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Origin and fate of dissolved inorganic carbon in a karst groundwater fed peatland using δ13CDIC

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Abstract

Continental hydrosystems and in particular peatlands play an important role in the carbon cycle of the Critical Zone (CZ). Peatlands are important sinks for organic carbon and have therefore been extensively studied. However, peatlands are not only important for the fate of organic carbon, but they also affect the cycle of Dissolved Inorganic Carbon (DIC) of the peatland and the surrounding watershed. The fate of DIC is particularly complex in peatlands in limestone-dominated regions, because bicarbonate concentrations in surface and groundwater are high and the interaction between peatlands and surrounding hydrosystems are facilitated by the presence of highly permeable karst aquifers. In the present paper we study the origin and the fractionation of DIC in a peatland located on top of a karst aquifer. The study is based on hydrochemical and isotopic (δ¹³CDIC) data from samples recovered during 2 campaigns (low flow, high flow) at various depths within the Forbonnet peatland (Jura Mountains, eastern France), at the peatland outlet and at adjacent karst springs representing the underlying aquifer. In order to evaluate secondary fractionation processes, the measured δ¹³CDIC compositions were compared to modeled values considering the origin of DIC and potentially associated fractionation and speciation processes. The main results are: (1) DIC is lost at the bog surface by CO2 outgassing. (2) The δ¹³CDIC compositions of deep catotelm pore waters from the bog were much heavier than the modeled values. We relate this discrepancy to methanogenesis and show that this process is favored by reduced conditions at pH ~ 6 and a HCO3⁻ content of ~1 mmol/L, most probably due to punctual groundwater inflows at the base of the bog. Finally, contrasted δ¹³CDIC compositions between the bog and the fen of the peatland reveal an additional ecohydrological control on DIC speciation.

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... The karst streams showed seasonal variations (Figure 3), with the lowest values when the surface of the peatland was frozen or covered with snow (late autumn, winter, and spring) and the highest in the summer. The melting of the ice released the lighter 16 O and therefore yielded lower 18 O values. In the summer, higher temperatures caused the preferential evaporation of the lighter oxygen isotope ( 16 O), causing the water to be enriched with 18 O. ...
... A difference in the EC values was also observed among the locations, as the average values for location P1 remained similar with depth (75-85 µS/cm), while in location P2, the values increased from 46 µS/cm (30 cm) to 115 µS/cm (90 cm). The consistent increase in pH and EC with depth at location P2 could be due to an additional water source that influenced the deeper layer of the peat profile, as shown in Lhosmot et al. [16]. The results of the Eh measurements were relatively high and indicated oxidizing conditions in all samples, due to the sampling method. ...
... Following a rapid increase in the dissolved oxygen content, the curve gradually flattened and stabilized. . The consistent increase in pH and EC with depth at location P2 could be due to an additional water source that influenced the deeper layer of the peat profile, as shown in Lhosmot et al. [16]. The results of the Eh measurements were relatively high and indicated oxidizing conditions in all samples, due to the sampling method. ...
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... Most of the time their pH is between 7.6 and 8.2 as in many other streams of the area, but at one time (April 2023) we measured a 6.8 pH. This very slight acidity of the water entering the network is probably due to sphagnum activity in the surrounding peatland, favoring low pH (Lhosmot et al., 2023) in water exported from the peat masses during rainy periods. This would favor the dissolution of the calcite drumlin matrix, acting together with mechanical piping process to create the suspected conduit in this upstream part of the cave network. ...
... Most of the time their pH is between 7.6 and 8.2 as in many other streams of the area, but at one time (April 2023) we measured a 6.8 pH. This very slight acidity of the water entering the network is probably due to sphagnum activity in the surrounding peatland, favoring low pH (Lhosmot et al., 2023) in water exported from the peat masses during rainy periods. This would favor the dissolution of the calcite drumlin matrix, acting together with mechanical piping process to create the suspected conduit in this upstream part of the cave network. ...
