Soluble metals are of nutritional and ecotoxicological interest as they are the most readily available form to the biota. Metal solubility in soils is mostly controlled by pH and the organic matter content. The rhizosphere is generally considered as an environment enriched in organic matter and often more acidic (depending on nutritional status of the plant) than the bulk soil. Yet, there is a lack of consensus on the distribution of metals at the soil-root interface. Consequently, the specific objectives of this paper are to compare the chemical properties and the water extractable metal concentrations of the rhizosphere and the bulk soil of forest soil (1) along a gradient in soil contamination and (2) under different tree species. Two study areas were used: (1) Rouyn-Noranda (Canada) where samples were collected along a gradient in metal contamination at a distance of 0.5, 2 and 8 km downwind from a copper smelter; (2) Saint-Hippolyte (Canada) where the effect of three tree species (Abies balsamea, Acer saccharum and Betula papyrifera) was studied. In the field, the rhizosphere was operationally defined as the soil adhering to the roots after agitation, soil falling from the roots and the rest of the soil composing the bulk soil. Once in laboratory, a second agitation was performed to separate the rhizosphere into an inner and an outer component. Water extractable metal concentrations (Al, Ca, Cd, Co, Cr, Cu, Fe, Li, Mg, Mn, Ni, Pb and Zn) were quantified either with an ICP-AES or a GFAAS. Measurements of pH, electrical conductivity (EC), water-extractable organic carbon (WEOC) and solid phase organic carbon (SPOC) were performed. Results systematically indicate that EC, WEOC and SPOC follow the sequence inner rhizosphere > outer rhizosphere > bulk soil. The pH is always lower in the inner rhizosphere than in the bulk soil, while the outer rhizosphere frequently shows an inconstant behaviour. The results also show a clear gradient following inner rhizosphere > outer rhizosphere > bulk soil for water extractable Al, Ca, Cd, Cu, Fe, Mg, Mn, Ni, Pb and Zn. Li, Co and Cr levels were below method detection limit in all cases. WEOC seems to be the main variable related to the water-extractable metals concentrations. The gradient in metal contamination at Rouyn-Noranda was not as expected in the water extracts with the site at 2 km frequently presenting higher metal concentrations than the sites at 0.5 and 8 km. Moreover, a tree species effect did not clearly immerge for any of the chemical properties studied. However, the water extractable Ca concentrations were higher in the soil under Acer saccharum. The effects of the metal gradient and of the tree species may be more pronounced if stronger extractants are used. The addition of an outer rhizosphere component is useful as its behaviour is not consistently intermediate between the inner rhizosphere and bulk soil.
