ALBERT

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Visser, A., Wankel, S. D., Niklaus, P. A., Byrne, J. M., Kappler, A. A., & Lehmann, M. F. Impact of reactive surfaces on the abiotic reaction between nitrite and ferrous iron and associated nitrogen and oxygen isotope dynamics. Biogeosciences, 17(16), (2020): 4355-4374, doi:10.5194/bg-17-4355-2020.

Description: Anaerobic nitrate-dependent Fe(II) oxidation (NDFeO) is widespread in various aquatic environments and plays a major role in iron and nitrogen redox dynamics. However, evidence for truly enzymatic, autotrophic NDFeO remains limited, with alternative explanations involving the coupling of heterotrophic denitrification with the abiotic oxidation of structurally bound or aqueous Fe(II) by reactive intermediate nitrogen (N) species (chemodenitrification). The extent to which chemodenitrification is caused (or enhanced) by ex vivo surface catalytic effects has not been directly tested to date. To determine whether the presence of either an Fe(II)-bearing mineral or dead biomass (DB) catalyses chemodenitrification, two different sets of anoxic batch experiments were conducted: 2 mM Fe(II) was added to a low-phosphate medium, resulting in the precipitation of vivianite (Fe3(PO4)2), to which 2 mM nitrite (NO−2) was later added, with or without an autoclaved cell suspension (∼1.96×108 cells mL−1) of Shewanella oneidensis MR-1. Concentrations of nitrite (NO−2), nitrous oxide (N2O), and iron (Fe2+, Fetot) were monitored over time in both set-ups to assess the impact of Fe(II) minerals and/or DB as catalysts of chemodenitrification. In addition, the natural-abundance isotope ratios of NO−2 and N2O (δ15N and δ18O) were analysed to constrain the associated isotope effects. Up to 90 % of the Fe(II) was oxidized in the presence of DB, whereas only ∼65 % of the Fe(II) was oxidized under mineral-only conditions, suggesting an overall lower reactivity of the mineral-only set-up. Similarly, the average NO−2 reduction rate in the mineral-only experiments (0.004±0.003 mmol L−1 d−1) was much lower than in the experiments with both mineral and DB (0.053±0.013 mmol L−1 d−1), as was N2O production (204.02±60.29 nmol L−1 d−1). The N2O yield per mole NO−2 reduced was higher in the mineral-only set-ups (4 %) than in the experiments with DB (1 %), suggesting the catalysis-dependent differential formation of NO. N-NO−2 isotope ratio measurements indicated a clear difference between both experimental conditions: in contrast to the marked 15N isotope enrichment during active NO−2 reduction (15εNO2=+10.3 ‰) observed in the presence of DB, NO−2 loss in the mineral-only experiments exhibited only a small N isotope effect (〈+1 ‰). The NO−2-O isotope effect was very low in both set-ups (18εNO2 〈1 ‰), which was most likely due to substantial O isotope exchange with ambient water. Moreover, under low-turnover conditions (i.e. in the mineral-only experiments as well as initially in experiments with DB), the observed NO−2 isotope systematics suggest, transiently, a small inverse isotope effect (i.e. decreasing NO−2 δ15N and δ18O with decreasing concentrations), which was possibly related to transitory surface complexation mechanisms. Site preference (SP) of the 15N isotopes in the linear N2O molecule for both set-ups ranged between 0 ‰ and 14 ‰, which was notably lower than the values previously reported for chemodenitrification. Our results imply that chemodenitrification is dependent on the available reactive surfaces and that the NO−2 (rather than the N2O) isotope signatures may be useful for distinguishing between chemodenitrification catalysed by minerals, chemodenitrification catalysed by dead microbial biomass, and possibly true enzymatic NDFeO.

Description: This research has been supported by the Deutsche Forschungsgemeinschaft (DFG; grant no. GRK 1708, “Molecular principles of bacterial survival strategies”) and the University of Basel, Switzerland.

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Eugster, W., Laundre, J., Eugster, J., & Kling, G. W. Long-term reliability of the figaro TGS 2600 solid-state methane sensor under low-Arctic conditions at Toolik Lake, Alaska. Atmospheric Measurement Techniques, 13(5), (2020): 2681-2695, doi:10.5194/amt-13-2681-2020.

Description: The TGS 2600 was the first low-cost solid-state sensor that shows a response to ambient levels of CH4 (e.g., range ≈1.8–2.7 µmol mol−1). Here we present an empirical function to correct the TGS 2600 signal for temperature and (absolute) humidity effects and address the long-term reliability of two identical sensors deployed from 2012 to 2018. We assess the performance of the sensors at 30 min resolution and aggregated to weekly medians. Over the entire period the agreement between TGS-derived and reference CH4 mole fractions measured by a high-precision Los Gatos Research instrument was R2=0.42, with better results during summer (R2=0.65 in summer 2012). Using absolute instead of relative humidity for the correction of the TGS 2600 sensor signals reduced the typical deviation from the reference to less than ±0.1 µmol mol−1 over the full range of temperatures from −41 to 27 ∘C. At weekly resolution the two sensors showed a downward drift of signal voltages indicating that after 10–13 years a TGS 2600 may have reached its end of life. While the true trend in CH4 mole fractions measured by the high-quality reference instrument was 10.1 nmolmol−1yr−1 (2012–2018), part of the downward trend in sensor signal (ca. 40 %–60 %) may be due to the increase in CH4 mole fraction because the sensor voltage decreases with increasing CH4 mole fraction. Weekly median diel cycles tend to agree surprisingly well between the TGS 2600 and reference measurements during the snow-free season, but in winter the agreement is lower. We suggest developing separate functions for deducing CH4 mole fractions from TGS 2600 measurements under cold and warm conditions. We conclude that the TGS 2600 sensor can provide data of research-grade quality if it is adequately calibrated and placed in a suitable environment where cross-sensitivities to gases other than CH4 are of no concern.

