Articles | Volume 8, issue 6
https://doi.org/10.5194/amt-8-2301-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
https://doi.org/10.5194/amt-8-2301-2015
© Author(s) 2015. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
Research article
| 
04 Jun 2015
Research article |
| 04 Jun 2015
A method for stable carbon isotope ratio and concentration measurements of ambient aromatic hydrocarbons
A. Kornilova
Centre for Atmospheric Chemistry, York University, Toronto, ON, M3J 1P3, Canada
S. Moukhtar
Centre for Atmospheric Chemistry, York University, Toronto, ON, M3J 1P3, Canada
M. Saccon
Centre for Atmospheric Chemistry, York University, Toronto, ON, M3J 1P3, Canada
Environment Canada, Toronto, ON, M3H 5T4, Canada
W. Zhang
Environment Canada, Toronto, ON, M3H 5T4, Canada
J. Rudolph
CORRESPONDING AUTHOR
Centre for Atmospheric Chemistry, York University, Toronto, ON, M3J 1P3, Canada
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Marina Saccon, Anna Kornilova, Lin Huang, and Jochen Rudolph
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As compound are emitted into the atmosphere, they can undergo chemical reactions to produce secondary products. This paper investigates the relations of compounds' unique chemical characteristics to the processes that formed them from emissions in the atmosphere. A model is applied to help with this investigation. The complexity of the atmosphere, including mixing of air masses and variability in precursor reactivity, is taken into consideration, and results are presented.
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Carbonate carbon (CC) is not negligible in Arctic total suspended particles (TSP). If not considered, CC biases the contribution of elemental and organic carbon. CC content in TSP was strongly reflected in the δ13C values of total carbon (TC). Carbon contribution from CaCO3 supports strong dependence of CC and δ13C on Ca. Finally, two hypothetical CC sources were identified based on the analysis of air mass back trajectories – dust resuspension and marine microorganisms.
Douglas E. J. Worthy, Michele K. Rauh, Lin Huang, Felix R. Vogel, Alina Chivulescu, Kenneth A. Masarie, Ray L. Langenfelds, Paul B. Krummel, Colin E. Allison, Andrew M. Crotwell, Monica Madronich, Gabrielle Pétron, Ingeborg Levin, Samuel Hammer, Sylvia Michel, Michel Ramonet, Martina Schmidt, Armin Jordan, Heiko Moossen, Michael Rothe, Ralph Keeling, and Eric J. Morgan
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Clara Betancourt, Christoph Küppers, Tammarat Piansawan, Uta Sager, Andrea B. Hoyer, Heinz Kaminski, Gerhard Rapp, Astrid C. John, Miriam Küpper, Ulrich Quass, Thomas Kuhlbusch, Jochen Rudolph, Astrid Kiendler-Scharr, and Iulia Gensch
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Wanmin Gong, Stephen R. Beagley, Sophie Cousineau, Mourad Sassi, Rodrigo Munoz-Alpizar, Sylvain Ménard, Jacinthe Racine, Junhua Zhang, Jack Chen, Heather Morrison, Sangeeta Sharma, Lin Huang, Pascal Bellavance, Jim Ly, Paul Izdebski, Lynn Lyons, and Richard Holt
Atmos. Chem. Phys., 18, 16653–16687, https://doi.org/10.5194/acp-18-16653-2018, https://doi.org/10.5194/acp-18-16653-2018, 2018
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Katrina M. Macdonald, Sangeeta Sharma, Desiree Toom, Alina Chivulescu, Andrew Platt, Mike Elsasser, Lin Huang, Richard Leaitch, Nathan Chellman, Joseph R. McConnell, Heiko Bozem, Daniel Kunkel, Ying Duan Lei, Cheol-Heon Jeong, Jonathan P. D. Abbatt, and Greg J. Evans
Atmos. Chem. Phys., 18, 3485–3503, https://doi.org/10.5194/acp-18-3485-2018, https://doi.org/10.5194/acp-18-3485-2018, 2018
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The sources of key contaminants in Arctic snow may be an important factor in understanding the rapid climate changes observed in the Arctic. Fresh snow samples collected frequently through the winter season were analyzed for major constituents. Temporally refined source apportionment via positive matrix factorization in conjunction with FLEXPART suggested potential source characteristics and locations. The identity of these sources and their relative contribution to key analytes is discussed.
W. Richard Leaitch, Lynn M. Russell, Jun Liu, Felicia Kolonjari, Desiree Toom, Lin Huang, Sangeeta Sharma, Alina Chivulescu, Dan Veber, and Wendy Zhang
Atmos. Chem. Phys., 18, 3269–3287, https://doi.org/10.5194/acp-18-3269-2018, https://doi.org/10.5194/acp-18-3269-2018, 2018
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Over 2 years of atmospheric aerosol organic functional group and microphysics measurements at the world's northernmost land observatory offer a unique high-latitude dataset. Lower organic mass (OM) concentrations and higher OM fractions accompany smaller particles during summer, with opposite results during winter to spring. Seasonally, the OM oxidation level is highest in winter, associated with primary marine alcohol groups. In summer, secondary processes dominate the marine influence on OM.
Sangeeta Sharma, W. Richard Leaitch, Lin Huang, Daniel Veber, Felicia Kolonjari, Wendy Zhang, Sarah J. Hanna, Allan K. Bertram, and John A. Ogren
Atmos. Chem. Phys., 17, 15225–15243, https://doi.org/10.5194/acp-17-15225-2017, https://doi.org/10.5194/acp-17-15225-2017, 2017
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A new and unique data set on BC properties at the highest latitude observatory in the world, at Alert, Canada, evaluates three techniques for estimating black carbon (BC) and gives seasonal best estimates of the BC mass concentrations and BC mass absorption coefficients (MAC) for 2.5 years of data. As a short-lived climate forcer, better estimates of the properties of BC are necessary to ensure accurate modelling of aerosol climate forcing of the Arctic atmosphere for mitigation purposes.
