Morphological, chemical and mineralogical characterization of some soils developed on hard carbonate rocks in Sardinia

This preliminary note considers 19 profiles of Sardinian soils developed on hard limestone, dolomitic limestone and dolomite of different age and territorial condition, reporting on the description of the profiles and their physical, chemical and mineralogical characteristics. The results indicate that the soils examined belong to xeric subgroups of three orders: Entisols, Inceptisols and Alfisols. All the profiles show a clay texture and the clayey constituents are related to the degree of soil evolution

Effects of Al substitution on goethite formation

Goethites containing up to 32.7 mole % Al were synthesized and characterized through diffractometry, spectrometry, DSC and chemical techniques. Results indicate that crystal growth was favoured or hindered depending on the percentage of aluminum incorporated into the structure. Goethites to which 5-10 mole % Al were initially added crystallized best, as shown by the highest crystallite dimensions calculated from X-ray and Mössbauer analyses, and by the lowest surface areas values. Over such substitution degree goethite crystallization was hindered and for sample synthesized in presence of 40 mole % Al the separation of a discrete amount of gibbsite and bayerite occurred. Both crystallinity and Al-substitution degree influenced the goethite dehydroxylation endothermic peak temperature playing a competitive action in the peak shift. In fact, the increase in the thermal stability induced by the presence of Al3+ ions into the structure was counteracted by the decrease due to the particle size reduction. The stabilizing effect of aluminum was confirmed by the oxalate treatment which removed from the Al-free sample a Fe amount higher than that from the sample containing about 20 mole % Al, although both had similar crystallinity

Role of the caffeic acid oxidation products on the iron mobilization at the soil-root interface

Previous results show that the reduction of Fe(III) by caffeiic acid (CAF) is strongly influenced by the pH of the reaction medium (DEIANA et al., 1995). In particular, it has been found that al pH > 3.8 the reducing activity of CAF towards the Fe(III) ions in solution is low, but it increases when Fe(III) is complexed as Fe(III)-polygalacturonate. The mobilization of the Fe(II) ions, which form upon the Fe(III) reduction, has been shown to depend mainly on the nature of the Fe(III)-polygalacturonate complexes (DEIANA et al., 1994a). In particular, it bas been observed a high redox activity of CAF towards Fe(III) when the metal ion is coordinated by the carboxilic groups of the macromolecule. The Fe(III) reduction has been found to decrease when an oxydrilic group was inserted in the Fe(III) coordination sphere. The Fe(II) produced partly diffuses into the external solution and partly is still strongly held by the polysaccharidic matrix. The oxidation of CAF by Fe(III) gives rise to the formation of products (OP) with different polymerization degree, some of which are similar to those found in natural systems (DEIANA et al., 1994b). In order to determine the role of these products in the Fe(III) reduction as well as in the mobilization of the Fe(II) produced it was set up an electrochemical method to synthetize these products (DEIANA et al., 1994b). Here are reported some results about the interaction which establish between the CAF oxidation products and iron in both oxidized and reduced form

Influenza dei metodi di estrazione e di purificazione sul dosaggio in HPLC degli idrossifenoli

Four different extraction methods were compard, in oder to optimize the HPLC separation and quantitation of hydroxyphenols in «Thymus capitatus». One method was not suitable for HPLC ansly,is, whereas the others partially destroyed the hydroxyphenols extracted from the plant. The Charpentier-Cowles me thod was, found the most effective allowing to analyse, in spite of the losses, most of the free phenolic acids and of those bounded extractable in hot acidic medium but not in ethanol. For the phenolics in free form a method whith recoverier greater than those obtained with Hagerman Nicholson and Horvat-Senter methods was developed

Electrochemical properties of Fe and Al hydroxides as affected by different supporting electrolytes

Potentiometric titration curves of Fe and Al hydroxides, carried out in presence of different electrolytes (KCI, Kbr, KI, KNO3, KCIO4) were elaborated by the Stern theory through a computered program. The zero points of charge (zpc), calculated from the intersection point of the titration curves at different ionic strenght, varied from pH 7.10 to pH 7.65 for Fe hydroxides and from pH 9.10 pH 9.45 for Al hydroxi des. For Fe compounds, a good match was found between the experimental values and those calculated by the Stern model. High deviations were observed only with KCIO4, in whose presence a lowering of the zpc was registered. Also in Al hydroxides the proposed model was not reliable below zpc, indicating that the surface interac tions are somewhat involved in specific adsorption phenomena

