Abstract. We present a compact, affordable and robust instrument based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) for simultaneous detection of NOx, IO, CHOCHO and O3 in the 400–475 nm wavelength region. The instrument relies on the injection of a high-power LED source in a high-finesse cavity (F∼33 100), with the transmission signal being detected by a compact spectrometer based on a high-order diffraction grating and a charge-coupled device (CCD) camera. A minimum detectable absorption of 2.0×10-10 cm−1 was achieved within ∼22 min of total acquisition, corresponding to a figure of merit of 1.8×10-10 cm−1 Hz-1/2 per spectral element. Due to the multiplexing broadband feature of the setup, multi-species detection can be performed with simultaneous detection of NO2, IO, CHOCHO and O3 achieving detection limits of 11, 0.3, 10 ppt (parts per trillion) and 47 ppb (parts per billion) (1σ) within 22 min of measurement, respectively (half of the time is spent on the acquisition of the reference spectrum in the absence of the absorber, and the other half is spent on the absorption spectrum). The implementation on the inlet gas line of a compact ozone generator based on electrolysis of water allows for the measurement of NOx (NO+NO2) and therefore an indirect detection of NO with detection limits for NOx and NO of 10 and 21 ppt (1σ), respectively. The device has been designed to fit in a 19 in., 3U (5.25 in.) rack-mount case; weighs 15 kg; and has a total electrical power consumption of <300 W. The instrument can be employed to address different scientific objectives such as better constraining the oxidative capacity of the atmosphere, studying the chemistry of highly reactive species in atmospheric chambers as well as in the field and looking at the sources of glyoxal in the marine boundary layer to study possible implications on the formation of secondary aerosol particles.
To fully decipher the role of nitrate photolysis on the atmospheric oxidative capacity in snow‐covered regions, NOx flux must be determined with more precision than existing estimates. Here, we introduce a method based on dynamic flux chamber measurements for evaluating the NOx production by photolysis of snowpack nitrate in Antarctica. Flux chamber experiments were conducted for the first time in Antarctica, at the French‐Italian station Concordia, Dome C (75°06'S, 123°20’E, 3233 m a.s.l) during the 2019–2020 summer campaign. Measurements were gathered with several snow samples of different ages ranging from newly formed drifted snow to 6‐year‐old firn. Contrary to existing literature expectations, the daily average photolysis rate coefficient, JNO3¯, did not significantly vary between differently aged snow samples, suggesting that the photolabile nitrate in snow behaves as a single‐family source with common photochemical properties, where a JNO3¯ = (2.37 ± 0.35) × 10−8 s−1 (1σ) has been calculated from December 10th 2019 to January 7th 2020. At Dome C summer daily average NOx flux, FNOx, based on measured NOx production rates was estimated to be (4.3 ± 1.2) × 108 molecules cm−2 s−1, which is 1.5–7 times less than the net NOx flux observed previously above snow at Dome C using the gradient flux method. Using these results, we extrapolated an annual continental snow sourced NOx budget of 0.017 ± 0.003 Tg·N y−1, ∼2 times the nitrogen budget, (N‐budget), of the stratospheric denitrification previously estimated for Antarctica. These quantifications of nitrate photolysis using flux chamber experiments provide a road‐map toward a new parameterization of the σNO3−(λ,0.25emT)ϕ(T,0.25empH) product that can improve future global and regional models of atmospheric chemistry.
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