[1] A High Resolution Time of Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was evaluated for its ability to quantify submicron sea salt mass concentrations. The evaluation included both laboratory and field studies. Quantification of the sea salt signal in the HR-ToF-AMS was achieved by taking the 23 Na 35 Cl + ion as a surrogate for sea salt and then identifying a calibration scaling factor through a comparison with mono-disperse laboratory generated sea salt aerosol. Ambient sea salt concentrations calculated using this method agreed well with those obtained by ion chromatography of filter samples, following a 1:1 regression slope and a correlation coefficient R = 0.93. A key advantage of this AMS-based method is that it allows for high time resolution measurements of sea salt (5 min) along with the speciation of other chemical compounds, including primary organics contributing to sea spray. The high-time resolution sea salt measurement capability enabled the quantification of sea salt mass in both increasing and decreasing wind speed regimes up to 26 m s À1 . A mass flux source function was also derived and found to have a power law wind speed dependency with an exponent of 3.1 for increasing winds and 2.3 for decreasing winds. Comparison of the mass flux relationship in this study suggests that previous schemes based on the Monahan whitecap-wind speed approach significantly over-estimate the submicron mass flux. Both the whitecap-wind speed component and the differential whitecap-aerosol productivity component of the source flux function contribute toward the over-estimation.

[1] High-time resolution measurements of primary marine organic sea-spray physico-chemical properties reveal an apparent dichotomous behavior in terms of water uptake: specifically sea-spray aerosol enriched in organic matter possesses a low hydroscopic Growth Factor (GF∼1.25) while simultaneously having a cloud condensation nucleus/ condensation nuclei (CCN/CN) activation efficiency of between 83% at 0.25% supersaturation and 100% at 0.75%. In contrast, the activation efficiency of particles dominated by non-sea-salt (nss)-sulfate ranged between 48-100% over supersaturation range of 0.25%-1%. Simultaneous retrieval of Cloud Droplet Number Concentration (CDNC) during primary organic aerosol plumes reveals CDNC concentrations of 350 cm −3 for organic mass concentrations 3-4 mg m −3 . It is demonstrated that the retrieved high CDNCs under clean marine conditions can only be explained by organic seaspray and corroborates the high CCN activation efficiency associated with primary organics. It is postulated that marine hydrogels are responsible for this dichotomous behavior.

Bursting bubbles at the ocean-surface produce airborne salt-water spray-droplets, in turn, forming climate-cooling marine haze and cloud layers. The reflectance and ultimate cooling effect of these layers is determined by the spray’s water-uptake properties that are modified through entrainment of ocean-surface organic matter (OM) into the airborne droplets. We present new results illustrating a clear dependence of OM mass-fraction enrichment in sea spray (OMss) on both phytoplankton-biomass, determined from Chlorophyll-a (Chl-a) and Net Primary Productivity (NPP). The correlation coefficient for OMss as a function of Chl-a increased form 0.67 on a daily timescale to 0.85 on a monthly timescale. An even stronger correlation was found as a function of NPP, increasing to 0.93 on a monthly timescale. We suggest the observed dependence is through the demise of the bloom, driven by nanoscale biological processes (such as viral infections), releasing large quantities of transferable OM comprising cell debris, exudates and other colloidal materials. This OM, through aggregation processes, leads to enrichment in sea-spray, thus demonstrating an important coupling between biologically-driven plankton bloom termination, marine productivity and sea-spray modification with potentially significant climate impacts.

As part of the EUCAARI Intensive Observing Period, a 4-week campaign to measure aerosol physical, chemical and optical properties, atmospheric structure, and cloud microphysics was conducted from mid-May to mid-June, 2008 at the Mace Head Atmospheric Research Station, located at the interface of Western Europe and the N. E. Atlantic and centered on the west Irish coastline. During the campaign, continental air masses comprising both young and aged continental plumes were encountered, along with polar, Arctic and tropical air masses. Polluted-continental aerosol concentrations were of the order of 3000 cm(-3), while background marine air aerosol concentrations were between 400-600 cm(-3). The highest marine air concentrations occurred in polar air masses in which a 15 nm nucleation mode, with concentration of 1100 cm(-3), was observed and attributed to open ocean particle formation. Continental air submicron chemical composition (excluding refractory sea salt) was dominated by organic matter, closely followed by sulphate mass. Although the concentrations and size distribution spectral shape were almost identical for the young and aged continental cases, hygroscopic growth factors (GF) and cloud condensation nuclei (CCN) to total condensation nuclei (CN) concentration ratios were significantly less in the younger pollution plume, indicating a more oxidized organic component to the aged continental plume. The difference in chemical composition and hygroscopic growth factor appear to result in a 40-50% impact on aerosol scattering coefficients and Aerosol Optical Depth, despite almost identical aerosol microphysical properties in both cases, with the higher values been recorded for the more aged case. For the CCN/CN ratio, the highest ratios were seen in the more age plume. In marine air, sulphate mass dominated the sub-micron component, followed by water soluble organic carbon, which, in turn, was dominated by methanesulphonic acid (MSA). Sulphate concentrations were highest in marine tropical air - even higher than in continental air. MSA was present at twice the concentrations of previously-reported concentrations at the same location and the same season. Both continental and marine air exhibited aerosol GFs significantly less than ammonium sulphate aerosol pointing to a significant organic contribution to all air mass aerosol properties

