Articles | Volume 14, issue 6
Research article 09 Jun 2021
Research article | 09 Jun 2021
Simultaneous measurement of δ13C, δ18O and δ17O of atmospheric CO2 – performance assessment of a dual-laser absorption spectrometer
Pharahilda M. Steur et al.
No articles found.
Timo Vesala, Kukka-Maaria Kohonen, Arnaud P. Praplan, Linda M. J. Kooijmans, Lenka Foltýnová, Pasi Kolari, Markku Kulmala, Jaana Bäck, David Nelson, Dan Yakir, Mark Zahniser, and Ivan Mammarella
Atmos. Chem. Phys. Discuss.,
Revised manuscript under review for ACPShort summary
Carbonyl sulfide (COS) provides new insights into carbon cycle research and impacts the climate. We present an easy-to-use flux parameterization and the longest forest-atmosphere COS exchange measurements, allowing to study both seasonal and interannual variability. We observed only uptake of COS by the forest on annual basis, with 37 % variability between years. Upscaling the boreal COS uptake by a biosphere model indicates a significant missing COS sink at high latitudes.
Linh N. T. Nguyen, Harro A. J. Meijer, Charlotte van Leeuwen, Bert A. M. Kers, Bert A. Scheeren, Anna E. Jones, Neil Brough, Thomas Barningham, Penelope A. Pickers, Andrew C. Manning, and Ingrid T. Luijkx
Earth Syst. Sci. Data Discuss.,
Revised manuscript under review for ESSDShort summary
We present 20-year flask sample records of atmospheric CO2, O2, and APO from stations Lutjewad (the Netherlands), Mace Head (Ireland), and Halley (Antarctica). Data from Lutjewad and Mace Head show similar long-term trends and seasonal cycles agreeing with measurements from another station (Weybourne, UK). Measurements from Halley agree partly with those conducted by other institutes. From our 2002–2018 records at Lutjewad and Mace Head, we find good agreement for the global ocean carbon uptake.
Yenny Gonzalez, Róisín Commane, Ethan Manninen, Bruce C. Daube, Luke D. Schiferl, J. Barry McManus, Kathryn McKain, Eric J. Hintsa, James W. Elkins, Stephen A. Montzka, Colm Sweeney, Fred Moore, Jose L. Jimenez, Pedro Campuzano Jost, Thomas B. Ryerson, Ilann Bourgeois, Jeff Peischl, Chelsea R. Thompson, Eric Ray, Paul O. Wennberg, John Crounse, Michelle Kim, Hannah M. Allen, Paul A. Newman, Britton B. Stephens, Eric C. Apel, Rebecca S. Hornbrook, Benjamin A. Nault, Eric Morgan, and Steven C. Wofsy
Atmos. Chem. Phys., 21, 11113–11132,Short summary
Vertical profiles of N2O and a variety of chemical species and aerosols were collected nearly from pole to pole over the oceans during the NASA Atmospheric Tomography mission. We observed that tropospheric N2O variability is strongly driven by the influence of stratospheric air depleted in N2O, especially at middle and high latitudes. We also traced the origins of biomass burning and industrial emissions and investigated their impact on the variability of tropospheric N2O.
Camille Yver-Kwok, Carole Philippon, Peter Bergamaschi, Tobias Biermann, Francescopiero Calzolari, Huilin Chen, Sebastien Conil, Paolo Cristofanelli, Marc Delmotte, Juha Hatakka, Michal Heliasz, Ove Hermansen, Kateřina Komínková, Dagmar Kubistin, Nicolas Kumps, Olivier Laurent, Tuomas Laurila, Irene Lehner, Janne Levula, Matthias Lindauer, Morgan Lopez, Ivan Mammarella, Giovanni Manca, Per Marklund, Jean-Marc Metzger, Meelis Mölder, Stephen M. Platt, Michel Ramonet, Leonard Rivier, Bert Scheeren, Mahesh Kumar Sha, Paul Smith, Martin Steinbacher, Gabriela Vítková, and Simon Wyss
Atmos. Meas. Tech., 14, 89–116,Short summary
The Integrated Carbon Observation System (ICOS) is a pan-European research infrastructure which provides harmonized and high-precision scientific data on the carbon cycle and the greenhouse gas (GHG) budget. All stations have to undergo a rigorous assessment before being labeled, i.e., receiving approval to join the network. In this paper, we present the labeling process for the ICOS atmospheric network through the 23 stations that were labeled between November 2017 and November 2019.
Dipayan Paul, Hubertus A. Scheeren, Henk G. Jansen, Bert A. M. Kers, John B. Miller, Andrew M. Crotwell, Sylvia E. Michel, Luciana V. Gatti, Lucas G. Domingues, Caio S. C. Correia, Raiane A. L. Neves, Harro A. J. Meijer, and Wouter Peters
Atmos. Meas. Tech., 13, 4051–4064,Short summary
For reliable measurements of CO2 mole fractions and its stable isotope composition in air samples, one needs to carefully dry them during collection. Here we describe evaluation of a portable, consumable-free and power-free Nafion-based drying system that is currently being used for sample collection over the Amazon. Laboratory tests indicate that this Nafion-based system does not influence the mole fraction measurements of CH4, CO, N2O, SF6, and CO2 and the stable isotope composition of CO2.
Haiyan Ni, Ru-Jin Huang, Junji Cao, Wenting Dai, Jiamao Zhou, Haoyue Deng, Anita Aerts-Bijma, Harro A. J. Meijer, and Ulrike Dusek
Atmos. Chem. Phys., 19, 10405–10422,Short summary
We apply radiocarbon source apportionment of more volatile organic carbon (mvOC) to winter aerosol samples from six Chinese cities. We find a consistently larger contribution of fossil sources to mvOC than to secondary or total organic carbon. Fossil mvOC concentrations are strongly correlated with primary fossil OC but not with secondary fossil OC. The variability in nonfossil mvOC seems to be related to both primary and secondary biomass burning sources.
Haiyan Ni, Ru-Jin Huang, Junji Cao, Weiguo Liu, Ting Zhang, Meng Wang, Harro A. J. Meijer, and Ulrike Dusek
Atmos. Chem. Phys., 18, 16363–16383,Short summary
Seasonal changes in organic carbon (OC) and elemental carbon (EC) sources in Xi'an, China, are investigated based on measurements of radiocarbon and the stable isotope 13C. Relative contributions to EC from biomass burning, coal combustion, and vehicle emissions change substantially between different seasons. Biomass burning contributes 60 % to the EC increment in winter. Comparing concentrations and sources of primary OC to total OC suggests non-negligible OC loss due to active photochemistry.
