hidróxidos duplos lamelares: síntese, estrutura, propriedades e aplicações

The layered double hydroxides, known as anionic clays and represented by the general formula [M2+1-x M3+x (OH) 2]x+ Am-x/m·nH 2O, are a group of materials which are of much interest currently. They present a variety of potential applications as adsorbents, catalysts and catalyst support, ion-exchangers, antacids and as a polymer stabilizer. It is possible to obtain a broad variety of layered double hydroxides (LDHs), depending on the identity and ratio of the cations M2+ and M3+, as well as the interlamelar anion. The aim of this review is to give out some information about this class of materials, concerning to the synthesis, characterization, properties and applications.

Argilas pilarizadas - uma introdução

The synthesis, characterization and some applications in catalysis of pillared clays are described at an introductory level. The use of x-ray diffraction, surface area measurements, thermal analysis, IR spectrophotometry and solid-state NMR in the characterization of pillared clays is briefly discussed. Pillarization followed by doping or introduction of metal clusters into clays could lead to the development of selective heterogeneous catalysts.

Termoquímica na Unicamp: depoimento sobre uma jornada de 25 anos

This article describes the progress of a group of investigation on thermochemistry, which started in 1972. A homemade calorimeter was employed to provide quantitative support to the information on interative effect between lanthanide cations and halides or pseudohalides, in non-aqueous solvents, previously derived from conductometric titrations. However, the features of this instrument were not able to detect the thermal effects. Therefore, the great input to the group came from the acquisition of an LKB commercial apparatus, by the University in 1975. Considering the historical development of the coordination chemistry in Brazil, which was previously dedicated to strutural features of adducts, without focusing the energetic envolved in any coordinationcompound. Since starting the thermochemistry study, numerous masters and doctoral thesis covering more than a hundred adducts and a reasonable number of chelates, were presented systematizing data in order to understand the behavior of this kind of coordination compounds (C. Airoldi and A. P. Chagas, Coord. Chem. Rev. 1992, 119, 29). This knowledge enabled an extension of the study to include some heterogeneous systems formed by natural or synthetic materials like immobilized silica gel, lamellar phosphate, phosphonate or sulphate compounds, clays, polysaccharides, chrysotile, soils, etc. Many students are now engaged as staff members in Universities, Research Instituitions or other private institutions, developing many activities. Due to a multiplying effect on the formation of researchers, the group is now reaching the fourth generation.