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Diode Laser-based Cavity Ring-down Instrument for No3, N2O5, No, No2 and O3 from Aircraft : Volume 4, Issue 2 (03/03/2011)

By Wagner, N. L.

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Book Id: WPLBN0003987842
Format Type: PDF Article :
File Size: Pages 37
Reproduction Date: 2015

Title: Diode Laser-based Cavity Ring-down Instrument for No3, N2O5, No, No2 and O3 from Aircraft : Volume 4, Issue 2 (03/03/2011)  
Author: Wagner, N. L.
Volume: Vol. 4, Issue 2
Language: English
Subject: Science, Atmospheric, Measurement
Collections: Periodicals: Journal and Magazine Collection, Copernicus GmbH
Publication Date:
Publisher: Copernicus Gmbh, Göttingen, Germany
Member Page: Copernicus Publications


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Ryerson, T. B., Young, C. J., Washenfelder, R. A., Wagner, N. L., Pollack, I. B., Brown, S. S., & Dubé, W. P. (2011). Diode Laser-based Cavity Ring-down Instrument for No3, N2O5, No, No2 and O3 from Aircraft : Volume 4, Issue 2 (03/03/2011). Retrieved from

Description: NOAA Earth System Research Laboratory, R/CSD7, 325 Broadway, Boulder, CO 80305, USA. This article presents a diode laser based, cavity ring-down spectrometer for simultaneous in situ measurements of four nitrogen oxide species, NO3, N2O5, NO, NO2, as well as O3, designed for deployment on aircraft. The instrument measures NO3 and NO2 by optical extinction at 662 nm and 405 nm, respectively; N2O5 is measured by thermal conversion to NO3, while NO and O3 are measured by chemical conversion to NO2. The instrument has several advantages over previous instruments developed by our group for measurement of NO2, NO3 and N2O5 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 NO2 at 405 nm is more sensitive than our previously reported 532 nm instrument, and does not have a measurable interference from O3. Third, the instrument includes chemical conversion of NO and O3 to NO2 to provide measurements of total NOx (= NO + NO2) and Ox (= NO2 + O3) on two separate channels; mixing ratios of NO and O3 are determined by subtraction of NO2. Finally, all five species are calibrated against a single standard based on 254 nm O3 absorption to provide high accuracy. Disadvantages include an increased sensitivity to water vapor on the 662 nm NO3 and N2O5 channels and a modest reduction in sensitivity for these species compared to the pulsed laser instrument. The measurement precision for both NO3 and N2O5 is below 1 pptv (2Σ, 1 s) and for NO, NO2 and O3 is 170, 46, and 56 pptv (2Σ, 1 s) respectively. The NO and NO2 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.

Diode laser-based cavity ring-down instrument for NO3, N2O5, NO, NO2 and O3 from aircraft

Atkinson, D. B.: Solving chemical problems of environmental importance using cavity ring-down spectroscopy, Analyst, 128, 117–125, doi:10.1039/b206699h, 2003.; Atkinson, R.: Kinetics and mechanisms of the gas-phase reactions of the NO3 radical with organic-compounds, J. Phys. Chem. Ref. Data, 20(3), 459–507, doi:10.1063/1.555887, 1991.; Ayers, J. D., Apodaca, L., Simpson, W. R., and Baer, D. S.: Off-axis cavity ring-down spectroscopy: Application to atmospheric nitrate radical detection, Appl. Optics, 44, 7239–7242, doi:10.1364/AO.44.007239, 2005.; Brown, S. S., Stark, H., Ciciora, S. J., McLaughlin, R. J., and Ravishankara, A. R.: Simultaneous in situ detection of atmospheric NO3 and N2O5 via cavity ring-down spectroscopy, Rev. Sci. Instrum., 73, 3291–3301, doi:10.1063/1.1499214, 2002.; Brown, S. S.: Absorption spectroscopy in high-finesse cavities for atmospheric studies, Chem. Rev., 103, 5219–5238, doi:10.1021/cr020645c, 2003.; Brown, S. S., Stark, H., and Ravishankara, A. R.: Applicability of the steady state approximation to the interpretation of atmospheric observations of NO3 and N2O5, J. Geophys. Res.-Atmos., 108(D17), 4539, doi:10.1029/2003JD003407, 2003.; Brown, S. S., Dubé, W. P., Osthoff, H. D., Stutz, J., Ryerson, T. B., Wollny, A. G., Brock, C. A., Warneke, C., de Gouw, J. A., Atlas, E., Neuman, J. A., Holloway, J. S., Lerner, B. M., Williams, E. J., Kuster, W. C., Goldan, P. D., Angevine, W. M., Trainer, M., Fehsenfeld, F. C., and Ravishankara, A. R.: Vertical profiles in NO3 and N2O5 measured from an aircraft: Results from the NOAA P-3 and surface platforms during NEAQS 2004, J. Geophys. Res., 112, D22304, doi:10.1029/2007JD008883, 2007a.; Brown, S. S., Dubé, W. P., Osthoff, H. D., Wolfe, D. E., Angevine, W. M., and Ravishankara, A. R.: High resolution vertical distributions of NO3 and N2O5 through the nocturnal boundary layer, Atmos. Chem. Phys., 7, 139–149, doi:10.5194/acp-7-139-2007, 2007b.; Busch, K. W. and Busch, M. A.: Cavity-ringdown spectroscopy, American Chemical Society, Washington, DC, 1999.; Dubé, W. P., Brown, S. S., Osthoff, H. D., Nunley, M. R., Ciciora, S. J., Paris, M. W., McLaughlin, R. J., and Ravishankara, A. R.: Aircraft instrument for simultaneous, in situ measurement of NO3 and N2O5 via pulsed cavity ring-down spectroscopy, Rev. Sci. Instrum., 77(3), 034101–034101-11, doi:10.1063/1.2176058, 2006.; Everest, M. A. and Atkinson, D. B.: Discrete sums for the rapid determination of exponential decay constants, Rev. Sci. Instrum., 79, 023108, doi:10.1063/1.2839918, 2008.; Finlayson-Pitts, B. J., Ezell, M. J., and Pitts, J. N.: Formation of chemically active chlorine compunds by reactions of atmospheric NaCl particles with gaseous N2O5 and ClONO2, Nature, 337, 241–244, doi:10.1038/337241a0, 1989.; Fuchs, H., Dubé, W. P., Ciciora, S. J., and Brown, S. S.: Determination of inlet transmission and conversion eff


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