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Kanduč, Tjaša, Simon Zavšek, Sergej Jamnikar, and Timotej Verbovšek. "Spatial distribution and origin of coalbed gases at the working faces of the Velenje Coal Basin, Slovenia, since the year 2000." Materials and Geoenvironment 63, no. 4 (October 1, 2016): 213–26. http://dx.doi.org/10.1515/rmzmag-2016-0019.
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AbstractGeochemical and isotopic monitoring of coalbed gases at the excavation fields of mining areas in Velenje Coal Basin, Slovenia, has been ongoing since the year 2000 with the aim of obtaining better insights into the distribution and origin of coalbed gases. Results from the mining areas Pesje and Preloge (active excavation fields) are presented here from the year 2000 up to the present. Composition and origin of coalbed gases were determined using mass spectrometry at the Jožef Stefan Institute. From a larger database of geochemical samples, 119 samples were used for analysis and spatial presentation in a geographical information system (GIS) environment. We have used geochemical (CH4, CO2 and N2) and isotopic (δ13CCO2 and δ13CCH4) tracers for geochemical and isotopic characterisation of coalbed gases from the active excavation fields. Concentrations of CO2 and the carbon dioxide–methane indices in the southern part of the basin are higher than in the northern part of the basin due to the vicinity of the active Šoštanj Fault. The value of δ13CCH4 at the active excavation field indicates a bacterial origin, with values greater than –50‰, and only some boreholes show elevated δ13CCH4 quantities as a consequence of the CO2 reduction process in Velenje Coal Basin. The value of δ13CCO2 indicates the bacterial and endogenic origin of carbon.
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Raco, B., R. Battaglini, and E. Dotsika. "New isotopic (δ13CCO2–δ13CCH4) fractionation factor limits and chemical characterization of landfill gas." Journal of Geochemical Exploration 145 (October 2014): 40–50. http://dx.doi.org/10.1016/j.gexplo.2014.05.003.
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Cao, Yuanhao, Wei Chen, Yinnan Yuan, Tengxi Wang, and Jiafeng Sun. "Gas Generation and Its Carbon Isotopic Composition during Pyrite-Catalyzed Pyrolysis of Shale with Different Maturities." Processes 10, no. 11 (November 4, 2022): 2296. http://dx.doi.org/10.3390/pr10112296.
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In this study, two shale samples with different maturities, from Geniai, Lithuania (Ro = 0.7%), and Wenjiaba, China (Ro = 2.7%), were selected for open-system pyrolysis experiments at 400 °C and 500 °C, respectively. The generation of isotopic gases from the shales with different maturities was investigated, and the effects of pyrite catalysis on the carbon isotopic compositions were also studied. It was found that CO2, CH4 and their isotopic gases were the main gaseous products of the pyrolysis of both shales, and more hydrocarbon gases were generated from the low-maturity Geniai shale. The δ13C1 values fluctuated from −40‰ to −38‰, and δ13C2 showed higher values (−38‰~−34‰) for the Geniai shale. In addition, its δ13CCO2 values ranged from −28‰ to −26‰. Compared with the Geniai shale, lower δ13C1 values (−43‰~−42‰) and higher δ13CCO2 values (−19‰~−14‰) were detected for the Wenjiaba shale. As temperature increased, CH4 became isotopically lighter and C2H6 became isotopically heavier, which changes were due to the mass-induced different reaction rates of 12C and 13C radicals. Furthermore, the pyrite made the kinetic isotope effect stronger and thus made the CH4 isotopically lighter for both shales, especially at the lower temperature of 400 °C.
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Baranovskaya, E. I., N. A. Kharitonova, E. A. Filimonova, A. A. Krasnova, and A. A. Maslov. "New data on the chemical and isotopic (H, O, C, S, N) composition of mineral waters of the Essentuki deposit." Moscow University Bulletin. Series 4. Geology, no. 5 (December 17, 2022): 120–36. http://dx.doi.org/10.33623/0579-9406-2022-5-120-136.
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The article presents modern data on the chemical, gas composition, the content of the stable isotopes of oxygen, hydrogen, carbon and sulfur in the natural mineral waters of the Essentuki field. A detailed study of the geological and hydrogeological features of the water circulation territory, their macro components composition, the content of organic matter in the water, temperature conditions and values of δ18ОSMOW, δDSMOW, δ13СDIC, δ18ОDIC, δ34SVCDT, δ13CCO2, δ13CCH4, δ15N revealed the genesis of the aqueous, gas and salt components of the natural mineral waters of the Essentuki field. Established that all natural mineral waters of the Essentuki field are meteoric infiltration waters. The heterogeneous component composition of the natural mineral waters, that circulate in various aquifers, represents the features of the lithological composition of the water-bearing rocks, the degree of openness or closeness of faults and the intensity of reactions in the water-rock-gas-organic matter system.
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Potter, Joanna, Frederick J. Longstaffe, and Sandra M. Barr. "Vein assemblages and fluid evolution in 18O-depleted Neoproterozoic igneous rocks of the Mira terrane, Cape Breton Island, Nova Scotia1This article is one of a series of papers published in CJES Special Issue: In honour of Ward Neale on the theme of Appalachian and Grenvillian geology.2Laboratory for Stable Isotope Science (LSIS) Contribution 251." Canadian Journal of Earth Sciences 49, no. 1 (January 2012): 359–78. http://dx.doi.org/10.1139/e11-074.
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Fluids responsible for regional 18O-depletion of Neoproterozoic igneous rocks in Avalonia are investigated here through a petrographic, microthermometric, and stable isotopic examination of fluid inclusions and minerals from the abundant vein networks of the Mira terrane, Cape Breton Island. Six categories of vein assemblages — from oldest to youngest — are present: (i) quartz–albite, (ii) quartz–epidote, (iii) quartz, (iv) quartz–chlorite–calcite, (v) quartz–calcite, and (vi) calcite. Vein system temperatures were initially as high as ∼300 °C and gradually decreased to ∼200 °C. Moderate salinities (<8 equivalent wt.% NaCl) characterize entrapped fluids in the early quartz–albite veins but decrease in later quartz–epidote and quartz–calcite veins to <1 equiv. wt.% NaCl. The limited range of fluid δ18O values (–1.9‰ to +1.4‰) calculated for most of the vein assemblages is suggestive of a seawater-dominated system, as are the δDH2O values (–12‰ to –3‰) obtained for epidote. Decreasing fluid salinities, however, suggest that meteoric water became dominant during later stages of vein formation. The carbon isotopic compositions of trace CO2 and CH4 from the fluid inclusions (δ13CCO2 = –22‰ to –4‰; δ13CCH4 = –52‰ to –37‰) are indicative of externally derived (i.e., non-magmatic) fluids of organic origin.
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Baranovskaya, Ekaterina I., Natalia A. Kharitonova, Georgy A. Chelnokov, Irina A. Tarasenko, and Alexey A. Maslov. "Chemical and Isotopic Features of a High pCO2 Natural Mineral Water from Essentuki Field (Caucasian Mineral Water Region, Russia)." Water 15, no. 5 (February 26, 2023): 901. http://dx.doi.org/10.3390/w15050901.
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This article presents the new data on the chemical and gas composition, the content of stable isotopes of oxygen, hydrogen, carbon, and sulfur in natural mineral waters of the Essentuki field. A detailed study of the geological and hydrogeological features of the water circulation area, its major chemical composition, the content of organic matter in water, temperature conditions and δ18OSMOW, δDSMOW, δ13CDIC, δ18ODIC, δ34SVCDT, δ13CCO2, δ13CCH4, δ15N values made it possible to specify the genesis of water, gas, and solute components of the Essentuki CO2-rich mineral water field. The stable isotopes values (δ18OSMOW and δDSMOW) in the water phase ranges from −13.75 to −9.69‰ and from −101.08 to −74.34‰, respectively. They correspond to GMWL, which indicates their predominantly infiltration genesis. The values of δ13CDIC in mineral waters of the Essentuki field vary widely from −14.43 to +8.59‰ and indicate their mixed genesis. δ15N gas values in mineral waters of the Essentuki field vary quite widely from −2.31 to 2.50‰ indicating a different source of this gas. Obtained data prove that all mineral waters in the Essentuki field are infiltration waters, and the heterogeneous component composition of waters circulating in different aquifers reflects the lithological composition of water-bearing strata, the rate of openness/closure of faults and the intensity of reactions in the «water-rock-gas-organic matter» system.
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Zhao, Rongsheng, Luquan Ren, Sunhua Deng, Youhong Sun, and Zhiyong Chang. "Constrain on Oil Recovery Stage during Oil Shale Subcritical Water Extraction Process Based on Carbon Isotope Fractionation Character." Energies 14, no. 23 (November 23, 2021): 7839. http://dx.doi.org/10.3390/en14237839.
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In this work, Huadian oil shale was extracted by subcritical water at 365 °C with a time series (2–100 h) to better investigate the carbon isotope fractionation characteristics and how to use its fractionation characteristics to constrain the oil recovery stage during oil shale in situ exploitation. The results revealed that the maximum generation of oil is 70–100 h, and the secondary cracking is limited. The carbon isotopes of the hydrocarbon gases show a normal sequence, with no “rollover” and “reversals” phenomena, and the existence of alkene gases and the CH4-CO2-CO diagram implied that neither chemical nor carbon isotopes achieve equilibrium in the C-H-O system. The carbon isotope (C1–C3) fractionation before oil generation is mainly related to kinetics of organic matter decomposition, and the thermodynamic equilibrium process is limited; when entering the oil generation area, the effect of the carbon isotope thermodynamic equilibrium process (CH4 + 2H2O ⇄ CO2 + 4H2) becomes more important than kinetics, and when it exceeds the maximum oil generation stage, the carbon isotope kinetics process becomes more important again. The δ13CCO2−CH4 is the result of the competition between kinetics and thermodynamic fractionation during the oil shale pyrolysis process. After oil begins to generate, δ13CCO2−CH4 goes from increasing to decreasing (first “turning”); in contrast, when exceeding the maximum oil generation area, it goes from decreasing to increasing (second “turning”). Thus, the second “turning” point can be used to indicate the maximum oil generation area, and it also can be used to help determine when to stop the heating process during oil shale exploitation and lower the production costs.
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Fernandez-Cortes, A., R. Perez-Lopez, S. Cuezva, J. M. Calaforra, J. C. Cañaveras, and S. Sanchez-Moral. "Geochemical Fingerprinting of Rising Deep Endogenous Gases in an Active Hypogenic Karst System." Geofluids 2018 (December 6, 2018): 1–19. http://dx.doi.org/10.1155/2018/4934520.
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The hydrothermal caves linked to active faulting can potentially harbour subterranean atmospheres with a distinctive gaseous composition with deep endogenous gases, such as carbon dioxide (CO2) and methane (CH4). In this study, we provide insight into the sourcing, mixing, and biogeochemical processes involved in the dynamic of deep endogenous gas formation in an exceptionally dynamic hypogenic karst system (Vapour Cave, southern Spain) associated with active faulting. The cave environment is characterized by a prevailing combination of rising warm air with large CO2 outgassing (>1%) and highly diluted CH4 with an endogenous origin. The δ13CCO2 data, which ranges from −4.5 to −7.5‰, point to a mantle-rooted CO2 that is likely generated by the thermal decarbonation of underlying marine carbonates, combined with degassing from CO2-rich groundwater. A pooled analysis of δ13CCO2 data from exterior, cave, and soil indicates that the upwelling of geogenic CO2 has a clear influence on soil air, which further suggests a potential for the release of CO2 along fractured carbonates. CH4 molar fractions and their δD and δ13C values (ranging from −77 to −48‰ and from −52 to −30‰, respectively) suggest that the methane reaching Vapour Cave is the remnant of a larger source of CH4, which was likely generated by microbial reduction of carbonates. This CH4 has been affected by a postgenetic microbial oxidation, such that the gas samples have changed in both molecular and isotopic composition after formation and during migration through the cave environment. Yet, in the deepest cave locations (i.e., 30 m below the surface), measured concentration values of deep endogenous CH4 are higher than in atmospheric with lighter δ13C values with respect to those found in the local atmosphere, which indicates that Vapour Cave may occasionally act as a net source of CH4 to the open atmosphere.
