Cristallochemical characterization of synthetic Zn-substituted maghemites (g-Fe2-xZn xO3)

Maghemite (g-Fe2O3) is the most usually found ferrimagnetic oxide in red basalt-derived soils. The variable degrees of ionic substitution of Fe3+ for different metals (e.g. Ti4+, Al3+, Mg2+, Zn2+, and Mn2+) and non-metals in the maghemite structure influence some cristallochemical features of this iron oxide. In this study, synthetic Zn-substituted maghemites were prepared by co-precipitation in alkaline aqueous media of FeSO4.7H2O with increasing amounts of ZnSO4.7H2O to obtain the following sequence of Fe3+ for Zn2+ substitutions: 0.0, 0.025, 0.05, 0.10, 0.15, 0.20, and 0.30 mol mol-1. The objective of this work was to evaluate the cristallochemical alterations of synthetic Zn-substituted maghemites. The dark black synthetic precipitated material was heated to 250 °C during 4 h forming a brownish maghemite that was characterized by chemical analysis as well as X ray diffraction (XRD), specific surface area and mass-specific magnetic susceptibility. The isomorphic substitution levels observed were of 0.0013, 0.0297, 0.0590, 0.1145, 0.1764, 0.2292 and 0.3404 mol mol-1, with the formation of a series of maghemites from Fe2Zn0O3 to Fe(1.49)Zn(0.770)O3 . The increase in Fe3+ for Zn2+ substitution, [Zn mol mol-1] increased the dimension a0 of the cubic unit cells of the studied maghemites according to the regression equation: a0 = 0.8343 + 0.02591Zn (R² = 0.98). On the other hand, the mean crystallite dimension and mass-specific magnetic susceptibility of the studied maghemites decreased with increasing isomorphic substitution.

Lead and zinc in the structure of organic and mineral soil components

In addition to the more reactive forms, metals can occur in the structure of minerals, and the sum of all these forms defines their total contents in different soil fractions. The isomorphic substitution of heavy metals for example alters the dimensions of the unit cell and mineral size. This study proposed a method of chemical fractionation of heavy metals, using more powerful extraction methods, to remove the organic and different mineral phases completely. Soil samples were taken from eight soil profiles (0-10, 10-20 and 20-40 cm) in a Pb mining and metallurgy area in Adrianópolis, Paraná, Brazil. The Pb and Zn concentrations were determined in the following fractions (complete phase removal in each sequential extraction): exchangeable; carbonates; organic matter; amorphous and crystalline Fe oxides; Al oxide, amorphous aluminosilicates and kaolinite; and residual fractions. The complete removal of organic matter and mineral phases in sequential extractions resulted in low participation of residual forms of Pb and Zn in the total concentrations of these metals in the soils: there was lower association of metals with primary and 2:1 minerals and refractory oxides. The powerful methods used here allow an identification of the complete metal-mineral associations, such as the occurrence of Pb and Zn in the structure of the minerals. The higher incidence of Zn than Pb in the structure of Fe oxides, due to isomorphic substitution, was attributed to a smaller difference between the ionic radius of Zn2+ and Fe3+.

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.

Composição elementar do aerossol atmosférico na região central da Bacia Amazônica

The processes and sources that regulate the elemental composition of aerosol particles were investigated in both fine and coarse modes during the dry and wet seasons. One hundred and nine samples were collected from the biological reserve Cuieiras - Manaus from February to October 2008, and analyzed together with 668 samples that were previously collected at Balbina from 1998 to 2002. Particle induced X-ray emission technique was used to determine the elemental composition, while the concentration of black carbon was obtained from the measurement of optical reflectance. Absolute principal factor analysis and positive matrix factorization were performed for source apportionment, which was complemented with back trajectory analysis. A regional identity for the natural biogenic aerosol was found for the Central Amazon Basin and can be used in dynamical chemical region models.

Distyly and variation in floral traits in natural populations of Psychotria ipecacuanha (Brot.) Stokes (Rubiaceae)

Psychotria ipecacuanha is a perennial, medicinal herb that grows in clusters in the understory of humid, shady areas of the Atlantic Rain Forest of southeastern Brazil. The present study characterized the variation in floral traits among 35 clusters from three natural populations of this plant species. Field observations showed that the clusters are isomorphic, that is, a given cluster will either set long-styled or short-styled flowers. Stigmas and anthers are reciprocally placed in each morph, a dimorphism characteristic of distyly. The populations are isoplethic, that is, a given population exhibits an equilibrium 1:1 ratio of floral morphs. Morphometric analyses revealed that anther length, stigma length, corolla diameter, and pollen grain diameter were consistently greater in short-styled flowers, regardless of the population investigated. Significant differences for floral traits in the short-styled morph were found among populations. Floral traits in the long-styled morph also showed some significant differences among populations, but not for stigma height and corolla length. Controlled pollinations carried out in natural populations showed that fruit production was higher after inter-morph pollination. Nevertheless, observations of pollen tube growth in style, and also fruit production after spontaneous self-pollination and intra-morph pollination, indicated partial intramorph compatibility in this plant species.