The spontaneous growth of cloud condensation nuclei (CCN) into cloud droplets under supersaturated water vapour conditions is described by classic Köhler theory. This spontaneous activation of CCN ...depends on the interplay between the Raoult effect, whereby activation potential increases with decreasing water activity or increasing solute concentration, and the Kelvin effect, whereby activation potential decreases with decreasing droplet size or increases with decreasing surface tension, which is sensitive to surfactants. Surface tension lowering caused by organic surfactants, which diminishes the Kelvin effect, is expected to be negated by a concomitant reduction in the Raoult effect, driven by the displacement of surfactant molecules from the droplet bulk to the droplet-vapour interface. Here we present observational and theoretical evidence illustrating that, in ambient air, surface tension lowering can prevail over the reduction in the Raoult effect, leading to substantial increases in cloud droplet concentrations. We suggest that consideration of liquid-liquid phase separation, leading to complete or partial engulfing of a hygroscopic particle core by a hydrophobic organic-rich phase, can explain the lack of concomitant reduction of the Raoult effect, while maintaining substantial lowering of surface tension, even for partial surface coverage. Apart from the importance of particle size and composition in droplet activation, we show by observation and modelling that incorporation of phase-separation effects into activation thermodynamics can lead to a CCN number concentration that is up to ten times what is predicted by climate models, changing the properties of clouds. An adequate representation of the CCN activation process is essential to the prediction of clouds in climate models, and given the effect of clouds on the Earth's energy balance, improved prediction of aerosol-cloud-climate interactions is likely to result in improved assessments of future climate change.
Coastal zones have been shown to provide a massive source of new, tidal‐related, aerosol particles in the atmospheric boundary layer with concentrations exceeding 1,000,000 cm−3 during nucleation ...bursts sustained over many hours O Dowd, 200O. While coastal regions are very strong sources of natural aerosol particles, hithertofore, it has not been demonstrated that these particles contribute to aerosol‐related radiative flux. In this brief report, evidence is presented for growth of these new particles, following tidal‐related particle formation, into radiatively active particle sizes (i.e. radius>50 nm) where an increase in concentration of more than 300% can be seen. This increase of radiatively active particles concomitantly results in more than a threefold enhancement in both aerosol scattering ability (thereby influencing direct radiative flux) and cloud condensation nuclei (CCN) availability (thereby influencing indirect radiative flux). These results provide direct evidence for coastal biogenic emissions significantly enhancing the radiative flux potential of atmospheric aerosols.
One of the most important natural aerosol systems at the global level is marine aerosol that comprises both organic and inorganic components of primary and secondary origin. The present paper reviews ...some new results on primary and secondary organic marine aerosol, achieved during the EU project MAP (Marine Aerosol Production), comparing them with those reported in the recent literature. Marine aerosol samples collected at the coastal site of Mace Head, Ireland, show a chemical composition trend that is influenced by the oceanic biological activity cycle, in agreement with other observations. Laboratory experiments show that sea-spray aerosol from biologically active sea water can be highly enriched in organics, and the authors highlight the need for further studies on the atmospheric fate of such primary organics. With regard to the secondary fraction of organic aerosol, the average chemical composition and molecular tracer (methanesulfonic-acid, amines) distribution could be successfully characterized by adopting a multitechnique analytical approach.
The global marine organic aerosol budget is investigated by a 3-dimensional chemistry-transport model considering recently proposed parameterisations of the primary marine organic aerosol (POA) and ...secondary organic aerosol (SOA) formation from the oxidation of marine volatile organic compounds. MODIS and SeaWiFS satellite data of Chlorophyll-a and ECMWF solar incoming radiation, wind speed, and temperature are driving the oceanic emissions in the model. Based on the adopted parameterisations, the SOA and the submicron POA marine sources are evaluated at about 5 Tg yr−1 (~1.5 Tg C yr−1) and 7 to 8 Tg yr−1 (~4 Tg C yr−1), respectively. The computed marine SOA originates from the dimethylsulfide oxidation (~78%), the potentially formed dialkyl amine salts (~21%), and marine hydrocarbon oxidation (~0.1%). Comparison of calculations with observations indicates an additional marine source of soluble organic carbon that could be partially encountered by marine POA chemical ageing.
Secondary organic aerosol (SOA) formation through isoprene oxidation was investigated with the regional-scale climate model REMOTE. The applied modeling scheme includes a treatment for marine primary ...organic aerosol emissions, aerosol microphysics, and SOA formation through the gas/particle partitioning of semivolatile, water-soluble oxidation products. The focus was on SOA formation taking place over the North-East Atlantic during a period of high biological activity. Isoprene SOA concentrations were up to ~5 ng m−3 over North Atlantic in the base case model runs, and isoprene oxidation made a negligible contribution to the marine organic aerosol (OA) mass. In particular, isoprene SOA did not account for the observed water-soluble organic carbon (WSOC) concentrations over North Atlantic. The performed model calculations, together with results from recent field measurements, imply a missing source of SOA over remote marine areas unless the isoprene oxidation products are considerably less volatile than the current knowledge indicates.
