Articles | Volume 17, issue 9
https://doi.org/10.5194/amt-17-2687-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/amt-17-2687-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
07 May 2024
Research article |
| 07 May 2024
| 07 May 2024
Extraction, purification, and clumped isotope analysis of methane (Δ13CDH3 and Δ12CD2H2) from sources and the atmosphere
Malavika Sivan
CORRESPONDING AUTHOR
Institute for Marine and Atmospheric research Utrecht (IMAU), Utrecht University, Utrecht, the Netherlands
Thomas Röckmann
Institute for Marine and Atmospheric research Utrecht (IMAU), Utrecht University, Utrecht, the Netherlands
Carina van der Veen
Institute for Marine and Atmospheric research Utrecht (IMAU), Utrecht University, Utrecht, the Netherlands
Maria Elena Popa
Institute for Marine and Atmospheric research Utrecht (IMAU), Utrecht University, Utrecht, the Netherlands
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Atmos. Chem. Phys., 26, 10043–10069, https://doi.org/10.5194/acp-26-10043-2026, https://doi.org/10.5194/acp-26-10043-2026, 2026
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The accuracy of methods used to estimate and report fugitive methane emissions from Australian coal mines remains unclear. This study compares airborne emission rate estimates with reported estimates from 17 coal mines in the Bowen Basin, a region accounting for 45 % of national coal production. Results show good agreement for underground coal mines, but poor agreement for surface coal mines, suggesting improvements to surface coal mine reporting methods is needed to improve inventory reporting.
Bibhasvata Dasgupta, Sudhanshu Pandey, Sander Houweling, Malika Menoud, Carina van der Veen, John Miller, Ben Riddell-Young, Sylvia Englund Michel, Peter Sperlich, Shinji Morimoto, Ryo Fujita, Stephen Platt, Christine Groot Zwaaftink, Ingeborg Levin, Cordelia Veidt, Cathrine Lund Myhre, Ceres Woolley Maisch, Rebecca Fisher, Euan G. Nisbet, James France, Rowena Moss, Nicola Warwick, and Thomas Röckmann
Atmos. Chem. Phys., 26, 8601–8616, https://doi.org/10.5194/acp-26-8601-2026, https://doi.org/10.5194/acp-26-8601-2026, 2026
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Methane is a strong greenhouse gas, and its rise since the mid-2000s is debated in terms of sources and sinks. Using top-down and bottom-up data, along with inversion models and methane isotopes (δ13C-CH4 and δD-CH4), we find that wetlands are the primary driver of post-2006 increases, followed by agriculture and fossil fuels. Methane's lifetime has decreased by about 0.1 years. We also assess how isotope signatures and sink processes influence uncertainties.
Lison Soussaintjean, Jochen Schmitt, Joël Savarino, J. Andy Menking, Edward J. Brook, Barbara Seth, Vladimir Lipenkov, Thomas Röckmann, and Hubertus Fischer
Biogeosciences, 23, 3939–3963, https://doi.org/10.5194/bg-23-3939-2026, https://doi.org/10.5194/bg-23-3939-2026, 2026
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Nitrous oxide (N2O) produced in dust-rich Antarctic ice complicates the reconstruction of past atmospheric levels from ice core records. Using isotope analysis, we show that N2O forms from two nitrogen precursors, one being nitrate. For the first time, we demonstrate that the site preference (SP) of N2O reflects the isotopic difference between these precursors, not the production pathway, which challenges the common interpretation of SP.
Liang Feng, Paul I. Palmer, Haolin Wang, Robert Parker, Hartmut Boesch, Sébastien C. Biraud, Łukasz Chmura, Emanuel Gloor, László Haszpra, Elena Kozlova, Euan G. Nisbet, Steffen M. Noe, Thomas Röckmann, Rodrigo Augusto Ferreira de Souza, and Martin Steinbacher
EGUsphere, https://doi.org/10.5194/egusphere-2026-2662, https://doi.org/10.5194/egusphere-2026-2662, 2026
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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Jacoline van Es, Juan Bettinelli, Jia Chen, Carina van der Veen, Stephan Henne, and Thomas Röckmann
EGUsphere, https://doi.org/10.5194/egusphere-2026-1813, https://doi.org/10.5194/egusphere-2026-1813, 2026
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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The increase in atmospheric methane needs to be reversed to mitigate ongoing global warming. To design effective mitigation strategies at the local/regional level, we need to know what the main sources in different regions. We show that in Hamburg, Germany, biogenic sources are the main contributor to local emissions, with additional contributions from waste and fossil CH4 sources. An unexpected source is the Elbe River, with spiking emissions at low tide when the river banks are exposed.
Elinor C. Tuffnell, Emma Leedham-Elvidge, William T. Sturges, Harald Bönisch, Karina E. Adcock, Paul J. Fraser, Paul B. Krummel, David E. Oram, Ray L. Langenfelds, Thomas Röckmann, Luke M. Western, Jens Mühle, and Johannes C. Laube
Atmos. Chem. Phys., 26, 4583–4599, https://doi.org/10.5194/acp-26-4583-2026, https://doi.org/10.5194/acp-26-4583-2026, 2026
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The greater the stratospheric lifetime of chlorofluorocarbons (CFCs), the longer they will deplete ozone. This paper investigates four longer-lived CFCs, and discovers two of them have much shorter lifetimes than previously believed. Demonstrating emissions of these compounds are higher than assumed, to account for their abundance. Unusually this paper uses stratospheric whole-air samples, rather than models or lab-based experiments, to derive policy-relevant metrics for these compounds.
Annalisa Delre, Thomas Röckmann, David J. Bonell Fontas, Julia C. Engelmann, and Helge Niemann
EGUsphere, https://doi.org/10.5194/egusphere-2026-1582, https://doi.org/10.5194/egusphere-2026-1582, 2026
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Estuaries are important natural sources of methane, a greenhouse gas that affects climate. We studied how methane changes along the Scheldt estuary by measuring gas concentrations, carbon isotopes and identification and quantification of methane oxidizing bacteria. We found that methane levels varied strongly and were not mainly controlled by salinity. Most methane escaped to the atmosphere, showing that estuaries may contribute more to climate change than previously thought.
Thomas Röckmann, Malika Menoud, Jacoline van Es, Carina van der Veen, Hossein Maazallahi, Pawel Jagoda, Jaroslav M. Necki, Jakub Bartyzel, Piotr Korben, Sara Defratyka, Martina Schmidt, Marius Corbu, Sebastian Iancu, Andreea Calcan, Magdalena Ardelean, Sorin Ghemulet, Cristian Pop, Andrei Radovici, Alexandru Mereuta, Horatiu Stefanie, and Calin Baciu
Atmos. Chem. Phys., 26, 723–731, https://doi.org/10.5194/acp-26-723-2026, https://doi.org/10.5194/acp-26-723-2026, 2026
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We report the isotopic composition of CH4 emitted from 48 installations in the gas production region of Transylvania, Romania which confirm the biogenic origin of the Transylvanian gas, produced by hydrogenotrophic CO2 reduction. This is similar to values reported previously from natural seeps and natural gas in a major city in the region. However, is more depleted in heavy isotopes than the oil-associated gas emitted in the Southern Romanian Plain, and gas leakages in the city of Bucharest.
