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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.

Back-barrier tidal flat systems are characterized by basins and inlets through which water is exchanged with the coastal sea by tidal water movements. The hydrographic and morphometric properties at the inlets and in the basins vary considerably, but there is little information available how biogeochemical properties in the water column at these different sites respond to these differences. Therefore, we investigated tidal dynamics of suspended particulate matter (SPM), particulate and dissolved organic carbon (DOC), chlorophyll a, phaeopigments, numbers of particle-associated (PA) and free-living bacteria (FL), bacterial biomass production, and concentrations of dissolved manganese (Mn). Samples were taken at the surface, a mid-depth and 1 m above the bottom at a fixed station at the inlet and in the basin of the Spiekeroog back-barrier tidal flat system in the German Wadden Sea. Five tidal cycles representative for typical seasonal situations, January (winter), April and May (late spring bloom), July (summer), and November (late fall) were studied in 2005 and 2006. In July, processes related to phytoplankton dynamics and bacterial decomposition were much more enhanced in the basin, whereas in April, these processes were enhanced at the inlet but were particularly low within the basin itself. The low values within the basin were a result of the settled phytoplankton spring bloom and represent a rather short period at the decline of this bloom. In November and January, differences were much less pronounced than during the growing season and restricted mainly to SPM and PA bacteria, exhibiting higher values in the basin. FL bacteria, DOC, and dissolved Mn exhibited different patterns and much less differences between the two stations, indicating that biogeochemical processes in the dissolved phase were controlled by different factors than PA biogeochemical processes. These differences reflect the retentive properties of the basin for particles and PA biogeochemical processes, particularly during the growing season, and in general emphasize the high productivity of back-barrier tidal flat systems.

The spatial and temporal distributions of chromophoric dissolved organic matter (CDOM) and dissolved organic carbon (DOC) was studied in the East-Frisian Wadden Sea (Southern North Sea) during several cruises between 2002 and 2005. The spatial distribution of CDOM in the German Bight shows a strong gradient towards the coast. Tidal and seasonal variations of dissolved organic matter (DOM) identify freshwater discharge via flood-gates at the coastline and pore water efflux from tidal flat sediments as the most important CDOM sources within the backbarrier area of the Island of Spiekeroog. However, the amount and pattern of CDOM and DOC is strongly affected by various parameters, e.g. changes in the amount of terrestrial run-off, precipitation, evaporation, biological activity and photooxidation. A decoupling of CDOM and DOC, especially during periods of pronounced biological activity (algae blooms and microbial activity), is observed in spring and especially in summer. Mixing of the endmembers freshwater, pore water, and open sea water results in the formation of a coastal transition zone. Whilst an almost conservative behaviour during mixing is observed in winter, summer data point towards non-conservative mixing.