The Quantitation of Aqueous Aluminum, P.R. Bloom and M.S. Erich Aqueous Equilibrium Data for Mononuclear Aluminum Species, D.K. Nordstrom and H.M. May Inorganic Aluminum Bearing Solid Phases, B.S. Hemingway and G. Sposito Aqueous Polynuclear Aluminum Species, P.M. Bertsch and D.R. Parker Environmental Chemistry of Aluminum-Organic Complexes, G.F. Vance, F.J. Stevenson, and F.J. Sikora Surface Reactions of Aqueous Aluminum Species, P.M. Jardine and L.W. Zelazny The Surface Chemistry of Aluminum Oxides and Hydroxides, S.R. Goldberg, J.A. Davis, and J.D. Hem The Solubility of Aluminum in Soils, W.L. Lindsay and P.M. Walthall The Chemistry of Aluminum in Surface Waters, C.T. Driscoll and K.M. Postek Aluminum Geochemistry at the Catchment Scale in Watersheds Influenced by Acidic Precipitation, W.H. Hendershot, F. Courchesne, and D.S. Jeffries Index

The Environmental Chemistry of Aluminum

Sorption and desorption of AsO 4 on or from different soil components may have a dominant role in regulating As mobility in soils. The objectives of this work were to provide information on the factors that influence the competitive sorption of AsO 4 and PO 4 in soil. We studied the competitive sorption of PO 4 and AsO 4 on selected phyllosilicates, metal oxides, synthetic organo-mineral complexes, and soil samples as affected by pH (4.0-8.0), ligands concentration, surface coverage of the oxyanions on the samples and the residence time. We found that Mn, Fe, and Ti oxides and phyllosilicates particularly rich in Fe (nontronite, ferruginous smectites) were more effective in sorbing AsO 4 than PO 4 . In fact, by adding AsO 4 and PO 4 as a mixture (AsO 4 /PO 4 molar ratio of 1) more AsO 4 , than PO 4 was usually sorbed on birnessite, pyrolusite, goethite, nontronite, and ferruginous smectite, but more PO 4 than AsO 4 was sorbed on noncrystalline Al precipitation products, gibbsite, boehmite, allophane, and kaolinite. For example, at pH 5.0 the sorbed AsO 4 /sorbed PO 4 molar ratio (rf) was 1.81 for bimessite, 1.05 for nontronite, but was only 0.45 for kaolinite and 0.14 for allophane. For montmorillonite, illite, and vermiculite the rf values were slightly <1. For soil samples, particularly rich in kaolinite, halloysite, allophane, and containing relatively large amounts of organic C, the rf values were usually much <1. For all the samples, the rf values increased by decreasing the pH and with the residence time of the oxyanions. The sorption of AsO 4 (or PO 4 ) on goethite and gibbsite decreased by increasing the initial PO 4 /AsO 4 (or ASO 4 / PO 4 molar ratio) up to 2.0. However, PO 4 inhibited AsO 4 sorption more on gibbsite than on goethite, whereas AsO 4 prevented PO 4 sorption more on goethite than on gibbsite. The data reported in this paper suggest that the mobility, the bioavailability, and the toxicity of As in soil environments may be greatly affected by the nature of soil components, pH, presence of anions (PO 4 ), and residence time.

Competitive Sorption of Arsenate and Phosphate on Different Clay Minerals and Soils

Soils formed in volcanic ejecta have many distinctive physical, chemical, and mineralogical properties that are rarely found in soils derived from other parent materials. These distinctive properties are largely attributable to the formation of noncrystalline materials (e.g., allophane, imogolite, ferrihydrite) containing variable charge surfaces, and the accumulation of organic matter. Formation of noncrystalline materials is directly related to the properties of volcanic ejecta as a parent material, namely the rapid weathering of glassy particles. The composition of the colloidal fraction forms a continuum between pure Al–humus complexes and pure allophane/imogolite, depending on the pH and organic matter characteristics of the weathering environment. For soil management purposes, volcanic soils are often divided into two groups based on the colloidal composition of the surface horizons: allophanic soils dominated by allophane and imogolite, and nonallophanic soils dominated by Al–humus complexes and 2:1 layer silicates. Volcanic soils exhibit a wide range of agricultural productivity, depending on the degree or intensity of pedogenic development and the colloidal composition of the rooting zone. The different charge characteristics of allophanic and nonallophanic soils is the most important factor regulating chemical fertility attributes. Phosphorus fixation, strong acidity, and aluminum toxicity are the primary chemical limitations to agricultural productivity. Volcanic soils generally have high physical fertility (tilth) and mature soils are relatively resilient to erosion and compaction. To maximize the productivity of volcanic soils, proper management based on an understanding of the unique physical, chemical, and mineralogical properties of these soils must be practiced.

