Complementary assessment of As, Cu and Zn environmental availability in a stabilised contaminated soil using large-bore column leaching, automatic microcolumn extraction and DGT analysis

Soil pollution with trace elements is a concerning issue worldwide. Monitoring of soil pollution and remediation protocols need still from valid complementary analytical approaches able to detect changes in speciation and lability of metals in soils (e.g. stabilization or mobility). In this work, we compare three different analytical approaches to assess potential changes in environmental availability of Cu, As and Zn in a Mediterranean polluted soil that was amended with different combinations of iron sulphate and alkaline paper sludge waste. The studied methods were: (i) a standard large-bore flow-through column system (macrocolumn), (ii) an automatic dynamic flow-through microcolumn extraction system, and (iii) the diffusive gradients in thin gels technique (DGT). The three analytical approaches tested showed immobilization of Zn and Cu in contaminated mine soils after co-application of paper sludge and iron sulphate, but they differ quantitatively in terms of As mobility. Interconversion between oxidation states of inorganic As is observed to occur to a larger extent in macrocolumn. Because this may only occur in very specific Mediterranean scenarios (i.e. organic matter application to intermittently flooded mine soils), macrocolumn extraction procedures might not appropriately mimic the environmental availability of As in soils with organic amendments (e.g., paper sludge waste). Microcolumn leaching is the fastest screening tool to ascertain the efficiency of chemical amendments, but DGT is a good alternative with less technical demands.