Lisa Ardoin, Catherine Larose, Jean-Louis Tison, Christoph Keuschnig, Vasileios Gkinis, Saïda El Amri, Pierre-Henry Blard, Paul Bierman, Thomas Blunier, Dorthe Dahl-Jensen, Charlotte Maistriau, Jørgen-Peder Steffensen, Thomas Röckmann, and François Fripiat
EGUsphere, https://doi.org/10.5194/egusphere-2025-6204, https://doi.org/10.5194/egusphere-2025-6204, 2026
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We investigated gas dynamics at the ice–bed interface of two Greenland ice cores to assess methane and carbon dioxide behaviour beneath ice sheets. At Camp Century, methane diffuses into the ice and is partly oxidized. At GRIP, methane remains preserved despite oxygen. These contrasts suggest that methane oxidation is controlled by local basal conditions, including ice thickness and substrate availability.
Paul Waldmann, Max Eckl, Leon Knez, Klaus-Dirk Gottschaldt, Alina Fiehn, Christian Mallaun, Michał Gałkowski, Christoph Kiemle, Ronald Hutjes, Thomas Röckmann, Huilin Chen, and Anke Roiger
Atmos. Meas. Tech., 19, 185–210, https://doi.org/10.5194/amt-19-185-2026, https://doi.org/10.5194/amt-19-185-2026, 2026
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Nitrous oxide and methane emissions from agriculture need to be reduced, therefore emissions must be understood to effectively mitigate them. This is the first approach to measure those emissions aircraft-based, to assess their magnitude and drivers. We identified emission hotspots and temporal changes in agricultural emissions in the Netherlands. Our approach is applicable to further greenhouse gas emitters, therefore it builds a step towards more comprehensive emission quantification.
Robbert P. J. Moonen, Getachew A. Adnew, Jordi Vilà-Guerau de Arellano, David J. Bonell Fontas, and Thomas Röckmann
EGUsphere, https://doi.org/10.5194/egusphere-2025-5969, https://doi.org/10.5194/egusphere-2025-5969, 2025
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We used high-frequency H₂O and CO₂ isotope measurements at ATTO to separate water vapour and carbon dioxide fluxes into their component processes. During midday, ~95 % of evapotranspiration came from plant transpiration. Isotopes also revealed the balance between photosynthesis and respiration, showing strong sensitivity to leaf CO₂ ratios. These results improve understanding of Amazon ecosystem function.
Sara M. Defratyka, Julianne M. Fernandez, Getachew A. Adnew, Guannan Dong, Peter M. J. Douglas, Daniel L. Eldridge, Giuseppe Etiope, Thomas Giunta, Mojhgan A. Haghnegahdar, Alexander N. Hristov, Nicole Hultquist, Iñaki Vadillo, Josue Jautzy, Ji-Hyun Kim, Jabrane Labidi, Ellen Lalk, Wil Leavitt, Jiawen Li, Li-Hung Lin, Jiarui Liu, Lucía Ojeda, Shuhei Ono, Jeemin H. Rhim, Thomas Röckmann, Barbara Sherwood Lollar, Malavika Sivan, Jiayang Sun, Gregory T. Ventura, David T. Wang, Edward D. Young, Naizhong Zhang, and Tim Arnold
Earth Syst. Sci. Data, 17, 6889–6910, https://doi.org/10.5194/essd-17-6889-2025, https://doi.org/10.5194/essd-17-6889-2025, 2025
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Measurement of methane’s doubly substituted isotopologues at natural abundances holds promise for better constraining the Earth’s atmospheric CH4 budget. We compiled 1475 measurements from field samples and laboratory experiments, conducted since 2014, to facilitate the differentiation of CH4 formation pathways and processes, to identify existing gaps limiting application of Δ13CH3D and Δ12CH2D2, and to develop isotope ratio source signature inputs for global CH4 flux modelling.
Bibhasvata Dasgupta, Malika Menoud, Carina van der Veen, Ingeborg Levin, Cordelia Veidt, Heiko Moossen, Sylvia Englund Michel, Peter Sperlich, Shinji Morimoto, Ryo Fujita, Taku Umezawa, Stephen Platt, Christine Groot Zwaaftink, Cathrine Lund Myhre, Rebecca Fisher, David Lowry, Euan G. Nisbet, James France, Ceres Woolley Maisch, Gordon Brailsford, Rowena Moss, Daisuke Goto, Sudhanshu Pandey, Sander Houweling, Nicola Warwick, and Thomas Röckmann
Atmos. Meas. Tech., 18, 6591–6607, https://doi.org/10.5194/amt-18-6591-2025, https://doi.org/10.5194/amt-18-6591-2025, 2025
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We combined long-term methane mole fraction and isotope measurements from eight laboratories that sample high-latitude stations to compare, offset correct and harmonise the datasets into a hemisphere merged timeseries. Because each laboratory uses slightly different methods, we adjusted the data to make it directly comparable. This allowed us to create a consistent record of atmospheric methane concentration and its isotopes from 1988 to 2023.
Sophie L. Baartman, Steven M. Driever, Maarten L. J. Wassenaar, Linda M. J. Kooijmans, Nerea Ubierna, Leon Mossink, Maria E. Popa, Ara Cho, Lisa Wingate, Thomas Röckmann, Steven M. A. C. van Heuven, and Maarten C. Krol
Biogeosciences, 22, 5683–5703, https://doi.org/10.5194/bg-22-5683-2025, https://doi.org/10.5194/bg-22-5683-2025, 2025
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Carbonyl sulfide (COS) is a proposed tracer for gross primary production. For the first time, COS and carbon dioxide (CO2) uptake fluxes and isotope discrimination were jointly measured in sunflower and papyrus plants, using a flow-through plant chamber approach and varying light availability. COS isotope discrimination did not differ significantly between the species, nor with changes in light. CO2 fluxes and isotope values provided additional valuable information for data interpretation.
