Assessing DOC export from a Sphagnum‐dominated peatland using δ13C and δ18O–H2O stable isotopes

Dissolved organic carbon (DOC) originating in peatlands can be mineralized to carbon dioxide (CO₂) and methane (CH₄), two potent greenhouse gases. Knowledge of the dynamics of DOC export via run‐off is needed for a more robust quantification of C cycling in peatland ecosystems, a prerequisite for realistic predictions of future climate change. We studied dispersion pathways of DOC in a mountain‐top peat bog in the Czech Republic (Central Europe), using a dual isotope approach. Although δ¹³C_DOC values made it possible to link exported DOC with its within‐bog source, δ¹⁸O_H2O values of precipitation and run‐off helped to understand run‐off generation. Our 2‐year DOC–H₂O isotope monitoring was complemented by a laboratory peat incubation study generating an experimental time series of δ¹³C_DOC values. DOC concentrations in run‐off during high‐flow periods were 20–30 mg L^?1. The top 2 cm of the peat profile, composed of decaying green moss, contained isotopically lighter C than deeper peat, and this isotopically light C was present in run‐off in high‐flow periods. In contrast, baseflow contained only 2–10 mg DOC L^?1, and its more variable C isotope composition intermittently fingerprinted deeper peat. DOC in run‐off occasionally contained isotopically extremely light C whose source in solid peat substrate was not identified. Pre‐event water made up on average 60% of the water run‐off flux, whereas direct precipitation contributed 40%. Run‐off response to precipitation was relatively fast. A highly leached horizon was identified in shallow catotelm. This peat layer was likely affected by a lateral influx of precipitation. Within 36 days of laboratory incubation, isotopically heavy DOC that had been initially released from the peat was replaced by isotopically lighter DOC, whose δ¹³C values converged to the solid substrate and natural run‐off. We suggest that δ¹³C systematics can be useful in identification of vertically stratified within‐bog DOC sources for peatland run‐off.     

Assessing Methane in Shallow Groundwater in Unconventional Oil and Gas Play Areas,Eastern Kentucky

The expanding use of horizontal drilling and hydraulic fracturing technology to produce oil and gas from tight rock formations has increased public concern about potential impacts on the environment, especially on shallow drinking water aquifers. In eastern Kentucky, horizontal drilling and hydraulic fracturing have been used to develop the Berea Sandstone and the Rogersville Shale. To assess baseline groundwater chemistry and evaluate methane detected in groundwater overlying the Berea and Rogersville plays, we sampled 51 water wells and analyzed the samples for concentrations of major cations and anions, metals, dissolved methane, and other light hydrocarbon gases. In addition, the stable carbon and hydrogen isotopic composition of methane (δ¹³C‐CH₄ and δ²H‐CH₄) was analyzed for samples with methane concentration exceeding 1 mg/L. Our study indicates that methane is a relatively common constituent in shallow groundwater in eastern Kentucky, where methane was detected in 78% of the sampled wells (40 of 51 wells) with 51% of wells (26 of 51 wells) exhibiting methane concentrations above 1 mg/L. The δ¹³C‐CH₄ and δ²H‐CH₄ ranged from ?84.0‰ to ?58.3‰ and from ?246.5‰ to ?146.0‰, respectively. Isotopic analysis indicated that dissolved methane was primarily microbial in origin formed through CO₂ reduction pathway. Results from this study provide a first assessment of methane in the shallow aquifers in the Berea and Rogersville play areas and can be used as a reference to evaluate potential impacts of future horizontal drilling and hydraulic fracturing activities on groundwater quality in the region.     