Jun-Wei Xu, Randall V. Martin, Andrew Morrow, Sangeeta Sharma, Lin Huang, W. Richard Leaitch, Julia Burkart, Hannes Schulz, Marco Zanatta, Megan D. Willis, Daven K. Henze, Colin J. Lee, Andreas B. Herber, and Jonathan P. D. Abbatt
Atmos. Chem. Phys., 17, 11971–11989, https://doi.org/10.5194/acp-17-11971-2017, https://doi.org/10.5194/acp-17-11971-2017, 2017
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We interpret a series of recent airborne and ground-based measurements with the GEOS-Chem model and its adjoint to attribute the sources of Arctic BC. Anthropogenic emissions in eastern and southern Asia make the largest contribution to Arctic BC. Gas flaring emissions from oilfields in western Siberia and from the Tarim oilfield in western China could have striking impacts on Arctic BC loadings.
Katrina M. Macdonald, Sangeeta Sharma, Desiree Toom, Alina Chivulescu, Sarah Hanna, Allan K. Bertram, Andrew Platt, Mike Elsasser, Lin Huang, David Tarasick, Nathan Chellman, Joseph R. McConnell, Heiko Bozem, Daniel Kunkel, Ying Duan Lei, Greg J. Evans, and Jonathan P. D. Abbatt
Atmos. Chem. Phys., 17, 5775–5788, https://doi.org/10.5194/acp-17-5775-2017, https://doi.org/10.5194/acp-17-5775-2017, 2017
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Rapid climate changes within the Arctic have highlighted existing uncertainties in the transport of contaminants to Arctic snow. Fresh snow samples collected frequently through the winter season were analyzed for major constituents creating a unique record of Arctic snow. Comparison with simultaneous atmospheric measurements provides insight into the driving processes in the transfer of contaminants from air to snow. The relative importance of deposition mechanisms over the season is proposed.
Andrew D. Teakles, Rita So, Bruce Ainslie, Robert Nissen, Corinne Schiller, Roxanne Vingarzan, Ian McKendry, Anne Marie Macdonald, Daniel A. Jaffe, Allan K. Bertram, Kevin B. Strawbridge, W. Richard Leaitch, Sarah Hanna, Desiree Toom, Jonathan Baik, and Lin Huang
Atmos. Chem. Phys., 17, 2593–2611, https://doi.org/10.5194/acp-17-2593-2017, https://doi.org/10.5194/acp-17-2593-2017, 2017
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We present a case study of an intense wildfire smoke plume from Siberia that affected the air quality across the Pacific Northwest on 6–10 July 2012. The transport, entrainment, and chemical composition of the plume are examined to characterize the event. Ambient O3 and PM2.5 from surface monitoring is contrast to modelled baseline air quality estimates to show the overall contribution of the plume to exceedances in O3 and PM2.5 air quality standards and objectives that occurred.
Anna Kornilova, Lin Huang, Marina Saccon, and Jochen Rudolph
Atmos. Chem. Phys., 16, 11755–11772, https://doi.org/10.5194/acp-16-11755-2016, https://doi.org/10.5194/acp-16-11755-2016, 2016
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The photochemical oxidation of organic compounds in the atmosphere results in the formation of important secondary pollutants such as ozone and fine particles. The extent of oxidation the organic compounds have been subjected too since there emissions is essential is key for understanding the formation of secondary pollutants. This paper demonstrates that measurements of the carbon isotope ratios allow determining the extent of photochemical processing for individual compounds.
M. Saccon, A. Kornilova, L. Huang, S. Moukhtar, and J. Rudolph
Atmos. Chem. Phys., 15, 10825–10838, https://doi.org/10.5194/acp-15-10825-2015, https://doi.org/10.5194/acp-15-10825-2015, 2015
S. Eckhardt, B. Quennehen, D. J. L. Olivié, T. K. Berntsen, R. Cherian, J. H. Christensen, W. Collins, S. Crepinsek, N. Daskalakis, M. Flanner, A. Herber, C. Heyes, Ø. Hodnebrog, L. Huang, M. Kanakidou, Z. Klimont, J. Langner, K. S. Law, M. T. Lund, R. Mahmood, A. Massling, S. Myriokefalitakis, I. E. Nielsen, J. K. Nøjgaard, J. Quaas, P. K. Quinn, J.-C. Raut, S. T. Rumbold, M. Schulz, S. Sharma, R. B. Skeie, H. Skov, T. Uttal, K. von Salzen, and A. Stohl
Atmos. Chem. Phys., 15, 9413–9433, https://doi.org/10.5194/acp-15-9413-2015, https://doi.org/10.5194/acp-15-9413-2015, 2015
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The concentrations of sulfate, black carbon and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality. In this study, we evaluate sulfate and BC concentrations from different updated models and emissions against a comprehensive pan-Arctic measurement data set. We find that the models improved but still struggle to get the maximum concentrations.
R. Zhao, A. K. Y. Lee, L. Huang, X. Li, F. Yang, and J. P. D. Abbatt
Atmos. Chem. Phys., 15, 6087–6100, https://doi.org/10.5194/acp-15-6087-2015, https://doi.org/10.5194/acp-15-6087-2015, 2015
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Aqueous-phase photochemical decay of light absorbing organic compounds, or atmospheric brown carbon (BrC), is investigated in this study. The absorptive change of laboratory surrogates of BrC, as well as biofuel combustion samples, were monitored during photolysis and OH oxidation experiments. The major finding is the rapid change in the absorptivity of BrC during such photochemical processing. This change should be taken into account to evaluate the importance of BrC in the atmosphere.
