Evidence for anaerobic oxidation of methane in sediments of a freshwater system (Lago di Cadagno)

Anaerobic oxidation of methane (AOM) has been investigated in sediments of a high alpine sulfate-rich lake. Hot spots of AOM could be identified based on geochemical and isotopic evidence. Very high fractionation of methane (α=1.031) during oxidation was observed in the uppermost sediment layers, where methane is oxidized most likely with sulfate-containing bottom waters. However, we could not exclude that other electron acceptors such as iron, or manganese might also be involved. Light carbon isotope values (δ13C=−10‰ vs. Vienna Pee Dee Belemnite [VPDB]) of sedimentary carbonates at 16-20 cm sediment depth are indicative of a zone where methane was oxidized and the resulting bicarbonate ions were used for carbonate precipitation. 16S rRNA gene analysis revealed the presence of sequences belonging to the marine benthic groups B, C, and D and to the recently described clade of AOM-associated archaea (AAA). Catalyzed reporter deposition-FISH analysis revealed a high abundance of Deltaproteobacteria, especially of free-living sulfate-reducing bacteria of the Desulfosarcina/Desulfococcus branch of Deltaproteobacteria in the AOM zone. Here, loose aggregations of AAA cells were found, suggesting that AAA might be responsible for oxidation of methane in Lake Cadagno sediment

Nitrogen removal processes in lakes of different trophic states from on-site measurements and historic data

Freshwater lakes are essential hotspots for the removal of excessive anthropogenic nitrogen (N) loads transported from the land to coastal oceans. The biogeochemical processes responsible for N removal, the corresponding transformation rates and overall removal efficiencies differ between lakes, however, it is unclear what the main controlling factors are. Here, we investigated the factors that moderate the rates of N removal under contrasting trophic states in two lakes located in central Switzerland. In the eutrophic Lake Baldegg and the oligotrophic Lake Sarnen, we specifically examined seasonal sediment porewater chemistry, organic matter sedimentation rates, as well as 33-year of historic water column data. We find that the eutrophic Lake Baldegg, which contributed to the removal of 20 ± 6.6 gN m; -2; year; -1; , effectively removed two-thirds of the total areal N load. In stark contrast, the more oligotrophic Lake Sarnen contributed to 3.2 ± 4.2 gN m; -2; year; -1; , and had removed only one-third of the areal N load. The historic dataset of the eutrophic lake revealed a close linkage between annual loads of dissolved N (DN) and removal rates (NRR = 0.63 × DN load) and a significant correlation of the concentration of bottom water nitrate and removal rates. We further show that the seasonal increase in N removal rates of the eutrophic lake correlated significantly with seasonal oxygen fluxes measured across the water-sediment interface (R; 2; = 0.75). We suggest that increasing oxygen enhances sediment mineralization and stimulates nitrification, indirectly enhancing denitrification activity.; The online version contains supplementary material available at 10.1007/s00027-021-00795-7

Anoxic chlorophyll maximum enhances local organic matter remineralization and nitrogen loss in Lake Tanganyika

In marine and freshwater oxygen-deficient zones, the remineralization of sinking organic matter from the photic zone is central to driving nitrogen loss. Deep blooms of photosynthetic bacteria, which form the suboxic/anoxic chlorophyll maximum (ACM), widespread in aquatic ecosystems, may also contribute to the local input of organic matter. Yet, the influence of the ACM on nitrogen and carbon cycling remains poorly understood. Using a suite of stable isotope tracer experiments, we examined the transformation of nitrogen and carbon under an ACM (comprising of Chlorobiaceae and Synechococcales) and a non-ACM scenario in the anoxic zone of Lake Tanganyika. We find that the ACM hosts a tight coupling of photo/litho-autotrophic and heterotrophic processes. In particular, the ACM was a hotspot of organic matter remineralization that controlled an important supply of ammonium driving a nitrification-anammox coupling, and thereby played a key role in regulating nitrogen loss in the oxygen-deficient zone

Comparison of different solid phase extraction sorbents for the qualitative assessment of dissolved organic nitrogen in freshwater samples using FT-ICR-MS

