The influence of environmental drivers on the enrichment of organic carbon in the sea surface microlayer and in submicron aerosol particles – measurements from the Atlantic Ocean

The export of organic matter from ocean to atmosphere represents a substantial carbon flux in the Earth system, yet the impact of environmental drivers on this transfer is not fully understood. This work presents dissolved and particulate organic carbon (DOC, POC) concentrations, their enrichment factors in the sea surface microlayer (SML), and equivalent measurements in marine aerosol particles across the Atlantic Ocean. DOC concentrations averaged 161 ± 139 μmol L–1 (n = 78) in bulk seawater and 225 ± 175 μmol L–1 (n = 79) in the SML; POC concentrations averaged 13 ± 11 μmol L–1 (n = 80) and 17 ± 10 μmol L–1 (n = 80), respectively. High DOC and POC enrichment factors were observed when samples had low concentrations, and lower enrichments when concentrations were high. The impacts of wind speed and chlorophyll-a levels on concentrations and enrichment of DOC and POC in seawater were insignificant. In ambient submicron marine aerosol particles the concentration of water-soluble organic carbon was approximately 0.2 μg m–3. Water-insoluble organic carbon concentrations varied between 0.01 and 0.9 μg m–3, with highest concentrations observed when chlorophyll-a concentrations were high. Concerted measurements of bulk seawater, the SML and aerosol particles enabled calculation of enrichment factors of organic carbon in submicron marine ambient aerosols, which ranged from 103 to 104 during periods of low chlorophyll-a concentrations and up to 105 when chlorophyll-a levels were high. The results suggest that elevated local biological activity enhances the enrichment of marine-sourced organic carbon on aerosol particles. However, implementation of the results in source functions based on wind speed and chlorophyll-a concentrations underestimated the organic fraction at low biological activity by about 30%. There may be additional atmospheric and oceanic parameters to consider for accurately predicting organic fractions on aerosol particles

Cloud water composition during HCCT-2010: Scavenging efficiencies, solute concentrations, and droplet size dependence of inorganic ions and dissolved organic carbon

Cloud water samples were taken in September/October 2010 at Mt. Schmücke in a rural, forested area in Germany during the Lagrange-type Hill Cap Cloud Thuringia 2010 (HCCT-2010) cloud experiment. Besides bulk collectors, a three-stage and a five-stage collector were applied and samples were analysed for inorganic ions (SO42−,NO3−, NH4+, Cl−, Na+, Mg2+, Ca2+, K+), H2O2 (aq), S(IV), and dissolved organic carbon (DOC). Campaign volume-weighted mean concentrations were 191, 142, and 39 µmol L−1 for ammonium, nitrate, and sulfate respectively, between 4 and 27 µmol L−1 for minor ions, 5.4 µmol L−1 for H2O2 (aq), 1.9 µmol L−1 for S(IV), and 3.9 mgC L−1 for DOC. The concentrations compare well to more recent European cloud water data from similar sites. On a mass basis, organic material (as DOC × 1.8) contributed 20–40 % (event means) to total solute concentrations and was found to have non-negligible impact on cloud water acidity. Relative standard deviations of major ions were 60–66 % for solute concentrations and 52–80 % for cloud water loadings (CWLs). The similar variability of solute concentrations and CWLs together with the results of back-trajectory analysis and principal component analysis, suggests that concentrations in incoming air masses (i.e. air mass history), rather than cloud liquid water content (LWC), were the main factor controlling bulk solute concentrations for the cloud studied. Droplet effective radius was found to be a somewhat better predictor for cloud water total ionic content (TIC) than LWC, even though no single explanatory variable can fully describe TIC (or solute concentration) variations in a simple functional relation due to the complex processes involved. Bulk concentrations typically agreed within a factor of 2 with co-located measurements of residual particle concentrations sampled by a counterflow virtual impactor (CVI) and analysed by an aerosol mass spectrometer (AMS), with the deviations being mainly caused by systematic differences and limitations of the approaches (such as outgassing of dissolved gases during residual particle sampling). Scavenging efficiencies (SEs) of aerosol constituents were 0.56–0.94, 0.79–0.99, 0.71–98, and 0.67–0.92 for SO42−, NO3−, NH4+, and DOC respectively when calculated as event means with in-cloud data only. SEs estimated using data from an upwind site were substantially different in many cases, revealing the impact of gas-phase uptake (for volatile constituents) and mass losses across Mt. Schmücke likely due to physical processes such as droplet scavenging by trees and/or entrainment. Drop size-resolved cloud water concentrations of major ions SO42−, NO3−, and NH4+ revealed two main profiles: decreasing concentrations with increasing droplet size and “U” shapes. In contrast, profiles of typical coarse particle mode minor ions were often increasing with increasing drop size, highlighting the importance of a species' particle concentration size distribution for the development of size-resolved solute concentration patterns. Concentration differences between droplet size classes were typically < 2 for major ions from the three-stage collector and somewhat more pronounced from the five-stage collector, while they were much larger for minor ions. Due to a better separation of droplet populations, the five-stage collector was capable of resolving some features of solute size dependencies not seen in the three-stage data, especially sharp concentration increases (up to a factor of 5–10) in the smallest droplets for many solutes