Robbert P. J. Moonen, Getachew A. Adnew, Jordi Vilà-Guerau de Arellano, Oscar K. Hartogensis, David J. Bonell Fontas, Shujiro Komiya, Sam P. Jones, and Thomas Röckmann
Atmos. Chem. Phys., 25, 12197–12212, https://doi.org/10.5194/acp-25-12197-2025, https://doi.org/10.5194/acp-25-12197-2025, 2025
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Understory ejections are distinct turbulent features emerging in prime tall-forest ecosystems. We share a method to isolate understory ejections based on H2O–CO2 anomaly quadrants. From these, we calculate the flux contributions of understory ejections and all flux quadrants. In addition, we show that a distinctly depleted isotopic composition can be found in the ejected water vapour. Finally, we explored the role of clouds as a potential trigger for understory ejections.
Johannes C. Laube, Tanja J. Schuck, Sophie Baartman, Huilin Chen, Markus Geldenhuys, Steven van Heuven, Timo Keber, Maria Elena Popa, Elinor Tuffnell, Florian Voet, Bärbel Vogel, Thomas Wagenhäuser, Alessandro Zanchetta, and Andreas Engel
Atmos. Meas. Tech., 18, 4087–4102, https://doi.org/10.5194/amt-18-4087-2025, https://doi.org/10.5194/amt-18-4087-2025, 2025
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A large balloon was launched in summer 2021 in the Arctic to carry instruments for trace gas measurements up to 32 km, above the reach of aircraft. The main aims were to evaluate different techniques and atmospheric processes. We focus on halogenated greenhouse gases and ozone-depleting substances. For this, air was collected with the AirCore technique and a cryogenic air sampler and measured after the flight. A companion paper reports observations of major greenhouse gases.
Judith Tettenborn, Daniel Zavala-Araiza, Daan Stroeken, Hossein Maazallahi, Carina van der Veen, Arjan Hensen, Ilona Velzeboer, Pim van den Bulk, Felix Vogel, Lawson Gillespie, Sebastien Ars, James France, David Lowry, Rebecca Fisher, and Thomas Röckmann
Atmos. Meas. Tech., 18, 3569–3584, https://doi.org/10.5194/amt-18-3569-2025, https://doi.org/10.5194/amt-18-3569-2025, 2025
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Measurements of methane with vehicle-based sensors are an effective method to identify and quantify leaks from urban gas distribution systems. We deliberately released methane in different environments and calibrated the response of different methane analysers when they transected the plumes in a vehicle. We derived an improved statistical function for consistent emission estimations using different instruments. Repeated transects reduce the uncertainty in emission rate estimates.
Getachew Agmuas Adnew, Gerbrand Koren, Neha Mehendale, Sergey Gromov, Maarten Krol, and Thomas Röckmann
Atmos. Meas. Tech., 18, 2701–2719, https://doi.org/10.5194/amt-18-2701-2025, https://doi.org/10.5194/amt-18-2701-2025, 2025
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This study presents high-precision measurements of ∆′17O(CO2). Key findings include the extension of the N2O–∆′17O correlation to the upper troposphere and the identification of significant differences in the N2O–∆′17O slope in StratoClim samples. Additionally, the ∆′17O measurements are used to estimate global stratospheric production and surface removal of ∆′17O, providing an independent estimate of global vegetation CO2 exchange.
Gerrit Kuhlmann, Foteini Stavropoulou, Stefan Schwietzke, Daniel Zavala-Araiza, Andrew Thorpe, Andreas Hueni, Lukas Emmenegger, Andreea Calcan, Thomas Röckmann, and Dominik Brunner
Atmos. Chem. Phys., 25, 5371–5385, https://doi.org/10.5194/acp-25-5371-2025, https://doi.org/10.5194/acp-25-5371-2025, 2025
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A measurement campaign in 2019 found that methane emissions from oil and gas in Romania were significantly higher than reported. In 2021, our follow-up campaign using airborne remote sensing showed a marked decreases in emissions by 20 %–60 % due to improved infrastructure. The study highlights the importance of measurement-based emission monitoring and illustrates the value of a multi-scale assessment integrating ground-based observations with large-scale airborne remote sensing campaigns.
Tanja J. Schuck, Johannes Degen, Timo Keber, Katharina Meixner, Thomas Wagenhäuser, Mélanie Ghysels, Georges Durry, Nadir Amarouche, Alessandro Zanchetta, Steven van Heuven, Huilin Chen, Johannes C. Laube, Sophie L. Baartman, Carina van der Veen, Maria Elena Popa, and Andreas Engel
Atmos. Chem. Phys., 25, 4333–4348, https://doi.org/10.5194/acp-25-4333-2025, https://doi.org/10.5194/acp-25-4333-2025, 2025
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A balloon was launched in 2021 in the Arctic to carry instruments for trace gas measurements up to 32 km. One purpose was to compare measurement techniques. We focus on the major greenhouse gases. To measure these, air was sampled with the AirCore technique and with flask sampling, and samples were analysed after the flight. In flight, observations were done with an optical method. In a companion paper, we report on observations of chlorine and bromine containing trace gases.
Hossein Maazallahi, Foteini Stavropoulou, Samuel Jonson Sutanto, Michael Steiner, Dominik Brunner, Mariano Mertens, Patrick Jöckel, Antoon Visschedijk, Hugo Denier van der Gon, Stijn Dellaert, Nataly Velandia Salinas, Stefan Schwietzke, Daniel Zavala-Araiza, Sorin Ghemulet, Alexandru Pana, Magdalena Ardelean, Marius Corbu, Andreea Calcan, Stephen A. Conley, Mackenzie L. Smith, and Thomas Röckmann
Atmos. Chem. Phys., 25, 1497–1511, https://doi.org/10.5194/acp-25-1497-2025, https://doi.org/10.5194/acp-25-1497-2025, 2025
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This article presents insights from airborne in situ measurements collected during the ROmanian Methane Emissions from Oil and gas (ROMEO) campaign supported by two models. Results reveal Romania's oil and gas methane emissions were significantly under-reported to the United Nations Framework Convention on Climate Change (UNFCCC) in 2019. A large underestimation was also found in the Emissions Database for Global Atmospheric Research (EDGAR) v7.0 for the study domain in the same year.
Hella van Asperen, Thorsten Warneke, Alessandro Carioca de Araújo, Bruce Forsberg, Sávio José Filgueiras Ferreira, Thomas Röckmann, Carina van der Veen, Sipko Bulthuis, Leonardo Ramos de Oliveira, Thiago de Lima Xavier, Jailson da Mata, Marta de Oliveira Sá, Paulo Ricardo Teixeira, Julie Andrews de França e Silva, Susan Trumbore, and Justus Notholt
Biogeosciences, 21, 3183–3199, https://doi.org/10.5194/bg-21-3183-2024, https://doi.org/10.5194/bg-21-3183-2024, 2024
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Carbon monoxide (CO) is regarded as an important indirect greenhouse gas. Soils can emit and take up CO, but, until now, uncertainty remains as to which process dominates in tropical rainforests. We present the first soil CO flux measurements from a tropical rainforest. Based on our observations, we report that tropical rainforest soils are a net source of CO. In addition, we show that valley streams and inundated areas are likely additional hot spots of CO in the ecosystem.