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The chemical components in water, and changes thereof, can control the ecology of peatlands and impact the accumulation of peat; while at the same time ecological characteristics, hydrology and interactions with the atmosphere and geosphere control peatland water chemistry. This review summarizes results from Canadian and northern European research published over the past two decades for major and minor, inorganic and organic constituents dissolved in surface or pore waters associated with bogs and fens. First those studies that describe natural peatlands are discussed, followed by those that involve peatlands that are disturbed by various direct or indirect anthropogenic influences. Finally several recommendations are made regarding future studies and how they can assist in modelling efforts that can inform peatland management and further scientific inquiry.
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At the Earth's surface, a complex suite of chemical, biological, and physical processes combines to create the engine that transforms bedrock into soil (Figure 1). Earth's weathering engine provides nutrients to nourish ecosystems and human society mediates the transport of toxic components within the biosphere, creates water flow paths that carve and weaken bedrock, and contributes to the evolution of landscapes at all temporal and spatial scales. At the longest time scales, the weathering engine sequesters CO 2 , thereby influencing long‐term climate change. Despite the importance of soil, our knowledge of the rate of soil formation is limited because the weathering zone forms a complex, ever‐changing interface, and because scientific approaches and funding paradigms have not promoted integrated research agendas to investigate such complex interactions. No national initiative has promoted a systems approach to investigation of weathering science across the broad array of geology, soil science, ecology and hydrology. Such a program is certainly needed, and this article describes a platform on which to build the initiative to answer the following question: How does the Earth weathering engine break down rock to nourish ecosystems, carve errestrial landscapes, and control carbon dioxide in the global atmosphere?
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Studies of Earth’s critical zone have largely focused on areas underlain by silicate bedrock, leaving gaps in our understanding of widespread and vital carbonate-dominated landscapes.
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Microbial methanogenesis is a major source of the greenhouse gas methane (CH4). It is the final step in the anaerobic degradation of organic matter when inorganic electron acceptors such as nitrate, ferric iron, or sulfate have been depleted. Knowledge of this degradation pathway is important for the creation of mechanistic models, prediction of future CH4 emission scenarios, and development of mitigation strategies. In most anoxic environments, CH4 is produced from either acetate (aceticlastic methanogenesis) or hydrogen (H2) plus carbon dioxide (CO2) (hydrogenotrophic methanogenesis). Hydrogen can be replaced by other CO2-type methanogenesis, using formate, carbon monoxide (CO), or alcohols as substrates. The ratio of these two pathways is tightly constrained by the stoichiometry of conversion processes. If the degradation of organic matter is complete (e.g., degradation of straw in rice paddies), then fermentation eventually results in production of acetate and H2 at a ratio of > 67% aceticlastic and < 33% hydrogenotrophic methanogensis. However, acetate production can be favored when heterotrophic or chemolithotrophic acetogenesis is enhanced, and H2 production can be favored when syntrophic acetate oxidation is enhanced. This typically occurs at low and elevated temperatures, respectively. Thus, temperature can strongly influence the methanogenic pathway, which may range from 100% aceticlastic methanogenesis at low temperatures to 100% hydrogenotrophic methanogenesis at high temperatures. However, if the degradation of organic matter is not complete (e.g., degradation of soil organic matter), the stoichiometry of fermentation is not tightly constrained, resulting, for example, in the preferential production of H2, followed by hydrogenotrophic methanogenesis. Preferential production of CH4 by either aceticlastic or hydrogenotrophic methanogenesis can also happen if one of the methanogenic substrates is not consumed by methanogens but is, instead, accumulated, volatilized, or utilized otherwise. Methylotrophic methanogens, which can use methanol as a substrate, are widespread, but it is unlikely that methanol is produced in similar quantities as acetate, CO2, and H2. Methylotrophic methanogenesis is important in saline environments, where compatible solutes are degraded to methyl compounds (trimethyl amine and dimethyl sulfide) and then serve as non-competitive substrates, while acetate and hydrogen are degraded by non-methanogenic processes, e.g., sulfate reduction.
