Articles | Volume 14, issue 12
https://doi.org/10.5194/amt-14-8041-2021
© Author(s) 2021. 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-14-8041-2021
© Author(s) 2021. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
23 Dec 2021
Research article |
| 23 Dec 2021
| 23 Dec 2021
Photochemical method for removing methane interference for improved gas analysis
Merve Polat
Copenhagen Center for Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5,
2100 Copenhagen Ø, Denmark
Jesper Baldtzer Liisberg
Physics of Ice Climate and Earth, Niels Bohr Institute, University of Copenhagen, 2100 Copenhagen Ø, Denmark
Morten Krogsbøll
Copenhagen Center for Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5,
2100 Copenhagen Ø, Denmark
Thomas Blunier
Physics of Ice Climate and Earth, Niels Bohr Institute, University of Copenhagen, 2100 Copenhagen Ø, Denmark
Copenhagen Center for Atmospheric Research, Department of Chemistry, University of Copenhagen, Universitetsparken 5,
2100 Copenhagen Ø, Denmark
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Julien Westhoff, Johannes Freitag, Anaïs Orsi, Patricia Martinerie, Ilka Weikusat, Michael Dyonisius, Xavier Faïn, Kevin Fourteau, and Thomas Blunier
The Cryosphere, 18, 4379–4397, https://doi.org/10.5194/tc-18-4379-2024, https://doi.org/10.5194/tc-18-4379-2024, 2024
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We study the EastGRIP area, Greenland, in detail with traditional and novel techniques. Due to the compaction of the ice, at a certain depth, atmospheric gases can no longer exchange, and the atmosphere is trapped in air bubbles in the ice. We find this depth by pumping air from a borehole, modeling, and using a new technique based on the optical appearance of the ice. Our results suggest that the close-off depth lies at around 58–61 m depth and more precisely at 58.3 m depth.
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.
Marie K. Mikkelsen, Jesper B. Liisberg, Maarten M. J. W. van Herpen, Kurt V. Mikkelsen, and Matthew S. Johnson
Aerosol Research, 2, 31–47, https://doi.org/10.5194/ar-2-31-2024, https://doi.org/10.5194/ar-2-31-2024, 2024
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We analyze the mechanism whereby sunlight and iron catalyze the production of chlorine from chloride in sea spray aerosol. This process occurs naturally over the North Atlantic and is the single most important source of chlorine. We investigate the mechanism using quantum chemistry, laboratory experiments, and aqueous chemistry modelling. The process will change depending on competing ions, light distribution, acidity, and chloride concentration.
Sindhu Vudayagiri, Bo Vinther, Johannes Freitag, Peter L. Langen, and Thomas Blunier
EGUsphere, https://doi.org/10.5194/egusphere-2024-237, https://doi.org/10.5194/egusphere-2024-237, 2024
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During the formation of ice from natural snowfall air is occluded in polar ice. The amount of air occluded (total air content) mainly reflects air pressure when the air is occluded and is therefore a proxy for elevation. However, there are several complications, such as melt, changes in firn structure and air pressure variability. We measured total air content in the RECAP ice core on the Renland Icecap in East Greenland. The core covers the period back to 121 thousand years before present.
Xavier Faïn, David M. Etheridge, Kévin Fourteau, Patricia Martinerie, Cathy M. Trudinger, Rachael H. Rhodes, Nathan J. Chellman, Ray L. Langenfelds, Joseph R. McConnell, Mark A. J. Curran, Edward J. Brook, Thomas Blunier, Grégory Teste, Roberto Grilli, Anthony Lemoine, William T. Sturges, Boris Vannière, Johannes Freitag, and Jérôme Chappellaz
Clim. Past, 19, 2287–2311, https://doi.org/10.5194/cp-19-2287-2023, https://doi.org/10.5194/cp-19-2287-2023, 2023
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We report on a 3000-year record of carbon monoxide (CO) levels in the Southern Hemisphere's high latitudes by combining ice core and firn air measurements with modern direct atmospheric samples. Antarctica [CO] remained stable (–835 to 1500 CE), decreased during the Little Ice Age, and peaked around 1985 CE. Such evolution reflects stable biomass burning CO emissions before industrialization, followed by growth from CO anthropogenic sources, which decline after 1985 due to improved combustion.
Michaela Mühl, Jochen Schmitt, Barbara Seth, James E. Lee, Jon S. Edwards, Edward J. Brook, Thomas Blunier, and Hubertus Fischer
Clim. Past, 19, 999–1025, https://doi.org/10.5194/cp-19-999-2023, https://doi.org/10.5194/cp-19-999-2023, 2023
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Our ice core measurements show that methane, ethane, and propane concentrations are significantly elevated above their past atmospheric background for Greenland ice samples containing mineral dust. The underlying co-production process happens during the classical discrete wet extraction of air from the ice sample and affects previous reconstructions of the inter-polar difference of methane as well as methane stable isotope records derived from dust-rich Greenland ice.
Louise Bøge Frederickson, Ruta Sidaraviciute, Johan Albrecht Schmidt, Ole Hertel, and Matthew Stanley Johnson
Atmos. Chem. Phys., 22, 13949–13965, https://doi.org/10.5194/acp-22-13949-2022, https://doi.org/10.5194/acp-22-13949-2022, 2022
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Low-cost sensors see additional pollution that is not seen with traditional regional air quality monitoring stations. This additional local pollution is sufficient to cause exceedance of the World Health Organization exposure thresholds. Analysis shows that a significant amount of the NO2 pollution we observe is local, mainly due to road traffic. This article demonstrates how networks of nodes containing low-cost pollution sensors can powerfully extend existing monitoring programmes.
Xavier Faïn, Rachael H. Rhodes, Philip Place, Vasilii V. Petrenko, Kévin Fourteau, Nathan Chellman, Edward Crosier, Joseph R. McConnell, Edward J. Brook, Thomas Blunier, Michel Legrand, and Jérôme Chappellaz
Clim. Past, 18, 631–647, https://doi.org/10.5194/cp-18-631-2022, https://doi.org/10.5194/cp-18-631-2022, 2022
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Carbon monoxide (CO) is a regulated pollutant and one of the key components determining the oxidizing capacity of the atmosphere. In this study, we analyzed five ice cores from Greenland at high resolution for CO concentrations by coupling laser spectrometry with continuous melting. By combining these new datasets, we produced an upper-bound estimate of past atmospheric CO abundance since preindustrial times for the Northern Hemisphere high latitudes, covering the period from 1700 to 1957 CE.
Andreas Plach, Bo M. Vinther, Kerim H. Nisancioglu, Sindhu Vudayagiri, and Thomas Blunier
Clim. Past, 17, 317–330, https://doi.org/10.5194/cp-17-317-2021, https://doi.org/10.5194/cp-17-317-2021, 2021
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In light of recent large-scale melting of the Greenland ice sheet
(GrIS), e.g., in the summer of 2012 several days with surface melt
on the entire ice sheet (including elevations above 3000 m), we use
computer simulations to estimate the amount of melt during a
warmer-than-present period of the past. Our simulations show more
extensive melt than today. This is important for the interpretation of
ice cores which are used to reconstruct the evolution of the ice sheet
and the climate.
James E. Lee, Edward J. Brook, Nancy A. N. Bertler, Christo Buizert, Troy Baisden, Thomas Blunier, V. Gabriela Ciobanu, Howard Conway, Dorthe Dahl-Jensen, Tyler J. Fudge, Richard Hindmarsh, Elizabeth D. Keller, Frédéric Parrenin, Jeffrey P. Severinghaus, Paul Vallelonga, Edwin D. Waddington, and Mai Winstrup
Clim. Past, 16, 1691–1713, https://doi.org/10.5194/cp-16-1691-2020, https://doi.org/10.5194/cp-16-1691-2020, 2020
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The Roosevelt Island ice core was drilled to investigate climate from the eastern Ross Sea, West Antarctica. We describe the ice age-scale and gas age-scale of the ice core for 0–763 m (83 000 years BP). Old ice near the bottom of the core implies the ice dome existed throughout the last glacial period and that ice streaming was active in the region. Variations in methane, similar to those used as evidence of early human influence on climate, were observed prior to significant human populations.
Anders Svensson, Dorthe Dahl-Jensen, Jørgen Peder Steffensen, Thomas Blunier, Sune O. Rasmussen, Bo M. Vinther, Paul Vallelonga, Emilie Capron, Vasileios Gkinis, Eliza Cook, Helle Astrid Kjær, Raimund Muscheler, Sepp Kipfstuhl, Frank Wilhelms, Thomas F. Stocker, Hubertus Fischer, Florian Adolphi, Tobias Erhardt, Michael Sigl, Amaelle Landais, Frédéric Parrenin, Christo Buizert, Joseph R. McConnell, Mirko Severi, Robert Mulvaney, and Matthias Bigler
Clim. Past, 16, 1565–1580, https://doi.org/10.5194/cp-16-1565-2020, https://doi.org/10.5194/cp-16-1565-2020, 2020
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We identify signatures of large bipolar volcanic eruptions in Greenland and Antarctic ice cores during the last glacial period, which allows for a precise temporal alignment of the ice cores. Thereby the exact timing of unexplained, abrupt climatic changes occurring during the last glacial period can be determined in a global context. The study thus provides a step towards a full understanding of elements of the climate system that may also play an important role in the future.
