Thallium cycling in pore waters of intertidal beach sediments

Pore water data of thallium (Tl) in marine environments are scarce. It has been suggested that anoxic sediments are a sink for dissolved Tl likely due to its incorporation into Fe sulfides. However, recent studies indicated that Tl is removed from solution prior to the onset of sulfidic conditions and that Tl is involved in biological cycles in coastal seawater. To assess the Tl behavior in marine sediments, pore waters of a high energy beach (Spiekeroog Island, Germany) were sampled during different seasons and on different spatial scales. The study site provides a perfect set of samples to assess trace metal behavior under various redox conditions. Samples were analyzed for the dissolved trace metals Tl, molybdenum (Mo), uranium (U), and rhenium (Re). Additionally, sediments were incubated to monitor trace metal removal or release under controlled conditions. On-site redox conditions were characterized using dissolved oxygen (O-2), manganese (Mn), and iron (Fe) concentrations. Our results indicated high enrichments of Tl in pore waters concurrently to aerobic organic matter (OM) degradation, exceeding seawater concentrations up to 6-fold. In contrast, Tl was completely removed in weakly reducing pore water characterized by more than 1 mu M Mn or Fe. The spatial Tl distribution in intertidal pore waters responded to the present dissolved Mn and Fe level, which varied in space and with season. We suggest, Tl release to be attributed to OM degradation, particle desorption, or reoxidation, whereas Tl removal is likely related to the presence of trace amounts of dissolved sulfide. In conclusion, the fast reaction kinetics of Tl led to fast and complete removal in comparison to Mo, U, and Re and we suggest the following order of removal: Tl > Re > U > Mo. The removal behavior as well as the high enrichments of Tl in pore waters implicate that sinks and sources in the marine environment are not yet fully understood. Although the intertidal sediments form an overall sink for Tl (U and Re), especially under mostly anoxic conditions in summer, sediments turn into a Tl net source in winter, when sediments are more oxic. For global marine Tl balances, Tl fluxes have been estimated based on pore water Tl/Mn ratios. Contrastingly, Tl removal from pore waters at low threshold concentrations of Mn at our site indicated that these Tl flux estimations may not be applicable in permeable sandy beach sediments and in many other types of sediments, which host mildly sulfidic conditions. (C) 2021 Elsevier Ltd. All rights reserved.