Truls Andersen, Bert Scheeren, Wouter Peters, and Huilin Chen
Atmos. Meas. Tech., 11, 2683–2699,Short summary
We developed and field-tested a UAV-based active AirCore for atmospheric measurements of CO2, CH4, and CO. AirCore is an innovative tool that passively samples air using the atmospheric pressure gradient during descent. Here we have taken further steps to change the “active” sampling process with a pump, miniaturize it, and deploy it on a UAV. The active AirCore system opens up a wide variety of opportunities, e.g., quantifying CH4 emissions from wetlands, landfills, other CH4 hot spots.
Peter Bergamaschi, Ute Karstens, Alistair J. Manning, Marielle Saunois, Aki Tsuruta, Antoine Berchet, Alexander T. Vermeulen, Tim Arnold, Greet Janssens-Maenhout, Samuel Hammer, Ingeborg Levin, Martina Schmidt, Michel Ramonet, Morgan Lopez, Jost Lavric, Tuula Aalto, Huilin Chen, Dietrich G. Feist, Christoph Gerbig, László Haszpra, Ove Hermansen, Giovanni Manca, John Moncrieff, Frank Meinhardt, Jaroslaw Necki, Michal Galkowski, Simon O'Doherty, Nina Paramonova, Hubertus A. Scheeren, Martin Steinbacher, and Ed Dlugokencky
Atmos. Chem. Phys., 18, 901–920,Short summary
European methane (CH4) emissions are estimated for 2006–2012 using atmospheric in situ measurements from 18 European monitoring stations and 7 different inverse models. Our analysis highlights the potential significant contribution of natural emissions from wetlands (including peatlands and wet soils) to the total European emissions. The top-down estimates of total EU-28 CH4 emissions are broadly consistent with the sum of reported anthropogenic CH4 emissions and the estimated natural emissions.
Heather Graven, Colin E. Allison, David M. Etheridge, Samuel Hammer, Ralph F. Keeling, Ingeborg Levin, Harro A. J. Meijer, Mauro Rubino, Pieter P. Tans, Cathy M. Trudinger, Bruce H. Vaughn, and James W. C. White
Geosci. Model Dev., 10, 4405–4417,Short summary
Modelling of carbon isotopes 13C and 14C in land and ocean components of Earth system models provides opportunities for new insights and improved understanding of global carbon cycling, and for model evaluation. We compiled existing historical datasets to define the annual mean carbon isotopic composition of atmospheric CO2 for 1850–2015 that can be used in CMIP6 and other modelling activities.
Ulrike Dusek, Regina Hitzenberger, Anne Kasper-Giebl, Magdalena Kistler, Harro A. J. Meijer, Sönke Szidat, Lukas Wacker, Rupert Holzinger, and Thomas Röckmann
Atmos. Chem. Phys., 17, 3233–3251,Short summary
Measurements of the radioactive carbon isotope 14C allow to identify the sources of aerosol carbon. We report an extensive 14C source apportionment record in the Netherlands with samples covering a whole year. We discovered that long-range transport has a large influence on aerosol carbon levels. Fossil fuel carbon is least influenced by long-range transport and more regional in origin. Biomass burning seems to be a minor source of aerosol carbon in the Netherlands.
Richard Wehr, Róisín Commane, J. William Munger, J. Barry McManus, David D. Nelson, Mark S. Zahniser, Scott R. Saleska, and Steven C. Wofsy
Biogeosciences, 14, 389–401,Short summary
Leaf stomata influence both photosynthesis and transpiration, coupling the carbon and water cycles, but there is no direct method for estimating stomatal behavior on the ecosystem scale. We use the ecosystem–atmosphere exchange of water, heat, and carbonyl sulfide to estimate canopy-integrated stomatal conductance by two independent methods. We then use that conductance to show that the seasonal dynamics of transpiration and evaporation are different than represented in current biosphere models.
Sander van der Laan, Swagath Manohar, Alex Vermeulen, Fred Bosveld, Harro Meijer, Andrew Manning, Michiel van der Molen, and Ingrid van der Laan-Luijkx
Atmos. Meas. Tech., 9, 5523–5533,Short summary
A new methodology is presented to estimate regional-scale surface fluxes of 222Rn. 222Rn is an increasingly important trace gas which is used to calculate regional-scale greenhouse gas emissions and to validate atmospheric transport models. We tested our method at two atmospheric research stations in the Netherlands and compared our results with measurements from accumulation chambers and two recently published 222Rn soil flux maps for Europe.
Linda M. J. Kooijmans, Nelly A. M. Uitslag, Mark S. Zahniser, David D. Nelson, Stephen A. Montzka, and Huilin Chen
Atmos. Meas. Tech., 9, 5293–5314,Short summary
The accuracy of carbon models, used for the prediction of global climate change, is limited by the knowledge of the uptake of carbon by plants through photosynthesis. Carbonyl sulfide (COS) has been suggested as a tracer for this process. To be able to further explore and verify the application of this novel tracer we have tested a laser spectrometer for its suitability to obtain accurate and high precision measurements of COS and CO2 with both laboratory experiments and field measurements.
Dipayan Paul, Huilin Chen, Henk A. Been, Rigel Kivi, and Harro A. J. Meijer
Atmos. Meas. Tech., 9, 4997–5006,Short summary
Here we describe the determination of C-14 concentration in stratospheric CO2 samples collected using the AirCore sampling method. Two stratospheric AirCore profiles, collected in Sodankylä, were used for this study. The stratospheric profile was divided into six sections. CO2 from each section was extracted and converted to graphite for the determination of C-14 using AMS. Through this study, we show that the AirCore is a viable and valuable sampling method for stratospheric C-14 measurements.
E. N. Koffi, P. Bergamaschi, U. Karstens, M. Krol, A. Segers, M. Schmidt, I. Levin, A. T. Vermeulen, R. E. Fisher, V. Kazan, H. Klein Baltink, D. Lowry, G. Manca, H. A. J. Meijer, J. Moncrieff, S. Pal, M. Ramonet, H. A. Scheeren, and A. G. Williams
Geosci. Model Dev., 9, 3137–3160,Short summary
We evaluate the capability of the TM5 model to reproduce observations of the boundary layer dynamics and the associated variability of trace gases close to the surface, using 222Rn. Focusing on the European scale, we compare the TM5 boundary layer heights with observations from radiosondes, lidar, and ceilometer. Furthermore, we compare TM5 simulations of 222Rn activity concentrations, using a novel, process-based 222Rn flux map over Europe, with 222Rn harmonized measurements from 10 stations.
