The methane cycle in ferruginous Lake Matano

In Lake Matano, Indonesia, the world’s largest known ferruginous basin, more than 50% of authigenic organic matter is degraded through methanogenesis, despite high abundances of Fe (hydr)oxides in the lake sediments. Biogenic CH₄ accumulates to high concentrations (up to 1.4 mmol L^?1) in the anoxic bottom waters, which contain a total of 7.4 × 10⁵ tons of CH₄. Profiles of dissolved inorganic carbon (ΣCO₂) and carbon isotopes (δ¹³C) show that CH₄ is oxidized in the vicinity of the persistent pycnocline and that some of this CH₄ is likely oxidized anaerobically. The dearth of NO₃^? and SO₄^2? in Lake Matano waters suggests that anaerobic methane oxidation may be coupled to the reduction of Fe (and/or Mn) (hydr)oxides. Thermodynamic considerations reveal that CH₄ oxidation coupled to Fe(III) or Mn(III/IV) reduction would yield sufficient free energy to support microbial growth at the substrate levels present in Lake Matano. Flux calculations imply that Fe and Mn must be recycled several times directly within the water column to balance the upward flux of CH₄. 16S gene cloning identified methanogens in the anoxic water column, and these methanogens belong to groups capable of both acetoclastic and hydrogenotrophic methanogenesis. We find that methane is important in C cycling, even in this very Fe‐rich environment. Such Fe‐rich environments are rare on Earth today, but they are analogous to conditions in the ferruginous oceans thought to prevail during much of the Archean Eon. By analogy, methanogens and methanotrophs could have formed an important part of the Archean Ocean ecosystem.     

Biogeochemical and physical controls on methane fluxes from two ferruginous meromictic lakes

Meromictic lakes with anoxic bottom waters often have active methane cycles whereby methane is generally produced biogenically under anoxic conditions and oxidized in oxic surface waters prior to reaching the atmosphere. Lakes that contain dissolved ferrous iron in their deep waters (i.e., ferruginous) are rare, but valuable, as geochemical analogues of the conditions that dominated the Earth's oceans during the Precambrian when interactions between the iron and methane cycles could have shaped the greenhouse regulation of the planet's climate. Here, we explored controls on the methane fluxes from Brownie Lake and Canyon Lake, two ferruginous meromictic lakes that contain similar concentrations (max. >1 mM) of dissolved methane in their bottom waters. The order Methanobacteriales was the dominant methanogen detected in both lakes. At Brownie Lake, methanogen abundance, an increase in methane concentration with respect to depths closer to the sediment, and isotopic data suggest methanogenesis is an active process in the anoxic water column. At Canyon Lake, methanogenesis occurred primarily in the sediment. The most abundant aerobic methane‐oxidizing bacteria present in both water columns were associated with the Gammaproteobacteria, with little evidence of anaerobic methane oxidizing organisms being present or active. Direct measurements at the surface revealed a methane flux from Brownie Lake that was two orders of magnitude greater than the flux from Canyon Lake. Comparison of measured versus calculated turbulent diffusive fluxes indicates that most of the methane flux at Brownie Lake was non‐diffusive. Although the turbulent diffusive methane flux at Canyon Lake was attenuated by methane oxidizing bacteria, dissolved methane was detected in the epilimnion, suggestive of lateral transport of methane from littoral sediments. These results highlight the importance of direct measurements in estimating the total methane flux from water columns, and that non‐diffusive transport of methane may be important to consider from other ferruginous systems.     

