Goethite and hematite variability via reductive dissolution in soils from tropical and subtropical regions

Iron oxides from 22 soil samples (19 from argillic B horizons; one from a plinthic B horizon; one from a cambic horizon and one from a C horizon) were subjected to selective dissolution with sodium dithionite-citrate-bicarbonate at 20 degrees C in time intervals of 5 to 3,840 minutes. Mean coherence lengths (MCL), specific surface area (SSA) and iron by aluminum substitution (Al3+-substitution) of goethite and hematite in untreated sub-samples and in selected sub-samples treated during selective dissolution were estimated by X ray diffraction analysis (XRD). The control of remaining goethite and hematite phases after each time interval of selective dissolution was carried out by differential X ray diffraction (DXRD). The crystal dissolution kinetics was described by segmentation of the iron dissolution curve as a time function at the intervals where dissolution occurred linearly. Dissolution rates of each linear segment were obtained by the angular coefficient of the straight line of each linear segment. In the latossolic goethitic samples, this methodology discriminated different phases of goethite (heterogeons populations) regarding Al3+-substitution, MCL and SSA, making possible to classify goethite stability degrees (low, medium, high, and very high stability). Goethite samples from young pedogenic environments and latossolic hematitic samples were characterized by higher crystal homogeneity, which were classified as being of low and medium stability. In goethitic samples, crystal proportion with high stability (high Al3+-substitution and crystallinity) in each population showed positive association with gibbisite proportion compared to caulinite in the samples. Hematite presented lower stability to dissolution reduction than goethite, except in goethite samples with low Al3+- substitution and low ASE. The characterization of heterogeneous goethite populations can increase the use of this oxide as indicator of pedogenic processes and contribute to a better understanding of the physical and chemical behavior of polygenetic soils.