Undine Zöll, Christian Brümmer, Frederik Schrader, Christof Ammann, Andreas Ibrom, Christophe R. Flechard, David D. Nelson, Mark Zahniser, and Werner L. Kutsch
Atmos. Chem. Phys., 16, 11283–11299,Short summary
Accurate quantification of atmospheric ammonia concentration and exchange fluxes with the land surface has been a major metrological challenge. We demonstrate the applicability of a novel laser device to identify concentration and flux patterns over a peatland ecosystem influenced by nearby agricultural practices. Results help to strengthen air quality monitoring networks, lead to better understanding of ecosystem functionality and improve parameterizations in air chemistry and transport models.
G. van der Wel, H. Fischer, H. Oerter, H. Meyer, and H. A. J. Meijer
The Cryosphere, 9, 1601–1616,Short summary
The diffusion of the stable water isotope signal during firnification of snow is a temperature-dependent process. Therefore, past local temperatures can be derived from the differential diffusion length. In this paper we develop a new method for determining this quantity and compare it with the existing method. Both methods are applied to a large number of synthetic data sets to assess the precision and accuracy of the reconstruction and to a section of the Antarctic EDML ice core record.
L. G. van der Wel, H. A. Been, R. S. W. van de Wal, C. J. P. P. Smeets, and H. A. J. Meijer
The Cryosphere, 9, 1089–1103,Short summary
We performed 2H isotope diffusion measurements in the upper 3 metres of firn at Summit, Greenland, by following over a 4-year period isotope-enriched snow that we deposited. We found that the diffusion process was much less rapid than in the most commonly used model. We discuss several aspects of the diffusion process that are still poorly constrained and might lead to this discrepancy. Quantitative knowledge of diffusion is necessary for use of the diffusion process itself as a climate proxy.
A. S. Lansø, J. Bendtsen, J. H. Christensen, L. L. Sørensen, H. Chen, H. A. J. Meijer, and C. Geels
Biogeosciences, 12, 2753–2772,Short summary
The air-sea CO2 exchange is investigated in the coastal region of the Baltic Sea and Danish inner waters. The impact of short-term variability in atmospheric CO2 on the air-sea CO2 exchange is examined, and it is found that ignoring short-term variability in the atmospheric CO2 creates a significant bias in the CO2 exchange. Atmospheric short-term variability is not always included in studies of the air-sea CO2 exchange, but based on the present study, we recommend it to be so in the future.
R. Locatelli, P. Bousquet, F. Hourdin, M. Saunois, A. Cozic, F. Couvreux, J.-Y. Grandpeix, M.-P. Lefebvre, C. Rio, P. Bergamaschi, S. D. Chambers, U. Karstens, V. Kazan, S. van der Laan, H. A. J. Meijer, J. Moncrieff, M. Ramonet, H. A. Scheeren, C. Schlosser, M. Schmidt, A. Vermeulen, and A. G. Williams
Geosci. Model Dev., 8, 129–150,
B. Xiang, D. D. Nelson, J. B. McManus, M. S. Zahniser, R. A. Wehr, and S. C. Wofsy
Atmos. Meas. Tech., 7, 4445–4453,Short summary
We designed and built a spectrometer, ABsolute Carbon dioxide (ABC), to measure atmospheric concentration of carbon dioxide. This instrument was tested in a forest environment for almost a year. Based on results from this long-term field deployment, we proved that ABC has the capability of performing high-accuracy, unattended, continuous field measurements with minimal use of reference gas cylinders.
D. Bozhinova, M. K. van der Molen, I. R. van der Velde, M. C. Krol, S. van der Laan, H. A. J. Meijer, and W. Peters
Atmos. Chem. Phys., 14, 7273–7290,
U. Dusek, M. Monaco, M. Prokopiou, F. Gongriep, R. Hitzenberger, H. A. J. Meijer, and T. Röckmann
Atmos. Meas. Tech., 7, 1943–1955,
G. W. Santoni, B. C. Daube, E. A. Kort, R. Jiménez, S. Park, J. V. Pittman, E. Gottlieb, B. Xiang, M. S. Zahniser, D. D. Nelson, J. B. McManus, J. Peischl, T. B. Ryerson, J. S. Holloway, A. E. Andrews, C. Sweeney, B. Hall, E. J. Hintsa, F. L. Moore, J. W. Elkins, D. F. Hurst, B. B. Stephens, J. Bent, and S. C. Wofsy
Atmos. Meas. Tech., 7, 1509–1526,
I. T. van der Laan-Luijkx, S. van der Laan, C. Uglietti, M. F. Schibig, R. E. M. Neubert, H. A. J. Meijer, W. A. Brand, A. Jordan, J. M. Richter, M. Rothe, and M. C. Leuenberger
Atmos. Meas. Tech., 6, 1805–1815,
B. Xiang, D. D. Nelson, J. B. McManus, M. S. Zahniser, and S. C. Wofsy
Atmos. Meas. Tech., 6, 1611–1621,
B. Tuzson, K. Zeyer, M. Steinbacher, J. B. McManus, D. D. Nelson, M. S. Zahniser, and L. Emmenegger
Atmos. Meas. Tech., 6, 927–936,
Related subject area
Subject: Gases | Technique: Laboratory Measurement | Topic: Instruments and PlatformsA simulation chamber for absorption spectroscopy in planetary atmospheresAn automated system for trace gas flux measurements from plant foliage and other plant compartmentsMeasurement of iodine species and sulfuric acid using bromide chemical ionization mass spectrometersPhotochemical method for removing methane interference for improved gas analysisA method for resolving changes in atmospheric He ∕ N2 as an indicator of fossil fuel extraction and stratospheric circulationApplication of chemical derivatization techniques combined with chemical ionization mass spectrometry to detect stabilized Criegee intermediates and peroxy radicals in the gas phaseAtomic emission detector with gas chromatographic separation and cryogenic pre-concentration (CryoTrap–GC–AED) for atmospheric trace gas measurementsNew 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 extractionHigh-precision laser spectrometer for multiple greenhouse gas analysis in 1 mL air from ice core samplesA thermal-dissociation–cavity ring-down spectrometer (TD-CRDS) for the detection of organic nitrates in gas and particle phasesInterference from alkenes in chemiluminescent NOx measurementsCalibration 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 spectrometryAn instrument for in situ measurement of total ozone reactivityPortable calibrator for NO based on the photolysis of N2O and a combined NO2∕NO∕O3 source for field calibrations of air pollution monitorsA new instrument for time-resolved measurement of HO2 radicalsInvestigation of adsorption and desorption behavior of small-volume cylinders and