Selenite Sorption Research Articles

Proton consumption and release of organic‐cabon, silicate, and sulfate by anion sorption on andosols

Abstracts Three anion (selenite, phosphate, and fluoride) sorption, and the concomitant release of silicate, sulphate, and organic matters from soils, and proton consumption with sorption were investigated using two andosols in Japan. The following sequence of sorption by the andosols was, fluoride (F) >> phosphate (P) > selenite (Se); concomitant proton consumption with sorption, F >> P > Se; organic matter released, P > Se > F; and sulfate released, P > Se >> F. There was quite a difference between an allophanic and a non‐allophanic andosols in silicate released with anion sorption. Our results suggest that the fluoride sorption mechanism is different from the others and that surface sites with OH groups for inner‐sphere complexes with selenite on soil particles which are restricted as compared to phosphate and fluoride.

Testing a mechanistic model. VII. The effects of pH and of electrolyte on the reaction of selenite and selenate with a soil

SUMMARYThe pH of samples of a soil was altered by mixing them either with acid or lime, and incubating the moistened samples at 60°C for a day. The sorption of selenate and of selenite was then measured using as background electrolytes, 0.01 M, 0.1 M and 1.0 M sodium chloride and also 0.01 M calcium chloride. The results were compared with previous studies with phosphate and fluoride.Selenite was sorbed more strongly than selenate, but not as strongly as phosphate or fluoride. Sorption of both selenite and selenate decreased with increasing pH. This decrease was more marked for selenate than for selenite; more marked in a sodium system than in a calcium one; and more marked with a dilute background electrolyte than a concentrated one. Under certain conditions, the steeper curves for the dilute electrolyte crossed the curves for the concentrated electrolyte giving points of zero salt effect. For selenite, these points of zero salt effect occurred near pH 6 and the greater the sorption the lower the pH for zero salt effect. For phosphate, the analogous value was near pH 5. For selenate, if a point of zero salt effect occurred, it was at such a high pH and such a low amount of sorption that it could not be measured. Thus, the larger the amount of sorption the lower the pH for the point of zero salt effect. This generalization applied both within and between different kinds of sorbates.The results were closely described by a model that had previously been applied to phosphate and fluoride. The model postulates that ions react with charged surfaces. The electric potentials of the reacting surfaces are affected by the identity and concentration of the background electrolyte and this produces the interactions between pH and electrolyte concentration. The model also postulates that there is a distribution of electric potentials. Anions react with surfaces which occur in the more positive tail of this distribution. The smaller the amount of the reaction the more positive the potential of the reacted surface and, therefore, the higher the pH required to decrease this potential to zero.

Testing a mechanistic model. VIII. The effects of time and temperature of incubation on the sorption and subsequent desorption of selenite and selenate by a soil

SUMMARYSeveral levels of both selenite and selenate were incubated with separate samples of soil for periods of up to 30 d and at temperatures between 5 and 60°C. The concentrations of selenite or of selenate which caused neither desorption nor further sorption–that is, the null‐point concentrations–were then measured at 25°C. In addition, the rate of desorption was measured after incubation at 60°C for 10 d. The ability of a mechanistic model to describe the results was tested.There were large decreases in the null‐point concentrations of selenite with both increasing period and increasing temperature of incubation. These effects were modelled as due to a relatively rapid diffusive penetration and a large activation energy for diffusion. Only a small proportion of the sorbed selenite was desorbed within 3 d but, at large solution:soil ratios, desorption appeared to be still continuing. These effects were fairly well predicted by the model applied to the sorption data. For example, the continuing desorption was ascribed to the slow reversal of the diffusive penetration. For selenate, the effects of period and temperature of incubation were much smaller. These effects were modelled as due to a slower diffusive penetration and a lower activation energy. Desorption was quicker and was more nearly complete. According to the model, a large proportion remained in the adsorbed form and was more quickly removed when desorption was induced. It is argued that the behaviour of selenite is consistent with diffusion into a crystal and the large activation energy is required to enable jumps over energy barriers. On the other hand, the lower activation energy for selenate is consistent with diffusion being limited to pores or cracks.It is suggested that the residual value of selenite fertilizers would decrease because of the continuing reaction, but that this effect would be unimportant for selenate.

Anion Sorption on a Calcareous, Montmorillonitic Soil‐Selenium

AbstractSelenite and selenate sorption on a calcareous, montmorillonitic soil was investigated as a function of solution pH (2–11) at two initial Se concentrations (1.9 mmol m−3 and 19 mmol m−3. Selenate sorption was not observed at any pH value for either initial Se concentration. Selenite sorption exhibited a maximum near pH 3, a sharp decline to pH 6, and a sorption plateau above pH 7. Selenite sorption as a function of pH was studied on reference minerals representative of the dominant mineral constituents of the soil: montmorillonite, kaolinite, and calcite. Selenite sorption on the clay minerals increased at low pH, exhibited a peak near pH 5, and decreased at higher pH. Selenite sorption on calcite increased from pH 6 to 8, peaked between pH 8 and 9, and decreased above pH 9. The constant capacitance model was able to describe selenite sorption on montmorillonite and kaolinite over the entire pH range studied and on the soil below pH 7. The soil sorption plateau above pH 7 virtually disappeared after removal of calcite, indicating that calcite plays an important role in selenite sorption of calcareous soils.