Cloud condensation nuclei (CCN) number concentrations alongside with submicrometer particle number size distributions and particle chemical composition have been measured at atmospheric observatories of the Aerosols, Clouds, and Trace gases Research InfraStructure (ACTRIS) as well as other international sites over multiple years. Here, harmonized data records from 11 observatories are summarized, spanning 98,677 instrument hours for CCN data, 157,880 for particle number size distributions, and 70,817 for chemical composition data. The observatories represent nine different environments, e.g., Arctic, Atlantic, Pacific and Mediterranean maritime, boreal forest, or high alpine atmospheric conditions. This is a unique collection of aerosol particle properties most relevant for studying aerosol-cloud interactions which constitute the largest uncertainty in anthropogenic radiative forcing of the climate. The dataset is appropriate for comprehensive aerosol characterization (e.g., closure studies of CCN), model-measurement intercomparison and satellite retrieval method evaluation, among others. Data have been acquired and processed following international recommendations for quality assurance and have undergone multiple stages of quality assessment.

[1] Measurements of marine aerosol chemistry, using state-of-the-art mass spectrometry, as well as aerosol microphysics, hygroscopicity and cloud condensation nuclei (CCN) activity were undertaken during new particle growth events. The events were detected in air advecting over North East (NE) Atlantic waters during the EUCAARI Intensive Observation Period in June 2008 at Mace Head, Ireland. During these growth events, the aerosol mass spectrometers illustrated increases in accumulation mode aerosol phase nitrogenated and aliphatic compounds thought to condense from the gas phase. Since the composition changes observed in the accumulation mode occurred simultaneously to the growth of the accumulation, Aitken and nucleation modes, the growth of both the nucleation mode and the Aitken mode is attributed to the condensation of these species. Nitrogenated compounds like amines are also plausible candidates in the nucleation process, as suggested by quantum mechanic calculations. It is also plausible that amides and organic nitrites, also identified by the mass spectrometers, are possible candidate chemical compounds, suggesting that multiple types of chemical species may be contributing. Given that these open ocean aerosol formation and growth events occur in very clean polar marine air masses, we suggest that the organic compounds responsible for particle formation and growth are mainly of biogenic origin. Despite increasing the particle number concentration, the initial effect is to suppress hygroscopicity and CCN activity.

[1] Direct climate aerosol radiative forcing is influenced by the light scattering of atmospheric aerosols. The chemical composition, the size distribution, and the ambient relative humidity (RH) determine the amount of visible light scattered by aerosols. We measured the aerosol light scattering coefficients at RH varying from 30% to 90% of the marine atmosphere at the Mace Head Atmospheric Research Station on the west coast of Ireland. At this site, two major air mass types can be distinguished: clean marine and polluted air. In this paper, we present measurements of light scattering enhancement factors f (RH) = s sp (RH)/s sp (dry) from a 1 month field campaign (January-February 2009). At this site in winter, the mean f (RH = 85%) (standard deviation) for marine air masses at the wavelength of 550 nm was 2.22 (±0.17) and 1.77 (±0.31) for polluted air. Measured s sp (RH) and f (RH) agreed well with calculations from Mie theory using measurements of the size distribution and hygroscopic diameter growth factors as input. In addition, we investigated the RH influence on additional intensive optical properties: the backscatter fraction and the single scattering albedo. The backscatter fraction decreased by about 20%, and the single scattering albedo increased on average by 1%-5% at 85% RH compared to dry conditions.

[1] Primary-produced sea spray aerosol, typically comprising sea-salt, but also enriched with organic matter (OM) in biologically active oceanic regions, impacts the global radiative budget through contributions to aerosol optical depth. We show that sea spray light-scattering enhancement, f(RH), as a function of relative humidity (RH) is suppressed when enriched with OM. A new hygroscopic growth factor parameterization reveals a dual hygroscopicity state, flipping from high hygroscopicity and high f(RH) to low hygroscopicity and low f(RH) as the OM mixing volume percentage exceeds~55% in sea spray. Under elevated wind speeds, this affects the Top-of-atmosphere direct radiative forcing (ΔF) by reducing the cooling contribution of sea spray by~5.5 times compared to pure sea-salt spray. These results suggest a positive feedback coupling between the marine biosphere, sea spray aerosol, and the direct radiative budget.