Jin Ma, Linda M. J. Kooijmans, Norbert Glatthor, Stephen A. Montzka, Marc von Hobe, Thomas Röckmann, and Maarten C. Krol
Atmos. Chem. Phys., 24, 6047–6070, https://doi.org/10.5194/acp-24-6047-2024, https://doi.org/10.5194/acp-24-6047-2024, 2024
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The global budget of atmospheric COS can be optimised by inverse modelling using TM5-4DVAR, with the co-constraints of NOAA surface observations and MIPAS satellite data. We found reduced COS biosphere uptake from inversions and improved land and ocean separation using MIPAS satellite data assimilation. Further improvements are expected from better quantification of COS ocean and biosphere fluxes.
Katrine A. Gorham, Sam Abernethy, Tyler R. Jones, Peter Hess, Natalie M. Mahowald, Daphne Meidan, Matthew S. Johnson, Maarten M. J. W. van Herpen, Yangyang Xu, Alfonso Saiz-Lopez, Thomas Röckmann, Chloe A. Brashear, Erika Reinhardt, and David Mann
Atmos. Chem. Phys., 24, 5659–5670, https://doi.org/10.5194/acp-24-5659-2024, https://doi.org/10.5194/acp-24-5659-2024, 2024
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Rapid reduction in atmospheric methane is needed to slow the rate of global warming. Reducing anthropogenic methane emissions is a top priority. However, atmospheric methane is also impacted by rising natural emissions and changing sinks. Studies of possible atmospheric methane removal approaches, such as iron salt aerosols to increase the chlorine radical sink, benefit from a roadmapped approach to understand if there may be viable and socially acceptable ways to decrease future risk.
Alina Fiehn, Maximilian Eckl, Julian Kostinek, Michał Gałkowski, Christoph Gerbig, Michael Rothe, Thomas Röckmann, Malika Menoud, Hossein Maazallahi, Martina Schmidt, Piotr Korbeń, Jarosław Neçki, Mila Stanisavljević, Justyna Swolkień, Andreas Fix, and Anke Roiger
Atmos. Chem. Phys., 23, 15749–15765, https://doi.org/10.5194/acp-23-15749-2023, https://doi.org/10.5194/acp-23-15749-2023, 2023
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During the CoMet mission in the Upper Silesian Coal Basin (USCB) ground-based and airborne air samples were taken and analyzed for the isotopic composition of CH4 to derive the mean signature of the USCB and source signatures of individual coal mines. Using δ2H signatures, the biogenic emissions from the USCB account for 15 %–50 % of total emissions, which is underestimated in common emission inventories. This demonstrates the importance of δ2H-CH4 observations for methane source apportionment.
Robbert P. J. Moonen, Getachew A. Adnew, Oscar K. Hartogensis, Jordi Vilà-Guerau de Arellano, David J. Bonell Fontas, and Thomas Röckmann
Atmos. Meas. Tech., 16, 5787–5810, https://doi.org/10.5194/amt-16-5787-2023, https://doi.org/10.5194/amt-16-5787-2023, 2023
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Isotope fluxes allow for net ecosystem gas exchange fluxes to be partitioned into sub-components like plant assimilation, respiration and transpiration, which can help us better understand the environmental drivers of each partial flux. We share the results of a field campaign isotope fluxes were derived using a combination of laser spectroscopy and eddy covariance. We found lag times and high frequency signal loss in the isotope fluxes we derived and present methods to correct for both.
Leonard Kirago, Örjan Gustafsson, Samuel Mwaniki Gaita, Sophie L. Haslett, Michael J. Gatari, Maria Elena Popa, Thomas Röckmann, Christoph Zellweger, Martin Steinbacher, Jörg Klausen, Christian Félix, David Njiru, and August Andersson
Atmos. Chem. Phys., 23, 14349–14357, https://doi.org/10.5194/acp-23-14349-2023, https://doi.org/10.5194/acp-23-14349-2023, 2023
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This study provides ground-observational evidence that supports earlier suggestions that savanna fires are the main emitters and modulators of carbon monoxide gas in Africa. Using isotope-based techniques, the study has shown that about two-thirds of this gas is emitted from savanna fires, while for urban areas, in this case Nairobi, primary sources approach 100 %. The latter has implications for air quality policy, suggesting primary emissions such as traffic should be targeted.
Hossein Maazallahi, Antonio Delre, Charlotte Scheutz, Anders M. Fredenslund, Stefan Schwietzke, Hugo Denier van der Gon, and Thomas Röckmann
Atmos. Meas. Tech., 16, 5051–5073, https://doi.org/10.5194/amt-16-5051-2023, https://doi.org/10.5194/amt-16-5051-2023, 2023
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Measurement methods are increasingly deployed to verify reported methane emissions of gas leaks. This study describes unique advantages and limitations of three methods. Two methods are rapidly deployed, but uncertainties and biases exist for some leak locations. In contrast, the suction method could accurately determine leak rates in principle. However, this method, which provides data for the German emission inventory, creates an overall low bias in our study due to non-random site selection.
Tim René de Groot, Anne Margriet Mol, Katherine Mesdag, Pierre Ramond, Rachel Ndhlovu, Julia Catherine Engelmann, Thomas Röckmann, and Helge Niemann
Biogeosciences, 20, 3857–3872, https://doi.org/10.5194/bg-20-3857-2023, https://doi.org/10.5194/bg-20-3857-2023, 2023
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This study investigates methane dynamics in the Wadden Sea. Our measurements revealed distinct variations triggered by seasonality and tidal forcing. The methane budget was higher in warmer seasons but surprisingly high in colder seasons. Methane dynamics were amplified during low tides, flushing the majority of methane into the North Sea or releasing it to the atmosphere. Methanotrophic activity was also elevated during low tide but mitigated only a small fraction of the methane efflux.