Stephen J. Harris, Jesper Liisberg, Longlong Xia, Jing Wei, Kerstin Zeyer, Longfei Yu, Matti Barthel, Benjamin Wolf, Bryce F. J. Kelly, Dioni I. Cendón, Thomas Blunier, Johan Six, and Joachim Mohn
Atmos. Meas. Tech., 13, 2797–2831, https://doi.org/10.5194/amt-13-2797-2020, https://doi.org/10.5194/amt-13-2797-2020, 2020
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The latest commercial laser spectrometers have the potential to revolutionize N2O isotope analysis. However, to do so, they must be able to produce trustworthy data. Here, we test the performance of widely used laser spectrometers for ambient air applications and identify instrument-specific dependencies on gas matrix and trace gas concentrations. We then provide a calibration workflow to facilitate the operation of these instruments in order to generate reproducible and accurate data.
Mai Winstrup, Paul Vallelonga, Helle A. Kjær, Tyler J. Fudge, James E. Lee, Marie H. Riis, Ross Edwards, Nancy A. N. Bertler, Thomas Blunier, Ed J. Brook, Christo Buizert, Gabriela Ciobanu, Howard Conway, Dorthe Dahl-Jensen, Aja Ellis, B. Daniel Emanuelsson, Richard C. A. Hindmarsh, Elizabeth D. Keller, Andrei V. Kurbatov, Paul A. Mayewski, Peter D. Neff, Rebecca L. Pyne, Marius F. Simonsen, Anders Svensson, Andrea Tuohy, Edwin D. Waddington, and Sarah Wheatley
Clim. Past, 15, 751–779, https://doi.org/10.5194/cp-15-751-2019, https://doi.org/10.5194/cp-15-751-2019, 2019
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We present a 2700-year timescale and snow accumulation history for an ice core from Roosevelt Island, Ross Ice Shelf, Antarctica. We observe a long-term slightly decreasing trend in accumulation during most of the period but a rapid decline since the mid-1960s. The latter is linked to a recent strengthening of the Amundsen Sea Low and the expansion of regional sea ice. The year 1965 CE may thus mark the onset of significant increases in sea-ice extent in the eastern Ross Sea.
Jonas Beck, Michael Bock, Jochen Schmitt, Barbara Seth, Thomas Blunier, and Hubertus Fischer
Biogeosciences, 15, 7155–7175, https://doi.org/10.5194/bg-15-7155-2018, https://doi.org/10.5194/bg-15-7155-2018, 2018
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Ice core concentration and stable isotope measurements of atmospheric CH4 give valuable insights into the CH4 cycle of the past. New carbon and hydrogen stable isotope CH4 data measured on ice from both Greenland and Antarctica over the Holocene allow us to draw conclusions on the methane emission processes. In particular, our results cast doubt on a hypothesis proposing early human land use to be responsible for the atmospheric methane concentration increase in the second half of the Holocene.
Taku Umezawa, Carl A. M. Brenninkmeijer, Thomas Röckmann, Carina van der Veen, Stanley C. Tyler, Ryo Fujita, Shinji Morimoto, Shuji Aoki, Todd Sowers, Jochen Schmitt, Michael Bock, Jonas Beck, Hubertus Fischer, Sylvia E. Michel, Bruce H. Vaughn, John B. Miller, James W. C. White, Gordon Brailsford, Hinrich Schaefer, Peter Sperlich, Willi A. Brand, Michael Rothe, Thomas Blunier, David Lowry, Rebecca E. Fisher, Euan G. Nisbet, Andrew L. Rice, Peter Bergamaschi, Cordelia Veidt, and Ingeborg Levin
Atmos. Meas. Tech., 11, 1207–1231, https://doi.org/10.5194/amt-11-1207-2018, https://doi.org/10.5194/amt-11-1207-2018, 2018
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Isotope measurements are useful for separating different methane sources. However, the lack of widely accepted standards and calibration methods for stable carbon and hydrogen isotopic ratios of methane in air has caused significant measurement offsets among laboratories. We conducted worldwide interlaboratory comparisons, surveyed the literature and assessed them systematically. This study may be of help in future attempts to harmonize data sets of isotopic composition of atmospheric methane.
Nancy A. N. Bertler, Howard Conway, Dorthe Dahl-Jensen, Daniel B. Emanuelsson, Mai Winstrup, Paul T. Vallelonga, James E. Lee, Ed J. Brook, Jeffrey P. Severinghaus, Taylor J. Fudge, Elizabeth D. Keller, W. Troy Baisden, Richard C. A. Hindmarsh, Peter D. Neff, Thomas Blunier, Ross Edwards, Paul A. Mayewski, Sepp Kipfstuhl, Christo Buizert, Silvia Canessa, Ruzica Dadic, Helle A. Kjær, Andrei Kurbatov, Dongqi Zhang, Edwin D. Waddington, Giovanni Baccolo, Thomas Beers, Hannah J. Brightley, Lionel Carter, David Clemens-Sewall, Viorela G. Ciobanu, Barbara Delmonte, Lukas Eling, Aja Ellis, Shruthi Ganesh, Nicholas R. Golledge, Skylar Haines, Michael Handley, Robert L. Hawley, Chad M. Hogan, Katelyn M. Johnson, Elena Korotkikh, Daniel P. Lowry, Darcy Mandeno, Robert M. McKay, James A. Menking, Timothy R. Naish, Caroline Noerling, Agathe Ollive, Anaïs Orsi, Bernadette C. Proemse, Alexander R. Pyne, Rebecca L. Pyne, James Renwick, Reed P. Scherer, Stefanie Semper, Marius Simonsen, Sharon B. Sneed, Eric J. Steig, Andrea Tuohy, Abhijith Ulayottil Venugopal, Fernando Valero-Delgado, Janani Venkatesh, Feitang Wang, Shimeng Wang, Dominic A. Winski, V. Holly L. Winton, Arran Whiteford, Cunde Xiao, Jiao Yang, and Xin Zhang
Clim. Past, 14, 193–214, https://doi.org/10.5194/cp-14-193-2018, https://doi.org/10.5194/cp-14-193-2018, 2018
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Temperature and snow accumulation records from the annually dated Roosevelt Island Climate Evolution (RICE) ice core show that for the past 2 700 years, the eastern Ross Sea warmed, while the western Ross Sea showed no trend and West Antarctica cooled. From the 17th century onwards, this dipole relationship changed. Now all three regions show concurrent warming, with snow accumulation declining in West Antarctica and the eastern Ross Sea.
Malte Winther, David Balslev-Harder, Søren Christensen, Anders Priemé, Bo Elberling, Eric Crosson, and Thomas Blunier
Biogeosciences, 15, 767–780, https://doi.org/10.5194/bg-15-767-2018, https://doi.org/10.5194/bg-15-767-2018, 2018
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Nitrous oxide (N2O) is an important and strong greenhouse gas in the atmosphere and part of climate. N2O is produced by microbes in terrestrial and aquatic ecosystems. The properties of each specific molecule can be used to determine the source. We implemented continuous measurements of N2O during incubation of denitrifying bacteria and believe that similar experiments will lead to a better understanding of N2O turnover and on the biotic mechanisms behind greenhouse gas exchange of the globe.
Carl Meusinger, Ulrike Dusek, Stephanie M. King, Rupert Holzinger, Thomas Rosenørn, Peter Sperlich, Maxime Julien, Gerald S. Remaud, Merete Bilde, Thomas Röckmann, and Matthew S. Johnson
Atmos. Chem. Phys., 17, 6373–6391, https://doi.org/10.5194/acp-17-6373-2017, https://doi.org/10.5194/acp-17-6373-2017, 2017
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Isotope studies can constrain budgets of secondary organic aerosol (SOA) that is pivotal to air pollution and climate. SOA from α-pinene ozonolysis was found to be enriched in 13C relative to the precursor. The observed difference in 13C between the gas and particle phases may arise from isotope-dependent changes in branching ratios. Alternatively, some gas-phase products involve carbon atoms from highly enriched and depleted sites, giving a non-kinetic origin to the observed fractionations.
Markella Prokopiou, Patricia Martinerie, Célia J. Sapart, Emmanuel Witrant, Guillaume Monteil, Kentaro Ishijima, Sophie Bernard, Jan Kaiser, Ingeborg Levin, Thomas Blunier, David Etheridge, Ed Dlugokencky, Roderik S. W. van de Wal, and Thomas Röckmann
Atmos. Chem. Phys., 17, 4539–4564, https://doi.org/10.5194/acp-17-4539-2017, https://doi.org/10.5194/acp-17-4539-2017, 2017
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Nitrous oxide is the third most important anthropogenic greenhouse gas with an increasing mole fraction. To understand its natural and anthropogenic sources
we employ isotope measurements. Results show that while the N2O mole fraction increases, its heavy isotope content decreases. The isotopic changes observed underline the dominance of agricultural emissions especially at the early part of the record, whereas in the later decades the contribution from other anthropogenic sources increases.
