Two soils contaminated with potentially toxic metals (PTMs) contrasting in pH and mineralogy were remediated with CaEDTA, and changes in soil organic matter (SOM) composition were investigated. Previous studies showed no significant loss of SOM from CaEDTA-treated soils, but the results of our study reflected significant decreases (from 46 to 49%) in the free fraction of humic acids (HAs). Remediation affected the composition of the free HA fraction via disturbance of intermolecular bonds — an increase in phenolic and aromatic groups with a simultaneous decrease in carbohydrates — which was confirmed by FTIR spectroscopy in both soils. Because non-radical molecules such as carbohydrates were selectively removed, the concentration of free radicals in the free HA fraction increased in acidic soil. The bound fraction of HAs and fulvic acids (FAs) in SOM, which are important due to their stability and the permanent effects they have on the soil’s physical properties, remained unchanged in both remediated soils. The effect of soil recultivation was observed only in the excitation emission matrix (EEM) fluorescence spectra of HAs. In terms of SOM, CaEDTA soil washing can be considered moderately conservative; however, the restoration of free humic fractions is likely to be a long-term process.

The Cananéia-Iguape estuarine–lagoon complex (São Paulo state, Brazil) is a natural laboratory to study metal binding by humic substances (HS) in subtropical settings. This transitional environment is evolving into a freshwater environment due to water input from the Ribeira River, funneled through the Valo Grande Canal (Iguape). Past mining activities in the Ribeira River basin and maritime traffic are suspected to be potential sources of trace metals in the system. In this study, the trace metal contents of Free Humic Acids (FHA), Bound Humic Acids (BHA), and Fulvic Acids (FA) extracted from sedimentary organic matter were investigated. Moreover, the sources of HS were traced using their stable carbon isotope compositions and C/N ratios. The results suggested a mixed marine–terrestrial source of FHA, BHA, and FA. Copper and Cr were the most abundant trace metals bound to HS. On average, Cu showed concentrations of 176, 115, and 37.9 μg g⁻¹ in FHA, BHA, and FA, respectively, whereas Cr showed average concentrations of 47.4, 86.3, and 43.9 μg g⁻¹ in FHA, BHA, and FA, respectively. Marine FHA showed the highest binding capacity for trace metals, whereas terrestrial FA derived from the decay of mangrove organic matter showed the lowest binding capacity.