Iron–manganese concretions contribute to benthic release of phosphorus and arsenic in anoxic conditions in the Baltic Sea

Abstract

Deposits of iron–manganese (Fe, Mn) concretions forming a large storage of phosphorus (P) and arsenic (As) are frequently under pressure of oscillating oxygen conditions in the eutrophic Gulf of Finland, the Baltic Sea. Yet, there is a poor understanding how anaerobic microbial processes regulate the cycling of elements in the concretions. The objective of this study was to highlight how the microbial processes control the release of elements from the concretions to brackish water during anoxia. Spherical concretions were collected from the oxic bottoms of the Gulf of Finland in the summer. Concretions and autoclaved controls were incubated in anoxic artificial brackish seawater with and without labile carbon, plus supplied with ammonium at 5, 10, and 20 °C for 15 weeks. Concentrations of Fe, Mn, P, and As were measured from the intact concretions and the ambient solutions during the experiment. Also, the consumption of the added ammonium and organic carbon and the formation of dissolved inorganic carbon were measured. At near-bottom temperature 5 °C, the concretions released at highest 0.12, 0.42, 0.02, and 0.0002 μmol g−1 day−1 of Fe, Mn, P, and As, respectively. The rates were significant only in the microcosms with added labile carbon, and only minor proportions (0.1–0.4 %) of their total contents were released during the incubations. The concretions removed completely the supplied ammonium only without carbon addition. We find that concretion deposit may form a local hot spot for the microbial reduction of Fe and Mn and release significant amounts of P and As, and participate in N cycling besides the bottom sediments of the Gulf of Finland during prolonged anoxia. However, the concretions may maintain their binding capacity for P and As longer than the fine-grained organic-rich sediment during anoxia. During anoxia concretion deposits may form a temporal source of bioavailable P having ecological significance in the Gulf of Finland when concretions have access to labile organic carbon. Concretions from the Baltic Sea, the oceans, lakes, and soils contain high concentrations of Mn and Fe, but their proportions vary considerably. Anaerobic microbial processes may thus affect the stability of concretions from the different environments, but the outcome may depend on the ambient geochemical conditions.