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.     

Effects of short-term drying and irrigation on CO2 and CH4 production and emission from mesocosms of a northern bog and an alpine fen

Atmospheric CO₂ and CH₄ exchange in peatlands is controlled by water table levels and soil moisture, but impacts of short periods of dryness and rainfall are poorly known. We conducted drying-rewetting experiments with mesocosms from an ombrotrophic northern bog and an alpine, minerotrophic fen. Efflux of CO₂ and CH₄ was measured using static chambers and turnover and diffusion rates were calculated from depth profiles of gas concentrations. Due to a much lower macroporosity in the fen compared to the bog peat, water table fluctuated more strongly when irrigation was stopped and resumed, about 11 cm in the fen and 5 cm in the bog peat. Small changes in air filled porosity caused CO₂ and CH₄ concentrations in the fen peat to be insensitive to changes in water table position. CO₂ emission was by a factor of 5 higher in the fen than in the bog mesocosms and changed little with water table position in both peats. This was probably caused by the importance of the uppermost, permanently unsaturated zone for auto- and heterotrophic CO₂ production, and a decoupling of air filled porosity from water table position. CH₄ emission was <0.4 mmol m^?2 day^?1 in the bog peat, and up to >12.6 mmol m^?2 day^?1 in the fen peat, where it was lowered by water table fluctuations. CH₄ production was limited to the saturated zone in the bog peat but proceeded in the capillary fringe of the fen peat. Water table drawdown partly led to inhibition of methanogenesis in the newly unsaturated zone, but CH₄ production appeared to continue after irrigation without time-lag. The identified effects of irrigation on soil moisture and respiration highlight the importance of peat physical properties for respiratory dynamics; but the atmospheric carbon exchange was fairly insensitive to the small-scale fluctuations induced.     

Activity and metabolic regulation of methane production in deep peat profiles of boreal bogs

The potential activity of methane production was determined in the vertical profiles of the peat deposits of three bogs in Tver oblast, which were representative of the boreal zone. In the minerotrophic fen, the rates of methane production measured throughout the profile did not change significantly with depth and comprised 3–6 ng CH₄-C g^?1 h^?1. In ombrotrophic peat bogs, the rate did not exceed 5 ng CH₄-C g^?1 h^?1 in the upper layer of the profile (up to 1.5 m) and increased to 15–30 ng CH₄-C g^?1 h^?1 in the deep layers of the peat deposits. The distribution of fermentative microorganisms and methanogens in the profiles of peat deposits was uniform in all the studied bogs. In bog water samples, the presence of butyrate (up to 14.1 mg 1^?1) and acetate (up to 2.4 mg 1^?1) was revealed throughout the whole profile; in the upper 0.5-m layer of the ombrotrophic bogs, formate (up to 8.9 mg 1^?1) and propionate (up to 0.3 mg 1^?1) were detected as well. The arrangement of local maxima of the fatty acid content and methanogenic activity in the peat deposits, as well as the decrease in the acetate concentrations during summer, support the hypothesis that the initial substrates for methanogenesis come from the upper peat layers. It was established that the addition of sulfate and nitrate inhibits methane production in peat samples; the changes in the concentrations, recorded in situ, may also influence the methane content in peat layers.     

Recovery of Methanogenesis Following Summer Drought in Soils from Two Cool Temperate Peatlands,New York State,USA

