Selenite reduction by mackinawite, magnetite and siderite: XAS characterization of redox products


Selenite reduction by mackinawite, magnetite and siderite: XAS characterization of redox products

Scheinost, A. C.; Charlet, L.

Suboxic soils and sediments contain the reactive Fe-bearing mineral phases mackinawite (FeS), siderite (FeCO3) and the Fe(II/III) oxide magnetite (Fe3O4), which should be able to reduce Se to oxidation states 0, -I and –II, forming elemental Se and iron selenides of low solubility. While the reduction of selenate or selenite to Se(0) by green rust, pyrite and by Fe2+ sorbed to montmorillonite in a slow (weeks), kinetically limited redox reaction has been demonstrated earlier, we show here that selenite is rapidly (within one day) reduced by nanoparticulate mackinawite and magnetite, while only 1/3 of selenite is reduced by the larger siderite crystals within one day. Depending on Fe(II)-bearing phase and pH, we observed four different reaction products, α-monoclinic and trigonal (hexagonal) elemental Se, and two iron selenides with structures similar to Fe7Se8 and FeSe. The thermodynamically most stable iron selenide, ferroselite (FeSe2) was not observed. The local structure suggests formation of nanoscale clusters, which may be much more soluble than the corresponding macrocrystalline solids, and mobile in case the physicochemical parameters of groundwater favor formation of stable colloidal suspensions (e.g. low IS and pH close to PZC).

  • Environmental Science & Technology 42(2008), 1984-1989

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Publ.-Id: 10180