its relevance for atmospheric trace gas analysisTowards an understanding of surface effects: testing of various materials in a small volume measurement chamber and its relevance for atmospheric trace gas analysisStability of halocarbons in air samples stored in stainless- steel canistersHigh-precision atmospheric oxygen measurement comparisons between a newly built CRDS analyzer and existing measurement techniquesCharacterisation of the transfer of cluster ions through an atmospheric pressure interface time-of-flight mass spectrometer with hexapole ion guidesAddition of fast gas chromatography to selected ion flow tube mass spectrometry for analysis of individual monoterpenes in mixturesMeasurements of delays of gas-phase compounds in a wide variety of tubing materials due to gas–wall interactionsEffects of gas–wall interactions on measurements of semivolatile compounds and small polar moleculesCharacterization of a commercial lower-cost medium-precision non-dispersive infrared sensor for atmospheric CO2 monitoring in urban areasEvaluating the performance of five different chemical ionization techniques for detecting gaseous oxygenated organic speciesCavity-enhanced photoacoustic sensor based on a whispering-gallery-mode diode laserUsing collision-induced dissociation to constrain sensitivity of ammonia chemical ionization mass spectrometry (NH4+ CIMS) to oxygenated volatile organic compoundsA broadband cavity-enhanced spectrometer for atmospheric trace gas measurements and Rayleigh scattering cross sections in the cyan region (470–540 nm)Large-volume air sample system for measuring 34S∕32S isotope ratio of carbonyl sulfideNew and improved infrared absorption cross sections for trichlorofluoromethane (CFC-11)Experiments with CO2-in-air reference gases in high-pressure aluminum cylindersPreflight calibration of the Chinese Environmental Trace Gases Monitoring Instrument (EMI)Production of highly oxygenated organic molecules (HOMs) from trace contaminants during isoprene oxidationPreparation and analysis of zero gases for the measurement of trace VOCs in air monitoringA steady-state continuous flow chamber for the study of daytime and nighttime chemistry under atmospherically relevant NO levelsOptical characterisation of three reference Dobsons in the ATMOZ Project – verification of G. M. B. Dobson's original specificationsA new photometric ozone reference in the Huggins bands: the absolute ozone absorption cross section at the 325 nm HeCd laser wavelengthAssessing the degree of plug flow in oxidation flow reactors (OFRs): a study on a potential aerosol mass (PAM) reactorEffects of gas–wall partitioning in Teflon tubing and instrumentation on time-resolved measurements of gas-phase organic compoundsSystem for δ13C–CO2 and xCO2 analysis of discrete gas samples by cavity ring-down spectroscopyA new method for atmospheric detection of the CH3O2 radicalInfluence of sample temperature and environmental humidity on measurements of benzene in ambient air by transportable GC-PIDThe effects of meteorological parameters and diffusive barrier reuse on the sampling rate of a passive air sampler for gaseous mercuryAn electrospray chemical ionization source for real-time measurement of atmospheric organic and inorganic vaporsCharacterization of interferences to in situ observations of δ13CH4 and C2H6 when using a cavity ring-down spectrometer at industrial sitesThe Caltech Photooxidation Flow Tube reactor: design, fluid dynamics and characterizationImproved methodologies for continuous-flow analysis of stable water isotopes in ice coresStratospheric Air Sub-sampler (SAS) and its application to analysis of Δ17O(CO2) from small air samples collected with an AirCoreSensitive detection of n-alkanes using a mixed ionization mode proton-transfer-reaction mass spectrometer
Marcel Snels, Stefania Stefani, Angelo Boccaccini, David Biondi, and Giuseppe Piccioni
Atmos. Meas. Tech., 14, 7187–7197,Short summary
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,Short summary
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.
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,Short summary
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.
Merve Polat, Jesper Baldtzer Liisberg, Morten Krogsbøll, Thomas Blunier, and Matthew S. Johnson
Atmos. Meas. Tech. Discuss.,
Revised manuscript accepted for AMTShort 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, and 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.
Benjamin Birner, William Paplawsky, Jeffrey Severinghaus, and Ralph F. Keeling
Atmos. Meas. Tech., 14, 2515–2527,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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,Short summary
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.
Benjamin L. Deming, Demetrios Pagonis, Xiaoxi Liu, Douglas A. Day, Ranajit Talukdar, Jordan E. Krechmer, Joost A. de Gouw, Jose L. Jimenez, and Paul J. Ziemann
Atmos. Meas. Tech., 12, 3453–3461,Short summary
Losses or measurement delays of gas-phase compounds sampled through tubing are important to atmospheric science. Here we characterize 14 tubing materials by measuring the effects on step changes in organic compound concentration. We find that polymeric tubings exhibit absorptive partitioning behaviour while glass and metal tubings show adsorptive partitioning. Adsorptive materials impart complex humidity, concentration, and VOC–VOC interaction dependencies that absorptive tubings do not.
Xiaoxi Liu, Benjamin Deming, Demetrios Pagonis, Douglas A. Day, Brett B. Palm, Ranajit Talukdar, James M. Roberts, Patrick R. Veres, Jordan E. Krechmer, Joel A. Thornton, Joost A. de Gouw, Paul J. Ziemann, and Jose L. Jimenez
Atmos. Meas. Tech., 12, 3137–3149,Short summary
Delays or losses of gases in sampling tubing and instrumental surfaces due to surface interactions can lead to inaccurate quantification. By sampling with several chemical ionization mass spectrometers and six tubing materials, we quantify delays of semivolatile organic compounds and small polar gases. Delay times generally increase with decreasing volatility or increasing polarity and also depend on materials. The method and results will inform inlet material selection and instrumental design.
