Abstract

Sorption of oxyanions by soils and mineral surfaces is of interest due to their role as nutrients or pollutants. Volcanic soils are variable charge soils, rich in active forms of aluminum and iron, and capable of sorbing anions. Sorption and desorption of vanadate, arsenate, and chromate by two African andosols was studied in laboratory experiments. Sorption isotherms were determined by equilibrating at 293 K soil samples with oxyanion solutions of concentrations between 0 and 100 mg L−1 V, As, or Cr, equivalent to 0−2.0 mmol V L−1, 0−1.3 mmol As L−1, and 0−1.9 mmol Cr L−1, in NaNO3; V, As, or Cr were determined by ICP-mass spectrometry in the equilibrium solution. After sorption, the soil samples were equilibrated with 0.02 M NaNO3 to study desorption. The isotherms were adjusted to mathematical models. After desorption with NaNO3, desorption experiments were carried out with a 1 mM phosphate. The sorption of vanadate and arsenate was greater than 90% of the amount added, while the chromate sorption was much lower (19–97%). The sorption by the Silandic Andosol is attributed to non-crystalline Fe and Al, while in the Vitric Andosol, crystalline iron species play a relevant role. The V and Cr sorption isotherms fitted to the Freundlich model, while the As sorption isotherms conformed to the Temkin model. For the highest concentrations of oxyanions in the equilibrating solution, the sorbed concentrations were 37–38 mmol V kg−1, 25 mmol As kg−1, and 7.2–8.8 mmol Cr kg−1. The desorption was low for V and As and high for Cr. The comparison of the sorption and desorption isotherms reveals a pronounced hysteresis for V in both andosols and for Cr in the Silandic Andosol. Phosphate induced almost no V desorption, moderate As desorption, and considerable Cr desorption.

Highlights

  • Sorption of oxyanions by soils and mineral surfaces has received considerable attention [1,2,3,4,5,6,7,8,9,10] because of their important role as nutrients or pollutants

  • The present paper aims to study the sorption and desorption of vanadate, arsenate, and chromate by the surface horizons of two soils representative of volcanic areas in Equatorial Africa: a Silandic Andosol [53] on volcanic ash (Rwanda) and a Vitric Andosol on basaltic material (São Tomé and Principe)

  • The V sorption was very similar in both andosols, indicating that non-crystalline iron and aluminum species, as well as crystalline iron compounds, efficiently sorb vanadate

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Summary

Introduction

Sorption of oxyanions by soils and mineral surfaces has received considerable attention [1,2,3,4,5,6,7,8,9,10] because of their important role as nutrients or pollutants. The presence of reactive aluminum and iron phases, such as oxides, hydroxides, oxyhydroxides, poorly crystalline aluminosilicates (allophane, imogolite), or Al (Fe)-humus complexes, endows soils with variable charge and anion retention capacity. According to Larsson et al [18,26], V toxicity to plants and soil microorganisms is controlled by the vanadium sorption capacity of soils. Adsorption of both V(IV) and V(V) by metal (oxyhydr)oxides occurs mainly through the formation of inner-sphere complexes [22,27]. Vanadate competes with other oxyanions for sorption sites on positively charged mineral surfaces, being bound even more strongly than phosphate and arsenate on Fe hydrous oxides [16,28,29]

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