Abstract: Chilean soils derived from volcanic ashes are a natural source of iron oxides. Due to their properties, mineralogy, and surface characteristics, iron oxides from Chilean soils are potential candidates for technological applications such as heterogeneous catalysis. However, before a direct application in catalysis, pre-treatment methods are necessary to concentrate iron oxides from bulk volcanic soils. Here, we provide a comprehensive review of pre-treatment strategies for iron oxide concentration including physical separation and selective chemical dissolutive methods for application in catalytic processes, such as the water gas shift (WGS) and Fenton reactions. For preparation of WGS catalyst from volcanic soils, thermal treatment has been demonstrated to be effective, yielding enhanced results for Andisols compared to Ultisols. Based on mineralogical characterisation, it seems that WGS reaction efficiency depends on mineralogical phase shift and the changes of Fe2+/Fe3+ ratio, produced through heating. In addition, Ultisols have shown as efficient catalysts in Fenton and Fenton-like processes, after application of physical and chemical pre-treatments to different size-fractions of the soil sample, improving the yield performance of catalysts. Magnetic separates from the Ultisol sand fraction (compared to the silt+clay fractions) demonstrate the best catalytic performance as Fenton reagent due to their natural magnetite and titanomagnetite content. Application of NaOH selective dissolutive treatment to silt+clay fraction of volcanic soils also produces Fenton and Fenton-like catalyst with improved performance. Our review indicates that catalytic performance can be explained not only by the iron oxide mineral content but also by their characteristics and magnetic properties. The application of the appropriate physical and chemical pre-treatment methods can modulate and enhance the catalytic capabilities of iron oxides from volcanic soils.

On this work, the iron oxide mineralogy of Chilean volcanic ashes derived soils have been reviewed, emphasizing on new finding linked to the application of Mössbauer spectroscopy. It has been established that free iron oxide layer contributes with positive variable surface charge to the clay-size soil particle, at soil pH. However, the importance of such contribution seems to depend on the evolutionary stage of the different volcanic soil orders, which defines the crystalline degree of their iron oxide contents. Mössbauer spectroscopy complemented with different physical, chemical and instrumental techniques revealed key aspects of iron oxide mineralogy on these Chilean volcanic soils. For instance, results for Ultisol revealed that the evolution of the soil particle could be followed just analysing the main component of their iron oxide mineralogy; thus, the iron oxide mineralogy change when passing from the volcanic ashes (magnetite), to sand-size magnetic separates (partially-oxidized magnetite), to silt-size (strongly-oxidized magnetite), and finally to clay-size (maghemite) soil samples. Therefore, it would seem that physical weathering of the Ultisol produces smaller and more oxidized particles. On the other hand, the Andisol samples, a young volcanic soil compared to Ultisol, seems to have a constant iron oxide mineralogy among all its different particle size fractions: paramagnetic Fe2+ and Fe3+ species with low crystalline degree, the last one possibly assignable to a ferrihydrite-like mineral. Therefore, on the case of Andisols, it seems that the high contents of organic matter somehow prevent mineral evolution towards higher oxidation and more crystalline levels, in agreement with past studies.

AbstractEffects of different β-glucan concentrations in maize flour on the properties of frozen maize tortillas were evaluated. Masa (dough), pre-cooked (PTs), frozen (FTs), thawed (TTs), and cooked tortillas (CTs) were made and analyzed. Moisture content of masa and tortillas significantly decreased as β-glucan concentration increased; however, the water absorption capacity (WAC), ice melting enthalpy, and frozen water in FTs increased. Texture and color of the masa, PTs, and CTs as well as sensory analysis showed differences only between tortillas with 0% and 4% β-glucans. β-glucans did not affect the texture of CTs. Soluble fiber increased by over threefold and fivefold in tortillas with 2% and 4% β-glucans, respectively, than in those without β-glucans. This result was consistent with the observed structural changes in tortillas, showing an increase in high-fiber aggregates with increasing β-glucan concentration. Tortillas with 2% β-glucans showed acceptable physicochemical, functional, and sensory properties, but over three times the soluble fiber. Therefore, it is possible to obtain frozen tortillas with high fiber content and increase their shelf life for subsequent cooking while maintaining good properties.