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Peatlands are habitats for a range of fragile flora and fauna species. Their eco-physicochemical characteristics make them as outstanding global carbon and water storage systems. These ecosystems occupy 3% of the worldwide emerged land surface but represent 30% of the global organic soil carbon and 10% of the global fresh water volumes. In such systems, carbon speciation depends to a large extent on specific redox conditions which are mainly governed by the depth of the water table. Hence, understanding their hydrological variability, that conditions both their ecological and biogeochemical functions, is crucial for their management, especially when anticipating their future evolution under climate change. This study illustrates how long-term monitoring of basic hydro-meteorological parameters combined with statistical modeling can be used as a tool to evaluate i) the horizontal (type of peat), ii) vertical (acrotelm/catotelm continuum) and iii) future hydrological variability. Using cross-correlations between meteorological data (precipitation, potential evapotranspiration) and water table depth (WTD), we primarily highlight the spatial heterogeneity of hydrological reactivity across the Sphagnum-dominated Frasne peatland (French Jura Mountain). Then, a multiple linear regression model allows performing hydrological projections until 2100, according to regionalized IPCC RCP4.5 and 8.5 scenarios. Although WTD remains stable during the first half of 21th century, seasonal trends beyond 2050 show lower WTD in winter and markedly greater WTD in summer. In particular, after 2050, more frequent droughts in summer and autumn should occur, increasing WTD. These projections are completed with risk evaluations for peatland droughts until 2100 that appear to be increasing especially for transition seasons, i.e. May-June and September-October. Comparing these trends with previous evaluations of phenol concentrations in water throughout the vegetative period, considered as a proxy of plant functioning intensity, highlights that these hydrological modifications during transitional seasons could be a great ecological perturbation, especially by affecting Sphagnum metabolism.
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Carbon dioxide (CO2) emissions from rivers are a vital part of the global carbon budget. However, data from subtropical areas, especially in the headwater streams, are scare. Spatiotemporal dynamics and drives of partial pressure of CO2 (pCO2) and water-air CO2 fluxes (FCO2) in a monsoonal headwater stream Jinshui River of the Yangtze were unraveled. Our findings suggested that natural process (i.e., hydrology, CO2 outgassing and lithology) and human activities were recognized as significant players in regulating the variability of riverine pCO2. The mean pCO2 was significantly higher in the dry season (1562 ± 975 µatm) than the wet season (834 ± 639 µatm), seasonal trends of pCO2 were controlled by in situ biogenic activities and rainfall events. The slight fluctuations of pCO2 from upstream to downstream along main stem implied the mixed influences of distinct water environments and anthropogenic disturbance. Correlation analysis showed that environmental factors, i.e., temperature, pH, TN and DOC were relevant to pronounced spatial and seasonal variability of pCO2. We highlighted that high water-air CO2 flux was estimated at 343 ± 413 mmol/m2/d (dry: 542 ± 477 mmol/m2/d vs wet: 192 ± 278 mmol/m2/d) in the monsoonal headwater stream, and the watershed-scale carbon budget demonstrated carbon loss via atmospheric exchange was 1.2 times the riverine dissolved carbon export. Our results would fill a large gap in the headwater stream of the Yangtze, and help to accurately estimate the regional to global CO2 outgassing from rivers to the atmosphere.
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Carbonate terrains (CT) underlie one-fifth of terrestrial, ice-free land and are an important supply of potable water to the world's population, and yet processes endemic to CT critical zones (CZ) and responses of these processes to climatic and anthropogenic pressures are not well understood. Given the rapid dissolution rates and ability to generate well-developed networks of secondary porosity these landscapes can be highly sensitive to impacts from climate change (e.g., modifications of temperature, precipitation, sea level) and human disturbance (e.g., water withdrawal/diversions, changes in land use/land cover). This special issue includes 16 papers focused on CT-CZ processes and potential responses to climatic and human perturbations. Five major themes emerge from these papers, namely: (1) anthropogenic climate and land use changes alter CT-CZ weathering rate and diagenesis, (2) metal and carbon fluxes in CT-CZ will respond to increasing hydrologic variance caused by climate change, (3) endogenous and exogenous processes operating over short time periods (<10,000 yrs) form landscape patterns in carbonate terrains, (4) rates of carbonate mineral dissolution depend on vadose zone and soil thickness, and (5) open systems may not always promote greater carbonate weathering rates in CT-CZ. These findings reflect the importance of carbonate minerals in Earth's CZ, both in terms of processes unique to carbonate minerals, as well as a predictor of future responses to anthropogenic and environmental changes.