Fate and reactivity of dissolved organic matter (DOM) is directly linked to its chemical composition. Therefore, molecular characterisation, for example using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), is used for a better understanding of those factors. To study organic compounds in the water column, an efficient extraction method is important. The commonly used extraction method for FT-ICR-MS is solid phase extraction (SPE) using a reversed-phase sorbent (BondElut PPL). But this method, to the best of our knowledge, was not evaluated for its ability to extract organic nitrogen compounds which are important building blocks of life and therefore an important fraction of DOM. In this study, several solid phase sorbents were tested for their ability to extract organic nitrogen compounds from water samples of natural aqueous environments. Different cartridges concerning their retention mechanism and pore size were tested. Three cartridges with different extraction mechanism (reversed phase, cation exchange or a mixture of both) or different pore size were tested. Except for one sorbent type, which heavily contaminated the samples with organic molecules, the tested cartridges leached neither a significant amount of dissolved organic carbon (DOC) nor dissolved organic nitrogen (DON). The sorbents were tested with lake water to be able to investigate their functionality in real conditions. It could be shown, that the molecular composition of the sample should be considered for the choice of the sorbent material. Additionally, it was shown that a mixed-bed sorbent is a valuable complementary SPE sorbent for the molecular characterisation of lacustrine samples using FT-ICR-MS and it might also be useful for a quantitative extraction. Furthermore, it could be shown that HyperSep Retain CX sorbent allows to extract a broader range of organic nitrogen compounds leading to a more comprehensive data set for investigating organic nitrogen compounds in lakes using FT-ICR-MS

Hypoxia causes preservation of labile organic matter and changes seafloor microbial community composition (Black Sea)

Bottom-water oxygen supply is a key factor governing the biogeochemistry and community composition of marine sediments. Whether it also determines carbon burial rates remains controversial. We investigated the effect of varying oxygen concentrations (170 to 0 μM O2) on microbial remineralization of organic matter in seafloor sediments and on community diversity of the northwestern Crimean shelf break. This study shows that 50% more organic matter is preserved in surface sediments exposed to hypoxia compared to oxic bottom waters. Hypoxic conditions inhibit bioturbation and decreased remineralization rates even within short periods of a few days. These conditions led to the accumulation of threefold more phytodetritus pigments within 40 years compared to the oxic zone. Bacterial community structure also differed between oxic, hypoxic, and anoxic zones. Functional groups relevant in the degradation of particulate organic matter, such as Flavobacteriia, Gammaproteobacteria, and Deltaproteobacteria, changed with decreasing oxygenation, and the microbial community of the hypoxic zone took longer to degrade similar amounts of deposited reactive matter. We conclude that hypoxic bottom-water conditions—even on short time scales—substantially increase the preservation potential of organic matter because of the negative effects on benthic fauna and particle mixing and by favoring anaerobic processes, including sulfurization of matter

Lake surface cooling drives littoral-pelagic exchange of dissolved gases

The extent of littoral influence on lake gas dynamics remains debated in the aquatic science community due to the lack of direct quantification of lateral gas transport. The prevalent assumption of diffusive horizontal transport in gas budgets fails to explain anomalies observed in pelagic gas concentrations. Here, we demonstrate through high-frequency measurements in a eutrophic lake that daily convective horizontal circulation generates littoral-pelagic advective gas fluxes one order of magnitude larger than typical horizontal fluxes used in gas budgets. These lateral fluxes are sufficient to redistribute gases at the basin-scale and generate concentration anomalies reported in other lakes. Our observations also contrast the hypothesis of pure, nocturnal littoral-to-pelagic exchange by showing that convective circulation transports gases such as oxygen and methane toward both the pelagic and littoral zones during the daytime. This study challenges the traditional pelagic-centered models of aquatic systems by showing that convective circulation represents a fundamental lateral transport mechanism to be integrated into gas budgets. Cooling-induced horizontal circulation redistributes gases daily between littoral and pelagic lake waters under calm conditions

Carbohydrate compositional trends throughout Holocene sediments of an alpine lake (Lake Cadagno)