Following a summer drought, intact cores of peat soil from two cool temperate peatlands (a rain-fed bog and a groundwater-fed swamp) were exposed experimentally to three different water table levels. The goal was to examine recovery of anaerobic methanogenesis and to evaluate peat soil decomposition to methane (CH₄), carbon dioxide (CO₂), and dissolved organic carbon (DOC) upon rewetting. Methane emission from soils to the atmosphere was greatest (mean = 80 μmol m^?2 s^?1) when the entire peat core was rewetted quickly; emission was negligible at low water level and when peat cores were rewetted gradually. Rates of CO₂ emission (mean = 1.0 μmol m^?2 s^?1) were relatively insensitive to water level. Concentrations of CH₄ in soil air spaces suggest that onset of methanogenesis induces, but later represses, aerobic oxidation of CH₄ above the water table. Concentrations of CO₂ suggest production at the soil surface of swamp peat versus at greater depths in bog peat. Portions of peat soil incubated in vitro without oxygen (O₂) exhibited a lag before the onset of methanogenesis, and the lag time was less in peat from the cores rewetted quickly. The inhibition of methanogenesis by the selective inhibitor 2-bromoethanesulfonic acid (BES) decreased CO₂ production by 20 to 30% but resulted in an increase in concentrations of DOC by 2 to 5 times. The results show that methanogens in peat soils tolerate moderate drought, and recovery varies among different peat types. In peat soils, the inhibition of methanogenesis might enhance DOC availability.     

Methane Production in Minnesota Peatlands

Rates of methane production in Minnesota peats were studied. Surface (10- to 25-cm) peats produced an average of 228 nmol of CH₄ per g (dry weight) per h at 25°C and ambient pH. Methanogenesis rates generally decreased with depth in ombrotrophic peats, but on occasion were observed to rise within deeper layers of certain fen peats. Methane production was temperature dependent, increasing with increasing temperature (4 to 30°C), except in peats from deeper layers. Maximal methanogenesis from these deeper regions occurred at 12°C. Methane production rates were also pH dependent. Two peats with pHs of 3.8 and 4.3 had an optimum rate of methane production at pH 6.0. The addition to peat of glucose and H₂-CO₂ stimulated methanogenesis, whereas the addition of acetate inhibited methanogenesis. Cysteine-sulfide, nitrogen-phosphorus-trace metals, and vitamins-yeast extract affected methane production very little. Various gases were found to be trapped or dissolved (or both) within peatland waters. Dissolved methane increased linearly to a depth of 210 cm. The accumulation of metabolic end products produced within peat bogs appears to be an important mechanism limiting carbon turnover in peatland environments.     

Hydrogenotrophic Methanogenesis by Moderately Acid-Tolerant Methanogens of a Methane-Emitting Acidic Peat

The emission of methane (1.3 mmol of CH₄ m⁻² day⁻¹), precursors of methanogenesis, and the methanogenic microorganisms of acidic bog peat (pH 4.4) from a moderately reduced forest site were investigated by in situ measurements, microcosm incubations, and cultivation methods, respectively. Bog peat produced CH₄ (0.4 to 1.7 μmol g [dry wt] of soil⁻¹ day⁻¹) under anoxic conditions. At in situ pH, supplemental H₂-CO₂, ethanol, and 1-propanol all increased CH₄ production rates while formate, acetate, propionate, and butyrate inhibited the production of CH₄; methanol had no effect. H₂-dependent acetogenesis occurred in H₂-CO₂-supplemented bog peat only after extended incubation periods. Nonsupplemented bog peat initially produced small amounts of H₂ that were subsequently consumed. The accumulation of H₂ was stimulated by ethanol and 1-propanol or by inhibiting methanogenesis with bromoethanesulfonate, and the consumption of ethanol was inhibited by large amounts of H₂; these results collectively indicated that ethanol- or 1-propanol-utilizing bacteria were trophically associated with H₂-utilizing methanogens. A total of 10⁹ anaerobes and 10⁷ hydrogenotrophic methanogens per g (dry weight) of bog peat were enumerated by cultivation techniques. A stable methanogenic enrichment was obtained with an acidic, H₂-CO₂-supplemented, fatty acid-enriched defined medium. CH₄ production rates by the enrichment were similar at pH 4.5 and 6.5, and acetate inhibited methanogenesis at pH 4.5 but not at pH 6.5. A total of 27 different archaeal 16S rRNA gene sequences indicative of Methanobacteriaceae, Methanomicrobiales, and Methanosarcinaceae were retrieved from the highest CH₄-positive serial dilutions of bog peat and methanogenic enrichments. A total of 10 bacterial 16S rRNA gene sequences were also retrieved from the same dilutions and enrichments and were indicative of bacteria that might be responsible for the production of H₂ that could be used by hydrogenotrophic methanogens. These results indicated that in this acidic bog peat, (i) H₂ is an important substrate for acid-tolerant methanogens, (ii) interspecies hydrogen transfer is involved in the degradation of organic carbon, (iii) the accumulation of protonated volatile fatty acids inhibits methanogenesis, and (iv) methanogenesis might be due to the activities of methanogens that are phylogenetic members of the Methanobacteriaceae, Methanomicrobiales, and Methanosarcinaceae.     