Origin and chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta,Botswana

The origin and the chemical and isotopic evolution of dissolved inorganic carbon (DIC) in groundwater of the Okavango Delta in semi-arid Botswana were investigated using DIC and major ion concentrations and stable oxygen, hydrogen and carbon isotopes (δD, δ¹⁸O and δ¹³C_DIC). The δD and δ¹⁸O indicated that groundwater was recharged by evaporated river water and unevaporated rain. The river water and shallow (<10 m) groundwater are Ca–Na–HCO₃ type and the deep (≥10 m) groundwater is Na–K–HCO₃ to HCO₃–Cl–SO₄ to Cl–SO₄–HCO₃. Compared to river water, the mean DIC concentrations were 2 times higher in shallow groundwater, 7 times higher in deep groundwater and 24 times higher in island groundwater. The δ¹³C_DIC indicate that DIC production in groundwater is from organic matter oxidation and in island groundwater from organic matter oxidation and dissolution of sodium carbonate salts. The ionic and isotopic evolution of the groundwater relative to evaporated river water indicates two independent pools of DIC.     

Discrimination of abiogenic and biogenic alkane gases

We have combined the analytical data of the carbon isotope distribution pattern, R/Ra and CH4/3He values of abiogenic and biogenic (referring to the thermogenic and bacterial or microbial) alkane gases in China with those of alkane gases from USA, Russia, Germany, Australia and other countries. Four discrimination criteria are derived from this comparative study: 1) Carbon isotopic composition is generally greater than -30‰ for abiogenic methane and less than -30‰ for biogenic methane; 2) Abiogenic alkane gases have a carbon isotopic reversal trend (δ 13C1> δ 13C2> δ 13C3> δ 13C4) with δ 13C1>-30‰ in general; 3) Gases with R/Ra >0.5 and δ 13C11 δ 13C2>0 are of abiogenic origin; 4) Gases (meth- ane) with CH4/3He≤106 are of abiogenic origin, whereas gases with CH4/3He≥1011 are of biogenic origin.     

Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central–Southern Italy)

This paper focuses on the chemical and isotopic features of dissolved gases (CH₄ and CO₂) from four meromictic lakes hosted in volcanic systems of Central–Southern Italy: Lake Albano (Alban Hills), Lake Averno (Phlegrean Fields), and Monticchio Grande and Piccolo lakes (Mt. Vulture). Deep waters in these lakes are characterized by the presence of a significant reservoir of extra-atmospheric dissolved gases mainly consisting of CH₄ and CO₂. The δ¹³C-CH₄ and δD-CH₄ values of dissolved gas samples from the maximum depths of the investigated lakes (from ?66.8 to ?55.6?‰ V-PDB and from ?279 to ?195?‰ V-SMOW, respectively) suggest that CH₄ is mainly produced by microbial activity. The δ¹³C-CO₂ values of Lake Grande, Lake Piccolo, and Lake Albano (ranging from ?5.8 to ?0.4?‰ V-PDB) indicate a significant CO₂ contribution from sublacustrine vents originating from (1) mantle degassing and (2) thermometamorphic reactions involving limestone, i.e., the same CO₂ source feeding the regional thermal and cold CO₂-rich fluid emissions. In contrast, the relatively low δ¹³C-CO₂ values (from ?13.4 to ?8.2?‰ V-PDB) of Lake Averno indicate a prevalent organic CO₂. Chemical and isotopic compositions of dissolved CO₂ and CH₄ at different depths are mainly depending on (1) CO₂ inputs from external sources (hydrothermal and/or anthropogenic); (2) CO₂–CH₄ isotopic exchange; and (3) methanogenic and methanotrophic activity. In the epilimnion, vertical water mixing, free oxygen availability, and photosynthesis cause the dramatic decrease of both CO₂ and CH₄ concentrations. In the hypolimnion, where the δ¹³C-CO₂ values progressively increase with depth and the δ¹³C-CH₄ values show an opposite trend, biogenic CO₂ production from CH₄ using different electron donor species, such as sulfate, tend to counteract the methanogenesis process whose efficiency achieves its climax at the water–bottom sediment interface. Theoretical values, calculated on the basis of δ¹³C-CO₂ values, and measured δ¹³C_TDIC values are not consistent, indicating that CO₂ and the main carbon-bearing ion species (HCO₃ ^?) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO₂ and CH₄. This study demonstrates that the vertical patterns of the CO₂/CH₄ ratio and of δ¹³C-CO₂ and δ¹³C-CH₄ are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO₂ input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.     