Cathy M. Trudinger, Paul J. Fraser, David M. Etheridge, William T. Sturges, Martin K. Vollmer, Matt Rigby, Patricia Martinerie, Jens Mühle, David R. Worton, Paul B. Krummel, L. Paul Steele, Benjamin R. Miller, Johannes Laube, Francis S. Mani, Peter J. Rayner, Christina M. Harth, Emmanuel Witrant, Thomas Blunier, Jakob Schwander, Simon O'Doherty, and Mark Battle
Atmos. Chem. Phys., 16, 11733–11754, https://doi.org/10.5194/acp-16-11733-2016, https://doi.org/10.5194/acp-16-11733-2016, 2016
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Perfluorocarbons (PFCs) are potent, long-lived and mostly man-made greenhouse gases released to the atmosphere mainly during aluminium production and semiconductor manufacture. Here we present the first continuous histories of three PFCs from 1800 to 2014, derived from measurements of these PFCs in the atmosphere and in air bubbles in polar ice. The records show how human actions have affected these important greenhouse gases over the past century.
Peter Sperlich, Nelly A. M. Uitslag, Jürgen M. Richter, Michael Rothe, Heike Geilmann, Carina van der Veen, Thomas Röckmann, Thomas Blunier, and Willi A. Brand
Atmos. Meas. Tech., 9, 3717–3737, https://doi.org/10.5194/amt-9-3717-2016, https://doi.org/10.5194/amt-9-3717-2016, 2016
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Isotope measurements in atmospheric CH4 are performed since more than 3 decades. However, standard gases to harmonize global measurements are not available to this day. We designed two methods to calibrate a suite of 8 CH4 gases with a wide range in isotopic composition to the VPDB and VSMOW scales with high precision and accuracy. Synthetic air mixtures with ~2 ppm of calibrated CH4 can be provided to the community by the ISOLAB of the Max Planck Institute for Biogeochemistry in Jena, Germany.
Theo Manuel Jenk, Mauro Rubino, David Etheridge, Viorela Gabriela Ciobanu, and Thomas Blunier
Atmos. Meas. Tech., 9, 3687–3706, https://doi.org/10.5194/amt-9-3687-2016, https://doi.org/10.5194/amt-9-3687-2016, 2016
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Atmospheric CO2 and δ13C-CO2 records from polar ice cores provide important constraints on the natural carbon cycle variability. Still, data exist only from a limited number of sampling sites and time periods due to demanding analytical challenges. Additional analytical state-of-the-art resources are desirable. This study describes such a new facility. Its analytical performance and new approaches for dealing with procedural blank contribution and analytical outliers are discussed in detail.
Malte Winther, David Balslev-Harder, Søren Christensen, Anders Priemé, Bo Elberling, Eric Crosson, and Thomas Blunier
Biogeosciences Discuss., https://doi.org/10.5194/bg-2016-258, https://doi.org/10.5194/bg-2016-258, 2016
Revised manuscript not accepted
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Nitrous oxide (N2O) is an important and strong greenhouse gas in the atmosphere and part of climate. N2O is produced by microbes in terrestrial and aquatic ecosystems. The properties of each specific molecule can be used to determine the source. We implemented continuous measurements of N2O during incubation of denitrifying bacteria and believe that similar experiments will lead to a better understanding of N2O turnover and on the biotic mechanisms behind greenhouse gas exchange of the Globe.
Anders B. Bluhme, Jonas L. Ingemar, Carl Meusinger, and Matthew S. Johnson
Atmos. Meas. Tech., 9, 2669–2673, https://doi.org/10.5194/amt-9-2669-2016, https://doi.org/10.5194/amt-9-2669-2016, 2016
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Hydrogen sulfide (H2S) is a malodorous, very poisonous, and flammable gas. It can be detected as SO2 using fluorescence after conversion using a hot catalyst. This technique is well established and as such also recommended by authorities such as the EPA. Our paper describes how at a relative humidity as low as 5 %, significant amounts of H2S pass the instrument undetected. At ambient levels of relative humidity, up to 1/3 of all H2S passes the instrument unnoticed.
Rachael H. Rhodes, Xavier Faïn, Edward J. Brook, Joseph R. McConnell, Olivia J. Maselli, Michael Sigl, Jon Edwards, Christo Buizert, Thomas Blunier, Jérôme Chappellaz, and Johannes Freitag
Clim. Past, 12, 1061–1077, https://doi.org/10.5194/cp-12-1061-2016, https://doi.org/10.5194/cp-12-1061-2016, 2016
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Local artifacts in ice core methane data are superimposed on consistent records of past atmospheric variability. These artifacts are not related to past atmospheric history and care should be taken to avoid interpreting them as such. By investigating five polar ice cores from sites with different conditions, we relate isolated methane spikes to melt layers and decimetre-scale variations as "trapping signal" associated with a difference in timing of air bubble closure in adjacent firn layers.
L. M. T. Joelsson, J. A. Schmidt, E. J. K. Nilsson, T. Blunier, D. W. T. Griffith, S. Ono, and M. S. Johnson
Atmos. Chem. Phys., 16, 4439–4449, https://doi.org/10.5194/acp-16-4439-2016, https://doi.org/10.5194/acp-16-4439-2016, 2016
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We present experimental kinetic isotope effects (KIE) for the OH oxidation of CH3D and 13CH3D and their temperature dependence. Our determination of the 13CH3D + OH KIE is novel and we find no "clumped" isotope effect within the experimental uncertainty.
C. Reutenauer, A. Landais, T. Blunier, C. Bréant, M. Kageyama, M.-N. Woillez, C. Risi, V. Mariotti, and P. Braconnot
Clim. Past, 11, 1527–1551, https://doi.org/10.5194/cp-11-1527-2015, https://doi.org/10.5194/cp-11-1527-2015, 2015
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Isotopes of atmospheric O2 undergo millennial-scale variations during the last glacial period, and systematically increase during Heinrich stadials.
Such variations are mostly due to vegetation and water cycle processes.
Our modeling approach reproduces the main observed features of Heinrich stadials in terms of climate, vegetation and rainfall.
It highlights the strong role of hydrology on O2 isotopes, which can be seen as a global integrator of precipitation changes over vegetated areas.
T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson
Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, https://doi.org/10.5194/acp-15-11243-2015, 2015
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In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
S. J. Allin, J. C. Laube, E. Witrant, J. Kaiser, E. McKenna, P. Dennis, R. Mulvaney, E. Capron, P. Martinerie, T. Röckmann, T. Blunier, J. Schwander, P. J. Fraser, R. L. Langenfelds, and W. T. Sturges
Atmos. Chem. Phys., 15, 6867–6877, https://doi.org/10.5194/acp-15-6867-2015, https://doi.org/10.5194/acp-15-6867-2015, 2015
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Stratospheric ozone protects life on Earth from harmful UV-B radiation. Chlorofluorocarbons (CFCs) are man-made compounds which act to destroy this barrier.
This paper presents (1) the first measurements of the stratospheric δ(37Cl) of CFCs -11 and -113; (2) the first quantification of long-term trends in the tropospheric δ(37Cl) of CFCs -11, -12 and -113.
This study provides a better understanding of source and sink processes associated with these destructive compounds.
