Antimony leaching from MSWI bottom ash: modelling of the effect of pH and carbonation

Development of treatment methods to reduce Sb leaching from municipal solid waste incinerator (MSWI) bottom ash, such as accelerated carbonation, is being complicated by insufficient understanding of Sb geochemistry. The leaching of antimonate (Sb(V)) and antimonite (Sb(III)) in MSWI bottom was studied as a function of pH and degree of carbonation. While total (Sb(V)+Sb(III)) leaching was lowest (1.2 mg kg(-1)) at the natural pH (i.e. 10.6) of uncarbonated bottom ash, HPLC-ICP-MS analysis showed that acidification and carbonation increased Sb(V) leaching, but decreased Sb(III) leaching, probably because Sb(III)(OH)(4)(-) became less stable. PHREEQC geochemical modelling suggested that Sb(V) concentrations approached equilibrium with the romeites, i.e. calcium antimonates, Ca(1.13)Sb(2)(OH)(0.26)·0.74H(2)O at pH=10.6 and Ca[Sb(OH)(6)](2) at pH=8. It is hypothesised that not interaction with ettringite but dissolution of romeite controls antimonate leaching in the pH range 8-11 in MSWI bottom ash, because while Ca is preferentially leached from romeite, the mineral structures containing more Ca at higher pH are less soluble. A model was proposed where acidification and carbonation both lead to lower Ca(2+) and/or hydroxyl concentration, which removes Ca(2+) and hydroxyls from the romeite structure and leads to comparably higher Sb(V) concentration in equilibrium with romeite. Sb solubility depends on pH and Ca(2+) availability in this model, which has implications for bottom ash valorisation and risk assessment.