Carbohydrates are a ubiquitous constituent of organisms and contribute significantly to sedimentary organic carbon pools. Yet, the factors that control the degradation and long-term preservation of sedimentary carbohydrates are not well understood. Here, we investigate carbohydrate pool sizes and chemical compositions in high-altitude, meromictic Lake Cadagno (Switzerland) over a 13,500-year-old sedimentary succession that has recorded past changes from oxic to anoxic conditions and consists mostly of intercalations of lacustrine sediments and terrestrial-derived sediments. Analyses of the organic matter chemical composition by pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) show that carbohydrates are selectively preserved over other organic matter constituents over time. The carbohydrate pyrolysis products levosugars (potentially cellulose-derived) and (alkyl)furans and furanones (potentially pectin-derived) dominate both lacustrine and terrestrially derived sediment layers, suggesting aquatic and terrestrial-derived sources of these compounds. Carbohydrate monomer analyses indicate galactose and glucose as dominant monomers and show no clear differences between aquatic and terrestrial organic matter. No clear impacts of past changes in redox conditions on carbohydrate compositions were observed. Our study shows that carbohydrates are a major contributor to sedimentary organic carbon burial in Lake Cadagno and indicates the effective preservation of both aquatic and terrestrial derived carbohydrates over millennia in lake sediments

Methanotrophy under Versatile Conditions in the Water Column of the Ferruginous Meromictic Lake La Cruz (Spain)

Lakes represent a considerable natural source of methane to the atmosphere compared to their small global surface area. Methanotrophs in sediments and in the water column largely control methane fluxes from these systems, yet the diversity, electron accepting capacity, and nutrient requirements of these microorganisms have only been partially identified. Here, we investigated the role of electron acceptors alternative to oxygen and sulfate in microbial methane oxidation at the oxycline and in anoxic waters of the ferruginous meromictic Lake La Cruz, Spain. Active methane turnover in a zone extending well below the oxycline was evidenced by stable carbon isotope-based rate measurements. We observed a strong methane oxidation potential throughout the anoxic water column, which did not vary substantially from that at the oxic/anoxic interface. Both in the redox-transition and anoxic zones, only aerobic methane-oxidizing bacteria (MOB) were detected by fluorescence in situ hybridization and sequencing techniques, suggesting a close coupling of cryptic photosynthetic oxygen production and aerobic methane turnover. Additions of nitrate, nitrite and to a lesser degree iron and manganese oxides also stimulated bacterial methane consumption. We could not confirm a direct link between the reduction of these compounds and methane oxidation and we cannot exclude the contribution of unknown anaerobic methanotrophs. Nevertheless, our findings from Lake La Cruz support recent laboratory evidence that aerobic methanotrophs may be able to utilize alternative terminal electron acceptors under oxygen limitation

Dark aerobic sulfide oxidation by anoxygenic phototrophs in anoxic waters

Anoxygenic phototrophic sulfide oxidation by green and purple sulfur bacteria (PSB) plays a key role in sulfide removal from anoxic shallow sediments and stratified waters. Although some PSB can also oxidize sulfide with nitrate and oxygen, little is known about the prevalence of this chemolithotrophic lifestyle in the environment. In this study, we investigated the role of these phototrophs in light‐independent sulfide removal in the chemocline of Lake Cadagno. Our temporally resolved, high‐resolution chemical profiles indicated that dark sulfide oxidation was coupled to high oxygen consumption rates of ~9 μM O2·h−1. Single‐cell analyses of lake water incubated with 13CO2 in the dark revealed that Chromatium okenii was to a large extent responsible for aerobic sulfide oxidation and it accounted for up to 40% of total dark carbon fixation. The genome of Chr. okenii reconstructed from the Lake Cadagno metagenome confirms its capacity for microaerophilic growth and provides further insights into its metabolic capabilities. Moreover, our genomic and single‐cell data indicated that other PSB grow microaerobically in these apparently anoxic waters. Altogether, our observations suggest that aerobic respiration may not only play an underappreciated role in anoxic environments but also that organisms typically considered strict anaerobes may be involved