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Streams and rivers emit significant amounts of CO2 and constitute a preferential pathway of carbon transport from terrestrial ecosystems to the atmosphere. However, the estimation of CO2 degassing based on the water-air CO2 gradient, gas transfer velocity and stream surface area is subject to large uncertainties. Furthermore, the stable isotope signature of dissolved inorganic carbon (δ13C-DIC) in streams is strongly impacted by gas exchange, which makes it a useful tracer of CO2 degassing under specific conditions. For this study, we characterized the annual transfers of dissolved inorganic carbon (DIC) along the groundwater-stream-river continuum based on dissolved inorganic carbon (DIC) concentrations, stable isotope composition and measurements of stream discharges. We selected a homogeneous, forested and sandy lowland watershed (Leyre River) as a study site, where the hydrology occurs almost exclusively through drainage of shallow groundwater (no surface runoff). We observed the first general spatial pattern of decreases in pCO2 and DIC and an increase in δ13C-DIC from groundwater to stream orders 1 and 2, which was due to the experimentally verified faster degassing of groundwater 12C-DIC compared to 13C-DIC. This downstream enrichment in 13C-DIC could be modelled by simply considering the isotopic equilibration of groundwater-derived DIC with the atmosphere during CO2 degassing. A second spatial pattern occurred between stream orders 2 and 4, consisting of an increase in the proportion of carbonate alkalinity to the DIC accompanied by the enrichment of 13C in the stream DIC, which was due to the occurrence of carbonate rock weathering downstream. We could separate the contribution of these two processes (gas exchange and carbonate weathering) in the stable isotope budget of the river network. Thereafter, we built a hydrological mass balance based on drainages and the relative contribution of groundwater in streams of increasing order. After combining with the dissolved CO2 concentrations, we quantified CO2 degassing for each stream order for the whole watershed. Approximately 75% of the total CO2 degassing from the watershed occurred in first- and second-order streams. Furthermore, from stream order 2 to 4, our CO2 degassing fluxes compared well with those based on stream hydraulic geometry, water pCO2, gas transfer velocity, and stream surface area. In first-order streams, however, our approach showed CO2 fluxes that were twice as large, suggesting that a fraction of degassing occurred as hotspots in the vicinity of groundwater resurgence and was missed by conventional stream sampling.
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Peatlands play important ecological, economic and cultural roles in human well-being. Although considered sensitive to climate change and anthropogenic pressures, the spatial extent of peatlands is poorly constrained. We report the development of an improved global peatland map, PEATMAP, based on a meta-analysis of geospatial information collated from a variety of sources at global, regional and national levels. We estimate total global peatland area to be 4.23 million km 2 , approximately 2.84% of the world land area. Our results suggest that previous global peatland inventories are likely to underestimate peat extent in the tropics, and to overestimate it in parts of mid-and high-latitudes of the Northern Hemisphere. Global wetland and soil datasets are poorly suited to estimating peatland distribution. For instance, tropical peatland extents are overestimated by Global Lakes and Wetlands Database – Level 3 (GLWD-3) due to the lack of ground-truthing data; and underestimated by the use of histosols to represent peatlands in the Harmonized World Soil Database (HWSD) v1.2, as large areas of swamp forest peat in the humid tropics are omitted. PEATMAP and its underlying data are freely available as a potentially useful tool for scientists and policy makers with interests in peatlands or wetlands. PEATMAP's data format and file structure are intended to allow it to be readily updated when previously undocumented peatlands are found and mapped, and when regional or national land cover maps are updated and refined.
