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The flow path of a river draining a lowland in the southern Baltic Sea, the Warnow River, was investigated to evaluate its freshwater composition as a source of dissolved substances to regional coastal waters. A spatial study was carried out once to follow the variations from the source to the estuary. A temporal study in the composition as a function of the season, during 6 years (2017-2022), was carried out at a site just before the river reaches the estuary. Surface water was sampled to analyze major and tracer elements, stable (H, C, O, S), and unstable (Ra) isotopes. The results show that the composition of the Warnow River along the flow path is controlled by a complex interplay between in-situ processes, exchange with the atmosphere, diffuse groundwater, and surface water inlets. On a temporal scale, pH, nutrient, and redox sensitive trace element concentrations are strongly impacted by pelagic primary production in spring. During summer and autumn, influences occurred by benthic microbial activity, associated diffusive release from soils/sediments, and surface water inlets. Throughout the investigation period, the Warnow River was a source of isotopically light CO2 to the atmosphere and DIC to the estuarine waters. The delivered DIC concentrations seem to vary with the season due to changes in biological pelagic and benthic activity. DOC was derived from a mixture of C3 organic sources and fertilizers. From concentration-discharge relationships, examples of dilution, mobilization, and chemostasis trends were found. Discharge-controlled seasonal trends are superimposed by system-internal processes and the hydrological consequences of river and drainage management. Our analysis thus provides new insights into the controls on the variations of water and solutes in a managed river at the land-sea interface as part of the regional hydrological cycle of a lowland catchment coastal water system. The study was supported by the DFG research training group BALTIC TRANSCOAST, DAAD , and the BMBF project CARBOSTORE/COOLSTYLE

Due to their pronounced bioactivity and limited availability from natural resources, metabolites of the soft coral Pseudopterogorgia elisabethae, such as erogorgiaene and the pseudopterosines, represent important target molecules for chemical synthesis. We have now developed a particularly short and efficient route towards these marine diterpenes exploiting an operationally convenient enantioselective cobalt‐catalyzed hydrovinylation as the chirogenic step. Other noteworthy C−C bond forming transformations include diastereoselective Lewis acid‐mediated cyclizations, a Suzuki coupling and a carbonyl ene reaction. Starting from 4‐methyl‐styrene the anti‐tubercular agent (+)‐erogorgiaene (>98 % ee) was prepared in only 7 steps with 46 % overall yield. In addition, the synthesis of the pseudopterosin A aglycone was achieved in 12 steps with 30 % overall yield and, surprisingly, was found to exhibit a similar anti‐inflammatory activity (inhibition of LPS‐induced NF‐κB activation) as a natural mixture of pseudopterosins A−D or iso‐pseudopterosin A, prepared by β‐D‐xylosylation of the synthetic aglycone., Applied metal catalysis: Exploiting a practical protocol for the asymmetric hydrovinylation of stryrenes in the opening move, the stereoselective total synthesis of bioactive constituents of the soft coral pseudopterogorgia elisabethae was efficiently achieved in sequence of metal‐mediated steps to provide sufficient material for further biological investigations.

Land-ocean interactions in the coastal zone are of particular interest regarding the exchange of substances, like nutrients, carbon, sulfur, metals, and water. The rising sea level is and will enhance the pressure of salty solutions on previously fresh water ecosystems. We present here new results on the isotope biogeochemistry of a rewetted peatland, at the southern Baltic Sea, that is impacted by event-type flooding with brackish seawater. Sediment cores on transects through the wetland were investigated for their pore water and solid phase (mineral and organic matter) composition. Different fractions of the soils and solutions were analyzed for the elemental composition, mineral micro-textures, and the stable isotope composition (H, C, O, S) to understand the changes in water and biogeochemical carbon-sulfur-metal cycles due to flooding and the consequence for the development of sulfur isotope signatures in authigenic mineral phases and organic matter.Flooding events with brackish water increased the availability of sulfate as an electron acceptor for microbial carbon transformations. This added sulfur impacted the remineralization capacity of organic substrates and created space for mineral authigenesis, with related iron sulfide textures. It yields isotope signals that are indicative for non-steady state biogeochemistry of coastal ecosystems and allow for a transfer of proxy information to other modern and past coastal organic-rich peatlands.The soil cores from the peatland reflects the intense activity of sulfate-reducing bacteria and the associated formation of iron sulfides (essentially pyrite) and provided the isotope evidence for site-dependent sulfurization of organic matter. Sedimentary sulfur fractions and their stable isotope signatures are controlled by the availability of dissolved organic matter and/or methane, reactive iron, and in particular dissolved sulfate and, thereby, from the relative position with respect to the coast line, and depend on the surface topography and soil characteristics. Further mechanistic investigations consider the role of DOS upon changing sulfur substrate availability. Acknowledgement for support by DFG-Baltic TRANSCOAST, ERASMUS, DAAD, Leibniz-IOW