Emmanuel Arzoumanian, Felix R. Vogel, Ana Bastos, Bakhram Gaynullin, Olivier Laurent, Michel Ramonet, and Philippe Ciais
Atmos. Meas. Tech., 12, 2665–2677,Short summary
We tested commercial lower-cost CO2 sensors in laboratory and field studies to see if they can measure atmospheric CO2 mole fractions with less than 1 ppm bias (with monthly calibration), to allow continuous urban CO2 monitoring. We find that the sensors' CO2 readings are influenced by temperature, atmospheric pressure and water vapour content, but this can be corrected for by adding sensors (T, p, RH) and carefully calibrating each sensor against a high-precision instrument.
Matthieu Riva, Pekka Rantala, Jordan E. Krechmer, Otso Peräkylä, Yanjun Zhang, Liine Heikkinen, Olga Garmash, Chao Yan, Markku Kulmala, Douglas Worsnop, and Mikael Ehn
Atmos. Meas. Tech., 12, 2403–2421,Short summary
The impact of aerosol particles on climate and air quality remains poorly understood due to multiple factors. One of the current limitations is the incomplete understanding of the contribution of oxygenated species, formed from the oxidation of volatile organic compounds (VOCs) to aerosol formation. Taking advantage of recent mass spectrometric developments, we have evaluated and compared the capability of multiple state-of-the-art mass spectrometers to detect a wide variety of oxygenated VOCs.
Yufeng Pan, Lei Dong, Hongpeng Wu, Weiguang Ma, Lei Zhang, Wangbao Yin, Liantuan Xiao, Suotang Jia, and Frank K. Tittel
Atmos. Meas. Tech., 12, 1905–1911,Short summary
Photoacoustic spectroscopy has one important advantage: its sensitivity is proportional to the excitation light power and thus the performance of PAS-based sensors can benefit from a high excitation light power. We developed a cavity-enhanced photoacoustic sensor in which a photoacoustic cell was placed into a high-finesse optical cavity. A signal gain factor of 166 was observed. For C2H2 detection, a 1σ detection limit of 0.45 ppmV was obtained at atmospheric pressure with a 1 s averaging time.
Alexander Zaytsev, Martin Breitenlechner, Abigail R. Koss, Christopher Y. Lim, James C. Rowe, Jesse H. Kroll, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 1861–1870,Short summary
We present the development of a chemical ionization mass spectrometer which can be operated with either ammonium (NH4+) or hydronium (H3O+) as the reagent ion. We describe a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of detected ammonium–organic ions and hence constrain the sensitivity of the instrument to a wide range of organic compounds that cannot be calibrated directly.
Nick Jordan, Connie Z. Ye, Satyaki Ghosh, Rebecca A. Washenfelder, Steven S. Brown, and Hans D. Osthoff
Atmos. Meas. Tech., 12, 1277–1293,Short summary
A new spectrometer to measure abundances of the atmospheric trace gases nitrogen dioxide and iodine is described. The spectrometer uses a light-emitting diode between 470 and 540 nm and two highly reflective mirrors to yield an effective absorption path of 6.3 km. We remeasured scattering cross sections of common atmospheric gases in the cyan region and present sample NO2 measurements that agreed with those made with a laser-based instrument.
Kazuki Kamezaki, Shohei Hattori, Enno Bahlmann, and Naohiro Yoshida
Atmos. Meas. Tech., 12, 1141–1154,Short summary
Knowledge related to sulfur isotopic composition of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. We present a new sampling system for collecting approx. 10 nmol of OCS from ambient air coupled with a purification system. The system presented herein is useful for application of sulfur isotopic compositions for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.
Jeremy J. Harrison
Atmos. Meas. Tech., 11, 5827–5836,Short summary
CFC-11 is a stratospheric-ozone-depleting molecule which is banned under the Montreal Protocol but still present in the atmosphere due to its long lifetime. Using infrared limb sounders on satellite platforms to monitor its concentration crucially requires accurate laboratory spectroscopic data. This paper describes a new high-resolution infrared absorption cross-section dataset for remote-sensing purposes; this improves upon the one currently available in the HITRAN and GEISA databases.
Michael F. Schibig, Duane Kitzis, and Pieter P. Tans
Atmos. Meas. Tech., 11, 5565–5586,Short summary
For long-term monitoring of CO2 in the atmosphere it is crucial that standard reference gas mixtures stored in high-pressure aluminum cylinders, used to calibrate global measurements, remain stable over their whole time of use. This study finds a reproducible small enrichment as a cylinder is emptied at a low-flow rate, as well as somewhat larger and variable effects when a cylinder is emptied using a high-flow rate.
Min Jie Zhao, Fu Qi Si, Hai Jin Zhou, Shi Mei Wang, Yu Jiang, and Wen Qing Liu
Atmos. Meas. Tech., 11, 5403–5419,Short summary
EMI is a nadir-viewing wide-field imaging spectrometer aiming to quantify the global distribution of tropospheric and stratospheric trace gases. The spectral range is 240–710 nm, with the spectral resolution 0.3–0.5 nm. The preflight accuracy of wavelength calibration is less than 0.05 nm; the accuracy of radiance calibration is less than 5 %. The obtained calibration key data are used for the L1b processor. In-orbit wavelength/radiometric calibration is used to monitor performance changes.
Anne-Kathrin Bernhammer, Lukas Fischer, Bernhard Mentler, Martin Heinritzi, Mario Simon, and Armin Hansel
Atmos. Meas. Tech., 11, 4763–4773,Short summary
During new particle formation (NPF) studies from pure isoprene oxidation in the CLOUD chamber at CERN we observed unexpected ion signals. We identified two origins of these signals: first secondary association reactions of protonated isoprene with isoprene within the PTR3 reaction chamber and, second, polymerization of isoprene inside the gas bottle. In order to study NPF from pure isoprene oxidation we had to install a cryogenic trap in the isoprene inlet line to remove polymerized isoprene.
Jennifer Englert, Anja Claude, Alessia Demichelis, Stefan Persijn, Annarita Baldan, Jianrong Li, Christian Plass-Duelmer, Katja Michl, Erasmus Tensing, Rina Wortman, Yousra Ghorafi, Maricarmen Lecuna, Guido Sassi, Maria Paola Sassi, and Dagmar Kubistin
Atmos. Meas. Tech., 11, 3197–3203,Short summary
For volatile organic compound (VOC) observations, zero gases free of VOC traces are essential for the characterisation of the measurement devices and procedures, for instrument operation as well as for calibrations. Three gas purifiers were tested for their removal efficiency of VOCs following a standardised procedure. Results show that not all purification methods removed VOCs from the zero gas and that a gas purifier needs to be tested before its intended application in the field.