Shifting microbial communities sustain multiyear iron reduction and methanogenesis in ferruginous sediment incubations

Reactive Fe(III) minerals can influence methane (CH₄) emissions by inhibiting microbial methanogenesis or by stimulating anaerobic CH₄ oxidation. The balance between Fe(III) reduction, methanogenesis, and CH₄ oxidation in ferruginous Archean and Paleoproterozoic oceans would have controlled CH₄ fluxes to the atmosphere, thereby regulating the capacity for CH₄ to warm the early Earth under the Faint Young Sun. We studied CH₄ and Fe cycling in anoxic incubations of ferruginous sediment from the ancient ocean analogue Lake Matano, Indonesia, over three successive transfers (500 days in total). Iron reduction, methanogenesis, CH₄ oxidation, and microbial taxonomy were monitored in treatments amended with ferrihydrite or goethite. After three dilutions, Fe(III) reduction persisted only in bottles with ferrihydrite. Enhanced CH₄ production was observed in the presence of goethite, highlighting the potential for reactive Fe(III) oxides to inhibit methanogenesis. Supplementing the media with hydrogen, nickel and selenium did not stimulate methanogenesis. There was limited evidence for Fe(III)‐dependent CH₄ oxidation, although some incubations displayed CH₄‐stimulated Fe(III) reduction. 16S rRNA profiles continuously changed over the course of enrichment, with ultimate dominance of unclassified members of the order Desulfuromonadales in all treatments. Microbial diversity decreased markedly over the course of incubation, with subtle differences between ferrihydrite and goethite amendments. These results suggest that Fe(III) oxide mineralogy and availability of electron donors could have led to spatial separation of Fe(III)‐reducing and methanogenic microbial communities in ferruginous marine sediments, potentially explaining the persistence of CH₄ as a greenhouse gas throughout the first half of Earth history.     

Particulate organic and dissolved inorganic carbon stable isotopic compositions in Taylor Valley lakes,Antarctica: the effect of legacy

In perennially ice-covered lakes of Taylor Valley, Antarctica, “legacy”, a carryover of past ecosystem events, has primarily been discussed in terms of nutrient and salinity concentrations and its effect on the current ecology of the lakes. In this study, we determine how residual pools of ancient carbon affect the modern carbon abundance and character in the water columns of Lakes Fryxell, Hoare, and Bonney. We measure the stable carbon isotopic compositions and concentrations of particulate organic carbon (POC) and dissolved inorganic carbon (DIC) in the water column of these lakes over four seasons (1999–2002). These data are presented and compared with all the previously published Taylor Valley lacustrine carbon stable isotopic data. Our results show that the carbon concentrations and isotopic compositions of the upper water columns of those lakes are controlled by modern processes, while the lower water columns are controlled to varying degrees by inherited carbon pools. The water column of the west lobe of Lake Bonney is dominated by exceptionally high concentrations of DIC (55,000–75,000 μmol l⁻¹) reflecting the long period of ice-cover on this lake. The east lobe of Lake Bonney has highly enriched δ¹³C_DIC values resulting from paleo-brine evaporation effects in its bottom waters, while its high DIC concentrations provide geochemical evidence that its middle depth waters are derived from West Lake Bonney during a hydrologically connected past. Although ancient carbon is present in both Lake Hoare and Lake Fryxell, the δ¹³C_DIC values in bottom waters suggest dominance by modern primary productivity-related processes. Anaerobic methanogenesis and methanotrophy are also taking place in the lower water column of Lake Fryxell with enough methane, oxidized anaerobically, to contribute to the DIC pool. We also show how stream proximity and high flood years are only a minor influence on the carbon isotopic values of both POC and DIC. The Taylor Valley lake system is remarkably stable in both inter-lake and intra-lake carbon dynamics. Handling editor: K. Martens     

Rates and pathways of CH4 oxidation in ferruginous Lake Matano,Indonesia

This study evaluates rates and pathways of methane (CH₄) oxidation and uptake using ¹⁴C‐based tracer experiments throughout the oxic and anoxic waters of ferruginous Lake Matano. Methane oxidation rates in Lake Matano are moderate (0.36 nmol L^?1 day^?1 to 117 μmol L^?1 day^?1) compared to other lakes, but are sufficiently high to preclude strong CH₄ fluxes to the atmosphere. In addition to aerobic CH₄ oxidation, which takes place in Lake Matano's oxic mixolimnion, we also detected CH₄ oxidation in Lake Matano's anoxic ferruginous waters. Here, CH₄ oxidation proceeds in the apparent absence of oxygen (O₂) and instead appears to be coupled to some as yet uncertain combination of nitrate (), nitrite (), iron (Fe) or manganese (Mn), or sulfate () reduction. Throughout the lake, the fraction of CH₄ carbon that is assimilated vs. oxidized to carbon dioxide (CO₂) is high (up to 93%), indicating extensive CH₄ conversion to biomass and underscoring the importance of CH₄ as a carbon and energy source in Lake Matano and potentially other ferruginous or low productivity environments.     

