Iron geochemistry under mussel rafts in the Galician ria system (Galicia-NW Spain)

The intensive mussel culture carried out in the past 40 years in the Rias of Vigo and Arousa (Galicia-NW Spain) has led to substantial changes in the ecology and geochemistry of the seabed in these areas. Organic C enrichment of the seabed has generated strongly reducing conditions that directly affect the geochemistry of Fe and S. In the present study a total of six sediment cores were collected from the seabed under mussel rafts, and two different layers were distinguished: the biodeposit generated by the mussels, and the sediment situated immediately below this. Samples of each were analyzed to determine the pH, redox potential, sulphate and chloride in the interstitial water, as well as total percentage of organic C (TOC), N and S. Sequential extraction of the samples differentiated six fractions of Fe: exchangeable, carbonate, ferrihydrite, lepidocrocite, goethite and pyrite. The contents of total Fe, Fe associated with silicates, Fe soluble in 1 M HCl and AVS-Fe were also determined. In general, both the biodeposit and the sediment were anoxic (Eh < 100 mV) and there were no significant differences between the two in the total Fe or in the Fe associated with silicates, which appears to indicate that the input of Fe to the system did not vary greatly. However, there were significant differences between the sediment and the biodeposit in terms of the forms of Fe in each layer. The concentrations of pyrite in the biodeposit (0.37 ± 0.25 μmol g−1) were high but significantly lower than in the sediment (1.10 ± 0.20 μmol g−1), and there remained large quantities of reactive-Fe that were susceptible to pyritisation. In contrast, in the sediment, the reactive-Fe was intensively pyritised, and judging from the ratio of TOC–DOP, it limited synthesis of pyrite. Furthermore, a plot of the concentration of pyrite-S against TOC revealed an excess of ∼15% of pyrite-S, which is explained by the partial decoupling of pyrite formation from organic matter accumulation, caused by the formation of pyrite from the H2S generated by the anaerobic oxidation of methane. The latter process also appears to favour, although to a lesser extent, the precipitation of Ca carbonate, with incorporation of Fe.