Comparison of soil solution sampling techniques to assess metal fluxes from contaminated soil to groundwater

The unsaturated zone plays a major role in elemental fluxes in terrestrial ecosystems. A representative chemical analysis of soil pore water is required for the interpretation of soil chemical phenomena and particularly to assess Trace Elements (TEs) mobility. This requires an optimal sampling system to avoid modification of the extracted soil water chemistry and allow for an accurate estimation of solute fluxes. In this paper, the chemical composition of soil solutions sampled by Rhizon® samplers connected to a standard syringe was compared to two other types of suction probes (Rhizon® + vacuum tube and Rhizon® + diverted flow system). We investigated the effects of different vacuum application procedures on concentrations of spiked elements (Cr, As, Zn) mixed as powder into the first 20 cm of 100-cm columns and non-spiked elements (Ca, Na, Mg) concentrations in two types of columns (SiO2 sand and a mixture of kaolinite + SiO2 sand substrates). Rhizon® was installed at different depths. The metals concentrations showed that (i) in sand, peak concentrations cannot be correctly sampled, thus the flux cannot be estimated, and the errors can easily reach a factor 2; (ii) in sand + clay columns, peak concentrations were larger, indicating that they could be sampled but, due to sorption on clay, it was not possible to compare fluxes at different depths. The different samplers tested were not able to reflect the elemental flux to groundwater and, although the Rhizon® + syringe device was more accurate, the best solution remains to be the use of a lysimeter, whose bottom is kept continuously at a suction close to the one existing in the soil.