Intensity of the Microbiological Processes of the Methane Cycle in Different Types of Baltic Lakes

The intensity of the microbiological processes of methane formation (MF) and methane oxidation (MO) was determined in the sediments and water of different types of Baltic lakes. The emission of methane from the lake sediments and methane distribution in the water column of the lakes were studied as functions of the lake productivity and hydrologic conditions. During summers, the intensity of MF in the lake sediments and waters varied from 0.001 to 106 ml CH₄/(dm³ day) and from 0 to 3.2 ml CH₄/(l day), respectively, and the intensity of MO in the sediments and water varied from 0 to 11.2 ml CH₄/(dm³ day) and from 0 to 1.1 ml CH₄/(l day), respectively. The total methane production (MP) in the lakes varied from 15 to 5000 ml CH₄/(m² day). In anoxic waters, the MP comprised 9–18% of the total PM in the lakes. The consumption of organic carbon for methanogenesis varied from 0.03 to 9.7 g/(m² day). The role of the methane cycle in the degradation of organic matter in the lakes increased with their productivity.     

Metal limitation of cyanobacterial N2 fixation and implications for the Precambrian nitrogen cycle

Nitrogen fixation is a critical part of the global nitrogen cycle, replacing biologically available reduced nitrogen lost by denitrification. The redox‐sensitive trace metals Fe and Mo are key components of the primary nitrogenase enzyme used by cyanobacteria (and other prokaryotes) to fix atmospheric N₂ into bioessential compounds. Progressive oxygenation of the Earth's atmosphere has forced changes in the redox state of the oceans through geologic time, from anoxic Fe‐enriched waters in the Archean to partially sulfidic deep waters by the mid‐Proterozoic. This development of ocean redox chemistry during the Precambrian led to fluctuations in Fe and Mo availability that could have significantly impacted the ability of prokaryotes to fix nitrogen. It has been suggested that metal limitation of nitrogen fixation and nitrate assimilation, along with increased rates of denitrification, could have resulted in globally reduced rates of primary production and nitrogen‐starved oceans through much of the Proterozoic. To test the first part of this hypothesis, we grew N₂‐fixing cyanobacteria in cultures with metal concentrations reflecting an anoxic Archean ocean (high Fe, low Mo), a sulfidic Proterozoic ocean (low Fe, moderate Mo), and an oxic Phanerozoic ocean (low Fe, high Mo). We measured low rates of cellular N₂ fixation under [Fe] and [Mo] estimated for the Archean ocean. With decreased [Fe] and higher [Mo] representing sulfidic Proterozoic conditions, N₂ fixation, growth, and biomass C:N were similar to those observed with metal concentrations of the fully oxygenated oceans that likely developed in the Phanerozoic. Our results raise the possibility that an initial rise in atmospheric oxygen could actually have enhanced nitrogen fixation rates to near modern marine levels, providing that phosphate was available and rising O₂ levels did not markedly inhibit nitrogenase activity.     

