Variables & measurement techniques

CiGas operates and supports instrumentation and observations collected of the following atmospheric reactive trace gases:

  1. non-Methane Hydrocarbons (NMHCs),
  2. Oxygenated VOCs (OVOCs), 
  3. Condensing vapours and direct aerosol precursors , and
  4. Nitrogen Oxides (NOx).

Data have to be reported in amount fractions (e.g. nmol/mol) in accordance with the measurement guidelines and the specifications set by the National Metrology Institutes.

 

VOC Canisters and Gas Chromatograph
Gas Chromatograph and Samling Canisters

 

Non-Methane Hydrocarbons

NMHCs are typically over 40 compounds subclassified into anthropogenic and biogenic.

Currently the following NMHCs can be traced back to certified standards obtained from the central calibration laboratory NPL:

Aliphatics (mostly anthropogenic)
Ethane Ethene
Ethyne Propane
Propene n-Butane
2-Methylpropane trans-But-2-ene
cis-But-2-ene But-1-ene
1,3-Butadiene Isoprene
2-Methylbutane n-Pentane
trans-Pent-2-ene Pent-1-ene
2-Methylpentane n-Hexane
n-Heptane n-Octane
2,2,4-Trimethylpentane  
Aromatics (anthropogenic)
Benzene Toluene
Ethylbenzene m-Xylene
p-Xylene o-Xylene
1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene
1,2,3-Trimethylbenzene  
Monoterpenes (mostly biogenic)
(+/-)-α-Pinene (+)-3-Carene
R-(+)-Limonene 1,8-Cineole


Currently CiGas-supported measurement techniques for NMHCs:

  • GC-FID

  • GC-MS

  • PTR-MS

  • PTR-TOF-MS

Oxygenated VOCs

Aldehydes, ketones, alcohols (e.g. methanol, formaldehyde, acetaldehyde, acetone)

Currently CiGas-supported measurement techniques for OVOCs:

  • GC-FID

  • GC-MS

  • PTR-MS

  • PTR-TOF-MS

  • DNPH-HPLC

 

Condensing vapours

Condensing vapours and direct aerosol precursors such as sulfuric acid and Highly Oxygenated Molecules (HOM; e.g. C10H14O9)

The definition of the term HOM is described in Chemical Review “Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol” https://pubs.acs.org/doi/10.1021/acs.chemrev.8b00395

Currently CiGas-supported measurement techniques for Condensables:

  • CI-APi-TOF

Aldehydes, ketones, alcohols (e.g. methanol, formaldehyde, acetaldehyde, acetone)

Currently CiGas-supported measurement techniques for OVOCs:

  • GC-FID

  • GC-MS

  • PTR-MS

  • PTR-TOF-MS

  • DNPH-HPLC

  •  

Nitrogen Oxides

Nitrogen oxides (NOx): Nitric oxide (NO) and nitrogen dioxide (NO2

  • Chemiluminescence technique for detection of NO

  • Photolytic conversion (PLC) for detection of NO2

  •  

 

Recent achievements

To be added

Publications & documents

Standard Operation Procedures

For NOx and VOC can be found here SOP for NOx and VOC (VOC: 2nd part of the document starting at page 24)

References

VOCs

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Apel, E.C. et al. (2008): Intercomparison of oxygenated volatile organic compound measurements at the SAPHIR atmosphere simulation chamber. Journal of Geophysical Research 113 (D20307).

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Helmig, D., J. Bottenheim, I. E. Galbally, A. Lewis, M. J. T. Milton, S. Penkett, C. Plass‐Duelmer, S. Reimann, P. Tans, and S. Thiel (2009): Volatile Organic Compounds in the Global Atmosphere, Eos Trans. AGU, 90(52): 513–514.

Hoerger, C. C., 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 (2015), ACTRIS none-methane hydrocarbon intercomparison experiment in Europe to support WMO GAW and EMEP observation networks. Atmos. Meas. Tech. 8, 2715-2736, DOI:10.5194/amt-8-2715-2015.

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 (2015), ACTRIS none-methane hydrocarbon intercomparison experiment in Europe to support WMO GAW and EMEP observation networks. Atmos. Meas. Tech. 8, 2715-2736, DOI:10.5194/amt-8-2715-2015.

Hopkins J.R., Lewis A.C., Read K.A. (2003): A two-column method for long-term monitoring of non-methane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (o-VOCs). Journal of Environmental Monitoring, 5(1).

Hopkins, J.R., Jones, C.E., Lewis, A.C. (2011): A dual channel gas chromatograph for atmospheric analysis of volatile organic compounds including oxygenated and monoterpene compounds. Journal of Environmental Monitoring DOI: 10.1039/c1em10050e.

Joint Committee for Guides in Metrology (JCGM) (2008): Evaluation of measurement data: Guide to the expression of uncertainty in measurement, https://www.bipm.org/utils/common/documents/jcgm/JCGM_100_2008_E.pdf, accessed Nov 2018.

