Search

Abstract. The aerosol-driven radiative effects on marine low-level cloud represent a large uncertainty in climate simulations, in particular over the Southern Ocean, which is also an important region for sea spray aerosol production. Observations of sea spray aerosol organic enrichment and the resulting impact on water uptake over the remote Southern Hemisphere are scarce, and therefore the region is under-represented in existing parameterisations. The Surface Ocean Aerosol Production (SOAP) voyage was a 23 d voyage which sampled three phytoplankton blooms in the highly productive water of the Chatham Rise, east of New Zealand. In this study we examined the enrichment of organics to nascent sea spray aerosol and the modifications to sea spray aerosol water uptake using in situ chamber measurements of seawater samples taken during the SOAP voyage. Primary marine organics contributed up to 23 % of the sea spray mass for particles with diameter less than approximately 1 µm and up to 79 % of the particle volume for 50 nm diameter sea spray. The composition of the submicron organic fraction was consistent throughout the voyage and was largely composed of a polysaccharide-like component, characterised by very low alkane-to-hydroxyl-concentration ratios of approximately 0.1–0.2. The enrichment of organics was compared to the output from the chlorophyll-a-based sea spray aerosol parameterisation suggested by Gantt et al. (2011) and the OCEANFILMS (Organic Compounds from Ecosystems to Aerosols: Natural Films and Interfaces via Langmuir Molecular Surfactants) models. OCEANFILMS improved on the representation of the organic fraction predicted using chlorophyll a, in particular when the co-adsorption of polysaccharides was included; however, the model still under-predicted the proportion of polysaccharides by an average of 33 %. Nascent 50 nm diameter sea spray aerosol hygroscopic growth factors measured at 90 % relative humidity averaged 1.93±0.08 and did not decrease with increasing sea spray aerosol organic fractions. The observed hygroscopicity was greater than expected from the assumption of full solubility, particularly during the most productive phytoplankton bloom (B1), during which organic fractions were greater than approximately 0.4. The water uptake behaviour observed in this study is consistent with that observed for other measurements of phytoplankton blooms and can be partially attributed to the presence of sea salt hydrates, which lowers the sea spray aerosol hygroscopicity when the organic enrichment is low. The inclusion of surface tension effects only marginally improved the modelled hygroscopicity, and a significant discrepancy between the observed and modelled hygroscopicity at high organic volume fractions remained. The findings from the SOAP voyage highlight the influence of biologically sourced organics on sea spray aerosol composition; these data improve the capacity to parameterise sea spray aerosol organic enrichment and water uptake.

Establishing the relationship between marine boundary layer (MBL) aerosols and surface water biogeochemistry is required to understand aerosol and cloud production processes over the remote ocean and represent them more accurately in earth system models and global climate projections. This was addressed by the SOAP (Surface Ocean Aerosol Production) campaign, which examined air.sea interaction over biologically productive frontal waters east of New Zealand. This overview details the objectives, regional context, sampling strategy and provisional findings of a pilot study, PreSOAP, in austral summer 2011 and the following SOAP voyage in late austral summer 2012. Both voyages characterized surface water and MBL composition in three phytoplankton blooms of differing species composition and biogeochemistry, with significant regional correlation observed between chlorophyll a and DMSsw. Surface seawater dimethylsulfide (DMSsw) and associated air.sea DMS flux showed spatial variation during the SOAP voyage, with maxima of 25 nmol L-1 and 100 molm-2 d-1, respectively, recorded in a dinoflagellate bloom. Inclusion of SOAP data in a regional DMSsw compilation indicates that the current climatological mean is an underestimate for this region of the southwest Pacific. Estimation of the DMS gas transfer velocity (kDMS/by independent techniques of eddy covariance and gradient flux showed good agreement, although both exhibited periodic deviations from model estimates. Flux anomalies were related to surface warming and sea surface microlayer enrichment and also reflected the heterogeneous distribution of DMSsw and the associated flux footprint. Other aerosol precursors measured included the halides and various volatile organic carbon compounds, with first measurements of the short-lived gases glyoxal and methylglyoxal in pristine Southern Ocean marine air indicating an unidentified local source. The application of a real-time clean sector, contaminant markers and a common aerosol inlet facilitated multi-sensor measurement of uncontaminated air. Aerosol characterization identified variable Aitken mode and consistent submicron-sized accumulation and coarse modes. Submicron aerosol mass was dominated by secondary particles containing ammonium sulfate/bisulfate under light winds, with an increase in sea salt under higher wind speeds. MBL measurements and chamber experiments identified a significant organic component in primary and secondary aerosols. Comparison of SOAP aerosol number and size distributions reveals an underprediction in GLOMAP (GLObal Model of Aerosol Processes)-mode aerosol number in clean marine air masses, suggesting a missing marine aerosol source in the model. The SOAP data will be further examined for evidence of nucleation events and also to identify relationships between MBL composition and surface ocean biogeochemistry that may provide potential proxies for aerosol precursors and production.