Tectonic control of bioalteration in modern and ancient oceanic crust as evidenced by carbon isotopes

Abstract We review the carbon‐isotope data for finely disseminated carbonates from bioaltered, glassy pillow rims of basaltic lava flows from in situ slow‐ and intermediate‐spreading oceanic crust of the central Atlantic Ocean (CAO) and the Costa Rica Rift (CRR). The δ¹³C values of the bioaltered glassy samples from the CAO show a large range, between ?17 and +3‰ (Vienna Peedee belemnite standard), whereas those from the CRR define a much narrower range, between ?17‰ and ?7‰. This variation can be interpreted as the product of different microbial metabolisms during microbial alteration of the glass. In the present study, the generally low δ¹³C values (less than ?7‰) are attributed to carbonate precipitated from microbially produced CO₂ during oxidation of organic matter. Positive δ¹³C values >0‰ likely result from lithotrophic utilization of CO₂ by methanogenic Archaea that produce CH₄ from H₂ and CO₂. High production of H₂ at the slow‐spreading CAO crust may be a consequence of fault‐bounded, high‐level serpentinized peridotites near or on the sea floor, in contrast to the CRR crust, which exhibits a layer‐cake pseudostratigraphy with much less faulting and supposedly less H₂ production. A comparison of the δ¹³C data from glassy pillow margins in two ophiolites interpreted to have formed at different spreading rates supports this interpretation. The Jurassic Mirdita ophiolite complex in Albania shows a structural architecture similar to that of the slow‐spreading CAO crust, with a similar range in δ¹³C values of biogenic carbonates. The Late Ordvician Solund–Stavfjord ophiolite complex in western Norway exhibits structural and geochemical evidence for evolution at an intermediate‐spreading mid‐ocean ridge and displays δ¹³C signatures in biogenic carbonates similar to those of the CRR. Based on the results of this comparative study, it is tentatively concluded that the spreading rate‐dependent tectonic evolution of oceanic lithosphere has a significant control on the evolution of microbial life and hence on the δ¹³C biosignatures preserved in disseminated biogenic carbonates in glassy, bioaltered lavas.     

A Stream‐Based Methane Monitoring Approach for Evaluating Groundwater Impacts Associated with Unconventional Gas Development

Gaining streams can provide an integrated signal of relatively large groundwater capture areas. In contrast to the point‐specific nature of monitoring wells, gaining streams coalesce multiple flow paths. Impacts on groundwater quality from unconventional gas development may be evaluated at the watershed scale by the sampling of dissolved methane (CH₄) along such streams. This paper describes a method for using stream CH₄ concentrations, along with measurements of groundwater inflow and gas transfer velocity interpreted by 1‐D stream transport modeling, to determine groundwater methane fluxes. While dissolved ionic tracers remain in the stream for long distances, the persistence of methane is not well documented. To test this method and evaluate CH₄ persistence in a stream, a combined bromide (Br) and CH₄ tracer injection was conducted on Nine‐Mile Creek, a gaining stream in a gas development area in central Utah. A 35% gain in streamflow was determined from dilution of the Br tracer. The injected CH₄ resulted in a fivefold increase in stream CH₄ immediately below the injection site. CH₄ and δ¹³C_CH4 sampling showed it was not immediately lost to the atmosphere, but remained in the stream for more than 2000 m. A 1‐D stream transport model simulating the decline in CH₄ yielded an apparent gas transfer velocity of 4.5 m/d, describing the rate of loss to the atmosphere (possibly including some microbial consumption). The transport model was then calibrated to background stream CH₄ in Nine‐Mile Creek (prior to CH₄ injection) in order to evaluate groundwater CH₄ contributions. The total estimated CH₄ load discharging to the stream along the study reach was 190 g/d, although using geochemical fingerprinting to determine its source was beyond the scope of the current study. This demonstrates the utility of stream‐gas sampling as a reconnaissance tool for evaluating both natural and anthropogenic CH₄ leakage from gas reservoirs into groundwater and surface water.     