M. Saccon, R. Busca, C. Facca, L. Huang, S. Irei, A. Kornilova, D. Lane, and J. Rudolph
Atmos. Meas. Tech., 6, 2965–2974, https://doi.org/10.5194/amt-6-2965-2013, https://doi.org/10.5194/amt-6-2965-2013, 2013
F. R. Vogel, L. Huang, D. Ernst, L. Giroux, S. Racki, and D. E. J. Worthy
Atmos. Meas. Tech., 6, 301–308, https://doi.org/10.5194/amt-6-301-2013, https://doi.org/10.5194/amt-6-301-2013, 2013
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Evaluation of cation exchange membrane performance under exposure to high Hg0 and HgBr2 concentrations
Gravimetrically prepared carbon dioxide standards in support of atmospheric research
The importance of cylinder passivation for preparation and long-term stability of multicomponent monoterpene primary reference materials
Dynamic–gravimetric preparation of metrologically traceable primary calibration standards for halogenated greenhouse gases
The water vapour self-continuum absorption in the infrared atmospheric windows: new laser measurements near 3.3 and 2.0 µm
Interlaboratory comparison of δ13C and δD measurements of atmospheric CH4 for combined use of data sets from different laboratories
Absolute, pressure-dependent validation of a calibration-free, airborne laser hygrometer transfer standard (SEALDH-II) from 5 to 1200 ppmv using a metrological humidity generator
An intercomparison of HO2 measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)
Abundances of isotopologues and calibration of CO2 greenhouse gas measurements
Intercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2 ∕ 12CO2 measurement
Development and evaluation of a suite of isotope reference gases for methane in air
MIPAS database: new HNO3 line parameters at 7.6 µm validated with MIPAS satellite measurements
Challenges associated with the sampling and analysis of organosulfur compounds in air using real-time PTR-ToF-MS and offline GC-FID
Twin-cuvette measurement technique for investigation of dry deposition of O3 and PAN to plant leaves under controlled humidity conditions
Gas adsorption and desorption effects on cylinders and their importance for long-term gas records
HOx radical chemistry in oxidation flow reactors with low-pressure mercury lamps systematically examined by modeling
ACTRIS non-methane hydrocarbon intercomparison experiment in Europe to support WMO GAW and EMEP observation networks
Zachary Finewax, Aparajeo Chattopadhyay, J. Andrew Neuman, James M. Roberts, and James B. Burkholder
Atmos. Meas. Tech., 17, 6865–6873, https://doi.org/10.5194/amt-17-6865-2024, https://doi.org/10.5194/amt-17-6865-2024, 2024
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This work provides a comprehensive sensitivity calibration of a chemical ionization instrument commonly used in field measurements for the measurement of the toxic isomers methyl isocyanate and hydroxyacetonitrile that are found in the atmosphere. The results from this work have demonstrated that the hydroyacetonitrile isomer was observed in previous field studies rather than the stated identification of methyl isocyanate.
Baigali Tsogt, Ji Hwan Kang, Seok-Young Oh, and Sangil Lee
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2024-132, https://doi.org/10.5194/amt-2024-132, 2024
Revised manuscript accepted for AMT
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We tested different cylinders and methods to create standard gas mixtures of acetonitrile, a chemical important for understanding air quality and climate change. We found making accurate mixtures at very low levels challenging due to the gas sticking to cylinder walls. However, we successfully created stable mixtures at higher levels. These can be used as reliable standards for global air monitoring. More research is needed to develop methods for making accurate mixtures at lower levels.
Stéphanie Alage, Vincent Michoud, Sergio Harb, Bénédicte Picquet-Varrault, Manuela Cirtog, Avinash Kumar, Matti Rissanen, and Christopher Cantrell
Atmos. Meas. Tech., 17, 4709–4724, https://doi.org/10.5194/amt-17-4709-2024, https://doi.org/10.5194/amt-17-4709-2024, 2024
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Calibration exercises are essential for determining the accuracy of instruments. We performed calibrations on a NO3¯ ToFCIMS instrument to determine its sensitivity and linearity for detecting various organic compounds. Our findings revealed significant variability, over several orders of magnitude, in the calibration factors obtained. The results suggest that relying on a single calibration factor from H2SO4 for the quantification of all compounds detected by this technique is not appropriate.
Tanita J. Ballé, Stefan Röttger, Florian Mertes, Anja Honig, Petr Kovar, Petr P. S. Otáhal, and Annette Röttger
Atmos. Meas. Tech., 17, 2055–2065, https://doi.org/10.5194/amt-17-2055-2024, https://doi.org/10.5194/amt-17-2055-2024, 2024
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Over 50 % of naturally occurring radiation exposure is due to 222Rn (progenies), but traceability of measurements to the International System of Units (SI) is lacking. To address this, two new 222Rn sources were developed to be used as calibration standards for reference instruments. These sources were investigated by comparing their estimated calibration factors for one instrument. Despite the small differences derived, all uncertainties are well within the intended target uncertainty of 10 %.
Teodor D. Andron, Warren T. Corns, Igor Živković, Saeed Waqar Ali, Sreekanth Vijayakumaran Nair, and Milena Horvat
Atmos. Meas. Tech., 17, 1217–1228, https://doi.org/10.5194/amt-17-1217-2024, https://doi.org/10.5194/amt-17-1217-2024, 2024
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Atmospheric mercury monitoring is an important activity in order to model the global trajectory of this toxic element and to assess if certain areas are polluted or not in accordance to global guidelines. One of the analysers tested in this work is globally used in this regard due to its practicality compared with other devices. Because it is only calibrated by the manufacturer at very high concentrations, we wanted to see how it performs at ambient mercury concentrations.
Heidi Hellén, Toni Tykkä, Simon Schallhart, Evdokia Stratigou, Thérèse Salameh, and Maitane Iturrate-Garcia
Atmos. Meas. Tech., 17, 315–333, https://doi.org/10.5194/amt-17-315-2024, https://doi.org/10.5194/amt-17-315-2024, 2024
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Even though online measurements of biogenic volatile organic compounds (BVOCs) are becoming more common, the use of sorbent tubes is expected to continue because they offer greater spatial coverage and no infrastructure is required for sampling. In this study the sorbent tube sampling method was optimized and evaluated for the determination of BVOCs in gas-phase samples. Tenax TA sorbent tubes were found to be suitable for the quantitative measurements of C10–C15 BVOCs.