The Nature, Properties and Management of Volcanic Soils

Sorption of DOM and DOM fractions to forest soils

Organic Amendments and Phosphorus Sorption by Soils

Influence of Organic Acids on Crystallization and Surface Properties of Precipitation Products of Aluminum

Hydroxide and oxyhydroxide products of aluminum were formed at room temperature at an initial Al concentration of 2 × 10-3 M, pH 8.2, and at varying concentrations of organic and inorganic ligands commonly found in nature. The effectiveness of the ligands in promoting the formation of noncrystalline products over crystalline Al(OH)3 polymorphs was found to be in the following order: phthalate ≅ succinate < glutamate < aspartate < oxalate < silicate ≅ fluoride < phosphate < salicylate ≅ malate < tannate < citrate < tartrate. The lowest ligand/Al molar ratio at which the production of Al hydroxides or oxyhydroxides was inhibited ranged from 0.02 to 15. Above critical ligand/Al ratios, crystalline products were inhibited and ligands coprecipitated with noncrystalline products which remained unchanged for at least 5 months. Polydentate and large ligands generally were more inhibitive than those with fewer functional groups or of smaller size.

Influence of Inorganic and Organic Ligands on the Formation of Aluminum Hydroxides and Oxyhydroxides

Substantial studies have been carried out to investigate the mechanism of the formation of Al(OH)3 polymorphs. The influence of the nature of Al precipitation products on the formation of Al(OH)3 polymorphs still remains obscure. In this study, X-ray diffraction, infrared and thermal analyses, and electron microscopic observations of the Al precipitates formed at the initial pH 8.2 and at a citric acid/Al molar ratio of 0.01 and aged for 3 hr to 60 days revealed that the transformation from the initially formed noncrystalline materials to pseudoboehmite occurred through the formation of intermediate materials with various degrees of ordering and sizes of particles that apparently had a wide range of solubility. By increasing the pH of the suspension of precipitation products of Al to 10.0 after 3 hr and 3, 11, 31, and 60 days or longer, the crystalline precipitation products were hayerite, nordstrandite and bayerite, nordstrandite and pseudoboehmite, pseudoboehmite and gibbsite, and pseudoboehmite, respectively. This work shows evidence that, as the nature of the starting Al precipitates changed, the rate of their dissolution apparently changed, and various Al(OH)3 polymorphs consequently formed. Therefore, the data substantiate the hypothesis that the mechanism of the formation of an Al(OH)3 polymorph is determined by the rate of its nucleation, which is, in turn, influenced by the rate of dissolution of the noncrystalline or poorly ordered Al-oxides initially formed.

Formation mechanism of aluminum hydroxide polymorphs

Impact of organic substances on the formation and transformation of metal oxides in soil environments.

Organic C contents, specific surface and P adsorption of pseudoboehmites or x-ray noncrystalline precipitation products of Al formed in the presence of various organic ligands (citric, tartaric, tannic or aspartic acid) and Cl were studied before and after oxidation treatment of NaOCl or H 2 O 2 . Contents of residual C after NaOCl or H 2 O 2 treatment ranged from 22 to 60% and from 55 to 90% of the original C, respectively. (…)

A. Violante

Papers

Influence of Organic Acids on Crystallization and Surface Properties of Precipitation Products of Aluminum

Influence of Inorganic and Organic Ligands on the Formation of Aluminum Hydroxides and Oxyhydroxides

Formation mechanism of aluminum hydroxide polymorphs

Impact of organic substances on the formation and transformation of metal oxides in soil environments.

Influence of Oxidation Treatments on Surface Properties and Reactivities of Short-Range Ordered Precipitation Products of Aluminum