Properties Of Marine Aerosols Research Articles

Important Roles and Formation of Atmospheric Organosulfates in Marine Organic Aerosols: Influence of Phytoplankton Emissions and Anthropogenic Pollutants.

Organosulfates (OSs) could be potentially important compounds in marine organic aerosols, while their formation in marine atmospheres is far from clear due to a lack of cruise observations. In this work, shipboard atmospheric observations were conducted over the Yellow Sea and Bohai Sea to investigate the abundance and formation of biogenic isoprene/monoterpene-OSs in marine aerosols. The quantified OSs and NOSs accounted for 0.04-6.9% of marine organic aerosols and were 0.07-2.2% of the non-sea-salt (nss) sulfate in terms of sulfur content. Isoprene-related (nitrooxy-)OSs occupied 27-87% of the total quantified OSs, following the abundance order of summer > autumn > spring or winter. This order was driven by the marine phytoplankton biomass and sea surface temperature (SST), which controlled the seawater and atmospheric isoprene concentration levels. Under the severe impacts of anthropogenic pollutants from the East Asia continent in winter, monoterpene nitrooxy-OSs, generated with NOx involved in, increased to 34.4 ± 35.5 ng/m3 and contributed 68% of the quantified (nitrooxy-)OSs. Our results highlight the notable roles of biogenic OSs in marine organic aerosols over regions with high biological activity and high SST. The formation of biogenic OSs and their roles in altering marine aerosol properties calls for elaboration through cruise observations in different marine environments.

Optical properties of marine aerosol: modelling the transition from dry, irregularly shaped crystals to brine-coated, dissolving salt particles

An aerosol-optics model for water-coated marine aerosols is introduced that accounts for irregularities in the geometry of dry salt particles, and that mimics the processes of water-adsorption, dissolution of salt, and rearrangement of the liquid mantle following dissolution. The model can be tuned to adjust how rapidly the dry salt particles become spherical as water is being added to them. Size-shape distributions of the model are generated and employed to compute the ensemble-averaged extinction and backscattering cross sections, the lidar ratio, and the linear backscatter depolarisation ratio (LDR). A power law distribution that is frequently used in chemical transport models yields lidar ratios and LDR values that are consistent with field and satellite observations. But the results are found to be quite sensitive to the assumed size distribution. A generic lognormal size distribution tends to produce higher extinction cross sections, backscattering cross sections, and somewhat higher lidar ratios than the power-law distribution, while the depolarisation ratios are of comparable magnitude. We further gauged the model’s performance by comparing it with homogeneous superellipsoids. For a salt mass fraction of 0.97, the cross sections and the lidar ratio of cubic superellipsoids (i.e., those with unit aspect ratios) agree best with the reference model over all effective radii at a superellipsoid roundness parameter of 0.6. The LDR is more challenging to reproduce. For a salt mass fraction of 0.97, cubic homogeneous superellipsoids mostly give lower LDR values than the reference model. However, by increasing one aspect ratio, the superellipsoids can be tuned to yield higher LDR values. For a salt mass fraction of 0.91, the reference model yields LDR values below 0.1. Homogeneous superellipsoids that match the cross sections and lidar ratio of the reference model tend to give LDR values exceeding the reference results, at least for super-micron particles.

Physical-Optical Properties of Marine Aerosols over the South China Sea: Shipboard Measurements and MERRA-2 Reanalysis

