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Published in

European Geosciences Union, Atmospheric Measurement Techniques, 6(4), p. 1227-1240, 2011

DOI: 10.5194/amt-4-1227-2011

European Geosciences Union, Atmospheric Measurement Techniques Discussions, 2(4), p. 1555-1591

DOI: 10.5194/amtd-4-1555-2011

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Diode laser-based cavity ring-down instrument for NO<sub>3</sub>, N<sub>2</sub>O<sub>5</sub>, NO, NO<sub>2</sub> and O<sub>3</sub> from aircraft

This paper is made freely available by the publisher.
This paper is made freely available by the publisher.

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Abstract

This article presents a diode laser-based, cavity ring-down spectrometer for simultaneous in situ measurements of four nitrogen oxide species, NO 3 , N 2 O 5 , NO, NO 2 , as well as O 3 , designed for deployment on aircraft. The instrument measures NO 3 and NO 2 by optical extinction at 662 nm and 405 nm, respectively; N 2 O 5 is measured by thermal conversion to NO 3 , while NO and O 3 are measured by chemical conversion to NO 2 . The instrument has several advantages over previous instruments developed by our group for measurement of NO 2 , NO 3 and N 2 O 5 alone, based on a pulsed Nd:YAG and dye laser. First, the use of continuous wave diode lasers reduces the requirements for power and weight and eliminates hazardous materials. Second, detection of NO 2 at 405 nm is more sensitive than our previously reported 532 nm instrument, and does not have a measurable interference from O 3 . Third, the instrument includes chemical conversion of NO and O 3 to NO 2 to provide measurements of total NO x (= NO + NO 2 ) and O x (= NO 2 + O 3 ) on two separate channels; mixing ratios of NO and O 3 are determined by subtraction of NO 2 . Finally, all five species are calibrated against a single standard based on 254 nm O 3 absorption to provide high accuracy. Disadvantages include an increased sensitivity to water vapor on the 662 nm NO 3 and N 2 O 5 channels and a modest reduction in sensitivity for these species compared to the pulsed laser instrument. The in-flight detection limit for both NO 3 and N 2 O 5 is 3 pptv (2 σ, 1 s) and for NO, NO 2 and O 3 is 140, 90, and 120 pptv (2 σ, 1 s) respectively. Demonstrated performance of the instrument in a laboratory/ground based environment is better by approximately a factor of 2–3. The NO and NO 2 measurements are less precise than research-grade chemiluminescence instruments. However, the combination of these five species in a single instrument, calibrated to a single analytical standard, provides a complete and accurate picture of nighttime nitrogen oxide chemistry. The instrument performance is demonstrated using data acquired during a recent field campaign in California.