Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
4546447 | Journal of Contaminant Hydrology | 2015 | 11 Pages |
•At pH < 7, SnII forms a S4-coordinated innersphere complex with mackinawite•At pH > 9, the mackinawite surface oxidizes and a FeII,III hydroxide precipitates•This FeII,III hydroxide structurally incorporates SnIV•Retention of SnII is high (Rd > 104 L/kg) across a wide pH range (5-11)
The interaction of SnII with metastable, highly reactive mackinawite is a complex process due to transient changes of the mackinawite surface in the sorption process. In this work, we show that tin redox state and local structure as investigated by Sn–K X-ray absorption spectroscopy (XAS) change with pH. We observe at pH < 7 that divalent Sn forms two short (2.38 Å) Sn–S bonds to the S-terminated surface of mackinawite, and two longer (2.59 Å) Sn–S bonds pointing most likely towards the solution phase, in line with a SnS4 innersphere sorption complex. Precipitation of SnS or formation of a solid solution with mackinawite could be excluded. At pH > 9, SnII is completely oxidized to SnIV by an FeII/FeIII (hydr)oxide, most likely green rust, forming on the surface of mackinawite. Six O atoms at 2.04 Å and 6 Fe atoms at 3.29 Å indicate a structural incorporation by green rust, with SnIV substituting for Fe in the crystal structure. The transition between SnII and SnIV and between sulfur and oxygen coordination takes place at a pH of 7 to 8 and an Eh of − 250 mV, close to the thermodynamically predicted transitions from mackinawite to Fe (hydr)oxide and from sulfide to sulfate. The uptake processes of SnII by mackinawite are largely in line with the uptake processes of divalent cations with soft Lewis-acid character like Cd, Hg and Pb, and lead to a strong retention of Sn with logRd values from 5 to 7 across the investigated pH range of 5 to 11.
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