Composites based on nanosized particles of magnetite and natural microsized zeolite were prepared and their efficiency to adsorb arsenate from aqueous systems was evaluated through kinetic data and adsorption isotherms, considering the proportion of magnetic iron oxide, composite:solution ratio and zeolite particle size. A well-crystallized nanomagnetite with an averaged particle size of 50 nm when supported on zeolite was obtained; the nanomagnetite enhances the arsenate adsorption of zeolite. The composite prepared with a nanomagnetite:zeolite mass ratio of 0.43:1 and 0.30:1 presented on zeolite milled 20 and 120 min, respectively, showed a similar adsorption capacity as that observed for pure magnetite. Supported nanomagnetite prevents risks of the nanoparticles contamination. The smaller the mean particle size of zeolite the lower the mass proportion of nanomagnetite in the composite required to reach the maximum adsorptive efficiency. Acidic conditions improve arsenate remotion, in agreement with the development of positive surface charge in the composite.

This research aimed to develop tortilla chips (TC) high in antioxidants from extruded and nixtamalized blue corn flours prepared with calcium hydroxide Ca(OH)2 and calcium lactate C6H10O6Ca. Tortilla chips were made with extruded flours [0.1% Ca(OH)2; 0.9% C6H10O6Ca; without calcium] and nixtamalized flours [1% Ca(OH)2; 2.95% C6H10O6Ca] using the frying process. Total anthocyanin, total phenolics content, antioxidant activity, color, texture, and oil content were determined. The color of tortilla chips from extruded flours (TCEF) showed high values of the parameters a* and b* indicating a reduction in the blue color. These color parameters were significantly different from those observed in tortilla chips from nixtamalized flours (TCNF), which tended to be more blue. The TCEF retained 15% anthocyanins, 34% phenolics, and 54% antioxidant activity. Pearson's correlation analysis indicated that anthocyanins and phenolics correlated significantly with antioxidant activity and color. TCEF with both calcium sources showed higher fracturability compared with that of TCNF. Oil absorption showed an opposite effect, with lower oil content in TCEF. Nixtamalization and extrusion with C6H10O6Ca resulted in flours and TC high in anthocyanins and antioxidant activity, representing an alternative production process for corn snack high in antioxidants.

The applicability of Rothmund-Kornfeld semiempirical approach to describe the binary cationic exchange equilibria K-Ca, K-Mg, Ca-Mg, and Ca-Zn carried out on variable surface charge synthetic aluminosilicates with and without coating (10 samples at all), was studied. The equivalent fraction of adsorbed ions and the equilibrium constan results were compared with those obtained by using the Gaines-Thomas approach, widely used and validated in cation exchange studies carried out on variable surface charge systems. The synthetic aluminosilicates (with and without coatings of iron oxides and organic matter) present a higher cationic exchange capacity (CEC) and K selectivity than similar soils and fractions. The equivalent fraction of adsorbed ions obtained by both aproaches correlates, r² ranges between 0.962-0.998. The natural logarithm of the thermodynamic constant determined by both approaches correlates with r²=0.992. The slight observed differences are probably due to integration errors associated with the resolution of equation involved in the Gaines-Thomas calculations. The Rothmund-Kornfeld model can be applied to the describe the binary cation exchange equilibria carried out on synthetic variable surface charge systems, with independence of K selectivity and CEC magnitude of samples.

Se estudió la aplicabilidad del modelo empírico de Rothmund-Kornfeld en el análisis de equilibrios de intercambio catiónico binarios K-Ca, K-Mg, Ca-Mg y Ca-Zn en muestras de aluminosilicatos sintéticos con y sin recubrimientos que presentan carga variable (10 diferentes equilibrios binarios en total). Los resultados se compararon con aquellos obtenidos a través del modelo termodinámico de Gaines-Thomas, ampliamente usado y validado para el estudio del equilibrio de intercambio catiónico en sistemas de carga variable. Los aluminosilicatos sintéticos son sistemas con mayor capacidad de intercambio catiónico (CIC) que los suelos y sus correspondientes fracciones, presentando asimismo una mayor selectividad por K. Los valores de fracciones equivalentes de los iones adsorbidos determinados por Gaines-Thomas y calculados por Rothmund-Kornfeld correlacionan entre si, con valores de r² en el rango 0.962-0.998 según sea el equilibrio binario considerado. Los logaritmos naturales de las constantes termodinámicas para los equilibrios binarios determinadas por ambos métodos presentan un r²=0.992 considerando las constantes de los 10 equilibrios binarios estudiados. Las diferencias observadas en las constantes se deben, probablemente, a la indeterminación en la resolución de la integral que involucra el cálculo de la constante de equilibrio planteada en el modelo de Gaines-Thomas. El modelo de Rothmund-Kornfeld resultó ser un método válido para describir el equilibrio de intercambio catiónico binario en sistemas sintéticos de carga variable de alta CIC y alta selectividad por K.