Abstract
Abstract. In order to promote the development of the passive DOAS technique the Multi Axis DOAS – Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany, from June to October 2013. Here, we systematically compare the differential slant column densities (dSCDs) of nitrous acid (HONO) derived from measurements of seven different instruments. We also compare the tropospheric difference of SCDs (delta SCD) of HONO, namely the difference of the SCDs for the non-zenith observations and the zenith observation of the same elevation sequence. Different research groups analysed the spectra from their own instruments using their individual fit software. All the fit errors of HONO dSCDs from the instruments with cooled large-size detectors are mostly in the range of 0.1 to 0.3 × 1015 molecules cm−2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7 × 1015 molecules cm−2. Although the HONO delta SCDs are normally smaller than 6 × 1015 molecules cm−2, consistent time series of HONO delta SCDs are retrieved from the measurements of different instruments. Both fits with a sequential Fraunhofer reference spectrum (FRS) and a daily noon FRS lead to similar consistency. Apart from the mini-MAX-DOAS, the systematic absolute differences of HONO delta SCDs between the instruments are smaller than 0.63 × 1015 molecules cm−2. The correlation coefficients are higher than 0.7 and the slopes of linear regressions deviate from unity by less than 16 % for the elevation angle of 1°. The correlations decrease with an increase in elevation angle. All the participants also analysed synthetic spectra using the same baseline DOAS settings to evaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3 × 1015 molecules cm−2, which is about half of the systematic difference between the real measurements.The differences of HONO delta SCDs retrieved in the selected three spectral ranges 335–361, 335–373 and 335–390 nm are considerable (up to 0.57 × 1015 molecules cm−2) for both real measurements and synthetic spectra. We performed sensitivity studies to quantify the dominant systematic error sources and to find a recommended DOAS setting in the three spectral ranges. The results show that water vapour absorption, temperature and wavelength dependence of O4 absorption, temperature dependence of Ring spectrum, and polynomial and intensity offset correction all together dominate the systematic errors. We recommend a fit range of 335–373 nm for HONO retrievals. In such fit range the overall systematic uncertainty is about 0.87 × 1015 molecules cm−2, much smaller than those in the other two ranges. The typical random uncertainty is estimated to be about 0.16 × 1015 molecules cm−2, which is only 25 % of the total systematic uncertainty for most of the instruments in the MAD-CAT campaign. In summary for most of the MAX-DOAS instruments for elevation angle below 5°, half daytime measurements (usually in the morning) of HONO delta SCD can be over the detection limit of 0.2 × 1015 molecules cm−2 with an uncertainty of ∼ 0.9 × 1015 molecules cm−2.
Highlights
Nitrous acid (HONO) is an important precursor of the OH radical, which prominently controls the self-cleaning capacity of the troposphere (Alicke et al, 2003; Kleffmann et al, 2005; Acker et al, 2006; Monks et al, 2009; Elshorbany et al, 2010)
HONO differential slant column densities (dSCDs) and delta SCDs derived from the seven MAX-DOAS instruments during the MAD-CAT campaign held in Mainz were systematically compared
The fit errors of the HONO dSCDs derived from the instruments with cooled large-size detectors were found to be in the range of about 0.1 to 0.3 × 1015 molecules cm−2 for an integration time of 1 min, while the fit error for the mini MAXDOAS instrument is around 0.7 × 1015 molecules cm−2
Summary
Nitrous acid (HONO) is an important precursor of the OH radical, which prominently controls the self-cleaning capacity of the troposphere (Alicke et al, 2003; Kleffmann et al, 2005; Acker et al, 2006; Monks et al, 2009; Elshorbany et al, 2010). Recent field measurements (Neftel et al, 1996; Kleffmann et al, 2005; Sörgel et al, 2011; Li et al, 2012, 2014; Wong et al, 2012) and laboratory studies (Akimoto et al, 1987; Rohrer et al, 2005) reported much larger HONO concentrations than predicted by the gas-phase reactions These findings imply some missing daytime sources of HONO. The surface HONO concentrations can be well quantified by ground-based in situ instruments, like the LOPAP (long-path absorption photometer) technique (Heland et al, 2001; Kleffmann et al, 2006; Li et al, 2012) and long-path DOAS (Trick, 2004, and references therein). Because of the large cost of operating such a flight platform, the corresponding data sets are limited in time and space
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