Zusatzbelastung aus Holzheizungen

Die Schriftenreihe informiert über das Ausmaß der Luftbelastung durch Holzheizungen in einem kleinen Ort. Die gesetzlichen Grenzwerte für die Luftqualität wurden nicht überschritten. Die Zusatzbelastung im Winter insbesondere bei ultrafeinen Partikeln, Ruß und dem als krebserzeugend eingestuften Benzo(a)pyren bedeutet eine nicht unerhebliche Verschlechterung der Luftqualität. Die Ergebnisse zu den Konzentrationen von Dioxinen und Furanen im Staubniederschlag sind in einem gesonderten Bericht zusammengefasst. Der Bericht richtet sich an Fachbehörden, Wissenschaft und interessierte Bürger. Redaktionsschluss: 09.04.202

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

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

Application of TXRF in monitoring trace metals in particulate matter and cloud water

Trace metals in ambient particulate matter and cloud are considered key elements of atmospheric processes as they affect air quality, environmental ecosystems, and cloud formation. However, they are often available at trace concentrations in these media such that their analysis requires high-precision and sensitive techniques. In this study, different analytical methods were applied to quantify trace metals in particulate matter (PM) samples collected on quartz and polycarbonate filters as well as cloud water, using the Total reflection X-Ray Fluorescence (TXRF) technique. These methods considered the measurement of filter samples directly without and with chemical pretreatment. Direct measurements involved the analysis of PM samples collected on polycarbonate filters and cloud water samples after they are brought onto TXRF carrier substrates. The chemical treatment method involved the assessment of different acid digestion procedures on PM sampled on quartz filters. The solutions applied were reverse aqua regia, nitric acid, and a combination of nitric acid and hydrogen peroxide. The effect of cold-plasma treatment of samples on polycarbonate filters before TXRF measurements was also investigated. Digestion with the reverse aqua regia solution provided lower blanks and higher recovery in comparison to other tested procedures. The detection limits of the elements ranged from 0.3 to 44 ng cm−2. Ca, K, Zn, and Fe showed the highest detection limits of 44, 35, 6, and 1 ng cm−2, while As and Se had the lowest of 0.3 and 0.8 ng cm−2, respectively. The method showed higher recovery for most trace metals when applied to commercially available reference materials and field samples. TXRF measurements showed good agreement with results obtained from ion chromatography measurements for elements such as Ca and K. Cold-plasma treatment did not significantly lead to an increase in the detected concentration, and the results were element specific. Baking of the quartz filters prior to sampling showed a reduction of more than 20 % of the filter blanks for elements such as V, Sr, Mn, Zn, and Sb. The methods were applied successfully on ambient particulate matter and cloud water samples collected from the Atlas Mohammed V station in Morocco and the Cape Verde Atmospheric Observatory. The obtained concentrations were within the range reported using different techniques from similar remote and background regions elsewhere, especially for elements of anthropogenic origins such as V, Pb, and Zn with concentrations of up to 10, 19, and 28 ng m−3, respectively. Enrichment factor analysis indicated that crustal matter dominated the abundance of most of the elements, while anthropogenic activities also contributed to the abundance of elements such as Sb, Se, and Pb. The results confirm that TXRF is a useful complementary sensitive technique for trace metal analysis of particulate matter in the microgram range as well as in cloud water droplets

Aerosole zur Indikation der Luftqualität im Raum Leipzig: Korngrößendifferenzierte chemisch-physikalische Aerosolcharakterisierung als Indikator der Veränderung der Luftqualität gegenüber 2000 in Leipzig und Sachsen

Der Bericht aus der Luftreinhaltung untersucht die Partikelzusammensetzung in der Außenluft. An vier Messorten in und um Leipzig wurden ultrafeine und feine Partikel nach Wetterlagen charakterisiert. Rund 90.000 Einzelanalysen führten zu den Verursachern. Bei östlicher Anströmung im Winter entstanden hohe Feinstaubwerte zu 80 % durch Kohle- und Holzheizungen und Sekundär-Partikel. Dabei lag meist überregionaler Ferntransport vor. Verkehrsemissionen dominierten bei westlicher Anströmung. Ruß, Metalle und polyzyklische Kohlenwasserstoffe reduzierten sich gegenüber 2000 deutlich

Extensive field evidence for the release of HONO from the photolysis of nitrate aerosols