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Tang, Junhong, Yue Xu, Guojian Wang, Jingang Huang, Wei Han, Zhitong Yao, and Zhenzhen Zhu. "Methane in Soil Gas and Its Migration to the Atmosphere in the Dawanqi Oilfield, Tarim Basin, China." Geofluids 2019 (July 9, 2019): 1–10. http://dx.doi.org/10.1155/2019/1693746.
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Methane microseepage is the result of natural gas migration from subsurface hydrocarbon accumulations to the Earth’s surface, and it is quite common in hydrocarbon-prone basins. In this study, by analyzing gas concentrations and isotope composition of soil gas, the potentials of CH4 gas transferred to the surface were studied at three measurement transects in Dawanqi oilfield, Tarim Basin, China. It was found that CH4 from deep-buried reservoirs could migrate upwards to the surface through faults, fissures, and permeable rocks, during which some CH4 was oxidized and the unoxidized methane remained in the soil or was emitted into the atmosphere. Soil gas samples had mean concentrations of 907.1, 62.3, 21.7, 11.0, and 5.8 ppmv for CH4, C2H6, C3H8, C4H10, and C5H12, respectively. The C1/C2+ (13.3 for soil gas and 3.75 for absorbed gas) and gas wetness ratio (12% for soil gas and 26% for absorbed gas) suggested that the hydrocarbons were derived from a thermogenic process. According to isotope composition analysis, the δ13CCO2, δ13CCH4, and δDCH4 values for the soil gas from Dawanqi oilfield varied from -15.5 to -17.2‰, -11‰ to -17‰, and -150 to -189‰, respectively. The extreme 13C enrichment in CH4 is possibly because of the fractionation effects of diffusional migration and methanotrophic oxidation. Soil gas and absorbed gas showed high CH4 concentrations at the edge of the fault block, which indicated that fault was conductive to gas migration. Also, gas migrated from the surface to the atmosphere in the center region of the fault block because of the high permeability and shallow depth of the reservoir in Dawanqi oilfield.
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Schmittner, A., and D. C. Lund. "Early deglacial Atlantic overturning decline and its role in atmospheric CO<sub>2</sub> rise inferred from carbon isotopes (δ<sup>13</sup>C)." Climate of the Past 11, no. 2 (February 5, 2015): 135–52. http://dx.doi.org/10.5194/cp-11-135-2015.
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Abstract. The reason for the initial rise in atmospheric CO2 during the last deglaciation remains unknown. Most recent hypotheses invoke Southern Hemisphere processes such as shifts in midlatitude westerly winds. Coeval changes in the Atlantic meridional overturning circulation (AMOC) are poorly quantified, and their relation to the CO2 increase is not understood. Here we compare simulations from a global, coupled climate–biogeochemistry model that includes a detailed representation of stable carbon isotopes (δ13C) with a synthesis of high-resolution δ13C reconstructions from deep-sea sediments and ice core data. In response to a prolonged AMOC shutdown initialized from a preindustrial state, modeled δ13C of dissolved inorganic carbon (δ13CDIC) decreases in most of the surface ocean and the subsurface Atlantic, with largest amplitudes (more than 1.5‰) in the intermediate-depth North Atlantic. It increases in the intermediate and abyssal South Atlantic, as well as in the subsurface Southern, Indian, and Pacific oceans. The modeled pattern is similar and highly correlated with the available foraminiferal δ13C reconstructions spanning from the late Last Glacial Maximum (LGM, ~19.5–18.5 ka BP) to the late Heinrich stadial event 1 (HS1, ~16.5–15.5 ka BP), but the model overestimates δ13CDIC reductions in the North Atlantic. Possible reasons for the model–sediment-data differences are discussed. Changes in remineralized δ13CDIC dominate the total δ13CDIC variations in the model but preformed contributions are not negligible. Simulated changes in atmospheric CO2 and its isotopic composition (δ13CCO2) agree well with ice core data. Modeled effects of AMOC-induced wind changes on the carbon and isotope cycles are small, suggesting that Southern Hemisphere westerly wind effects may have been less important for the global carbon cycle response during HS1 than previously thought. Our results indicate that during the early deglaciation the AMOC decreased for several thousand years. We propose that the observed early deglacial rise in atmospheric CO2 and the decrease in δ13CCO2 may have been dominated by an AMOC-induced decline of the ocean's biologically sequestered carbon storage.
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Da, Jiawei, Yi Ge Zhang, Gen Li, and Junfeng Ji. "Aridity-driven decoupling of δ13C between pedogenic carbonate and soil organic matter." Geology 48, no. 10 (June 12, 2020): 981–85. http://dx.doi.org/10.1130/g47241.1.
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Abstract Pedogenic carbonate is an invaluable archive for reconstructing continental paleoclimate and paleoecology. The δ13C of pedogenic carbonate (δ13Cc) has been widely used to document the rise and expansion of C4 plants over the Cenozoic. This application requires a fundamental presumption that in soil pores, soil-respired CO2 dominates over atmospheric CO2 during the formation of pedogenic carbonates. However, the decoupling between δ13Cc and δ13C of soil organic matter (δ13CSOM) have been observed, particularly in arid regions, suggesting that this presumption is not always valid. To evaluate the influence of atmospheric CO2 on soil δ13Cc, here we performed systematic δ13C analyses of paleosols across the Chinese Loess Plateau, with the sample ages spanning three intervals: the Holocene, the Late Pleistocene, and the mid-Pliocene warm period. Our paired δ13Cc and δ13CSOM data reveal broadly divergent trending patterns. Using a two-component CO2-mixing model, we show substantial incorporations of atmospheric CO2 (up to 60%) into soil pore space during carbonate precipitation. This result readily explains the enrichment of δ13Cc and its divergence from δ13CSOM. As a consequence, δ13C of pedogenic carbonates formed under semiarid and/or arid conditions are largely driven by regional aridity through its control on soil CO2 composition, and thus cannot be used to evaluate the relative abundance of C3 versus C4 plants. Nonetheless, these carbonates can be applied for atmospheric CO2 reconstructions, even for periods with low CO2 levels.
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Tao, Shizhen, Changwei Li, Weijiao Ma, Deliang Liu, Jingkui Mi, and Zhenglian Pang. "Geochemical analysis and origin of gas in volcanic reservoirs in the Songliao Basin." Energy Exploration & Exploitation 35, no. 3 (February 15, 2017): 295–314. http://dx.doi.org/10.1177/0144598717690089.
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Volcanic reservoirs are extensive in the Songliao Basin and mainly include intermediate-basic rocks in the northern part, intermediate-acidic rocks in Xujiaweizi in the southern part, and acidic rocks in the Jinglin block. The natural gas in the volcanic reservoirs of the Songliao Basin has a wide range of compositions, with alkanes being dominant in most cases, although carbon dioxide is dominant in some wells. Generally, the gas in the volcanic rocks near deep faults has high contents of carbon dioxide, whereas the natural gas in volcanic rocks far from faults has low carbon dioxide contents. The gas in the volcanic reservoirs is of multiple origins, including abiogenic gas of probable mantle origin (generally found in wells with high carbon dioxide contents) and organic gas mainly derived from organic matter in the basin. The abiogenic alkanes have δ13C values in the order of δ13C1 > δ13C2 > δ13C3 > δ13C4, which is opposite that of alkanes of organic origin. The 3He/4He ratios of the fluid inclusions from the volcanic reservoirs range from 0.286 × 10−6 to 7.33 × 10−6, with an average of 2.48 × 10−6, and the R/Ra ratios range from 0.26 to 5.24, with most values being greater than 1.0, indicating mixed origins of noble gases from the crust and the mantle. The gas in fluid inclusions from the volcanic reservoirs has δ13C1 values ranging from −17.1 to −28.7‰ (PDB), δ13C2 values ranging from −23.4 to −32.4‰ (mostly approximately −25‰), and δ13Cco2 values ranging from −10.97 to −21.73‰, which are significantly different from the isotopic compositions of the gas in the present reservoirs, suggesting that some abiogenic alkanes may have been charged into the reservoirs during the geologic history of the basin. The early charged CO2 is mainly organic in origin, while the abiogenic CO2 was charged during the main accumulation period, producing a mix of origins for the gas in the volcanic reservoirs of the Songliao Basin. The abiogenic alkanes, He, and CO2 in the natural gas indicate the addition of some abiogenic gas to the gas. According to the relationship between the distribution and attitude of volcanic rocks and faults, we found that the abiogenic gas reservoirs are located near fault zones, whereas the organic and mixed gas reservoirs are located far from fault zones. The geochemical study of natural gas is helpful in determining the origin and spatial distribution patterns of gas in deep volcanic reservoirs and for directing further gas exploration in the Songliao Basin.
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Meisel, Ove H., Joshua F. Dean, Jorien E. Vonk, Lukas Wacker, Gert-Jan Reichart, and Han Dolman. "Porewater <i>δ</i><sup>13</sup>C<sub>DOC</sub> indicates variable extent of degradation in different talik layers of coastal Alaskan thermokarst lakes." Biogeosciences 18, no. 7 (April 6, 2021): 2241–58. http://dx.doi.org/10.5194/bg-18-2241-2021.
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Abstract. Thermokarst lakes play an important role in permafrost environments by warming and insulating the underlying permafrost. As a result, thaw bulbs of unfrozen ground (taliks) are formed. Since these taliks remain perennially thawed, they are zones of increased degradation where microbial activity and geochemical processes can lead to increased greenhouse gas emissions from thermokarst lakes. It is not well understood though to what extent the organic carbon (OC) in different talik layers below thermokarst lakes is affected by degradation. Here, we present two transects of short sediment cores from two thermokarst lakes on the Arctic Coastal Plain of Alaska. Based on their physiochemical properties, two main talik layers were identified. A “lake sediment” is identified at the top with low density, sand, and silicon content but high porosity. Underneath, a “taberite” (former permafrost soil) of high sediment density and rich in sand but with lower porosity is identified. Loss on ignition (LOI) measurements show that the organic matter (OM) content in the lake sediment of 28±3 wt % (1σ, n=23) is considerably higher than in the underlying taberite soil with 8±6 wt % (1σ, n=35), but dissolved organic carbon (DOC) leaches from both layers in high concentrations: 40±14 mg L−1 (1σ, n=22) and 60±14 mg L−1 (1σ, n=20). Stable carbon isotope analysis of the porewater DOC (δ13CDOC) showed a relatively wide range of values from −30.74 ‰ to −27.11 ‰ with a mean of -28.57±0.92 ‰ (1σ, n=21) in the lake sediment, compared to a relatively narrow range of −27.58 ‰ to −26.76 ‰ with a mean of -27.59±0.83 ‰ (1σ, n=21) in the taberite soil (one outlier at −30.74 ‰). The opposite was observed in the soil organic carbon (SOC), with a narrow δ13CSOC range from −29.15 ‰ to −27.72 ‰ in the lake sediment (-28.56±0.36 ‰, 1σ, n=23) in comparison to a wider δ13CSOC range from −27.72 ‰ to −25.55 ‰ in the underlying taberite soil (-26.84±0.81 ‰, 1σ, n=21). The wider range of porewater δ13CDOC values in the lake sediment compared to the taberite soil, but narrower range of comparative δ13CSOC, along with the δ13C-shift from δ13CSOC to δ13CDOC indicates increased stable carbon isotope fractionation due to ongoing processes in the lake sediment. Increased degradation of the OC in the lake sediment relative to the underlying taberite is the most likely explanation for these differences in δ13CDOC values. As thermokarst lakes can be important greenhouse gas sources in the Arctic, it is important to better understand the degree of degradation in the individual talik layers as an indicator for their potential in greenhouse gas release, especially, as predicted warming of the Arctic in the coming decades will likely increase the number and extent (horizontal and vertical) of thermokarst lake taliks.
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Tschumi, T., F. Joos, M. Gehlen, and C. Heinze. "Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO<sub>2</sub> rise." Climate of the Past 7, no. 3 (July 22, 2011): 771–800. http://dx.doi.org/10.5194/cp-7-771-2011.
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Abstract. The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global 3-D ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.