M. Guillevic, L. Bazin, A. Landais, C. Stowasser, V. Masson-Delmotte, T. Blunier, F. Eynaud, S. Falourd, E. Michel, B. Minster, T. Popp, F. Prié, and B. M. Vinther
Clim. Past, 10, 2115–2133, https://doi.org/10.5194/cp-10-2115-2014, https://doi.org/10.5194/cp-10-2115-2014, 2014
E. J. K. Nilsson, J. A. Schmidt, and M. S. Johnson
Atmos. Chem. Phys., 14, 551–558, https://doi.org/10.5194/acp-14-551-2014, https://doi.org/10.5194/acp-14-551-2014, 2014
J. Chappellaz, C. Stowasser, T. Blunier, D. Baslev-Clausen, E. J. Brook, R. Dallmayr, X. Faïn, J. E. Lee, L. E. Mitchell, O. Pascual, D. Romanini, J. Rosen, and S. Schüpbach
Clim. Past, 9, 2579–2593, https://doi.org/10.5194/cp-9-2579-2013, https://doi.org/10.5194/cp-9-2579-2013, 2013
P. Sperlich, C. Buizert, T. M. Jenk, C. J. Sapart, M. Prokopiou, T. Röckmann, and T. Blunier
Atmos. Meas. Tech., 6, 2027–2041, https://doi.org/10.5194/amt-6-2027-2013, https://doi.org/10.5194/amt-6-2027-2013, 2013
V. V. Petrenko, P. Martinerie, P. Novelli, D. M. Etheridge, I. Levin, Z. Wang, T. Blunier, J. Chappellaz, J. Kaiser, P. Lang, L. P. Steele, S. Hammer, J. Mak, R. L. Langenfelds, J. Schwander, J. P. Severinghaus, E. Witrant, G. Petron, M. O. Battle, G. Forster, W. T. Sturges, J.-F. Lamarque, K. Steffen, and J. W. C. White
Atmos. Chem. Phys., 13, 7567–7585, https://doi.org/10.5194/acp-13-7567-2013, https://doi.org/10.5194/acp-13-7567-2013, 2013
L. Bazin, A. Landais, B. Lemieux-Dudon, H. Toyé Mahamadou Kele, D. Veres, F. Parrenin, P. Martinerie, C. Ritz, E. Capron, V. Lipenkov, M.-F. Loutre, D. Raynaud, B. Vinther, A. Svensson, S. O. Rasmussen, M. Severi, T. Blunier, M. Leuenberger, H. Fischer, V. Masson-Delmotte, J. Chappellaz, and E. Wolff
Clim. Past, 9, 1715–1731, https://doi.org/10.5194/cp-9-1715-2013, https://doi.org/10.5194/cp-9-1715-2013, 2013
D. Veres, L. Bazin, A. Landais, H. Toyé Mahamadou Kele, B. Lemieux-Dudon, F. Parrenin, P. Martinerie, E. Blayo, T. Blunier, E. Capron, J. Chappellaz, S. O. Rasmussen, M. Severi, A. Svensson, B. Vinther, and E. W. Wolff
Clim. Past, 9, 1733–1748, https://doi.org/10.5194/cp-9-1733-2013, https://doi.org/10.5194/cp-9-1733-2013, 2013
H. C. Steen-Larsen, S. J. Johnsen, V. Masson-Delmotte, B. Stenni, C. Risi, H. Sodemann, D. Balslev-Clausen, T. Blunier, D. Dahl-Jensen, M. D. Ellehøj, S. Falourd, A. Grindsted, V. Gkinis, J. Jouzel, T. Popp, S. Sheldon, S. B. Simonsen, J. Sjolte, J. P. Steffensen, P. Sperlich, A. E. Sveinbjörnsdóttir, B. M. Vinther, and J. W. C. White
Atmos. Chem. Phys., 13, 4815–4828, https://doi.org/10.5194/acp-13-4815-2013, https://doi.org/10.5194/acp-13-4815-2013, 2013
M. Guillevic, L. Bazin, A. Landais, P. Kindler, A. Orsi, V. Masson-Delmotte, T. Blunier, S. L. Buchardt, E. Capron, M. Leuenberger, P. Martinerie, F. Prié, and B. M. Vinther
Clim. Past, 9, 1029–1051, https://doi.org/10.5194/cp-9-1029-2013, https://doi.org/10.5194/cp-9-1029-2013, 2013
A. Svensson, M. Bigler, T. Blunier, H. B. Clausen, D. Dahl-Jensen, H. Fischer, S. Fujita, K. Goto-Azuma, S. J. Johnsen, K. Kawamura, S. Kipfstuhl, M. Kohno, F. Parrenin, T. Popp, S. O. Rasmussen, J. Schwander, I. Seierstad, M. Severi, J. P. Steffensen, R. Udisti, R. Uemura, P. Vallelonga, B. M. Vinther, A. Wegner, F. Wilhelms, and M. Winstrup
Clim. Past, 9, 749–766, https://doi.org/10.5194/cp-9-749-2013, https://doi.org/10.5194/cp-9-749-2013, 2013
C. M. Trudinger, I. G. Enting, P. J. Rayner, D. M. Etheridge, C. Buizert, M. Rubino, P. B. Krummel, and T. Blunier
Atmos. Chem. Phys., 13, 1485–1510, https://doi.org/10.5194/acp-13-1485-2013, https://doi.org/10.5194/acp-13-1485-2013, 2013
J. A. Schmidt, M. S. Johnson, S. Hattori, N. Yoshida, S. Nanbu, and R. Schinke
Atmos. Chem. Phys., 13, 1511–1520, https://doi.org/10.5194/acp-13-1511-2013, https://doi.org/10.5194/acp-13-1511-2013, 2013
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and Platforms
Ammonium CI-Orbitrap: a tool for characterizing the reactivity of oxygenated organic molecules
A high-accuracy dynamic dilution method for generating reference gas mixtures of carbonyl sulfide at sub-nanomole-per-mole levels for long-term atmospheric observation
Optimizing the iodide-adduct chemical ionization mass spectrometry (CIMS) quantitative method for toluene oxidation intermediates: experimental insights into functional-group differences
Characterization of a new Teflon chamber and on-line analysis of isomeric multifunctional photooxidation products
A versatile water vapor generation module for vapor isotope calibration and liquid isotope measurements
Extraction, purification, and clumped isotope analysis of methane (Δ13CDH3 and Δ12CD2H2) from sources and the atmosphere
Response of protonated, adduct, and fragmented ions in Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS)
Evaluation of a reduced pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species
Absorption of volatile organic compounds (VOCs) by polymer tubing: implications for indoor air and use as a simple gas-phase volatility separation technique
High precision δ18O measurements of atmospheric dioxygen using optical-feedback cavity-enhanced absorption spectroscopy (OF-CEAS)
A flexible device to produce a gas stream with a precisely controlled water vapour mixing ratio and isotope composition based on microdrop dispensing technology
Revision of an open-split-based dual-inlet system for elemental and isotope ratio mass spectrometers with a focus on clumped-isotope measurements
Characterisation of gaseous iodine species detection using the multi-scheme chemical ionisation inlet 2 with bromide and nitrate chemical ionisation methods
A novel inlet for enriching concentrations of reactive organic gases in low sampling flows
Characterizing the automatic radon flux transfer standard system Autoflux: laboratory calibration and field experiments
Water vapor stable isotope memory effects of common tubing materials
Influence of ozone and humidity on PTR-MS and GC-MS VOC measurements with and without a Na2S2O3 ozone scrubber
Laser-induced sublimation extraction for centimeter-resolution multi-species greenhouse gas analysis on ice cores
Ozone reactivity measurement of biogenic volatile organic compound emissions
Comparison of two photolytic calibration methods for nitrous acid
Measurement of enantiomer percentages for five monoterpenes from six conifer species by cartridge-tube-based passive sampling adsorption–thermal desorption (ps-ATD)
Identification, monitoring, and reaction kinetics of reactive trace species using time-resolved mid-infrared quantum cascade laser absorption spectroscopy: development, characterisation, and initial results for the CH2OO Criegee intermediate
Air pollution monitoring: development of ammonia (NH3) dynamic reference gas mixtures at nanomoles per mole levels to improve the lack of traceability of measurements
Formaldehyde and glyoxal measurement deploying a selected ion flow tube mass spectrometer (SIFT-MS)
Fragmentation inside proton-transfer-reaction-based mass spectrometers limits the detection of ROOR and ROOH peroxides
MULTICHARME: a modified Chernin-type multi-pass cell designed for IR and THz long-path absorption measurements in the CHARME atmospheric simulation chamber
Silicone tube humidity generator
A source for the continuous generation of pure and quantifiable HONO mixtures
A simulation chamber for absorption spectroscopy in planetary atmospheres
An automated system for trace gas flux measurements from plant foliage and other plant compartments
Simultaneous measurement of δ13C, δ18O and δ17O of atmospheric CO2 – performance assessment of a dual-laser absorption spectrometer
Measurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometers
A method for resolving changes in atmospheric He ∕ N2 as an indicator of fossil fuel extraction and stratospheric circulation
Application of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phase
Atomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap–GC–AED) for atmospheric trace gas measurements
New technique for high-precision, simultaneous measurements of CH4, N2O and CO2 concentrations; isotopic and elemental ratios of N2, O2 and Ar; and total air content in ice cores by wet extraction
High-precision laser spectrometer for multiple greenhouse gas analysis in 1 mL air from ice core samples
A thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) for the detection of organic nitrates in gas and particle phases
Interference from alkenes in chemiluminescent NOx measurements
Calibration of an airborne HOx instrument using the All Pressure Altitude-based Calibrator for HOx Experimentation (APACHE)
Measurement of ammonia, amines and iodine compounds using protonated water cluster chemical ionization mass spectrometry
An instrument for in situ measurement of total ozone reactivity
Portable calibrator for NO based on the photolysis of N2O and a combined NO2∕NO∕O3 source for field calibrations of air pollution monitors
A new instrument for time-resolved measurement of HO2 radicals
Investigation of adsorption and desorption behavior of small-volume cylinders and its relevance for atmospheric trace gas analysis
Towards an understanding of surface effects: testing of various materials in a small volume measurement chamber and its relevance for atmospheric trace gas analysis
Stability of halocarbons in air samples stored in stainless- steel canisters
High-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniques
Characterisation of the transfer of cluster ions through an atmospheric pressure interface time-of-flight mass spectrometer with hexapole ion guides
Addition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixtures
Dandan Li, Dongyu Wang, Lucia Caudillo, Wiebke Scholz, Mingyi Wang, Sophie Tomaz, Guillaume Marie, Mihnea Surdu, Elias Eccli, Xianda Gong, Loic Gonzalez-Carracedo, Manuel Granzin, Joschka Pfeifer, Birte Rörup, Benjamin Schulze, Pekka Rantala, Sébastien Perrier, Armin Hansel, Joachim Curtius, Jasper Kirkby, Neil M. Donahue, Christian George, Imad El-Haddad, and Matthieu Riva
Atmos. Meas. Tech., 17, 5413–5428, https://doi.org/10.5194/amt-17-5413-2024, https://doi.org/10.5194/amt-17-5413-2024, 2024
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Due to the analytical challenges of measuring organic vapors, it remains challenging to identify and quantify organic molecules present in the atmosphere. Here, we explore the performance of the Orbitrap chemical ionization mass spectrometer (CI-Orbitrap) using ammonium ion chemistry. This study shows that ammonium-ion-based chemistry associated with the high mass resolution of the Orbitrap mass analyzer can measure almost all inclusive compounds.
