Escoube,R., Rouxel,O.J., Sholkovitz,E. and Donard,O.F.X.(2009): Iron isotope systematics in estuaries: The case of North River, Massachusetts (USA). Geochimica et Cosmochimica Acta, 73, 4045-4059.

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wAbstract
@Recent studies have suggested that rivers may present in isotopically light Fe source to the oceans. Since the input of dissolved iron from river water is generally controlled by flocculation processes that occur during estuarine mixing, it is important to investigate potential fractionation of Fe-isotopes during this process. In this study, we investigate the influence of the flocculation of Fe-rich colloids on the iron isotope composition of pristine estuarine waters and suspended particles. The samples were collected along a salinity gradient from the fresh water to the ocean in the North River estuary (MA, USA). Estuarine samples were filtered at 0.22ƒÊm and the iron isotope composition of the two fractions (dissolved and particles) were analyzed using high-resolution MC-ICP-MS after chemical purification. Dissolved iron results show positive ƒÂ56Fe values (with an average of 0.43}0.04ñ) relative to the IRMM-14 standard and do not display any relationships with salinity or with percentage of colloid flocculation. The iron isotopic composition of the particles suspended in fresh water is characterized by more negative ƒÂ56Fe values than for dissolved Fe and correlate with the percentage of Fe flocculation. Particulate ƒÂ56Fe values vary from -0.09ñ at no flocculation to `0.1ñ at the flocculation maximum, which reflect mixing effects between river-borne particles, lithogenic particles derived from coastal seawaters and newly precipitated colloids. Since the process of flocculation produces minimal Fe-isotope fractionation in the dissolved Fe pool, we suggest that the pristine iron isotope composition of fresh water is preserved during estuarine mixing and that the value of the global riverine source into the ocean can be identified from the fresh water values. However, this study also suggests that ƒÂ56Fe composition of rivers can also be characterized by more positive ƒÂ56Fe values (up to 0.3ñ) relative to the crust than previously reported. In order to improve our current understanding of the oceanic iron isotope cycling, further work is now required to determine the processes controlling the fractionation of Fe-isotopes during continental run-off.x

1. Introduction
2. Materials and location
3. Analytical method
@3.1. Sample filtration
@3.2. Chemical analysis
@3.3. Iron isotope analysis
4. Results
@4.1. River end-member composition
@4.2. Element behavior in North River estuary
@4.3. Determination of the flocculation factor
5. Discussion
@5.1. Fe-isotope systematics in colloidal and particulate pools in the river end member
@5.2. Fe-isotope systematics of dissolved Fe during flocculation process in estuaries
@5.3. Fe-isotope systematics in the particulate pool
@5.4. Implication for coastal seawater Fe sources
6. Conclusion
Acknowledgements
References


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