Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR

Hendrik Fuchs, Anna Novelli, Michael Rolletter, Andreas Hofzumahaus, Eva Y. Pfannerstill, Stephan Kessel, Achim Edtbauer, Jonathan Williams, Vincent Michoud, Sebastien Dusanter, Nadine Locoge, Nora Zannoni, Valerie Gros, Francois Truong, Roland Sarda-Esteve, Danny R. Cryer, Charlotte A. Brumby, Lisa K. Whalley, Daniel Stone, Paul W. SeakinsDwayne E. Heard, Coralie Schoemaecker, Marion Blocquet, Sebastien Coudert, Sebastien Batut, Christa Fittschen, Alexander B. Thames, William H. Brune, Cheryl Ernest, Hartwig Harder, Jennifer B.A. Muller, Thomas Elste, Dagmar Kubistin, Stefanie Andres, Birger Bohn, Thorsten Hohaus, Frank Holland, Xin Li, Franz Rohrer, Astrid Kiendler-Scharr, Ralf Tillmann, Robert Wegener, Zhujun Yu, Qi Zou, Andreas Wahner

Research output: Contribution to journalArticle

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Abstract

Hydroxyl (OH) radical reactivity (kOH) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection <1 s-1 at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactiv-Published by Copernicus Publications on behalf of the European Geosciences Union. ity method (CRM) has a higher limit of detection of 2 s-1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flowtube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (<15 s-1) and low NO (<5 ppbv) conditions.

Original languageEnglish (US)
Pages (from-to)4023-4053
Number of pages31
JournalAtmospheric Measurement Techniques
Volume10
Issue number10
DOIs
StatePublished - Oct 27 2017

Fingerprint

nitric oxide
water vapor
hydroxyl radical
nitrogen oxides
carbon monoxide
organic compound
simulation
terpene
alkene
experiment
mixing ratio
alkane
volatile organic compound
ionization
mass spectrometry
atmosphere
chemical
comparison
detection
method

All Science Journal Classification (ASJC) codes

  • Atmospheric Science

Cite this

Fuchs, H., Novelli, A., Rolletter, M., Hofzumahaus, A., Pfannerstill, E. Y., Kessel, S., ... Wahner, A. (2017). Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR. Atmospheric Measurement Techniques, 10(10), 4023-4053. https://doi.org/10.5194/amt-10-4023-2017
Fuchs, Hendrik ; Novelli, Anna ; Rolletter, Michael ; Hofzumahaus, Andreas ; Pfannerstill, Eva Y. ; Kessel, Stephan ; Edtbauer, Achim ; Williams, Jonathan ; Michoud, Vincent ; Dusanter, Sebastien ; Locoge, Nadine ; Zannoni, Nora ; Gros, Valerie ; Truong, Francois ; Sarda-Esteve, Roland ; Cryer, Danny R. ; Brumby, Charlotte A. ; Whalley, Lisa K. ; Stone, Daniel ; Seakins, Paul W. ; Heard, Dwayne E. ; Schoemaecker, Coralie ; Blocquet, Marion ; Coudert, Sebastien ; Batut, Sebastien ; Fittschen, Christa ; Thames, Alexander B. ; Brune, William H. ; Ernest, Cheryl ; Harder, Hartwig ; Muller, Jennifer B.A. ; Elste, Thomas ; Kubistin, Dagmar ; Andres, Stefanie ; Bohn, Birger ; Hohaus, Thorsten ; Holland, Frank ; Li, Xin ; Rohrer, Franz ; Kiendler-Scharr, Astrid ; Tillmann, Ralf ; Wegener, Robert ; Yu, Zhujun ; Zou, Qi ; Wahner, Andreas. / Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR. In: Atmospheric Measurement Techniques. 2017 ; Vol. 10, No. 10. pp. 4023-4053.
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Fuchs, H, Novelli, A, Rolletter, M, Hofzumahaus, A, Pfannerstill, EY, Kessel, S, Edtbauer, A, Williams, J, Michoud, V, Dusanter, S, Locoge, N, Zannoni, N, Gros, V, Truong, F, Sarda-Esteve, R, Cryer, DR, Brumby, CA, Whalley, LK, Stone, D, Seakins, PW, Heard, DE, Schoemaecker, C, Blocquet, M, Coudert, S, Batut, S, Fittschen, C, Thames, AB, Brune, WH, Ernest, C, Harder, H, Muller, JBA, Elste, T, Kubistin, D, Andres, S, Bohn, B, Hohaus, T, Holland, F, Li, X, Rohrer, F, Kiendler-Scharr, A, Tillmann, R, Wegener, R, Yu, Z, Zou, Q & Wahner, A 2017, 'Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR', Atmospheric Measurement Techniques, vol. 10, no. 10, pp. 4023-4053. https://doi.org/10.5194/amt-10-4023-2017

Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR. / Fuchs, Hendrik; Novelli, Anna; Rolletter, Michael; Hofzumahaus, Andreas; Pfannerstill, Eva Y.; Kessel, Stephan; Edtbauer, Achim; Williams, Jonathan; Michoud, Vincent; Dusanter, Sebastien; Locoge, Nadine; Zannoni, Nora; Gros, Valerie; Truong, Francois; Sarda-Esteve, Roland; Cryer, Danny R.; Brumby, Charlotte A.; Whalley, Lisa K.; Stone, Daniel; Seakins, Paul W.; Heard, Dwayne E.; Schoemaecker, Coralie; Blocquet, Marion; Coudert, Sebastien; Batut, Sebastien; Fittschen, Christa; Thames, Alexander B.; Brune, William H.; Ernest, Cheryl; Harder, Hartwig; Muller, Jennifer B.A.; Elste, Thomas; Kubistin, Dagmar; Andres, Stefanie; Bohn, Birger; Hohaus, Thorsten; Holland, Frank; Li, Xin; Rohrer, Franz; Kiendler-Scharr, Astrid; Tillmann, Ralf; Wegener, Robert; Yu, Zhujun; Zou, Qi; Wahner, Andreas.

In: Atmospheric Measurement Techniques, Vol. 10, No. 10, 27.10.2017, p. 4023-4053.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR

AU - Fuchs, Hendrik

AU - Novelli, Anna

AU - Rolletter, Michael

AU - Hofzumahaus, Andreas

AU - Pfannerstill, Eva Y.

AU - Kessel, Stephan

AU - Edtbauer, Achim

AU - Williams, Jonathan

AU - Michoud, Vincent

AU - Dusanter, Sebastien

AU - Locoge, Nadine

AU - Zannoni, Nora

AU - Gros, Valerie

AU - Truong, Francois

AU - Sarda-Esteve, Roland

AU - Cryer, Danny R.

AU - Brumby, Charlotte A.

AU - Whalley, Lisa K.

AU - Stone, Daniel

AU - Seakins, Paul W.

AU - Heard, Dwayne E.

AU - Schoemaecker, Coralie

AU - Blocquet, Marion

AU - Coudert, Sebastien

AU - Batut, Sebastien

AU - Fittschen, Christa

AU - Thames, Alexander B.

AU - Brune, William H.

AU - Ernest, Cheryl

AU - Harder, Hartwig

AU - Muller, Jennifer B.A.

AU - Elste, Thomas

AU - Kubistin, Dagmar

AU - Andres, Stefanie

AU - Bohn, Birger

AU - Hohaus, Thorsten

AU - Holland, Frank

AU - Li, Xin

AU - Rohrer, Franz

AU - Kiendler-Scharr, Astrid

AU - Tillmann, Ralf

AU - Wegener, Robert

AU - Yu, Zhujun

AU - Zou, Qi

AU - Wahner, Andreas

PY - 2017/10/27

Y1 - 2017/10/27

N2 - Hydroxyl (OH) radical reactivity (kOH) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection <1 s-1 at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactiv-Published by Copernicus Publications on behalf of the European Geosciences Union. ity method (CRM) has a higher limit of detection of 2 s-1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flowtube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (<15 s-1) and low NO (<5 ppbv) conditions.

AB - Hydroxyl (OH) radical reactivity (kOH) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection <1 s-1 at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactiv-Published by Copernicus Publications on behalf of the European Geosciences Union. ity method (CRM) has a higher limit of detection of 2 s-1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flowtube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (<15 s-1) and low NO (<5 ppbv) conditions.

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Fuchs H, Novelli A, Rolletter M, Hofzumahaus A, Pfannerstill EY, Kessel S et al. Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR. Atmospheric Measurement Techniques. 2017 Oct 27;10(10):4023-4053. https://doi.org/10.5194/amt-10-4023-2017