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere.

The aerosol driven radiative effects on marine low-level cloud represent a large uncertainty in climate simulations, in particular over the Southern Ocean, which is also an important region for sea spray aerosol production. Observations of sea spray aerosol organic enrichment and the resulting impact on water uptake over the remote southern hemisphere are scarce, and are therefore the region is under-represented in existing parameterisations. The Surface Ocean Aerosol Production (SOAP) voyage was a 23 day voyage which sampled three phytoplankton blooms in the highly productive water of the Chatham Rise, east of New Zealand. In this study we examined the enrichment of organics to nascent sea spray aerosol and the modifications to sea spray aerosol water uptake using in-situ chamber measurements of seawater samples taken during the SOAP voyage. Primary marine organics contributed up to 23 % of the sea spray mass for particles with diameter less than approximately 1 μm, and up to 87 % of the particle volume in the Aitken mode. The composition of the organic fraction was consistent throughout the voyage and was largely comprised of a polysaccharide-like component, characterised by very low alkane to hydroxyl concentration ratios of approximately 0.1–0.2. The enrichment of organics was compared to the output from the chlorophyll-a based sea spray aerosol parameterisation suggested by Gantt et al. (2011) and the OCEANFILMS models. OCEANFILMS improved on the representation of the organic fraction predicted using chlorophyll-a, in particular when the co-adsoprtion of polysaccharides was included, however the model still under predicted the proportion of polysaccharides by an average of 33 %. Nascent sea spray aerosol hygroscopic growth factors averaged 1.93 ± 0.08, and did not decrease with increasing sea spray aerosol organic fractions. The observed hygroscopicity was greater than expected from the assumption of full solubility, particularly during the most productive phytoplankton bloom (B1), during which organic fractions were greater than approximately 0.4. The water uptake behaviour observed in this study is consistent with that observed for other measurements of phytoplankton blooms, and was attributed to the surface partitioning of the organic components which leads to a decrease in particle surface tension and an increase in hygroscopicity. The compressed film model was used to estimate the influence of surface partitioning and the error in the modelled hygroscopicity was low only when the entire organic fraction was available to partition to the particle surface. The modelled sea spray aerosol hygroscopicity at high organic fractions was underestimated when only a portion of the organic component was available to be partitioned to the surface. The findings from the SOAP voyage highlight the influence of biologically-sourced organics on sea spray aerosol composition, these data improve the capacity to parameterise sea spray aerosol organic enrichment and water uptake. [ABSTRACT FROM AUTHOR]

