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.

Atmospheric nitrate concentrations and isotope composition for samples collected in the marine boundary layer in 2006 and 2007

The comprehensive isotopic composition of atmospheric nitrate (i.e., the simultaneous measurement of all its stable isotope ratios: 15N/14N, 17O/16O and 18O/16O) has been determined for aerosol samples collected in the marine boundary layer (MBL) over the Atlantic Ocean from 65°S (Weddell Sea) to 79°N (Svalbard), along a ship-borne latitudinal transect. In nonpolar areas, the d15N of nitrate mostly deriving from anthropogenically emitted NOx is found to be significantly different (from 0 to 6 per mil) from nitrate sampled in locations influenced by natural NOx sources (-4 ± 2) per mil. The effects on d15N(NO3-) of different NOx sources and nitrate removal processes associated with its atmospheric transport are discussed. Measurements of the oxygen isotope anomaly (D17O = d17O - 0.52 × d18O) of nitrate suggest that nocturnal processes involving the nitrate radical play a major role in terms of NOx sinks. Different D17O between aerosol size fractions indicate different proportions between nitrate formation pathways as a function of the size and composition of the particles. Extremely low d15N values (down to -40 per mil) are found in air masses exposed to snow-covered areas, showing that snowpack emissions of NOx from upwind regions can have a significant impact on the local surface budget of reactive nitrogen, in conjunction with interactions with active halogen chemistry. The implications of the results are discussed in light of the potential use of the stable isotopic composition of nitrate to infer atmospherically relevant information from nitrate preserved in ice cores.

(Table 1) Conditions of vertical near-bottom profiling and the main parameters of the benthic boundary layer in several regions of the Black Sea shelf

Measurements of 14 vertical profiles of currents and hydrological parameters in the near-bottom layer with depth resolution of 0.1 m were carried out in several regions of the Black Sea shelf, at five points over the continental slope, and in three deep water regions. The upper boundary of the benthic boundary layer (BBL) was reliably determined at a point at distance from 5-7 to 35-40 m from the bottom where the gradients of density and current velocity changed. Experimental data obtained were used to determine the coefficient of bottom friction, friction velocity, coefficients of vertical diffusion of momentum and density, and vertical fluxes of temperature and salinity in the BBL.

Sensible and latent heat fluxes in the atmospheric surface layer over the equatorial Atlantic (Appendix)

During a four weeks anchoring station of R.V. ,,Meteor" on the equator at 30° W longitude, vertical profiles of wind, temperature, and humidity were measured by means of a meteorological buoy carrying a mast of 10 m height. After eliminating periods of instrumental failure, 18 days are available for the investigation of the diurnal variations of the meteorological parameters and 9 days for the investigation of the vertical heat fluxes. The diurnal variations of the above mentioned quantities are caused essentially by two periodic processes: the 24-hourly changing solar energy supply and the 12-hourly oscillation of air pressure, which both originate in the daily rotation of the earth. While the temperature of the water and of the near water layers of the air show a 24 hours period in their diurnal course, the wind speed, as a consequence of the pressure wave, has a 12 hours period, which is also observable in evaporation and, consequently, in the water vapor content of the surface layer. Concerning the temperature, a weak dependence of the daily amplitude on height was determined. Further investigation of the profiles yields relations between the vertical gradients of wind, temperature, and water vapor and the wind speed, the difference between sea and air of temperature and water vapor, respectively, thus giving a contribution to the problem of parameterizing the vertical fluxes. Mean profile coefficients for the encountered stabilities, which were slightly unstable, are presented, and correction terms are given due to the fact that the conditions at the very surface are not sufficiently represented by measuring in a water depth of 20 cm and assuming water vapor saturation. This is especially true for the water vapor content, where the relation between the gradient and the air-sea difference suggests a reduction of relative humidity to appr. 96% at the very surface, if the gradients are high. This effect may result in an overestimation of the water vapor flux, if a ,,bulk"-formula is used. Finally sensible and latent heat fluxes are computed by means of a gradient-formula. The influence of stability on the transfer process is taken into account. As the air-sea temperature differences are small, sensible heat plays no important role in that region, but latent heat shows several interesting features. Within the measuring period of 18 days, a regular variation by a factor of ten is observed. Unperiodic short term variations are superposed by periodic diurnal variations. The mean diurnal course shows a 12-hours period caused by the vertical wind speed gradient superposed by a 24-hours period due to the changing stabilities. Mean values within the measuring period are 276 ly/day for latent heat and 9.41y/day for sensible heat.