Komenda, M., Schaub, A., Koppmann, R., 2003. Description and characterization of an on-line system for long-term measurements of isoprene, methyl vinyl ketone, and methacrolein in ambient air. Journal of Chromatography A 995, 185-201.

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Lamanna, M.S., Goldstein, A.H. (1999): In situ measurements of C2-C10 volatile organic compounds above a Sierra Nevada ponderosa pine plantation. Journal of Geophysical Research 104 (D17): 21,247-21,262.

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Lee, J.H., Batterman, S.A., Jia, C., Chernyak, S. (2006): Ozone artifacts and carbonyl measurements using Tenax GR, Tenax TA, Carbopack B, and Carbopack X adsorbents. Journal Air & Waste Management Association 56: 1503-1517.

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Leibrock, E., Slemr, J. (1997): Method for measurement of volatile oxygenated hydrocarbons in ambient air. Atmospheric Environment 31 (20): 3329-3339.

Lewis, A.C. et al. (1995): Programmed temperature vaporization injection (PTV) for in situ field measurements of isoprene, and selected oxidation products in a eucalyptus forest. Atmospheric Environment 29 (15): 1871-1875.

Lindinger, W., A. Hansel., and A. Jordan (1998): Proton‐transfer‐reaction mass spectrometry (PTR‐MS): On‐line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev., 27, 347–354.

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Palluau F., Ph Mirabel , M Millet (2007): Influence of ozone on the sampling and storage of volatile organic compounds in canisters, Environ Chem. Lett. 5, 51–55.

Plass-Dülmer, C., Michl, K., Ruf, R., Berresheim, H. (2002), C2 - C8 hydrocarbon measurement and quality control procedures at the Global Atmosphere Watch Observatory Hohenpeissenberg. J. Chromatogr. 953, 175-197.

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Pollmann J., Ortega J., and Helmig D. (2005) Analysis of atmospheric sesquiterpenes: sampling losses and mitigation of ozone interferences. Environ. Sci. and Technol. 39, 9620-9629.

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Roukos, J. et al. (2009): Development and validation of an automated monitoring system for oxygenated volatile organic compounds and nitrile compounds in ambient air. Journal of Chromatography A 1216: 8642-8651.

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Condensables

Bianchi, F. et al. (2019): Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol. Chem. Rev., 119, 6, 3472–3509, https://doi.org/10.1021/acs.chemrev.8b00395

Eisele, F. L. and Tanner, D. J. (1993): Measurement of the gas phase concentration of H2SO4 and methane sulfonic acid and estimates of H2SO4 production and loss in the atmosphere, J. Geophys. Res.-Atmos., 98, 9001–9010, https://doi.org/10.1029/93JD00031.

Jokinen, T., Sipilä, M., Junninen, H., Ehn, M., Lönn, G., Hakala, J., Petäjä, T., Mauldin III, R. L., Kulmala, M., and Worsnop, D. R. (2012): Atmospheric sulphuric acid and neutral cluster measurements using CI-APi-TOF, Atmos. Chem. Phys., 12, 4117–4125, https://doi.org/10.5194/acp-12-4117-2012.

Kulmala, M., Petäjä, T., Ehn, M., Thornton, J., Sipilä, M., Worsnop, D.R. and Kerminen, V.-M. (2014): Chemistry of Atmospheric Nucleation: On the Recent Advances on Precursor Characterization and Atmospheric Cluster Composition in Connection with Atmospheric New Particle Formation Annu. Rev. Phys. Chem., 65, 21-37, https://doi.org/10.1146/annurev-physchem-040412-110014.

Rissanen, M. P., Mikkilä, J., Iyer, S., and Hakala, J.(2019): Multi-scheme chemical ionization inlet (MION) for fast switching of reagent ion chemistry in atmospheric pressure chemical ionization mass spectrometry (CIMS) applications, Atmos. Meas. Tech., 12, 6635–6646, https://doi.org/10.5194/amt-12-6635-2019.

 

NOx      

Andersen, S. T., Carpenter, L. J., Nelson, B. S., Neves, L., Read, K. A., Reed, C., Ward, M., Rowlinson, M. J., and Lee, J. D.: Long-term NOx measurements in the remote marine tropical troposphere, Atmospheric Measurement Techniques, 14, 3071-3085, https://doi.org/10.5194/amt-14-3071-2021, 2021.

Fehsenfeld, F. C., Dickerson, R. R., Hübler, G., Luke, W. T., Nunnermacker, L. J., Williams, E. J., Roberts, J. M., Calvert, J. G., Curran, C. M., Delany, A. C., Eubank, C. S., Fahey, D. W., Fried, A., Gandrud, B. W., Langford, A. O., Murphy, P. C., Norton, R. B., Pickering, K. E., and Ridley, B. A.: A ground-based intercomparison of NO, NOx, and NOy measurement techniques, Journal of Geophysical Research: Atmospheres, 92, 14710-14722, 1987.

