A fungal bioremediation method using P. frequentans removed up to 75% of phenanthrene with the addition of water and nutrients over a period of 30 d. During the bioremediation process, changes in metal behavior were monitored by an in situ technique (diffusive gradients in thin-films, DGT) and by soil solution chemistry. DGT provided absolute data on fluxes from the solid phase to the DGT device and relative trends of concentrations of the most labile metal species. DGT response indicated that bioremediation increases metal mobilization from the solid phase. Filtration provided data on the concentrations of solution phase (<0.45 microm) metal. In all case, metal fluxes and concentrations significantly increased after the bioremediation process began. Fluxes increased from <0.1 pg cm(-2)s(-1) before bioremediation to between 0.2 and 0.5 pg cm(-2)s(-1) after bioremediation. Metal concentrations in the soils solution (filtration at 0.45 microm) increased from 2 to 10 microg l(-1) (Cu), 1-4 microgl(-1) (Pb) and from 40 to 140 microg l(-1) (Ni) after bioremediation. Although over a short time period, these data strongly indicated that there was remobilization of metal from solid to solution (and thus to the DGT device) directly due to the bioremediation process. Although the mechanism was not unambiguously identified, it was shown not to be related to small changes in bulk pH over time and was attributed to the microbial action on the surface of the soil solid phase, releasing metal into solution. Additionally, differences in metal concentration and flux were observed in sterilized and non-sterilized soils and in the absence or presence of phenanthrene. The results indicated that the bioremediation of soil by P. frequentans increased the flux, lability and mobility of trace metal species and therefore the likely metal bioavailability to plants.