Foteini Stavropoulou, Katarina Vinković, Bert Kers, Marcel de Vries, Steven van Heuven, Piotr Korbeń, Martina Schmidt, Julia Wietzel, Pawel Jagoda, Jaroslav M. Necki, Jakub Bartyzel, Hossein Maazallahi, Malika Menoud, Carina van der Veen, Sylvia Walter, Béla Tuzson, Jonas Ravelid, Randulph Paulo Morales, Lukas Emmenegger, Dominik Brunner, Michael Steiner, Arjan Hensen, Ilona Velzeboer, Pim van den Bulk, Hugo Denier van der Gon, Antonio Delre, Maklawe Essonanawe Edjabou, Charlotte Scheutz, Marius Corbu, Sebastian Iancu, Denisa Moaca, Alin Scarlat, Alexandru Tudor, Ioana Vizireanu, Andreea Calcan, Magdalena Ardelean, Sorin Ghemulet, Alexandru Pana, Aurel Constantinescu, Lucian Cusa, Alexandru Nica, Calin Baciu, Cristian Pop, Andrei Radovici, Alexandru Mereuta, Horatiu Stefanie, Alexandru Dandocsi, Bas Hermans, Stefan Schwietzke, Daniel Zavala-Araiza, Huilin Chen, and Thomas Röckmann
Atmos. Chem. Phys., 23, 10399–10412, https://doi.org/10.5194/acp-23-10399-2023, https://doi.org/10.5194/acp-23-10399-2023, 2023
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In this study, we quantify CH4 emissions from onshore oil production sites in Romania at source and facility level using a combination of ground- and drone-based measurement techniques. We show that the total CH4 emissions in our studied areas are much higher than the emissions reported to UNFCCC, and up to three-quarters of the detected emissions are related to operational venting. Our results suggest that oil and gas production infrastructure in Romania holds a massive mitigation potential.
Andreas Forstmaier, Jia Chen, Florian Dietrich, Juan Bettinelli, Hossein Maazallahi, Carsten Schneider, Dominik Winkler, Xinxu Zhao, Taylor Jones, Carina van der Veen, Norman Wildmann, Moritz Makowski, Aydin Uzun, Friedrich Klappenbach, Hugo Denier van der Gon, Stefan Schwietzke, and Thomas Röckmann
Atmos. Chem. Phys., 23, 6897–6922, https://doi.org/10.5194/acp-23-6897-2023, https://doi.org/10.5194/acp-23-6897-2023, 2023
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Large cities emit greenhouse gases which contribute to global warming. In this study, we measured the release of one important green house gas, methane, in Hamburg. Multiple sources that contribute to methane emissions were located and quantified. Methane sources were found to be mainly caused by human activity (e.g., by release from oil and gas refineries). Moreover, potential natural sources have been located, such as the Elbe River and lakes.
Truls Andersen, Zhao Zhao, Marcel de Vries, Jaroslaw Necki, Justyna Swolkien, Malika Menoud, Thomas Röckmann, Anke Roiger, Andreas Fix, Wouter Peters, and Huilin Chen
Atmos. Chem. Phys., 23, 5191–5216, https://doi.org/10.5194/acp-23-5191-2023, https://doi.org/10.5194/acp-23-5191-2023, 2023
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The Upper Silesian Coal Basin, Poland, is one of the hot spots of methane emissions in Europe. Using an uncrewed aerial vehicle (UAV), we performed atmospheric measurements of methane concentrations downwind of five ventilation shafts in this region and determined the emission rates from the individual shafts. We found a strong correlation between quantified shaft-averaged emission rates and hourly inventory data, which also allows us to estimate the methane emissions from the entire region.
Bryce F. J. Kelly, Xinyi Lu, Stephen J. Harris, Bruno G. Neininger, Jorg M. Hacker, Stefan Schwietzke, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Carina van der Veen, Malika Menoud, and Thomas Röckmann
Atmos. Chem. Phys., 22, 15527–15558, https://doi.org/10.5194/acp-22-15527-2022, https://doi.org/10.5194/acp-22-15527-2022, 2022
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This study explores using the composition of methane of in-flight atmospheric air samples for greenhouse gas inventory verification. The air samples were collected above one of the largest coal seam gas production regions in the world. Adjacent to these gas fields are coal mines, Australia's largest cattle feedlot, and over 1 million grazing cattle. The results are also used to identify methane mitigation opportunities.
Malika Menoud, Carina van der Veen, Dave Lowry, Julianne M. Fernandez, Semra Bakkaloglu, James L. France, Rebecca E. Fisher, Hossein Maazallahi, Mila Stanisavljević, Jarosław Nęcki, Katarina Vinkovic, Patryk Łakomiec, Janne Rinne, Piotr Korbeń, Martina Schmidt, Sara Defratyka, Camille Yver-Kwok, Truls Andersen, Huilin Chen, and Thomas Röckmann
Earth Syst. Sci. Data, 14, 4365–4386, https://doi.org/10.5194/essd-14-4365-2022, https://doi.org/10.5194/essd-14-4365-2022, 2022
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Emission sources of methane (CH4) can be distinguished with measurements of CH4 stable isotopes. We present new measurements of isotope signatures of various CH4 sources in Europe, mainly anthropogenic, sampled from 2017 to 2020. The present database also contains the most recent update of the global signature dataset from the literature. The dataset improves CH4 source attribution and the understanding of the global CH4 budget.
Stephen M. Platt, Øystein Hov, Torunn Berg, Knut Breivik, Sabine Eckhardt, Konstantinos Eleftheriadis, Nikolaos Evangeliou, Markus Fiebig, Rebecca Fisher, Georg Hansen, Hans-Christen Hansson, Jost Heintzenberg, Ove Hermansen, Dominic Heslin-Rees, Kim Holmén, Stephen Hudson, Roland Kallenborn, Radovan Krejci, Terje Krognes, Steinar Larssen, David Lowry, Cathrine Lund Myhre, Chris Lunder, Euan Nisbet, Pernilla B. Nizzetto, Ki-Tae Park, Christina A. Pedersen, Katrine Aspmo Pfaffhuber, Thomas Röckmann, Norbert Schmidbauer, Sverre Solberg, Andreas Stohl, Johan Ström, Tove Svendby, Peter Tunved, Kjersti Tørnkvist, Carina van der Veen, Stergios Vratolis, Young Jun Yoon, Karl Espen Yttri, Paul Zieger, Wenche Aas, and Kjetil Tørseth
Atmos. Chem. Phys., 22, 3321–3369, https://doi.org/10.5194/acp-22-3321-2022, https://doi.org/10.5194/acp-22-3321-2022, 2022
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Here we detail the history of the Zeppelin Observatory, a unique global background site and one of only a few in the high Arctic. We present long-term time series of up to 30 years of atmospheric components and atmospheric transport phenomena. Many of these time series are important to our understanding of Arctic and global atmospheric composition change. Finally, we discuss the future of the Zeppelin Observatory and emerging areas of future research on the Arctic atmosphere.