Distribution of stable carbon isotope in coalbed methane from the east margin of Ordos Basin

The commercial recovery of methane from coal is well established in the coalbed methane (CBM) blocks at the east margin of Ordos Basin, China. CBM forms with various carbon isotopic ratios (δ¹³C_PDB) due to the carbon isotopic fractionation in biogenical or thermogenical processes. Based on the geologic evolution of coalbed reservoir and studies on the characteristics of δ¹³C_PDB values distributed spatially (e.g., horizontal CBM well location area, vertical coal burial zone, coal rank, etc.) and temporally (e.g., geologic evolution history), we explored the formation mechanism of carbon isotopic of methane. The relatively low δ¹³C_PDB values are widely distributed along the research area, indicating a trend of “lighter-heavier-lighter” from north to south. From a combination analysis of the relationship between δ¹³C_PDB and the relative effects, the essential aspects in determining CBM carbon isotope being light in the study area are: the genesis of secondary biogas in the north; water soluble effects in the active hydrodynamic areas in the middle; desorption fractionation effect promoted by tectonic evolution in the south; and the sudden warming hydrocarbon fractionation accelerated by magmatic event in particular areas (e.g., Linxian).     

Measuring Concentrations of Dissolved Methane and Ethane and the 13C of Methane in Shale and Till

Baseline characterization of concentrations and isotopic values of dissolved natural gases is needed to identify contamination caused by the leakage of fugitive gases from oil and gas activities. Methods to collect and analyze baseline concentration‐depth profiles of dissolved CH₄ and C₂H₆ and δ¹³C‐CH₄ in shales and Quaternary clayey tills were assessed at two sites in the Williston Basin, Canada. Core and cuttings samples were stored in Isojars^® in a low O₂ headspace prior to analysis. Measurements and multiphase diffusion modeling show that the gas concentrations in core samples yield well‐defined and reproducible depth profiles after 31‐d equilibration. No measurable oxidative loss or production during core sample storage was observed. Concentrations from cuttings and mud gas logging (including IsoTubes^®) were much lower than from cores, but correlated well. Simulations suggest the lower concentrations from cuttings can be attributed to drilling time, and therefore their use to define gas concentration profiles may have inherent limitations. Calculations based on mud gas logging show the method can provide estimates of core concentrations if operational parameters for the mud gas capture cylinder are quantified. The δ¹³C‐CH₄ measured from mud gas, IsoTubes^®, cuttings, and core samples are consistent, exhibiting slight variations that should not alter the implications of the results in identifying the sources of the gases. This study shows core and mud gas techniques and, to a lesser extent, cuttings, can generate high‐resolution depth profiles of dissolved hydrocarbon gas concentrations and their isotopes.     

Geochemical evidence for mixing of magmatic fluids with seawater,Nisyros hydrothermal system,Greece

The chemical and isotopic compositions (δD_H2O, δ¹⁸O_H2O, δ¹⁸O_CO2, δ¹³C_CO2, δ³⁴S, and He/N₂ and He/Ar ratios) of fumarolic gases from Nisyros, Greece, indicate that both arc-type magmatic water and local seawater feed the hydrothermal system. Isotopic composition of the deep fluid is estimated to be +4.9±0.5‰ for δ¹⁸O and ?11±5‰ for δD corresponding to a magmatic water fraction of 0.7. Interpretation of the stable water isotopes was based on liquid–vapor separation conditions obtained through gas geothermometry. The H₂–Ar, H₂–N₂, and H₂–H₂O geothermometers suggest reservoir temperatures of 345±15 °C, in agreement with temperatures measured in deep geothermal wells, whereas a vapor/liquid separation temperature of 260±30 °C is indicated by gas equilibria in the H₂O–H₂–CO₂–CO–CH₄ system. The largest magmatic inputs seem to occur below the Stephanos–Polybotes Micros crater, whereas the marginal fumarolic areas of Phlegeton–Polybotes Megalos craters receive a smaller contribution of magmatic gases.     

