Measurements of seawater and aerosol particles during POLARSTERN cruise ANT-XXVII/4

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 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 (GLY) and 196 ng/l (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.

Underway measurements of halocarbons (air) during POSEIDON cruise POS399 in June 2010

During the DRIVE (Diurnal and Regional Variability of Halogen Emissions) ship campaign we investigated the variability of the halogenated very short-lived substances (VSLS) bromoform (CHBr3), dibromomethane (CH2Br2) and methyl iodide (CH3I) in the marine atmospheric boundary layer in the eastern tropical and subtropical North Atlantic Ocean during May/June 2010. The highest VSLS mixing ratios were found near the Mauritanian coast and close to Lisbon (Portugal). With backward trajectories we identified predominantly air masses from the open North Atlantic with some coastal influence in the Mauritanian upwelling area, due to the prevailing NW winds. The maximum VSLS mixing ratios above the Mauritanian upwelling were 8.92 ppt for bromoform, 3.14 ppt for dibromomethane and 3.29 ppt for methyl iodide, with an observed maximum range of the daily mean up to 50% for bromoform, 26% for dibromomethane and 56% for methyl iodide. The influence of various meteorological parameters - such as wind, surface air pressure, surface air and surface water temperature, humidity and marine atmospheric boundary layer (MABL) height - on VSLS concentrations and fluxes was investigated. The strongest relationship was found between the MABL height and bromoform, dibromomethane and methyl iodide abundances. Lowest MABL heights above the Mauritanian upwelling area coincide with highest VSLS mixing ratios and vice versa above the open ocean. Significant high anti-correlations confirm this relationship for the whole cruise. We conclude that especially above oceanic upwelling systems, in addition to sea-air fluxes, MABL height variations can influence atmospheric VSLS mixing ratios, occasionally leading to elevated atmospheric abundances. This may add to the postulated missing VSLS sources in the Mauritanian upwelling region (Quack et al., 2007).

Underway water measurements of halocarbons during POSEIDON cruise POS399 in June 2010

Methyl iodide (CH3I), bromoform (CHBr3) and dibromomethane (CH2Br2), which are produced naturally in the oceans, take part in ozone chemistry both in the troposphere and the stratosphere. The significance of oceanic upwelling regions for emissions of these trace gases in the global context is still uncertain although they have been identified as important source regions. To better quantify the role of upwelling areas in current and future climate, this paper analyzes major factors that influenced halocarbon emissions from the tropical North East Atlantic including the Mauritanian upwelling during the DRIVE expedition. Diel and regional variability of oceanic and atmospheric CH3I, CHBr3 and CH2Br2 was determined along with biological and meteorological parameters at six 24 h-stations. Low oceanic concentrations of CH3I from 0.1-5.4 pmol/L were equally distributed throughout the investigation area. CHBr3 of 1.0-42.4 pmol/L and CH2Br2 of 1.0-9.4 pmol/L were measured with maximum concentrations close to the Mauritanian coast. Atmospheric mixing rations of CH3I of up to 3.3, CHBr3 to 8.9 and CH2Br2 to 3.1 ppt above the upwelling and 1.8, 12.8, respectively 2.2 ppt at a Cape Verdean coast were detected during the campaign. While diel variability in CH3I emissions could be mainly ascribed to oceanic non-biological production, no main driver was identified for its emissions in the entire study region. In contrast, oceanic bromocarbons resulted from biogenic sources which were identified as regional drivers of their sea-to-air fluxes. The diel impact of wind speed on bromocarbon emissions increased with decreasing distance to the coast. The height of the marine atmospheric boundary layer (MABL) was determined as an additional factor influencing halocarbon emissions. Oceanic and atmospheric halocarbons correlated well in the study region and in combination with high oceanic CH3I, CHBr3 and CH2Br2 concentrations, local hot spots of atmospheric halocarbons could solely be explained by marine sources. This conclusion is in contrast with previous studies that hypothesized the occurrence of elevated atmospheric halocarbons over the eastern tropical Atlantic mainly originating from the West-African continent.