Iron isotope variations in Holocene sediments of the Gotland Deep, Baltic Sea

Holocene sediments from the Gotland Deep basin in the Baltic Sea were investigated for their Fe isotopic composition in order to assess the impact of changes in redox conditions and a transition from freshwater to brackish water on the isotope signature of iron. The sediments display variations in delta Fe-56 (differences in the Fe-56/Fe-54 ratio relative to the IRMM-14 standard) from -0.27 +/- 0.09 parts per thousand to +0.21 +/- 0.08 parts per thousand. Samples deposited in a mainly limnic environment with oxygenated bottom water have a mean delta Fe-56 of +0.08 +/- 0.13 parts per thousand, which is identical to the mean Fe isotopic composition of igneous rocks and oxic marine sediments. In contrast, sediments that formed in brackish water under periodically euxinic conditions display significantly lighter Fe isotope signatures with a mean delta Fe-56 of -0.14 +/- 0.19 parts per thousand. Negative correlations of the delta Fe-56 values with the Fe/Al ratio and S content of the samples suggest that the isotopically light Fe in the periodically euxinic samples is associated with reactive Fe enrichments and sulfides. This is supported by analyses of pyrite separates from this unit that have a mean Fe isotopic composition of -1.06 +/- 0.20 parts per thousand for delta Fe-56. The supply of additional Fe with a light Fe isotopic signature can be explained with the shelf to basin Fe shuttle model. According to the Fe shuttle model, oxides and benthic ferrous Fe that is derived from dissimilatory iron reduction from shelves is transported and accumulated in euxinic basins. The data furthermore suggest that the euxinic water has a negative dissolved delta Fe-56 value of about -1.4 parts per thousand to -0.9 parts per thousand. If negative Fe isotopic signatures are characteristic for euxinic sediment formation, widespread euxinia in the past might have shifted the Fe isotopic composition of dissolved Fe in the ocean towards more positive delta Fe-56 values. (c) 2007 Elsevier Ltd. All rights reserved.