Controls on Methane Occurrences in Aquifers Overlying the Eagle Ford Shale Play,South Texas

Assessing natural vs. anthropogenic sources of methane in drinking water aquifers is a critical issue in areas of shale oil and gas production. The objective of this study was to determine controls on methane occurrences in aquifers in the Eagle Ford Shale play footprint. A total of 110 water wells were tested for dissolved light alkanes, isotopes of methane, and major ions, mostly in the eastern section of the play. Multiple aquifers were sampled with approximately 47 samples from the Carrizo‐Wilcox Aquifer (250‐1200 m depth range) and Queen City‐Sparta Aquifer (150‐900 m depth range) and 63 samples from other shallow aquifers but mostly from the Catahoula Formation (depth <150 m). Besides three shallow wells with unambiguously microbial methane, only deeper wells show significant dissolved methane (22 samples >1 mg/L, 10 samples >10 mg/L). No dissolved methane samples exhibit thermogenic characteristics that would link them unequivocally to oil and gas sourced from the Eagle Ford Shale. In particular, the well water samples contain very little or no ethane and propane (C1/C2+C3 molar ratio >453), unlike what would be expected in an oil province, but they also display relatively heavier δ¹³C_methane (>?55‰) and δD_methane (>?180‰). Samples from the deeper Carrizo and Queen City aquifers are consistent with microbial methane sourced from syndepositional organic matter mixed with thermogenic methane input, most likely originating from deeper oil reservoirs and migrating through fault zones. Active oxidation of methane pushes δ¹³C_methane and δD_methane toward heavier values, whereas the thermogenic gas component is enriched with methane owing to a long migration path resulting in a higher C1/C2+C3 ratio than in the local reservoirs.     

Natural gas seepage in the Gulf of Mexico

Hydrocarbon compositions and δ¹³C values for methane of fourteen natural seep gases and four underwater vents in the northwestern Gulf of Mexico are reported. The C₁/(C₂ + C₃) ratios of the seep gas samples ranged from 68 to greater than 1000, whereas δ_PDB¹³C values varied from ?39.9 to ?65.5‰. Compositions suggest that eleven of the natural gas seeps are produced by microbial degradation whereas the remaining three have a significant thermocatalytically produced component. Contradictions in the inferences drawn from molecular and isotopic compositions make strict interpretation of the origins of a few of the samples impossible.     

Chemostratigraphy of the Ediacaran basinal setting on the Yangtze platform,South China: Oceanographic and diagenetic aspects of the carbon isotopic depth gradient

