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Thermal dissociation cavity-enhanced absorption spectrometer for measuring NO2, RO2NO2, and RONO2 in the atmosphere
Atmospheric Measurement Techniques ( IF 3.2 ) Pub Date : 2021-06-03 , DOI: 10.5194/amt-14-4033-2021 Chunmeng Li , Haichao Wang , Xiaorui Chen , Tianyu Zhai , Shiyi Chen , Xin Li , Limin Zeng , Keding Lu
Atmospheric Measurement Techniques ( IF 3.2 ) Pub Date : 2021-06-03 , DOI: 10.5194/amt-14-4033-2021 Chunmeng Li , Haichao Wang , Xiaorui Chen , Tianyu Zhai , Shiyi Chen , Xin Li , Limin Zeng , Keding Lu
We developed thermal dissociation cavity-enhanced absorption
spectroscopy (TD-CEAS) for the in situ measurement of NO2, total peroxy
nitrates (PNs, RO2NO2), and total alkyl nitrates (ANs, RONO2)
in the atmosphere. PNs and ANs were thermally converted to NO2 at the
corresponding pyrolytic temperatures and detected by CEAS at 435–455 nm. The
instrument sampled sequentially from three channels at ambient temperature,
453 and 653 K, with a cycle of 3 min, to measure NO2, NO2+ PNs,
and NO2+ PNs + ANs. The absorptions between the three channels were
used to derive the mixing ratios of PNs and ANs by spectral fitting. The
detection limit (LOD, 1σ) for retrieving NO2 was 97 parts per
trillion by volume (pptv) in 6 s. The measurement uncertainty of NO2 was 9 %,
while the uncertainties of PN and AN detection were larger than those of
NO2 due to chemical interferences that occurred in the heated channels,
such as the reaction of NO (or NO2) with the peroxy radicals produced
by the thermal dissociation of organic nitrates. Based on laboratory
experiments and numerical simulations, we created a lookup table method to
correct these interferences in PN and AN channels under various ambient
organic nitrates, NO, and NO2. Finally, we present the first field
deployment and compare it with other instruments during a field campaign in
China. The advantages and limitations of this instrument are outlined.
更新日期：2021-06-03
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