Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO2, total peroxy nitrate, total alkyl nitrate, and HNO3

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Abstract

A four-channel thermal dissociation laser induced fluorescence (TD-LIF) instrument has been developed for simultaneous measurements of nitrogen dioxide (NO2), total peroxy nitrate (ΣPNs), total alkyl nitrate (ΣANs) and nitric acid (HNO3). NO2 is measured directly by LIF at 532 nm, whereas organic nitrates and nitric acid are thermally dissociated at distinct temperatures in the inlet to form NO 2, which is then measured by LIF. The concentrations of each dissociated species are derived by the differences in measured NO2 relative to the reference colder inlet channel. The TD-LIF was adapted to fly on board the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe 146-301 atmospheric research aircraft in summer 2010, and to date has successfully flown in five field campaigns. This paper reports novel improvements in the TD-LIF instrumentations, including (1) the use of a single wavelength laser, which makes the system compact and relatively cheap; (2) the use of a single beam laser that allows easy alignment and optical stability against the vibrational aircraft environment; and (3) the optical assembly of four detection cells that allow simultaneous and fast (time resolution up to 0.1 s) measurements of NO2, ΣPNs, ΣANs and HNO3. Laboratory-generated mixtures of PNs, ANs and HNO3 in zero air are converted into NO 2 and used to fix the dissociation temperatures of each heated inlet to test the selectivity of the instrument and potential interferences due to recombination reactions of the dissociated products. The effectiveness of the TD-LIF was demonstrated during the RONOCO aircraft campaign (summer 2010). A chemiluminescence system that was measuring NO2 and a broadband cavity enhanced absorption spectrometer (BBCEAS) that was measuring one of the PNs (N2O5) were installed on the same aircraft during the campaign. The in-flight intercomparison of the new TD-LIF with the chemiluminescence system for NO2 measurements and the intercomparison between ΣPNs measured by the TD-LIF and N2O5 by the BBCEAS are used to assess the performance of the TD-LIF. © Author(s) 2013.

Figures

  • Fig. 1. The optical layout of the TD-LIF with schematics of the inlet system. Note that, to simplify the scheme the tube lengths are different here, but in the instrument the length of each of them from the inlet to the detection cell is identical to ensure the same residence time. PD1–PD4 are the four photodiodes monitoring the laser power.
  • Fig. 3. Temperature scan when the TD-LIF sampled synthetic PAN, ethyl nitrates and HNO3, generated in the laboratory to identify the temperatures where these compounds are thermally dissociated into NO2.
  • Fig. 2. A photograph of the TD-LIF installed in the rack for use on board the FAAM BAe 146-301 research aircraft. The inlet box includes the quartz tubes with heater for thermal dissociation of organic nitrates and HNO3 into NO2.
  • Fig. 4. Interc mparison between the first ell a d the other three cells when the ommon inlet sampled different conc ntrations of NO2, sent using the calibration system of the TD-LIF.
  • Fig. 5. Measurements of a mixture of NO2, PAN and ethyl nitrate with distinct cells of the TD-LIF generated in a laboratory test. Zero air is sent periodically to check the capability of the system to flush the organic nitrates.
  • Fig. 6. Upper panel: temperature scan of the ∑ ANs inlet channel when the TD-LIF sampled a mixture of ethyl nitrate and NO2. After the first temperature scan the concentration of ethyl nitrate was doubled. For all the experiments the NO2 cell sampled air at ambient temperature. Lower panel: temperature scan of the ∑ ANs inlet channel when the TD-LIF sampled a mixture of ethyl nitrate and PAN. For all the experiments the ∑ PNs inlet channel was heated to 200 ◦C to detect PAN.
  • Fig. 7. Measurements of
  • Fig. 8. Measurements of

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APA

Di Carlo, P., Aruffo, E., Busilacchio, M., Giammaria, F., Dari-Salisburgo, C., Biancofiore, F., … Ouyang, B. (2013). Aircraft based four-channel thermal dissociation laser induced fluorescence instrument for simultaneous measurements of NO2, total peroxy nitrate, total alkyl nitrate, and HNO3. Atmospheric Measurement Techniques, 6(4), 971–980. https://doi.org/10.5194/amt-6-971-2013

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