Partitioning pathways of CO2 production in peatlands with stable carbon isotopes

Although methanogenic pathways generally produce equimolar amounts of carbon dioxide and methane, CO₂ concentrations are often reported to be higher than CH₄ concentrations in both field and laboratory incubation studies of peat decomposition. In field settings, higher pore water concentrations of CO₂ may result from the loss of methane by: (1) ebullition due to the low solubility of methane in pore water and (2) vascular-plant transport. Higher CO₂ concentrations may also be caused by: (1) production of additional CO₂ by high-molecular weight (HMW) organic matter (OM) fermentation and/or (2) respiration from non-methanogenic pathways. In this study of a peatland where advection and transverse dispersion were the dominant pore water solute transport mechanisms, an isotope-mass balance approach was used to determine the proportions of CO₂ formed from non-fractionating OM respiration and HMW fermentation relative to CO₂ production from methanogenesis. This approach also allowed us to estimate the loss of CH₄ from the belowground system. The pathways of CO₂ production varied with depth and surface vegetation type. In a Carex-dominated fen, methane production initially produced 40 % of the total CO₂ and then increased to 90–100 % with increasing depth. In a Sphagnum-dominated bog, methanogenesis resulted in 60 % of total CO₂ production which increased to 100 % at depth. Both bogs and fens showed 85–100 % of methane loss from pore waters. Our results indicate that the isotopic composition of dissolved CO₂ is a powerful indicator to allow partitioning of the processes affecting peat remineralization and methane production.     

Linking Belowground Carbon Allocation to Anaerobic CH4 and CO2 Production in a Forested Peatland,New York State

Heterotrophic soil microorganisms rely on carbon (C) allocated belowground in plant production, but belowground C allocation (BCA) by plants is a poorly quantified part of ecosystem C cycling, especially, in peat soil. We applied a C balance approach to quantify BCA in a mixed conifer-red maple (Acer rubrum) forest on deep peat soil. Direct measurements of CH₄ and CO₂ fluxes across the soil surface (soil respiration), production of fine and small plant roots, and aboveground litterfall were used to estimate respiration by roots, by mycorrhizae and by free-living soil microorganisms. Measurements occurred in two consecutive years. Soil respiration rates averaged 1.2 bm μmol m^{? 2} s^{? 1} for CO₂ and 0.58 nmol m^{? 2} s^{? 1} for CH₄ (371 to 403 g C m^{? 2} year^{? 1}). Carbon in aboveground litter (144 g C m^{? 2} year^{? 1}) was 84% greater than C in root production (78 g C m^{? 2} year^{? 1}). Complementary in vitro assays located high rates of anaerobic microbial activity, including methanogenesis, in a dense layer of roots overlying the peat soil and in large-sized fragments within the peat matrix. Large-sized fragments were decomposing roots and aboveground leaf and twig litter, indicating that relatively fresh plant production supported most of the anaerobic microbial activity. Respiration by free-living soil microorganisms in deep peat accounted for, at most, 29 to 38 g C m^{? 2} year^{? 1}. These data emphasize the close coupling between plant production, ecosystem-level C cycling and soil microbial ecology, which BCA can help reveal.     

