Atmospheric dissolved iron deposition to the global oceans: effects of oxalate-promoted Fe dissolution, photochemical redox cycling, and dust mineralogy

Mineral dust deposition is suggested to be a significant atmospheric supply pathway of bioavailable iron (Fe) to Fe-depleted surface oceans. In this study, mineral dust and dissolved Fe (Fe-d) deposition rates are predicted for March 2009 to February 2010 using the 3-D chemical transport model GEOS-Chem implemented with a comprehensive dust-Fe dissolution scheme. The model simulates Fe-d production during the atmospheric transport of mineral dust, taking into account inorganic and organic (oxalate)promoted Fe dissolution processes, photochemical redox cycling between ferric (Fe(III)) and ferrous (Fe(II)) forms of Fe, dissolution of three different Fe-containing minerals (hematite, goethite, and aluminosilicates), and detailed mineralogy of wind-blown dust from the major desert regions. Our calculations suggest that during the year-long simulation similar to 0.26 Tg (1 Tg = 10(12) g) of Fe-d was deposited to global oceanic regions. Compared to simulations only taking into account proton-promoted Fe dissolution, the addition of oxalate and Fe(II)/Fe(III) redox cycling to the dust-Fe mobilization scheme increased total annual model-predicted Fe-d deposition to global oceanic regions by similar to 75 %. The implementation of Fe(II)/Fe(III) photochemical redox cycling in the model also allows for the distinction between different oxidation states of deposited Fe-d. Our calculations suggest that during the daytime, large fractions of Fe-d deposited to the global oceans is likely to be in Fe(II) form, while nocturnal fluxes of Fe-d are largely in Fe(III) form. Model sensitivity simulations suggest Fe-d fluxes to the oceans can range from similar to 50% reduction to similar to 150% increase associated with the uncertainty in Fe-containing minerals commonly found in dust particles. This study indicates that Fe-d deposition to the oceans is controlled by total dust-Fe mass concentrations, mineralogy, the surface area of dust particles, atmospheric chemical composition, cloud processing, and meteorological parameters and exhibits complex and spatiotemporally variable patterns. Our study suggests that the explicit model representation of individual processes leading to Fe-d production within mineral dust are needed to improve the understanding of the atmospheric Fe cycle, and quantify the effect of dust-Fe on ocean biological productivity, carbon cycle, and climate.