Thesis
La France, à l'instar de nombreux pays européens, connaît un recul assez net de sa population paysanne et par la même occasion de son potentiel agricole. Cette baisse sensible, enregistrée sur les trente dernières années est la conséquence directe de l'exode massif des populations vers les grandes agglomérations. Cette mutation s'est accompagnée de la fermeture progressive des paysages, marqués le plus souvent par une colonisation rapide par des espèces forestières. Ces évolutions sont également dues au changement climatique qui favorise certaines espèces par rapport à d'autres. Du point de vue de la gestion du bassin versant, il est très important de savoir comment ces changements pourraient affecter les ressources en eau. La mise en œuvre de la directive-cadre sur l'eau du 24 octobre 2012, définit des structures de gestion de l'eau sur des unités hydrologiques (bassin versant, nappe d'eau souterraine) pour un bon état des eaux en 2015, et le respect des objectifs pour 2027 dans le cadre d'une nouvelle directive-cadre sur l'eau (DCE). Cette mise en œuvre nécessite de prendre en compte la diversité spatiale et thématique des données sur l'unité hydrologique considérée. La télédétection et les Systèmes d'Information Géographiques (SIG) sont des outils utiles permettant de représenter cette diversité. Ils servent à la fois à l'organisation, à l'actualisation et à l'analyse des données spatiales. Ils sont utiles également pour le paramétrage de modèles hydrogéochimiques afin de modéliser la variabilité spatio-temporelle des ressources en eau. L'intérêt de la télédétection et des SIG couplés au modèle hydrogéochimique WARMF, est mis en évidence dans l'étude du cas d'un grand bassin versant du Massif Jura : l'Ain (4780 km²). Une telle étude répond aux problèmes qui se posent lors d'une DCE : estimation des quantités des eaux sur des secteurs non-mesurés, prévision des quantités en fonction de scénarii de l'occupation des sols et de scénarii météorologiques, vulnérabilité des ressources en eau superficielles, effet de la matière organique sur la qualité des eaux. Cette étude fournit une base scientifique pour la formulation de stratégies pour la gestion de la ressource en eau. Le couplage de la télédétection et des SIG au modèle hydrogéochimique est une nouvelle approche offrant de grands avantages en matière de disponibilité des données, de construction des scénarii, et d'interprétation des résultats. Cette approche sera un outil efficace d'aide à la décision pour la gestion intégrée de la ressource en eau des lacs et plus largement du bassin versant (oxygène, pH, etc.).
Article
The total dissolved inorganic carbon (TDIC) and 13CTDIC have been used as chemical and isotopic tracers to evaluate the contribution of different water components discharging at the Fontaine de Vaucluse karst spring near Avignon. At the same time they have been used to separate its flood hydrograph. Waters flowing from unsaturated zone (UZ) and saturated zone (SZ) show similar concentration in TDIC. In UZ and SZ water rock interactions do not obey to the same kinetic. The mixing rate between water coming from the UZ characterised by a short residence time and water from the SZ with a longer residence time has been evaluated in the spring discharge. In a hydrodynamic system, which is rather complex as it is open to the soil CO2 in UZ and closed to the same CO2 in the SZ, 13CTDIC has excellent characteristics as an environmental tracer.In order to better describe the inwardness of mass movements within the aquifer, the apparent contrasting information obtained using two different isotopes (18O of water molecules and 13C of TDIC) must be combined. 18O informs whether the hydrodynamic system acts as piston flow (PF) or follows a well mixing model (WMM). Conversely, 13C gives more complete information on the UZ contributes to the total discharge.
Article
The acrotelm–catotelm model of peatland hydrological and biogeochemical processes posits that the permeability of raised bogs is largely homogenous laterally but varies strongly with depth through the soil profile; uppermost peat layers are highly permeable while deeper layers are, effectively, impermeable. We measured down‐core changes in peat permeability, plant macrofossil assemblages, dry bulk density and degree of humification beneath two types of characteristic peatland microform – ridges and hollows – at a raised bog in Wales. Six ¹⁴ C dates were also collected for one hollow and an adjacent ridge. Contrary to the acrotelm–catotelm model, we found that deeper peat can be as highly permeable as near‐surface peat and that its permeability can vary by more than an order of magnitude between microforms over horizontal distances of 1–5 m. Our palaeoecological data paint a complicated picture of microform persistence. Some microforms can remain in the same position on a bog for millennia, growing vertically upwards as the bog grows. However, adjacent areas on the bog (< 10 m distant) show switches between microform type over time, indicating a lack of persistence. Synthesis . We suggest that the acrotelm–catotelm model should be used cautiously; spatial variations in peatland permeability do not fit the simple patterns suggested by the model. To understand how peatlands as a whole function both hydrologically and ecologically, it is necessary to understand how patterns of peat physical properties and peatland vegetation develop and persist.
