A laboratory study of the biogeochemical cycling of Fe,Mn, Zn and Cu across the sediment-water interface of a productive lake

Laboratory incubation experiments were carried out on sediment cores collected from Esthwaite Water, U.K., during April 1987, when the sediments displayed a characteristic surface (1.5 to 2 cm) oxide floc. The experiments were undertaken at 10°C, in the dark, under variable redox and pH conditions for periods of ~ 720 h (30 d). In some cases, realistic amounts of decomposing lake algae were added to simulate the deposition of an algal bloom. Pore waters and overlying waters were obtained from the incubated sediment cores at various time intervals and the samples analysed for pH and dissolved Fe, Mn, Zn and Cu by AAS. The results demonstrated that trace metal concentrations at the sediment-water interface can show rapid, pulsed responses to episodic events associated with controlling factors such as algal deposition and mixing conditions. The variations in dissolved Fe and Mn concentrations could generally be explained by their well known redox behaviour. Appreciable loss of Mn from solution under conditions of well-developed anoxia was consistent with adsorption of Mn²⁺ by FeS. Cu and Zn were both rapidly (24 h) released into solution during incubation of sediment cores prior to the development of anoxia in the overlying waters. Their most likely sources were the reductive remobilization of Mn oxides and the decomposition of organic matter. The addition of decomposing algae to a series of cores resulted in even higher interfacial dissolved concentrations of Cu and Zn, probably through acting as a supplementary source of the metals and through increased oxide dissolution. Switching from anoxic to oxic conditions also rapidly increased dissolved Cu and Zn concentrations, possibly due to their release during the oxidation of metal sulphides. The enhanced releases of dissolved Cu and Zn were generally short-lived with removal being attributed to the formation of sulphides during anoxia and to adsorption by Fe and Mn oxides under oxic conditions.