Anoxic degradation of biogenic debris in sediments of eutrophic subalpine Lake Bled (Slovenia)

Anoxic degradation of sedimentary biogenic debris using closed sediment incubation experiments was studied in eutrophic subalpine Lake Bled (NW Slovenia) which, for most of the year, has an anoxic hypolimnion. Production rates of dissolved inorganic carbon (DIC), NH₄ ⁺, PO₄ ^3- and dissolved Si, and reduction rates of SO₄ ^2- were measured and anoxic mineralization rates were modelled using G-model. The depth profiles indicated major mineralization of biogenic debris and SO₄ ^2- reduction near the sediment surface. A comparison between depth integrated anoxic mineralization rates and diffusive benthic fluxes of DIC, NH₄ ⁺ and PO₄ ^3- showed that the anoxic incubation experiments provide a good estimate of N degradation of biogenic debris. The contributions of SO₄ ^2- reduction and acetate fermentation in NH₄ ⁺ production are about 30 and 70%, respectively. The DIC production accounted for only 15% of DIC benthic flux, indicating that methanogenesis and oxidation of methane provides 80% of this flux. Only about 30% of PO₄ ^3- was released because phosphate precipitated in the closed incubation experiments. The depth integrated production of Si accounts for 70–80% of Si benthic fluxes indicating intense dissolution of biogenic Si in the surficial lake sediment.     

Deep‐water anoxygenic photosythesis in a ferruginous chemocline

Ferruginous Lake Matano, Indonesia hosts one of the deepest anoxygenic photosynthetic communities on Earth. This community is dominated by low‐light adapted, BChl e‐synthesizing green sulfur bacteria (GSB), which comprise ~25% of the microbial community immediately below the oxic‐anoxic boundary (OAB; 115‐120 m in 2010). The size of this community is dependent on the mixing regime within the lake and the depth of the OAB—at ~117 m, the GSB live near their low‐light limit. Slow growth and C‐fixation rates suggest that the Lake Matano GSB can be supported by sulfide even though it only accumulates to scarcely detectable (low μm to nm ) concentrations. A model laboratory strain (Chlorobaculum tepidum) is indeed able to access HS^? for oxidation at nm concentrations. Furthermore, the GSB in Lake Matano possess a full complement of S‐oxidizing genes. Together, this physiological and genetic information suggests that deep‐water GSB can be supported by a S‐cycle, even under ferruginous conditions. The constraints we place on the metabolic capacity and physiology of GSB have important geobiological implications. Biomarkers diagnostic of GSB would be a good proxy for anoxic conditions but could not discriminate between euxinic and ferruginous states, and though GSB biomarkers could indicate a substantial GSB community, such a community may exist with very little metabolic activity. The light requirements of GSB indicate that at light levels comparable to those in the OAB of Lake Matano or the Black Sea, GSB would have contributed little to global ocean primary production, nutrient cycling, and banded iron formation (BIF) deposition in the Precambrian. Before the proliferation of oxygenic photosynthesis, shallower OABs and lower light absorption in the ocean's surface waters would have permitted greater light availability to GSB, potentially leading to a greater role for GSB in global biogeochemical cycles.     

Depleted methane-derived carbon in waters of Lake Baikal,Siberia

Results of hydrochemical and stable isotope measurements during the ice-breaking period on Lake Baikal indicate an apparent lack of relationship between measured δ¹³C of dissolved inorganic carbon (DIC) and phytoplankton below the trophogenic layer. While planktonic values of −31.7 to −33.5‰ are within a typical lacustrine range, the δ¹³C values of DIC turned out to be very negative, from −28.9 to −35.6‰. These isotopic values of DIC appear to be associated with oxidation of methane that accumulated during winter ice cover period. At the time of sampling, however, the observed depletion did not affect the phytoplankton/DIC fractionation relationship, because the difference between phytoplankton and DIC (−20 to −22‰ in surface waters) lies within the expected range of the fractionation coefficient. By analogy with small lakes, we explain this lack of relationship by the time lag between peak productivity and peak methane oxidation. Our interpretation of the Baikal DIC isotopic signature is consistent with methanogenesis in bottom sediments and with the known presence of widespread unstable gas hydrates and active methane seeps on the lake floor. Our findings suggest that methane is an important component of the Baikal carbon cycle, that late winter concentrations of methane in Baikal under ice may be 3–4 orders of magnitude higher than previously reported values for summer, and that the lake may be emitting a significant amount of methane to the atmosphere.     

