ALBERT

Description: Deep-sea sediment samples were taken from the (wider) Kairei hydrothermal field area (25°S, 70°E) as well as a remote site (26°S, 71°E) in the Indian Ocean during the INDEX cruise 2016 with the N/O Pourquoi pas? (Ifremer, France). Push core samples from different areas of the Kairei vent field, as well as a sample from the remote site (~200 km south-east from the Kairei), were recovered with the help of the ROV VICTOR 6000 (Ifremer, France). All subsampling steps were carried out shipboard at 4 °C. With sterile syringes (nozzles removed) 3 ml of 2 cm layers of sediment were transferred into sterile falcon tubes for DNA extraction and stored at –80 °C. The remaining sediment was cut into 2 cm slices, freeze-dried, and partially milled to 〈75 mm for geochemical analyses. The sediment was analyzed for carbon chemistry, i.e. total organic carbon (TOC) and total inorganic carbon (TIC) with routine standard methods (IR-detection after combustion, ISO 10694, LECO CS 230 analyzer). Elemental composition of Kairei sediments was estimated by the accredited Actlab Laboratories, Canada (Multimethod mix called Ultratrace 3 program, using INAA, 4-Acid Digestion, ICP-OES, and ICP-MS). Sediments from the remote station were analyzed by routine WD-XRF after fusion with Li-Metaborate/Li-Bromide (XRF spectrometers Philips PW 2400 und Philips PW 1480).

Description: Deep-sea sediment samples were taken from the (wider) Kairei hydrothermal field area (25°S, 70°E) as well as a remote site (26°S, 71°E) in the Indian Ocean during the INDEX cruise 2016 with the N/O Pourquoi pas? (Ifremer, France). Push core samples from different areas of the Kairei vent field, as well as a sample from the remote site (~200 km south-east from the Kairei), were recovered with the help of the ROV VICTOR 6000 (Ifremer, France). All subsampling steps were carried out shipboard at 4 °C. Porewater from push cores was extracted with rhizons (CSS, 5 cm Rhizosphere Research Products B.V., Netherlands) at a resolution of 2-3 cm, fixed with 1% HNO3 for trace element analyses and stored at 4 °C. With sterile syringes (nozzles removed) 3 ml of 2 cm layers of sediment were transferred into sterile falcon tubes for DNA extraction and stored at –80 °C. Concentrations of minor and trace elements Li, Al, Rb, Cs, Sr, Ba, V, Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Tl, Pb, In, Sn, Sb, Bi, W, Mo, U, Au, As, and L were determined by highresolution ICP-SF-MS (Element XR, Thermo Scientific) after 25-fold dilution and spiking with Y and Re for internal standardization using appropriate mass resolution settings.

Description: Coral-based reconstructions of sea surface temperatures (SSTs) using Sr/Ca, U/Ca and δ18O are important tools for quantitative analysis of past climate variabilities. However, post-depositional alteration of coral aragonite, particularly early diagenesis, restrict the accuracy of calibrated proxies even on young corals. Considering the diagenetic effects, we present new Mid to Late Holocene SST reconstructions on well-dated (U/Th: ∼70 yr to 5.4 ka) fossil Porites sp. collected from the Society Islands, French Polynesia. For few corals, quality pre-screening routines revealed the presence of secondary aragonite needles inside primary pore space, resulting in a mean increase in Sr/Ca ratios between 5-30%, in contrast to the massive skeletal parts. Characterized by a Sr/Ca above 10 mmol/mol, we interpret this value as the threshold between diagenetically altered and unaltered coral material. At a high-resolution, observed intra-skeletal variability of 5.4 to 9.9 mmol/mol probably reflects the physiological control of corals over their trace metal uptake, and individual variations controlled by CaCO3– precipitation rates. Overall, the Sr/Ca, U/Ca and δ18O trends are well correlated, but we observed a significant offset up to ± 7°C among the proxies on derived palaeo-SST estimates. It appears that the related alteration process tends to amplify temperature extremes, resulting in increased SST-U/Ca and SST-Sr/Ca gradients, and consequently their apparent temperature sensitivities. A relative SST reconstruction is still feasible by normalizing our records to their individual mean value defined as ΔSST. This approach shows that ΔSST records derived from different proxies agree with an amplitudinal variability of up to ± 2°C with respect to their Holocene mean value. Higher ΔSST values than the mean SSTs (Holocene warm periods) were recorded from ∼1.8 to ∼2.8 ka (Interval I), ∼3.7 to 4.0 ka (Interval III) and before ∼5 ka, while lower ΔSST values (Holocene cold periods, Interval II and IV) were recorded in between. The ensuing SST periodicity of ∼1.5 ka in the Society Islands record is in line with the solar activity reconstructed from 10Be and 14C production (Vonmoos et al., 2006), emphasizing the role of solar activity on climate variability during the Late Holocene.