The Ediacaran Yangtze platform in South China, which represents depositional settings ranging from coastal to basinal, provides valuable information for understanding climate changes and animal evolution during the Ediacaran Period. Although the shallower settings have been investigated, research on the basinal sections has been limited. This has hampered efforts to establish stratigraphic correlations and understand the oceanographic setting of the Yangtze platform. In this paper, the chemostratigraphy of a basinal section at Fengtan, Hunan Province, is reported based on analyses of stable carbon isotope profiles in carbonates (δ¹³C_carb), organic matter (δ¹³C_org), total organic carbon, ⁸⁷Sr/⁸⁶Sr ratios, and Mn, Rb, and Sr concentrations. The basinal section of the Doushantuo Formation, which is represented at Fengtan, provides data supporting regional correlations and oceanography. Three intervals in the Doushantuo Formation are correlated with the Three Gorges: (i) a negative δ¹³C_carb anomaly with stable δ¹³C_org values and altered ⁸⁷Sr/⁸⁶Sr ratios in the lower section can be correlated to the boundary between Doushantuo Members 2 and 3 (Interval A); (ii) a relatively high δ¹³C_carb anomaly with unaltered ⁸⁷Sr/⁸⁶Sr ratios (up to 0.7086) in the middle section corresponding to the lower part of Doushantuo Member 3 (Interval B); and (iii) a negative δ¹³C_carb anomaly with lowered δ values in the upper section can be correlated to the long interval of negative δ¹³C_carb (Interval C). The Gaskiers glaciation is likely represented in Interval A, and Interval C corresponds to the Shuram excursion reported for other Ediacaran localities. Our correlations confirm the depth gradient of δ¹³C_carb in the Yangtze platform and imply that reductive conditions prevailed in the basinal section from the Early to Middle Ediacaran. Under such conditions, anaerobic degradation of organic carbon or methane perturbed the inorganic carbon isotopic compositions and was at least partly responsible for the depth gradient of δ¹³C_carb.     

Excess of bottom-released methane in an Arctic shelf sea polynya in winter

Latent heat polynyas are regions generating strong ice formation, convection and extensive water mass formation. Here we report on the effects of these processes on resuspension of sediments and subsequent methane release from the seafloor and on the resulting excess methane concentration in surface water on a polar shelf during winter. The study is based on measurements of concentration and δ¹³C values of methane, water temperature, salinity, light transmission and sea ice data collected in March 2003 in Storfjorden, southern Svalbard. In winter, strong and persistent northeasterly winds create polynyas in eastern Storfjorden and cause ice formation. The resulting brine-enriched water cascades from the Storfjordbanken into the central depression thereby enhancing the turbulence near the seafloor. A distinct benthic nepheloid layer was observed reflecting the resuspension of sediments by the cascading dense bottom water. High concentrations of ¹³C-depleted methane suggest submarine discharge of methane with the resuspended sediments. As the source of the submarine methane, we propose recent bacterial methanogenesis near the sediment surface because of extremely high accumulation rates of organic carbon in Storfjorden. Convective mixing transports newly released methane from the bottom to the sea surface. This eventually results in an excess concentration in surface water with respect to the atmospheric equilibrium, and a sea-air flux of methane during periods of open water. When a new ice cover is formed, methane becomes trapped in the water column and subsequently oxidized. Thus, the residual methane is strongly enriched in ¹³C in relation to the δ¹³_CCH4${\delta }^{13}{\mathrm{C}}_{{\mathrm{CH}}_4}$ signature of atmospheric methane. Our results show that latent heat polynyas may induce a direct pathway for biogases like methane from sediments to the atmosphere through coupling of biogeochemical and oceanographic processes. Extrapolating these processes to all Arctic ocean polynyas, we estimate a transfer of CH₄ between 0.005 and 0.02 Tg yr⁻¹. This is not a large contribution but the fluxes from the polynyas are 20–200 times larger than the ocean average and the methane evasion process in polynyas is certainly one that can be altered under climate change.     

Hydrocarbon‐Rich Groundwater above Shale‐Gas Formations: A Karoo Basin Case Study