Redox heterogeneity of subsurface waters in the Mesoproterozoic ocean

A substantial body of evidence suggests that subsurface water masses in mid‐Proterozoic marine basins were commonly anoxic, either euxinic (sulfidic) or ferruginous (free ferrous iron). To further document redox variations during this interval, a multiproxy geochemical and paleobiological investigation was conducted on the approximately 1000‐m‐thick Mesoproterozoic (Lower Riphean) Arlan Member of the Kaltasy Formation, central Russia. Iron speciation geochemistry, supported by organic geochemistry, redox‐sensitive trace element abundances, and pyrite sulfur isotope values, indicates that basinal calcareous shales of the Arlan Member were deposited beneath an oxygenated water column, and consistent with this interpretation, eukaryotic microfossils are abundant in basinal facies. The Rhenium–Osmium (Re–Os) systematics of the Arlan shales yield depositional ages of 1414 ± 40 and 1427 ± 43 Ma for two horizons near the base of the succession, consistent with previously proposed correlations. The presence of free oxygen in a basinal environment adds an important end member to Proterozoic redox heterogeneity, requiring an explanation in light of previous data from time‐equivalent basins. Very low total organic carbon contents in the Arlan Member are perhaps the key—oxic deep waters are more likely (under any level of atmospheric O₂) in oligotrophic systems with low export production. Documentation of a full range of redox heterogeneity in subsurface waters and the existence of local redox controls indicate that no single stratigraphic section or basin can adequately capture both the mean redox profile of Proterozoic oceans and its variance at any given point in time.     

Intensity of the microbiological processes of the methane cycle in different types of Baltic lakes

The intensity of the microbiological processes of methane formation (MF) and methane oxidation (MO) was determined in the sediments and water of different types of Baltic lakes. The emission of methane from the lake sediments and methane distribution in the water column of the lakes were studied as functions of the lake productivity and hydrologic conditions. During summers, the intensity of MF in the lake sediments and waters varied from 0.001 to 106 ml CH4/(dm3 day) and from 0 to 3.2 ml CH4/(1 day), respectively, and the intensity of MO in the sediments and water varied from 0 to 11.2 ml CH4/(dm3 day) and from 0 to 1.1 ml CH4/(1 day), respectively. The total methane production (MP) in the lakes varied from 15 to 5000 ml CH4/(m2 day). In anoxic waters, the MP comprised 9-18% of the total PM in the lakes. The consumption of organic carbon for methanogenesis varied from 0.03 to 9.7 g/(m2 day). The role of the methane cycle in the degradation of organic matter in the lakes increased with their productivity.     

Using modern low-oxygen marine ecosystems to understand the nitrogen cycle of the Paleo- and Mesoproterozoic oceans

During the productive Paleoproterozoic (2.4–1.8 Ga) and less productive Mesoproterozoic (1.8–1.0 Ga), the ocean was suboxic to anoxic and multicellular organisms had not yet evolved. Here, we link geologic information about the Proterozoic ocean to microbial processes in modern low-oxygen systems. High iron concentrations and rates of Fe cycling in the Proterozoic are the largest differences from modern oxygen-deficient zones. In anoxic waters, which composed most of the Paleoproterozoic and ~40% of the Mesoproterozoic ocean, nitrogen cycling dominated. Rates of N₂ production by denitrification and anammox were likely linked to sinking organic matter fluxes and in situ primary productivity under anoxic conditions. Additionally autotrophic denitrifiers could have used reduced iron or methane. 50% of the Mesoproterozoic ocean may have been suboxic, promoting nitrification and metal oxidation in the suboxic water and N₂O and N₂ production by partial and complete denitrification in anoxic zones in organic aggregates. Sulfidic conditions may have composed ~10% of the Mesoproterozoic ocean focused along continental margins. Due to low nitrate concentrations in offshore regions, anammox bacteria likely dominated N₂ production immediately above sulfidic zones, but in coastal regions, higher nitrate concentrations probably promoted complete S-oxidizing autotrophic denitrification at the sulfide interface.     