Article
Arctic soils contain a large pool of terrestrial C and are of interest due to their potential for releasing significant carbon dioxide (CO2) and methane (CH4) to the atmosphere. Due to substantial landscape heterogeneity, predicting ecosystem-scale CH4 and CO2 production is challenging. This study assessed dissolved inorganic carbon (DIC = Σ (total) dissolved CO2) and CH4 in watershed drainages in Barrow, Alaska as critical convergent zones of regional geochemistry, substrates, and nutrients. In July and September of 2013, surface waters and saturated subsurface pore waters were collected from 17 drainages. Based on simultaneous DIC and CH4 cycling, we synthesized isotopic and geochemical methods to develop a subsurface CH4 and DIC balance by estimating mechanisms of CH4 and DIC production and transport pathways and oxidation of subsurface CH4. We observed a shift from acetoclastic (July) towards hydrogenotropic (September) methanogenesis at sites located towards the end of major freshwater drainages, adjacent to salty estuarine waters, suggesting an interesting landscape-scale effect on CH4 production mechanism. The majority of subsurface CH4 was transported upward by plant-mediated transport and ebullition, predominantly bypassing the potential for CH4 oxidation. Thus, surprisingly CH4 oxidation only consumed approximately 2.51 ± 0.82% (July) and 0.79 ± 0.79% (September) of CH4 produced at the frost table, contributing to < 0.1% of DIC production. DIC was primarily produced from respiration, with iron and organic matter serving as likely e- acceptors. This work highlights the importance of spatial and temporal variability of CH4 production at the watershed scale, and suggests broad scale investigations are required to build better regional or pan-Arctic representations of CH4 and CO2 production.
Article
Accurately estimating methane (CH4) flux in terrestrial ecosystems is critically important for investigating and predicting biogeochemistry-climate feedbacks. Improved simulations of CH4 flux require explicit representations of the microbial processes that account for CH4 dynamics. A microbial functional group-based module was developed, building on the decomposition subroutine of the Community Land Model 4.5. This module considers four key mechanisms for CH4 production and consumption: methanogenesis from acetate or from single-carbon compounds and CH4 oxidation using molecular oxygen or other inorganic electron acceptors. Four microbial functional groups perform these processes: acetoclastic methanogens, hydrogenotrophic methanogens, aerobic methanotrophs, and anaerobic methanotrophs. This module was used to simulate dynamics of carbon dioxide (CO2) and CH4 concentrations from an incubation experiment with permafrost soils. The results show that the model captures the dynamics of CO2 and CH4 concentrations in microcosms with top soils, mineral layer soils, and permafrost soils under natural and saturated moisture conditions and three temperature conditions of À2°C, 3°C, and 5°C (R2 > 0.67; P < 0.001). The biases for modeled results are less than 30% across the soil samples and moisture and temperature conditions. Sensitivity analysis confirmed the importance of acetic acid's direct contribution as substrate and indirect effects through pH feedback on CO2 and CH4 production and consumption. This study suggests that representing the microbial mechanisms is critical for modeling CH 4 production and consumption; it is urgent to incorporate microbial mechanisms into Earth system models for better predicting trace gas dynamics and the behavior of the climate system.
Article
Quantifying the sink strength of northern hemisphere peatlands requires measurements or realistic estimates of all major C flux terms. Whilst assessments of the net ecosystem carbon balance (NECB) routinely include annual measurements of net ecosystem exchange and lateral fluxes of dissolved organic carbon (DOC), they rarely include estimates of evasion (degassing) of CO2 and CH4 from the water surface to the atmosphere, despite supersaturation being a consistent feature of peatland streams. Instantaneous gas exchange measurements from temperate UK peatland streams suggest that the CO2 evasion fluxes scaled to the whole catchment are a significant component of the aquatic C flux (23.3 ± 6.9 g C m−2 catchment y−1) and comparable in magnitude to the downstream DOC flux (29.1 ± 12.9 g C m−2 catchment y−1). Inclusion of the evasion flux term in the NECB would be justified if evaded CO2 and CH4 were isotopically “young” and derived from a “within-ecosystem” source, such as peat or in-stream processing of DOC. Derivation from “old” biogenic or geogenic sources would indicate a separate origin and age of C fixation, disconnected from the ecosystem accumulation rate that the NECB definition implies. Dual isotope analysis (δ13C and 14C) of evasion CO2 and DOC strongly suggest that the source and age of both are different and that evasion CO2 is largely derived from allochthonous (non-stream) sources. Whilst evasion is an important flux term relative to the other components of the NECB, isotopic data suggest that its source and age are peatland-specific. Evidence suggests that a component of the CO2-C evading from stream surfaces was originally fixed from the atmosphere at a significantly earlier time (pre-AD1955) than modern (post-AD1955) C fixation by photosynthesis.