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Tschumi, T., F. Joos, M. Gehlen, and C. Heinze. "Deep ocean ventilation, carbon isotopes, marine sedimentation and the deglacial CO<sub>2</sub> rise." Climate of the Past Discussions 6, no. 5 (September 27, 2010): 1895–958. http://dx.doi.org/10.5194/cpd-6-1895-2010.
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Abstract. The link between the atmospheric CO2 level and the ventilation state of the deep ocean is an important building block of the key hypotheses put forth to explain glacial-interglacial CO2 fluctuations. In this study, we systematically examine the sensitivity of atmospheric CO2 and its carbon isotope composition to changes in deep ocean ventilation, the ocean carbon pumps, and sediment formation in a global three-dimensional ocean-sediment carbon cycle model. Our results provide support for the hypothesis that a break up of Southern Ocean stratification and invigorated deep ocean ventilation were the dominant drivers for the early deglacial CO2 rise of ~35 ppm between the Last Glacial Maximum and 14.6 ka BP. Another rise of 10 ppm until the end of the Holocene is attributed to carbonate compensation responding to the early deglacial change in ocean circulation. Our reasoning is based on a multi-proxy analysis which indicates that an acceleration of deep ocean ventilation during the early deglaciation is not only consistent with recorded atmospheric CO2 but also with the reconstructed opal sedimentation peak in the Southern Ocean at around 16 ka BP, the record of atmospheric δ13CCO2, and the reconstructed changes in the Pacific CaCO3 saturation horizon.
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Tombros, S. F., K. Seymour, P. G. Spry, and T. A. Bonsall. "THE ISOTOPIC SIGNATURE OF THE MINERALIZING FLUID OF THE LAVRION CARBONATE-REPLACEMENT PB-ZN-AG DISTRICT." Bulletin of the Geological Society of Greece 43, no. 5 (July 31, 2017): 2406. http://dx.doi.org/10.12681/bgsg.11641.
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The Pb-Zn-Ag carbonate-replacement deposits in the Lavrion district are genetically related to a 7- 10 Ma-old granodiorite, felsic dikes and sills. These deposits are hosted in the Upper and Lower marble and schists of the Cyclades Blueschist unit and occur along the major Legraina detachment fault. Carbonate-replacement orebodies occur as “mantos” and veins, dominated by base metal sulfides and Ag, Bi, Sn, Sb, As, and Pb sulfosalts. Calculated carbon and oxygen isotope compositions of the hydrothermal fluid range from δ13CCO2 of -13.7 to 0.8 per mil and δ18OH2O of 4.2 to 27.4 per mil, at 400º, 350º, 320º, 300º, 250º and 200ºC. These isotopic compositions reveal water-torock ratios ranging from 4.8 to 52.6%, which reflect intense interaction of the ore fluid with the host rock in a water-dominated, transitional closed to open hydrothermal system. The range of δ34SH2S for sulfides in the deposits were from -8.5 to 6.8 per mil, for similar temperatures, whereas for barite-fluorite veins from δ34SH2S of -43.6 to -16.4 per mil, at 200º, 150º and 100ºC. This range implies that there was contribution from a magmatic sulfur component exsolved from the Plaka pluton, as well as contribution from a metasedimentary component. Based on the isotopic signature of sulfur for barite, the ranges from -6.7 to -7.6, comprising an increase in the fluid influx. Isotopic temperatures based on pyrite-galena and sphalerite-pyrite pairs revealed at least three major events of carbonate-replacement ore deposition, (i) at ~ 360º, (ii) 320º-280ºand (iii) 260º-200ºC.
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Fu, Deliang, Guosheng Xu, Li Ma, Fu Yang, Dan He, Zhonghui Duan, and Yu Ma. "Gas generation from coal: taking Jurassic coal in the Minhe Basin as an example." International Journal of Coal Science & Technology 7, no. 3 (April 23, 2020): 611–22. http://dx.doi.org/10.1007/s40789-020-00318-z.
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Abstract The gas generation features of coals at different maturities were studied by the anhydrous pyrolysis of Jurassic coal from the Minhe Basin in sealed gold tubes at 50 MPa. The gas component yields (C1, C2, C3, i-C4, n-C4, i-C5, n-C5, and CO2); the δ13C of C1, C2, C3, and CO2; and the mass of the liquid hydrocarbons (C6+) were measured. On the basis of these data, the stage changes of δ13C1, δ13C2, δ13C3, and δ13CO2 were calculated. The diagrams of δ13C1–δ13C2 vs ln (C1/C2) and δ13C2–δ13C1 vs δ13C3–δ13C2 were used to evaluate the gas generation features of the coal maturity stages. At the high maturity evolution stage (T > 527.6 °C at 2 °C/h), the stage change of δ13C1 and the CH4 yield are much higher than that of CO2, suggesting that high maturity coal could still generate methane. When T < 455 °C, CO2 is generated by breaking bonds between carbons and heteroatoms. The reaction between different sources of coke and water may be the reason for the complicated stage change in $$\delta^{{{13}}} {\text{C}}_{{{\text{CO}}_{{2}} }}$$ δ 13 C CO 2 when the temperature was higher than 455 °C. With increasing pyrolysis temperature, δ13C1–δ13C2 vs ln (C1/C2) has four evolution stages corresponding to the early stage of breaking bonds between carbon and hetero atoms, the later stage of breaking bonds between carbon and hetero atoms, the cracking of C6+ and coal demethylation, and the cracking of C2–5. The δ13C2–δ13C1 vs δ13C3–δ13C2 has three evolution stages corresponding to the breaking bonds between carbon and hetero atoms, demethylation and cracking of C6+, and cracking of C2–5.
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Zimmer, Martin, Bettina Strauch, Axel Zirkler, Samuel Niedermann, and Andrea Vieth-Hillebrand. "Origin and Evolution of Gas in Salt Beds of a Potash Mine." Advances in Geosciences 54 (September 22, 2020): 15–21. http://dx.doi.org/10.5194/adgeo-54-15-2020.
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Abstract. In order to better understand both the fixation and migration of gases in evaporites, investigations were performed in five horizontal boreholes drilled in an underground potash seam. One of the five boreholes was pressurised with Ar and the pressure signal and chemical gas composition were then monitored in the other holes. A further gas sample from a separate borehole was characterised for the chemical composition and for noble gas and carbon isotopic compositions to conclude on the origin and evolution of the gas in the salt rocks. Additionally, in order to determine the total gas amount in the salt rocks, a potash-bearing salt sample was dissolved in water and from the mass of 1 kg salt sample, 9 cm(STP)3 gas was liberated. Due to the relatively large permeability of the disturbed salt rocks (4×10-17 to 4×10-18 m2), which is about 3–4 orders of magnitude higher than in undisturbed salt rocks, we assume that the migration of injected Ar most likely takes place along micro-cracks produced during the mining process. The geogenic gas concentrations found in the observation holes correlate directly to the Ar concentration, suggesting that they were stripped from the rocks in between the holes. According to the He-isotopes (0.092 Ra), a small contribution of mantle gas can be found in the geogenic salt gas. The δ13CCO2-isotopic composition (−7.8 ‰ to 6.7 ‰) indicates a magmatic source, whereas 13C∕12C of CH4 (−22.2 ‰ to −21.3 ‰) is typical for a thermogenic gas. We assume that CO2 and CH4 are related to volcanic activity, where they isotopically equilibrated at temperatures of 513 to 519 ∘C about 15–16 Ma ago.
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Ramnarine, R., C. Wagner-Riddle, K. E. Dunfield, and R. P. Voroney. "Contributions of carbonates to soil CO2 emissions." Canadian Journal of Soil Science 92, no. 4 (May 2012): 599–607. http://dx.doi.org/10.4141/cjss2011-025.
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Ramnarine, R., Wagner-Riddle, C., Dunfield, K. E. and Voroney, R. P. 2012. Contributions of carbonates to soil CO 2 emissions. Can. J. Soil Sci. 92: 599–607. Carbon dioxide (CO2) is released in soil as a by-product of microbial and root respiration, but soil carbonates may also be a source of CO2 emissions in calcareous soils. Global estimates of inorganic carbon range from 700 to 900 Pg as carbonates stored in soils, representing a significant potential source of CO2 to the atmosphere. While previous studies have focused on the total CO2 efflux from the soil, our goal was to identify the various sources and their contribution to total CO2 emissions, by measuring the isotopic signature of the CO2 emitted from the soil. Calcareous Luvisolic silt loam soil samples were obtained from conventional tillage (CT) and no-tillage (NT) plots in southern Ontario, Canada. Soil samples (root- and residue-free) were laboratory-incubated for 14 d and the isotopic signature of the CO2 (δ13CCO2) released was analyzed using isotope ratio mass spectrometry. Isotopic measurement was essential in quantifying the abiotic CO2 production from carbonates, due to the unique δ13C signature of carbonates and soil organic matter. A two-end member mixing model was used to estimate the proportion of CO2 evolved from soil carbonates and soil organic matter decomposition. Analysis of emitted CO2 collected after the 14-d incubation indicate that the proportion of CO2 originating from soil inorganic carbon was 62 to 74% for CT soil samples, and 64 to 80% for NT soil samples. Further work is recommended in the quantification of CO2 emissions from calcareous soils, and to determine the transferability of laboratory results to field studies.
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Zimmer, Martin, Alexandra Szizybalski, Ben Norden, Andrea Vieth-Hillebrand, and Axel Liebscher. "Monitoring of the gas composition and stable carbon isotopes during side track drilling in Ktzi 203 at the Ketzin CO<sub>2</sub> storage pilot site, Germany." Advances in Geosciences 45 (July 16, 2018): 7–11. http://dx.doi.org/10.5194/adgeo-45-7-2018.
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Abstract. Between 2004 and 2017 the storage of CO2 in a deep saline aquifer was investigated in detail at the Ketzin pilot site close to Berlin. The series of research projects, coordinated by the GFZ German Research Centre for Geosciences, also incorporated an interdisciplinary scientific monitoring program during all phases of the storage process which provided a reliable insight into the overall behaviour of CO2 during storage in the underground. Prior to abandonment and cementing of the Ktzi 203 observation well, two side tracks were cored from 643.1 to 662.6 m and from 624.5 to 654.5 m, respectively. The drilled sections included the transition zone from the cap rock (Weser Formation) to the reservoir in the Stuttgart Formation which had been exposed to the injected CO2 for more than nine years. During the drilling operation continuous mud gas logging was performed by applying a mud gas separator, a mass spectrometer and a CO2 isotope-analyser for continuous separation and analyses of the extracted gas. Drill cores were shrink-wrapped with plastic foil to collect discharging gases. CO2 concentrations in the cap rock were relatively low and their isotopic compositions were in accord with typical Upper Triassic formation fluids providing no evidence for a significant CO2 infiltration from the underlying reservoir into the cap rock. A clear increase in the CO2 concentration and a shift in δ13CCO2 between the cap rock and the reservoir indicated the presence of the injected CO2 in the sandstone formation. The comparison with samples collected five years earlier in 2012 showed similar concentrations and isotopic depth trends which indicate a rather stagnant CO2 plume at depth and the tightness and integrity of the cap rock and the borehole cementing.
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Ryan, Brooks H., Stephen E. Kaczmarek, and John M. Rivers. "Multi-episodic recrystallization and isotopic resetting of early-diagenetic dolomites in near-surface settings." Journal of Sedimentary Research 91, no. 1 (January 31, 2021): 146–66. http://dx.doi.org/10.2110/jsr.2020.056.