Establishing the relationship between marine boundary layer (MBL) aerosols and surface water biogeochemistry over the remote ocean is required to understand aerosol and cloud production processes, and also represent them accurately in Earth System Models and global climate projections. This was addressed in the SOAP (Surface Ocean Aerosol Production) campaign, which examined air-sea interaction over biologically-productive frontal waters east of New Zealand. This overview details the objectives, regional context, sampling strategy, and provisional findings of a pilot study, PreSOAP, in austral summer 2011, and the following SOAP voyage in late austral summer 2012. Both voyages characterised surface water and MBL composition in three phytoplankton blooms of differing species composition and biogeochemistry, with significant regional correlation observed between chlorophyll-a and DMSsw. Surface seawater dimethylsulfide (DMSsw) and associated air-sea DMS flux showed spatial variation during the SOAP voyage, with maxima of 25 nmol L-1 and 100 μmol m-2 d-1, respectively, recorded in a dinoflagellate bloom. Inclusion of SOAP data in a regional DMSsw compilation confirmed that the current climatological mean is an underestimate for this region of the South-west Pacific. Estimation of the DMS gas transfer velocity (kDMS) by independent techniques of eddy covariance and gradient flux showed good agreement, although both exhibited periodic deviations from model estimates. Flux anomalies were related to surface warming and sea surface microlayer enrichment, and also reflected the heterogeneous distribution of DMSsw and the associated flux footprint. Other aerosol precursors measured included the halides and various volatile organic carbon compounds, with the first measurements of the short-lived gases glyoxal and methylglyoxal in pristine Southern Ocean marine air indicating an unidentified local source. The application of a real-time clean-sector, contaminant markers, and a common aerosol inlet facilitated multi-sensor measurement of uncontaminated air. Aerosol characterisation identified variable Aitken mode, and consistent sub-micron sized accumulation and coarse modes. Sub-micron aerosol mass was dominated by secondary particles containing ammonium sulfate/bisulfate under light winds, with an increase in sea-salt under higher wind-speeds. MBL measurements and chamber experiments identified a significant organic component in primary and secondary aerosols. Comparison of SOAP aerosol number and size distributions reveals an underprediction in GLOMAP-mode aerosol number in clean marine air masses, suggesting a missing marine aerosol source in the model. The SOAP data will be further examined for evidence of nucleation events, and also for relationships between MBL composition and surface ocean biogeochemistry with the aim of identifying potential proxies for aerosol precursors and production. [ABSTRACT FROM AUTHOR]

We applied two tandem differential mobility analyzer methods to shed light on the evolution of the nucleation- and Aitken-mode-particle compositions at a virgin boreal-forest site during nucleation events in varying conditions. The overall results show a clear anthropogenic influence on the nucleation- and Aitken-mode-particle compositions during the events. The SO2/MTOP and NOx/MTOP (monoterpene oxidation products) ratios best explain the variation in the nucleation mode composition dining clean and pollution affected events, suggesting also the importance of organic sulfur compounds, in addition to other sulfur, nitrogen and organic compounds, in particle formation, composition and properties. During the cleanest events, MTOP explain well the time behaviour of the 10-nm particle composition with an estimated organic fraction of over 95%. [ABSTRACT FROM AUTHOR]

The Second Pallas Cloud Experiment (Second PACE) was conducted at the Pallas Sodankylä Global Atmosphere Watch (GAW) station in northern Finland from 16 September to 6 October 2005. Measured parameters included aerosol number size distribution, aerosol chemical composition, aerosol hygroscopic growth factor, cloud droplet number size distribution and meteorological parameters. Air mass back trajectories were also calculated. The particulate volume and the inorganic fraction (IO) of particulate mass depended strongly on the air mass history: central European air masses contain much more particulate matter and have higher IO than marine air masses. The hygroscopic growth factor of particles was positively correlated with the IO. Aerosol activation into cloud drop lets was studied for accumulation mode particles (dp > 100 nm). The activation of these particles did not show clear dependency on the number concentration of accumulation mode particles or on IO. These two parameters were positively correlated mid their effects on the particle activation could not be separated. [ABSTRACT FROM AUTHOR]

We measured the number concentrations and size distributions of aerosol particles and air ions with a differential mobility particle sizer and air ion spectrometer, respectively, during a roadside campaign conducted in Kuopio (Savilahti), Finland, between 16 June and 2 July 2004. The average cluster ion (0.3-1.8 nm) concentrations were quite low (around 320 cm-3 and 280 cm-3 for negative and positive ions) during the whole period. For comparison, cluster ion concentrations in a rural SMEAR II station in Hyytiälä, southern Finland, were at the same time almost three times higher. Negative intermediate ions (1.8-7.5 nm) reached maximum concentrations of 620 cm-3 in Kuopio, while the average concentrations were in the range 60-80 cm-3 depending slightly on the wind direction. Positive intermediate ion concentrations were lower. We observed higher amounts of the intermediate ions usually during rain but also during non-rain periods indicative of short-term secondary particle formation. Large ion (7.5--40 nm) concentrations (average values of 500-800 cm-3) were 2-3 times higher in Kuopio than at the SMEAR II station. Straightforward impact of traffic was observed when the wind blew from file road: all increase in the traffic density increased concentrations of large ions. [ABSTRACT FROM AUTHOR]