Aerosols play an important role in the Earth–atmosphere system. Their impacts on the weather and climate are highly dependent on spatiotemporal distributions as well as physical-optical properties. Physical-optical properties of the aerosols over the Asian continent have been widely investigated, but there are relatively few observations in maritime locations, especially the South China Sea (SCS). Here, with the combination of in situ ship-based observations from June and July 2019 as well as long-term MERRA-2 reanalysis datasets from January 2012 to December 2021, the physical and optical properties of marine aerosols in the SCS are explored. The impacts of meteorological factors, particularly frontal systems, on the aerosol properties are further analyzed based on detailed observations. The observed results show that aerosols are vertically concentrated below 3 km and the extinction coefficient reaches the maximum value of 0.055 km−1 near 480 m. Moreover, the particles are composed of an accumulation and a coarse particle mode, and they conform to the lognormal distribution. The synoptic-scale case study demonstrates that both the cold front and stationary front lead to an increase in aerosol optical thickness (AOD), which is due to the enhanced wind speed and the hygroscopic growth of fine particles, respectively. The long-term analysis indicates that AOD decreases from northwest to southeast with the increasing distance away from the continent, and it reflects higher values in spring and winter than in summer and autumn. Sulfate and sea salt dominate AOD in this region when compared with other components. The overall AOD shows a significant negative trend of −0.0027 year−1. This work will help us further understand the physical and optical properties of marine aerosols over the SCS and then contribute to quantifying the aerosol radiative forcing in the future.

Mass and number concentration distribution of marine aerosol in the Western Pacific and the influence of continental transport

We quantify for the first time marine aerosol properties and their differences in the offshore and remote ocean in the mid-latitude South Asian waters, low-latitude South Asian waters, and equatorial waters of the Western Pacific Ocean, based on shipboard cruise observations conducted by the Western Pacific Ocean Scientific Observation Network in winter 2018, and further investigate the effects of long-range transport of continental aerosols on the marine environment. During the overall observation period, the average number concentration of particle matter which aerodynamic diameters<2.5 μm (PM2.5N) was 35.1 ± 87.4 cm−3 and the mass concentration (PM2.5M) was 12.3 ± 9.1 μg/m3. The PM2.5N and PM2.5M during the continental air mass transport period were 7.2 and 1.3 times higher than those during the non-transport period (109.2 ± 169.3 cm−3, 15.9 ± 14.9 μg/m3), respectively. Excluding transport period, the average PM2.5N and PM2.5M are reduced by 120% and 7%. Coarse mode particle number concentration (PM2.5–10N) and mass concentration (PM2.5–10M) are not significantly influenced by continental air masses (only a reduction of 7% and 2%). The variation of marine aerosol concentrations in different latitudes zones is greatly influenced by continental aerosol transport. The offshore PM2.5M/PM10M was 30%, 21%, and 22% in the mid-latitude sea of South Asia, a low-latitude sea of South Asia, and the equatorial sea, respectively. In comparison, in the remote ocean, the distribution ratio of PM2.5M/PM10M tended to be steady (22%–23%), and the background characteristics of marine aerosols were clearly represented. The aerosol concentration decreases with the increase of wind speed during the transport period, and the wind speed reflects the scavenging effect on aerosol. In the non-transport period, the wind speed at the sea surface promotes the generation of marine aerosols, and the impact in wind speed is strongest in the PM2.5–PM5 particle size range.

Marine aerosol properties over the Southern Ocean in relation to the wintertime meteorological conditions