Horizontal drilling and hydraulic fracturing have enhanced unconventional hydrocarbon recovery but raised environmental concerns related to water quality. Because most basins targeted for shale‐gas development in the USA have histories of both active and legacy petroleum extraction, confusion about the hydrogeological context of naturally occurring methane in shallow aquifers overlying shales remains. The Karoo Basin, located in South Africa, provides a near‐pristine setting to evaluate these processes, without a history of conventional or unconventional energy extraction. We conducted a comprehensive pre‐industrial evaluation of water quality and gas geochemistry in 22 groundwater samples across the Karoo Basin, including dissolved ions, water isotopes, hydrocarbon molecular and isotopic composition, and noble gases. Methane‐rich samples were associated with high‐salinity, NaCl‐type groundwater and elevated levels of ethane, ⁴He, and other noble gases produced by radioactive decay. This endmember displayed less negative δ¹³C‐CH₄ and evidence of mixing between thermogenic natural gases and hydrogenotrophic methane. Atmospheric noble gases in the methane‐rich samples record a history of fractionation during gas‐phase migration from source rocks to shallow aquifers. Conversely, methane‐poor samples have a paucity of ethane and ⁴He, near saturation levels of atmospheric noble gases, and more negative δ¹³C‐CH₄; methane in these samples is biogenic and produced by a mixture of hydrogenotrophic and acetoclastic sources. These geochemical observations are consistent with other basins targeted for unconventional energy extraction in the USA and contribute to a growing data base of naturally occurring methane in shallow aquifers globally, which provide a framework for evaluating environmental concerns related to unconventional energy development (e.g., stray gas).     

Isotope shifts in the Late Permian of the Delaware Basin,Texas, precisely timed by varved sediments

Closely spaced samples (285 in number) of varved sediments from the Upper Permian in Delaware Basin, Texas, have been analyzed for δ¹³C_carb, δ¹³C_org, δ¹⁸O_carb, C_org, C_carb, and calcite/dolomite. δ¹³C records a dramatic rise from ?2.8 to +5.7‰ in only 4400 years, detected in three sections across the basin, extrapolating smoothly through a 600-year interruption by a local (west side of the basin) fresh-water inflow evidenced by low δ¹⁸O. This continuity and low C_org within the basin, both indicate that the excess net deposition of C_org, necessary to generate the rise in δ¹³C, took place in the ocean external to the Delaware Basin. Correlation with similar records from the Zechstein Basin suggest that the event was world-wide, although this poses obvious difficulties for the carbon cycle. The rate of rise of δ¹³C, and its sustained high level, must imply conversions of oxidized carbon to reduced carbon that are very large depending on which reservoirs were involved.     

Characteristics of δ13CDIC in lakes on the Tibetan Plateau and its implications for the carbon cycle

Dissolved inorganic carbon isotope (δ¹³C_DIC) is an important tool to reveal the carbon cycle in lake systems. However, there are only few studies focusing on the spatial variation of δ¹³C_DIC of closed lakes. Here we analyze the characteristics of δ¹³C_DIC of 24 sampled lakes (mainly closed lakes) across the Qiangtang Plateau (QTP) and identify the driving factors for its spatial variation. The δ¹³C_DIC value of these observed lakes varies in the range of ? 15·0 to 3·2‰, with an average value of ? 1·2‰. The δ¹³C_DIC value of closed lakes is close to the atmospheric isotopic equilibrium value, much higher than that in rivers and freshwater lakes reported before. The high δ¹³C_DIC value of closed lakes is mainly attributed to the significant contribution of carbonate weathering in the catchment and the evasion of dissolved CO₂ induced by the strong evaporation of lake water. The δ¹³C_DIC value of closed lakes has a logarithmic correlation with water chemistry (TDS, DIC and pCO₂), also suggesting that the evapo‐concentration of lake water can influence the δ¹³C_DIC value. The δ¹³C_DIC value shows two opposite logarithmic correlations with lake size depending on the δ¹³C_DIC range. This study suggests that the δ¹³C in carbonates in lacustrine sediments can be taken as an indicator of lake volume variation in closed lakes on QTP. Copyright © 2011 John Wiley & Sons, Ltd.     