Development of floating rafts after the rewetting of cut-over bogs: the importance of peat quality

The usual method of restoring cut-over bogs is to rewet the peat surface, but this often leads to the remaining peat layers being deeply inundated. For Sphagnum-dominated vegetation to develop at deeply inundated locations, it is important for floating rafts of buoyant residual peat to develop. In this study, the chemical and physical characteristics of buoyant and inundated peat collected from rewetted cut-over bog were compared. In general, buoyant peat was poorly humified; high methane (CH₄) production rates (≥2?µmol?g^?1?DW?day^?1) were important to ensure buoyancy. Although the peat water CH₄ concentrations increased with depth, the CH₄ production rates were higher in the uppermost peat layers. High CH₄ production rates were related positively with P concentrations and negatively with lignin concentrations. The pH to bulk density ratio (≥0.05) also appeared to be a good indicator of CH₄ production rates, providing an easy and cheap way to measure the variable for restoration practitioners. Our results indicated that analysing certain simple characteristics of the residual peat can greatly improve the success of the rewetting measures taken in cut-over bogs. If the analysis reveals that the residual peat is unsuitable for floating raft formation, deep inundation is inappropriate unless suitable peat from other locations can be introduced.     

Evidence for Anaerobic CH 4 Oxidation in Freshwater Peatlands

This study involved in vitro assays of peat soil to investigate the occurrence, importance and potential mechanism(s) of anaerobic methane oxidation (AOM) in several northern peatlands ranging from ombrotrophic bog to minerotrophic fen. Although strong evidence suggests that AOM is linked to sulfate reduction in marine sediments, very little is known about AOM in freshwater systems such as northern peatlands, which have large methane (CH ₄ ) production and are a significant source of atmospheric CH ₄ . Our results showed a mean net AOM rate of 17 ± 2.6 nmol kg ^{? 1} s ^{? 1} with a maximum rate of 176 nmol kg ^{? 1} s ^{? 1} for a minerotrophic fen in central New York. AOM was demonstrated with three independent methods to verify our results: (a) additions of methanogenic inhibitors, (b) stable isotope enrichment ( ¹³ C-CH ₄ ), and (c) natural abundance stable isotope analysis ( ¹³ C-CH ₄ ). These experiments confirmed that AOM occurs simultaneously with methanogenesis, consumes a significant portion of gross CH ₄ production, and significantly fractionates C isotopes (～ ?127‰). Experiments using a variety of potential electron acceptors demonstrated that Fe(III) and SO₄ ^{2 ?} are not quantitatively important, while the role of NO ₃ ^? is uncertain and deserves more attention. The exact mechanism(s) for AOM in peat soils remains unclear; however the AOM rates reported in this study are similar to those reported for CH ₄ production and aerobic CH ₄ oxidation in northern peatlands, suggesting that AOM may be an important control on CH ₄ fluxes in northern peatland ecosystems.     

Effects of extreme experimental drought and rewetting on CO2 and CH4 exchange in mesocosms of 14 European peatlands with different nitrogen and sulfur deposition

The quantitative impact of intense drought and rewetting on gas exchange in ombrotrophic bogs is still uncertain. In particular, we lack studies investigating multitudes of sites with different soil properties and nitrogen (N) and sulfur (S) deposition under consistent environmental conditions. We explored the timing and magnitude of change in CO₂ (Respiration, Gross Primary Production – GPP, and Net Exchange – NE) and CH₄ fluxes during an initial wet, a prolonged dry (~100 days), and a subsequent wet period (~230 days) at 12 °C in 14 Sphagnum peat mesocosms collected in hollows from bogs in the UK, Ireland, Poland, and Slovakia. The relationship of N and S deposition with GPP, respiration, and CH₄ exchange was investigated. Nitrogen deposition increased CO₂ fluxes and GPP more than respiration, at least up to about 15 kg N ha^?1 yr^?1. All mesocosms became CO₂ sources during drying and most of them when the entire annual period was considered. Response of GPP to drying was faster than that of respiration and contributed more to the change in NE; the effect was persistent and few sites recovered “predry” GPP by the end of the wet phase. Respiration was higher during the dry phase, but did not keep increasing as WT kept falling and peaked within the initial 33 days of drying; the change was larger when differences in humification with depth were small. CH₄ fluxes strongly peaked during early drought and water table decline. After rewetting, methanogenesis recovered faster in dense peats, but CH₄ fluxes remained low for several months, especially in peats with higher inorganic reduced sulfur content, where sulfate was generated and methanogenesis remained suppressed. Based on a range of European sites, the results support the idea that N and S deposition and intense drought can substantially affect greenhouse gas exchange on the annual scale.     

