Geert Cornelis

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.

Geochemical modelling of arsenic and selenium leaching in alkaline water treatment sludge from the production of non-ferrous metals.

Geochemical modelling of leaching of oxyanion forming elements such as arsenic (As) and selenium (Se) is frequently not successful. A consistent thermodynamic dataset of As and Se was therefore composed, not only including precipitation, but also adsorption and solid solution, and was applied to the pH-dependent leaching behaviour of As and Se in an alkaline residue with a pH 11.1 from the lime treatment of sulphuric acid wastewaters from the production of non-ferrous metals. The As and Se content ranged up to 6.7 wt% and 0.29 wt%, respectively and speciation analysis showed that 96.3% of As occured as arsenate whereas Se speciation comprised 79% selenate and 21.0% selenite. XRD and SEM/EDX analysis showed that arsenate occurred as rauenthalite (Ca(3)(AsO(4))(2).10H(2)O), associated with gypsum, the most important mineral. Arsenate and arsenite concentrations were only slightly below equilibrium with rauenthalite and calciumarsenite (CaHAsO(3)), respectively and consideration of adsorption and solid solution only marginally improved model predictions. Selenate (Se(VI)) and selenite (Se(IV)), on the other hand, were far from equilibrium with their corresponding calcium metalate. The application of solid solutions and adsorption of Se(VI) and Se(IV) oxyanions with gypsum, calcite and ettringite significantly improved model predictions but missing thermodynamic data and especially the lack of a comprehensive model for solid solution and surface exchange with calcite and ettringite still hampered efficient modelling.