Formaldehyde and hydroperoxide distribution around the Arabian Peninsula – evaluation of EMAC model results with ship-based measurements

Abstract

Abstract. Formaldehyde (HCHO), hydrogen peroxide (H2O2) and organic hydroperoxides (ROOH) play a key role in atmospheric oxidation processes. They act as sources and sinks for HOx radicals (OH + HO2), with OH as the primary oxidant that governs the atmospheric self-cleaning capacity. Measurements of these species allow for evaluation of chemistry-transport models which need to account for multifarious source distributions, transport, complex photochemical reaction pathways and deposition processes of these species. HCHO is an intermediate during the oxidation of volatile organic compounds (VOCs) and is an indicator of photochemical activity and combustion-related emissions. In this study, we use in situ observations of HCHO, H2O2 and ROOH in the marine boundary layer (MBL) to evaluate results of the general circulation model EMAC (ECHAM5/MESSy2 Atmospheric Chemistry; European Center HAMburg, Modular Earth Submodel System). The dataset was obtained during the Air Quality and Climate Change in the Arabian Basin (AQABA) ship campaign around the Arabian Peninsula in summer 2017. This region is characterized by high levels of photochemical air pollution, humidity and solar irradiation, especially in the areas around the Suez Canal and the Arabian Gulf. High levels of air pollution with up to 12 ppbv HCHO, 2.3 ppbv ROOH and relatively low levels of H2O2 (≤0.5 ppbv) were detected over the Arabian Gulf. We find that EMAC failed to predict absolute mixing ratios of HCHO and ROOH during high-pollution events over the Arabian Gulf, while it reproduced HCHO on average within a factor of 2. Dry deposition velocities were determined for HCHO and H2O2 at night with 0.77±0.29 cm s−1 for HCHO and 1.03±0.52 cm s−1 for H2O2 over the Arabian Sea, which were matched by EMAC. The photochemical budget of H2O2 revealed elevated HOx radical concentrations in EMAC, which resulted in an overestimation of H2O2 by more than a factor of 5 for the AQABA dataset. The underestimated air pollution over the Arabian Gulf was related to EMAC's coarse spatial resolution and missing anthropogenic emissions in the model.

Measurement report: Hydrogen peroxide in the upper tropical troposphere over the Atlantic Ocean and western Africa during the CAFE-Africa aircraft campaign

“…Further information on the mixing ratios of individual organic peroxides cannot be provided by the monitor, due to the characteristics of the measurement technique. Please note that, especially within the boundary layer and due to biomass burning, a variety of organic peroxides might contribute to the total measured signal of organic peroxide (Fels and Junkermann, 1994;Slemr and Tremmel, 1994;Valverde-Canossa et al, 2005;Hua et al, 2008;Dienhart et al, 2023).…”

HYPHOP: a tool for high-altitude, long-range monitoring of hydrogen peroxide and higher organic peroxides in the atmosphere

“…More re-Z. Hamryszczak et al: HYPHOP: H 2 O 2 and ROOH monitor cent studies on the hydroperoxides have provided insights into their tropospheric abundance and their importance in atmospheric oxidative processes (Gunz and Hoffmann, 1990;Sakugawa et al, 1990;Reeves and Penkett, 2003;Klippel et al, 2011;Fischer et al, 2019;Hottmann et al, 2020;Allen et al, 2022a, b;Hamryszczak et al, 2022;Dienhart et al, 2023;Hamryszczak et al, 2023). Thus, it is not surprising that over the past decades, numerous hydroperoxide measurement methods have been established to investigate the species in both the gaseous and aqueous phases of the atmosphere.…”