Evidence of potassium fixation through mono and divalent ion exchange

Mono and divalent cation exchange in some algerian major soil types was studied following empirical ap· proach. The reaction 2 Na-Soil + Ca2+ = Ca-Soil + 2 Na+ did not show complete reversibility possibly due to high Ca selectivity of soils. The soils exhibited divalent over monovalent ion affinity but for monovalent ion exchange the affinity in few cases remained almost the same. Gapon's equation did not seem to describe Ca-K exchange very satisfactorily because exchangeable potassium ratio (EKR) and potassium adsorption ratio (KAR) are not related linearly. The latter seems to be due to potassium fixing ten· dency of soils investigated

Describing the adsorption of potential determining ions on variable charge mineral surfaces

A computer program was developed to elaborate the titration curves of amphoteric surfaces according to the double layer theory. The zpc, identified from the intersection point of the titration curves carried out at different ionic strengths, fell at pH 3.15, 9.45 and 7.65 for Si, AI and Fe hydroxides, respectively. The Stern model described quite satisfactorily the relation between σ0 and ψ0. Some problem was presented by Si surfaces which were then treated by a different calculation procedure. The δ values, the Stern layer thickness, were very high for the SI surfaces and increased with decreasing ionic strength. A different behaviour was showed by AI and Fe hydroxides; in these cases δ values were very low and increased with increasing electrolyte concentration. These results were discussed in terms of surface structures and activity of the supporting electrolyte

Reduction of Cr(VI) by caffeic acid

In the soil-plant system, the Cr(VI) toxicity can be moderated through redox reactions involving phenolic substances. In such a context, we report the reducing activity of caffeic acid (CAF) towards Cr(VI) in aqueous phase. The redox reaction between Cr(VI) and CAF was studied as a function of both time and pH at different initial metal concentrations. The reaction was particularly effective at pH 2.5. The kinetic data indicate that the reaction proceeds through two steps: the first is faster and involves four electrons, the latter, which is slower, five electrons. The chromatograms evidence the formation of oxidation products (OP) with a different redox activity towards Cr(VI). A yield of Cr(III) equal to that obtained at pH 2.5 and pH 3.1 in about 7 and 25 h, respectively, was reached at pH 4.2 only after a much longer reaction time (50 h). At pH > 4.2 the reaction occurred even more slowly, and its kinetic trend was more and more difficult to study at pH values higher than 5.0 due to the formation of precipitates. Other phenolics investigated (o-, m-, p-coumaric acids) showed a reducing activity negligible compared to that of CAF: about 30% of p-coumaric acid was oxidized at pH 2.5 only after two months of reaction

Oxidation of caffeic acid by Fe(III) trapped in a Ca-polygalacturonate network

With the aim to verify if Fe(III) ions accumulated in a network of Ca-polygalacturonate (PGA) may promote the oxidation of caffeic acid (CAF) the interaction at pH 5.0 between CAF and Fe(III) ions trapped in a PGA was studied. The sorption kinetics evidenced a great affinity of CAF towards the Fe-PGA matrix. Chromatographic tests showed that the interaction leads to the formation of products which can be considered as CAF oligomers characterized by FT-IR spectra similar to those of natural humic acids. Tests carried out under nitrogen suggest that at pH 5.0 oxygen does not affect the nature of these oxidation products. Oxygen was hypothesized to exert a direct action on the redox process by oxidizing the Fe(II) ions, produced by oxidation of CAF, to Fe(III) thus regenerating oxidizing sites. A possible mechanism of formation of the polymers was proposed that implies that the CAF oxidation leads to highly reactive species such as semiquinones which give rise, by an oxidative coupling reaction, to the formation of oligomers that can aggregate through secondary bonds to produce more complex structures as those that characterize humic acids

Possibile role of the polyuronic components in accumulation and mobilization of iron and phosphate at the soil-root interface

With the aim to investigate the role of the polyuronic components in the accumulation of iron and phosphate at the soil-root interface, the interactions of Ca-polygalacturonates (PGAs) with Fe(III) and P ions and of Fe(III)-Ca-polygalacturonates (Fe-PGAs) with P ions were studied at pH 4.7. The role of citric, malic and pyruvic acids in the mobilization of Fe(III) and P, in the presence and absence of Ca(II) 2.5 mM, was also investigated. The sorption kinetics evidenced that P diffuses freely through the calcium polysaccharidic matrix whereas Fe(III) accumulates as an hydroxypolymer. The sorption kinetics of P by the Fe-PGA indicated that the amount of P sorbed increases with increasing its initial concentration up to a constant value equal to 0.98 μmol/3.87 μmol mg-1 of Fe(III)-polymer trapped. The FT-IR spectra of the P-Fe-PGA systems, show bands attributable to P-O(H) stretching vibrations. The study of systems with a constant initial P amount and varying Fe(III) amounts allowed to hypothesize that phosphate settles down inside holes formed by the carboxylate groups of galacturonic units. Citric and malic acids showed to be active in the mobilization of both Fe and P whereas pyruvic acid appeared inactive