Annual review of marine science

. This study presents measurements of free amino acids (FAA) in the marine environment to elucidate their transfer from the ocean into the atmosphere to marine aerosol particles and to clouds. FAA were investigated in seawater (underline water (ULW), sea surface microlayer (SML)), in ambient marine size-segregated aerosol particle samples at two heights (ground based at the Cape Verde Atmospheric Observatory (CVAO) and at the Mt. Verde, 744 m height) and in cloud water using concerted measurements. The ∑FAA concentration in the SML varied between 0.13–3.64 µmol L−1, in the ULW between 0.01–1.10 µmol L−1 and a strong enrichment of ∑FAA in the SML (EFSML: 1.1–298.4, average of 57.2) was observed. In the submicron (0.05–1.2 µm) aerosol particles at the CVAO, the composition of FAA was more complex and higher atmospheric concentration of ∑FAA (up to 6.3 ng m−3) compared to the supermicron (1.2–10 µm) aerosol particles (maxima of 0.5 ng m−3) were observed. The total ∑FAA concentration (PM10) was between 1.8–6.8 ng m−3 and tended to increase during the campaign. Averaged ∑FAA concentrations on the aerosol particles at the Mt. Verde were lower (submicron: 1.5 ng m−3, supermicron: 1.2 ng m−3) compared to the CVAO. A similar percentage contribution of ∑FAA to dissolved organic carbon (DOC) in the seawater (up to 7.6t%) and to water-soluble organic carbon (WSOC) on the submicron aerosol particles (up to 5.3 %) indicated a related transfer process of FAA and DOC in the marine environment. The FAA were strongly enriched in the submicron aerosol particles (EFaer(∑FAA) 4∙102–3∙104, EFaer(WSOC) 2∙103–1∙104), possibly resulting from film droplet formation. The enrichment in supermicron aerosol particles was several orders of magnitude lower compared to supermicron size range with EFaer(∑FAA) 1∙101–2∙101, EFaer(WSOC) 3∙102–4∙102. A case study showed that several amino acids were transported from the ocean up to cloud level (e.g. aspartic acid, glutamic acid, proline) while other amino acids might not be transferred or quickly degraded (e.g. phenylalanine, tyrosine) or produced (e.g. GABA). The cloud water samples exhibited a similar composition of FAA compared to the SML but a strong variation of the atmospheric concentration of ∑FAA during the campaign (11.2–489.9 ng m−3). FAA in cloud water samples showed a strong enrichment by a factor of 4∙103 compared to the SML. The presence of high concentrations of FAA in general and of biologically produced FAA (aspartic acid) in particular together with the presence of inorganic marine tracers (sodium, methane sulfonic acid) demonstrates the influence of oceanic sources on marine clouds.

/pdf/concerted-measurements-of-free-amino-acids-at-the-cabo-verde-4wtpfsh22k.pdf

Concerted measurements of free amino acids at the Cabo Verde islands: high enrichments in submicron sea spray aerosol particles and cloud droplets

16 pages, 7 figures, 3 tables, supporting information https://pubs.acs.org/doi/10.1021/acsearthspacechem.0c00351.-- All data are available on the public repository PANGAEA: https://doi.pangaea.de/10.1594/PANGAEA.927565 (for aerosol particles) and https://doi.pangaea.de/10.1594/PANGAEA.927566 (for seawater)

Aerosol Marine Primary Carbohydrates and Atmospheric Transformation in the Western Antarctic Peninsula

Sea Spray Aerosol Chamber Study on Selective Transfer and Enrichment of Free and Combined Amino Acids

Abstract. Transparent exopolymer particles (TEPs) exhibit the properties of gels and
are ubiquitously found in the world oceans. TEPs may enter the
atmosphere as part of sea-spray aerosol. Here, we report number concentrations of TEPs with a diameter > 4.5 µm, hence covering a part of the supermicron particle range, in ambient aerosol and
cloud water samples from the tropical Atlantic Ocean as well as in generated aerosol particles using a plunging waterfall tank that was filled with the ambient seawater. The ambient TEP concentrations ranged between 7×102 and 3×104 #TEP m−3 in the aerosol particles and correlations with sodium (Na+) and calcium (Ca2+) (R2=0.5) suggested some contribution via bubble bursting. Cloud water TEP concentrations were between 4×106 and 9×106 #TEP L−1 and, according to the
measured cloud liquid water content, corresponding to equivalent air
concentrations of 2–4×103 #TEP m−3. Based on Na+ concentrations in seawater and in the atmosphere, the enrichment factors for TEPs in the atmosphere were calculated. The tank-generated TEPs were enriched by a factor of 50 compared with seawater and, therefore, in-line with published enrichment factors for supermicron organic matter in general and TEPs specifically. TEP enrichment in the ambient atmosphere was on average 1×103 in cloud water and
9×103 in ambient aerosol particles and therefore about two orders of magnitude higher than the corresponding enrichment from the tank study. Such high enrichment of supermicron particulate organic constituents in the
atmosphere is uncommon and we propose that atmospheric TEP concentrations
resulted from a combination of enrichment during bubble bursting transfer
from the ocean and a secondary TEP in-situ formation in atmospheric phases.
Abiotic in-situ formation might have occurred from aqueous reactions of
dissolved organic precursors that were present in particle and cloud water
samples, whereas biotic formation involves bacteria, which were abundant in
the cloud water samples. The ambient TEP number concentrations were two orders of magnitude higher
than recently reported ice nucleating particle (INP) concentrations measured at the same location. As TEPs likely possess good properties to act as INPs, in future experiments it is worth studying if a certain part of TEPs
contributes a fraction of the biogenic INP population.