Douglas E. J. Worthy, Michele K. Rauh, Lin Huang, Felix R. Vogel, Alina Chivulescu, Kenneth A. Masarie, Ray L. Langenfelds, Paul B. Krummel, Colin E. Allison, Andrew M. Crotwell, Monica Madronich, Gabrielle Pétron, Ingeborg Levin, Samuel Hammer, Sylvia Michel, Michel Ramonet, Martina Schmidt, Armin Jordan, Heiko Moossen, Michael Rothe, Ralph Keeling, and Eric J. Morgan
Atmos. Meas. Tech., 16, 5909–5935, https://doi.org/10.5194/amt-16-5909-2023, https://doi.org/10.5194/amt-16-5909-2023, 2023
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Network compatibility is important for inferring greenhouse gas fluxes at global or regional scales. This study is the first assessment of the measurement agreement among seven individual programs within the World Meteorological Organization community. It compares co-located flask air measurements at the Alert Observatory in Canada over a 17-year period. The results provide stronger confidence in the uncertainty estimation while using those datasets in various data interpretation applications.
Shasha Tian, Kexin Zu, Huabin Dong, Limin Zeng, Keding Lu, and Qi Chen
Atmos. Meas. Tech., 16, 5525–5535, https://doi.org/10.5194/amt-16-5525-2023, https://doi.org/10.5194/amt-16-5525-2023, 2023
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We developed an online NH3 monitoring system based on a selective colorimetric reaction and a long-path absorption photometer (SAC-LOPAP), which can run statically for a long time and be applied to the continuous online measurement of low concentrations of ambient air by optimizing the reaction conditions, adding a constant-temperature module and liquid flow controller. It is well suited for the investigation of the NH3 budget for urban to rural conditions in China.
Frank A. F. Winiberg, William J. Warman, Charlotte A. Brumby, Graham Boustead, Iustinian G. Bejan, Thomas H. Speak, Dwayne E. Heard, Daniel Stone, and Paul W. Seakins
Atmos. Meas. Tech., 16, 4375–4390, https://doi.org/10.5194/amt-16-4375-2023, https://doi.org/10.5194/amt-16-4375-2023, 2023
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OH and HO2 are key reactive intermediates in the Earth's atmosphere. Accurate measurements in either the field or simulation chambers provide a good test for chemical mechanisms. Fluorescence techniques have the appropriate sensitivity for detection but require calibration. This paper compares different methods of calibration and specifically how calibration factors vary across a temperature range relevant to atmospheric and chamber determinations.
James P. Williams, Khalil El Hachem, and Mary Kang
Atmos. Meas. Tech., 16, 3421–3435, https://doi.org/10.5194/amt-16-3421-2023, https://doi.org/10.5194/amt-16-3421-2023, 2023
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Methane is powerful greenhouse gas; thus, to reduce methane emissions, it is important that the methods used to measure methane are tested and validated. The static chamber method is an enclosure-based technique that directly measures methane emissions; however, it has not been thoroughly tested for the new variety of methane sources that it is currently being used for. We find that the static chamber method can accurately measure methane emissions under a wide range of methane emission rates.
David R. Worton, Sergi Moreno, Kieran O'Daly, and Rupert Holzinger
Atmos. Meas. Tech., 16, 1061–1072, https://doi.org/10.5194/amt-16-1061-2023, https://doi.org/10.5194/amt-16-1061-2023, 2023
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Proton-transfer-reaction mass spectrometry is widely used in the environmental, health, and food and beverage sectors. As a result, there is a need for accurate and comparable measurements. In this work we have developed a 20-component gravimetrically prepared traceable primary reference material (gas standard in a high-pressure cylinder) to enable quantitative and comparable measurements. The accuracy of all components was better than 3 %–10 % with stabilities of better than 1–2 years.
Guo Li, Hang Su, Meng Li, Uwe Kuhn, Guangjie Zheng, Lei Han, Fengxia Bao, Ulrich Pöschl, and Yafang Cheng
Atmos. Meas. Tech., 15, 6433–6446, https://doi.org/10.5194/amt-15-6433-2022, https://doi.org/10.5194/amt-15-6433-2022, 2022
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A large fraction of previous work using dynamic flow chambers was to quantify gas exchange in terms of flux or deposition/emission rate. Here, we extended the usage of this technique to examine uptake kinetics on sample surfaces. The good performance of the chamber system was validated. This technique can be further used for liquid samples and real atmospheric aerosol samples without complicated coating procedures, which complements the existing techniques in atmospheric kinetic studies.
Nobuyuki Aoki, Shigeyuki Ishidoya, Shohei Murayama, and Nobuhiro Matsumoto
Atmos. Meas. Tech., 15, 5969–5983, https://doi.org/10.5194/amt-15-5969-2022, https://doi.org/10.5194/amt-15-5969-2022, 2022
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The CO2 concentration in a cylinder is affected by carbon dioxide (CO2) adsorption to a cylinder’s internal surface and fractionation of CO2 and air in the preparation of standard mixtures. We demonstrate that the effects make the CO2 molar fractions deviate in standard mixtures prepared by diluting pure CO2 with air three times. This means that CO2 standard gases are difficult to gravimetrically prepare through multistep dilution.
Sophie Dixneuf, Albert A. Ruth, Rolf Häseler, Theo Brauers, Franz Rohrer, and Hans-Peter Dorn
Atmos. Meas. Tech., 15, 945–964, https://doi.org/10.5194/amt-15-945-2022, https://doi.org/10.5194/amt-15-945-2022, 2022
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Atmospheric chambers, like SAPHIR in Jülich (Germany), are used to experimentally simulate specific atmospheric scenarios to improve our understanding of the complex chemical reactions occurring in our atmospheres. These facilities hence require cutting-edge gas-sensing capabilities to detect trace gases at the lowest level and in a short time. One important trace gas is HONO, for which we custom-built an optical sensing setup, capable of detecting one HONO molecule in ~40 billion in 1 min.
