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| Author(s): |
Marcelo Eduardo Alves
Total Authors: 1
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| Document type: | Doctoral Thesis |
| Press: | Piracicaba. |
| Institution: | Universidade de São Paulo (USP). Escola Superior de Agricultura Luiz de Queiroz (ESALA/BC) |
| Defense date: | 2002-04-09 |
| Examining board members: |
Arquimedes Lavorenti;
Luis Reynaldo Ferracciu Alleoni;
Leonardo Theodoro Bull;
Jose Carlos Casagrande;
Pablo Vidal Torrado
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| Advisor: | Arquimedes Lavorenti |
| Abstract | |
The present research aimed at studying the relationships between the mineralogical composition of representative soils from São Paulo State and some of their electrochemical properties, particularly the point of zero salt effect (PZSE) and the anion exchange capacity (AEC). Additionally, it was given special attention to the presence of permanent negative charges in those soils, whose magnitudes were also associated with the mineralogical composition of their clay fractions, which was evaluated by using qualitative and semiquantitative approaches. Besides the above mentioned electrochemical properties, the adsorption and desorption of sulfate, the main inorganic form of sulfur found in soils under aerobic conditions, were studied in order to associate the representative indexes of these phenomena with mineralogical, chemical and electrochemical soil properties. Initially, samples collected in subsurface layers of fifteen soils situated in different regions of São Paulo State were highly characterized as for their mineralogical, chemical and electrochemical properties Besides these evaluations, the soil samples were used as adsorbents in studies of sulfate adsorption and desorption reactions. After this, and through the statistical analyses of data, it was aimed at verifying the individual relationships of the evaluated properties with the PZSE, AEC, sulfate adsorption and desorption indexes. The experimental results obtained during the evaluation of the PZSE values of samples, gave us the possibility of the development of one software for mathematical manipulation of them in order to allow the analytical determination of the above mentioned electrochemical property. The software was evaluated through the analyses of potentiometric titration data from experiments of other authors. The results showed very good agreement between PZSE values calculated by the software and those determined by the authors. By this reason, this approach can be considered very useful for this determination. In relation to surface charges, it was possible to verify reasonable amounts of permanent negative charges in evaluated soil samples and good correspondence of them with soil mineralogical properties. However, more studies are necessary in order to compare the results of cesium adsorption method, employed for this determination in the present research, with ones from other methodologies. The determination of cation exchange capacity (CEC) values through different approaches have shown that the soil samples with acric character were among the ones that present the biggest discrepancies. These results suggest the necessity of reevaluation for the usual methods employed to measurements of CEC values in soils with acric character. The methods used in this research allowed us to verify that the contents of amorphous aluminum oxides in the clay fraction present direct associations with PZSE and AEC values determined in soil samples. In relation to sulfate adsorption, it was also observed the positive effect of amorphous aluminum oxides on the sulfate adsorptive capacities of the studied soils. In the same way, the content of above mentioned oxides present significative and direct correlation with the affinity of surfaces by sulfate ions. The gibbsite and amorphous aluminum oxides are the clay fraction constituents associated with the restriction to sulfate desorption in evaluated soil samples; on the other hand, the transference of sulfate ions from solid surfaces to soil solutions was favored by the high kaolinite contents. These data suggest that the use of gypsum in kaolinitic soils with low contents of oxides must be done with more criteria.Considering the soil properties whose determinations are not time consuming, the pH values evaluated in suspensions of soil-NaF 1 mol L -1 solution (pH NaF) presented very good associations with the aluminum oxides contents of soil samples and, by this reason, it showed also significative correlations with soil sulfate adsorption capacity. These founds indicate that the pH NaF is a very promising index for the indirect evaluation of the anion retention capacity of samples from subsurface layers of tropical soils. Finally, the great number of non-significative correlations verified in this research between crystalline iron oxides (hematite and goethite) contents and electrochemical properties or sulfate adsorption/desorption indexes suggest the existence of non-systematic variations in their intrinsic properties. So, it is very important the establishment of new researches with the objective of acquiring more information about the influence of morphology and crystals size and crystallinity of these adsorbents on their electrochemical properties and adsorptive capacities. These considerations are also applied to gibbsite, since there is no information about this topic associated to this mineral. (AU) | |