Abstract. Given the vast expanse of oceans on our planet, marine aerosols (and sea salt in particular) play an important role in the climate system via multitude of direct and indirect effects. The efficacy of their net impact, however, depends strongly on the local meteorological conditions that influence their physical, optical and chemical properties. Understanding the coupling between aerosol properties and meteorological conditions is therefore important. It has been historically difficult to statistically quantify this coupling over larger oceanic areas due to the lack of suitable observations, leading to large uncertainties in the representation of aerosol processes in climate models. Perhaps no other region shows higher uncertainties in the representation of marine aerosols and their effects than the Southern Ocean. During winter the Southern Ocean boundary layer is dominated by sea salt emissions. Here, using 10 years of austral winter period (June, July and August, 2007–2016) space-based aerosol profiling by CALIOP-CALIPSO in combination with meteorological reanalysis data, we investigated the sensitivity of marine aerosol properties over the Southern Ocean (40–65∘ S) to various meteorological parameters, such as vertical relative humidity (RH), surface wind speed and sea surface temperature (SST) in terms of joint histograms. The sensitivity study is done for the climatological conditions and for the enhanced cyclonic and anticyclonic conditions in order to understand the impact of large-scale atmospheric circulation on the aerosol properties. We find a clear demarcation in the 532 nm aerosol backscatter and extinction at RH around 60 %, irrespective of the state of the atmosphere. The backscatter and extinction increase at higher relative humidity as a function of surface wind speed. This is mainly because of the water uptake by the wind-driven sea salt aerosols at high RH near the ocean surface resulting in an increase in size, which is confirmed by the decreased depolarization for the wet aerosols. An increase in aerosol backscatter and extinction is observed during the anticyclonic conditions compared to cyclonic conditions for the higher wind speeds and relative humidity, mainly due to aerosols being confined to the boundary layer, and their proximity to the ocean surface facilitates the growth of the particles. We further find a very weak dependency of aerosol backscatter on SSTs at lower wind speeds. However, when the winds are stronger than about 12 m s−1, the backscattering coefficient generally increases with SST. When aerosol properties are investigated in terms of aerosol verticality and in relation to meteorological parameters, it is seen that the aerosol backscatter values in the free troposphere (pressure &lt;850 hPa) are much lower than in the boundary layer, irrespective of the RH and the three weather states. This indicates that the local emissions from the ocean surface make the dominant contribution to aerosol loads over the Southern Ocean. A clear separation of particulate depolarization is observed in the free and lower troposphere, more prominent in the climatological mean and the cyclonic states. For RH &gt; 60 %, low depolarization values are noticeable in the lower troposphere, which is an indication of the dominance of water-coated and mostly spherical sea salt particles. For RH &lt; 60 %, there are instances when the aerosol depolarization increases in the boundary layer; this is more prominent in the mean and anticyclonic cases, which can be associated with the presence of drier aerosol particles. Based on the joint histograms investigated here, we provide third-degree polynomials to obtain aerosol extinction and backscatter as a function of wind speed and relative humidity. Additionally, backscattering coefficient is also expressed jointly in terms of wind speed and sea surface temperature. Furthermore, depolarization is expressed as a function of relative humidity. These fitting functions would be useful to test and improve the parameterizations of sea salt aerosols in the climate models. We also note some limitations of our study. For example, interpreting the verticality of aerosol properties (especially depolarization) in relation to the meteorological conditions in the free and upper troposphere (pressure &lt;850 hPa) was challenging. Furthermore, we do not see any direct evidence of sudden crystallization (efflorescence), deliquescence or hysteresis effects of the aerosols. Observing such effects will likely require a targeted investigation of individual cases considering tracer transport, rather than the statistical sensitivity study that entails temporally and geographically averaged large data sets.

Optical properties of water-coated sea salt model particles

We investigate the optical properties of marine aerosol in dependence of the water content. To this end we develop a model geometry that realistically mimics the morphological changes as the salt particles take up more water. The results are compared to morphologically simpler models, namely, homogeneous and inhomogeneous superellipsoids, as well as cube-sphere hybrids. The reference model yields depolarization ratios, depending on size and water uptake, in the range from 0 to 0.36 ± 0.12. Overall, the simple models can reproduce optical properties of the reference model. The overall nonsphericity, as well as inhomogeneity are identified as key morphological parameter, while rounding of edges only has a minor impact on optical properties.

Secondary Marine Aerosol Plays a Dominant Role over Primary Sea Spray Aerosol in Cloud Formation.

