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. We developed thermal dissociation cavity-enhanced absorptionspectroscopy (TD-CEAS) for the in situ measurement of NO2, total peroxynitrates (PNs, RO2NO2), and total alkyl nitrates (ANs, RONO2)in the atmosphere. PNs and ANs were thermally converted to NO2 at thecorresponding pyrolytic temperatures and detected by CEAS at 435–455 nm. Theinstrument 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 wereused to derive the mixing ratios of PNs and ANs by spectral fitting. Thedetection limit (LOD, 1σ) for retrieving NO2 was 97 parts pertrillion 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 ofNO2 due to chemical interferences that occurred in the heated channels,such as the reaction of NO (or NO2) with the peroxy radicals producedby the thermal dissociation of organic nitrates. Based on laboratoryexperiments and numerical simulations, we created a lookup table method tocorrect these interferences in PN and AN channels under various ambientorganic nitrates, NO, and NO2. Finally, we present the first fielddeployment and compare it with other instruments during a field campaign inChina. The advantages and limitations of this instrument are outlined.

atmospheric measurement techniques

Thermal dissociation cavity-enhanced absorption spectrometer for measuring NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, RO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, and RONO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; in the atmosphere