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ABSTRACT The lower Eocene Rus Formation in Qatar reflects carbonate deposition in a semirestricted to fully restricted marine setting on a shallow ramp. Petrographic, mineralogical, and geochemical evidence from three research cores show early diagenesis has extensively altered nearly every petrological attribute of these rocks despite not having been deeply buried. In southern Qatar, the lower Rus (Traina Mbr.) consists of fabric-retentive dolomite intervals that preserve mudstone, wackestone, and packstone textures that are interbedded with depositional gypsum beds. In northern Qatar, the same member is dominated by fabric-destructive planar-e dolomite, and evaporites are absent. In both northern and southern Qatar, the upper Rus (Al Khor Mbr.) is composed of fabric-retentive dolomite intervals as well as limestone intervals rich with Microcodium textures that display evidence of dedolomitization. Geochemical analysis reveals that the limestones have an average δ18Ocal of –10.73‰ VPDB and δ13Ccal of –7.84‰ VPDB, whereas average dolomite δ18Odol is significantly higher (–1.06‰ VPDB) but δ13Cdol values (–3.04‰ VPDB; range –10 to 0‰) overlap with δ13Ccal values. Additionally, δ13Cdol trends toward normal marine values with depth away from the calcite–dolomite contact in all three cores. Petrographic observations demonstrate that dolomite crystals are commonly included in calcite and partially to completely replaced by calcite in these intervals and suggests that dolomite formed before calcite in the Microcodium-bearing intervals. Furthermore, the dolomites are commonly cemented by gypsum in the Traina Mbr. in southern Qatar, suggesting that dolomitization may have also occurred before, or concurrent with, bedded gypsum formation and indicates that dolomitization occurred early. Early dolomites were subsequently replaced by Microcodium-bearing limestones at and immediately below paleo-exposure surfaces, and at greater depths recrystallized in mixed marine–meteoric fluids, producing a negative δ13Cdol signature that trends toward more positive values away from the limestone–dolomite contact. Lastly, the dolomites underwent another phase of recrystallization in either marine-dominated fluids or possibly a well-mixed aquifer setting, resulting in a near-0‰ δ18Odol signature but retaining the negative δ13C signature. These findings thus have implications for reconstructing the diagenetic history of carbonate rocks, as they suggest that early diagenesis of carbonates can be extremely complex, resulting in multiple stages of mineral replacement and isotopic exchange in meteoric and shallow marine fluids before significant burial. Furthermore, this study shows that dolomitization of a limestone does not necessarily prevent additional early diagenesis and multiple recrystallization events. Lastly, it emphasizes the importance of incorporating petrographic observations with geochemical data when interpreting the diagenetic history of carbonate rocks.
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Marques, J. M., P. M. Carreira, L. A. Aires-Barros, F. A. Monteiro Santos, M. Antunes da Silva, and P. Represas. "Assessment of Chaves Low-Temperature CO2-Rich Geothermal System (N-Portugal) Using an Interdisciplinary Geosciences Approach." Geofluids 2019 (February 25, 2019): 1–24. http://dx.doi.org/10.1155/2019/1379093.
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This paper reviews the results of a multi- and interdisciplinary approach, including geological, geomorphological, tectonic, geochemical, isotopic, and geophysical studies, on the assessment of a Chaves low-temperature (77°C) CO2-rich geothermal system, occurring in the northern part of the Portuguese mainland. This low-temperature geothermal system is ascribed to an important NNE-trending fault, and the geomorphology is dominated by the “Chaves Depression,” a graben whose axis is oriented NNE-SSW. The study region is situated in the tectonic unit of the Middle Galicia/Trás-os-Montes subzone of the Central Iberian Zone of the Hesperic Massif comprising mainly Variscan granites and Paleozoic metasediments. Chaves low-temperature CO2-rich geothermal waters belong to the Na-HCO3-CO2-rich-type waters, with pH≈7. Total dissolved solids range between 1600 and 1850 mg/L. Free CO2 is of about 500 mg/L. The results of SiO2 and K2/Mg geothermometers give estimations of reservoir temperature around 120°C. δ18O and δ2H values of Chaves low-temperature CO2-rich geothermal waters indicate a meteoric origin for these waters. No significant 18O-shift was observed, consistent with the results from the chemical geothermometry. δ13CCO2 values vary between −7.2 and −5.1‰ vs. V-PDB, and CO2/3He ratios range from 1×108 to 1×109, indicating a deep (upper mantle) source for the CO2. 3He/4He ratios are of about 0.9 (R/Ra). The Chaves low-temperature CO2-rich geothermal waters present similar 87Sr/86Sr ratios (between 0.728035 and 0.716713) to those of the plagioclases from granitic rocks (between 0.72087 and 0.71261) suggesting that water mineralization is strongly ascribed to Na-plagioclase hydrolysis. Geophysical methods (e.g., resistivity and AMT soundings) detected conductive zones concentrated in the central part of the Chaves graben as a result of temperature combined with the salinity of the Chaves low-temperature CO2-rich geothermal waters in fractured and permeable rock formations. This paper demonstrates the added value of an integrated and multi- and interdisciplinary approach for a given geothermal site characterization, which could be useful for other case studies linking the assessment of low-temperature CO2-rich geothermal waters and cold CO2-rich mineral waters emerging in a same region.
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Jardine, Kolby J., Joseph Lei, Suman Som, Daisy Souza, Chaevien S. Clendinen, Hardeep Mehta, Pubudu Handakumbura, Markus Bill, and Robert P. Young. "Light-Dependence of Formate (C1) and Acetate (C2) Transport and Oxidation in Poplar Trees." Plants 11, no. 16 (August 9, 2022): 2080. http://dx.doi.org/10.3390/plants11162080.
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Although apparent light inhibition of leaf day respiration is a widespread reported phenomenon, the mechanisms involved, including utilization of alternate respiratory pathways and substrates and light inhibition of TCA cycle enzymes are under active investigation. Recently, acetate fermentation was highlighted as a key drought survival strategy mediated through protein acetylation and jasmonate signaling. Here, we evaluate the light-dependence of acetate transport and assimilation in Populus trichocarpa trees using the dynamic xylem solution injection (DXSI) method developed here for continuous studies of C1 and C2 organic acid transport and light-dependent metabolism. Over 7 days, 1.0 L of [13C]formate and [13C2]acetate solutions were delivered to the stem base of 2-year old potted poplar trees, while continuous diurnal observations were made in the canopy of CO2, H2O, and isoprene gas exchange together with δ13CO2. Stem base injection of 10 mM [13C2]acetate induced an overall pattern of canopy branch headspace 13CO2 enrichment (δ13CO2 +27‰) with a diurnal structure in δ13CO2 reaching a mid-day minimum followed by a maximum shortly after darkening where δ13CO2 values rapidly increased up to +12‰. In contrast, 50 mM injections of [13C]formate were required to reach similar δ13CO2 enrichment levels in the canopy with δ13CO2 following diurnal patterns of transpiration. Illuminated leaves of detached poplar branches pretreated with 10 mM [13C2]acetate showed lower δ13CO2 (+20‰) compared to leaves treated with 10 mM [13C]formate (+320‰), the opposite pattern observed at the whole plant scale. Following dark/light cycles at the leaf-scale, rapid, strong, and reversible enhancements in headspace δ13CO2 by up to +60‰ were observed in [13C2]acetate-treated leaves which showed enhanced dihydrojasmonic acid and TCA cycle intermediate concentrations. The results are consistent with acetate in the transpiration stream as an effective activator of the jasmonate signaling pathway and respiratory substrate. The shorter lifetime of formate relative to acetate in the transpiration stream suggests rapid formate oxidation to CO2 during transport to the canopy. In contrast, acetate is efficiently transported to the canopy where an increased allocation towards mitochondrial dark respiration occurs at night. The results highlight the potential for an effective integration of acetate into glyoxylate and TCA cycles and the light-inhibition of citrate synthase as a potential regulatory mechanism controlling the diurnal allocation of acetate between anabolic and catabolic processes.
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Ballantyne, A. P., J. B. Miller, I. T. Baker, P. P. Tans, and J. W. C. White. "Novel applications of carbon isotopes in atmospheric CO<sub>2</sub>: what can atmospheric measurements teach us about processes in the biosphere?" Biogeosciences Discussions 8, no. 3 (May 12, 2011): 4603–31. http://dx.doi.org/10.5194/bgd-8-4603-2011.
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Abstract. Conventionally, measurements of carbon isotopes in atmospheric CO2 (δ13CO2) have been used to partition fluxes between terrestrial and ocean carbon pools. However, novel analytical approaches combined with an increase in the spatial extent and frequency of δ13CO2 measurements allow us to conduct a global analysis of δ13CO2 variability to infer the isotopic composition of source CO2 to the atmosphere (δs). This global analysis yields coherent seasonal patterns of isotopic enrichment. Our results indicate that seasonal values of δs are more highly correlated with vapor pressure deficit (r=0.404) than relative humidity (r=0.149). We then evaluate two widely used stomatal conductance models and determine that Leuning Model, which is primarily driven by vapor pressure deficit is more effective globally at predicting δs (RMSE = 1.7 ‰) than the Ball-Berry model, which is driven by relative humidity (RMSE = 2.8) ‰. Thus stomatal conductance on a global scale may be more sensitive to changes in vapor pressure deficit than relative humidity. This approach highlights a new application of using δ13CO2 measurements to test global models.
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Ballantyne, A. P., J. B. Miller, I. T. Baker, P. P. Tans, and J. W. C. White. "Novel applications of carbon isotopes in atmospheric CO<sub>2</sub>: what can atmospheric measurements teach us about processes in the biosphere?" Biogeosciences 8, no. 10 (October 31, 2011): 3093–106. http://dx.doi.org/10.5194/bg-8-3093-2011.
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Abstract. Conventionally, measurements of carbon isotopes in atmospheric CO2 (δ13CO2) have been used to partition fluxes between terrestrial and ocean carbon pools. However, novel analytical approaches combined with an increase in the spatial extent and frequency of δ13CO2 measurements allow us to conduct a global analysis of δ13CO2 variability to infer the isotopic composition of source CO2 to the atmosphere (δs). This global analysis yields coherent seasonal patterns of isotopic enrichment. Our results indicate that seasonal values of δs are more highly correlated with vapor pressure deficit (r = 0.404) than relative humidity (r = 0.149). We then evaluate two widely used stomatal conductance models and determine that the Leuning Model, which is primarily driven by vapor pressure deficit is more effective globally at predicting δs (RMSE = 1.6‰) than the Ball-Woodrow-Berry model, which is driven by relative humidity (RMSE = 2.7‰). Thus stomatal conductance on a global scale may be more sensitive to changes in vapor pressure deficit than relative humidity. This approach highlights a new application of using δ13CO2 measurements to validate global models.
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Henley, S. F., A. L. Annett, R. S. Ganeshram, D. S. Carson, K. Weston, X. Crosta, A. Tait, J. Dougans, A. E. Fallick, and A. Clarke. "Factors influencing the stable carbon isotopic composition of suspended and sinking organic matter in the coastal Antarctic sea ice environment." Biogeosciences 9, no. 3 (March 27, 2012): 1137–57. http://dx.doi.org/10.5194/bg-9-1137-2012.
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Abstract. A high resolution time-series analysis of stable carbon isotopic signatures in particulate organic carbon (δ13CPOC) and associated biogeochemical parameters in sea ice and surface waters provides an insight into the factors affecting δ13CPOC in the coastal western Antarctic Peninsula sea ice environment. The study covers two austral summer seasons in Ryder Bay, northern Marguerite Bay between 2004 and 2006. A shift in diatom species composition during the 2005/06 summer bloom to near-complete biomass dominance of Proboscia inermis is strongly correlated with a large ~10 ‰ negative isotopic shift in δ13CPOC that cannot be explained by a concurrent change in concentration or isotopic signature of CO2. We hypothesise that the δ13CPOC shift may be driven by the contrasting biochemical mechanisms and utilisation of carbon-concentrating mechanisms (CCMs) in different diatom species. Specifically, very low δ13CPOC in P. inermis may be caused by the lack of a CCM, whilst some diatom species abundant at times of higher δ13CPOC may employ CCMs. These short-lived yet pronounced negative δ13CPOC excursions drive a 4 ‰ decrease in the seasonal average δ13CPOC signal, which is transferred to sediment traps and core-top sediments and consequently has the potential for preservation in the sedimentary record. This 4 ‰ difference between seasons of contrasting sea ice conditions and upper water column stratification matches the full amplitude of glacial-interglacial Southern Ocean δ13CPOC variability and, as such, we invoke phytoplankton species changes as a potentially important factor influencing sedimentary δ13CPOC. We also find significantly higher δ13CPOC in sea ice than surface waters, consistent with autotrophic carbon fixation in a semi-closed environment and possible contributions from post-production degradation, biological utilisation of HCO3− and production of exopolymeric substances. This study demonstrates the importance of surface water diatom speciation effects and isotopically heavy sea ice-derived material for δ13CPOC in Antarctic coastal environments and underlying sediments, with consequences for the utility of diatom-based δ13CPOC in the sedimentary record.
