Description: Cloud samples for the isotopic analysis were collected in the framework of the Hill Cap Cloud Thuringia 2010 (HCCT-2010) campaign on Schmücke (50° 39'N/ 10° 46'E, 937 m a.s.l.; Germany) in September and October 2010 with a three-stage Caltech Active Strand Cloudwater Collector (CASCC) during 13 different cloud events with a temporal resolution of 1 to 3 hours. In a first step, we ensured that no additional fractionation occurred during sampling with the CASCC. The d values of the three sizes classes of the CASCC (4 µm to 16 µm, 16 µm to 22 µm and 〉22 µm) did not differ significantly, revealing that the cloud droplets of different sizes quickly equilibrate their delta value with the one of the surrounding vapor. delta values in the cloud droplets varied from -77 per mil to -15 per mil in d2H and from -12.1 per mil to -3.9 per mil in d18O and were fitted by d2H =7.8*d18O +13*10**-3. delta values decreased with temperature as well as towards the end of the campaign, representing a seasonal trend which is known from d values in precipitation. The deuterium excess of the cloud samples was generally higher than the Local Meteoric Water Line of the closest GNIP (Global Network of Isotopes in Precipitation) station. Rain decreases its deuterium excess during falling through an unsaturated air column, while the cloud droplets conserve the deuterium excess of the initial evaporation and thus have been found to be a good indicator for the airmass source region: higher deuterium excess was measured for polar air masses and lower deuterium excess for Mediterranean air masses. Changes in d values during one cloud event were up to 3.6 per mil (d2H) and 0.23 per mil (d18O), except for frontal passages, which were associated with increases of ~6 per mil per hour (d2H) and ~0.6 per mil per hour (d18O). Using a box model, we showed that the influence of condensation only was able to explain the variation in the isotope signal of two cloud passages. Consequently, we deduced that the water vapor "feeding" the cloud advected the measured changes. A trajectory analysis and moisture source diagnostic revealed that it is very likely that the variations were either related to rain out along the trajectories or to meteorological changes in the moisture source region. This was the first study using stable water isotopologues in cloud water manifesting their potential in the context of atmospheric water vapor circulation.

Description: Sub-micron marine aerosol particles (PM1) were collected during the MERIAN cruise MSM 18/3 between 22 June 2011 and 21 July 2011 from the Cape Verde island Sao Vicente to Gabun crossing the tropical Atlantic Ocean and passing equatorial upwelling areas. According to air mass origin and chemical composition of the aerosol particles, three main regimes could be established. Aerosol particles in the first part of the cruise were mainly of marine origin, in the second part was marine and slightly biomass burning influenced (increasing tendency) and in the in last part of the cruise, approaching the African mainland, biomass burning influences became dominant. Generally aerosols were dominated by sulfate (caverage = 1.99 µg/m**3) and ammonium ions (caverage = 0.72 µg/m**3) that are well correlated and slightly increasing along the cruise. High concentrations of water insoluble organic carbon (WISOC) averaging 0.51 µg/m**3 were found probably attributed to the high oceanic productivity in this region. Water soluble organic carbon (WSOC) was strongly increasing along the cruise from concentrations of 0.26 µg/m**3 in the mainly marine influenced part to concentrations up to 3.3 µg/m**3 that are probably caused by biomass burning influences. Major organic constituents were oxalic acid, methansulfonic acid (MSA) and aliphatic amines. MSA concentrations were quite constant along the cruise (caverage = 43 ng/m**3). While aliphatic amines were more abundant in the first mainly marine influenced part with concentrations of about 20 ng/m**3, oxalic acid showed the opposite pattern with average concentrations of 12 ng/m**3 in the marine and 158 ng/m**3 in the biomass burning influenced part. The alpha dicarbonyl compounds glyoxal and methylglyoxal were detected in the aerosol particles in the low ng/m**3 range and followed oxalic acid closely. MSA and aliphatic amines accounted for biogenic marine (secondary) aerosol constituents whereas oxalic acid and the alpha dicarbonyl compounds were believed to result mainly from biomass burning. N-alkane concentrations increased along the cruise from 0.81 to 4.66 ng/m**3, PAHs and hopanes were abundant in the last part of the cruise (caverage of PAHs = 0.13 ng/m**3, caverage of hopanes = 0.19 ng/m**3). Levoglucosan was identified in several samples of the last part of the cruise in concentrations around 2 ng/m**3, pointing to (aged) biomass burning influences. The investigated organic compounds could explain 9.5% of WSOC in the mainly marine influenced part (dominating compounds: aliphatic amines and MSA) and 2.7% of WSOC in the biomass burning influenced part (dominating compound: oxalic acid) of the cruise.