Land-ocean interactions in the coastal zone (LOICZ) are of particular interest regarding the exchange of water and elements, like nutrients, carbon, sulfur, and metals. Processes impacting groundwater fluxes at these boundaries belong to the still unsolved problems in hydrology (Blöschl et al., 2019). Stable isotope signatures (H, C, O, S), major and trace element contents in surface waters of a rewetted coastal peatland were investigated to understand the impact of storm-induced flooding by brackish seawater on hydrology and biogeochemical element cycling.The study area is the Hütelmoor, a wetland located at the coastline of the southern Baltic Sea. The area is characterized by a continuous release of fresh water to the Baltic Sea via submarine groundwater discharge (Jurasinski et al., 2018). Surface water is partly drained to a nearby river, but the introduction of brackish waters into the peatland is typically precluded by a small dune and limited to storm-induced flooding events. In the present study, the spatially distributed composition of surface waters was investigated briefly after a flooding event. The results are compared with previous campaigns without actual salt water impact. Conservative elements and water isotopes demonstrate the importance of seasonal variations due to varying evapotranspiration during pre-flood times and allow for a quantification of mixing processes in the post-flood waters. The impact of soil respired CO2, and/or the mineralization of organic matter or methane on the surface waters is indicated by a shift of the C isotope composition of DIC towards lighter data. The S and O isotopic composition of dissolved sulfate indicates an impact by solutions modified by net microbial sulfate reduction on pre-flood surface waters and a potential oxidation of reduced sulfur species in post-flooding solutions. Previous flooding events already impacted element cycling in the peatland’s past and are also reflected by a sulfidization of peat layers (Fernández-Fernández et al., 2017) and the observation of local areas with enhanced dissolved concentrations in the central part of the peatland.The study is supported by DFG during GK Baltic TRANSCOAST, DAAD, and Leibniz IOW. References:Blöschl G. et al. (2019) Twenty-three unsolved problems in hydrology (UPH) – a community perspective. Hydrol. Sci. J. 64, 1141-1158. Jurasinski G. et al. (2018) Understanding the coastal ecocline: Assessing sea-land-interactions at non-tidal, low-lying coasts through interdisciplinary research. Front. Mar. Sci. 5, 1-22. Fernández-Fernández L.E. et al. (2017) Sulfur isotope biogeochemistry of soils from an episodically flooded coastal wetland, southern Baltic Sea. Geophys. Res. Abs. 19, EGU2017-14335.

The interface of land and sea is of particular interest regarding the exchange of elements, like nutrients, carbon and sulfur. Submarine groundwater discharge (SGD) is an important pathway for element exchange from the terrestrial to the marine environment and vice versa. The discharging water can not only consist of fresh ground water but also of a considerable proportion of recirculated often brackish seawater.Here, we followed the water and element exchange and associated biogeochemical transformation processes in front of a rewetted peatland at the southern Baltic Sea. Vertical pore water profiles were retrieved via up to 5 m long multi-port pore water samplers on a seasonal base. An extrodinary storm event in early 2019 not only led to the partial flooding of an associated coastal peatland with brackish water but also pushed Baltic Sea water into the coastal aquifers allowing to investigate the time-dependent return to previous subterrestrial ‚normal‘ conditions via SGD-induced freshening. Weekly sampling was carried out to follow the changes after the storm event in the sediments in front of a coastal peatland. Here we present new results of the pre- and after storm event pore water profiles. A focus was set on the investigation of tracers for concentration gradients of major and redox-sensitive trace elements, nutrients and the stable isotope composition (H, C, S, O) of water, dissolved inorganic carbon (DIC) and sulfate to understand the mixing processes and superimposing biogeochemical transformation reactions.We found evidence for a strong control of the bottom-pore water exchange by lithology and a high activity of dissimilatory sulfate-reducing microorganisms in the coastal sediments leading to the accumulation of substantial DIC superimposed by corrosion of sedimentary carbonates. Acknowledgement: This study is supported by the DFG research training group Baltic TRANSCOAST and the Leibniz IOW.

The seminal synthesis of the sesquiterpene (±)-α-cedrene reported by Wender in 1981 offers a uniquely short and elegant access to the bridged-tricyclic target compound by exploiting an intramolecular arene-olefin photocycloaddition. However, the synthesis was performed only in the racemic series so far. This synthesis was now re-investigated and the catalytic methods for the enantioselective preparation of the chiral key intermediate were evaluated. It was found that Cu-catalyzed allylic substitution of a cinnamyl chloride with MeMgBr in the presence of a Taddol-derived chiral phosphine-phosphite ligand affords the corresponding (1-methylallyl)arene with high enantioselectivity (94% ee). Hydroboration and subsequent Suzuki coupling gave (R)-curcuphenol methyl ether from which (–)-α-cedrene was prepared along the route paved by Wender.