Methanogenesis and Methanogen Diversity in Three Peatland Types of the Discontinuous Permafrost Zone,Boreal Western Continental Canada

Because recent patterns of permafrost collapse in boreal peatlands appear to enhance emissions of CH ₄ to the atmosphere, we examined methanogenesis and methanogen diversity in peat soil from peatlands with and without permafrost in two peatland complexes situated in continental western Canada. Peat soil from the active layer of permafrost bogs had very low rates of CH ₄ production (ca. 10 nmol g ^?1 day ^?1 ), and we were unable to PCR-amplify 16s rRNA gene sequences using Archaea-specific primers in four peat samples. Surface peat soil from continental bogs with no permafrost supported moderate rates of CH ₄ production (20–600 nmol g ^?1 day ^?1 ), with maximum rates in soil located close to the mean water table level. Additions of ethanol stimulated CH ₄ production rates, suggesting metabolic substrate limitations. Peat from internal lawns, which have experienced surface permafrost degradation in the past 150 years, had very rapid rates of CH₄ production (up to 800 nmol g ^?1 day ^?1 ) occurring within the soil profile. Concomitant rates of anaerobic CO ₂ production were greater in continental bogs (ca. 6 μmol g ^?1 day ^?1 ) than in internal lawns (ca. 4 μ mol g ^?1 day ^?1 ) or in permafrost bogs (2.8 μ mol g ^?1 day ^?1 ). Analysis of the 16s rRNA gene for Archaea in the continental bog indicated mostly sequences associate with Methanobacteriales and RC-I with a Methanosarcinaceae sequence in the deepest peat soil. In the internal lawn, Methanosarcinaceae were most common in peat soil with a Methanosaetaceae sequence in the deepest peat soil. This study showed that patterns of discontinuous permafrost and ongoing permafrost degradation in boreal regions create patchy soil environments for methanogens and rates of methanogenesis.     

Functional-Structural Analysis of Nitrogen-Cycle Bacteria in a Hypersaline Mat from the Omani Desert

Anaerobic microbial activity in northern peat soils most often results in more carbon dioxide (CO ₂ ) production than methane (CH₄) production. This study examined why methanogenic conditions (i.e., equal molar amounts of CH₄ production and CO₂ production) prevail so infrequently. We used peat soils from two ombrotrophic bogs and from two rheotrophic fens. The former two represented a relatively dry bog hummock and a wet bog hollow, and the latter two represented a forested fen and a sedge-dominated fen. We quantified gas production rates in soil samples incubated in vitro with and without added metabolic substrates (glucose, ethanol, H₂/CO₂). None of the peat soils exhibited methanogenic conditions when incubated in vitro for a short time (< 5 days) and without added substrates. Incubating some samples > 50 days without added substrates led to methanogenic conditions in only one of four experiments. The anaerobic CO₂:CH₄ production ratio ranged from 5:1 to 40:1 in peat soil without additions and was larger in samples from the dry bog hummock and forested fen than the wet bog hollow and sedge fen. Adding ethanol or glucose separately to peat soils led to methanogenic conditions within 5 days after the addition by stimulating rates of CH₄ production, suggesting CH₄ production from both hydrogenotrophic and acetoclastic methanogenesis. Our results suggest that methanogenic conditions in peat soils rely on a constant supply of easily decomposable metabolic substrates. Sample handling and incubation procedures might obscure methanogenic conditions in peat soil incubated in vitro.     

