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Publication . Other literature type . Article . 2019

Diurnal variability, photochemical production and loss processes of hydrogen peroxide in the boundary layer over Europe

H. Fischer; R. Axinte; H. Bozem; H. Bozem; J. N. Crowley; C. Ernest; C. Ernest; +22 Authors
Open Access
Published: 25 Sep 2019
Country: Germany
Hydrogen peroxide (H2O2) plays a significant role in the oxidizing capacity of the atmosphere. It is an efficient oxidant in the liquid phase and serves as a temporary reservoir for the hydroxyl radical (OH), the most important oxidizing agent in the gas phase. Due to its high solubility, removal of H2O2 due to wet and dry deposition is efficient, being a sink of HOx (OH+HO2) radicals. In the continental boundary layer, the H2O2 budget is controlled by photochemistry, transport and deposition processes. Here we use in situ observations of H2O2 and account for chemical source and removal mechanisms to study the interplay between these processes. The data were obtained during five ground-based field campaigns across Europe from 2008 to 2014 and bring together observations in a boreal forest, two mountainous sites in Germany, and coastal sites in Spain and Cyprus. Most campaigns took place in the summer, while the measurements in the south-west of Spain took place in early winter. Diel variations in H2O2 are strongly site-dependent and indicate a significant altitude dependence. While boundary-layer mixing ratios of H2O2 at low-level sites show classical diel cycles with the lowest values in the early morning and maxima around local noon, diel profiles are reversed on mountainous sites due to transport from the nocturnal residual layer and the free troposphere. The concentration of hydrogen peroxide is largely governed by its main precursor, the hydroperoxy radical (HO2), and shows significant anti-correlation with nitrogen oxides (NOx) that remove HO2. A budget calculation indicates that in all campaigns, the noontime photochemical production rate through the self-reaction of HO2 radicals was much larger than photochemical loss due to reaction with OH and photolysis, and that dry deposition is the dominant loss mechanism. Estimated dry deposition velocities varied between approximately 1 and 6 cm s−1, with relatively high values observed during the day in forested regions, indicating enhanced uptake of H2O2 by vegetation. In order to reproduce the change in H2O2 mixing ratios between sunrise and midday, a variable contribution from transport (10 %–100 %) is required to balance net photochemical production and deposition loss. Transport is most likely related to entrainment from the residual layer above the nocturnal boundary layer during the growth of the boundary layer in the morning.
Subjects by Vocabulary

Dewey Decimal Classification: ddc:550

Microsoft Academic Graph classification: Hydroxyl radical chemistry.chemical_compound chemistry Environmental science Boundary layer Oxidizing agent Deposition (aerosol physics) Troposphere Diel vertical migration Sunrise Photochemistry Hydrogen peroxide

Library of Congress Subject Headings: lcsh:Physics lcsh:QC1-999 lcsh:Chemistry lcsh:QD1-999


Environment, Environment & Sustainability, Urbanisation, Atmospheric Science

54 references, page 1 of 6

Acker, K., Kezele, N., Klasnic, L., Möller, D., Pehenec, G., Sorgo, G., Wieprecht, W., and Zuzul, S.: Atmospheric H2O2 measurement and modeling campaign during summer 2004 in Zagreb, Croatia, Atmos. Environ., 42, 2530-2542,, 2008.

Adame, J. A., Martínez, M., Sorribas, M., Hidalgo, P. J., Harder, H., Diesch, J.-M., Drewnick, F., Song, W., Williams, J., Sinha, V., Hernández-Ceballos, M. A., Vilà-Guerau de Arellano, J., Sander, R., Hosaynali-Beygi, Z., Fischer, H., Lelieveld, J., and De la Morena, B.: Meteorology during the DOMINO campaign and its connection with trace gases and aerosols, Atmos. Chem. Phys., 14, 2325-2342,, 2014. [OpenAIRE]

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox , HOx , NOx and SOx species, Atmos. Chem. Phys., 4, 1461-1738,, 2004.

Axinte, R.: The oxidation photochemistry and transport of hydrogen peroxide and formaldehyde at three site in Europe: trends budgets and 3D model simulations, PhD thesis, University of Mainz, Germany, 2016.

Baer, M. and Nester, K.: Parameterization of trace gas dry deposition velocities for a regional mesoscale diffusion model, Ann. Geophys., 10, 912-923, 1992.

Berkes, F., Hoor, P., Bozem, H., Kunkel, D., Sprenger, M., and Henne, S.: Airborne observation of mixing across the entrainment zone during PARADE 2011, Atmos. Chem. Phys., 16, 6011-6025,, 2016. [OpenAIRE]

Crowley, J. N., Pouvesle, N., Phillips, G. J., Axinte, R., Fischer, H., Petäjä, T., Nölscher, A., Williams, J., Hens, K., Harder, H., Martinez-Harder, M., Novelli, A., Kubistin, D., Bohn, B., and Lelieveld, J.: Insights into HOx and ROx chemistry in the boreal forest via measurement of peroxyacetic acid, peroxyacetic nitric anhydride (PAN) and hydrogen peroxide, Atmos. Chem. Phys., 18, 13457-13479, 2018, 2018.

Derstroff, B., Hüser, I., Bourtsoukidis, E., Crowley, J. N., Fischer, H., Gromov, S., Harder, H., Janssen, R. H. H., Kesselmeier, J., Lelieveld, J., Mallik, C., Martinez, M., Novelli, A., Parchatka, U., Phillips, G. J., Sander, R., Sauvage, C., Schuladen, J., Stönner, C., Tomsche, L., and Williams, J.: Volatile organic compounds (VOCs) in photochemically aged air from the eastern and western Mediterranean, Atmos. Chem. Phys., 17, 9547-9566,, 2017. [OpenAIRE]

de Reus, M., Fischer, H., Sander, R., Gros, V., Kormann, R., Salisbury, G., Van Dingenen, R., Williams, J., Zöllner, M., and Lelieveld, J.: Observations and model calculations of trace gas scavenging in a dense Saharan dust plume during MINATROC, Atmos. Chem. Phys., 5, 1787-1803,, 2005. [OpenAIRE]

Fels, M. and Junkermann, W.: The occurrence of organic peroxides in air at a mountain site, Geophys. Res. Lett., 21, 341-344,, 1994. [OpenAIRE]

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