Chemistry of submarine hydrothermal solutions at 21 °N, East Pacific Rise

Publisher Summary This chapter reviews the work done with soils and with hydrous oxides of iron and aluminum, with particular reference to mechanisms and structural aspects of anion adsorption. Anion adsorption on clay minerals and calcium carbonate is also discussed. The determination of adsorption isotherms is one of the most useful experimental procedures in the study of the interaction of anions with hydrous oxides or soils. Anion adsorption involves an electrostatic interaction and some chemical interaction between the surface and the ion. The Langmuir model is incomplete in describing this adsorption because it takes no account of charge. The adsorption of anions is dependent on pH, with maximum adsorption usually occurring for fully dissociated ions at low pH where the surface becomes positively charged, owing to protonation of surface M·OH groups. Maximum adsorption of anions of incompletely dissociated acids occurs at a pH value close to the pK of the acid. Anion adsorption reactions in soil are complicated by competition for adsorption sites from anions, including carboxylates, and also by the presence of cations, such as calcium and aluminum.

Anion Adsorption by Soils and Soil Materials

Summary
The relationship between adsorption and pH, termed the adsorption envelope, varies with the pKa, of the conjugate acid of the anion, for several adsorbents in presence of an excess of specifically adsorbed anions. At pH values where the acid is fully dissociated, specific adsorption occurs only to the extent of the positive charge of the surface and little specific adsorption is found at pH values more alkaline than the zero point of charge (zpc).

With incompletely dissociated acids, anion adsorption can also take place at pH values more alkaline than the zpc providing the pH is somewhere near a pKa value of the acid, where the energy required to abstract a proton from the acid is at a minimum. The proton is required for the removal of a surface OH which provides a site for the anion.

Specific anion adsorption (i) from a fully dissociated acid can reduce the positive charge of the surface to zero and (ii) from a weak acid can make even a negative surface more negative. Thus specific adsorption shifts the zpc to more acid values.

The relationship between anion adsorption and OH release is not necessarily simple.

The ideas proposed for anion adsorption have implications for cation adsorption and incorporation in an oxide surface.

Anion adsorption by goethite and gibbsite

Selenium in agriculture and the environment

Selenium (Se) is an essential element for humans and animals, which occurs ubiquitously in the environment. It is present in trace amounts in both organic and inorganic forms in marine and freshwater systems, soils, biomass and in the atmosphere. Low Se levels in certain terrestrial environments have resulted in Se deficiency in humans, while elevated Se levels in waters and soils can be toxic and result in the death of aquatic wildlife and other animals. Human dietary Se intake is largely governed by Se concentrations in plants, which are controlled by root uptake of Se as a function of soil Se concentrations, speciation and bioavailability. In addition, plants and microorganisms can biomethylate Se, which can result in a loss of Se to the atmosphere. The mobilization of Se across soil-plant-atmosphere interfaces is thus of crucial importance for human Se status. This review gives an overview of current knowledge on Se cycling with a specific focus on soil-plant-atmosphere interfaces. Sources, speciation and mobility of Se in soils and plants will be discussed as well as Se hyperaccumulation by plants, biofortification and biomethylation. Future research on Se cycling in the environment is essential to minimize the adverse health effects associated with unsafe environmental Se levels.

L. H. P. Jones

Papers

Solubility and redox criteria for the possible forms of selenium in soils

Solubility and redox criteria for the possible forms of selenium in soils.