Particulate nitrate ([Formula: see text]) has long been considered a permanent sink for NO(x) (NO and NO(2)), removing a gaseous pollutant that is central to air quality and that influences the global self-cleansing capacity of the atmosphere. Evidence is emerging that photolysis of [Formula: see text] can recycle HONO and NO(x) back to the gas phase with potentially important implications for tropospheric ozone and OH budgets; however, there are substantial discrepancies in “renoxification” photolysis rate constants. Using aircraft and ground-based HONO observations in the remote Atlantic troposphere, we show evidence for renoxification occurring on mixed marine aerosols with an efficiency that increases with relative humidity and decreases with the concentration of [Formula: see text] , thus largely reconciling the very large discrepancies in renoxification photolysis rate constants found across multiple laboratory and field studies. Active release of HONO from aerosol has important implications for atmospheric oxidants such as OH and O(3) in both polluted and clean environments

Eddy Study to Understand Physical-Chemical-Biological Coupling and the Biological Carbon Pump as a Function of Eddy Type off West Africa, Cruise No. M160, 23.11.2019 - 20.12.2019, Mindelo (Cabo Verde) - Mindelo (Cabo Verde)

Cruise M160 is part of concerted MOSES/REEBUS Eddy Study featuring three major research expeditions (M156, M160, MSM104). It aims to develop both a qualitative and quantitative understanding of the role of physical-chemical-biological coupling in eddies for the biological pump. The study is part of the MOSES “Ocean Eddies” event chain, which follows three major hypotheses to be addressed by the MOSES/REEBUS field campaigns: (1) Mesoscale and sub-mesoscale eddies play an important role in transferring energy along the energy cascade from the large-scale circulation to dissipation at the molecular level. (2) Mesoscale and sub-mesoscale eddies are important drivers in determining onset, magnitude and characteristics of biological productivity in the ocean and contribute significantly to global primary production and particle export and transfer to the deep ocean. (3) Mesoscale and sub-mesoscale eddies are important for shaping extreme biogeochemical environments (e.g., pH, oxygen) in the oceans, thus acting as a source/sink function for greenhouse gases. In contrast to the other two legs, MOSES Eddy Study II during M160 did not include any benthic work but focused entirely on the pelagic dynamics within eddies. It accomplished a multi-disciplinary, multi-parameter and multi-platform study of two discrete cyclonic eddies in an unprecedented complexity. The pre-cruise search for discrete eddies suitable for detailed study during M160 had already started a few months prior to the cruise. Remote sensing data products (sea surface height, sea surface temperature, ocean color/chlorophyll a) were used in combination with eddy detection algorithms and numerical modelling to identify and track eddies in the entire eddy field off West Africa. In addition, 2 gliders and 1 waveglider had been set out from Mindelo/Cabo Verde for pre-cruise mapping of the potential working area north of the Cabo Verdean archipelago. At the start of M160, a few suitable eddies – mostly of cyclonic type – had been identified, some of which were outside the safe operation range of the motorglider plane. As technical problems delayed the flight operations, the first eddy (center at 14.5°N/25°W) for detailed study was chosen to the southwest of the island of Fogo. It was decided to carry out a first hydrographic survey there followed by the deployment of a suite of instruments (gliders, waveglider, floats, drifter short-term mooring). Such instrumented, we left this first eddy and transited – via a strong anticyclonic feature southwest of the island of Santiago – to the region northeast of the island of Sal, i.e. in the working range of the glider plane. During the transit, a full suite of underway measurements as well as CTD/RO section along 22°W (16°-18.5°N) were carried in search for sub-surface expressions of anticyclonic eddy features. In the northeast, we had identified the second strong cyclonic eddy (center at 18°N/22.5°W) which was chosen for detailed study starting with a complete hydrographic survey (ADCP, CTD/RO, other routine station work). After completion of the mesoscale work program, we identified a strong frontal region at the southwestern rim of the cyclonic eddy, which was chosen for the first sub-mesoscale study with aerial observation component. There, the first dye release experiment was carried out which consisted of the dye release itself followed by an intense multi-platforms study of the vertical and horizontal spreading of the initial dye streak. This work was METEOR-Berichte, Cruise M160, Mindelo – Mindelo, 23.11.2019 4 – 20.12.2019 supported and partly guided by aerial observation of the research motorglider Stemme, which was still somewhat compromised by technical issues and meteorological conditions (high cloud cover, Saharan dust event). Nevertheless, this first dye release experiment was successful and showed rapid movement of the dynamic meandering front. After completion of work on this second eddy and execution of a focused sampling program at the Cape Verde Ocean Observation, RV METEOR returned to the first eddy for continuation of the work started there in the beginning of the cruise. This was accompanied by a relocation of the airbase of Stemme from the international airport of Sal to the domestic airport of Fogo. The further execution of the eddy study at this first eddy, which again included a complete hydrographic survey followed by a mesoscale eddy study with dye release, was therefore possible with aerial observations providing important guidance for work on RV METEOR. Overall, M160 accomplished an extremely intense and complex work program with 212 instrument deployments during station work, 137 h of observation with towed instruments and a wide range of underway measurements throughout the cruise. Up to about 30 individually tracked platforms (Seadrones, glider, wavegliders, drifters, floats) were in the water at the same time providing unprecedented and orchestrated observation capabilities in an eddy. All planned work components were achieved and all working groups acquired the expected numbers of instrument deployments and sampling opportunities