Roland Vernooij, Ulrike Dusek, Maria Elena Popa, Peng Yao, Anupam Shaikat, Chenxi Qiu, Patrik Winiger, Carina van der Veen, Thomas Callum Eames, Natasha Ribeiro, and Guido R. van der Werf
Atmos. Chem. Phys., 22, 2871–2890, https://doi.org/10.5194/acp-22-2871-2022, https://doi.org/10.5194/acp-22-2871-2022, 2022
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Landscape fires are a major source of greenhouse gases and aerosols, particularly in sub-tropical savannas. Stable carbon isotopes in emissions can be used to trace the contribution of C3 plants (e.g. trees or shrubs) and C4 plants (e.g. savanna grasses) to greenhouse gases and aerosols if the process is well understood. This helps us to link individual vegetation types to emissions, identify biomass burning emissions in the atmosphere, and improve the reconstruction of historic fire regimes.
Juhi Nagori, Narcisa Nechita-Bândă, Sebastian Oscar Danielache, Masumi Shinkai, Thomas Röckmann, and Maarten Krol
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-68, https://doi.org/10.5194/acp-2022-68, 2022
Publication in ACP not foreseen
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The sulfur isotopes (32S and 34S) were studied to understand the sources, sinks and processes of carbonyl sulphide (COS) in the atmosphere. COS is an important source of sulfur aerosol in the stratosphere (SSA). Few measurements of COS and SSA exist, but with our 1D model, we were able to match them and show the importance of COS to sulfate formation. Moreover, we are able to highlight some important processes for the COS budget and where measurements may fill a gap in current knowledge.
Malika Menoud, Carina van der Veen, Jaroslaw Necki, Jakub Bartyzel, Barbara Szénási, Mila Stanisavljević, Isabelle Pison, Philippe Bousquet, and Thomas Röckmann
Atmos. Chem. Phys., 21, 13167–13185, https://doi.org/10.5194/acp-21-13167-2021, https://doi.org/10.5194/acp-21-13167-2021, 2021
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Using measurements of methane isotopes in ambient air and a 3D atmospheric transport model, in Krakow, Poland, we mainly detected fossil-fuel-related sources, coming from coal mining in Silesia and from the use of natural gas in the city. Emission inventories report large emissions from coal mine activity in Silesia, which is in agreement with our measurements. However, methane sources in the urban area of Krakow related to the use of fossil fuels might be underestimated in the inventories.
Cited articles
Adnew, G. A., Hofmann, M. E. G., Paul, D., Laskar, A., Surma, J., Albrecht, N., Pack, A., Schwieters, J., Koren, G., Peters, W., and Röckmann, T.: Determination of the triple oxygen and carbon isotopic composition of CO2 from atomic ion fragments formed in the ion source of the 253 Ultra high-resolution isotope ratio mass spectrometer, Rapid Commun. Mass Sp., 33, 1363–1380, https://doi.org/10.1002/rcm.8478, 2019.
Archer, D., Eby, M., Brovkin, V., Ridgwell, A., Cao, L., Mikolajewicz, U., Caldeira, K., Matsumoto, K., Munhoven, G., Montenegro, A., and Tokos, K.: Atmospheric Lifetime of Fossil Fuel Carbon Dioxide, Annu. Rev. Earth Pl. Sc., 37, 117–134, https://doi.org/10.1146/annurev.earth.031208.100206, 2009.
Assonov, S., Groening, M., Fajgelj, A., Hélie, J. F., and Hillaire-Marcel, C.: Preparation and characterisation of IAEA-603, a new primary reference material aimed at the VPDB scale realisation for δ(13) C and δ(18) O determination, Rapid Commun. Mass Sp., 34, e8867, https://doi.org/10.1002/rcm.8867, 2020.
Beck, V., Chen, H., Gerbig, C., Bergamaschi, P., Bruhwiler, L., Houweling, S., Röckmann, T., Kolle, O., Steinbach, J., Koch, T., Sapart, C. J., van der Veen, C., Frankenberg, C., Andreae, M. O., Artaxo, P., Longo, K. M., and Wofsy, S. C.: Methane airborne measurements and comparison to global models during BARCA, J. Geophys. Res.-Atmos., 117, D15310, https://doi.org/10.1029/2011JD017345, 2012.
Bergamaschi, P., Brenninkmeijer, C. A. M., Hahn, M., Röckmann, T., Scharffe, D. H., Crutzen, P. J., Elansky, N. F., Belikov, I. B., Trivett, N. B. A., and Worthy, D. E. J.: Isotope analysis based source identification for atmospheric CH4 and CO sampled across Russia using the Trans-Siberian railroad, J. Geophys. Res.-Atmos., 103, 8227–8235, https://doi.org/10.1029/97JD03738, 1998.
Bergamaschi, P., Bräunlich, M., Marik, T., and Brenninkmeijer, C. A. M.: Measurements of the carbon and hydrogen isotopes of atmospheric methane at Izaña, Tenerife: Seasonal cycles and synoptic-scale variations, J. Geophys. Res.-Atmos., 105, 14531–14546, https://doi.org/10.1029/1999JD901176, 2000.
Cantrell, C. A., Shetter, R. E., McDaniel, A. H., Calvert, J. G., Davidson, J. A., Lowe, D. C., Tyler, S. C., Cicerone, R. J., and Greenberg, J. P.: Carbon kinetic isotope effect in the oxidation of methane by the hydroxyl radical, J. Geophys. Res.-Atmos., 95, 22455–22462, https://doi.org/10.1029/JD095iD13p22455, 1990.
Chung, E. and Arnold, T.: Potential of Clumped Isotopes in Constraining the Global Atmospheric Methane Budget, Global Biogeochem. Cy., 35, e2020GB006883, https://doi.org/10.1029/2020GB006883, 2021.
Conrad, R.: Control of microbial methane production in wetland rice fields, Nutr. Cycl. Agroecosys., 64, 59–69, https://doi.org/10.1023/A:1021178713988, 2002.
Douglas, P. M. J., Stolper, D. A., Eiler, J. M., Sessions, A. L., Lawson, M., Shuai, Y., Bishop, A., Podlaha, O. G., Ferreira, A. A., Santos Neto, E. V., Niemann, M., Steen, A. S., Huang, L., Chimiak, L., Valentine, D. L., Fiebig, J., Luhmann, A. J., Seyfried, W. E., Etiope, G., Schoell, M., Inskeep, W. P., Moran, J. J., and Kitchen, N.: Methane clumped isotopes: Progress and potential for a new isotopic tracer, Org. Geochem., 113, 262–282, https://doi.org/10.1016/j.orggeochem.2017.07.016, 2017.
Eiler, J. M.: “Clumped-isotope” geochemistry – The study of naturally-occurring, multiply-substituted isotopologues, Earth Planet. Sc. Lett., 262, 309–327, https://doi.org/10.1016/j.epsl.2007.08.020, 2007.
Eiler, J. M., Clog, M., Magyar, P., Piasecki, A., Sessions, A., Stolper, D., Deerberg, M., Schlueter, H.-J., and Schwieters, J.: A high-resolution gas-source isotope ratio mass spectrometer, Int. J. Mass Spectrom., 335, 45–56, https://doi.org/10.1016/j.ijms.2012.10.014, 2013.
