Challenges in geochemical modelling of metal(loid) solubility and binding mechanisms along a soil profile at a multi-contaminated site

Recognising the need for robust models in predicting groundwater contamination risks from metal(loid)s in contaminated topsoil, this study focuses on the geochemical behaviour of As, Cd, Cu, Pb, Sb and Zn in one of Sweden's most heavily contaminated areas. Samples were collected from the waste zone and underlying subsoil down to 5 m and batch experiments were carried out to assess pH-dependent solubility. The results indicate that Cd, Cu, Pb and Zn are efficiently immobilized in the waste zone, while As(V) and Sb(V) are more easily leached. With the exception of Pb and Cu at high pH, the mobilized metals appear to be predominantly in a truly dissolved state, as confirmed by ultrafiltration at 10 kDa. Speciation modelling using Visual MINTEQ did not suggest a significant role of precipitates such as Zn or Pb arsenates and phosphates, although their involvement could not be ruled out. To better understand sorption/ desorption patterns, a multi-surface geochemical model was established, drawing on the Stockholm Humic and CD-MUSIC models for organic matter and Fe/Al (hydr)oxide sorption. However, when default parameters were used, the model consistently overestimated the solubility of Cd, Cu, Pb and Zn in both the waste zone and the uncontaminated subsoil. In contrast, As(V) solubility was generally underestimated, also when the reactive surface area of the Fe- and Al (hydr)oxides was decreased in the model. The model's performance was better for Sb(V), though not without imperfections. When the parameters for organic matter were adjusted such that 100% of the solid-phase organic matter was active with respect to ion binding, but only 25% of the dissolved organic matter, the model description improved considerably for Pb and Cu in the upper soil layers. The model revealed distinct differences in the adsorption behaviour of the metal cations, with Pb being sorbed mostly to Fe/Al (hydroxides), whereas a considerable part of Cu was sorbed to organic matter, particularly in the waste zone. Possibly, the dissolution of easily weatherable metal-containing mineral phases may have contributed to the poor model performance for Cd, Zn and for Cu in the deeper soil layers, although other factors, such as a contribution of hydrous SiO2 or Mn oxides to metal binding, could not be ruled out. Metal sorption to carbonate phases may also have been a contributing factor in the waste zone. Lastly, the reactivity of Fe- and Al (hydr) oxides may have been overestimated by oxalate extraction when default parameters for high-surface-area ferrihydrite were applied. These findings provide valuable insights for environmental management and underscore the need for a more detailed characterization of metal(loid) sorption in contaminated soils, as well as the development of improved modelling strategies to enhance solubility predictions.