scholarly journals Supplementary material to "Importance of isomerization reactions for the OH radical regeneration from the photo-oxidation of isoprene investigated in the atmospheric simulation chamber SAPHIR"

Author(s):  
Anna Novelli ◽  
Luc Vereecken ◽  
Hans-Peter Dorn ◽  
Andreas Hofzumahaus ◽  
Frank Holland ◽  
...  
2014 ◽  
Vol 14 (13) ◽  
pp. 6941-6952 ◽  
Author(s):  
S. Nehr ◽  
B. Bohn ◽  
H.-P. Dorn ◽  
H. Fuchs ◽  
R. Häseler ◽  
...  

Abstract. Current photochemical models developed to simulate the atmospheric degradation of aromatic hydrocarbons tend to underestimate OH radical concentrations. In order to analyse OH budgets, we performed experiments with benzene, toluene, p-xylene and 1,3,5-trimethylbenzene in the atmosphere simulation chamber SAPHIR. Experiments were conducted under low-NO conditions (typically 0.1–0.2 ppb) and high-NO conditions (typically 7–8 ppb), and starting concentrations of 6–250 ppb of aromatics, dependent on OH rate constants. For the OH budget analysis a steady-state approach was applied in which OH production and destruction rates (POH and DOH) have to be equal. The POH were determined from measurements of HO2, NO, HONO, and O3 concentrations, considering OH formation by photolysis and recycling from HO2. The DOH were calculated from measurements of the OH concentrations and total OH reactivities. The OH budgets were determined from DOH/POH ratios. The accuracy and reproducibility of the approach were assessed in several experiments using CO as a reference compound where an average ratio DOH/POH = 1.13 ± 0.19 was obtained. In experiments with aromatics, these ratios ranged within 1.1–1.6 under low-NO conditions and 0.9–1.2 under high-NO conditions. The results indicate that OH budgets during photo-oxidation experiments with aromatics are balanced within experimental accuracies. Inclusion of a further, recently proposed OH production via HO2 + RO2 reactions led to improvements under low-NO conditions but the differences were small and insignificant within the experimental errors.


2014 ◽  
Vol 14 (5) ◽  
pp. 5535-5560 ◽  
Author(s):  
S. Nehr ◽  
B. Bohn ◽  
H.-P. Dorn ◽  
H. Fuchs ◽  
R. Häseler ◽  
...  

Abstract. Current photochemical models developed to simulate the atmospheric degradation of aromatic hydrocarbons tend to underestimate OH radical concentrations. In order to analyse OH budgets, we performed experiments with benzene, toluene, p-xylene, and 1,3,5-trimethylbenzene in the atmosphere simulation chamber SAPHIR. Experiments were conducted under low-NO conditions (typically 0.1–0.2 ppb) and high-NO conditions (typically 7–8 ppb), and starting concentrations of 6–250 ppb of aromatics, dependent on OH rate constants. For the OH budget analysis a steady-state approach was applied where OH production and destruction rates (POH and DOH) have to be equal. The POH were determined from measurements of HO2, NO, HONO, and O3 concentrations, considering OH formation by photolysis and recycling from HO2. The DOH were calculated from measurements of the OH concentrations and total OH reactivities. The OH budgets were determined from DOH / POH ratios. The accuracy and reproducibility of the approach were assessed in several experiments using CO as a reference compound where an average ratio DOH / POH = 1.13 ± 0.19 was obtained. In experiments with aromatics, these ratios ranged within 1.1–1.6 under low-NO conditions and 0.9–1.2 under high-NO conditions. The results indicate that OH budgets during photo-oxidation experiments with aromatics are balanced within experimental accuracies. Inclusion of a further, recently proposed OH production via HO2 + RO2 reactions led to improvements under low-NO conditions but the differences were small and insignificant within the experimental errors.


2019 ◽  
Author(s):  
Michael Rolletter ◽  
Martin Kaminski ◽  
Ismail-Hakki Acir ◽  
Birger Bohn ◽  
Hans-Peter Dorn ◽  
...  

2017 ◽  
Author(s):  
Hendrik Fuchs ◽  
Anna Novelli ◽  
Michael Rolletter ◽  
Andreas Hofzumahaus ◽  
Eva Y. Pfannerstill ◽  
...  

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 took part 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 vapor, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection


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