Jan Gačnik, Igor Živković, Sergio Ribeiro Guevara, Radojko Jaćimović, Jože Kotnik, Gianmarco De Feo, Matthew A. Dexter, Warren T. Corns, and Milena Horvat
Atmos. Meas. Tech., 14, 6619–6631, https://doi.org/10.5194/amt-14-6619-2021, https://doi.org/10.5194/amt-14-6619-2021, 2021
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Atmospheric mercury and knowledge of its transformations and processes are of great importance for lowering its anthropogenic emissions. To ensure that, it is crucial to have a tested and validated measurement procedure. Since this is not always the case, we performed experiments that provided insight into commonly used atmospheric mercury sampling methods. The results showed that some sampling methods are unsuitable, and some are useful if we consider the results obtained from this work.
Nobuyuki Aoki, Shigeyuki Ishidoya, Yasunori Tohjima, Shinji Morimoto, Ralph F. Keeling, Adam Cox, Shuichiro Takebayashi, and Shohei Murayama
Atmos. Meas. Tech., 14, 6181–6193, https://doi.org/10.5194/amt-14-6181-2021, https://doi.org/10.5194/amt-14-6181-2021, 2021
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Observing the minimal long-term change in atmospheric O2 molar fraction combined with CO2 observation enables us to estimate terrestrial biospheric and oceanic CO2 uptakes separately. In this study, we firstly identified the span offset between the laboratory O2 scales using our developed high-precision standard mixtures, suggesting that the result may allow us to estimate terrestrial biospheric and oceanic CO2 uptakes precisely.
Ruth E. Hill-Pearce, Aimee Hillier, Eric Mussell Webber, Kanokrat Charoenpornpukdee, Simon O'Doherty, Joachim Mohn, Christoph Zellweger, David R. Worton, and Paul J. Brewer
Atmos. Meas. Tech., 14, 5447–5458, https://doi.org/10.5194/amt-14-5447-2021, https://doi.org/10.5194/amt-14-5447-2021, 2021
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There is currently a need for gas reference materials with well-characterised delta values for monitoring N2O amount fractions. We present work towards the preparation of gas reference materials for calibration of in-field monitoring equipment, which target the WMO-GAW data quality objectives for comparability of amount fraction and demonstrate the stability of δ15Nα, δ15Nβ and δ18O values with pressure and effects of cylinder passivation.
Fides Lefrancois, Markus Jesswein, Markus Thoma, Andreas Engel, Kieran Stanley, and Tanja Schuck
Atmos. Meas. Tech., 14, 4669–4687, https://doi.org/10.5194/amt-14-4669-2021, https://doi.org/10.5194/amt-14-4669-2021, 2021
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Synthetic halocarbons can contribute to stratospheric ozone depletion or to climate change. In many applications they have been replaced over the last years. The presented non-target analysis shows an application approach to quantify those replacements retrospectively, using recorded data of air measurements with gas chromatography coupled to time-of-flight mass spectrometry. We focus on the retrospective analysis of the fourth-generation halocarbons, detected at Taunus Observatory in Germany.
Bradley D. Hall, Andrew M. Crotwell, Duane R. Kitzis, Thomas Mefford, Benjamin R. Miller, Michael F. Schibig, and Pieter P. Tans
Atmos. Meas. Tech., 14, 3015–3032, https://doi.org/10.5194/amt-14-3015-2021, https://doi.org/10.5194/amt-14-3015-2021, 2021
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We have recently revised the carbon dioxide calibration scale used by numerous laboratories that measure atmospheric CO2. The revision follows from an improved understanding of the manometric method used to determine the absolute amount of CO2 in an atmospheric air sample. The new scale is 0.18 μmol mol−1 (ppm) greater than the previous scale at 400 ppm CO2. While this difference is small in relative terms (0.045 %), it is significant in terms of atmospheric monitoring.
Iris de Krom, Wijnand Bavius, Ruben Ziel, Elizabeth A. McGhee, Richard J. C. Brown, Igor Živković, Jan Gačnik, Vesna Fajon, Jože Kotnik, Milena Horvat, and Hugo Ent
Atmos. Meas. Tech., 14, 2317–2326, https://doi.org/10.5194/amt-14-2317-2021, https://doi.org/10.5194/amt-14-2317-2021, 2021
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To demonstrate the robustness and comparability of the novel primary mercury gas standard, the results of comparisons are presented with current calibration methods maintained, using the bell jar in combination with the Dumarey equation or NIST liquid standard reference material. The results show that the primary standard and the NIST reference material are comparable, whereas a difference of −8 % exists between results traceable to the primary standard and the Dumarey equation.
Shujiro Komiya, Fumiyoshi Kondo, Heiko Moossen, Thomas Seifert, Uwe Schultz, Heike Geilmann, David Walter, and Jost V. Lavric
Atmos. Meas. Tech., 14, 1439–1455, https://doi.org/10.5194/amt-14-1439-2021, https://doi.org/10.5194/amt-14-1439-2021, 2021
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The Amazon basin influences the atmospheric and hydrological cycles on local to global scales. To better understand how, we plan to perform continuous on-site measurements of the stable isotope composition of atmospheric water vapour. For making accurate on-site observations possible, we have investigated the performance of two commercial analysers and determined the best calibration strategy. Well calibrated, both analysers will allow us to record natural signals in the Amazon rainforest.
Axel Fouqueau, Manuela Cirtog, Mathieu Cazaunau, Edouard Pangui, Pascal Zapf, Guillaume Siour, Xavier Landsheere, Guillaume Méjean, Daniele Romanini, and Bénédicte Picquet-Varrault
Atmos. Meas. Tech., 13, 6311–6323, https://doi.org/10.5194/amt-13-6311-2020, https://doi.org/10.5194/amt-13-6311-2020, 2020
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An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals in the CSA simulation chamber at LISA. The optical cavity allows a high sensitivity for NO3 detection up to 6 ppt for an integration time of 10 s. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (with rate constants up to 10−10 cm3 molecule−1 s−1).