Methane production in meromictic Ace Lake,Antarctica

Methane occurred in the monimolimnion, at depths greater than 11 m, of an antarctic meromictic lake, Ace Lake (depth 24.7 m). Although the water of the lake was of approximate marine salinity, bottom waters were depleted in sulfate (less than 1 mmol 1^–1). The temperature of the bottom waters of the lake were constantly between 1 °C and 2 °C. Rates of methanogenesis from ¹⁴C-labelled precursors (bicarbonate, formate and acetate) were determined in time course experiments with the detection of ¹⁴CH₄ produced by a gas chromatography-gas proportional counting system. Rates of ¹⁴CH₄ production were difficult to determine as the reactions were always near our limit of detection.Reliable determinations of rates of methanogenesis at some depths using some precursors were obtained, the fastest rate being 2.5 µmol kg^–1 day^–1 at depth 20 m. Assuming constant rates of methanogenesis with time, this would equate to a turnover of methane in the lake every two years.The slow rate of methanogenesis suggests that the methanogens in Ace Lake may be working at well below their optimum temperature although definitive statements regarding the presence of psychrophilic methanogens in this antarctic lake must await isolation attempts or longer field studies using alternative methodologies.     

Redox reactions of organic matter decomposition in a soft water lake

During a three year study (1985–1987) we used a mass balance approach to study the oxidation and reduction reactions related to decomposition of organic carbon in Mirror Lake, New Hampshire. The stoichiometry of the reactions allows us to calculate an electron transfer budget for the summer stratification period in the lake, as well as in benthic chambers and sealed jars.The average decomposition rate measured as dissolved inorganic carbon (DIC) production was 5.33 mmol m^–2 d^–1. The proportions of decomposition accounted for by the various electron acceptors varied both during the summer, as well as from year to year. On average, oxygen accounted for 43% of DIC production, while the processes involving sulfate, nitrate, iron and methane formation together accounted for 20%. Despite conservative assumptions we could not account for 37% of the DIC production. The general pattern, including excess DIC production, was also observed in chamber studies conducted over shallow-water sediments and in sealed-jar experiments.Data on burial rates of reduced iron minerals indicate that such minerals are not sufficient to account for the discrepancy in the electron budget. Our analysis suggests that another electron acceptor such as organic carbon reduction, either via fermentation or selective oxidation, is the most likely explanation of excess DIC production.     

Ecosystem-Scale Oxygen Manipulations Alter Terminal Electron Acceptor Pathways in a Eutrophic Reservoir

Lakes and reservoirs globally are experiencing unprecedented changes in land use and climate, depleting dissolved oxygen (DO) in the bottom waters (hypolimnia) of these ecosystems. Because DO is the most energetically favorable terminal electron acceptor (TEA) for organic carbon mineralization, its availability controls the onset of alternate TEA pathways (for example, denitrification, manganese reduction, iron reduction, sulfate reduction, methanogenesis). Low DO concentrations can trigger organic carbon mineralization via alternate TEA pathways in the water column and sediments, which has important implications for greenhouse gas production [carbon dioxide (CO₂) and methane (CH₄)]. In this study, we experimentally injected supersaturated DO into the hypolimnion of a eutrophic reservoir and measured concentrations of TEAs and terminal electron products (TEPs) in the experimental reservoir and an upstream reference reservoir. We calculated the electron equivalents yielded from each TEA pathway and estimated the contributions of each TEA pathway to organic carbon processing in both reservoirs. DO additions to the hypolimnion of the experimental reservoir promoted aerobic respiration, suppressing most alternate TEA pathways and resulting in elevated CO₂ accumulation. In comparison, organic carbon mineralization in the reference reservoir’s anoxic hypolimnion was dominated by alternate TEA pathways, resulting in both CH₄ and CO₂ accumulation. Our ecosystem-scale experiments demonstrate that the alternate TEA pathways that succeed aerobic respiration in lakes and reservoirs can be manipulated at the ecosystem scale. Moreover, changes in the DO dynamics of freshwater lakes and reservoirs may result in concomitant changes in the redox reactions in the water column that control organic carbon mineralization and greenhouse gas accumulation.

