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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U2 - 10.5194/amt-10-4023-2017
DO - 10.5194/amt-10-4023-2017
M3 - Article
AN - SCOPUS:85032363735
SN - 1867-1381
VL - 10
SP - 4023
EP - 4053
JO - Atmospheric Measurement Techniques
JF - Atmospheric Measurement Techniques
IS - 10
ER -