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Henley, S. F., A. L. Annett, R. S. Ganeshram, D. S. Carson, K. Weston, X. Crosta, A. Tait, J. Dougans, A. E. Fallick, and A. Clarke. "Factors influencing the stable carbon isotopic composition of suspended and sinking organic matter in the coastal Antarctic sea ice environment." Biogeosciences Discussions 8, no. 6 (November 16, 2011): 11041–88. http://dx.doi.org/10.5194/bgd-8-11041-2011.
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Abstract. A high resolution time-series analysis of stable carbon isotopic signatures in particulate organic carbon (δ13CPOC) and associated biogeochemical parameters in sea ice and surface waters provides an insight into the factors affecting δ13CPOC in the coastal western Antarctic Peninsula (WAP) sea ice environment. The study covers two austral summer seasons in Ryder Bay, northern Marguerite Bay between 2004 and 2006. A shift in diatom species composition during the 2005/2006 summer bloom to near-complete biomass dominance of Proboscia inermis is strongly correlated with a large ~10‰ negative isotopic shift in δ13CPOC that cannot be explained by a concurrent change in concentration or isotopic signature of CO2. We hypothesise that the δ13CPOC shift may be driven by the contrasting biochemical mechanisms and utilisation of carbon-concentrating mechanisms in different diatom species. These short-lived yet pronounced negative δ13CPOC excursions drive a 4‰ decrease in the seasonal average δ13CPOC signal, which is transferred to sediment traps and core-top sediments and consequently has the potential for preservation in the sedimentary record. This 4‰ difference between seasons of contrasting sea ice conditions and upper water column stratification matches the full amplitude of glacial-interglacial Southern Ocean δ13CPOC variability and, as such, we invoke phytoplankton species changes as a potentially important factor influencing sedimentary δ13CPOC. We also find significantly higher δ13CPOC in sea ice than surface waters, consistent with autotrophic carbon fixation in a semi-closed environment and possible contributions from post-production degradation, biological utilisation of HCO3- and production of exopolymeric substances (EPS). This study demonstrates the importance of surface water diatom speciation effects and isotopically heavy sea ice-derived material for δ13CPOC in Antarctic coastal environments and underlying sediments, with consequences for the utility of diatom-based δ13CPOC in the sedimentary record.
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Stinchcomb, Gary E., Timothy C. Messner, Forrest C. Williamson, Steven G. Driese, and Lee C. Nordt. "Climatic and human controls on Holocene floodplain vegetation changes in eastern Pennsylvania based on the isotopic composition of soil organic matter." Quaternary Research 79, no. 3 (May 2013): 377–90. http://dx.doi.org/10.1016/j.yqres.2013.02.004.
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AbstractA paleoenvironmental time-series spanning the Holocene was constructed using 29 radiocarbon ages and 149 standardized δ13Csom values from alluvial terrace profiles along the middle Delaware River valley. There is good agreement between increasing δ13Csom and Panicoideae phytolith concentrations, suggesting that variations in C4 biomass are a major contributor to changes in the soil δ13C. A measurement error deconvolution curve over time reveals two isotope stages (II–I), with nine sub-stages exhibiting variations in average δ13Csom (average %C4). Stage II, ~ 10.7–4.3 ka, shows above-average δ13Csom (increase %C4) values with evidence of an early Holocene warming and dry interval (sub-stage IIb, 9.8–8.3 ka) that coincides with rapid warming and cool-dry abrupt climate-change events. Sub-stage IId, 7.0–4.3 ka, is an above average δ13Csom (increase %C4) interval associated with the mid-Holocene warm-dry hypsithermal. The Stage II–I shift at 4.3 ka documents a transition toward below average δ13Csom (decrease %C4) values and coincides with decreasing insolation and hydroclimatic change. Sub-stages Ib and Id (above average %C4) coincide with the first documented occurrence of maize in the northeastern USA and a substantial increase in human population during the Late Woodland. These associations suggest that people influenced δ13Csom during the late Holocene.
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Kelly, Bryce F. J., Xinyi Lu, Stephen J. Harris, Bruno G. Neininger, Jorg M. Hacker, Stefan Schwietzke, Rebecca E. Fisher, et al. "Atmospheric methane isotopes identify inventory knowledge gaps in the Surat Basin, Australia, coal seam gas and agricultural regions." Atmospheric Chemistry and Physics 22, no. 23 (December 12, 2022): 15527–58. http://dx.doi.org/10.5194/acp-22-15527-2022.
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Abstract. In-flight measurements of atmospheric methane (CH4(a)) and mass balance flux quantification studies can assist with verification and improvement in the UNFCCC National Inventory reported CH4 emissions. In the Surat Basin gas fields, Queensland, Australia, coal seam gas (CSG) production and cattle farming are two of the major sources of CH4 emissions into the atmosphere. Because of the rapid mixing of adjacent plumes within the convective boundary layer, spatially attributing CH4(a) mole fraction readings to one or more emission sources is difficult. The primary aims of this study were to use the CH4(a) isotopic composition (δ13CCH4(a)) of in-flight atmospheric air (IFAA) samples to assess where the bottom–up (BU) inventory developed specifically for the region was well characterised and to identify gaps in the BU inventory (missing sources or over- and underestimated source categories). Secondary aims were to investigate whether IFAA samples collected downwind of predominantly similar inventory sources were useable for characterising the isotopic signature of CH4 sources (δ13CCH4(s)) and to identify mitigation opportunities. IFAA samples were collected between 100–350 m above ground level (m a.g.l.) over a 2-week period in September 2018. For each IFAA sample the 2 h back-trajectory footprint area was determined using the NOAA HYSPLIT atmospheric trajectory modelling application. IFAA samples were gathered into sets, where the 2 h upwind BU inventory had > 50 % attributable to a single predominant CH4 source (CSG, grazing cattle, or cattle feedlots). Keeling models were globally fitted to these sets using multiple regression with shared parameters (background-air CH4(b) and δ13CCH4(b)). For IFAA samples collected from 250–350 m a.g.l. altitude, the best-fit δ13CCH4(s) signatures compare well with the ground observation: CSG δ13CCH4(s) of −55.4 ‰ (confidence interval (CI) 95 % ± 13.7 ‰) versus δ13CCH4(s) of −56.7 ‰ to −45.6 ‰; grazing cattle δ13CCH4(s) of −60.5 ‰ (CI 95 % ± 15.6 ‰) versus −61.7 ‰ to −57.5 ‰. For cattle feedlots, the derived δ13CCH4(s) (−69.6 ‰, CI 95 % ± 22.6 ‰), was isotopically lighter than the ground-based study (δ13CCH4(s) from −65.2 ‰ to −60.3 ‰) but within agreement given the large uncertainty for this source. For IFAA samples collected between 100–200 m a.g.l. the δ13CCH4(s) signature for the CSG set (−65.4 ‰, CI 95 % ± 13.3 ‰) was isotopically lighter than expected, suggesting a BU inventory knowledge gap or the need to extend the population statistics for CSG δ13CCH4(s) signatures. For the 100–200 m a.g.l. set collected over grazing cattle districts the δ13CCH4(s) signature (−53.8 ‰, CI 95 % ± 17.4 ‰) was heavier than expected from the BU inventory. An isotopically light set had a low δ13CCH4(s) signature of −80.2 ‰ (CI 95 % ± 4.7 ‰). A CH4 source with this low δ13CCH4(s) signature has not been incorporated into existing BU inventories for the region. Possible sources include termites and CSG brine ponds. If the excess emissions are from the brine ponds, they can potentially be mitigated. It is concluded that in-flight atmospheric δ13CCH4(a) measurements used in conjunction with endmember mixing modelling of CH4 sources are powerful tools for BU inventory verification.
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Lu, Xinyi, Stephen J. Harris, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Thomas Röckmann, et al. "Isotopic signatures of major methane sources in the coal seam gas fields and adjacent agricultural districts, Queensland, Australia." Atmospheric Chemistry and Physics 21, no. 13 (July 14, 2021): 10527–55. http://dx.doi.org/10.5194/acp-21-10527-2021.
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Abstract. In regions where there are multiple sources of methane (CH4) in close proximity, it can be difficult to apportion the CH4 measured in the atmosphere to the appropriate sources. In the Surat Basin, Queensland, Australia, coal seam gas (CSG) developments are surrounded by cattle feedlots, grazing cattle, piggeries, coal mines, urban centres and natural sources of CH4. The characterization of carbon (δ13C) and hydrogen (δD) stable isotopic composition of CH4 can help distinguish between specific emitters of CH4. However, in Australia there is a paucity of data on the various isotopic signatures of the different source types. This research examines whether dual isotopic signatures of CH4 can be used to distinguish between sources of CH4 in the Surat Basin. We also highlight the benefits of sampling at nighttime. During two campaigns in 2018 and 2019, a mobile CH4 monitoring system was used to detect CH4 plumes. Sixteen plumes immediately downwind from known CH4 sources (or individual facilities) were sampled and analysed for their CH4 mole fraction and δ13CCH4 and δDCH4 signatures. The isotopic signatures of the CH4 sources were determined using the Keeling plot method. These new source signatures were then compared to values documented in reports and peer-reviewed journal articles. In the Surat Basin, CSG sources have δ13CCH4 signatures between −55.6 ‰ and −50.9 ‰ and δDCH4 signatures between −207.1 ‰ and −193.8 ‰. Emissions from an open-cut coal mine have δ13CCH4 and δDCH4 signatures of -60.0±0.6 ‰ and -209.7±1.8 ‰ respectively. Emissions from two ground seeps (abandoned coal exploration wells) have δ13CCH4 signatures of -59.9±0.3 ‰ and -60.5±0.2 ‰ and δDCH4 signatures of -185.0±3.1 ‰ and -190.2±1.4 ‰. A river seep had a δ13CCH4 signature of -61.2±1.4 ‰ and a δDCH4 signature of -225.1±2.9 ‰. Three dominant agricultural sources were analysed. The δ13CCH4 and δDCH4 signatures of a cattle feedlot are -62.9±1.3 ‰ and -310.5±4.6 ‰ respectively, grazing (pasture) cattle have δ13CCH4 and δDCH4 signatures of -59.7±1.0 ‰ and -290.5±3.1 ‰ respectively, and a piggery sampled had δ13CCH4 and δDCH4 signatures of -47.6±0.2 ‰ and -300.1±2.6 ‰ respectively, which reflects emissions from animal waste. An export abattoir (meat works and processing) had δ13CCH4 and δDCH4 signatures of -44.5±0.2 ‰ and -314.6±1.8 ‰ respectively. A plume from a wastewater treatment plant had δ13CCH4 and δDCH4 signatures of -47.6±0.2 ‰ and -177.3±2.3 ‰ respectively. In the Surat Basin, source attribution is possible when both δ13CCH4 and δDCH4 are measured for the key categories of CSG, cattle, waste from feedlots and piggeries, and water treatment plants. Under most field situations using δ13CCH4 alone will not enable clear source attribution. It is common in the Surat Basin for CSG and feedlot facilities to be co-located. Measurement of both δ13CCH4 and δDCH4 will assist in source apportionment where the plumes from two such sources are mixed.
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Guo, Na, Shijie Lv, Guangyi Lv, Xuebao Xu, Hongyun Yao, Zhihui Yu, Xiao Qiu, Zhanyi Wang, and Chengjie Wang. "Effects of Warming and Precipitation on Soil CO2 Flux and Its Stable Carbon Isotope Composition in the Temperate Desert Steppe." Sustainability 14, no. 6 (March 12, 2022): 3351. http://dx.doi.org/10.3390/su14063351.