Long-term ozone effects on vegetation, microbial community and methane dynamics of boreal peatland microcosms in open-field conditions

To study the effects of elevated ozone concentration on methane dynamics and a sedge species, Eriophorum vaginatum, we exposed peatland microcosms, isolated by coring from an oligotrophic pine fen, to double ambient ozone concentration in an open‐air ozone exposure field for four growing seasons. The field consists of eight circular plots of which four were fumigated with elevated ozone concentration and four were ambient controls. At the latter part of the first growing season (week 33, 2003), the methane emission was 159±14 mg CH₄ m^?2 day^?1 (mean±SE) in the ozone treatment and 214±8 mg CH₄ m^?2 day^?1 under the ambient control. However, towards the end of the experiment the ozone treatment slightly, but consistently, enhanced the methane emission. At the end of the third growing season (2005), microbial biomass (estimated by phospholipid fatty acid biomarkers) was higher in peat exposed to ozone (1975±108 nmol g^?1 dw) than in peat of the control microcosms (1589±115 nmol g^?1 dw). The concentrations of organic acids in peat pore water showed a similar trend. Elevated ozone did not affect the shoot length or the structure of the sedge E. vaginatum leaves but it slightly increased the total number of sedge leaves towards the end of the experiment. Our results indicate that elevated ozone concentration enhances the general growth conditions of microbes in peat by increasing their substrate availability. However, the methane production did not reflect the increase in the concentration of organic acids, probably because hydrogenotrophic methane production dominated in the peat studied. Although, we used isolated peatland microcosms with limited size as study material, we did not find experimental factors that could have hampered the basic conclusions on the effects of ozone.     

Carbon fluxes in forested bog margins along a human impact gradient: could vegetation structure be used as an indicator of peat carbon emissions?

Bog ecosystems are sensitive to anthropogenic disturbance, including drainage and air pollution. Carbon (C) balance measurements to determine the effect of disturbance on bog functioning are laborious; therefore reliable proxies for C fluxes that could facilitate upscaling from single studies to a larger scale would be valuable. We measured peat CO₂ emissions (R _s), CH₄ efflux and vegetation characteristics in four bog areas that formed a gradient from pristine to severely disturbed peatlands, affected by drainage, peat mining, alkaline air pollution and underground oil-shale mining. We expected that sites experiencing higher human impact (i.e., the vegetation was more distinct from that of a natural bog) would have higher R _s and lower CH₄ emissions, but differences in peat C emissions between the most disturbed and pristine sites were not significant. Growing period median R _s ranged from 0.5 to 2.2 g C m^?2 day^?1 for our plots; methane emissions, measured from July to December were an order of magnitude lower, ranging from ?5.9 to 126.7 mg C m^?2 day^?1. R _s and CH₄ emissions were primarily determined by water table depth, as was tree stand productivity. Therefore, stand structural parameters could potentially be good indicators of soil C emissions from poorly drained forested bogs.     

Modeling the carbon cycle in Lake Matano

Lake Matano, Indonesia, is a stratified anoxic lake with iron‐rich waters that has been used as an analogue for the Archean and early Proterozoic oceans. Past studies of Lake Matano report large amounts of methane production, with as much as 80% of primary production degraded via methanogenesis. Low δ¹³C values of DIC in the lake are difficult to reconcile with this notion, as fractionation during methanogenesis produces isotopically heavy CO₂. To help reconcile these observations, we develop a box model of the carbon cycle in ferruginous Lake Matano, Indonesia, that satisfies the constraints of CH₄ and DIC isotopic profiles, sediment composition, and alkalinity. We estimate methane fluxes smaller than originally proposed, with about 9% of organic carbon export to the deep waters degraded via methanogenesis. In addition, despite the abundance of Fe within the waters, anoxic ferric iron respiration of organic matter degrades <3% of organic carbon export, leaving methanogenesis as the largest contributor to anaerobic organic matter remineralization, while indicating a relatively minor role for iron as an electron acceptor. As the majority of carbon exported is buried in the sediments, we suggest that the role of methane in the Archean and early Proterozoic oceans is less significant than presumed in other studies.     