Marine aerosols play a critical role in impacting our climate by seeding clouds over the oceans. Despite decades of research, key questions remain regarding how ocean biological activity changes the composition and cloud-forming ability of marine aerosols. This uncertainty largely stems from an inability to independently determine the cloud-forming potential of primary versus secondary marine aerosols in complex marine environments. Here, we present results from a unique 6-day mesocosm experiment where we isolated and studied the cloud-forming potential of primary and secondary marine aerosols over the course of a phytoplankton bloom. The results from this controlled laboratory approach can finally explain the long-observed changes in the hygroscopic properties of marine aerosols observed in previous field studies. We find that secondary marine aerosols, consisting of sulfate, ammonium, and organic species, correlate with phytoplankton biomass (i.e., chlorophyll-a concentrations), whereas primary sea spray aerosol does not. Importantly, the measured CCN activity (κapp = 0.59 ± 0.04) of the resulting secondary marine aerosol matches the values observed in previous field studies, suggesting secondary marine aerosols play the dominant role in affecting marine cloud properties. Given these findings, future studies must address the physical, chemical, and biological factors controlling the emissions of volatile organic compounds that form secondary marine aerosol, with the goal of improving model predictions of ocean biology on atmospheric chemistry, clouds, and climate.

Seasonal Variations in Western North Atlantic Remote Marine Aerosol Properties

AbstractThe impact of ocean ecosystems on marine boundary layer aerosols and clouds has been the subject of much research but remains uncertain. Five experiments were recently conducted in the western North Atlantic to assess if the seasonally recurring phytoplankton bloom affects aerosol properties. These experiments include the second Western Atlantic Climate Study and four North Atlantic Aerosols and Marine Ecosystem Study cruises. Measurements of unheated and heated number size distributions, cloud condensation nucleus (CCN) concentrations, and aerosol composition were used to identify primary and secondary aerosol components that could be related to the state of the bloom. Only periods of clean marine air, as defined by radon, particle number concentrations, aerosol light absorption coefficient, and back trajectories, were included in the analysis. Nonvolatile material was found to be prevalent in the Aitken mode size range after heating to 230°, likely due to downward mixing from the free troposphere. CCN concentrations at 0.1% supersaturation were best correlated (r2 = 0.73) with accumulation mode nss SO4=. Sea spray aerosol was only correlated with CCN during November when bloom accumulation had not yet occurred and dimethylsulfide concentrations were at a minimum. The fraction of CCN attributable to sea spray aerosol was less than 20% during March, May/June, and September, indicating the limited contribution of sea spray aerosol to the CCN population of the western North Atlantic atmosphere. The strongest link between the plankton bloom and aerosol and cloud properties appears to be due to biogenic non‐sea salt SO4=.

Surfactant Charge Modulates Structure and Stability of Lipase-Embedded Monolayers at Marine-Relevant Aerosol Surfaces.

Lipases, as well as other enzymes, are present and active within the sea surface microlayer (SSML). Upon bubble bursting, lipases partition into sea spray aerosol (SSA) along with surface-active molecules such as lipids. Lipases are likely to be embedded in the lipid monolayer at the SSA surface and thus have the potential to influence SSA interfacial structure and chemistry. Elucidating the structure of the lipid monolayer at SSA interfaces and how this structure is altered upon interaction with a protein system like lipase is of interest, given the importance of how aerosols interact with sunlight, influence cloud formation, and provide surfaces for chemical reactions. Herein, we report an integrated experimental and computational study of Burkholderia cepacia lipase (BCL) embedded in a lipid monolayer and highlight the important role of electrostatic, rather than hydrophobic, interactions as a driver for monolayer stability. Specifically, we combine Langmuir film experiments and molecular dynamics (MD) simulations to examine the detailed interactions between the zwitterionic dipalmitoylphosphatidylcholine (DPPC) monolayer and BCL. Upon insertion of BCL from the underlying subphase into the lipid monolayer, it is shown that BCL permeates and largely disorders the monolayer while strongly interacting with zwitterionic DPPC molecules, as experimentally observed by Langmuir adsorption curves and infrared reflectance absorbance spectroscopy. Explicitly solvated, all-atom MD is then used to provide insights into inter- and intramolecular interactions that drive these observations, with specific attention to the formation of salt bridges or ionic-bonding interactions. We show that after insertion into the DPPC monolayer, lipase is maintained at high surface pressures and in large BCL concentrations by forming a salt-bridge-stabilized lipase-DPPC complex. In comparison, when embedded in an anionic monolayer at low surface pressures, BCL preferentially forms intramolecular salt bridges, reducing its total favorable interactions with the surfactant and partitioning out of the monolayer shortly after injection. Overall, this study shows that the structure and dynamics of lipase-embedded SSA surfaces vary based on surface charge and pressure and that these variations have the potential to differentially modulate the properties of marine aerosols.