Description: We acknowledge support received from Arctic LTER grants (grant nos. NSF-DEB-1637459, 1026843, 1754835, and NSF-PLR 1504006) and supplemental funding from the NSF-NEON and OPP-AON programs. Gaius R. Shaver (MBL) is acknowledged for initiating the study and supporting our activities in all aspects. ETH is acknowledge for supporting the purchase of the Fast Greenhouse Gas Analyzer that replaced the older Fast Methane Analyzer in 2016 (grant no. 0-43683-11).

Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Ashley, K. E., McKay, R., Etourneau, J., Jimenez-Espejo, F. J., Condron, A., Albot, A., Crosta, X., Riesselman, C., Seki, O., Mass, G., Golledge, N. R., Gasson, E., Lowry, D. P., Barrand, N. E., Johnson, K., Bertler, N., Escutia, C., Dunbar, R., & Bendle, J. A. Mid-Holocene Antarctic sea-ice increase driven by marine ice sheet retreat. Climate of the Past, 17(1), (2021): 1-19, https://doi.org/10.5194/cp-17-1-2021.

Description: Over recent decades Antarctic sea-ice extent has increased, alongside widespread ice shelf thinning and freshening of waters along the Antarctic margin. In contrast, Earth system models generally simulate a decrease in sea ice. Circulation of water masses beneath large-cavity ice shelves is not included in current Earth System models and may be a driver of this phenomena. We examine a Holocene sediment core off East Antarctica that records the Neoglacial transition, the last major baseline shift of Antarctic sea ice, and part of a late-Holocene global cooling trend. We provide a multi-proxy record of Holocene glacial meltwater input, sediment transport, and sea-ice variability. Our record, supported by high-resolution ocean modelling, shows that a rapid Antarctic sea-ice increase during the mid-Holocene (∼ 4.5 ka) occurred against a backdrop of increasing glacial meltwater input and gradual climate warming. We suggest that mid-Holocene ice shelf cavity expansion led to cooling of surface waters and sea-ice growth that slowed basal ice shelf melting. Incorporating this feedback mechanism into global climate models will be important for future projections of Antarctic changes.

Description: This research has been supported by the Natural Environment Research Council (CENTA PhD; NE/L002493/1 and Standard Grant Ne/I00646X/1), Japanese Society for the Promotion of Science (JSPS/FF2/60 no. L-11523), NZ Marsden Fund (grant nos. 18-VUW-089 and 15-VUW-131), NSF (grant nos. PLR-1443347 and ACI-1548562), the U.S. Dept. of Energy (grant no. DE-SC0016105), ERC (StG ICEPROXY, 203441; ANR CLIMICE, FP7 Past4Future, 243908), L'Oréal-UNESCO New Zealand For Women in Science Fellowship, University of Otago Research Grant, the IODP U.S. Science Support Program, Spanish Ministry of Science and Innovation (grant no. CTM2017-89711-C2-1-P), and the European Union (FEDER).

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Baldry, K., Saderne, V., McCorkle, D. C., Churchill, J. H., Agust, S., & Duarte, C. M. Anomalies in the carbonate system of Red Sea coastal habitats. Biogeosciences, 17(2), (2020): 423-439, doi:10.5194/bg-17-423-2020.

Description: We use observations of dissolved inorganic carbon (DIC) and total alkalinity (TA) to assess the impact of ecosystem metabolic processes on coastal waters of the eastern Red Sea. A simple, single-end-member mixing model is used to account for the influence of mixing with offshore waters and evaporation–precipitation and to model ecosystem-driven perturbations on the carbonate system chemistry of coral reefs, seagrass meadows and mangrove forests. We find that (1) along-shelf changes in TA and DIC exhibit strong linear relationships that are consistent with basin-scale net calcium carbonate precipitation; (2) ecosystem-driven changes in TA and DIC are larger than offshore variations in 〉70 % of sampled seagrass meadows and mangrove forests, changes which are influenced by a combination of longer water residence times and community metabolic rates; and (3) the sampled mangrove forests show strong and consistent contributions from both organic respiration and other sedimentary processes (carbonate dissolution and secondary redox processes), while seagrass meadows display more variability in the relative contributions of photosynthesis and other sedimentary processes (carbonate precipitation and oxidative processes). The results of this study highlight the importance of resolving the influences of water residence times, mixing and upstream habitats on mediating the carbonate system and coastal air–sea carbon dioxide fluxes over coastal habitats in the Red Sea.

Description: This research has been supported by the King Abdullah University of Science and Technology (KAUST) (grant nos. BAS/1/1071-01-01 and BAS/1/1072-01-01) and the Investment in Science fund at WHOI.