Paper No. 119-3
Presentation Time: 9:30 AM
IRON ISOTOPE SIGNATURE IN SEDIMENTS OF AN OLIGOTROPHIC LAKE
This study investigated iron isotope compositions of pore waters and solid-associated Fe phases in natural lacustrine sediments at Lake Tantaré, Québec, Canada. Lake Tantaré, an oligotrophic lake located in an undisturbed boreal catchment, is a well constrained natural laboratory, where previous modelling work has shown that dissimilatory Fe(III) reduction (DIR) is the main Fe reduction pathway in the sediments with minor contribution from abiotic reduction by sulfides. The Fe concentration profiles for sediments indicate that intense Fe cycling includes upward migration of aqueous Fe(II), generated by DIR, followed by oxidation and precipitation of Fe(III) oxyhydroxides at the sediment-water interface (SWI). The sediment-water interface therefore works as a barrier to prevent upward flux of Fe, which in turn confines sorption of trace elements, limiting transport of many elements across the SWI. Our speciation measurements show that a significant fraction of Fe in pore water likely exists as ferric Fe, complexed with organic matter and/or in colloidal phase. We found isotopically light aqueous Fe(II) in pore waters and sorbed Fe(II) on sediments, in contrast to previous findings of isotopically light Fe only in water column in other lacustrine systems. DIR is likely to be assisted by electron shuttling by humic substances in Lake Tantaré sediments. The highly negative δ56Fe values of aqueous Fe(II) (‒2.12±0.60‰) is consistent with previous experimental work, which showed that δ56Fe values of aqueous Fe(II) produced by DIR can vary between ‒3‰ and ‒1‰ depending on different proportions of Fe species (Fe(II)aq, Fe(II)sorb, Fe(III)am) in the system. The apparent isotope fractionation factor between aqueous Fe(II) and Fe(III) oxyhydroxides is ‒2.7±0.7‰ in Lake Tantaré sediments, which is consistent with previous experimental work on the isotopic fractionations produced by dissimilatory Fe(III) reduction. These findings have provided for the first time a clear Fe isotope signature of DIR from natural lacustrine sediments and have improved our understanding of the stable isotope effects of Fe redox cycling in lacustrine environments.