Melodie Lao, Leigh R. Crilley, Leyla Salehpoor, Teles C. Furlani, Ilann Bourgeois, J. Andrew Neuman, Andrew W. Rollins, Patrick R. Veres, Rebecca A. Washenfelder, Caroline C. Womack, Cora J. Young, and Trevor C. VandenBoer
Atmos. Meas. Tech., 13, 5873–5890, https://doi.org/10.5194/amt-13-5873-2020, https://doi.org/10.5194/amt-13-5873-2020, 2020
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Nitrous acid (HONO) is a key intermediate in the generation of oxidants and fate of nitrogen oxides in the atmosphere. High-purity calibration sources that produce stable atmospherically relevant levels under field conditions have not been made to date, reducing measurement accuracy. In this study a simple salt-coated tube humidified with water vapor is demonstrated to produce pure stable low levels of HONO, with modifications allowing the generation of higher amounts.
Aku Helin, Hannele Hakola, and Heidi Hellén
Atmos. Meas. Tech., 13, 3543–3560, https://doi.org/10.5194/amt-13-3543-2020, https://doi.org/10.5194/amt-13-3543-2020, 2020
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A thermal desorption–gas chromatography–mass spectrometry method following sorbent tube sampling was developed for the determination of terpenes in gas-phase samples. The main focus was on the analysis of diterpenes, which have been limited in study in gas-phase samples. The analytical figures of merit were fit for purpose (e.g. quantitation limits <10 pptv and reproducibility <10 % for terpenes). Diterpenes could be detected and identified in emissions from spruce and pine samples.
Ann-Sophie Lehnert, Thomas Behrendt, Alexander Ruecker, Georg Pohnert, and Susan E. Trumbore
Atmos. Meas. Tech., 13, 3507–3520, https://doi.org/10.5194/amt-13-3507-2020, https://doi.org/10.5194/amt-13-3507-2020, 2020
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Volatile organic compounds (VOCs) like scents can appear and disappear quickly. For example, when a bug starts on a tree, the tree releases VOCs that warn the trees around him. Thus, one needs instruments measuring their concentration in real time and identify which VOC is measured. In our study, we compared two instruments doing that, PTR-MS and SIFT-MS. Both work similarly, but we found that the PTR-MS can measure lower concentrations, but the SIFT-MS can identify VOCs better.
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.
Lavinia Onel, Alexander Brennan, Michele Gianella, James Hooper, Nicole Ng, Gus Hancock, Lisa Whalley, Paul W. Seakins, Grant A. D. Ritchie, and Dwayne E. Heard
Atmos. Meas. Tech., 13, 2441–2456, https://doi.org/10.5194/amt-13-2441-2020, https://doi.org/10.5194/amt-13-2441-2020, 2020
Dezhao Liu, Li Rong, Jesper Kamp, Xianwang Kong, Anders Peter S. Adamsen, Albarune Chowdhury, and Anders Feilberg
Atmos. Meas. Tech., 13, 259–272, https://doi.org/10.5194/amt-13-259-2020, https://doi.org/10.5194/amt-13-259-2020, 2020
Jiajue Chai, David J. Miller, Eric Scheuer, Jack Dibb, Vanessa Selimovic, Robert Yokelson, Kyle J. Zarzana, Steven S. Brown, Abigail R. Koss, Carsten Warneke, and Meredith Hastings
Atmos. Meas. Tech., 12, 6303–6317, https://doi.org/10.5194/amt-12-6303-2019, https://doi.org/10.5194/amt-12-6303-2019, 2019
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Isotopic analysis offers a potential tool to distinguish between sources and interpret transformation pathways of atmospheric species. We applied recently developed techniques in our lab to characterize the isotopic composition of reactive nitrogen species (NOx, HONO, HNO3, pNO3-) in fresh biomass burning emissions. Intercomparison with other techniques confirms the suitability of our methods, allowing for future applications of our techniques in a variety of environments.
Joshua D. Shutter, Norton T. Allen, Thomas F. Hanisco, Glenn M. Wolfe, Jason M. St. Clair, and Frank N. Keutsch
Atmos. Meas. Tech., 12, 6079–6089, https://doi.org/10.5194/amt-12-6079-2019, https://doi.org/10.5194/amt-12-6079-2019, 2019
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A new mid-infrared and ultra-portable formaldehyde (HCHO) sensor from Aeris Technologies is characterized and evaluated against well-established laser-induced fluorescence (LIF) instrumentation. The Aeris sensor displays linear behavior (R squared > 0.94) and shows good agreement with LIF instruments. While the compact sensor is not currently a replacement for the most sensitive research-grade instrumentation available, its sub-ppbv precision is sufficient for indoor and outdoor HCHO monitoring.
Jesper Nørlem Kamp, Albarune Chowdhury, Anders Peter S. Adamsen, and Anders Feilberg
Atmos. Meas. Tech., 12, 2837–2850, https://doi.org/10.5194/amt-12-2837-2019, https://doi.org/10.5194/amt-12-2837-2019, 2019
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We tested the performance of a cavity ring-down spectroscopy (CRDS) instrument from Picarro for measuring ammonia. Interference tests with 10 volatile organic compounds (VOCs) were conducted to find potential interference of these VOCs. Calibrations show excellent linearity over a large dynamic range of NH3 concentrations. There is negligible interference from humidity and few of the tested VOCs. Overall, the CRDS system performs well with only negligible influence from other compounds.