Description: Brachiopods present a key fossil group for Phanerozoic palaeo-environmental and palaeo-oceanographical reconstructions, owing to their good preservation and abundance in the geological record. Yet to date, hardly any geochemical proxies have been calibrated in cultured brachiopods and only little is known on the mechanisms that control the incorporation of various key elements into brachiopod calcite. To evaluate the feasibility and robustness of multiple Element/Ca ratios as proxies in brachiopods, specifically Li/Ca, B/Ca, Na/Ca, Mg/Ca, Sr/Ca, Ba/Ca, as well as Li/Mg, we cultured Magellania venosa, Terebratella dorsata and Pajaudina atlantica under controlled experimental settings over a period of more than two years with closely monitored ambient conditions, carbonate system parameters and elemental composition of the culture medium. The experimental setup comprised of two control aquariums (pH0 = 8.0 and 8.15, T = 10 °C) and treatments where pCO2−pH (pH1 = 7.6 and pH2 = 7.35), temperature (T = 16 °C) and chemical composition of the culture medium were manipulated. Our results indicate that the incorporation of Li and Mg is strongly influenced by temperature, growth effects as well as carbonate chemistry, complicating the use of Li/Ca, Mg/Ca and Li/Mg ratios as straightforward reliable proxies. Boron partitioning varied greatly between the treatments, however without a clear link to carbonate system parameters or other environmental factors. The partitioning of both Ba and Na varied between individuals, but was not systematically affected by changes in the ambient conditions. We highlight Sr as a potential proxy for DIC, based on a positive trend between Sr partitioning and carbonate chemistry in the culture medium. To explain the observed dependency and provide a quantitative framework for exploring elemental variations, we devise the first biomineralisation model for brachiopods, which results in a close agreement between modelled and measured Sr distribution coefficients. We propose that in order to sustain shell growth under increased DIC, a decreased influx of Ca2+ to the calcifying fluid is necessary, driving the preferential substitution of Sr2+ for Ca2+ in the crystal lattice. Finally, we conducted micro-computed tomography analyses of the shells grown in the different experimental treatments. We present pore space – punctae – content quantification that indicates that shells built under increased environmental stress, and in particular elevated temperature, contain relatively more pore space than calcite, suggesting this parameter as a potential novel proxy for physiological stress and even environmental conditions.

Description: Microbial metabolisms in sediments play a pivotal role in marine element cycling. In hydrothermal sediments chemosynthetic microorganisms likely prevail, while in non-hydrothermally impacted sediment regimes microorganisms associated with organic matter decomposition are primarily recognized. To test how these microorganisms are distributed along the hitherto neglected transition zone influenced to different degrees by hydrothermal input we sampled four sediment sites: these were (i) near an active vent, (ii) the outer rim, and (iii) the inactive area of the Kairei hydrothermal field as well as (iv) sediments roughly 200 km south-east of the Kairei field. Chemistry and microbial community compositions were different at all sampling sites. Against expectations, the sediments near the active vent did not host typical chemosynthetic microorganisms and chemistry did not indicate current, extensive hydrothermal venting. Data from the outer rim area of the active Kairei field suggested microbially mediated saponite production and diffuse hydrothermal flow from below accompanied by increased metal concentrations. A steep redox gradient in the inactive Kairei field points towards significant redox driven processes resulting in dissolution of hydrothermal precipitates and intense metal mobilization. Local microorganisms were primarily Chloroflexi, Bacillales, Thermoplasmata, and Thaumarchaeota.

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: The fate of plastic debris entering the oceans is largely unconstrained. Currently, intensified research is devoted to the abiotic and microbial degradation of plastic floating near the ocean surface for an extended period of time. In contrast, the impacts of environmental conditions in the deep sea on polymer properties and rigidity are virtually unknown. Here, we present unique results of plastic items identified to have been introduced into deep-sea sediments at a water depth of 4150 m in the eastern equatorial Pacific Ocean more than two decades ago. The results, including optical, spectroscopic, physical and microbial analyses, clearly demonstrate that the bulk polymer materials show no apparent sign of physical or chemical degradation. Solely the polymer surface layers showed reduced hydrophobicity, presumably caused by microbial colonization. The bacterial community present on the plastic items differed significantly (p 〈 0.1%) from those of the adjacent natural environment by a dominant presence of groups requiring steep redox gradients (Mesorhizobium, Sulfurimonas) and a remarkable decrease in diversity. The establishment of chemical gradients across the polymer surfaces presumably caused these conditions. Our findings suggest that plastic is stable over extended times under deep-sea conditions and that prolonged deposition of polymer items at the seafloor may induce local oxygen depletion at the sediment-water interface.

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: 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.