The speciation of marine particulate iron adjacent to active and passive continental margins

Abstract

We use synchrotron-based chemical-species mapping techniques to compare the speciation of suspended (1–51μm) marine particulate iron collected in two open ocean environments adjacent to active and passive continental margins. Chemical-species mapping provides speciation information for heterogeneous environmental samples, and is especially good for detecting spectroscopically distinct trace minerals and species that could not be detectable by other methods. The average oxidation state of marine particulate iron determined by chemical-species mapping is comparable to that determined by standard bulk X-ray Absorption Near Edge Structure spectroscopy. Using chemical-species mapping, we find that up to 43% of particulate Fe in the Northwest Pacific at the depth of the adjacent active continental margin is in the Fe(II) state, with the balance Fe(III). In contrast, particulate iron in the eastern tropical North Atlantic, which receives the highest dust deposition on Earth and is adjacent to a passive margin, is dominated by weathered and oxidized Fe compounds, with Fe(III) contributing 90% of total iron. The balance is composed primarily of Fe(II)-containing species, but we detected individual pyrite particles in some samples within an oxygen minimum zone in the upper thermocline. Several lines of evidence point to the adjacent Mauritanian continental shelf as the source of pyrite to the water column. The speciation of suspended marine particulate iron reflects the mineralogy of iron from the adjacent continental margins. Since the solubility of particulate iron has been shown to be a function of its speciation, this may have implications for the bioavailability of particulate iron adjacent to passive compared to active continental margins.