Hideki Nara, Takuya Saito, Taku Umezawa, and Yasunori Tohjima
Atmos. Meas. Tech., 17, 5187–5200, https://doi.org/10.5194/amt-17-5187-2024, https://doi.org/10.5194/amt-17-5187-2024, 2024
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We have developed a high-accuracy dynamic dilution system for generating reference gas mixtures containing carbonyl sulfide (COS). Although COS at ambient levels generally has poor storage stability, our approach involves the dilution of a gas mixture containing micromole-per-mole levels of COS, the stability of which was validated for more than 1 decade. The developed system has excellent dilution performance and will facilitate accurate instrumental calibration for atmospheric COS observation.
Mengdi Song, Shuyu He, Xin Li, Ying Liu, Shengrong Lou, Sihua Lu, Limin Zeng, and Yuanhang Zhang
Atmos. Meas. Tech., 17, 5113–5127, https://doi.org/10.5194/amt-17-5113-2024, https://doi.org/10.5194/amt-17-5113-2024, 2024
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We introduce detailed and improved quantitation and semi-quantitation methods of iodide-adduct time-of-flight chemical ionization mass spectrometry (I-CIMS) to measure toluene oxidation intermediates. We assess the experimental sensitivity of various functional group species and their binding energy with iodide ions in I-CIMS. A novel classification approach was introduced to significantly enhance the accuracy of semi-quantitative methods (improving R2 values from 0.52 to beyond 0.88).
Finja Löher, Esther Borrás, Amalia Muñoz, and Anke Christine Nölscher
Atmos. Meas. Tech., 17, 4553–4579, https://doi.org/10.5194/amt-17-4553-2024, https://doi.org/10.5194/amt-17-4553-2024, 2024
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We constructed and characterized a new indoor Teflon atmospheric simulation chamber. We evaluated wall losses, photolysis rates, and secondary reactions of multifunctional photooxidation products in the chamber. To measure these products on-line, we combined chromatographic and mass spectrometric analyses to obtain both isomeric information and a high temporal resolution. For method validation, we studied the formation yields of the main ring-retaining products of toluene.
Hans Christian Steen-Larsen and Daniele Zannoni
Atmos. Meas. Tech., 17, 4391–4409, https://doi.org/10.5194/amt-17-4391-2024, https://doi.org/10.5194/amt-17-4391-2024, 2024
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The water vapor generation module is completely scalable, allowing autonomous calibrations to use N standards and providing integration times only restricted by sample availability. We document improved reproducibility in 17O-excess liquid measurements. This module makes spectroscopy measurements comparable to mass spectrometry. We document that the vapor generation module can be used to analyze instrument performance and for vapor isotope calibration during field campaign measurements.
Malavika Sivan, Thomas Röckmann, Carina van der Veen, and Maria Elena Popa
Atmos. Meas. Tech., 17, 2687–2705, https://doi.org/10.5194/amt-17-2687-2024, https://doi.org/10.5194/amt-17-2687-2024, 2024
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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.
Fangbing Li, Dan Dan Huang, Linhui Tian, Bin Yuan, Wen Tan, Liang Zhu, Penglin Ye, Douglas Worsnop, Ka In Hoi, Kai Meng Mok, and Yong Jie Li
Atmos. Meas. Tech., 17, 2415–2427, https://doi.org/10.5194/amt-17-2415-2024, https://doi.org/10.5194/amt-17-2415-2024, 2024
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The responses of protonated, adduct, and fragmented ions of 21 volatile organic compounds (VOCs) were investigated with varying instrument settings and relative humidity (RH) in a Vocus proton-transfer-reaction mass spectrometer (PTR-MS). The protonated ions of most VOCs studied show < 15 % variation in sensitivity, except for some long-chain aldehydes. The relationship between sensitivity and PTR rate constant is complicated by the influences from ion transmission and protonated ion fraction.
Matthieu Riva, Veronika Pospisilova, Carla Frege, Sebastien Perrier, Priyanka Bansal, Spiro Jorga, Patrick Sturm, Joel Thornton, Urs Rohner, and Felipe Lopez-Hilfiker
EGUsphere, https://doi.org/10.5194/egusphere-2024-945, https://doi.org/10.5194/egusphere-2024-945, 2024
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We present a newly designed reduced-pressure chemical ionization reactor for the detection of gas phase organic and inorganic species. The system operates through the combined use of VUV ionization and photosensitizers to generate numerous adduct ionization schemes. As a result, it offers the ability to simultaneously measure a wide variety of organic and inorganic species in terms of compound volatility and functionality, while being largely independent of changes in the sample humidity.
Melissa A. Morris, Demetrios Pagonis, Douglas A. Day, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 17, 1545–1559, https://doi.org/10.5194/amt-17-1545-2024, https://doi.org/10.5194/amt-17-1545-2024, 2024
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Polymer absorption of volatile organic compounds (VOCs) is important to characterize for atmospheric sampling setups (as interactions cause sampling delays) and indoor air quality. Here we test different polymer materials and quantify their absorptive capacities through modeling. We found the main polymers in carpets to be highly absorptive, acting as large reservoirs for indoor pollution. We also demonstrated how polymer tubes can be used as a low-cost gas separation technique.
Clément Piel, Daniele Romanini, Morgane Farradèche, Justin Chaillot, Clémence Paul, Nicolas Bienville, Thomas Lauwers, Joana Sauze, Kévin Jaulin, Frédéric Prié, and Amaëlle Landais
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2024-14, https://doi.org/10.5194/amt-2024-14, 2024
Revised manuscript accepted for AMT
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This paper introduces a new optical gas analyzer based on the Optical-Feedback Cavity-Enhanced Absorption Spectroscopy technique (OF-CEAS) enabling high temporal resolution and high precision measurement of δ18O and concentration of atmospheric O2. The results underscore the good agreement with dual inlet IRMS measurements and the ability of the instrument to monitor biological processes.
Harald Sodemann, Alena Dekhtyareva, Alvaro Fernandez, Andrew Seidl, and Jenny Maccali
Atmos. Meas. Tech., 16, 5181–5203, https://doi.org/10.5194/amt-16-5181-2023, https://doi.org/10.5194/amt-16-5181-2023, 2023
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We describe a device that allows one to produce a continuous stream of water vapour with a specified level of humidity. As a main innovation, we can mix waters with different water isotope composition. Through a series of tests we show that the performance characteristics of the device are in line with specifications. We present two laboratory applications where the device proves useful, first in characterizing instruments, and second for the analysis of water contained in stalagmites.
Stephan Räss, Peter Nyfeler, Paul Wheeler, Will Price, and Markus Christian Leuenberger
Atmos. Meas. Tech., 16, 4489–4505, https://doi.org/10.5194/amt-16-4489-2023, https://doi.org/10.5194/amt-16-4489-2023, 2023
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Due to technological advances clumped-isotope studies have gained importance in recent years. Typically, these studies are performed with high-resolution isotope ratio mass spectrometers (IRMSs) along with a changeover-valve-based dual-inlet system (DIS). We are taking a different approach, namely performing clumped-isotope measurements with a compact low-resolution IRMS with an open-split-based DIS. Currently, we are working with pure-oxygen gas for which we are providing a proof of concept.
Xu-Cheng He, Jiali Shen, Siddharth Iyer, Paxton Juuti, Jiangyi Zhang, Mrisha Koirala, Mikko M. Kytökari, Douglas R. Worsnop, Matti Rissanen, Markku Kulmala, Norbert M. Maier, Jyri Mikkilä, Mikko Sipilä, and Juha Kangasluoma
Atmos. Meas. Tech., 16, 4461–4487, https://doi.org/10.5194/amt-16-4461-2023, https://doi.org/10.5194/amt-16-4461-2023, 2023
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In this study, the upgraded multi-scheme chemical ionisation inlet 2 is presented. Sulfuric acid, hypoiodous acid, iodine, sulfur dioxide, and hydroperoxyl radicals are calibrated, and the improved ion optics allow us to detect sulfuric acid and iodine-containing molecules at as low as a few parts per quadrillion by volume. Additionally, we confirm the reliable detection of iodic acid using both the nitrate and bromide chemical ionisation methods under atmospherically relevant conditions.
