Sensitive Detection of Ambient Formaldehyde by Incoherent Broadband Cavity Enhanced Absorption Spectroscopy.

Formaldehyde (HCHO) is the most abundant atmospheric carbonyl compound and plays an important role in the troposphere. However, HCHO detection via traditional incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) is limited by short optical path lengths and weak light intensity. Thus, a new light-emitting diode (LED)-based IBBCEAS was developed herein to measure HCHO in ambient air. Two LEDs (325 and 340 nm) coupled by a Y-type fiber bundle were used as an IBBCEAS light source, which provided both high light intensity and a wide spectral fitting range. The reflectivity of the two cavity mirrors used herein was 0.99965 (1 - reflectivity = 350 ppm loss) at 350 nm, which corresponded with an effective optical path length of 2.15 km within a 0.84 m cavity. At an integration time of 30 s, the measurement precision (1σ) for HCHO was 380 parts per trillion volume (pptv), and the corresponding uncertainty was 8.3%. The instrument was successfully deployed for the first time in a field campaign and delivered results that correlated well with those of a commercial wet-chemical instrument based on Hantzsch fluorimetry (R2 = 0.769). The combined light source based on a Y-type fiber bundle overcomes the difficulty of measuring ambient HCHO via IBBCEAS in near-ultraviolet range, which may extend IBBCEAS technology to measure other atmospheric trace gases with high precision.

Observations and modeling of OH and HO2 radicals in Chengdu, China in summer 2019.

This study reports on the first continuous measurements of ambient OH and HO2 radicals at a suburban site in Chengdu, Southwest China, which were collected during 2019 as part of a comprehensive field campaign 'CompreHensive field experiment to explOre the photochemical Ozone formation mechaniSm in summEr - 2019 (CHOOSE-2019)'. The mean concentrations (11:00-15:00) of the observed OH and HO2 radicals were 9.5 × 106 and 9.0 × 108 cm-3, respectively. To investigate the state-of-the-art chemical mechanism of radical, closure experiments were conducted with a box model, in which the RACM2 mechanism updated with the latest isoprene chemistry (RACM2-LIM1) was used. In the base run, OH radicals were underestimated by the model for the low-NO regime, which was likely due to the missing OH recycling. However, good agreement between the observed and modeled OH concentrations was achieved when an additional species X (equivalent to 0.25 ppb of NO mixing ratio) from one new OH regeneration cycle (RO2 + X â†’ HO2, HO2 + X â†’ OH) was added into the model. Additionally, in the base run, the model could reproduce the observed HO2 concentrations. Discrepancies in the observed and modeled HO2 concentrations were found in the sensitivity runs with HO2 heterogeneous uptake, indicating that the impact of the uptake may be less significant in Chengdu because of the relatively low aerosol concentrations. The ROx (= OH + HO2 + RO2) primary source was dominated by photolysis reactions, in which HONO, O3, and HCHO photolysis accounted for 34%, 19%, and 23% during the daytime, respectively. The efficiency of radical cycling was quantified by the radical chain length, which was determined by the NO to NO2 ratio successfully. The parameterization of the radical chain length may be very useful for the further determinations of radical recycling.