Eldridge, D. L., Korol, R., Lloyd, M. K., Turner, A. C., Webb, M. A., Miller III, T. F., and Stolper, D. A.: Comparison of Experimental vs. Theoretical Abundances of 13CH3D and 12CH2D2 for Isotopically Equilibrated Systems from 1 to 500 °C, ACS Earth and Space Chemistry, 3, 2747–2764, https://doi.org/10.1021/acsearthspacechem.9b00244, 2019.
Etiope, G. and Sherwood Lollar, B.: Abiotic Methane on Earth, Rev. Geophys., 51, 276–299, https://doi.org/10.1002/rog.20011, 2013.
Fernandez, J. M., Maazallahi, H., France, J. L., Menoud, M., Corbu, M., Ardelean, M., Calcan, A., Townsend-Small, A., van der Veen, C., Fisher, R. E., Lowry, D., Nisbet, E. G., and Röckmann, T.: Street-level methane emissions of Bucharest, Romania and the dominance of urban wastewater, Atmospheric Environment: X, 13, 100153, https://doi.org/10.1016/j.aeaoa.2022.100153, 2022.
Giunta, T., Young, E. D., Warr, O., Kohl, I., Ash, J. L., Martini, A., Mundle, S. O. C., Rumble, D., Pérez-Rodríguez, I., Wasley, M., LaRowe, D. E., Gilbert, A., and Sherwood Lollar, B.: Methane sources and sinks in continental sedimentary systems: New insights from paired clumped isotopologues 13CH3D and 12CH2D2, Geochim. Cosmochim. Ac., 245, 327–351, https://doi.org/10.1016/j.gca.2018.10.030, 2019.
Gonfiantini, R.: Standards for stable isotope measurements in natural compounds, Nature, 271, 534–536, https://doi.org/10.1038/271534a0, 1978.
Haghnegahdar, M. A., Schauble, E. A., and Young, E. D.: A model for 12CH2D2 and 13CH3D as complementary tracers for the budget of atmospheric CH4, Global Biogeochem. Cy., 31, 1387–1407, https://doi.org/10.1002/2017GB005655, 2017.
Haghnegahdar, M. A., Sun, J., Hultquist, N., Hamovit, N. D., Kitchen, N., Eiler, J., Ono, S., Yarwood, S. A., Kaufman, A. J., Dickerson, R. R., Bouyon, A., Magen, C., and Farquhar, J.: Tracing sources of atmospheric methane using clumped isotopes, P. Natl. Acad. Sci. USA, 120, e2305574120, https://doi.org/10.1073/pnas.2305574120, 2023.
IPCC: Climate Change 2022: Impacts, Adaptation, and Vulnerability. Contribution of Working Group II to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Pörtner, H.-O., Roberts, D. C., Tignor, M., Poloczanska, E. S., Mintenbeck, K., Alegría, A., Craig, M., Langsdorf, S., Löschke, S., Möller, V., Okem, A., and Rama, B., Cambridge University Press, Cambridge University Press, Cambridge, UK and New York, NY, USA, 3056 pp., https://doi.org/10.1017/9781009325844, 2022.
Kelly, B. F. J., Lu, X., Harris, S. J., Neininger, B. G., Hacker, J. M., Schwietzke, S., Fisher, R. E., France, J. L., Nisbet, E. G., Lowry, D., van der Veen, C., Menoud, M., and Röckmann, T.: Atmospheric methane isotopes identify inventory knowledge gaps in the Surat Basin, Australia, coal seam gas and agricultural regions, Atmos. Chem. Phys., 22, 15527–15558, https://doi.org/10.5194/acp-22-15527-2022, 2022.
Khalil, M. A. K., Shearer, M. J., and Rasmussen, R. A.: Methane Sinks Distribution, Atmospheric Methane: Sources, Sinks, and Role in Global Change, Springer Berlin Heidelberg, 168–179, ISBN: 978-3-642-84605-2, 1993.
Lan, X., Thoning, K. W., and Dlugokencky, E. J.: Trends in globally-averaged CH4, N2O, and SF6, NOAA Global Monitoring Laboratory measurements, Version 2024-04, https://doi.org/10.15138/P8XG-AA10, 2022.
Li, Q., Fernandez, R. P., Hossaini, R., Iglesias-Suarez, F., Cuevas, C. A., Apel, E. C., Kinnison, D. E., Lamarque, J.-F., and Saiz-Lopez, A.: Reactive halogens increase the global methane lifetime and radiative forcing in the 21st century, Nat. Commun., 13, 2768, https://doi.org/10.1038/s41467-022-30456-8, 2022.
Loyd, S. J., Sample, J., Tripati, R. E., Defliese, W. F., Brooks, K., Hovland, M., Torres, M., Marlow, J., Hancock, L. G., Martin, R., Lyons, T., and Tripati, A. E.: Methane seep carbonates yield clumped isotope signatures out of equilibrium with formation temperatures, Nat. Commun., 7, 12274, https://doi.org/10.1038/ncomms12274, 2016.
Lu, X., Harris, S. J., Fisher, R. E., France, J. L., Nisbet, E. G., Lowry, D., Röckmann, T., van der Veen, C., Menoud, M., Schwietzke, S., and Kelly, B. F. J.: Isotopic signatures of major methane sources in the coal seam gas fields and adjacent agricultural districts, Queensland, Australia, Atmos. Chem. Phys., 21, 10527–10555, https://doi.org/10.5194/acp-21-10527-2021, 2021.
Menoud, M., van der Veen, C., Scheeren, B., Chen, H., Szénási, B., Morales, R. P., Pison, I., Bousquet, P., Brunner, D., and Röckmann, T.: Characterisation of methane sources in Lutjewad, The Netherlands, using quasi-continuous isotopic composition measurements, Tellus B, 72, 1–20, https://doi.org/10.1080/16000889.2020.1823733, 2020.
Menoud, M., van der Veen, C., Necki, J., Bartyzel, J., Szénási, B., Stanisavljević, M., Pison, I., Bousquet, P., and Röckmann, T.: Methane (CH4) sources in Krakow, Poland: insights from isotope analysis, Atmos. Chem. Phys., 21, 13167–13185, https://doi.org/10.5194/acp-21-13167-2021, 2021.
Menoud, M., van der Veen, C., Lowry, D., Fernandez, J. M., Bakkaloglu, S., France, J. L., Fisher, R. E., Maazallahi, H., Stanisavljević, M., Nȩcki, J., Vinkovic, K., Łakomiec, P., Rinne, J., Korbeń, P., Schmidt, M., Defratyka, S., Yver-Kwok, C., Andersen, T., Chen, H., and Röckmann, T.: New contributions of measurements in Europe to the global inventory of the stable isotopic composition of methane, Earth Syst. Sci. Data, 14, 4365–4386, https://doi.org/10.5194/essd-14-4365-2022, 2022.