Namrata Shanmukh Panji and Gabriel Isaacman-VanWertz
Atmos. Meas. Tech., 16, 4319–4330, https://doi.org/10.5194/amt-16-4319-2023, https://doi.org/10.5194/amt-16-4319-2023, 2023
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Measuring volatile organic compounds (VOCs) in the atmosphere is crucial for understanding air quality and environmental impact. Since these compounds are present in low concentrations, preconcentration of samples is often necessary for accurate detection. To address this issue, we have developed a novel inlet that uses selective permeation to concentrate organic gases in small sample flows. This device offers a promising approach for accurately detecting low levels of VOCs in the atmosphere.
Claudia Grossi, Daniel Rabago, Scott Chambers, Carlos Sáinz, Roger Curcoll, Peter P. S. Otáhal, Eliška Fialová, Luis Quindos, and Arturo Vargas
Atmos. Meas. Tech., 16, 2655–2672, https://doi.org/10.5194/amt-16-2655-2023, https://doi.org/10.5194/amt-16-2655-2023, 2023
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The automatic and low-maintenance radon flux system Autoflux, completed with environmental soil and atmosphere sensors, has been theoretically and experimentally characterized and calibrated under laboratory conditions to be used as transfer standard for in situ measurements. It will offer for the first time long-term measurements to validate radon flux maps used by the climate and the radiation protection communities for assessing the radon gas emissions in the atmosphere.
Alexandra L. Meyer and Lisa R. Welp
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2023-56, https://doi.org/10.5194/amt-2023-56, 2023
Revised manuscript accepted for AMT
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Water molecules stick to air intake tubing wall surfaces and exchange with ambient vapor. This can slow signal change measurements. We tested whether material type affects this stickiness. Less stickiness would lead to an instrument seeing signal changes faster. We unexpectedly saw no difference in signal speed between material types. Water vapor stable isotope users can more confidently use plastic tubing and compare measurements across observation systems that used different tubing materials.
Lisa Ernle, Monika Akima Ringsdorf, and Jonathan Williams
Atmos. Meas. Tech., 16, 1179–1194, https://doi.org/10.5194/amt-16-1179-2023, https://doi.org/10.5194/amt-16-1179-2023, 2023
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Atmospheric ozone can induce artefacts in volatile organic compound measurements. Laboratory tests were made using GC-MS and PTR-MS aircraft systems under tropospheric and stratospheric conditions of humidity and ozone, with and without sodium thiosulfate filter scrubbers. Ozone in dry air produces some carbonyls and degrades alkenes. The scrubber lifetime depends on ozone concentration, flow rate and humidity. For the troposphere with scrubber, no significant artefacts were found over 14 d.
Lars Mächler, Daniel Baggenstos, Florian Krauss, Jochen Schmitt, Bernhard Bereiter, Remo Walther, Christoph Reinhard, Béla Tuzson, Lukas Emmenegger, and Hubertus Fischer
Atmos. Meas. Tech., 16, 355–372, https://doi.org/10.5194/amt-16-355-2023, https://doi.org/10.5194/amt-16-355-2023, 2023
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We present a new method to extract the gases from ice cores and measure their greenhouse gas composition. The ice is sublimated continuously with a near-infrared laser, releasing the gases, which are then analyzed on a laser absorption spectrometer. The main advantage over previous efforts is a low effective resolution of 1–2 cm. This capability is crucial for the analysis of highly thinned ice, as expected from ongoing drilling efforts to extend ice core history further back in time.
Detlev Helmig, Alex Guenther, Jacques Hueber, Ryan Daly, Wei Wang, Jeong-Hoo Park, Anssi Liikanen, and Arnaud P. Praplan
Atmos. Meas. Tech., 15, 5439–5454, https://doi.org/10.5194/amt-15-5439-2022, https://doi.org/10.5194/amt-15-5439-2022, 2022
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This research demonstrates a new method for determination of the chemical reactivity of volatile organic compounds that are emitted from the leaves and needles of trees. These measurements allow elucidating if and how much of these emissions and their associated reactivity are captured and quantified by currently applicable chemical analysis methods.
Andrew J. Lindsay and Ezra C. Wood
Atmos. Meas. Tech., 15, 5455–5464, https://doi.org/10.5194/amt-15-5455-2022, https://doi.org/10.5194/amt-15-5455-2022, 2022
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Nitrous acid (HONO) is an important source of the main atmospheric oxidant – the hydroxyl radical (OH). Advances in nitrous acid measurement techniques and calibration methods therefore improve our understanding of atmospheric oxidation processes. In this paper, we present two calibration methods based on photo-dissociating water vapor. These calibration methods are useful alternatives to conventional calibrations that involve a reacting hydrogen chloride vapor with sodium nitrite.
Ying Wang, Wentai Luo, Todd N. Rosenstiel, and James F. Pankow
Atmos. Meas. Tech., 15, 4651–4661, https://doi.org/10.5194/amt-15-4651-2022, https://doi.org/10.5194/amt-15-4651-2022, 2022
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A rapid, sensitive, and precise analytical method was developed for measuring the fractional amounts of the (−) and (+) forms of chiral enantiomeric forms of monoterpenes in air containing biogenic plant emissions. The method uses passive air sampling onto adsorption–thermal desorption (ATD) gas sampling cartridge tubes; this is followed by automatable thermal desorption onto a chiral gas chromatography (GC) column, followed by detection with mass spectrometry (MS).
Zara S. Mir, Matthew Jamieson, Nicholas R. Greenall, Paul W. Seakins, Mark A. Blitz, and Daniel Stone
Atmos. Meas. Tech., 15, 2875–2887, https://doi.org/10.5194/amt-15-2875-2022, https://doi.org/10.5194/amt-15-2875-2022, 2022
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In this work we describe the development and characterisation of an experiment using laser flash photolysis coupled with time-resolved mid-infrared (mid-IR) quantum cascade laser (QCL) absorption spectroscopy, with initial results reported for measurements of the infrared spectrum, kinetics, and product yields for the reaction of the CH2OO Criegee intermediate with SO2. This work has significance for the identification and measurement of reactive trace species in complex systems.
Tatiana Macé, Maitane Iturrate-Garcia, Céline Pascale, Bernhard Niederhauser, Sophie Vaslin-Reimann, and Christophe Sutour
Atmos. Meas. Tech., 15, 2703–2718, https://doi.org/10.5194/amt-15-2703-2022, https://doi.org/10.5194/amt-15-2703-2022, 2022
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LNE developed, with the company 2M PROCESS, a gas reference generator to dynamically generate NH3 reference gas mixtures in the air at very low fractions between 1 and 400 nmol/mol. The procedure defined by LNE for calibrating NH3 analyzers used for monitoring air quality guarantees relative expanded uncertainties lower than 2 % for this measurement range. The results of a comparison organized between METAS and LNE allowed the validation of LNE's reference generator and calibration procedure.
Antonia G. Zogka, Manolis N. Romanias, and Frederic Thevenet
Atmos. Meas. Tech., 15, 2001–2019, https://doi.org/10.5194/amt-15-2001-2022, https://doi.org/10.5194/amt-15-2001-2022, 2022
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We emphasize the application of SIFT-MS to detect two important atmospheric pollutants, i.e., formaldehyde (FM) and glyoxal (GL). FM and GL are secondary products formed by volatile organic compound oxidation in indoor and outdoor environments and play a key role in air quality and climate. We show that SIFT-MS is able to monitor these species selectively and in real time, overcoming the limitations of other, classical analytical techniques used to monitor these species in the atmosphere.
Haiyan Li, Thomas Golin Almeida, Yuanyuan Luo, Jian Zhao, Brett B. Palm, Christopher D. Daub, Wei Huang, Claudia Mohr, Jordan E. Krechmer, Theo Kurtén, and Mikael Ehn
Atmos. Meas. Tech., 15, 1811–1827, https://doi.org/10.5194/amt-15-1811-2022, https://doi.org/10.5194/amt-15-1811-2022, 2022
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This work evaluated the potential for PTR-based mass spectrometers to detect ROOR and ROOH peroxides both experimentally and through computations. Laboratory experiments using a Vocus PTR observed only noisy signals of potential dimers during α-pinene ozonolysis and a few small signals of dimeric compounds during cyclohexene ozonolysis. Quantum chemical calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation.
Jean Decker, Éric Fertein, Jonas Bruckhuisen, Nicolas Houzel, Pierre Kulinski, Bo Fang, Weixiong Zhao, Francis Hindle, Guillaume Dhont, Robin Bocquet, Gaël Mouret, Cécile Coeur, and Arnaud Cuisset
Atmos. Meas. Tech., 15, 1201–1215, https://doi.org/10.5194/amt-15-1201-2022, https://doi.org/10.5194/amt-15-1201-2022, 2022
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We present a multiple pass system developed for the CHamber for Atmospheric Reactivity and Metrology of the Environment. This multi-pass cell allows monitoring of atmospheric species at trace levels by high-resolution spectroscopy with long interaction path lengths in the IR and for the first time in the terahertz range. Interesting prospects are highlighted in this frequency domain, such as a high degree of selectivity or the possibility to monitor in real-time atmospheric processes.
