Field and laboratory studies reveal that the mineral ferrihydrite, formed a
s a result of abiotic oxidation of aqueous ferrous to ferric Fe, contains F
e that is isotopically heavy relative to coexisting aqueous Fe. Because the
electron transfer step of the oxidation process at pH >5 is essentially ir
reversible and should favor the lighter Fe isotopes in the ferric iron prod
uct, this result suggests that relatively heavy Fe isotopes are preferentia
lly partitioned into the readily oxidized Fe(II)(OH)(x(aq)) species or thei
r transition complexes prior to oxidation. The apparent Fe isotope fraction
ation factor, alpha (ferrihydrite-water), depends primarily on the relative
abundances of the Fe(II)((aq)) species. This study demonstrates that abiot
ic processes can fractionate the Fe isotopes to the same extent as biotic p
rocesses, and thus Fe isotopes on their own do not provide an effective bio
signature.