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Abstract: The dissolution kinetics in 2 M H2SO4 of variously dehydroxylated nickeliferous goethites was investigated for five oxide-type lateritic nickel deposits. Goethite was the main constituent with minor amounts of quartz, talc, kaolinite and Mn oxides. Dissolution of Fe from heated materials followed the Kabai equation. There was a 9–34-fold increase in the Kabai dissolution rate constant (k) for samples heated at 340–400 °C due to both the increased surface area (1.5–2.6 fold) and higher density of structural defects (5–10 fold) in the variously dehydroxylated products. The presence of structural Al and Cr in goethite appears to reduce dissolution rate possibly through the greater M3+–OH, O bond strength relative to Fe3+, Ni2+–OH, O. Nickel showed congruent dissolution with Fe indicating that Ni was uniformly incorporated in the goethite structure. Pre-heating goethite to 600–800 °C for 30 min resulted in incongruent dissolution of Fe and Ni. It is postulated that some Ni is ejected from the neo-formed hematite structure and resides on the crystal surface or in voids. These results may contribute to the development of more efficient procedures for Ni extraction including heap leaching of lateritic nickel ores. [Copyright &y& Elsevier]

To increase the analytical precision in identifying structural forms of heavy metals, it is necessary to refine the methodology for analysis of mineral crystals. The aim of this study was to characterize clay crystals in soils, and relate their mineralogy to the structural occurrence of Pb using scanning transmission electron microscopy (STEM) together with energy dispersive X-ray (EDX) spectrometry. We sampled soils from two areas naturally rich in heavy metals, with known occurrences of mineral deposits (PbS) in carbonate and phyllite/mica schist rocks. There was an association of P with Pb, and the main mineral phase containing Pb in the soil clay fractions was plumbogummite. No associations between Pb and Fe oxides were observed. Secondary phyllosilicate minerals, such as kaolinite and smectite, did not contain structural Pb. There was isomorphous substitution of Ti by Pb in an anatase crystal, despite the differences in ionic radii. The chemical analysis of individual crystals by STEM-EDX was hampered by the high occurrence of microaggregates of clay minerals. [ABSTRACT FROM AUTHOR]

Abstract: Potassium (K) deficiency is widespread in crops on highly weathered upland soils under a tropical monsoonal climate. Critical assessment of the forms of K in soils and of the ability of soils to release K for plant uptake is important for the proper management of K in crop production. The relationships between different pools of K were investigated as a function of silt and clay mineralogy for 14 upland Oxisols and 26 upland Ultisols soils from Thailand. Most soils contained no K-minerals in the silt fraction. XRD showed that kaolinite is the dominant clay mineral with variously minor or moderate amounts of illite, hydroxy-Al interlayered vermiculite and smectite present in some soils. For some soils, both conventional and synchrotron XRD were unable to detect illite. Analytical TEM including EFTEM of individual clay crystals showed that clay in the apparently illite-free samples contained very small amounts of illite. Many kaolinite particles appear to contain K which may be present in illite interleaved with kaolinite crystals. A glasshouse K-depletion experiment was conducted to assess the K supply capacity and changes in chemical forms of K and K-minerals using exhaustive K depletion by Guinea grass (Panicum maximum). Potassium deficiency symptoms and mortality of plants occurred on light textured soils, whereas plants survived for six harvests for Oxisols with clay texture, relatively high CEC and higher NH4OAc-K (exchangeable K plus water-soluble K). There is a strong linear relationship of unit slope between NH4OAc-K and cumulative K uptake by plants indicating that NH4OAc-K is a major form of K available to plants. Thus K-bearing minerals contributed little K to plants over the time scale of the experiment and XRD patterns of whole soil samples, silt and clay from soils after cropping mostly showed no change from those for the initial soil. An exception was for a single surface soil clay where a minor amount of smectite was formed from illite by K release to plants. [Copyright &y& Elsevier]

Abstract: Phosphate (P) sorption and desorption characteristics have been investigated for sixty-two representative samples of the major Thai upland agricultural soils which are Oxisols and Ultisols formed on diverse parent materials and under various climatic conditions. P sorption characteristics are well described by Langmuir and Freundlich equations. Values of Langmuir P sorption maximum (X m) and b coefficient range from 47 to 1250µgg−1 soil and 0.5 to 30mLµg−1, respectively and the Freundlich k varies between 12 and 1694µgg−1 and B coefficient 0.09 and 0.67. Soils derived from basalt have larger values of P sorption maximum than soils on other parent materials. Both P sorption maximum and Freundlich k are closely related to pH (NaF), SSA, total titanium, aluminum and iron, dithionite and oxalate extractable Fe and Al, and other soil properties that reflect specific surface area. Soil pH in NaF is highly effective in predicting the P sorption capacity of Thai upland soils explaining 79% of the variation in P sorption by these soils. P desorption curves for adsorbed P are well described by the Freundlich equation. The Freundlich k d coefficient for P desorption is highly, linearly related to the Freundlich k coefficient of P sorption indicating that the above soil factors that contribute to P sorption similarly affect P desorption. [Copyright &y& Elsevier]