Robert F. Berg, Nicola Chiodo, and Eric Georgin
Atmos. Meas. Tech., 15, 819–832, https://doi.org/10.5194/amt-15-819-2022, https://doi.org/10.5194/amt-15-819-2022, 2022
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We made a humidity generator that adds water vapor to a flowing gas. Its range of humidity is useful for calibrating balloon-borne probes to the Earth's stratosphere. The generator’s novel feature is a saturator that comprises 5 m of silicone tubing immersed in water. The length was enough to ensure that the saturator’s output was independent of the dimensions and permeability of the tube. This simple, low-cost design provides an accuracy that is acceptable for many applications.
Guillermo Villena and Jörg Kleffmann
Atmos. Meas. Tech., 15, 627–637, https://doi.org/10.5194/amt-15-627-2022, https://doi.org/10.5194/amt-15-627-2022, 2022
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A continuous source for the generation of pure HONO mixtures was developed and characterized, which is based on the Henry's law solubility of HONO in acidic aqueous solutions. The source shows a fast time response and an excellent long-term stability and can be easily adjusted to HONO mixing ratios in the range 0.05–500 ppb. A general equation based on Henry's law is developed, whereby the HONO concentration of the source can be absolutely calculated with an accuracy of better than 10 %.
Marcel Snels, Stefania Stefani, Angelo Boccaccini, David Biondi, and Giuseppe Piccioni
Atmos. Meas. Tech., 14, 7187–7197, https://doi.org/10.5194/amt-14-7187-2021, https://doi.org/10.5194/amt-14-7187-2021, 2021
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A novel simulation chamber, PASSxS (Planetary Atmosphere Simulation System for Spectroscopy), has been developed for absorption measurements with a Fourier transform spectrometer (FTS) and possibly a cavity ring-down (CRD) spectrometer, with a sample temperature ranging from 100 K up to 550 K, while the pressure of the gas can be varied up to 60 bar. These temperature and pressure ranges cover a significant part of the planetary atmospheres in the solar system and possibly extrasolar planets.
Lukas Kohl, Markku Koskinen, Tatu Polvinen, Salla Tenhovirta, Kaisa Rissanen, Marjo Patama, Alessandro Zanetti, and Mari Pihlatie
Atmos. Meas. Tech., 14, 4445–4460, https://doi.org/10.5194/amt-14-4445-2021, https://doi.org/10.5194/amt-14-4445-2021, 2021
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We present ShoTGa-FluMS, a measurement system designed for continuous and automated measurements of trace gas and volatile organic compound (VOC) fluxes from plant shoots. ShoTGa-FluMS uses transparent shoot enclosures equipped with cooling elements, automatically replaces fixated CO2, and removes transpired water from the enclosure, thus solving multiple technical problems that have so far prevented automated plant shoot trace gas flux measurements.
Pharahilda M. Steur, Hubertus A. Scheeren, Dave D. Nelson, J. Barry McManus, and Harro A. J. Meijer
Atmos. Meas. Tech., 14, 4279–4304, https://doi.org/10.5194/amt-14-4279-2021, https://doi.org/10.5194/amt-14-4279-2021, 2021
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For understanding the sources and sinks of atmospheric CO2, measurement of stable isotopes has proven to be highly valuable. We present a new method using laser absorption spectroscopy to simultaneously conduct measurements of three CO2 isotopes, directly on dry-air samples. This new method reduces sample preparation time significantly, compared to the conventional method in which measurements are conducted on pure CO2, and avoids measurement biases introduced by CO2 extraction.
Mingyi Wang, Xu-Cheng He, Henning Finkenzeller, Siddharth Iyer, Dexian Chen, Jiali Shen, Mario Simon, Victoria Hofbauer, Jasper Kirkby, Joachim Curtius, Norbert Maier, Theo Kurtén, Douglas R. Worsnop, Markku Kulmala, Matti Rissanen, Rainer Volkamer, Yee Jun Tham, Neil M. Donahue, and Mikko Sipilä
Atmos. Meas. Tech., 14, 4187–4202, https://doi.org/10.5194/amt-14-4187-2021, https://doi.org/10.5194/amt-14-4187-2021, 2021
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Atmospheric iodine species are often short-lived with low abundance and have thus been challenging to measure. We show that the bromide chemical ionization mass spectrometry, compatible with both the atmospheric pressure and reduced pressure interfaces, can simultaneously detect various gas-phase iodine species. Combining calibration experiments and quantum chemical calculations, we quantify detection sensitivities to HOI, HIO3, I2, and H2SO4, giving detection limits down to < 106 molec. cm-3.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech., 14, 2515–2527, https://doi.org/10.5194/amt-14-2515-2021, https://doi.org/10.5194/amt-14-2515-2021, 2021
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The atmospheric helium-to-nitrogen ratio is a promising indicator for circulation changes in the upper atmosphere and fossil fuel burning by humans. We present a very precise analysis method to determine changes in the helium-to-nitrogen ratio of air samples. The method relies on stabilizing the gas flow to a mass spectrometer and continuous removal of reactive gases. These advances enable new insights and monitoring possibilities for anthropogenic and natural processes.
Alexander Zaytsev, Martin Breitenlechner, Anna Novelli, Hendrik Fuchs, Daniel A. Knopf, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 14, 2501–2513, https://doi.org/10.5194/amt-14-2501-2021, https://doi.org/10.5194/amt-14-2501-2021, 2021
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We have developed an online method for speciated measurements of organic peroxy radicals and stabilized Criegee intermediates using chemical derivatization combined with chemical ionization mass spectrometry. Chemical derivatization prevents secondary radical reactions and eliminates potential interferences. Comparison between our measurements and results from numeric modeling shows that the method can be used for the quantification of a wide range of atmospheric radicals and intermediates.
Einar Karu, Mengze Li, Lisa Ernle, Carl A. M. Brenninkmeijer, Jos Lelieveld, and Jonathan Williams
Atmos. Meas. Tech., 14, 1817–1831, https://doi.org/10.5194/amt-14-1817-2021, https://doi.org/10.5194/amt-14-1817-2021, 2021
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A gas measurement device was developed to measure trace gases (ppt level) in the air based on an atomic emission detector. It combines a cryogenic pre-concentrator (CryoTrap), a gas chromatograph (GC), and a new high-resolution atomic emission detector (AED). The CryoTrap–GC–AED instrumental setup, limits of detection, and elemental performance are presented and discussed. Two measurement case studies are reported: one in a Finnish boreal forest and the other based on an aircraft campaign.
Ikumi Oyabu, Kenji Kawamura, Kyotaro Kitamura, Remi Dallmayr, Akihiro Kitamura, Chikako Sawada, Jeffrey P. Severinghaus, Ross Beaudette, Anaïs Orsi, Satoshi Sugawara, Shigeyuki Ishidoya, Dorthe Dahl-Jensen, Kumiko Goto-Azuma, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Meas. Tech., 13, 6703–6731, https://doi.org/10.5194/amt-13-6703-2020, https://doi.org/10.5194/amt-13-6703-2020, 2020
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Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
Bernhard Bereiter, Béla Tuzson, Philipp Scheidegger, André Kupferschmid, Herbert Looser, Lars Mächler, Daniel Baggenstos, Jochen Schmitt, Hubertus Fischer, and Lukas Emmenegger
Atmos. Meas. Tech., 13, 6391–6406, https://doi.org/10.5194/amt-13-6391-2020, https://doi.org/10.5194/amt-13-6391-2020, 2020
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The record of past greenhouse gas composition from ice cores is crucial for our understanding of global climate change. Deciphering this archive requires highly accurate and spatially resolved analysis of the very small amount of gas that is trapped in the ice. This is achieved with a mid-IR laser absorption spectrometer that provides simultaneous, high-precision measurements of CH4, N2O, CO2, and δ13C(CO2) and which will be coupled to a quantitative sublimation extraction method.
Natalie I. Keehan, Bellamy Brownwood, Andrey Marsavin, Douglas A. Day, and Juliane L. Fry
Atmos. Meas. Tech., 13, 6255–6269, https://doi.org/10.5194/amt-13-6255-2020, https://doi.org/10.5194/amt-13-6255-2020, 2020
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This paper describes a new instrument (a thermal-dissociation–cavity ring-down spectrometer, TD-CRDS) for the measurement of key atmospheric gaseous and particle-phase molecules containing the nitrate functional group. Several operational considerations affecting the measurements are described, as well as several characterization experiments comparing the TD-CRDS measurements to analogous measurements from other instruments. Examples are given using a TD-CRDS for ambient and laboratory studies.
