Cadmium speciation in cacao beans changes during a fermentation-like incubation

Cadmium (Cd) concentrations in cacao often exceed food limits. Recently, it was shown that cacao bean fermentation enhances Cd solubility, opening potential for Cd mitigation in cacao products. This study was set-up to identify changes in Cd speciation during fermentation. X-Ray absorption spectroscopy (XAS) complemented with speciation calculations, were used on samples collected from high and low Cd farms, that were subjected to a fermentation-like incubation that reached high temperatures (>45 degrees C) and acidic pH (<5). Incubation decreased nib Cd concentration up to a factor 1.5 and changed Cd complexation in high Cd beans from sulphur to oxygen ligands, likely due to pH changes. In beans with lower Cd concentrations, Cd was complexed before and after incubation with oxygen-ligands. A combination of pH changes and/or phytate breakdown may explain the migration of Cd outward from the nib. XAS and speciation calculations proved complimentary techniques and indicated similar speciation changes during fermentation.