Nobuyuki Aoki, Shigeyuki Ishidoya, Nobuhiro Matsumoto, Takuro Watanabe, Takuya Shimosaka, and Shohei Murayama
Atmos. Meas. Tech., 12, 2631–2646, https://doi.org/10.5194/amt-12-2631-2019, https://doi.org/10.5194/amt-12-2631-2019, 2019
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Observation of atmospheric O2 requires highly precise standard gas mixtures with uncertainty of less than 1 ppm for the O2 mole fraction or 5 per meg for O2 / N2. The uncertainty had not been achieved due unknown uncertainty factors in mass determination of the filled source gases. We first developed the primary standard mixtures with 1 ppm for the O2 mole fraction or 5 per meg by identifying and reducing the unknown uncertainty factors.
Cristina Romero-Trigueros, María Esther González, Marta Doval Miñarro, and Enrique González Ferradás
Atmos. Meas. Tech., 12, 1685–1695, https://doi.org/10.5194/amt-12-1685-2019, https://doi.org/10.5194/amt-12-1685-2019, 2019
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Determining benzene in ambient air is mandatory in the European Union. The reference measuring technique is by gas chromatography (GC), and a photometric ionisation detector is recommended. This study shows that the simultaneous presence of benzene and tetrachloromethane causes a significant decrease in GC–photoionisation detector (GC-PID) readings. Given the importance of this behaviour, a possible mechanism was proposed. This study highlights the uncertainty of measuring benzene with a GC-PID.
Matthieu B. Miller, Sarrah M. Dunham-Cheatham, Mae Sexauer Gustin, and Grant C. Edwards
Atmos. Meas. Tech., 12, 1207–1217, https://doi.org/10.5194/amt-12-1207-2019, https://doi.org/10.5194/amt-12-1207-2019, 2019
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This study was undertaken to demonstrate that a cation exchange membrane (CEM) material used for sampling reactive mercury (RM) does not possess an inherent tendency to collect gaseous elemental mercury (GEM). Using a custom-built mercury vapor permeation system, we found that the CEM material has a very small GEM uptake of approximately 0.004 %, too small to create a significant artifact. We also found that a representative RM compound was collected by the CEM material with high efficiency.
Bradley D. Hall, Andrew M. Crotwell, Benjamin R. Miller, Michael Schibig, and James W. Elkins
Atmos. Meas. Tech., 12, 517–524, https://doi.org/10.5194/amt-12-517-2019, https://doi.org/10.5194/amt-12-517-2019, 2019
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We have used a one-step method for gravimetric preparation of CO2-in-air standards in aluminum cylinders. We consider both adsorption to stainless steel surfaces used in the transfer of highly pure CO2 and adsorption of CO2 to cylinder walls. This work compliments ongoing efforts to support atmospheric monitoring of CO2.
Nicholas D. C. Allen, David R. Worton, Paul J. Brewer, Celine Pascale, and Bernhard Niederhauser
Atmos. Meas. Tech., 11, 6429–6438, https://doi.org/10.5194/amt-11-6429-2018, https://doi.org/10.5194/amt-11-6429-2018, 2018
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This paper investigates the stability of trace level static terpene primary reference materials (PRMs) and how the choice of passivation affects this process. For the first time, sampling canisters that can be used in the field are tested and demonstrated to be suitable for terpene mixtures. The PRMs were compared against a novel dynamic generator system based on dilution of pure limonene vapour emitted from a permeation tube. The effect of cylinder pressure and decanting are also investigated.
Myriam Guillevic, Martin K. Vollmer, Simon A. Wyss, Daiana Leuenberger, Andreas Ackermann, Céline Pascale, Bernhard Niederhauser, and Stefan Reimann
Atmos. Meas. Tech., 11, 3351–3372, https://doi.org/10.5194/amt-11-3351-2018, https://doi.org/10.5194/amt-11-3351-2018, 2018
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We present new primary calibration scales for five halogenated greenhouse gases. The preparation method, newly applied to halocarbons, is dynamic and gravimetric
and allows the generation of reference gas mixtures at near-ambient levels (pmol mol−1). Each prepared molar fraction is traceable to the
realisation of SI units (International System of Units) and is assigned an uncertainty estimate following international guidelines.
Loic Lechevallier, Semen Vasilchenko, Roberto Grilli, Didier Mondelain, Daniele Romanini, and Alain Campargue
Atmos. Meas. Tech., 11, 2159–2171, https://doi.org/10.5194/amt-11-2159-2018, https://doi.org/10.5194/amt-11-2159-2018, 2018
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The amplitude, the temperature dependence, and the physical origin of the water vapour absorption continuum are a long standing issue in molecular spectroscopy with a direct impact in atmospheric and planetary sciences. Using highly sensitive laser spectrometers, the water self continuum has been determined with unprecedented sensitivity in infrared atmospheric transparency windows.
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.
Bernhard Buchholz and Volker Ebert
Atmos. Meas. Tech., 11, 459–471, https://doi.org/10.5194/amt-11-459-2018, https://doi.org/10.5194/amt-11-459-2018, 2018
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This paper describes the absolute validation of the novel, calibration-free SEALDH-II hygrometer at a traceable humidity generator. During 23 days of permanent operation, 15 H2O mole fractions levels (5–1200 ppmv) at 6 gas pressures (65–950 hPa) were validated. With this validation, SEALDH-II is the first metrologically validated humidity transfer standard which links several scientific airborne and laboratory measurement campaigns to the international metrological water vapor scale.
Lavinia Onel, Alexander Brennan, Michele Gianella, Grace Ronnie, Ana Lawry Aguila, Gus Hancock, Lisa Whalley, Paul W. Seakins, Grant A. D. Ritchie, and Dwayne E. Heard
Atmos. Meas. Tech., 10, 4877–4894, https://doi.org/10.5194/amt-10-4877-2017, https://doi.org/10.5194/amt-10-4877-2017, 2017
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Hydroperoxy (HO2) radicals are key intermediates participating in a rapid chemical cycling at the centre of the tropospheric oxidation. Fluorescence assay by gas expansion (FAGE) technique is the most commonly used for the HO2 measurements in the atmosphere. However, FAGE is an indirect technique, requiring calibration. This work finds a good agreement between the indirect FAGE method and the direct cavity ring-down spectroscopy method and hence validates FAGE and the FAGE calibration method.
