Dissolved iron(II) in the Pacific Ocean: Measurements from the PO2 and P16N CLIVAR/CO2 repeat hydrography expeditions

The redox speciation of dissolved iron in seawater was evaluated at 121 locations in the Pacific Ocean at depths of 15-1000 m, using the method of luminol chemiluminescence. The results indicate that reduced iron, Fe(II), is ubiquitous in surface seawater with a relatively consistent pattern of occurrence. Surface maxima were present in most profiles, with median concentrations of 25-30 pM representing 12-14% of the total dissolved iron. Concentrations decreased monotonically with depth to<12 pM within the upper euphotic zone. This pattern was observed during both day and nighttime sampling events, which suggests that non-photochemical production mechanisms can produce photochemical-like signatures. Further, if theoretical rates of Fe(II) oxidation are applicable to the open ocean, then the employed sampling methods precluded assessment of photochemically-produced Fe(II), regardless of ambient light conditions. For this and other reasons, the concentrations reported here for the upper water column likely represent lower limits of labile iron concentration, and suggest that dissolved iron may be more available for uptake than previously believed. Deeper in the water column, Fe(II) was also frequently detected, though it constituted a small fraction of the total dissolved iron. Possible source mechanisms at these depths include thermal (dark) reduction of Fe(III) organic complexes or remineralization of sinking biogenic particles containing Fe(II). In the northern Philippine Sea between the Japanese coast and the Izu-Bonin volcanic arc system, Fe(II) concentrations were found to be atypically high, possibly because of high atmospheric dust deposition near the surface and transport of sediment-derived iron at depth.