The biogeochemical cycles of iron and organic carbon are strongly interlinked. In oceanic waters, organic ligands have been shown to control the concentration of dissolved iron. In soils, solid iron phases shelter and preserve organic carbon, but the role of iron in the preservation of organic matter in sediments has not been clearly established. Here we use an iron reduction method previously applied to soils to determine the amount of organic carbon associated with reactive iron phases in sediments of various mineralogies collected from a wide range of depositional environments. Our findings suggest that 21.5 ± 8.6 per cent of the organic carbon in sediments is directly bound to reactive iron phases. We further estimate that a global mass of (19-45) × 10(15) grams of organic carbon is preserved in surface marine sediments as a result of its association with iron. We propose that these associations between organic carbon and iron, which are formed primarily through co-precipitation and/or direct chelation, promote the preservation of organic carbon in sediments. Because reactive iron phases are metastable over geological timescales, we suggest that they serve as an efficient 'rusty sink' for organic carbon, acting as a key factor in the long-term storage of organic carbon and thus contributing to the global cycles of carbon, oxygen and sulphur.
The sinking of particulate organic matter from ocean surface waters transports carbon to the ocean interior, where almost all is then recycled. The unrecycled fraction of this organic matter can become buried in ocean sediments, thus sequestering carbon and so influencing atmospheric carbon dioxide concentrations. The processes controlling the extensive biodegradation of sinking particles remain unclear, partly because of the difficulty in resolving the composition of the residual organic matter at depth with existing chromatographic techniques. Here, using solid-state 13C NMR spectroscopy, we characterize the chemical structure of organic carbon in both surface plankton and sinking particulate matter from the Pacific Ocean and the Arabian Sea. We found that minimal changes occur in bulk organic composition, despite extensive (>98%) biodegradation, and that amino-acid-like material predominates throughout the water column in both regions. The compositional similarity between phytoplankton biomass and the small remnant of organic matter reaching the ocean interior indicates that the formation of unusual biochemicals, either by chemical recombination or microbial biosynthesis, is not the main process controlling the preservation of particulate organic carbon within the water column at these two sites. We suggest instead that organic matter might be protected from degradation by the inorganic matrix of sinking particles.
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