Article
While it is widely recognized that peatlands are important in the global carbon cycle, there is limited information on belowground gas production in tropical peatlands. We measured porewater methane (CH4) and carbon dioxide (CO2) concentrations and δ13C isotopic composition and CH4 and CO2 production rates in peat incubations from the Changuinola wetland in Panama. Our most striking finding was that CH4 was depleted in 13C (-94‰ in porewater and produced at -107‰ in incubated peat) relative to CH4 found in most temperate and northern wetlands, potentially impacting the accuracy of approaches that use carbon isotopes to constrain global mass balance estimates. Fractionation factors between CH4 and CO2 showed that hydrogenotrophic methanogenesis was the dominant CH4 production pathway, with up to 100% of the CH4 produced via this route. Far more CO2 than CH4 (7 to 100 X) was measured in porewater, due in part to loss of CH4 through ebullition or oxidation and to the production of CO2 from pathways other than methanogenesis. We analyzed data on 58 wetlands from the literature to determine the dominant factors influencing the relative proportions of CH4 produced by hydrogenotrophic and acetoclastic methanogenesis and found that a combination of environmental parameters including pH, vegetation type, nutrient status and latitude are correlated to the dominant methanogenic pathway. Methane production pathways in tropical peatlands do not correlate with these variables in the same way as their more northerly counterparts and thus may be differently affected by climate change.
Article
By using 13C as a tracer in karstic aquifers, one can distinguish between water from the unsaturated and the saturated zones, because the system behaves as one open to the biogenic CO 2 in the unsaturated zone. This method shows that a significant reserve remains in the unsaturated zone at the end of the minimal flow. It is therefore likely that the unsaturated zone contributes to the outflow during this period.
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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.
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To elucidate the roles of hydrology and vegetation in belowground carbon cycling within peatlands, radiocarbon values were obtained for pore water dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), CH4, and peat from the Glacial Lake Agassiz peatland. The major implication of this work is that the rate of microbial respiration within a peat column is greater than the peat decomposition rate. The radiocarbon content of DOC at both bog and fen was enriched relative to solid-phase peat by ~150-300% consistent with the advection of recently photosynthesized DOC downward into the peat column. Fen Delta14C values for DIC and CH4 closely track the Delta14C of pore water DOC at depth, indicating that this recent plant production was the predominant substrate for microbial respiration. Aceticlastic methanogenesis apparently dominated the upper third of the peat column (alpha=1.05), shifting toward CO2 reduction with depth (1.05
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This paper presents a theoretical treatment of the evolution of the carbon isotopes C13 and C14 in natural waters and in precipitates which derive from such waters. The effects of an arbitrary number of sources (such as dissolution of carbonate minerals and oxidation of organic material) and sinks (such as mineral precipitation, CO2 degassing and production of methane), and of equilibrium fractionation between solid, gas and aqueous phases are considered. The results are expressed as equations relating changes in isotopic composition to changes in conventional carbonate chemistry. One implication of the equations is that the isotopic composition of an aqueous phase may approach a limiting value whenever there are simultaneous inputs and outputs of carbonate. In order to unambiguously interpret isotopic data from carbonate precipitates and identify reactants and products in reacting natural waters, it is essential that isotopic changes are determined chiefly by reactant and product stoichiometry, independent of reaction path. We demonstrate that this is so by means of quantitative examples. The evolution equations are applied to: 1.(1) carbon-14 dating of groundwaters;2.(2) interpretation of the isotopic composition of carbonate precipitates, carbonate cements and diagenetically altered carbonates; and3.(3) the identification of chemical reaction stoichiometry. These applications are illustrated by examples which show the variation of δC13 in solutions and in precipitates formed under a variety of conditions involving incongruent dissolution, CO2 degassing, methane production and mineral precipitation.