Effect of air masses motion on the rapid change of aerosols in marine atmosphere

The impact of air masses motion on marine aerosol properties was investigated using an on-board single particle mass spectrometer (SPAMS) deployed for the determination of single particle size resolved chemical composition over Southeast China Sea. Two aerosol blooms (E1 and E2) were observed during the cruise. High average particle number count occurred in E1 (7320), followed by E2 (5850), which was more than 100–150 times of the average particle number count during normal periods. Particles were classified as four major sources, including continental source, shipping source, marine source, and transport source based on the mass spectral similarity. Transport source was identified as those particles with high particle number count occurred only during aerosol bloom period. Three sub-types of EC-Ca, OC-Ca, and Al-rich were classified as transport source. EC-Ca was the dominant particles of the transport source, accounting for more than 70% of the total particles in aerosol bloom events. A uni-modal size distribution in the size range of 0.1–2.0 μm was observed during normal period, while a bimodal distribution with a tiny mode (<0.3 μm) and a coarse mode between 0.4 and 0.6 μm was present during aerosol bloom. The variation of aerosol source is consistent with air masses back trajectories, for the reason that most of the long-range air trajectories are from the ocean, while short air trajectories originate in the continental regions, which means that air masses have a significant impact on the aerosol physical–chemical properties along their tracks.

The influence of terrestrial transport on visibility and aerosol properties over the coastal East China Sea

Air pollutants from East Asia continent can affect the physio-chemical and optical properties of marine aerosols under seasonal winds. We investigated the change of visibility and haze frequency from 1974 to 2017 over the coastal East China Sea (ECS), and reconstructed the light extinction coefficients according to the chemical compositions of PM2.5 samples collected at Huaniao Island in the ECS. The annual average visibility significantly decreased from over 25 km in the early 1970s to <18 km in recent 4 years. The occurrence of daily maximum haze frequency was approximately 3-h later with respect to land sites, which could be explained by the diffusion of air pollutants from nearby cities (haze peak around rush hour) to the coastal ECS as well as the formation of secondary aerosols enhanced by photochemical reactions around noon at the condition of affluent gaseous precursors. Meanwhile, anthropogenic chloride transported from the land could increase the concentration of Cl− in marine aerosol, which may weaken the Cl− depletion phenomenon over coastal ECS and even induced considerable Cl− enrichment during the severe haze event in Jan. 2013. The largest contributor to the light extinction was (NH4)2SO4 followed by NH4NO3 and OM in almost all seasons. Especially in winter and spring, (NH4)2SO4 accounted for 45% and 52% of total light extinction, respectively. The estimated bext was lower than the monitored values, suggesting that the contribution of some aerosol components (e.g. NH4Cl and large mode components) might be underestimated. Further study on the combination of observation and estimation of specific aerosol contribution to the visibility impairment are needed.

The Cloud Nucleating Properties and Mixing State of Marine Aerosols Sampled along the Southern California Coast

Marine aerosols are a globally significant contributor to aerosol-cloud-climate interactions; however, the impact that different sources of pollution and natural emissions from the ocean have on the water uptake properties of marine aerosols remains largely underexplored. Here we present measurements of the cloud condensation nuclei (CCN) activation of marine aerosols taken in a coastal, marine environment impacted by sea spray aerosol and different sources of pollution. The hygroscopicity parameter, κ, was found to range from &lt;0.1 up to 1.4 with a campaign-average value of 0.22 ± 0.12. Smaller particles were less hygroscopic than larger ones, and κ varied diurnally and temporally as a function of air mass transport conditions. Measurements made using aerosol time-of-flight mass spectrometry (ATOFMS) revealed that heterogeneous reactions, sulfates, and temporal differences in the observed particle types had the largest impacts on the observed κ values. The aerosol mixing-state was also found to affect κ. Temporal differences between freshly-emitted soot and aged soot internally mixed with sulfates, likely emitted from ships, had the largest impact on diurnal variations in κ. Our results further demonstrate the significant impact that pollution and the aerosol mixing-state have on aerosol-cloud interactions in the marine boundary layer.