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The stable carbon (C) isotope of soil CO2 efflux (δ13CO2e) is closely associated with soil C dynamics, which have a complex feedback relationship with climate. Three levels of warming (T0: ambient temperature (15.7 °C); T1: T0 + 2 °C; T2: T0 + 4 °C) were combined with three levels of increased precipitation (W0: ambient precipitation (245.2 mm); W1: W0 + 25%; W2: W0 + 50%) in order to quantify soil CO2 flux and its δ13CO2e values under nine treatment conditions (T0W0, T0W1, T0W2, T1W0, T1W1, T1W2, T2W0, T2W1, and T2W2) in desert steppe in an experimental beginning in 2015. A non-steady state chamber system relying on Keeling plots was used to estimate δ13CO2e. The temperature (ST) and moisture (SM) of soil as well as soil organic carbon content (SOC) and δ13C values (δ13Csoil) were tested in order to interpret variations in soil CO2 efflux and δ13CO2e. Sampling was carried out during the growing season in 2018 and 2019. During the experiment, the ST and SM correspondingly increased due to warming and increased precipitation. CO2 flux ranged from 37 to 1103 mg m−2·h−1, and emissions peaked in early August in the desert steppe. Warming of 2 °C to 4 °C stimulated a 14% to 30.9% increase in soil CO2 efflux and a 0.4‰ to 1.8‰ enrichment in δ13CO2e, respectively. Increased precipitation raised soil CO2 efflux by 14% to 19.3%, and decreased δ13CO2e by 0.5‰ to 0.9‰. There was a positive correlation between soil CO2 efflux and ST and SOC indicating that ST affected soil CO2 efflux by changing SOC content. Although the δ13CO2e was positively correlated with ST, it was negatively correlated to SM. The decline of δ13CO2e with soil moisture was predominantly due to intensified and increased diffusive fractionation. The mean δ13CO2e value (−20.2‰) was higher than that of the soil carbon isotope signature at 0–20 cm (δ13Csoil = −22.7‰). The difference between δ13CO2e and δ13Csoil (Δe-s) could be used to evaluate the likelihood of substrate utilization. 13C enriched stable C pools were more likely to be utilized below 20 cm under warming of 2 °C in the desert steppe. Moreover, the interaction of T × W neither altered the CO2 emitted by soil nor the δ13CO2e or Δe-s, indicating that warming combined with precipitation may alleviate the SOC oxidation of soil enriched in 13C in the desert steppe.
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Kayler, Zachary E., Lisa Ganio, Mark Hauck, Thomas G. Pypker, Elizabeth W. Sulzman, Alan C. Mix, and Barbara J. Bond. "Bias and uncertainty of δ13CO2 isotopic mixing models." Oecologia 163, no. 1 (December 31, 2009): 227–34. http://dx.doi.org/10.1007/s00442-009-1531-6.
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van der Laan-Luijkx, I. T., S. van der Laan, C. Uglietti, M. F. Schibig, R. E. M. Neubert, H. A. J. Meijer, W. A. Brand, et al. "Atmospheric CO<sub>2</sub>, δ(O<sub>2</sub>/N<sub>2</sub>) and δ<sup>13</sup>CO<sub>2</sub> measurements at Jungfraujoch, Switzerland: results from a flask sampling intercomparison program." Atmospheric Measurement Techniques Discussions 5, no. 5 (September 26, 2012): 7293–322. http://dx.doi.org/10.5194/amtd-5-7293-2012.
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Abstract. We present results from an intercomparison program of CO2, δ(O2/N2) and δ13CO2 measurements from atmospheric flask samples. Flask samples are collected on a bi-weekly basis at the High Altitude Research Station Jungfraujoch in Switzerland for three European laboratories: the University of Bern, Switzerland, the University of Groningen, the Netherlands and the Max Planck Institute for Biogeochemistry in Jena, Germany. Almost 4 yr of measurements of CO2, δ(O2/N2) and δ13CO2 are compared in this paper to assess the measurement compatibility of the three laboratories. While the average difference for the CO2 measurements between the laboratories in Bern and Jena meets the required compatibility goal as defined by the World Meteorological Organisation, the standard deviation of the average differences between all laboratories is not within the required goal. However, the obtained annual trend and seasonalities are the same within their estimated uncertainties. For δ(O2/N2) significant differences are observed between the three laboratories. The comparison for δ13CO2 yields the least compatible results and the required goals are not met between the three laboratories. Our study shows the importance of regular intercomparison exercises to identify potential biases between laboratories and the need to improve the quality of atmospheric measurements.
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van der Laan-Luijkx, I. T., S. van der Laan, C. Uglietti, M. F. Schibig, R. E. M. Neubert, H. A. J. Meijer, W. A. Brand, et al. "Atmospheric CO<sub>2</sub>, δ(O<sub>2</sub>/N<sub>2</sub>) and δ<sup>13</sup>CO<sub>2</sub> measurements at Jungfraujoch, Switzerland: results from a flask sampling intercomparison program." Atmospheric Measurement Techniques 6, no. 7 (July 30, 2013): 1805–15. http://dx.doi.org/10.5194/amt-6-1805-2013.
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Abstract. We present results from an intercomparison program of CO2, δ(O2/N2) and δ13CO2 measurements from atmospheric flask samples. Flask samples are collected on a bi-weekly basis at the High Altitude Research Station Jungfraujoch in Switzerland for three European laboratories: the University of Bern, Switzerland, the University of Groningen, the Netherlands and the Max Planck Institute for Biogeochemistry in Jena, Germany. Almost 4 years of measurements of CO2, δ(O2/N2) and δ13CO2 are compared in this paper to assess the measurement compatibility of the three laboratories. While the average difference for the CO2 measurements between the laboratories in Bern and Jena meets the required compatibility goal as defined by the World Meteorological Organization, the standard deviation of the average differences between all laboratories is not within the required goal. However, the obtained annual trend and seasonalities are the same within their estimated uncertainties. For δ(O2/N2) significant differences are observed between the three laboratories. The comparison for δ13CO2 yields the least compatible results and the required goals are not met between the three laboratories. Our study shows the importance of regular intercomparison exercises to identify potential biases between laboratories and the need to improve the quality of atmospheric measurements.
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Lambert, T., A. C. Pierson-Wickmann, G. Gruau, A. Jaffrezic, P. Petitjean, J. N. Thibault, and L. Jeanneau. "DOC sources and DOC transport pathways in a small headwater catchment as revealed by carbon isotope fluctuation during storm events." Biogeosciences 11, no. 11 (June 11, 2014): 3043–56. http://dx.doi.org/10.5194/bg-11-3043-2014.
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Abstract. Monitoring the isotopic composition (δ13CDOC) of dissolved organic carbon (DOC) during flood events can be helpful for locating DOC sources in catchments and quantifying their relative contribution to stream DOC flux. High-resolution (< hourly basis) δ13CDOC data were obtained during six successive storm events occurring during the high-flow period in a small headwater catchment in western France. Intra-storm δ13CDOC values exhibit a marked temporal variability, with some storms showing large variations (> 2 ‰), and others yielding a very restricted range of values (< 1 ‰). Comparison of these results with previously published data shows that the range of intra-storm δ13CDOC values closely reflects the temporal and spatial variation in δ13CDOC observed in the riparian soils of this catchment during the same period. Using δ13CDOC data in conjunction with hydrometric monitoring and an end-member mixing approach (EMMA), we show that (i) > 80% of the stream DOC flux flows through the most superficial soil horizons of the riparian domain and (ii) the riparian soil DOC flux is comprised of DOC coming ultimately from both riparian and upland domains. Based on its δ13C fingerprint, we find that the upland DOC contribution decreases from ca.~30% of the stream DOC flux at the beginning of the high-flow period to < 10% later in this period. Overall, upland domains contribute significantly to stream DOC export, but act as a size-limited reservoir, whereas soils in the wetland domains act as a near-infinite reservoir. Through this study, we show that δ13CDOC provides a powerful tool for tracing DOC sources and DOC transport mechanisms in headwater catchments, having a high-resolution assessment of temporal and spatial variability.
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Lenz, Olaf Klaus, Mara Montag, Volker Wilde, Katharina Methner, Walter Riegel, and Andreas Mulch. "Early Eocene carbon isotope excursions in a lignite-bearing succession at the southern edge of the proto-North Sea (Schöningen, Germany)." Climate of the Past 18, no. 10 (October 12, 2022): 2231–54. http://dx.doi.org/10.5194/cp-18-2231-2022.
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Abstract. Situated at the southern edge of the proto-North Sea, the lower Eocene Schöningen Formation of the Helmstedt Lignite Mining District, Lower Saxony, Germany, is characterized by several lignite seams alternating with estuarine to brackish interbeds. Here, we present carbon isotope data for bulk organic matter (δ13CTOC), total organic carbon content (%TOC), and palynomorphs from a 98 m thick sequence of the Schöningen Formation in combination with a new robust age model, which is based on eustatic sea level changes, biostratigraphy, and a correlation with existing radiometric ages. Based on the δ13CTOC data we observe six negative carbon isotope excursions (CIEs) reflecting massive short-term carbon cycle perturbations. A strong CIE of −2.6 ‰ in δ13CTOC values in the Main Seam and the succeeding marine interbed can be related to the Paleocene–Eocene Thermal Maximum (PETM). The subsequent CIE of −1.7 ‰ in δ13CTOC values may be correlated with the Eocene Thermal Maximum 2 (ETM2) or slightly older events preceding the ETM2. High-amplitude climate fluctuations including at least four minor CIEs with a maximum negative shift of −1.3 ‰ in δ13CTOC in the upper part of the studied section are characteristic of the Early Eocene Climatic Optimum (EECO). Palynological analysis across the Main Seam proved that shifts in δ13CTOC values are correlated with changes in the peat-forming wetland vegetation, specifically the change from a mixed angiosperm and gymnosperm flora to angiosperm-dominated vegetation at the onset of the PETM. The PETM-related CIE shows a distinct rebound to higher δ13CTOC values shortly after the onset of the CIE, which is recognized here as a common feature of terrestrial and marginal marine PETM records worldwide and may reflect a stepwise injection of carbon into the atmosphere.
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Hicks Pries, Caitlin, Alon Angert, Cristina Castanha, Boaz Hilman, and Margaret S. Torn. "Using respiration quotients to track changing sources of soil respiration seasonally and with experimental warming." Biogeosciences 17, no. 12 (June 17, 2020): 3045–55. http://dx.doi.org/10.5194/bg-17-3045-2020.
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Abstract. Developing a more mechanistic understanding of soil respiration is hampered by the difficulty in determining the contribution of different organic substrates to respiration and in disentangling autotrophic-versus-heterotrophic and aerobic-versus-anaerobic processes. Here, we use a relatively novel tool for better understanding soil respiration: the apparent respiration quotient (ARQ). The ARQ is the amount of CO2 produced in the soil divided by the amount of O2 consumed, and it changes according to which organic substrates are being consumed and whether oxygen is being used as an electron acceptor. We investigated how the ARQ of soil gas varied seasonally, by soil depth, and by in situ experimental warming (+4 ∘C) in a coniferous-forest whole-soil-profile warming experiment over 2 years. We then compared the patterns in ARQ to those of soil δ13CO2. Our measurements showed strong seasonal variations in ARQ, from ≈0.9 during the late spring and summer to ≈0.7 during the winter. This pattern likely reflected a shift from respiration being fueled by oxidized substrates like sugars and organic acids derived from root and root respiration during the growing season to more reduced substrates such as lipids and proteins derived from microbial necromass during the winter. This interpretation was supported by δ13CO2 values, which were lower, like lipids, in the winter and higher, like sugars, in the summer. Furthermore, experimental warming significantly changed how both ARQ and δ13CO2 responded to soil temperature. Wintertime ARQ and δ13CO2 values were higher in heated than in control plots, probably due to the warming-driven increase in microbial activity that may have utilized oxidized carbon substrates, while growing-season values were lower in heated plots. Experimental warming and phenology change the sources of soil respiration throughout the soil profile. The sensitivity of ARQ to these changes demonstrates its potential as a tool for disentangling the biological sources contributing to soil respiration.
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Verwega, Maria-Theresia, Christopher J. Somes, Markus Schartau, Robyn Elizabeth Tuerena, Anne Lorrain, Andreas Oschlies, and Thomas Slawig. "Description of a global marine particulate organic carbon-13 isotope data set." Earth System Science Data 13, no. 10 (October 26, 2021): 4861–80. http://dx.doi.org/10.5194/essd-13-4861-2021.