     

Microbial Methanogenesis and Acetate Metabolism in a Meromictic Lake

Methanogenesis and the anaerobic metabolism of acetate were examined in the sediment and water column of Knaack Lake, a small biogenic meromictic lake located in central Wisconsin. The lake was sharply stratified during the summer and was anaerobic below a depth of 3 m. Large concentrations (4,000 μmol/liter) of dissolved methane were detected in the bottom waters. A methane concentration maximum occurred at 4 m above the sediment. The production of ¹⁴CH₄ from ¹⁴C-labeled HCOOH, HCO₃⁻, and CH₃OH and [2-¹⁴C]acetate demonstrated microbial methanogenesis in the water column of the lake. The maximum rate of methanogenesis calculated from reduction of H¹⁴CO₃⁻ by endogenous electron donors in the surface sediment (depth, 22 m) was 7.6 nmol/h per 10 ml and in the water column (depth, 21 m) was 0.6 nmol/h per 10 ml. The methyl group of acetate was simultaneously metabolized to CH₄ and CO₂ in the anaerobic portions of the lake. Acetate oxidation was greatest in surface waters and decreased with water depth. Acetate was metabolized primarily to methane in the sediments and water immediately above the sediment. Sulfide inhibition studies and temperature activity profiles demonstrated that acetate metabolism was performed by several microbial populations. Sulfide additions (less than 5 μg/ml) to water from 21.5 m stimulated methanogenesis from acetate, but inhibited CO₂ production. Sulfate addition (1 mM) had no significant effect on acetate metabolism in water from 21.5 m, whereas nitrate additions (10 to 14,000 μg/liter) completely inhibited methanogenesis and stimulated CO₂ formation.     

Carbon Cycling of Lake Kivu (East Africa): Net Autotrophy in the Epilimnion and Emission of CO2 to the Atmosphere Sustained by Geogenic Inputs

We report organic and inorganic carbon distributions and fluxes in a large (>2000 km²) oligotrophic, tropical lake (Lake Kivu, East Africa), acquired during four field surveys, that captured the seasonal variations (March 2007–mid rainy season, September 2007–late dry season, June 2008–early dry season, and April 2009–late rainy season). The partial pressure of CO₂ (pCO₂) in surface waters of the main basin of Lake Kivu showed modest spatial (coefficient of variation between 3% and 6%), and seasonal variations with an amplitude of 163 ppm (between 579±23 ppm on average in March 2007 and 742±28 ppm on average in September 2007). The most prominent spatial feature of the pCO₂ distribution was the very high pCO₂ values in Kabuno Bay (a small sub-basin with little connection to the main lake) ranging between 11213 ppm and 14213 ppm (between 18 and 26 times higher than in the main basin). Surface waters of the main basin of Lake Kivu were a net source of CO₂ to the atmosphere at an average rate of 10.8 mmol m⁻² d⁻¹, which is lower than the global average reported for freshwater, saline, and volcanic lakes. In Kabuno Bay, the CO₂ emission to the atmosphere was on average 500.7 mmol m⁻² d⁻¹ (∼46 times higher than in the main basin). Based on whole-lake mass balance of dissolved inorganic carbon (DIC) bulk concentrations and of its stable carbon isotope composition, we show that the epilimnion of Lake Kivu was net autotrophic. This is due to the modest river inputs of organic carbon owing to the small ratio of catchment area to lake surface area (2.15). The carbon budget implies that the CO₂ emission to the atmosphere must be sustained by DIC inputs of geogenic origin from deep geothermal springs.     

