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Recent investigations have revealed significant fractionation of 238U/235U between organic-rich sediments of anoxic marginal seas and seawater, indicating redox-dependent U isotope fractionation. This study explores the conditions controlling U isotope fractionation in selected modern anoxic basins (Baltic Sea: Landsort and Gotland Deeps and the Kyllaren fjord in Norway) and compares U with Mo isotope fractionation. Therefore, the concentrations and isotope compositions of dissolved U and Mo from the water column and organic-rich sediments from three currently anoxic basins have been analysed. The water column samples from the Kyllaren fjord display a moderate depletion of U and a strong depletion of Mo with increasing depth. These variations are associated with a decrease in δ238U and an increase in δ98Mo with depth, from − 0.35 ‰ to − 0.70 ‰ and from 2.4 ‰ to 2.6 ‰, respectively. From the U isotope composition of the deep euxinic water column of the Kyllaren fjord, a minimum value of Δ238Ured ≈ 0.7 ‰ for the U isotope fractionation during reduction is inferred. Due to the high sedimentation rate in the Kyllaren fjord, surface sediment samples are only moderately enriched in U and Mo (~ 4 μg/g and 6 μg/g to 37 μg/g, respectively) and display δ238U and δ98Mo averages of − 0.26 ‰ ± 0.10 ‰ and 2.18 ‰ ± 0.21 ‰, respectively. Water column samples from the Baltic Sea display a minor decrease in the U and Mo concentrations and only negligible U and Mo isotope fractionation compared to open seawater. The sediment layers from the Baltic Sea (Landsort Deep), which were deposited under mostly anoxic conditions, are moderately enriched in U (up to 8 μg/g) and highly enriched in Mo (up to 222 μg/g). However, U and Mo isotopic compositions are significantly lighter (with δ238U of − 0.36 ‰ ± 0.08 ‰ and δ98Mo of − 0.04 ‰ ± 0.11 ‰) than those of typical organic-rich sediments from anoxic basins. These findings reveal that compared to Mo, the U isotopic composition of sediments in restricted and strongly euxinic basins like the Kyllaren fjord is significantly more dependent on (1) the extent of U removal from the water column, which is lower than that of Mo, and on (2) the sedimentation rate (i.e., the fraction of authigenic U relative to detrital U in the sediment), which is also lower compared to that of Mo. In more open and only temporarily euxinic basins such as the investigated basins of the Baltic Sea, strong Mo is coupled with weak U isotope fractionation between water and sediment. These signatures were likely the result of isotope fractionation under weakly sulfidic conditions and the generation of isotopically light Mo during frequently occurring flushing events with oxygen-rich water from the open sea. This implies that Mo and U isotope signatures of sediments only record paleo-water column redox conditions of restricted basins if the water column was permanently stratified.

Here we present stable isotope data for vertical profiles of dissolved molybdenum of the modern euxinic water columns of the Black Sea and two deeps of the Baltic Sea. Dissolved molybdenum in all water samples is depleted in salinity-normalized concentration and enriched in the heavy isotope (δ98Mo values up to + 2.9‰) compared to previously published isotope data of sedimentary molybdenum from the same range of water depths. Furthermore, δ98Mo values of all water samples from the Black Sea and anoxic deeps of the Baltic Sea are heavier than open ocean water. The observed isotope fractionation between sediments and the anoxic water column of the Black Sea are in line with the model of thiomolybdates that scavenge to particles under reducing conditions. An extrapolation to a theoretical pure MoS42− solution indicates a fractionation constant between MoS42− and authigenic solid Mo of 0.5 ± 0.3‰. Measured waters with all thiomolybdates coexisting in various proportions show larger but non-linear fractionation. The best explanation for our field observations is Mo scavenging by the thiomolybdates, dominantly — but not exclusively — present in the form of MoS42−. The Mo isotopic compositions of samples from the sediments and anoxic water column of the Baltic Sea are in overall agreement with those of the Black Sea at intermediate depth and corresponding sulphide concentrations. The more dynamic changes of redox conditions in the Baltic deeps complicate the Black Sea-derived relationship between thiomolybdates and Mo isotopic composition. In particular, the occasional flushing/mixing, of the deep waters, affects the corresponding water column and sedimentary data. δ98Mo values of the upper oxic waters of both basins are higher than predicted by mixing models based on salinity variations. The results can be explained by non-conservative behaviour of Mo under suboxic to anoxic conditions in the shallow bottom parts of the basin, most pronounced on the NW shelf of the Black Sea.

Three drill cores from the marshlands of NW Germany, which cover the entire Holocene, were analyzed at high-resolution for bulk composition, Al, Fe, selected trace metals, and stable sulfur isotopes. The drill cores contain two lithological types of peat: (i) basal peats overlying Pleistocene sands and (ii) intercalated peats situated between clastic sediments of predominantly marine origin. The peat layers are characterized by distinct enrichments in pyrite due to microbial sulfate reduction under almost open system conditions with respect to seawater sulfate as shown by sulfur isotope partitioning. The main Fe source seems to be the freshwater environment. The determination of dissolved and particulate Fe of channels and small rivers close to the study area revealed a 50-fold higher Fe content of the freshwater environment when compared with North Sea water. Pyrite enrichments are explained by two scenarios: (i) pyrite formation coincides with fen reed peat growth (basal and intercalated) under the influence of a brackish water zone (salinity app. 5–15) and (ii) pyrite was formed after peat growth in the lowest limnic basal peat intervals. Maximum pyrite accumulation (TS 28%) occurs in latter peats that contain thin clastic layers as a result of tidal channel activities after peat formation. The occurrence of clastic layers may have favoured the inflow of saline groundwater. The peat layers are also characterized by enrichments in redox-sensitive trace metals (As, Mo, Re, U) and Cd, whereas Co, Cr, Cu, Mn, Ni, Pb, Tl, and Zn reflect the geogenic background. Leaching experiments have shown that As, Co, Cu, Mo, Re, and Tl are predominantly fixed as sulfides and/or incorporated into pyrite. The remaining trace metals show no distinct trends, only Cr reveals a strong relation to the lithogenic detritus. Seawater is the dominating source for As, Cd, Mo, Re, and U. The remaining trace elements seem to have a freshwater source similar to Fe. In contrast to the distribution of pyrite, highest amounts of redox-sensitive trace metals are seen in fen reed peats (basal and intercalated) that were formed under a direct influence of seawater and brackish water, respectively. Therefore, we suggest that saline groundwater entering the basal peats was probably depleted in redox-sensitive trace metals, e.g. owing to microbially induced reduction of trace metals and subsequent precipitation as sulfides or fixation by organic matter.