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    Concerted measurements of free amino acids at the Cabo Verde islands: high enrichments in submicron sea spray aerosol particles and cloud droplets
    (Katlenburg-Lindau : European Geosciences Union, 2021) Triesch, Nadja; van Pinxteren, Manuela; Engel, Anja; Herrmann, Hartmut
    Measurements of free amino acids (FAAs) in the marine environment to elucidate their transfer from the ocean into the atmosphere, to marine aerosol particles and to clouds, were performed at the MarParCloud (marine biological production, organic aerosol particles and marine clouds: a process chain) campaign at the Cabo Verde islands in autumn 2017. According to physical and chemical specifications such as the behavior of air masses, particulate MSA concentrations and MSA=sulfate ratios, as well as particulate mass concentrations of dust tracers, aerosol particles predominantly of marine origin with low to medium dust influences were observed. FAAs were investigated in different compartments: they were examined in two types of seawater underlying water (ULW) and in the sea surface microlayer (SML), as well as in ambient marine size-segregated aerosol particle samples at two heights (ground height based at the Cape Verde Atmospheric Observatory, CVAO, and at 744m height on Mt. Verde) and in cloud water using concerted measurements. The ΣFAA concentration in the SML varied between 0.13 and 3.64 μmol L-1, whereas it was between 0.01 and 1.10 μmol L-1in the ULW; also, a strong enrichment of ΣFAA (EFSML: 1.1-298.4, average of 57.2) was found in the SML. In the submicron (0.05-1.2 μm) aerosol particles at the CVAO, the composition of FAAs was more complex, and higher atmospheric concentrations of ΣFAA (up to 6.3 ngm-3) compared to the supermicron (1.2-10 μm) aerosol particles (maximum of 0.5 ngm-3) were observed. The total ΣFAA concentration (PM10) was between 1.8 and 6.8 ngm-3and tended to increase during the campaign. Averaged ΣFAA concentrations in the aerosol particles on Mt. Verde were lower (submicron: 1.5 ngm-3; supermicron: 1.2 ngm-3) compared to the CVAO. A similar contribution percentage of ΣFAA to dissolved organic carbon (DOC) in the seawater (up to 7.6 %) and to water-soluble organic carbon (WSOC) in the submicron aerosol particles (up to 5.3 %) indicated a related transfer process of FAAs and DOC in the marine environment. Considering solely ocean-atmosphere transfer and neglecting atmospheric processing, high FAA enrichment factors were found in both aerosol particles in the submicron range (EFaer(ΣFAA):2×103-6×103) and medium enrichment factors in the supermicron range (EFaer(ΣFAA):1×101-3×101). In addition, indications for a biogenic FAA formation were observed. Furthermore, one striking finding was the high and varying FAA cloud water concentration (11.2-489.9 ngm-3), as well as enrichments (EFCW:4×103and 1×104compared to the SML and ULW, respectively), which were reported here for the first time. The abundance of inorganic marine tracers (sodium, methanesulfonic acid) in cloud water suggests an influence of oceanic sources on marine clouds. Finally, the varying composition of the FAAs in the different matrices shows that their abundance and ocean- atmosphere transfer are influenced by additional biotic and abiotic formation and degradation processes. Simple physicochemical parameters (e.g., surface activity) are not sufficient to describe the concentration and enrichments of the FAAs in the marine environment. For a precise representation in organic matter (OM) transfer models, further studies. © 2021 American Institute of Physics Inc.. All rights reserved.
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    Characterization of aerosol particles at Cabo Verde close to sea level and at the cloud level – Part 2: Ice-nucleating particles in air, cloud and seawater
    (Katlenburg-Lindau : EGU, 2020) Gong, Xianda; Wex, Heike; van Pinxteren, Manuela; Triesch, Nadja; Fomba, Khanneh Wadinga; Lubitz, Jasmin; Stolle, Christian; Robinson, Tiera-Brandy; Müller, Thomas; Herrmann, Hartmut; Stratmann, Frank
    Ice-nucleating particles (INPs) in the troposphere can form ice in clouds via heterogeneous ice nucleation. Yet, atmospheric number concentrations of INPs (NINP) are not well characterized, and, although there is some understanding of their sources, it is still unclear to what extend different sources contribute or if all sources are known. In this work, we examined properties of INPs at Cabo Verde (a.k.a. Cape Verde) from different environmental compartments: the oceanic sea surface microlayer (SML), underlying water (ULW), cloud water and the atmosphere close to both sea level and cloud level. Both enrichment and depletion of NINP in SML compared to ULW were observed. The enrichment factor (EF) varied from roughly 0.4 to 11, and there was no clear trend in EF with ice-nucleation temperature. NINP values in PM10 sampled at Cape Verde Atmospheric Observatory (CVAO) at any particular ice-nucleation temperature spanned around 1 order of magnitude below −15 ∘C, and about 2 orders of magnitude at warmer temperatures (>−12  ∘C). Among the 17 PM10 samples at CVAO, three PM10 filters showed elevated NINP at warm temperatures, e.g., above 0.01 L−1 at −10 ∘C. After heating samples at 95 ∘C for 1 h, the elevated NINP at the warm temperatures disappeared, indicating that these highly ice active INPs were most likely biological particles. INP number concentrations in PM1 were generally lower than those in PM10 at CVAO. About 83±22 %, 67±18 % and 77±14 % (median±standard deviation) of INPs had a diameter >1 µm at ice-nucleation temperatures of −12, −15 and −18 ∘C, respectively. PM1 at CVAO did not show such elevated NINP at warm temperatures. Consequently, the difference in NINP between PM1 and PM10 at CVAO suggests that biological ice-active particles were present in the supermicron size range. NINP in PM10 at CVAO was found to be similar to that on Monte Verde (MV, at 744 m a.s.l.) during noncloud events. During cloud events, most INPs on MV were activated to cloud droplets. When highly ice active particles were present in PM10 filters at CVAO, they were not observed in PM10 filters on MV but in cloud water samples instead. This is direct evidence that these INPs, which are likely biological, are activated to cloud droplets during cloud events. For the observed air masses, atmospheric NINP values in air fit well to the concentrations observed in cloud water. When comparing concentrations of both sea salt and INPs in both seawater and PM10 filters, it can be concluded that sea spray aerosol (SSA) only contributed a minor fraction to the atmospheric NINP. This latter conclusion still holds when accounting for an enrichment of organic carbon in supermicron particles during sea spray generation as reported in literature.