/pdf/high-number-concentrations-of-transparent-exopolymer-39yfgjak.pdf

High number concentrations of transparent exopolymer particles in ambient aerosol particles and cloud water – a case study at the tropical Atlantic Ocean

 The project MarParCloud (Marine biological production, organic
aerosol Particles and marine Clouds: a process
chain) aims to improve our understanding of the genesis, modification and
impact of marine organic matter (OM) from its biological production, to
its export to marine aerosol particles and, finally, to its ability to
act as ice-nucleating particles (INPs) and cloud condensation nuclei (CCN) A
field campaign at the Cape Verde Atmospheric Observatory (CVAO) in the
tropics in September–October 2017 formed the core of this project that was
jointly performed with the project MARSU (MARine atmospheric
Science Unravelled) A suite of chemical,
physical, biological and meteorological techniques was applied, and
comprehensive measurements of bulk water, the sea surface microlayer (SML),
cloud water and ambient aerosol particles collected at a ground-based and a
mountain station took place Key variables comprised the chemical characterization of the atmospherically
relevant OM components in the ocean and the atmosphere as well as
measurements of INPs and CCN Moreover, bacterial cell counts, mercury
species and trace gases were analyzed To interpret the results, the
measurements were accompanied by various auxiliary parameters such as air
mass back-trajectory analysis, vertical atmospheric profile analysis, cloud
observations and pigment measurements in seawater Additional modeling
studies supported the experimental analysis During the campaign, the CVAO exhibited marine air masses with low and
partly moderate dust influences The marine boundary layer was well mixed as
indicated by an almost uniform particle number size distribution within the
boundary layer Lipid biomarkers were present in the aerosol particles in
typical concentrations of marine background conditions Accumulation- and
coarse-mode particles served as CCN and were efficiently transferred to the
cloud water The ascent of ocean-derived compounds, such as sea salt and
sugar-like compounds, to the cloud level, as derived from chemical analysis
and atmospheric transfer modeling results, denotes an influence of marine
emissions on cloud formation Organic nitrogen compounds (free amino acids)
were enriched by several orders of magnitude in submicron aerosol particles
and in cloud water compared to seawater However, INP measurements also indicated
a significant contribution of other non-marine sources to the local INP
concentration, as (biologically active) INPs were mainly present in
supermicron aerosol particles that are not suggested to undergo strong
enrichment during ocean–atmosphere transfer In addition, the number of CCN
at the supersaturation of 030 % was about 25 times higher during dust
periods compared to marine periods Lipids, sugar-like compounds, UV-absorbing (UV: ultraviolet) humic-like substances and low-molecular-weight neutral components
were important organic compounds in the seawater, and highly surface-active
lipids were enriched within the SML The selective enrichment of specific
organic compounds in the SML needs to be studied in further detail and
implemented in an OM source function for emission modeling to better
understand transfer patterns, the mechanisms of marine OM transformation in the
atmosphere and the role of additional sources In summary, when looking at particulate mass, we see oceanic compounds
transferred to the atmospheric aerosol and to the cloud level, while from a
perspective of particle number concentrations, sea spray aerosol (ie,
primary marine aerosol) contributions to both CCN and INPs are rather
limited

/pdf/marine-organic-matter-in-the-remote-environment-of-the-cape-3n5v23ja7t.pdf

Marine organic matter in the remote environment of the Cape Verde Islands – An introduction and overview to the MarParCloud campaign

Manuela van Pinxteren, Khanneh Wadinga Fomba, Nadja Triesch, Christian Stolle, 4 Oliver Wurl, Enno Bahlmann Xianda Gong, Jens Voigtländer, Heike Wex, Tiera5 Brandy Robinson, Stefan Barthel, Sebastian Zeppenfeld, Erik H. Hoffmann, Marie 6 Roveretto, Chunlin Li , Benoit Grosselin, Veronique Daële, Fabian Senf, Dominik van 7 Pinxteren, Malena Manzi, Nicolás Zabalegui, Sanja Frka, Blaženka Gašparović, Ryan 8 Pereira, Tao Li, Liang Wen, Jiarong Li, Chao Zhu, Hui Chen, Jianmin Chen, Björn 9 Fiedler, Wolf von Tümpling, Katie A. Read, Shalini Punjabi, Alastair C. Lewis, 10 James R. Hopkins, Lucy J. Carpenter, Ilka Peeken, Tim Rixen, Detlef Schulz-Bull, 11 María Eugenia Monge, Abdelwahid Mellouki , Christian George, Frank Stratmann, 12 Hartmut Herrmann 13

/pdf/marine-organic-matter-in-the-remote-environment-of-the-cape-4kcu9tbz8x.pdf

Marine organic matter in the remote environment of the Cape Verde Islands - An introduction and overview to the MarParCloud campaign

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Marine organic matter in the remote environment of the Cape Verde Islands – An introduction and overview to the MarParCloud campaign

Marine organic matter in the remote environment of the Cape Verde Islands - An introduction and overview to the MarParCloud campaign