Oxidation and emission of methane in a monomictic lake (Rotsee, Switzerland)

The build-up of methane in the hypolimnion of the eutrophic Lake Rotsee (Lucerne, Switzerland) was monitored over a full year. Sources and sinks of methane in the water column were characterized by measuring concentrations and carbon isotopic composition. In fall, high methane concentrations (up to 1 mM) were measured in the anoxic water layer. In the oxic layer, methane concentrations were much lower and the isotopic composition shifted towards heavy carbon isotopes. Methane oxidation rates peaked at the interface between oxic and anoxic water layers at around 8–10 m depth. The electron balance between the oxidants oxygen, sulphate, and nitrate, and the reductants methane, sulphide and ammonium, matched very well in the chemocline during the stratified season. The profile of carbon isotopic composition of methane showed strong indications for methane oxidation at the chemocline (including the oxycline). Aerobic methane oxidizing bacteria were detected at the interface using fluorescence in situ hybridization. Sequencing the responsible organisms from DGGE bands revealed that aerobic methanotrophs type I closely related to Methylomonas were present. Sulphate consumption occurred at the sediment surface and, only towards the end of the stagnation period, matched with a zone of methane consumption. In any case, the flux of sulphate below the chemocline was not sufficient to oxidize all the methane and other oxidants like nitrate, iron or manganese are necessary for the observed methane oxidation. Although most of the methane was oxidized either aerobically or anaerobically, Lake Rotsee was still a source of methane to the atmosphere with emission rates between 0.2 mg CH₄ m^?2 day^?1 in February and 7 mg CH₄ m^?2 day^?1 in November.     

Dissolved inorganic carbon isotopes of a typical alpine river on the Tibetan Plateau revealing carbon sources,wetland effect and river recharge

The Nyangqu River, the largest right bank tributary of the Yarlung Zangbo River in the Qinghai–Tibet Plateau, was representative of an alpine riverine carbon cycle experiencing climate change. In this study, dissolved inorganic carbon (DIC) spatial and seasonal variations, as well as their carbon isotopic compositions (δ¹³C_DIC) in river water and groundwater were systematically investigated to provide constraints on DIC sources, recharge and cycling. Significant changes in the δ¹³C_DIC values (from −2.9‰ to −23.4‰) of the water samples were considered to be the result of different contributions of two dominant DIC origins: soil CO₂ dissolution and carbonate weathering. Three types of rock weathering (dissolution of carbonate minerals by H₂CO₃ and H₂SO₄, and silicate dissolution by H₂CO₃) were found to control the DIC input into the riverine system. In DIC cycling, groundwater played a significant role in delivering DIC to the surface water, and DIC supply from tributaries to the main stream increased from the dry season to the wet season. Notably, the depleted δ¹³C_DIC ‘peak’ around the 88.9° longitude, especially in the September groundwater samples, indicated the presence of ‘special’ DIC, which was attributed to the oxidation of methane from the Jiangsa wetland located nearby. This wetland could provide large amounts of soil organic matter available for bacterial degradation, producing ¹³C-depleted methane. Our study provided insights regarding the role of wetlands in riverine carbon cycles and highlighted the contribution of groundwater to alpine riverine DIC cycles.     

Using environmental isotopes to investigate the groundwater recharge mechanisms and dynamics in the North-eastern Basin,Palestine

ABSTRACT

This study aims to differentiate the potential recharge areas and flow mechanisms in the North-eastern Basin, Palestine. The results differentiate the recharge into three main groups. The first is related to springs and some of the deep wells close to the Anabta Anticline, through the Upper Aquifer (Turonian) formation, with depleted δ¹⁸O and δ²H. The second is through the Upper Cenomanian formation surrounding the Rujeib Monocline in the southeast, where the lineament of the Faria Fault plays an important role, with relatively enriched δ¹³C_DIC values of about ?4‰ (VPDB). The third is the Jenin Sub-series, which shows higher δ¹³C_DIC values, with enriched δ¹⁸O and δ²H and more saline content. The deep wells from the Nablus area in the south of the basin indicate low δ¹³C_DIC values due to their proximity to freshwater infiltrating faults. The deep wells located to the northwest of the basin have δ¹³C_DIC values from ?8 to ?9‰ (VPDB), with enriched δ¹⁸O signatures, indicating slow recharge through thick soil.