In some cases difficult-to-read learning materials lead to better performance than easy to-read materials. This phenomenon is called the disfluency effect and is attributed to a subjective feeling of task difficulty resulting in a deeper learning approach. In two studies (n1 = 67, n2 = 73) we investigated the impact of three increasing disfluency levels compared to a fluent condition on learning outcomes, in the second study we additionally addressed effects on cognitive load and time on task. The first study revealed significant differences of the experimental groups and on a descriptive level a reversed u-shape pattern, i.e., learning performance increases with increasing disfluency but decreases when the text becomes too illegible. The same pattern could be found significantly in the second study for recall and transfer performance, engagement and time on task and the reversed pattern for extraneous load. Results indicate that there is in fact an optimal level of disfluency on performance that comes along with increased engagement and that there is a breaking point of disfluency where the extraneous load seems to be too high.

An efficient and practical protocol for the enantioselective cobalt-catalyzed hydrovinylation of vinylarenes with ethylene at low (1.2 bar) pressure has been developed. As precatalysts, stable [L2 CoCl2 ] complexes are employed that are activated in situ with Et2 AlCl. A modular chiral TADDOL-derived phosphine-phosphite ligand was identified that allows the conversion of a broad spectrum of substrates, including heterocyclic vinylarenes and vinylferrocene, to smoothly afford the branched products with up to 99 % ee and virtually complete regioselectivity. Even polar functional groups, such as OH, NH2 , CN, and CO2 R, are tolerated.

In natural coastal wetlands, high supplies of marine sulfate suppress methanogenesis. Coastal wetlands are, however, often subject to disturbance by diking and drainage for agricultural use and can turn to potent methane sources when rewetted for remediation. This suggests that preceding land use measures can suspend the sulfate-related methane suppressing mechanisms. Here, we unravel the hydrological relocation and biogeochemical S and C transformation processes that induced high methane emissions in a disturbed and rewetted peatland despite former brackish impact. The underlying processes were investigated along a transect of increasing distance to the coastline using a combination of concentration patterns, stable isotope partitioning, and analysis of the microbial community structure. We found that diking and freshwater rewetting caused a distinct freshening and an efficient depletion of the brackish sulfate reservoir by dissimilatory sulfate reduction (DSR). Despite some legacy effects of brackish impact expressed as high amounts of sedimentary S and elevated electrical conductivities, contemporary metabolic processes operated mainly under sulfate-limited conditions. This opened up favorable conditions for the establishment of a prospering methanogenic community in the top 30–40 cm of peat, the structure and physiology of which resemble those of terrestrial organic-rich environments. Locally, high amounts of sulfate persisted in deeper peat layers through the inhibition of DSR, probably by competitive electron acceptors of terrestrial origin, for example Fe(III). However, as sulfate occurred only in peat layers below 30–40 cm, it did not interfere with high methane emissions on an ecosystem scale. Our results indicate that the climate effect of disturbed and remediated coastal wetlands cannot simply be derived by analogy with their natural counterparts. From a greenhouse gas perspective, the re-exposure of diked wetlands to natural coastal dynamics would literally open up the floodgates for a replenishment of the marine sulfate pool and therefore constitute an efficient measure to reduce methane emissions.

An efficient and practical protocol for the enantioselective cobalt-catalyzed hydrovinylation of vinylarenes with ethylene at low (1.2 bar) pressure has been developed. As precatalysts, stable [L2 CoCl2 ] complexes are employed that are activated in situ with Et2 AlCl. A modular chiral TADDOL-derived phosphine-phosphite ligand was identified that allows the conversion of a broad spectrum of substrates, including heterocyclic vinylarenes and vinylferrocene, to smoothly afford the branched products with up to 99 % ee and virtually complete regioselectivity. Even polar functional groups, such as OH, NH2 , CN, and CO2 R, are tolerated.

We report first results from a study on water and element exchange across the land-ocean boundary at the southern Baltic Sea. The focus is set on ferruginous fresh ground waters escaping at the shore line, flowing in air contact before entering a subterranean mixing zone with brackish Baltic Sea water. The present study combines the results from multiple sampling campaigns that investigated the composition of several springs as well as the surface and subsurface development of fresh waters on the way to the Baltic Sea. This is achieved by a combination of hydroand solid-phase geochemical and stable isotope measurements with ground water dating. Results are compared to the composition of groundwaters recovered from wells in the catchment area and the local isotope meteoric water line developed for Warnemünde. The spring water is shown to be impacted by the dissolution of biogenic carbon dioxide and marine carbonate as well as the oxidation of pyrite in glacial sediments. Dating yields a surprisingly high diversity between some closely associated springs with average ages of about 25 to 32 years, but different mixing proportions with older tritium-free ground-water.

A concise (5 to 6 steps), stereodivergent, highly diastereoselective (dr up to >19:1 for both stereoisomers) and scalable synthesis (up to 14 g) of cis- and trans-2-substituted 3-piperidinols, a core motif in numerous bioactive compounds, is presented. This sequence allowed an efficient synthesis of the NK-1 inhibitor L-733,060 in 8 steps. Additionally, a cyclodehydration-realizing simple triethylphosphite as a substitute for triphenylphosphine is developed. Here the stoichiometric oxidized P(V)-byproduct (triethylphosphate) is easily removed during the work up through saponification overcoming separation difficulties usually associated to triphenylphosphine oxide.