Carbon isotopic heterogeneity of coenzyme F430 and membrane lipids in methane‐oxidizing archaea

Archaeal ANaerobic MEthanotrophs (ANME) facilitate the anaerobic oxidation of methane (AOM), a process that is believed to proceed via the reversal of the methanogenesis pathway. Carbon isotopic composition studies indicate that ANME are metabolically diverse and able to assimilate metabolites including methane, methanol, acetate, and dissolved inorganic carbon (DIC). Our data support the interpretation that ANME in marine sediments at methane seeps assimilate both methane and DIC, and the carbon isotopic compositions of the tetrapyrrole coenzyme F430 and the membrane lipids archaeol and hydroxy‐archaeol reflect their relative proportions of carbon from these substrates. Methane is assimilated via the methyl group of CH₃‐tetrahydromethanopterin (H₄MPT) and DIC from carboxylation reactions that incorporate free intracellular DIC. F430 was enriched in ¹³C (mean δ¹³C = ?27‰ for Hydrate Ridge and ?80‰ for the Santa Monica Basin) compared to the archaeal lipids (mean δ¹³C = ?97‰ for Hydrate Ridge and ?122‰ for the Santa Monica Basin). We propose that depending on the side of the tricarboxylic acid (TCA) cycle used to synthesize F430, its carbon was derived from 76% DIC and 24% methane via the reductive side or 57% DIC and 43% methane via the oxidative side. ANME lipids are predicted to contain 42% DIC and 58% methane, reflecting the amount of each assimilated into acetyl‐CoA. With isotope models that include variable fractionation during biosynthesis for different carbon substrates, we show the estimated amounts of DIC and methane can result in carbon isotopic compositions of ? 73‰ to ? 77‰ for F430 and ? 105‰ for archaeal lipids, values close to those for Santa Monica Basin. The F430 δ¹³C value for Hydrate Ridge was ¹³C‐enriched compared with the modeled value, suggesting there is divergence from the predicted two carbon source models.     

Suppression of methanogenesis by dissimilatory Fe(III)-reducing bacteria in tropical rain forest soils: implications for ecosystem methane flux

Tropical forests are an important source of atmospheric methane (CH₄), and recent work suggests that CH₄ fluxes from humid tropical environments are driven by variations in CH₄ production, rather than by bacterial CH₄ oxidation. Competition for acetate between methanogenic archaea and Fe(III)‐reducing bacteria is one of the principal controls on CH₄ flux in many Fe‐rich anoxic environments. Upland humid tropical forests are also abundant in Fe and are characterized by high organic matter inputs, steep soil oxygen (O₂) gradients, and fluctuating redox conditions, yielding concomitant methanogenesis and bacterial Fe(III) reduction. However, whether Fe(III)‐reducing bacteria coexist with methanogens or competitively suppress methanogenic acetate use in wet tropical soils is uncertain. To address this question, we conducted a process‐based laboratory experiment to determine if competition for acetate between methanogens and Fe(III)‐reducing bacteria influenced CH₄ production and C isotope composition in humid tropical forest soils. We collected soils from a poor to moderately drained upland rain forest and incubated them with combinations of ¹³C‐bicarbonate, ¹³C‐methyl labeled acetate (¹³CH₃COO^?), poorly crystalline Fe(III), or fluoroacetate. CH₄ production showed a greater proportional increase than Fe²⁺ production after competition for acetate was alleviated, suggesting that Fe(III)‐reducing bacteria were suppressing methanogenesis. Methanogenesis increased by approximately 67 times while Fe²⁺ production only doubled after the addition of ¹³CH₃COO^?. Large increases in both CH₄ and Fe²⁺ production also indicate that the two process were acetate limited, suggesting that acetate may be a key substrate for anoxic carbon (C) metabolism in humid tropical forest soils. C isotope analysis suggests that competition for acetate was not the only factor driving CH₄ production, as ¹³C partitioning did not vary significantly between ¹³CH₃COO^? and ¹³CH₃COO^?+Fe(III) treatments. This suggests that dissimilatory Fe(III)‐reduction suppressed both hydrogenotrophic and aceticlastic methanogenesis. These findings have implications for understanding the CH₄ biogeochemistry of highly weathered wet tropical soils, where CH₄ efflux is driven largely by CH₄ production.     