Xuan Zhang, John Ortega, Yuanlong Huang, Stephen Shertz, Geoffrey S. Tyndall, and John J. Orlando
Atmos. Meas. Tech., 11, 2537–2551,Short summary
We present the development and characterization of the NCAR Atmospheric Simulation Chamber, which is operated in steady state continuous flow mode for simulating atmospheric daytime and nighttime chemistry over chemical regimes not accessible in traditional static chamber experiments. We focus on establishing an
intermediate NOregime characterized by a constant steady-state NO level ranging from tens of ppt to a few ppb in the chamber.
Ulf Köhler, Saulius Nevas, Glen McConville, Robert Evans, Marek Smid, Martin Stanek, Alberto Redondas, and Fritz Schönenborn
Atmos. Meas. Tech., 11, 1989–1999,Short summary
Laboratory investigations of optical characteristics of three standard Dobsons provide real wavelength settings and slit functions. These parameters were compared with the original values given in the manuals. The differences between real and nominal values are not too large, but their application will in any case improve the quality of the total ozone column measurements in the global network. This improvement was the main objective of the ATMOZ project funding these activities.
Christof Janssen, Hadj Elandaloussi, and Julian Gröbner
Atmos. Meas. Tech., 11, 1707–1723,Short summary
Monitoring ozone layer recovery at a rate of few percent per decade requires dedicated instrumentation and spectroscopic data of the highest quality. Highly accurate absorption cross sections of ozone are rare, especially in the important UV region between 300 and 340 nm. Our measurement provides the first reference point with permil level of accuracy in this range. Interestingly, our value is lower than currently used data. This might resolve an inconsistency between UV and IR measurements.
Dhruv Mitroo, Yujian Sun, Daniel P. Combest, Purushottam Kumar, and Brent J. Williams
Atmos. Meas. Tech., 11, 1741–1756,Short summary
In light of the widespread use of chemical reactors that simulate daytime atmospheric chemistry, a more critical analysis of the engineering behind new ones is needed. This work seeks to evaluate the geometry and flow dynamics inside a novel reactor, the potential aerosol mass (PAM) reactor, to help researchers tailor its use based upon what chemistry is investigated.
Demetrios Pagonis, Jordan E. Krechmer, Joost de Gouw, Jose L. Jimenez, and Paul J. Ziemann
Atmos. Meas. Tech., 10, 4687–4696,Short summary
Laboratory studies were conducted to investigate gas-wall partitioning of atmospheric organic compounds in Teflon tubing and inside an instrument used to monitor concentrations. Rapid partitioning caused time delays in instrument response that vary with tubing length and diameter, flow rate, and compound volatility. Tubing delay times of seconds to hours were described using a model that also included effects of instrument surfaces. The results can enable better design of air sampling systems.
Dane Dickinson, Samuel Bodé, and Pascal Boeckx
Atmos. Meas. Tech., 10, 4507–4519,Short summary
Cavity ring-down spectroscopy (CRDS) is an increasingly popular technology for isotope analysis of trace gases. However, most commercial CRDS instruments are designed for continuous gas sampling and cannot reliably measure small discrete samples. We present a novel technical adaptation that allows routine analysis of 50 mL syringed samples on an isotopic-CO2 CRDS unit. Our method offers excellent accuracy and precision, fast sample throughput, and is easily implemented in other CRDS instruments.
Lavinia Onel, Alexander Brennan, Paul W. Seakins, Lisa Whalley, and Dwayne E. Heard
Atmos. Meas. Tech., 10, 3985–4000,Short summary
Methyl peroxy (CH3O2) radicals are the most abundant organic peroxy radical species and are critical intermediates in rapid chemical cycling at the heart of tropospheric oxidation. Despite their importance, at present CH3O2 radicals are not specifically measured in the atmosphere by any direct or indirect method. This work presents a new method for the selective and sensitive detection of CH3O2 radicals and its use for the measurement of CH3O2 in the atmospheric simulation chamber HIRAC.
Cristina Romero-Trigueros, Marta Doval Miñarro, Esther González Duperón, and Enrique González Ferradás
Atmos. Meas. Tech., 10, 4013–4022,Short summary
Benzene is a well-known carcinogen which is present in ambient air. Its concentrations have to be continuosly monitored by law. To obtain reliable and comparable measurements, benzene analysers have to be calibrated with standards. These standards are usually prepared without humidity. However, real measurements can be influenced by it. In this work we have found that ambient humidity has an effect on measurements, which depends on both the absolute humidity and the benzene concentration.
David S. McLagan, Carl P. J. Mitchell, Haiyong Huang, Batual Abdul Hussain, Ying Duan Lei, and Frank Wania
Atmos. Meas. Tech., 10, 3651–3660,Short summary
Laboratory experiments indicate that the sampling rate of a passive air sampler for gaseous mercury is (1) not affected by relative humidity, (2) increases slightly with increasing temperature because of the effect of temperature on molecular diffusivity, (3) increases only slightly with wind speed as long as the wind speed is at least 1 m/s, and (4) is not changed when previously deployed diffusive barriers are used.
Yue Zhao, Jeremy K. Chan, Felipe D. Lopez-Hilfiker, Megan A. McKeown, Emma L. D'Ambro, Jay G. Slowik, Jeffrey A. Riffell, and Joel A. Thornton
Atmos. Meas. Tech., 10, 3609–3625,Short summary
We present a novel atmospheric pressure electrospray chemical ionization (ESCI) source that can generate intense and stable currents of several specific reagent ions using a range of salt solutions prepared in methanol. We couple the ESCI source to a high-resolution time-of-flight mass spectrometer (HRToF-MS) and assess instrument performance through calibrations using different gas standards and measurements of organic mixtures formed by ozonolysis of α-pinene.
Sabina Assan, Alexia Baudic, Ali Guemri, Philippe Ciais, Valerie Gros, and Felix R. Vogel
Atmos. Meas. Tech., 10, 2077–2091,Short summary
This study is dedicated to improving measurement methods when using a Cavity Ring Down Spectroscopy instrument to measure methane at sites with elevated ethane concentrations such as Oil and Gas sites. The research was undertaken after measurements of natural gas samples suggested biased δ13CH4 results. Two instruments were extensively tested to characterize the cross sensitivities to ethane and δ13CH4 and propose corrections. Results indicate that it is imperative to account for the biases.
