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- ItemSolar 27-day signatures in standard phase height measurements above central Europe(Katlenburg-Lindau : EGU, 2019) von Savigny, Christian; Peters, Dieter H.W.; Entzian, GünterWe report on the effect of solar variability at the 27-day and the 11-year timescales on standard phase heightmeasurements in the ionospheric D region carried out in cen-tral Europe. Standard phase height corresponds to the re-flection height of radio waves (for constant solar zenith dis-tance) in the ionosphere near 80 km altitude, where NO isionized by solar Lyman-αradiation. Using the superposedepoch analysis (SEA) method, we extract statistically highlysignificant solar 27-day signatures in standard phase heights.The 27-day signatures are roughly inversely correlated to so-lar proxies, such as the F10.7 cm radio flux or the Lyman-αflux. The sensitivity of standard phase height change to so-lar forcing at the 27-day timescale is found to be in goodagreement with the sensitivity for the 11-year solar cycle,suggesting similar underlying mechanisms. The amplitude ofthe 27-day signature in standard phase height is larger duringsolar minimum than during solar maximum, indicating thatthe signature is not only driven by photoionization of NO. Weidentified statistical evidence for an influence of ultra-longplanetary waves on the quasi 27-day signature of standardphase height in winters of solar minimum periods.
- ItemHigh-molecular-weight esters in α-pinene ozonolysis secondary organic aerosol: Structural characterization and mechanistic proposal for their formation from highly oxygenated molecules(Katlenburg-Lindau : EGU, 2018) Kahnt, Ariane; Vermeylen, Reinhilde; Iinuma, Yoshiteru; Safi Shalamzari, Mohammad; Maenhaut, Willy; Claeys, MagdaStable high-molecular-weight esters are present in α-pinene ozonolysis secondary organic aerosol (SOA) with the two most abundant ones corresponding to a hydroxypinonyl ester of cis-pinic acid with a molecular weight (MW) of 368 (C19H28O7) and a diaterpenylic ester of cis-pinic acid with a MW of 358 (C17H26O8). However, their molecular structures are not completely elucidated and their relationship with highly oxygenated molecules (HOMs) in the gas phase is still unclear. In this study, liquid chromatography in combination with positive ion electrospray ionization mass spectrometry has been performed on high-molecular-weight esters present in α-pinene ozonolysis SOA with and without derivatization into methyl esters. Unambiguous evidence could be obtained for the molecular structure of the MWg368 ester in that it corresponds to an ester of cis-pinic acid where the carboxyl substituent of the dimethylcyclobutane ring and not the methylcarboxyl substituent is esterified with 7-hydroxypinonic acid. The same linkage was already proposed in previous work for the MWg358 ester (Yasmeen et al., 2010), but could be supported in the present study. Guided by the molecular structures of these stable esters, we propose a formation mechanism from gas-phase HOMs that takes into account the formation of an unstable C19H28O11 product, which is detected as a major species in α-pinene ozonolysis experiments as well as in the pristine forest atmosphere by chemical ionization-atmospheric pressure ionization-time-of-flight mass spectrometry with nitrate clustering (Ehn et al., 2012, 2014). It is suggested that an acyl peroxy radical related to cis-pinic acid (RO2•) and an alkoxy radical related to 7- or 5-hydroxypinonic acid (R′O•) serve as key gas-phase radicals and combine according to a RO2g+gR′O•→ gRO3R′ radical termination reaction. Subsequently, the unstable C19H28O11 HOM species decompose through the loss of oxygen or ketene from the inner part containing a labile trioxide function and the conversion of the unstable acyl hydroperoxide groups to carboxyl groups, resulting in stable esters with a molecular composition of C19H28O7 (MWg368) and C17H26O8 (MWg358), respectively. The proposed mechanism is supported by several observations reported in the literature. On the basis of the indirect evidence presented in this study, we hypothesize that RO2g+gR′O•→ gRO3R′ chemistry is at the underlying molecular basis of high-molecular-weight ester formation upon α-pinene ozonolysis and may thus be of importance for new particle formation and growth in pristine forested environments.
- ItemGround-based noontime D-region electron density climatology over northern Norway(Katlenburg-Lindau : EGU, 2023) Renkwitz, Toralf; Sivakandan, Mani; Jaen, Juliana; Singer, WernerThe bottom part of the Earth's ionosphere is the so-called D region, which is typically less dense than the upper regions. Despite the comparably lower electron density, the ionization state of the D region has a significant influence on signal absorption for propagating lower to medium radio frequencies. We present local noon climatologies of electron densities in the upper middle atmosphere (50-90km) at high latitudes as observed by an active radar experiment. The radar measurements cover 9 years (2014-2022) from the solar maximum of cycle 24 to the beginning of cycle 25. Reliable electron densities are derived by employing signal processing, applying interferometry methods, and applying the Faraday-International Reference Ionosphere (FIRI) model. For all years a consistent spring-fall asymmetry of the electron density pattern with a gradual increase during summer as well as a sharp decrease at the beginning of October was found. These findings are consistent with very low frequency (VLF) studies showing equivalent signatures for nearby propagation paths. It is suggested that the meridional circulation associated with downwelling in winter could cause enhanced electron densities through NO transport. However, this mechanism can not explain the reduction in electron density in early October.