Description: We show that inflows of oxygenated waters into sulfidic layers have a strong impact on biogeochemical transformation at oxic/anoxic transition zones. Taking the pelagic methane dynamics in the Gotland Basin as an example, we performed our studies when one of the largest inflows ever recorded entered the Baltic Sea in March 2015. An inflowing gravity current transported oxic waters into the sulfidic deep layers and freshly generated a near-bottom secondary redox interface. At the upper slope, where the inflowing water masses were vigorously turbulent and the main and secondary redox interfaces in close contact to each other, methane oxidation rates inside the transition zone were found to be higher compared to the weakly turbulent basin interior. At the main redox interface in the basin center, lateral intrusions of oxygenated waters into intermediate water depth may have stimulated the growth of the methanotrophic community and their activity.

Description: A site at the gas hydrate stability limit was investigated offshore northwestern Svalbard to study methane transport in sediment. The site was characterized by chemosynthetic communities (sulfur bacteria mats, tubeworms) and gas venting. Sediments were sampled with in‐situ porewater collectors and by gravity coring followed by analyses of porewater constituents, sediment and carbonate geochemistry, and microbial activity, taxonomy, and lipid biomarkers. Sulfide and alkalinity concentrations showed concentration maxima in near‐surface sediments at the bacterial mat and deeper maxima at the gas vent site. Sediments at the periphery of the chemosynthetic field were characterized by two sulfate‐methane transition zones (SMTZ) at ~204 and 45 cm depth, where activity maxima of microbial anaerobic oxidation of methane (AOM) with sulfate were found. Amplicon sequencing and lipid biomarker indicate that AOM at the SMTZs was mediated by ANME‐1 archaea. A 1D numerical transport reaction model suggests that the deeper SMTZ‐1 formed on centennial scale by vertical advection of methane, while the shallower SMTZ‐2 could only be reproduced by non‐vertical methane injections starting on decadal scale. Model results were supported by age distribution of authigenic carbonates, showing youngest carbonates within SMTZ‐2. We propose that non‐vertical methane injection was induced by increasing blockage of vertical transport or formation of sediment fractures. Our study further suggests that the methanotrophic response to the non‐vertical methane injection was commensurate with new methane supply. This finding provides new information about for the response time and efficiency of the benthic methane filter in environments with fluctuating methane transport.

Description: Subsurface flows, particularly hyporheic exchange fluxes, driven by streambed topography, permeability, channel gradient and dynamic flow conditions provide prominent ecological services such as nitrate removal from streams and aquifers. Stream flow dynamics cause strongly nonlinear and often episodic contributions of nutrient concentrations in river-aquifer systems. Using a fully coupled transient flow and reactive transport model, we investigated the denitrification potential of hyporheic zones during peak-flow events. The effects of streambed permeability, channel gradient and bedform amplitude on the spatio-temporal distribution of nitrate and dissolved organic carbon in streambeds and the associated denitrification potential were explored. Distinct peak-flow events with different intensity, duration and hydrograph shape were selected to represent a wide range of peak-flow scenarios. Our results indicated that the specific hydrodynamic characteristics of individual flow events largely determine the average positive or negative nitrate removal capacity of hyporheic zones, however the magnitude of this capacity is controlled by geomorphological settings (i.e. channel slope, streambed permeability and bedform amplitude). Specifically, events with longer duration and higher intensity were shown to promote higher nitrate removal efficiency with higher magnitude of removal efficiency in the scenarios with higher slope and permeability values. These results are essential for better assessment of the subsurface nitrate removal capacity under the influence of flow dynamics and particularly peak-flow events in order to provide tailored solutions for effective restoration of interconnected river-aquifer systems.

Description: Carbonates that exhibit obvious diagenetic alteration are usually excluded as archives in palaeoenvironmental studies. However, the potential impact of microbial alteration during early diagenesis is still poorly explored. To investigate the sensitivity of sulphur concentration, distribution, oxidation state and isotopic composition in marine aragonite to microbial alteration, Arctica islandica bivalves and Porites sp. corals were experimentally exposed to anaerobic microbial activity. The anoxic incubation media included a benthic bacterial strain Shewanella sediminis and a natural anoxic sediment slurry with a natural microbial community of unknown species. Combined fluorescence microscopy and synchrotron‐based analysis of the sulphur distribution and oxidation state enabled a comparison of organic matter and sulphur content in the two materials. Results revealed a higher proportion of reduced sulphur species and locally stronger fluorescence within the pristine bivalve shell compared to the pristine coral skeleton. Within the pristine bivalve specimen, reduced sulphur was enriched in layers along the inner shell margin. After incubation in the anoxic sediment slurry, this region revealed rust‐brown staining and a patchy S2‐ distribution pattern rather than S2‐‐layers. Another effect on sulphur distribution was rust‐brown coloured fibres along one growth line, revealing a locally higher proportion of sulphur. The δ34S value of carbonate‐associated sulphate remained largely unaffected by both incubation media, but a lower δ34S value of water‐soluble sulphate reflected the degradation of insoluble organic matter by microbes in both experiments. No significant alteration was detected in the coral samples exposed to microbial alteration. The data clearly identified a distinct sensitivity of organically bound sulphur in biogenic aragonite to microbial alteration even when “traditional” geochemical proxies such as δ18OCARB or δ13CCARB in the carbonate didn’t show any effect. Differences in the intensity of microbial alteration documented are likely due to inherent variations in the concentration and nature of original organic compositions in the samples.

Description: Methods for measuring aerobic methane oxidation (MOx) rates in aquatic environments are often based on the incubation of water samples, during which the consumption of methane (CH4) is monitored. Typically, incubation vessels are sealed with butyl rubber because these elastomers are essentially impermeable for gases. We report on the potential toxicity of five different commercially available, lab-grade butyl stoppers on MOx activity in samples from marine and lacustrine environments. MOx rates in incubations sealed with non-halogenated butyl were 〉 50% lower compared to parallel incubations with halogenated butyl rubber stoppers, suggesting toxic effects associated with the use of the non-halogenated butyl type. Aqueous extracts of non-halogenated butyl rubber were contaminated with high amounts of various organic compounds including potential bactericides such as benzyltoluenes and phenylalkanes. Comparably small amounts of organic contaminants were liberated from the halogenated butyl rubber stoppers but only two halogenated stopper types were found that did not seem to leach any organics into the incubation medium. Furthermore, the non-halogenated and two types of the halogenated butyl elastomers additionally leached comparably high amounts of zinc. While the source of the apparent toxicity with the use of the non-halogenated rubber stoppers remains elusive, our results indicate that leaching of contaminants from some butyl rubber stoppers can severely interfere with the activity of MOx communities, highlighting the importance of testing rubber stoppers for their respective contamination potential. The impact of leachates from butyl rubber on the assessment of biogeochemical reaction rates other than MOx seems likely but needs to be verified.