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The micronutrient iron is now recognized to be important in regulating the magnitude and dynamics of ocean primary productivity, making it an integral component of the ocean's biogeochemical cycles. In this Review, we discuss how a recent increase in observational data for this trace metal has challenged the prevailing view of the ocean iron cycle. Instead of focusing on dust as the major iron source and emphasizing iron's tight biogeochemical coupling to major nutrients, a more complex and diverse picture of the sources of iron, its cycling processes and intricate linkages with the ocean carbon and nitrogen cycles has emerged.

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In nearly a dozen open‐ocean fertilization experiments conducted by more than 100 researchers from nearly 20 countries, adding iron at the sea surface has led to distinct increases in photosynthesis rates and biomass. These experiments confirmed the hypothesis proposed by the late John Martin [Martin, 1990] that dissolved iron concentration is a key variable that controls phytoplankton processes in ocean surface waters However, the measurement of dissolved iron concentration in seawater remains a difficult task [Bruland and Rue, 2001] with significant interlaboratory differences apparent at times. The availability of a seawater reference solution with well‐known dissolved iron (Fe) concentrations similar to open‐ocean values, which could be used for the calibration of equipment or other tasks, would greatly alleviate these problems [National Research Council (NRC), 2002[.

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Dissolved iron (Fe) speciation in the Columbia River plume, the San Francisco Bay plume, and the Columbia River estuary was investigated using competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) with the added ligand salicylaldoxime. A stronger L 1 -type Fe-binding ligand class was measured in all surface samples, and in the Columbia River estuary. A weaker L 2 -type ligand class was present in the far-field Columbia River plume and the San Francisco Bay plume but was not observed in the low-salinity (S 5 1.4-22.5) waters of the near-field Columbia River plume or estuary. Concentrations of total dissolved Fe were correlated with the concentrations of the stronger L 1 -type ligand in nonestuarine (S . 13) surface samples. Leachable particulate (.0.4 mm) Fe concentrations in the Columbia River plume were measured to supplement existing data from the San Francisco Bay plume. There is a large concentration of readily leachable particulate Fe in the two plumes, yet it is the concentration of ambient L 1 -type ligands that appears to dictate the concentration of dissolved Fe in these waters and, consequently, the supply of dissolved Fe to neighboring coastal waters. The correlation between dissolved Fe and L 1 ligand concentrations in both plume waters, as well as in California Current and upwelled surface waters, suggests that this relationship will persist in other coastal environments and should be considered when evaluating and modeling coastal Fe cycling and supply.

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