Microbiological and isotopic geochemical investigation of Lake Kislo-Sladkoe,a meromictic water body at the Kandalaksha Bay shore (White Sea)

Microbiological, biogeochemical, and isotopic geochemical investigation of Lake Kislo-Sladkoe (Polusolenoe in early publications) at the Kandalaksha Bay shore (White Sea) was carried out in September 2010. Lake Kislo-Sladkoe was formed in the mid-1900s out of a sea gulf due to a coastal heave. At the time of investigation, the surface layer was saturated with oxygen, while near-bottom water contained sulfide (up to 32 mg/L). Total number of microorganisms was high (12.3 × 10⁶ cells/mL on average). Light CO₂ fixation exhibited two pronounced peaks. In the oxic zone, the highest rates of photosynthesis were detected at 1.0 and 2.0 m. The second, more pronounced peak of light CO₂ fixation was associated with activity of anoxygenic phototrophic bacteria in the anoxic layer at the depth of 2.9 m (413 μg C L^?1 day^?1). Green-colored green sulfur bacteria (GSB) predominated in the upper anoxic layer (2.7–2.9 m), their numbers being as high as 1.12 × 10⁴ cells/mL, while brown-colored GSB predominated in the lower horizons. The rates of both sulfate reduction and methanogenesis peaked in the 2.9 m horizon (1690 μg S L^?1 day^?1 and 2.9 μL CH₄ L^?1 day^-1). The isotopic composition of dissolved methane from the near-bottom water layer (δ¹³C (CH₄) = ?87.76‰) was significantly lighter than in the upper horizons (δ¹³C (CH₄) = ?77.95‰). The most isotopically heavy methane (δ¹³C (CH₄) = ?72.61‰) was retrieved from the depth of 2.9 m. The rate of methane oxidation peaked in the same horizon. As a result of these reactions, organic matter (OM) carbon of the 2.9 m horizon became lighter (?36.36‰), while carbonate carbon became heavier (?7.56‰). Thus, our results demonstrated that Lake Kislo-Sladkoe is a stratified meromictic lake with active microbial cycles of carbon and sulfur. Suspended matter in the water column was mostly of autochthonous origin. Anoxygenic photo-synthesis coupled to utilization of reduced sulfur compounds contributed significantly to OM production.     

Transport,anoxia and end-product accumulation control carbon dioxide and methane production and release in peat soils

Anaerobic respiration and methanogenesis have been found to slow-down in water saturated peat soils with accumulation of metabolic end-products, i.e. dissolved inorganic carbon (DIC) and methane (CH₄), due to a lack of solute and gas transport. So far it is not well understood how solute and gas transport may control this effect. We conducted a column experiment with homogenized ombrotrophic peat over a period of 300 days at 20 °C. We specifically evaluated the effects of diffusive flux as control, downward advective water flux, intensified ebullition by conduit gas transport and diffusive oxygen supply on controlling anaerobic decomposition rates and carbon (C) turnover. To simulate advective flux, water and solutes were recirculated downward through the column after stripping of dissolved gases. We analyzed DIC and CH₄ concentrations, production rates and fluxes, gas filled porosity, oxygen profiles (O₂) and microbial C biomass over time. DIC residence time thereby served as proxy to characterize transport. A slowdown of anaerobic respiration and methanogenesis evolved with the accumulation of the end-products DIC and CH₄ and set in after 150 days. This slow-down was accompanied by a decrease in the distribution of microbial biomass C with depths. Anaerobic DIC and CH₄ production rates were fastest close to the water table and sharply slowed with depth. Accumulation of DIC and CH₄ in the homogeneous peat material throughout the column decreased decomposition constants from about 10^?5 near the surface to 10^?9 year^?1 deeper in the profile. Advective water transport extended the zone of active methanogenesis compared to a diffusive system; experimental enhancement of ebullition had little or no effect as well as strictly anoxic conditions. DIC residence time was negatively correlated to anaerobic respiration suggesting this parameter to be a predictor of anaerobic peat decomposition in peatlands. Overall, this study suggests that burial of peat and accumulation of metabolic end-products effectively slows decomposition and that this effect needs to be considered to explain peat accumulation and the response of peat mineralization rates to changes in environmental conditions.