Measurements of ozone fluxes using the eddy-correlation (EC) technique were carried out for the first time at the Mace Head atmospheric research station, on the west coast of Ireland between ...August-October 2009. Vertical exchange of ozone was measured from a tower platform at 22 m above mean sea level to study fluxes over coastal waters excluding the tidal region. The results were averaged over 30 min and exhibited predominantly downward but also upward transport of ozone in the boundary layer. Data quality was found to be high based on inspection of cospectra and micrometeorological measurements. During the study period, a major physical influence on O3 fluxes was found to be wind speed. Measured fluxes were of the same magnitude as reported in previous open ocean studies ranging from approximately +0.2 to −0.5 μg m−2 s−1 (−0.017 μg m−2 s−1 on average, corresponding to a deposition velocity of 0.25 mm s−1 or a surface resistance of 4.13 s mm−1). These results are considered to represent ozone fluxes over shallow coastal waters west of Ireland for conditions during summer and fall not affected by phytoplankton blooms.
The Mulcahy (Mulcahy et al., 2008) power-law parameterization, derived at the coastal Atlantic station Mace Head, between clean marine aerosol optical depth (AOD) and wind speed is compared to open ...ocean MODIS-derived AOD versus wind speed. The reported AOD versus wind speed (U) was a function of ~U2. The open ocean MODIS-derived AOD at 550 nm and 860 nm wavelengths, while in good agreement with the general magnitude of the Mulcahy parameterization, follows a power-law with the exponent ranging from 0.72 to 2.47 for a wind speed range of 2–18 m s−1. For the four cases examined, some MODIS cases underestimated AOD while other cases overestimated AOD relative to the Mulcahy scheme. Overall, the results from MODIS support the general power-law relationship of Mulcahy, although some linear cases were also encountered in the MODIS dataset. Deviations also arise between MODIS and Mulcahy at higher wind speeds (>15 m s−1), where MODIS-derived AOD returns lower values as compared to Mulcahy. The results also support the suggestion than wind generated sea spray, under moderately high winds, can rival anthropogenic pollution plumes advecting out into marine environments with wind driven AOD contributing to AOD values approaching 0.3.
A modal atmospheric aerosol model (M7) is evaluated in terms of predicting marine new particle formation and growth. Simulations were carried out for three different nucleation schemes involving (1) ...kinetic self-nucleation of OIO (2) nucleation via OIO activation by H2SO4 and (3) nucleation via OIO activation by H2SO4 plus condensation of a low-volatility organic vapour. Peak OIO and H2SO4 vapour concentrations were both limited to 6×106 molecules cm-3 at noontime while the peak organic vapour concentration was limited to 12×106 molecules cm-3. All simulations produced significant concentrations of new particles in the Aitken mode. From a base case particle concentration of 222 cm-3 at radii >15 nm, increases in concentrations to 366 cm-3 were predicted from the OIO-OIO case, 722 cm-3 for the OIO-H2SO4 case, and 1584 cm-3 for the OIO-H2SO4 case with additional condensing organic vapours. The results indicate that open ocean new particle production is feasible for clean conditions; however, new particle production becomes most significant when an additional condensable organic vapour is available to grow the newly formed particles to larger sizes. Comparison to sectional model for a typical case study demonstrated good agreement and the validity of using the modal model.
Twenty-one cases of boundary-layer structure were retrieved by three co-located remote sensors, One LIDAR and two ceilometers at the coastal site of Mace Head, Ireland. Data were collected during the ...ICOS field campaign held at the GAW Atmospheric Station of Mace Head, Ireland, from 8th to 28th of June, 2009. The study is a two-step investigation of the BL structure based on (i) the intercomparison of the backscatter profiles from the three laser sensors, namely the Leosphere ALS300 LIDAR, the Vaisala CL31 ceilometer and the Jenoptik CHM15K ceilometer; (ii) and the comparison of the backscatter profiles with twenty-three radiosoundings performed during the period from the 8th to the 15th of June, 2009. The sensor-independent Temporal Height-Tracking algorithm was applied to the backscatter profiles as retrieved by each instrument to determine the decoupled structure of the BL over Mace Head. The LIDAR and ceilometers-retrieved BL heights were compared to the radiosoundings temperature profiles. The comparison between the remote and the in-situ data proved the existence of the inherent link between temperature and aerosol backscatter profiles and opened at future studies focusing on the further assessment of LIDAR-ceilometer comparison.
Frequency and intensity of cyclones over the North Atlantic are investigated using 2 data sets from simulations with the Rossby Centre regional climate model RCA3. The model domain comprises large ...parts of the North Atlantic and the adjacent continents. RCA3 is driven by ECHAM5-OM1 general circulation model data for May to December from 1985 to 2000 and May to December from 2085 to 2100 assuming the SRES-A2 emission scenario. We apply an objective algorithm to identify and track tropical and extratropical cyclones, as well as extratropical transition. The simulation indicates increase in the count of strong hurricanes and extratropical cyclones. Contrasting, and generally weaker, changes are seen for the less extreme events. Decreases of 18% in the count of extratropical cyclones and 13% in the count of tropical cyclones with wind speeds of ≥18 m s⁻¹ can be found. Furthermore, there is a pronounced shift in the tracks of hurricanes and their extratropical transition in November and December—more hurricanes are seen over the Gulf of Mexico, the Caribbean Sea and the western Sargasso Sea and less over the southern North Atlantic.
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