Photoreductive dissolution of ferrihydrite by methanesulfinic acid: Evidence of a direct link between dimethylsulfide and iron-bioavailability

Within open-ocean regions where excess macronutrients are present, phytoplankton growth is limited by the bioavailability of iron supplied to these areas primarily within atmospheric aerosols of crustal origin. However, processes that control the abundance of biologically accessible iron in these aerosols are largely unknown. Here we show that dissolution of ferrihydrite, a surrogate iron(oxy) hydroxide phase found in atmospheric waters, is enhanced in the presence of methanesulfinic acid (MSIA, CH3SO2H, a dimethylsulfide (DMS) oxidation intermediate) in laboratory irradiation experiments with aqueous suspensions that simulate marine aerosol particles. The increased release of soluble Fe(II) is attributed to a species specific and direct photochemical reduction rather than a proton-promoted effect, and suggests an efficient mechanism by which iron-starved phytoplankton can actively increase aerosol iron-bioavailability by increasing DMS emissions.