Fontijn, A., Sabadell, A. J., and Ronco, R. J.: Homogeneous chemiluminescent measurement of nitric oxide with ozone. Implications for continuous selective monitoring of gaseous air pollutants, Analytical Chemistry, 42, 575-579, https://doi.org/10.1021/ac60288a034, 1970.

Fuchs, H., Ball, S. M., Bohn, B., Brauers, T., Cohen, R. C., Dorn, H. P., Dubé, W. P., Fry, J. L., Häseler, R., Heitmann, U., Jones, R. L., Kleffmann, J., Mentel, T. F., Müsgen, P., Rohrer, F., Rollins, A. W., Ruth, A. A., Kiendler-Scharr, A., Schlosser, E., Shillings, A. J. L., Tillmann, R., Varma, R. M., Venables, D. S., Villena Tapia, G., Wahner, A., Wegener, R., Wooldridge, P. J., and Brown, S. S.: Intercomparison of measurements of NO2 concentrations in the atmosphere simulation chamber SAPHIR during the NO3Comp campaign, Atmos. Meas. Tech., 3, 21-37, https://doi.org/10.5194/amt-3-21-2010,  2010.

Gherman, T., Venables, D. S., Vaughan, S., Orphal, J., and Ruth, A. A.: Incoherent Broadband Cavity-Enhanced Absorption Spectroscopy in the near-Ultraviolet: Application to HONO and NO2, Environmental Science & Technology, 42, 890-895, https://doi.org/10.1021/es0716913, 2008.

Horbanski, M., Pöhler, D., Lampel, J., and Platt, U.: The ICAD (iterative cavity-enhanced DOAS) method, Atmospheric Measurement Techniques, 12, 3365-3381, https://doi.org/10.5194/amt-12-3365-2019, 2019.

Kebabian, P. L., Wood, E. C., Herndon, S. C., and Freedman, A.: A Practical Alternative to Chemiluminescence-Based Detection of Nitrogen Dioxide: Cavity Attenuated Phase Shift Spectroscopy, Environmental Science & Technology, 42, 6040-6045, https://doi.org/10.1021/es703204j, 2008.

Platt, U., Meinen, J., Pöhler, D., and Leisner, T.: Broadband Cavity Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) - applicability and corrections, Atmospheric Measurement Techniques, 2, 713-723, https://doi.org/10.5194/amt-2-713-2009, 2009.

Reed, C., Evans, M. J., Di Carlo, P., Lee, J. D., and Carpenter, L. J.: Interferences in photolytic NO2 measurements: explanation for an apparent missing oxidant?, Atmospheric Chemistry and Physics, 16, 4707-4724, https://doi.org/10.5194/acp-16-4707-2016, 2016.

Reimann, S., Wegener, R., Claude, A., Sauvage S.: ACTRIS Updated Measurement Guideline for NOx and VOCs, 2018.

https://www.actris.eu/sites/default/files/inline-files/WP3_D3.17_M42_0.pdf

Sauer, C. G., Pisano, J. T., and Fitz, D. R.: Tunable diode laser absorption spectrometer measurements of ambient nitrogen dioxide, nitric acid, formaldehyde, and hydrogen peroxide in Parlier, California, Atmospheric Environment, 37, 1583-1591, https://doi.org/10.1016/S1352-2310(03)00004-9, 2003.

Sobanski, N., Tuzson, B., Scheidegger, P., Looser, H., Kupferschmid, A., Iturrate, M., Pascale, C., Hüglin, C., and Emmenegger, L.: Advances in High-Precision NO2 Measurement by Quantum Cascade Laser Absorption Spectroscopy, Applied Sciences, 11, https://doi.org/10.3390/app11031222, 2021.

Tuzson, B., Zeyer, K., Steinbacher, M., McManus, J. B., Nelson, D. D., Zahniser, M. S., and Emmenegger, L.: Selective measurements of NO, NO2 and NOy in the free troposphere using quantum cascade laser spectroscopy, Atmospheric Measurement Techniques, 6, 927-936, https://doi.org/10.5194/amt-6-927-2013, 2013.

Thornton, J. A., Wooldridge, P. J., and Cohen, R. C.: Atmospheric NO2:  In Situ Laser-Induced Fluorescence Detection at Parts per Trillion Mixing Ratios, Analytical Chemistry, 72, 528-539, https://doi.org/10.1021/ac9908905, 2000.

Villena, G., Bejan, I., Kurtenbach, R., Wiesen, P., and Kleffmann, J.: Interferences of commercial NO2 instruments in the urban atmosphere and in a smog chamber, Atmospheric Measurement Techniques, 5, 149-159, https://doi.org/10.5194/amt-5-149-2012, 2012.