Ono, S., Rhim, J. H., Gruen, D. S., Taubner, H., Kölling, M., and Wegener, G.: Clumped isotopologue fractionation by microbial cultures performing the anaerobic oxidation of methane, Geochim. Cosmochim. Ac., 293, 70–85, https://doi.org/10.1016/j.gca.2020.10.015, 2021.
Röckmann, T., Eyer, S., van der Veen, C., Popa, M. E., Tuzson, B., Monteil, G., Houweling, S., Harris, E., Brunner, D., Fischer, H., Zazzeri, G., Lowry, D., Nisbet, E. G., Brand, W. A., Necki, J. M., Emmenegger, L., and Mohn, J.: In situ observations of the isotopic composition of methane at the Cabauw tall tower site, Atmos. Chem. Phys., 16, 10469–10487, https://doi.org/10.5194/acp-16-10469-2016, 2016a.
Röckmann, T., Popa, M. E., Krol, M. C., and Hofmann, M. E. G.: Statistical clumped isotope signatures, Sci. Rep.-UK, 6, 31947, https://doi.org/10.1038/srep31947, 2016b.
Saueressig, G., Crowley, J. N., Bergamaschi, P., Brühl, C., Brenninkmeijer, C. A. M., and Fischer, H.: Carbon 13 and D kinetic isotope effects in the reactions of CH4 with O(1D) and OH: New laboratory measurements and their implications for the isotopic composition of stratospheric methane, J. Geophys. Res.-Atmos., 106, 23127–23138, https://doi.org/10.1029/2000JD000120, 2001.
Sherwood, O. A., Schwietzke, S., Arling, V. A., and Etiope, G.: Global Inventory of Gas Geochemistry Data from Fossil Fuel, Microbial and Burning Sources, version 2017, Earth Syst. Sci. Data, 9, 639–656, https://doi.org/10.5194/essd-9-639-2017, 2017.
Sherwood Lollar, B., Lacrampe-Couloume, G., Slater, G. F., Ward, J., Moser, D. P., Gihring, T. M., Lin, L. H., and Onstott, T. C.: Unravelling abiogenic and biogenic sources of methane in the Earth's deep subsurface, Chem. Geol., 226, 328–339, https://doi.org/10.1016/j.chemgeo.2005.09.027, 2006.
Sivan, M.: Extraction, purification, and clumped isotope analysis of methane (Δ13CDH3 and Δ12CD2H2) from different sources and the atmosphere, Version v1, Zenodo [data set], https://doi.org/10.5281/zenodo.8269713, 2023.
Stolper, D. A., Sessions, A. L., Ferreira, A. A., Santos Neto, E. V., Schimmelmann, A., Shusta, S. S., Valentine, D. L., and Eiler, J. M.: Combined 13C–D and D–D clumping in methane: Methods and preliminary results, Geochim. Cosmochim. Ac., 126, 169–191, https://doi.org/10.1016/j.gca.2013.10.045, 2014.
Stolper, D. A., Lawson, M., Formolo, M. J., Davis, C. L., Douglas, P. M. J., and Eiler, J. M.: The utility of methane clumped isotopes to constrain the origins of methane in natural gas accumulations, Geological Society, London, Special Publications, 468, 23–52, https://doi.org/10.1144/SP468.3, 2018.
Topp, E. and Pattey, E.: Soils as sources and sinks for atmospheric methane, Can. J. Soil Sci., 77, 167–177, https://doi.org/10.4141/s96-107, 1997.
Wang, D. T., Gruen, D. S., Lollar, B. S., Hinrichs, K. U., Stewart, L. C., Holden, J. F., Hristov, A. N., Pohlman, J. W., Morrill, P. L., Könneke, M., Delwiche, K. B., Reeves, E. P., Sutcliffe, C. N., Ritter, D. J., Seewald, J. S., McIntosh, J. C., Hemond, H. F., Kubo, M. D., Cardace, D., Hoehler, T. M., and Ono, S.: Methane cycling. Nonequilibrium clumped isotope signals in microbial methane, Science, 348, 428–431, https://doi.org/10.1126/science.aaa4326, 2015.
Whitehill, A. R., Joelsson, L. M. T., Schmidt, J. A., Wang, D. T., Johnson, M. S., and Ono, S.: Clumped isotope effects during OH and Cl oxidation of methane, Geochim. Cosmochim. Ac., 196, 307–325, https://doi.org/10.1016/j.gca.2016.09.012, 2017.
Whiticar, M. and Schaefer, H.: Constraining past global tropospheric methane budgets with carbon and hydrogen isotope ratios in ice, Philos. T. Roy. Soc. A, 365, 1793–1828, https://doi.org/10.1098/rsta.2007.2048, 2007.
Whiticar, M. J.: Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane, Chem. Geol., 161, 291–314, https://doi.org/10.1016/S0009-2541(99)00092-3, 1999.
Whiticar, M. J., Faber, E., and Schoell, M.: Biogenic methane formation in marine and freshwater environments: CO2 reduction vs. acetate fermentation – Isotope evidence, Geochim. Cosmochim. Ac., 50, 693–709, https://doi.org/10.1016/0016-7037(86)90346-7, 1986.
Yeung, L. Y.: Combinatorial effects on clumped isotopes and their significance in biogeochemistry, Geochim. Cosmochim. Ac., 172, 22–38, https://doi.org/10.1016/j.gca.2015.09.020, 2016.
Young, E. D., Kohl, I. E., Sherwood Lollar, B., Etiope, G., Rumble, D., Li, S., Haghnegahdar, M. A., Schauble, E. A., McCain, K. A., Foustoukos, D. I., Sutclife, C., Warr, O., Ballentine, C. J., Onstott, T. C., Hosgormez, H., Neubeck, A., Marques, J. M., Pérez-Rodríguez, I., Rowe, A. R., LaRowe, D. E., Magnabosco, C., Yeung, L. Y., Ash, J. L., and Bryndzia, L. T.: The relative abundances of resolved 12CH2D2 and 13CH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases, Geochim. Cosmochim. Ac., 203, 235–264, https://doi.org/10.1016/j.gca.2016.12.041, 2017.
Short summary
We have set up a measurement system for methane-clumped isotopologues. We have built an extraction and purification system to extract pure methane for these measurements, for samples of various origins, including atmospheric air, for which we need to process about 1000 L of air for one measurement. We report here the technical setup for extraction and measurements, as well as the calibration, and we give an overview of the samples measured so far.
We have set up a measurement system for methane-clumped isotopologues. We have built an...
