Iron isotope fractionation in subterranean estuaries

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2008-04-25Author
Rouxel, Olivier J.
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Sholkovitz, Edward R.
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Charette, Matthew A.
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Edwards, Katrina J.
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https://hdl.handle.net/1912/2352As published
https://doi.org/10.1016/j.gca.2008.05.001Abstract
Dissolved Fe concentrations in subterranean estuaries, like their river-seawater
counterparts, are strongly controlled by non-conservative behavior during mixing of groundwater
and seawater in coastal aquifers. Previous studies at a subterranean estuary of Waquoit Bay on
Cape Cod, USA demonstrate extensive precipitation of groundwater-borne dissolved ferrous iron
and subsequent accumulation of iron oxides onto subsurface sands. Waquoit Bay is thus an
excellent natural laboratory to assess the mechanisms of Fe-isotope fractionation in redoxstratified
environments and determine potential Fe-isotope signatures of groundwater sources to
coastal seawater. Here, we report Fe isotope compositions of iron-coated sands and porewaters
beneath the intertidal zone of Waquoit Bay. The distribution of pore water Fe shows two distinct
sources of Fe: one residing in the upward rising plume of Fe-rich groundwater and the second in
the salt-wedge zone of pore water. The groundwater source has high Fe(II) concentration
consistent with anoxic conditions and yield δ56Fe values between 0.3 and –1.3‰. In contrast,
sediment porewaters occurring in the mixing zone of the subterranean estuary have very low
δ56Fe values down to –5‰. These low δ56Fe values reflect Fe-redox cycling and result from the
preferential retention of heavy Fe-isotopes onto newly formed Fe-oxyhydroxides. Analysis of Feoxides
precipitated onto subsurface sands in two cores from the subterranean estuary revealed
strong δ56Fe and Fe concentration gradients over less than 2m, yielding an overall range of δ56Fe
values between –2 and 1.5‰. The relationship between Fe concentration and δ56Fe of Fe-rich
sands can be modeled by the progressive precipitation of Fe-oxides along fluid flow through the
subterranean estuary. These results demonstrate that large-scale Fe isotope fractionation (up to
5‰) can occur in subterranean estuaries, which could lead to coastal seawater characterized by
very low δ56Fe values relative to river values.
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Author Posting. © Elsevier B.V., 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 72 (2008): 3413-3430, doi:10.1016/j.gca.2008.05.001.
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Preprint: Rouxel, Olivier J., Sholkovitz, Edward R., Charette, Matthew A., Edwards, Katrina J., "Iron isotope fractionation in subterranean estuaries", 2008-04-25, https://doi.org/10.1016/j.gca.2008.05.001, https://hdl.handle.net/1912/2352Related items
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