In Ecuador, DINAGE (known today as the Servicio Geológico Nacional) and the German Federal Institute for Geosciences and Natural Resources have discovered a huge allophane deposit covering an area of >4000 km2. This study presents the results from an investigation of a 16-m thick vertical sequence from this deposit, supposedly the weathering product of two different volcanic ash deposits. In particular, the distribution of alkali metals within the uppermost layer indicates that the weathering process is still ongoing.According to the mineralogical composition, an allophane-rich layer (allophane facies) could be distinguished from the underlying halloysite-rich layer (halloysite facies). A 2-m thick transition zone is characterized by the presence of gibbsite and intermediate specific surface area values. Only a few imogolite fibers could be identified (by scanning electron microscopy), indicating the dominance of allophane over imogolite in the allophane facies. Single allophane particles were investigated by atomic force microscopy, though this method was less accurate than transmission electron microscopy with respect to the determination of the primary particle diameter. Carbon isotope analysis (14C) suggested an age of ∼20,000 y for the allophane layer.Within the allophane facies, a 4-m thick layer occurs containing 70–80 wt.% allophane with an N2-BET specific surface area of >300 m2/g. Based on infrared and energy-dispersive X-ray diffraction measurements, an Al/Si ratio of 1.3–1.4 was established for this allophane, which is between Al-rich and Si-rich allophane. The allophane layer may be of economic value due to the large allophane content, the small amount of organic matter, and the significant thickness of the deposit.
Allophane is a very fine-grained clay mineral which is especially common in Andosols. Its importance in soils derives from its large reactive surface area. Owing to its short-range order, allophane cannot be quantified by powder X-ray diffraction (XRD) directly. It is commonly dissolved from the soil by applying extraction methods. In the present study the standard extraction method (oxalate) was judged to be unsuitable for the quantification of allophane in a soil/clay deposit from Ecuador, probably because of the large allophane content (>60 wt.%). This standard extraction method systematically underestimated the allophane content but the weakness was less pronounced in samples with small allophane contents. In the case of allophane-rich materials, the Rietveld XRD technique, using an internal standard to determine the sum of X-ray amorphous phases, is recommended if appropriate structural models are available for the other phases present in the sample. The allophane (+imogolite) content is measured by subtracting the amount of oxalate-soluble phases (e.g. ferrihydrite). No correction would be required if oxalate-soluble Fe were incorporated in the allophane structure. The present study, however, provides no evidence for this hypothesis. Mössbauer and scanning electron microscopy investigations indicate that goethite and poorly ordered hematite are the dominant Fe minerals and occur as very fine grains (or coatings) being dispersed in the cloud-like allophane aggregates.Allophane is known to adsorb appreciable amounts of water, depending on ambient conditions. The mass fraction of the sample attributed to this mineral thus changes accordingly; the choice of a reference hydration state is, therefore, a fundamental factor in the quantification of allophane in a sample. Results from the present study revealed that (1) drying at 105ºC produced a suitable reference state, and (2) water adsorption has no effect on quantification by XRD analysis.
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