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Abstract. Marine particulate organic carbon stable isotope ratios (δ13CPOC) provide insights into understanding carbon cycling through the atmosphere, ocean and biosphere. They have for example been used to trace the input of anthropogenic carbon in the marine ecosystem due to the distinct isotopically light signature of anthropogenic emissions. However, δ13CPOC is also significantly altered during photosynthesis by phytoplankton, which complicates its interpretation. For such purposes, robust spatio-temporal coverage of δ13CPOC observations is essential. We collected all such available data sets and merged and homogenized them to provide the largest available marine δ13CPOC data set (https://doi.org/10.1594/PANGAEA.929931; Verwega et al., 2021). The data set consists of 4732 data points covering all major ocean basins beginning in the 1960s. We describe the compiled raw data, compare different observational methods, and provide key insights in the temporal and spatial distribution that is consistent with previously observed large-scale patterns. The main different sample collection methods (bottle, intake, net, trap) are generally consistent with each other when comparing within regions. An analysis of 1990s median δ13CPOC values in a meridional section across the best-covered Atlantic Ocean shows relatively high values (≥-22 ‰) in the low latitudes (<30∘) trending towards lower values in the Arctic Ocean (∼-24 ‰) and Southern Ocean (≤-28 ‰). The temporal trend since the 1960s shows a decrease in the median δ13CPOC by more than 3 ‰ in all basins except for the Southern Ocean, which shows a weaker trend but contains relatively poor multi-decadal coverage.
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Cozzi, Stefano, and Carolina Cantoni. "Stable isotope (δ13C and δ15N) composition of particulate organic matter, nutrients and dissolved organic matter during spring ice retreat at Terra Nova Bay." Antarctic Science 23, no. 1 (September 2, 2010): 43–56. http://dx.doi.org/10.1017/s0954102010000611.
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AbstractConcentration and isotope composition of particulate organic matter were analysed from five coastal sites on the annual fast ice and in the underlying water column at Terra Nova Bay. The highest increases of POC (< 2767 μM C) and PON (< 420 μM N) were reached in bottom ice and the unconsolidated platelet layer, linked with a large accumulation of nutrients and dissolved organic matter. Isotope POM composition in ice habitats was highly varied (δ13CPOC: -30.7 to -15.0‰, δ15NPON: 1.8–9.9‰). Constant negative δ13CPOC (> -29.3‰) and positive δ15NPON (< 9.4‰) values characterized the upper ice horizons, indicating the prevalence of aged detritus in these assemblages. By contrast, isotope composition (δ13CPOC: -15.0 to -29.7‰, δ15NPON: 1.8–9.6‰) and POC/PON ratios (6.2–12.6) changed markedly in bottom ice and interstitial water, even on short time scales, because of the combined effects of internal growth and mixing among freshly produced biomass. Sea ice breakout caused a large settling of particulates in the water column. It changed δ13CPOC (from 7.9 to 1.8‰) and δ15NPON (7.9–1.8‰) values in suspended particulate matter, indicating that inputs from fast ice strongly affect the isotopic signature of the particulate assemblage Antarctic coastal waters.
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Khim, Boo-Keun, Jongmin Lee, Sanbeom Ha, Jingu Park, Dhananjai K. Pandey, Peter D. Clift, Denise K. Kulhanek, et al. "Variations in δ13C values of sedimentary organic matter since late Miocene time in the Indus Fan (IODP Site 1457) of the eastern Arabian Sea." Geological Magazine 157, no. 6 (January 7, 2019): 1012–21. http://dx.doi.org/10.1017/s0016756818000870.
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AbstractA 1108.6 m long core was recovered at Site U1457 located on the Indus Fan in the Laxmi Basin of the eastern Arabian Sea during IODP Expedition 355. Shipboard examinations defined five lithologic units (I to V) of the lower Paleocene to Holocene sedimentary sequence. In this study, δ13C values of sedimentary organic matter (SOM) confirm the differentiation of the lithologic units and further divide units III and IV into two subunits (1 and 2). Based on the underlying assumption that the SOM is decided primarily by a mixture of marine and terrestrial origins, δ13CSOM values at Site U1457 provide information on the terrestrial catchment conditions since late Miocene time. Low δ13CSOM values from late Miocene to late Pleistocene times are similar (c. −22.0 ‰) for the most part, reflecting a consistent contribution of terrestrial organic matter from the catchment areas characterized by dominant C3 land plants. Significantly lower δ13CSOM values (c. −24.0 ‰) in Unit III-2 (∼8 to ∼7 Ma) might be due to a greater input of C3 terrestrial organic matter. The increase in δ13CSOM values at ∼7 Ma and the appearance of high δ13CSOM values (c. −18.0 ‰) within Unit III-1 (∼7 to ∼2 Ma) indicate that C4 biomass overwhelmed the terrestrial catchment environment as a result of enhanced terrestrial aridity in the Himalayan foreland. The three-end-member simple mixing model, estimating the relative contributions of SOM from terrestrial C3 and C4 plants and marine phytoplankton, supports our interpretation of the distribution of C3 and C4 land plants in the terrestrial catchment environment.
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Liu, Man, Guilin Han, Qian Zhang, and Zhaoliang Song. "Variations and Indications of δ13CSOC and δ15NSON in Soil Profiles in Karst Critical Zone Observatory (CZO), Southwest China." Sustainability 11, no. 7 (April 10, 2019): 2144. http://dx.doi.org/10.3390/su11072144.
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Soil carbon and nitrogen storage and stabilization are the key to solving the problems of mitigation of global warming and maintaining of crop productivity. In this study, the contents of soil organic carbon (SOC) and soil organic nitrogen (SON) and their stable isotope compositions (δ13CSOC and δ15NSON) in soil profiles were determined in two agricultural lands (including a farmland and an abandoned farmland) and four non-agricultural lands (including two shrub-grass lands and two shrub lands) in the karst critical zone observatory (CZO), Southwest China. The contents of SOC and SON were used for research on the effects of land use on SOC and SON storage, and the change of δ13CSOC and δ15NSON values in soil profiles were used to indicate SOC and SON stabilization. The results showed that agricultural activities reduced SOC and SON storage in the whole soil layers of farmland compared to non-agricultural lands, and farmland abandonment slightly increased SOC and SON storage. Crop rotation between peanut (C3) and corn (C4) affected the δ13CSOC in surface soils of agricultural lands (−21.6‰), which were intermediate between shrub lands (−22.7‰) and shrub-grass lands (−19.6‰). 15N-depleted SON in surface soils in farmland compared to those soil in other lands possibly associated with synthetic N fertilizer application. In soil layers below 30 cm depth the δ13CSOC deceased with depth, while the δ15NSON displayed irregular fluctuation. The change in δ13CSOC and δ15NSON through soil profiles in karst soils were more intensive than those in semiarid grassland soils indicating the less stabilization of SOC and SON in karst soils.
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Hammer, S., D. W. T. Griffith, G. Konrad, S. Vardag, C. Caldow, and I. Levin. "Assessment of a multi-species in situ FTIR for precise atmospheric greenhouse gas observations." Atmospheric Measurement Techniques 6, no. 5 (May 7, 2013): 1153–70. http://dx.doi.org/10.5194/amt-6-1153-2013.
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Abstract. We thoroughly evaluate the performance of a multi-species, in situ Fourier transform infrared (FTIR) analyser with respect to high-accuracy needs for greenhouse gas monitoring networks. The in situ FTIR analyser is shown to measure CO2, CO, CH4 and N2O mole fractions continuously, all with better reproducibility than the inter-laboratory compatibility (ILC) goals, requested by the World Meteorological Organization (WMO) for the Global Atmosphere Watch (GAW) programme. Simultaneously determined δ13CO2 reaches reproducibility as good as 0.03‰. Second-order dependencies between the measured components and the thermodynamic properties of the sample, (temperature, pressure and flow rate) and the cross sensitivities among the sample constituents are investigated and quantified. We describe an improved sample delivery and control system that minimises the pressure and flow rate variations, making post-processing corrections for those quantities non-essential. Temperature disequilibrium effects resulting from the evacuation of the sample cell are quantified and improved by the usage of a faster temperature sensor. The instrument has proven to be linear for all measured components in the ambient concentration range. The temporal stability of the instrument is characterised on different time scales. Instrument drifts on a weekly time scale are only observed for CH4 (0.04 nmol mol−1 day−1) and δ13CO2 (0.02‰ day−1). Based on 10 months of continuously collected quality control measures, the long-term reproducibility of the instrument is estimated to ±0.016 μmol mol−1 CO2, ±0.03‰ δ13CO2, ±0.14 nmol mol−1 CH4, ±0.1 nmol mol−1 CO and ±0.04 nmol mol−1 N2O. We propose a calibration and quality control scheme with weekly calibrations of the instrument that is sufficient to reach WMO-GAW inter-laboratory compatibility goals.
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Tuerena, Robyn E., Raja S. Ganeshram, Matthew P. Humphreys, Thomas J. Browning, Heather Bouman, and Alexander P. Piotrowski. "Isotopic fractionation of carbon during uptake by phytoplankton across the South Atlantic subtropical convergence." Biogeosciences 16, no. 18 (September 24, 2019): 3621–35. http://dx.doi.org/10.5194/bg-16-3621-2019.
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Abstract. The stable isotopic composition of particulate organic carbon (δ13CPOC) in the surface waters of the global ocean can vary with the aqueous CO2 concentration ([CO2(aq)]) and affects the trophic transfer of carbon isotopes in the marine food web. Other factors such as cell size, growth rate and carbon concentrating mechanisms decouple this observed correlation. Here, the variability in δ13CPOC is investigated in surface waters across the south subtropical convergence (SSTC) in the Atlantic Ocean, to determine carbon isotope fractionation (εp) by phytoplankton and the contrasting mechanisms of carbon uptake in the subantarctic and subtropical water masses. Our results indicate that cell size is the primary determinant of δ13CPOC across the Atlantic SSTC in summer. Combining cell size estimates with CO2 concentrations, we can accurately estimate εp within the varying surface water masses in this region. We further utilize these results to investigate future changes in εp with increased anthropogenic carbon availability. Our results suggest that smaller cells, which are prevalent in the subtropical ocean, will respond less to increased [CO2(aq)] than the larger cells found south of the SSTC and in the wider Southern Ocean. In the subantarctic water masses, isotopic fractionation during carbon uptake will likely increase, both with increasing CO2 availability to the cell, but also if increased stratification leads to decreases in average community cell size. Coupled with decreasing δ13C of [CO2(aq)] due to anthropogenic CO2 emissions, this change in isotopic fractionation and lowering of δ13CPOC may propagate through the marine food web, with implications for the use of δ13CPOC as a tracer of dietary sources in the marine environment.
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Lambert, T., A. C. Pierson-Wickmann, G. Gruau, A. Jaffrezic, P. Petitjean, J. N. Thibault, and L. Jeanneau. "New insights from the use of carbon isotopes as tracers of DOC sources and DOC transport processes in headwater catchments." Biogeosciences Discussions 10, no. 11 (November 20, 2013): 17965–8007. http://dx.doi.org/10.5194/bgd-10-17965-2013.
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Abstract. Monitoring the isotopic composition (δ13CDOC) of dissolved organic carbon (DOC) during flood events can be helpful for locating DOC sources in catchments and quantifying their relative contribution to DOC stream flux. High-resolution (< hourly basis) δ13CDOC data were obtained on six successive storm events occurring during the high-flow period in a small headwater catchment from western France. Intra-storm δ13CDOCvalues exhibit a marked temporal variability, with some storms showing large variations (>2‰), and others yielding a very restricted range of values (<1‰). Comparison of these results with previously published data shows that the range of intra-storm δ13CDOC values closely reflects the temporal and spatial variation in δ13CDOC observed in the riparian soils of this catchment during the same period. Using δ13C data in conjunction with hydrometric monitoring and an end-member mixing approach, we show that (i) >80% of the stream DOC flux flows through the most superficial soil horizons of the riparian domain and (ii) the soil DOC flux is comprised of DOC coming ultimately from both riparian and upland domains. Based on its δ13C fingerprint, we find that the upland DOC contribution decreases from ca. 30% of the stream DOC flux at the beginning of the high-flow period to <10% later in this period. Overall, upland domains contribute significantly to stream DOC export, but act as a size-limited reservoir, whereas soils in the wetland domains act as a near-infinite reservoir. Through this study, we show that δ13CDOC provides a powerful tool for tracing DOC sources and DOC transport mechanisms in headwater catchments.