Oxygen effects on methane production and oxidation in humid tropical forest soils

We investigated the effects of oxygen (O₂) concentration on methane (CH₄) production and oxidation in two humid tropical forests that differ in long‐term, time‐averaged soil O₂ concentrations. We identified sources and sinks of CH₄ through the analysis of soil gas concentrations, surface emissions, and carbon isotope measurements. Isotope mass balance models were used to calculate the fraction of CH₄ oxidized in situ. Complementary laboratory experiments were conducted to determine the effects of O₂ concentration on gross and net rates of methanogenesis. Field and laboratory experiments indicated that high levels of CH₄ production occurred in soils that contained between 9±1.1% and 19±0.2% O₂. For example, we observed CH₄ concentrations in excess of 3% in soils with 9±1.1% O₂. CH₄ emissions from the lower O₂ sites were high (22–101 nmol CH₄ m^?2 s^?1), and were equal in magnitude to CH₄ emissions from natural wetlands. During peak periods of CH₄ efflux, carbon dioxide (CO₂) emissions became enriched in ¹³C because of high methanogenic activity. Gross CH₄ production was probably greater than flux measurements indicated, as isotope mass balance calculations suggested that 48–78% of the CH₄ produced was oxidized prior to atmospheric egress. O₂ availability influenced CH₄ oxidation more strongly than methanogenesis. Gross CH₄ production was relatively insensitive to O₂ concentrations in laboratory experiments. In contrast, methanotrophic bacteria oxidized a greater fraction of total CH₄ production with increasing O₂ concentration, shifting the δ¹³C composition of CH₄ to values that were more positive. Isotopic measurements suggested that CO₂ was an important source of carbon for methanogenesis in humid forests. The δ¹³C value of methanogenesis was between ?84‰ and ?98‰, which is well within the range of CH₄ produced from CO₂ reduction, and considerably more depleted in ¹³C than CH₄ formed from acetate.     

Soil–Methanogen Interactions in Two Peatlands (Bog,Fen) in Central New York State

Rates of methanogenesis vary widely in peat soils, yet the reasons are poorly known. We examined rates of methanogenesis and methanogen diversity in relation to soil chemical and biological characteristics in 2 peatlands in New York State. One was an acidic (pH < 4.5) bog dominated by Sphagnum mosses and ericaceous shrubs, although deeper peat was derived from sedges. The other was a fen dominated by Carex lacustris sedges with near-neutral pH soil. At both sites, the most active rates of methanogenesis occurred in the top 20 cm of the peat profile, even when using a substrate-induced methanogenesis technique with added glucose that stimulated rates up to 2 μ mol g ^{? 1} day ^?1 in the bog and 6 μ mol g ^?1 day ^?1 in the fen. Rates of anaerobic CO ₂ production were greater in the bog (0–36 μ mol g ^?1 day ^?1 ) than in the fen (0–5 μ mol g ^?1 day ^?1 ), and added glucose induced greater rates in the sedge-derived peat from the bog than the fen. The peat soil was much more decomposed throughout the profile in the fen. Analysis of chemical elements in the peat profile revealed a striking anomaly: a very high concentration of Pb in surface peat of the bog, which might have constrained methanogenesis. Application of T-RFLP analysis to methanogens revealed dominance by a Methanomicrobiales E2 clade of H ₂ /CO ₂ users in the acidic peat soil of the bog, whereas deeper peat had a different Methanomicrobiales E1 clade, uncultured euryarchaeal rice cluster (RC)-I and RC-II groups, marine benthic group D (MBD) and a new cluster called subaqueous cluster (SC). In contrast, T-RFLP analysis of peat from the fen revealed co-dominance by Methanosaetaceae and Methanomicrobiales E1. The results showed complex relationships between rates of methanogenesis, methanogen populations and metabolic substrate availability with idiosyncratic interactions of trace chemical elements.