Pieter P. Tans, Andrew M. Crotwell, and Kirk W. Thoning
Atmos. Meas. Tech., 10, 2669–2685, https://doi.org/10.5194/amt-10-2669-2017, https://doi.org/10.5194/amt-10-2669-2017, 2017
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We describe a new CO2 calibration system for the Central Calibration Laboratory of the World Meteorological Organization Global Atmosphere Watch program. The system uses two laser spectroscopic instruments to measure the three major CO2 isotopologues individually. We account for isotopic differences between standards in the calibration hierarchy when assigning CO2 mole fraction, eliminating bias due to variations in the isotopic composition.
Jiaping Pang, Xuefa Wen, Xiaomin Sun, and Kuan Huang
Atmos. Meas. Tech., 9, 3879–3891, https://doi.org/10.5194/amt-9-3879-2016, https://doi.org/10.5194/amt-9-3879-2016, 2016
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.
Agnès Perrin, Jean-Marie Flaud, Marco Ridolfi, Jean Vander Auwera, and Massimo Carlotti
Atmos. Meas. Tech., 9, 2067–2076, https://doi.org/10.5194/amt-9-2067-2016, https://doi.org/10.5194/amt-9-2067-2016, 2016
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Improved line positions and intensities have been generated for the 7.6 µm spectral region of nitric acid, relying on a recent laboratory reinvestigation and comparisons of HNO3 volume mixing ratios retrieved from Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) radiances in the 11 and 7.6 µm regions. The much improved consistency of line intensities in both regions will make it possible to use them simultaneously to retrieve atmospheric HNO3.
Véronique Perraud, Simone Meinardi, Donald R. Blake, and Barbara J. Finlayson-Pitts
Atmos. Meas. Tech., 9, 1325–1340, https://doi.org/10.5194/amt-9-1325-2016, https://doi.org/10.5194/amt-9-1325-2016, 2016
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Gas phase organosulfur compounds in air serve as precursors of particles which impact human health, visibility, and climate. We compare here two different approaches to measuring these compounds, one an online mass spectrometry technique and the other canister sampling followed by offline analysis by gas chromatography. We show that each approach has its own advantages and limitations in measuring these compounds in complex mixtures, including some artifacts due to reactions on surfaces.
Shang Sun, Alexander Moravek, Lisa von der Heyden, Andreas Held, Matthias Sörgel, and Jürgen Kesselmeier
Atmos. Meas. Tech., 9, 599–617, https://doi.org/10.5194/amt-9-599-2016, https://doi.org/10.5194/amt-9-599-2016, 2016
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We present a dynamic twin-cuvette system for quantifying the trace gas exchange fluxes between plants and the atmosphere under controlled temperature, light, and humidity conditions. We found out that at a relative humidity of 40 %, the deposition velocity ratio of O3 and PAN was determined to be 0.45. At that humidity, the O3-deposition to the plant leaves was found to be only controlled by leaf stomata. For PAN, an additional resistance inhibited the uptake of PAN by the leaves.
M. C. Leuenberger, M. F. Schibig, and P. Nyfeler
Atmos. Meas. Tech., 8, 5289–5299, https://doi.org/10.5194/amt-8-5289-2015, https://doi.org/10.5194/amt-8-5289-2015, 2015
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Adsorption/desorption effects of trace gases in gas cylinders were investigated. Our measurements indicate a rather strong effect on steel cylinders for CO2 that becomes easily visible through enhanced concentrations for low (<20 bars) gas pressure. Much smaller effects are observed for CO and CH4. Significantly smaller effects are measured for all gas species investigated on aluminium cylinders. Careful selection of gas cylinders for high-precision calibration purposes is recommended.
Z. Peng, D. A. Day, H. Stark, R. Li, J. Lee-Taylor, B. B. Palm, W. H. Brune, and J. L. Jimenez
Atmos. Meas. Tech., 8, 4863–4890, https://doi.org/10.5194/amt-8-4863-2015, https://doi.org/10.5194/amt-8-4863-2015, 2015
C. C. Hoerger, A. Claude, C. Plass-Duelmer, S. Reimann, E. Eckart, R. Steinbrecher, J. Aalto, J. Arduini, N. Bonnaire, J. N. Cape, A. Colomb, R. Connolly, J. Diskova, P. Dumitrean, C. Ehlers, V. Gros, H. Hakola, M. Hill, J. R. Hopkins, J. Jäger, R. Junek, M. K. Kajos, D. Klemp, M. Leuchner, A. C. Lewis, N. Locoge, M. Maione, D. Martin, K. Michl, E. Nemitz, S. O'Doherty, P. Pérez Ballesta, T. M. Ruuskanen, S. Sauvage, N. Schmidbauer, T. G. Spain, E. Straube, M. Vana, M. K. Vollmer, R. Wegener, and A. Wenger
Atmos. Meas. Tech., 8, 2715–2736, https://doi.org/10.5194/amt-8-2715-2015, https://doi.org/10.5194/amt-8-2715-2015, 2015
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The performance of 20 European laboratories involved in long-term non-methane hydrocarbon (NMHC) measurements was assessed with respect to ACTRIS and GAW data quality objectives. The participants were asked to measure both a 30-component NMHC mixture in nitrogen and whole air. The NMHCs were analysed either by GC-FID or GC-MS. Most systems performed well for the NMHC in nitrogen, whereas in air more scatter was observed. Reasons for this are explained in the paper.
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Short summary
A technique for compound specific analysis of stable carbon isotope ratios and concentration of ambient volatile organic compounds (VOC) is presented. It is based on selective VOC sampling onto adsorbent filled cartridges. Examples of measurements conducted demonstrate that the ability to make accurate measurements in air with low VOC mixing ratios is important to avoid bias from an overrepresentation of samples that are strongly impacted by recent emissions.
A technique for compound specific analysis of stable carbon isotope ratios and concentration of...