Description: An analytical method for the determination of the alpha dicarbonyls glyoxal (GLY) and methylglyoxal (MGLY) from seawater and marine aerosol particles is presented. The method is based on derivatization with o-(2,3,4,5,6-Pentafluorobenzyl)-hydroxylamine (PFBHA) reagent, solvent extraction and GC-MS (SIM) analysis. The method showed good precision (RSD 〈 10%), sensitivity (detection limits in the low ng L−1 range), and accuracy (good agreement between external calibration and standard addition). The method was applied to determine GLY and MGLY in oceanic water sampled during the Polarstern cruise ANT XXVII/4 from Capetown to Bremerhaven in spring 2011. GLY and MGLY were determined in the sea surface microlayer (SML) of the ocean and corresponding bulk water (BW) with average concentrations of 228 ng L−1 (GLY) and 196 ng L−1 (MGLY). The results show a significant enrichment (factor of 4) of GLY and MGLY in the SML. Furthermore, marine aerosol particles (PM1) were sampled during the cruise and analyzed for GLY (average concentration 0.19 ng m−3) and MGLY (average concentration 0.15 ng m−3). On aerosol particles, both carbonyls show a very good correlation with oxalate, supporting the idea of a secondary formation of oxalic acid via GLY and MGLY. Concentrations of GLY and MGLY in seawater and on aerosol particles were correlated to environmental parameters such as global radiation, temperature, distance to the coastline and biological activity. There are slight hints for a photochemical production of GLY and MGLY in the SML (significant enrichment in the SML, higher enrichment at higher temperature). However, a clear connection of GLY and MGLY to global radiation as well as to biological activity cannot be concluded from the data. A slight correlation between GLY and MGLY in the SML and in aerosol particles could be a hint for interactions, in particular of GLY, between seawater and the atmosphere.

Description: The chemical characterization of filter high volume (HV) and Berner impactor (BI) samples PM during RHaMBLe (Reactive Halogens in the Marine Boundary Layer) 2007 shows that the Cape Verde aerosol particles are mainly composed of sea salt, mineral dust and associated water. Minor components are nss-salts, OC and EC. The influence from the African continent on the aerosol constitution was generally small but air masses which came from south-western Europe crossing the Canary Islands transported dust to the sampling site together with other loadings. The mean mass concentration was determined for PM10 to 17 μg/m3 from impactor samples and to 24.2 μg/m3 from HV filter samples. Non sea salt (nss) components of PM were found in the submicron fractions and nitrate in the coarse mode fraction. Bromide was found in all samples with much depleted concentrations in the range 1–8 ng/m3 compared to fresh sea salt aerosol indicating intense atmospheric halogen chemistry. Loss of bromide by ozone reaction during long sampling time is supposed and resulted totally in 82±12% in coarse mode impactor samples and in filter samples in 88±6% bromide deficits. A chloride deficit was determined to 8% and 1% for the coarse mode particles (3.5–10 μm; 1.2–3.5 μm) and to 21% for filter samples. During 14 May with high mineral dust loads also the maximum of OC (1.71μg/m3) and EC (1.25 μg/m3) was measured. The minimum of TC (0.25 μg/m3) was detected during the period 25 to 27 May when pure marine air masses arrived. The concentrations of carbonaceous material decrease with increasing particle size from 60% for the ultra fine particles to 2.5% in coarse mode PM. Total iron (dust vs. non-dust: 0.53 vs. 0.06 μg m3), calcium (0.22 vs. 0.03 μg m3) and potassium (0.33 vs. 0.02 μg m3) were found as good indicators for dust periods because of their heavily increased concentration in the 1.2 to 3.5 μm fraction as compared to their concentration during the non-dust periods. For the organic constituents, oxalate (78–151 ng/m3) and methanesulfonic acid (MSA, 25–100 ng/m3) are the major compounds identified. A good correlation between nss-sulphate and MSA was found for the majority of days indicating active DMS chemistry and low anthropogenic influences.

Description: Mass deposition fluxes of mineral dust to the tropical northeast Atlantic Ocean were determined within this study. In the framework of SOPRAN (Surface Ocean Processes in the Anthropocene), the interaction between the atmosphere and the ocean in terms of material exchange were investigated at the Cape Verde atmospheric observatory (CVAO) on the island Sao Vicente for January 2009. Five different methods were applied to estimate the deposition flux, using different meteorological and physical measurements, remote sensing, and regional dust transport simulations. The set of observations comprises micrometeorological measurements with an ultra-sonic anemometer and profile measurements using 2-D anemometers at two different heights, and microphysical measurements of the size-resolved mass concentrations of mineral dust. In addition, the total mass concentration of mineral dust was derived from absorption photometer observations and passive sampling. The regional dust model COSMO-MUSCAT was used for simulations of dust emission and transport, including dry and wet deposition processes. This model was used as it describes the AOD's and mass concentrations realistic compared to the measurements and because it was run for the time period of the measurements. The four observation-based methods yield a monthly average deposition flux of mineral dust of 12–29 ng m−2 s−1. The simulation results come close to the upper range of the measurements with an average value of 47 ng m−2 s−1. It is shown that the mass deposition flux of mineral dust obtained by the combination of micrometeorological (ultra-sonic anemometer) and microphysical measurements (particle mass size distribution of mineral dust) is difficult to compare to modeled mass deposition fluxes when the mineral dust is inhomogeneously distributed over the investigated area.