Prediction of free metal ion activity in contaminated soils using WHAM VII, baker soil test and solubility model

Bioavailability and ecotoxicity of metals in contaminated soils depend largely on their solubility. The present investigation was carried out to predict the free ion activity of Zn²⁺, Cu²⁺, Ni²⁺, Pb²⁺ and Cd²⁺ in contaminated soils as a function of pH, organic carbon content and extractable metal concentration. Twenty-five composite soil samples were collected from various locations which had a history of receiving sewage sludge (Keshopur and IARI, Delhi), municipal solid waste (Kolkata, West Bengal), polluted river water (Madanpur, Delhi) and industrial effluents (Debari, Rajasthan and Sonepat, Haryana). Four composite soil samples were also collected from adjacent fields which had not received contaminated amendments. Free ion activities (-log₁₀ values), viz. pZn²⁺, pCu²⁺, pNi²⁺, pPb²⁺ and pCd²⁺ as measured by the Baker soil test, were 10.1 ± 1.12, 13.4 ± 1.23, 12.9 ± 0.85, 11.6 ± 0.74 and 12.6 ± 2.26, respectively. Free metal ion activities were also determined using the geochemical speciation model WHAM-VII following extraction of soil solution with porous Rhizon samplers from the rhizosphere of growing plants. pH dependent Freundlich model based on soil properties could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pPb²⁺ and pCd²⁺ to the extent of 84, 52, 73, 60 and 70%, respectively, in the case of data from Rhizon samplers coupled with speciation modelling. Whereas, C-Q model could explain 84, 57, 82, 72 and 74% variability in pZn²⁺, pCu²⁺, pNi²⁺, pPb²⁺ and pCd²⁺, respectively, based on soil properties and free metal ion activity as determined with integrated use of Rhizon-WHAM-VII. Modelling approach was superior compared to that based on the Baker soil test solution.