Relationship Between Iron Oxides and Surface Charge Characteristics in Soils

The relationship between iron oxides and surface charge characteristics in variable charge soils ( latosol and red earth ) was studied in following three ways. ( 1 ) Remove free iron oxides ( Fed ) and amorphous iron oxides ( Feo ) from the soils with sodium dithionite and acid ammonium oxalate solution respectively. ( 2 ) Add 2% glucose ( on the basis of air-dry soil weight ) to soils and incubate under submerged condition to activate iron oxides, and then the mixtures are dehydrated and air-dried to age iron oxides. ( 3 ) Precipitate various crystalline forms of iron oxides onto kaolinite. The results showed that free iron oxides ( Fed ) were the chief carrier of variable positive charges. Of which crystalline iron oxides ( Fed-Feo ) presented mainly as discrete particles in the soils and could only play a role of the carrier of positive charges, and did little influence on negative charges. Whereas the amorphous iron oxides ( Feo ) , which presented mainly as a coating with a large specific surface area, not only had positive charges, but also blocked the negative charge sites in soils. Submerged incubation activated iron oxides in the soils, and increased the amount of amorphous iron oxides and the degree of activation of iron oxide, which resulted in the increase of positive and negative charges of soils. Dehydration and air-dry aged iron oxides in soils and decreased the amount of amorphous iron oxides and the degree of activation of iron oxide, and also led to the decrease of positive and negative charges. Both the submerged incubation and the dehydration and air-dry had no significant influence on net charges. Precipitation of iron oxides onto kaolinite markedly increased positive charges and decreased negative charges. Amorphous iron oxide having a larger surface area contributed more positive charge sites and blocked more negative charge sites in kaolinite than crystalline goethite.

Effect of Electrolytes on Surface Charge Characteristics of Red Soils

The zero point of charge (ZPC) and the remaining charge σp at ZPC are two important parameters characterizing surface charge of red soils.Fourteen red soil samples of different soil type and parent material were treated with dithionite-citrate-dicarbonate (DCB) and Na2CO3 respectively.ZPC and σp of the samples in three indifferent electrolytes (NaCl,Na2SO4,and NaH2PO4) were determined.Kaolinite was used as reference.The results showed that ZPC of red soils was affected by the composition of parent materials and clay minerals and in significantly positive correlation with the content of total iron oxide (Fet),free iron oxide (Fed),amorphous iron oxide (Feo),aluminum oxide (Alo) and clay,but it was negatively correlated with the content of total silica (Sit).The σp of red soils was also markedly influenced by mineral components.Organic components were also contributing factor to the value of σp.The surface charges of red soils were evidently affected by the constitution of the electrolytes.Specific adsorption of anions in the electrolytes tended to make the ZPC of red soils shift to a higher pH value and to increase positive surface charges of the soils,thus leading to change of the σp value and decrease of the remaining net negative charges,even to the soils becoming net positive charge carriers.The effect of phosphate anion was greater than that of sulfate ion.

Titratable Acidity and Alkalinity of Red Soil Surfaces

The surfaces of red soils have an apparent amphotenc character, carrying titratable acidity and titratable alkalinity simultaneously. The titratable acidity arises from deprotonation of hydroxyl groups of hydrous oxide-type surfaces and dissociation of weak-acid functional groups of soil organic matter, while the titratable alkalinity is derived from release of hydroxyl groups of hydrous oxide-type surfaces. The titratable acidity and titratable alkalinity mainly depended on the composition and content of iron and aluminum oxides in the soils. The results showed that the titratable acidity and titratable alkalinity were in significantly positive correlation not only with the content of amorphous aluminum oxide(Alo) and iron oxide(Feo) extracted with acid ammonium oxalate solution, free iron ox-ide(Fed) extracted with sodium dithionite-citrate-bicarbonate (DCB) and clays, but also with the zero point of charge (ZPC) of the samples. Organic matter made an important contribution to the titratable acidity. The titratable alkalinity was closely correlated with the amount of fluoride ions adsorbed. The titratable acidity and titratable alkalinity of red soils were influenced by parent materials, being in the order of red soil derived from basalt > that from tuff > that from granite. The titratable acidity and titratable alkalinity were closely related with origination of the variable charges of red soils, and to a certain extent were responsible for variable negative and positive charges of the soils.