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 reactivity 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 flow-tube 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.
Citation
ID:
144732
Ref Key:
fuchs2017atmosphericcomparison