Yuanlong Huang, Matthew M. Coggon, Ran Zhao, Hanna Lignell, Michael U. Bauer, Richard C. Flagan, and John H. Seinfeld
Atmos. Meas. Tech., 10, 839–867,Short summary
We report on the development of a new laminar flow tube reactor for the study of gas-phase atmospheric chemistry and secondary organic aerosol formation. The present paper is devoted to the design and fluid dynamical characterization of the reactor. The results of gas and particle residence time distribution experiments in the reactor, together with an evaluation of the effect of non-isothermal conditions, are reported.
Tyler R. Jones, James W. C. White, Eric J. Steig, Bruce H. Vaughn, Valerie Morris, Vasileios Gkinis, Bradley R. Markle, and Spruce W. Schoenemann
Atmos. Meas. Tech., 10, 617–632,Short summary
New measurement systems have been developed that continuously melt ice core samples, in contrast to other methods that analyze a single sample at a time. These newer systems are capable of reducing analysis time by many years and improving data set resolution. In this study, we introduce improved methodologies that optimize the speed, accuracy, and precision of a water isotope continuous-flow system. The presented system will be used for Antarctic and Greenland ice core projects.
Dorota Janina Mrozek, Carina van der Veen, Magdalena E. G. Hofmann, Huilin Chen, Rigel Kivi, Pauli Heikkinen, and Thomas Röckmann
Atmos. Meas. Tech., 9, 5607–5620,Short summary
Stratospheric Air Sub-sampler (SAS) is a device to collect and to store the stratospheric profile of air collected with an AirCore (Karion et al., 2010) in numerous sub-samples. The sub-samples (each of 25 mL at ambient temperature and pressure) can be later introduced to the continuous flow systems to measure for example the isotopic composition of CO2. The performance of the coupled system is demonstrated for a set of air samples from an AirCore flight in November 2014 near Sodankylä, Finland.
Omar Amador-Muñoz, Pawel K. Misztal, Robin Weber, David R. Worton, Haofei Zhang, Greg Drozd, and Allen H. Goldstein
Atmos. Meas. Tech., 9, 5315–5329,Short summary
Proton transfer reaction mass spectrometry (PTR-MS) was used to detect n-alkanes that generally have a lower proton affinity than water and therefore proton transfer (PT) by reaction with H3O+ is not an effective mechanism for their detection. In this study, we developed a method using a conventional PTR-MS to detect n-alkanes by optimizing ion source and drift tube conditions to vary the relative amounts of different primary ions (H3O+, O2+, NO+) in the reaction chamber (drift tube).
Adnew, G. A., Hofmann, M. E., 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 Spectrom., 33, 1363–1380, https://doi.org/10.1002/rcm.8478, 2019. a, b
Allison, C. and Francey, R.: High precision stable isotope measurements of atmospheric trace gases, Reference and intercomparison materials for stable isotopes of light elements, IAEA-TECDOC, Vienna, 131–154, 1995. a
Allison, C., Francey, R., and Meijer, H.: Recommendations for the reporting of stable isotope measurements of carbon and oxygen in CO2 gas, IAEA-TECDOC, Vienna, 155–162, 1995. a
Becker, J. F., Sauke, T. B., and Loewenstein, M.: Stable isotope analysis using tunable diode laser spectroscopy, Appl. Optics, 31, 1921–1927, 1992. a
Flores, E., Viallon, J., Moussay, P., Griffith, D. W. T., and Wielgosz, R. I.: Calibration Strategies for FT-IR and Other Isotope Ratio Infrared Spectrometer Instruments for Accurate δ13C and δ18O Measurements of CO2 in Air, Anal. Chem., 89, 3648–3655, https://doi.org/10.1021/acs.analchem.6b05063, 2017. a, b, c, d, e
Gordon, I. E., Rothman, L. S., Hill, C., Kochanov, R. V., Tan, Y., Bernath, P. F., Birk, M., Boudon, V., Campargue, A., Chance, K. V., Drouin, B. J., Flaud, J. M., Gamache, R. R., Hodges, J. T., Jacquemart, D., Perevalov, V. I., Perrin, A., Shine, K. P., Smith, M. A., Tennyson, J., Toon, G. C., Tran, H., Tyuterev, V. G., Barbe, A., Császár, A. G., Devi, V. M., Furtenbacher, T., Harrison, J. J., Hartmann, J. M., Jolly, A., Johnson, T. J., Karman, T., Kleiner, I., Kyuberis, A. A., Loos, J., Lyulin, O. M., Massie, S. T., Mikhailenko, S. N., Moazzen-Ahmadi, N., Müller, H. S., Naumenko, O. V., Nikitin, A. V., Polyansky, O. L., Rey, M., Rotger, M., Sharpe, S. W., Sung, K., Starikova, E., Tashkun, S. A., Auwera, J. V., Wagner, G., Wilzewski, J., Wcisło, P., Yu, S., and Zak, E. J.: The HITRAN2016 molecular spectroscopic database, J. Quant. Spectrosc. Ra., 203, 3–69, https://doi.org/10.1016/j.jqsrt.2017.06.038, 2017. a
Harris, S. J., Liisberg, J., Xia, L., Wei, J., Zeyer, K., Yu, L., Barthel, M., Wolf, B., Kelly, B. F., Cendón, D. I., Blunier, T., Six, J., and Mohn, J.: N2O isotopocule measurements using laser spectroscopy: Analyzer characterization and intercomparison, Atmos. Meas. Tech., 13, 2797–2831, https://doi.org/10.5194/amt-13-2797-2020, 2020. a
Hofmann, M. and Pack, A.: Development of a technique for high-precision analysis of triple oxygen isotope ratios in carbon dioxide, Anal. Chem., 82, 4357–4361, 2010. a
Hofmann, M. E. G., Horváth, B., Schneider, L., Peters, W., Schützenmeister, K., and Pack, A.: Atmospheric measurements of Δ17O in CO2 in Göttingen, Germany reveal a seasonal cycle driven by biospheric uptake, Geochim. Cosmochim. Ac., 199, 143–163, https://doi.org/10.1016/j.gca.2016.11.019, 2017. a, b, c
