Trace metal dynamics in the water column and pore waters in a temperate tidal system: response to the fate of algae-derived organic matter

Abstract

Tidal and seasonal behaviour of the redox-sensitive trace metals Mn, Fe, Mo, U, and V have been investigated in the open-water column and shallow pore waters of the backbarrier tidal flats of the island of Spiekeroog (Southern North Sea) in 2002 and 2007. The purpose was to study the response of trace metal cycles on algae blooms, which are assumed to cause significant changes in the redox state of the entire ecosystem. Trace metal data were complemented by measurements of nutrients and enumeration of algae cells in 2007. Generally, Mn and V show a tidal cyclicity in the water column with maximum values during low tide which is most pronounced in summer due to elevated microbial activity in the sediments. Mo and U behave almost conservatively throughout the year with slightly increasing levels towards high tide. Exceptions are observed for both metals after summer algae blooms. Thus, the seasonal behaviour of the trace metals appear to be significantly influenced by productivity in the water column as the occurrence of algae blooms is associated with an intense release of organic matter (e.g. transparent exopolymer particles, TEP) thereby forming larger organic-rich aggregates. Along with elevated temperatures in summer, the deposition of such aggregates favours microbial activity within the surface sediments and release of DOC, nutrients and trace metals (Mn, Mo and V) during the degradation of the aggregates. Additionally, pronounced reducing conditions lead to the reduction of Mn(IV)-oxides and Fe(III)-(oxihydr)oxides, thereby releasing formerly scavenged compounds as V and phosphate. Therefore, pore-water profiles show significant enrichments in trace metals especially from July to September. Finally, the trace metals are released to the open water column via draining pore waters (esp. Mo, Mn, and V) and/or fixed in the sediment as sulphides (Fe, Mo) and bound to organic matter (U). Non-conservative behaviour of Mo in oxygenated seawater, first observed in the investigation area by Dellwig et al. (Geochim Cosmochim Acta 71:2745–2761, 2007a), was shown to be a recurrent phenomenon which is closely coupled to bacterial activity after the breakdown of algae blooms. In addition to the postulated fixation of Mo in oxygen-depleted micro-zones of the aggregates or by freshly formed organic matter, a direct removal of Mo from the water column by reduced sediment surfaces may also play an important role.