In this study, we present a multilevel in situ pore water sampler that allows pore water sampling down to 5 m sediment depth. The sampler forms a crucial tool to study biogeochemical processes on different time scales in advective pore water systems. After insertion into the sediment, the sampler stays on site, allowing repetitive sampling at identical locations and depth intervals. The sampler has been successfully tested for 1 year in sandy sediments in the backbarrier tidal flats of Spiekeroog Island at the German North Sea coast. Depth profiles of redox-sensitive elements show a high depth resolution and are not affected by oxidation artifacts during extraction. Seasonal variations because of advection and changing microbial activity are apparent for some element species even at sediment depths of 5 m.
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). Nonconservative 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 microzones 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.
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