IAEA: Stable isotope measurement techniques for atmospheric greenhouse gases, IAEA-TECDOC, Vienna, 2002. a
IAEA: Reference Sheet: Certified Reference Material: IAEA-603 (calcite) – Stable Isotope Reference Material, available at: https://nucleus.iaea.org/rpst/ReferenceProducts/ReferenceMaterials/Stable_Isotopes/13C18and7Li /IAEA-603.htm (last access: 28 May 2021), 2016. a
Koren, G., Schneider, L., van der Velde, I. R., van Schaik, E., Gromov, S. S., Adnew, G. A., Mrozek Martino, D. J., Hofmann, M. E. G., Liang, M.-C., Mahata, S., Bergamaschi, P., van der Laan-Luijkx, I. T., Krol, M. C., Röckmann, T., and Peters, W.: Global 3-D Simulations of the Triple Oxygen Isotope Signature Δ17O in Atmospheric CO2, J. Geophys. Res.-Atmos., 124, 8808–8836, https://doi.org/10.1029/2019jd030387, 2019. a, b
Levin, I., Facklam, C., Schmidt, M., Ramonet, M., Ciais, P., Xueref, I., Langenfelds, R., Allison, C., Francey, R., Jordan, A., Rothe, M., Brand, W. A., Neubert, R. E., Meijer, H. A. J., Machida, T., and Mukai, H.: Results of inter-comparison programme for analysis of “sausage” flask air samples, Special report 2, Terrestrial and Atmospheric Carbon Observing System Infrastructure, Gif-Sur-Yvette, France, 2004. a, b
Luz, B., Barkan, E., and Bender, M. L.: Triple-isotope composition of atmospheric oxygen as a tracer of biosphere productivity, Lett. Nat., 400, 547–550, 1999. a
Mrozek, D. J., Van Der Veen, C., Hofmann, M. E., Chen, H., Kivi, R., Heikkinen, P., and Röckmann, T.: Stratospheric Air Sub-sampler (SAS) and its application to analysis of Δ17O(CO2) from small air samples collected with an AirCore, Atmos. Meas. Tech., 9, 5607–5620, https://doi.org/10.5194/amt-9-5607-2016, 2016. a
Murnick, D. E. and Peer, B. J.: Laser-based analysis of carbon isotope ratios, Science, 263, 945–947, 1994. a
Nakamichi, S., Kawaguchi, Y., Fukuda, H., Enami, S., Hashimoto, S., Kawasaki, M., Umekawa, T., Morino, I., Suto, H., and Inoue, G.: Buffer-gas pressure broadening for the (3001)III (0 0 0) band of CO2 measured with continuous-wave cavity ring-down spectroscopy, Chem. Phys., 8, 364–368, https://doi.org/10.1039/B511772K, 2006. a
Nara, H., Tanimoto, H., Tohjima, Y., Mukai, H., Nojiri, Y., Katsumata, K., and Rella, C. W.: Effect of air composition (N2, O2, Ar, and H2O) on CO2 and CH4 measurement by wavelength-scanned cavity ring-down spectroscopy: calibration and measurement strategy, Atmos. Meas. Tech., 5, 2689–2701, https://doi.org/10.5194/amt-5-2689-2012, 2012. a
Neubert, R. E., Spijkervet, L. L., Schut, J. K., Been, H. A., and Meijer, H. A. J.: A computer-controlled continuous air drying and flask sampling system, J. Atmos. Ocean. Tech., 21, 651–659, https://doi.org/10.1175/1520-0426(2004)021<0651:ACCADA>2.0.CO;2, 2004. a
Roeloffzen, J. C., Mook, W. G., and Keeling, C. D.: Trend and variations in stable carbon isotopes of atmospheric carbon dioxide, Stable isotopes in plant nutrition, soil fertility and environmental studies, IAEA, Vienna, 601–618, 1991. a
Rothman, L. S., Gordon, I. E., Babikov, Y., Barbe, A., Chris Benner, D., Bernath, P. F., Birk, M., Bizzocchi, L., Boudon, V., Brown, L. R., Campargue, A., Chance, K., Cohen, E. A., Coudert, L. H., Devi, V. M., Drouin, B. J., Fayt, A., Flaud, J. M., Gamache, R. R., Harrison, J. J., Hartmann, J. M., Hill, C., Hodges, J. T., Jacquemart, D., Jolly, A., Lamouroux, J., Le Roy, R. J., Li, G., Long, D. A., Lyulin, O. M., Mackie, C. J., Massie, S. T., Mikhailenko, S., Müller, H. S., Naumenko, O. V., Nikitin, A. V., Orphal, J., Perevalov, V., Perrin, A., Polovtseva, E. R., Richard, C., Smith, M. A., Starikova, E., Sung, K., Tashkun, S., Tennyson, J., Toon, G. C., Tyuterev, V. G., and Wagner, G.: The HITRAN2012 molecular spectroscopic database, J. Quant. Spectrosc. Ra., 130, 4–50, https://doi.org/10.1016/j.jqsrt.2013.07.002, 2013. a, b, c
Sakai, S., Matsuda, S., Hikida, T., Shimono, A., McManus, J. B., Zahniser, M., Nelson, D., Dettman, D. L., Yang, D., and Ohkouchi, N.: High-Precision Simultaneous , , and Analyses for Microgram Quantities of CaCO3 by Tunable Infrared Laser Absorption Spectroscopy, Anal. Chem., 89, 11846–11852, https://doi.org/10.1021/acs.analchem.7b03582, 2017. a
Tuzson, B., Mohn, J., Zeeman, M. J., Werner, R. A., Eugster, W., Zahniser, M. S., Nelson, D. D., McManus, J. B., and Emmenegger, L.: High precision and continuous field measurements of δ13C and δ18O in carbon dioxide with a cryogen-free QCLAS, Appl. Phys. B, 92, 451–458, https://doi.org/10.1007/s00340-008-3085-4, 2008. a, b, c
Wehr, R., Munger, J. W., Nelson, D. D., McManus, J. B., Zahniser, M. S., Wofsy, S. C., and Saleska, S. R.: Long-term eddy covariance measurements of the isotopic composition of the ecosystem-atmosphere exchange of CO2 in a temperate forest, Agr. Forest Meteorol., 181, 69–84, https://doi.org/10.1016/j.agrformet.2013.07.002, 2013. a
Zhou, L., Conway, T. J., White, J. W. C., Mukai, H., Zhang, X., Wen, Y., Li, J., and Macclune, K.: Long-term record of atmospheric CO2 and stable isotopic ratios at Waliguan Observatory: Background features and possible drivers, 1991–2002, Global Biogeochem. Cy., 19, 1–9, https://doi.org/10.1029/2004GB002430, 2005. a
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.
For understanding the sources and sinks of atmospheric CO2, measurement of stable isotopes has...