Mohammed S. Alam, Leigh R. Crilley, James D. Lee, Louisa J. Kramer, Christian Pfrang, Mónica Vázquez-Moreno, Milagros Ródenas, Amalia Muñoz, and William J. Bloss
Atmos. Meas. Tech., 13, 5977–5991, https://doi.org/10.5194/amt-13-5977-2020, https://doi.org/10.5194/amt-13-5977-2020, 2020
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We report on the interference arising in measurements of nitrogen oxides (NOx) from the presence of a range of alkenes in sampled air when using the most widespread air quality monitoring technique for chemiluminescence detection. Interferences of up to 11 % are reported, depending upon the alkene present and conditions used. Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high volatile organic compound and low NOx environments.
Daniel Marno, Cheryl Ernest, Korbinian Hens, Umar Javed, Thomas Klimach, Monica Martinez, Markus Rudolf, Jos Lelieveld, and Hartwig Harder
Atmos. Meas. Tech., 13, 2711–2731, https://doi.org/10.5194/amt-13-2711-2020, https://doi.org/10.5194/amt-13-2711-2020, 2020
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In this study, a calibration device for OH and HO2 instruments is characterized at pressures of 275 to 1000 mbar, allowing instrument pressure sensitivity to be quantified to an accuracy of 22 % (1σ). Computational fluid dynamic simulations supporting the understanding of interactions between generated HOx and the instrument inlet led to enhanced determination of factors affecting instrument sensitivity.
Joschka Pfeifer, Mario Simon, Martin Heinritzi, Felix Piel, Lena Weitz, Dongyu Wang, Manuel Granzin, Tatjana Müller, Steffen Bräkling, Jasper Kirkby, Joachim Curtius, and Andreas Kürten
Atmos. Meas. Tech., 13, 2501–2522, https://doi.org/10.5194/amt-13-2501-2020, https://doi.org/10.5194/amt-13-2501-2020, 2020
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Ammonia is an important atmospheric trace gas that affects secondary aerosol formation and, together with sulfuric acid, the formation of new particles. A measurement technique is presented that uses high-resolution mass spectrometry and protonated water clusters for the ultrasensitive detection of ammonia at single-digit parts per trillion by volume levels. The instrument is further capable of measuring amines and a suite of iodine compounds at sub-parts per trillion by volume levels.
Roberto Sommariva, Louisa J. Kramer, Leigh R. Crilley, Mohammed S. Alam, and William J. Bloss
Atmos. Meas. Tech., 13, 1655–1670, https://doi.org/10.5194/amt-13-1655-2020, https://doi.org/10.5194/amt-13-1655-2020, 2020
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Ozone is a key atmospheric pollutant formed through chemical processing of natural and anthropogenic emissions and removed by reaction with organic compounds emitted by plants. We describe a new instrument – the
Total Ozone Reactivity Systemor TORS – that measures the total loss of ozone in the troposphere. The objective of the TORS instrument is to provide an estimate of the organic compounds emitted by plants which are not measured and thus to improve our understanding of the ozone budget.
John W. Birks, Andrew A. Turnipseed, Peter C. Andersen, Craig J. Williford, Stanley Strunk, Brian Carpenter, and Christine A. Ennis
Atmos. Meas. Tech., 13, 1001–1018, https://doi.org/10.5194/amt-13-1001-2020, https://doi.org/10.5194/amt-13-1001-2020, 2020
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We describe a portable calibration source of nitric oxide (NO) based on the photolysis of nitrous oxide. Combining this with a previous photolytic ozone (O3) source yields a calibrator that produces known mixing ratios of NO, O3, and nitrogen dioxide (NO2); NO2 is produced by the reaction of NO with O3. This portable
NO2/NO/O3 calibration source requires no external gas cylinders and can be used as a standard to calibrate O3 and NOx air pollution monitors in the field.
Thomas H. Speak, Mark A. Blitz, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 13, 839–852, https://doi.org/10.5194/amt-13-839-2020, https://doi.org/10.5194/amt-13-839-2020, 2020
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OH and HO2 radicals are important trace constituents of the atmosphere that are closely coupled via several types of reaction. This paper describes a new laboratory method to simultaneously determine OH kinetics and HO2 yields from chemical processes. The instrument also provides some time resolution on HO2 detection allowing one to separate HO2 produced from the target reaction from HO2 arising from secondary chemistry. Examples of applications are presented.
Ece Satar, Peter Nyfeler, Bernhard Bereiter, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 101–117, https://doi.org/10.5194/amt-13-101-2020, https://doi.org/10.5194/amt-13-101-2020, 2020
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Good-quality measurements of atmospheric trace gases are only possible with regular calibrations and stable measurements from the standard cylinders. This study investigates instabilities due to surface effects on newly built aluminum and steel cylinders. We present measurements over a set of temperature and pressure ranges for the amount fractions of CO2, CO, CH4 and H2O using a commercial and a novel laser spectroscopic analyzer.
Ece Satar, Peter Nyfeler, Céline Pascale, Bernhard Niederhauser, and Markus Leuenberger
Atmos. Meas. Tech., 13, 119–130, https://doi.org/10.5194/amt-13-119-2020, https://doi.org/10.5194/amt-13-119-2020, 2020
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To ensure the best preparation and measurement conditions for trace gases, usage of coated materials is in demand in gas metrology and atmospheric measurement communities. In this article, the previously introduced aluminum measurement chamber is used to investigate materials such as glass, aluminum, copper, brass, steel and three different commercially available coatings. Our measurements focus on temperature and pressure dependencies for the species CO2, CO, CH4 and H2O using a CRDS analyzer.
Tanja J. Schuck, Ann-Katrin Blank, Elisa Rittmeier, Jonathan Williams, Carl A. M. Brenninkmeijer, Andreas Engel, and Andreas Zahn
Atmos. Meas. Tech., 13, 73–84, https://doi.org/10.5194/amt-13-73-2020, https://doi.org/10.5194/amt-13-73-2020, 2020
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Air sample collection aboard aircraft is a tool to measure atmospheric trace gas mixing ratios at altitude. We present results on the stability of 28 halocarbons during storage of air samples collected in stainless-steel flasks inside an automated air sampling unit which is part of the CARIBIC instrument package. Selected fluorinated compounds grew during the experiments while short-lived compounds were depleted. Individual substances were additionally influenced by high mixing ratios of ozone.
Tesfaye A. Berhanu, John Hoffnagle, Chris Rella, David Kimhak, Peter Nyfeler, and Markus Leuenberger
Atmos. Meas. Tech., 12, 6803–6826, https://doi.org/10.5194/amt-12-6803-2019, https://doi.org/10.5194/amt-12-6803-2019, 2019
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Accurate measurement of variations in atmospheric O2 can provide useful information about atmospheric, biospheric, and oceanic processes, which is a challenge for existing measurement techniques. Here, we introduce a newly built high-precision, stable CRDS analyzer (Picarro G2207) that can measure O2 mixing ratios with a short-term precision of < 1 ppm and only requires calibration every 12 h. Measurements from tower and mountain sites are also presented.
Markus Leiminger, Stefan Feil, Paul Mutschlechner, Arttu Ylisirniö, Daniel Gunsch, Lukas Fischer, Alfons Jordan, Siegfried Schobesberger, Armin Hansel, and Gerhard Steiner
Atmos. Meas. Tech., 12, 5231–5246, https://doi.org/10.5194/amt-12-5231-2019, https://doi.org/10.5194/amt-12-5231-2019, 2019
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We introduce an alternative type of atmospheric pressure interface time-of-flight mass spectrometer (APi-TOF) with the main difference of using hexapole instead of quadrupole ion guides. The transfer of cluster ions through the hexapoles was characterised with focus on transmission efficiency, mass range and fragmentation of cluster ions. At the CERN CLOUD experiment we compared the performance of the ioniAPi-TOF with a standard quadrupole APi-TOF under controlled conditions.
Michal Lacko, Nijing Wang, Kristýna Sovová, Pavel Pásztor, and Patrik Španěl
Atmos. Meas. Tech., 12, 4965–4982, https://doi.org/10.5194/amt-12-4965-2019, https://doi.org/10.5194/amt-12-4965-2019, 2019
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The soft chemical ionization analytical technique of selected ion flow tube mass spectrometry, SIFT-MS, was enhanced by a fast GC pre-separation unit to identify individual isomers. Experiments were carried out with two GC columns, MXT-1 and MXT-Volatiles, using two reagent ions, H3O+ and NO+, on monoterpene samples (an artificial mixture and coniferous needles). Analyses of product ion ratios allowed for quantification of multiple monoterpenes in partially separated chromatograms.
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Short summary
We have designed a process for removing methane from a gas stream so that nitrous oxide can be measured without interference. These are both key long-lived greenhouse gases frequently studied in relation to ice cores, plants, water treatment and so on. However, many researchers are not aware of the problem of methane interference, and in addition there have not been good methods available for solving the problem. Here we present and evaluate such a method.
We have designed a process for removing methane from a gas stream so that nitrous oxide can be...