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MARKIČ, Miloš, and Tjaša KANDUČ. "Carbon isotopic composition of methane and its origin in natural gas from the Petišovci-Dolina oil and gas field (Pannonian Basin System, NE Slovenia) – a preliminary study." Geologija 65, no. 1 (July 22, 2022): 59–72. http://dx.doi.org/10.5474/geologija.2022.004.
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The carbon isotopic composition of methane (δ13CCH4) in natural gas from the Petišovci-Dolina oil and gas field (NE Slovenia) was measured for the first time in August and September 2021. The gas samples from different depths were taken from three wells: Dolina-deep (Pg-6) from the depth interval 3102–3104 m, Petišovci-deep (Pg-5) from the depth interval 2772–2795 m, and Petišovci-shallow (D-5) from the depth interval 1212–1250 m. According to the available composition dataset of gas, available from the Petrol Geo d.o.o. documentation, the “deep” gases sampled from the Pg-6 and Pg-5 wells consist of 85 % methane (C1), 11 % hydrocarbons heavier than methane (C2–C6) and 4 % CO2. The “shallow” gas from well D-5 contains more than 89 % methane, up to 11 % C2–C6 gases, while the CO2 content is negligible. The “deep« gas from the Pg-6 and Pg-5 wells has δ13CCH4 -36.7 ‰ and -36.6 ‰, respectively, while the “shallow” gas from the D-5 well has the δ13CCH4 of -38.6 ‰. The methane from the “shallow” gas is slightly enriched in the lighter 12C isotope. δ13CCH4 in the range from -38.6 to -36.6 ‰ clearly indicates the thermogenic origin of methane formed during the catagenesis phase of gas formation.
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Dotsika, Elissavet, Maria Tassi, Petros Karalis, Anastasia Chrysostomou, Dimitra Ermioni Michael, Anastasia Elektra Poutouki, Katerina Theodorakopoulou, and Georgios Diamantopoulos. "Stable Isotope and Radiocarbon Analysis for Diet, Climate and Mobility Reconstruction in Agras (Early Iron Age) and Edessa (Roman Age), Northern Greece." Applied Sciences 12, no. 1 (January 5, 2022): 498. http://dx.doi.org/10.3390/app12010498.
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In this article we present an isotopic analysis of human bone collagen (δ13Ccol, and δ15Ncol) and bone apatite (δ13C) for diet reconstruction, as well as δ18Oap of human bone apatite for climate reconstruction, using samples from Northern Greece. Radiocarbon dating analysis was conducted on three of the Agras samples and the results (from 1000 to 800 BC) correspond to the Early Iron Age. Isotopic values for δ13Ccol range from −20.5‰ to −16‰ and for δ15Ncol from 6‰ to 11.1‰—a strong indication of a C3-based diet, with contributions by C4 and freshwater fish elements. The results were compared to the ones from Roman Edessa, and Alexandreia (a contemporary city near Edessa), as well as to other Early Iron sites in Greece and wider Europe. In general, the results from Agras are in good agreement with the results from Northern Greece, with the exception of the Makriyalos site, and are quite close to those of Croatia’s and Hungary’s sites. Additionally, from the δ18Oap results we calculated the oxygen isotopic composition of consumed water for Agras (from −9.6‰ to −10.9‰) and for Roman Edessa (from −9.6‰ to −11.2‰) for the palaeoclimate and palaeomobility reconstruction.
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Jeltsch-Thömmes, Aurich, and Fortunat Joos. "Modeling the evolution of pulse-like perturbations in atmospheric carbon and carbon isotopes: the role of weathering–sedimentation imbalances." Climate of the Past 16, no. 2 (March 4, 2020): 423–51. http://dx.doi.org/10.5194/cp-16-423-2020.
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Abstract. Measurements of carbon isotope variations in climate archives and isotope-enabled climate modeling advance the understanding of the carbon cycle. Perturbations in atmospheric CO2 and in its isotopic ratios (δ13C, Δ14C) are removed by different processes acting on different timescales. We investigate these differences on timescales of up to 100 000 years in pulse-release experiments with the Bern3D-LPX Earth system model of intermediate complexity and by analytical solutions from a box model. On timescales from years to many centuries, the atmospheric perturbations in CO2 and δ13CO2 are reduced by air–sea gas exchange, physical transport from the surface to the deep ocean, and by the land biosphere. Isotopic perturbations are initially removed much faster from the atmosphere than perturbations in CO2 as explained by aquatic carbonate chemistry. On multimillennial timescales, the CO2 perturbation is removed by carbonate compensation and silicate rock weathering. In contrast, the δ13C perturbation is removed by the relentless flux of organic and calcium carbonate particles buried in sediments. The associated removal rate is significantly modified by spatial δ13C gradients within the ocean, influencing the isotopic perturbation of the burial flux. Space-time variations in ocean δ13C perturbations are captured by principal components and empirical orthogonal functions. Analytical impulse response functions for atmospheric CO2 and δ13CO2 are provided. Results suggest that changes in terrestrial carbon storage were not the sole cause for the abrupt, centennial-scale CO2 and δ13CO2 variations recorded in ice during Heinrich stadials HS1 and HS4, though model and data uncertainties prevent a firm conclusion. The δ13C offset between the Penultimate Glacial Maximum and Last Glacial Maximum reconstructed for the ocean and atmosphere is most likely caused by imbalances between weathering, volcanism, and burial fluxes. Our study highlights the importance of isotopic fluxes connected to weathering–sedimentation imbalances, which so far have been often neglected on glacial–interglacial timescales.
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Bouillon, S., A. Yambélé, R. G. M. Spencer, D. P. Gillikin, P. J. Hernes, J. Six, R. Merckx, and A. V. Borges. "Organic matter sources, fluxes and greenhouse gas exchange in the Oubangui River (Congo River basin)." Biogeosciences Discussions 9, no. 1 (January 3, 2012): 63–108. http://dx.doi.org/10.5194/bgd-9-63-2012.
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Abstract. The Oubangui is a major tributary of the Congo River, draining an area of ~ 500 000 km2 mainly consisting of wooded savannahs. Here, we report results of a one year long 2-weekly sampling campaign in Bangui (Central African Republic) since March 2010 for a suite of physico-chemical and biogeochemical characteristics, including total suspended matter (TSM), bulk concentration and stable isotope composition of particulate organic carbon (POC and δ13CPOC), particulate nitrogen (PN and δ15NPN), dissolved organic carbon (DOC and δ13CDOC), dissolved inorganic carbon (DIC and δ13CDIC), dissolved greenhouse gases (CO2, CH4 and N2O), and dissolved lignin composition. We estimated the total annual flux of TSM, POC, PN, DOC and DIC to be 2.33 Tg yr−1, 0.14 Tg C yr−1, 0.014 Tg N yr−1, 0.70 Tg C yr−1, and 0.49 Tg C yr−1, respectively. Most elements showed clear hysteresis over the hydrograph. δ13C signatures of both POC and DOC showed strong seasonal variations (−30.6 to −25.8 ‰, and −31.8 to −27.1 ‰, respectively) but with contrasting patterns. Our data indicate that the origins of POC and DOC may vary strongly over the hydrograph and are largely uncoupled, differing up to 6 ‰ in δ13C signatures. The low POC/PN ratios, high % POC and low and variable δ13CPOC signatures during low flow conditions suggest that during this period, the majority of the POC pool consists of in situ produced phytoplankton, consistent with concurrent pCO2 (partial pressure of CO2) values only slightly above and occasionally, below, atmospheric equilibrium. Dissolved lignin characteristics (carbon-normalised yields, cinnamyl:vanillyl phenol ratios, and vanillic acid to vanillin ratios) showed marked differences between high and low discharge conditions. We observed a~strong seasonality in pCO2, ranging between 470 ± 203 ppm for Q<1000 m3 s−1 (n=10) to a maximum of 3750 ppm during the first stage of the rising discharge. Water-atmosphere CO2 fluxes were estimated to average ~ 105 g C m−2 yr−1, i.e. more than an order of magnitude lower than current estimates for large tropical rivers globally. While our TSM and POC fluxes are similar to previous estimates for the Oubangui, DOC fluxes were ~ 30 % higher and bicarbonate fluxes were ~ 35 % lower than previous reports. DIC represented 58 % of the total annual C flux, and under the assumptions that carbonate weathering represents 25 % of the DIC flux and that CO2 from respiration drives chemical weathering, this flux is equivalent to ~ 50 % of terrestrial-derived riverine C transport. Although tropical rivers are often assumed to show much higher CO2 effluxes compared to temperate systems, we show that in situ production may be high enough to dominate the particulate organic carbon pool, and lower pCO2 values to near equilibrium values during low discharge conditions.
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Bouillon, S., A. Yambélé, R. G. M. Spencer, D. P. Gillikin, P. J. Hernes, J. Six, R. Merckx, and A. V. Borges. "Organic matter sources, fluxes and greenhouse gas exchange in the Oubangui River (Congo River basin)." Biogeosciences 9, no. 6 (June 8, 2012): 2045–62. http://dx.doi.org/10.5194/bg-9-2045-2012.
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Abstract. The Oubangui is a major tributary of the Congo River, draining an area of ~500 000 km2 mainly consisting of wooded savannahs. Here, we report results of a one year long, 2-weekly sampling campaign in Bangui (Central African Republic) since March 2010 for a suite of physico-chemical and biogeochemical characteristics, including total suspended matter (TSM), bulk concentration and stable isotope composition of particulate organic carbon (POC and δ13CPOC), particulate nitrogen (PN and δ15NPN), dissolved organic carbon (DOC and δ13CDOC), dissolved inorganic carbon (DIC and δ13CDIC), dissolved greenhouse gases (CO2, CH4 and N2O), and dissolved lignin composition. δ13C signatures of both POC and DOC showed strong seasonal variations (−30.6 to −25.8‰, and −31.8 to −27.1‰, respectively), but their different timing indicates that the origins of POC and DOC may vary strongly over the hydrograph and are largely uncoupled, differing up to 6‰ in δ13C signatures. Dissolved lignin characteristics (carbon-normalised yields, cinnamyl:vanillyl phenol ratios, and vanillic acid to vanillin ratios) showed marked differences between high and low discharge conditions, consistent with major seasonal variations in the sources of dissolved organic matter. We observed a strong seasonality in pCO2, ranging between 470 ± 203 ppm for Q < 1000 m3 s−1 (n=10) to a maximum of 3750 ppm during the first stage of the rising discharge. The low POC/PN ratios, high %POC and low and variable δ13CPOC signatures during low flow conditions suggest that the majority of the POC pool during this period consists of in situ produced phytoplankton, consistent with concurrent pCO2 (partial pressure of CO2) values only slightly above and, occasionally, below atmospheric equilibrium. Water-atmosphere CO2 fluxes estimated using two independent approaches averaged 105 and 204 g C m−2 yr−1, i.e. more than an order of magnitude lower than current estimates for large tropical rivers globally. Although tropical rivers are often assumed to show much higher CO2 effluxes compared to temperate systems, we show that in situ production may be high enough to dominate the particulate organic carbon pool, and lower pCO2 values to near equilibrium values during low discharge conditions. The total annual flux of TSM, POC, PN, DOC and DIC are 2.33 Tg yr−1, 0.14 Tg C yr−1, 0.014 Tg N yr−1, 0.70 Tg C yr−1, and 0.49 Tg C yr−1, respectively. While our TSM and POC fluxes are similar to previous estimates for the Oubangui, DOC fluxes were ~30% higher and bicarbonate fluxes were ~35% lower than previous reports. DIC represented 58% of the total annual C flux, and under the assumptions that carbonate weathering represents 25% of the DIC flux and that CO2 from respiration drives chemical weathering, this flux is equivalent to ~50% of terrestrial-derived riverine C transport.
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Risk, D., N. Nickerson, C. L. Phillips, L. Kellman, and M. Moroni. "Drought alters respired δ13CO2 from autotrophic, but not heterotrophic soil respiration." Soil Biology and Biochemistry 50 (July 2012): 26–32. http://dx.doi.org/10.1016/j.soilbio.2012.01.025.
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