Water-Soluble Organic Composition of the Arctic Sea Surface Microlayer and Association with Ice Nucleation Ability.

Organic matter in the sea surface microlayer (SML) may be transferred to the atmosphere as sea spray and hence influence the composition and properties of marine aerosol. Recent work has demonstrated that the SML contains material capable of heterogeneously nucleating ice, but the nature of this material remains largely unknown. Water-soluble organic matter was extracted from SML and underlying seawater from the Arctic and analyzed using a combination of mass spectrometric approaches. High performance liquid chromatography-ion trap mass spectrometry (LC-IT-MS), and Fourier transform ion cyclotron resonance MS (FT-ICR-MS), showed seawater extracts to be compositionally similar across all stations, whereas microlayer extracts had a different and more variable composition. LC-IT-MS demonstrated the enrichment of particular ions in the microlayer. Ice nucleation ability (defined as the median droplet freezing temperature) appeared to be related to the relative abundances of some ions, although the extracts themselves did not retain this property. Molecular formulas were assigned using LC-quadrupole time-of-flight MS (LC-TOF-MS2) and FT-ICR-MS. The ice nucleation tracer ions were associated with elevated biogenic trace gases, and were also observed in atmospheric aerosol collected during the summer, but not early spring suggesting a biogenic source of ice nuclei in the Arctic microlayer.

Reduced Condensing and Ordering Effects by 7-Ketocholesterol and 5β,6β-Epoxycholesterol on DPPC Monolayers.

The exposure of organic-coated marine aerosols containing cholesterol (Chol) to radiation and/or an oxidizing atmosphere results in the formation of oxidized derivatives or oxysterols and will likely change aerosol surface properties. However, the intermolecular interactions between oxysterols and other lipid components and their influence on the surface properties of marine aerosols are not well-known. To address this question, the interfacial behavior and domain morphology of model Langmuir monolayers of two ring-substituted oxysterols, 7-ketocholesterol (7-KChol) and 5β,6β-epoxycholesterol (5,6β-EChol), mixed with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) were investigated by means of compression isotherms and Brewster angle microscopy (BAM) over a broad range of surface pressures and sterol molar ratios. Mixed DPPC/cholesterol (Chol) monolayers were also measured for comparison. The results of compression experiments showed that the condensing effect induced on mixed DPPC/sterol monolayers at low surface pressures and for intermediate molar ratios (0.3 ≤ X(sterol) ≤ 0.7) was weaker for oxysterols than for Chol. Additionally, mixed DPPC/oxysterol monolayers exhibited markedly smaller (∼2-3-fold) interfacial rigidity. Examination of the excess free energy of mixing further revealed that DPPC monolayers containing 7-KChol and Chol were thermodynamically more stable at high surface pressures than those with 5,6β-EChol, indicating that the strength of interactions between DPPC and 5,6β-EChol was the smallest. Finally, BAM images in the LE-LC phase of DPPC revealed that in comparison to Chol the addition of small amounts of oxysterols results in larger and less numerous domains, showing that oxysterols are not as effective in fluidizing the condensed phase of DPPC. Taken together, these results suggest that the strength of van der Waals interactions of DPPC alkyl chains with sterols follows the sterol hydrophobicity, with Chol being the most hydrophobic and oxysterols more hydrophilic due to their ketone and epoxy moieties. The difference in the condensing ability and stability of 7-KChol and 5,6β-EChol on DPPC likely originates from the distinct molecular structure and position of oxidation on the steroid nucleus. As suggested by recent MD simulations, depending on the oxidation position, ring-substituted oxysterols have a broader angular distribution of orientation than Chol in bilayers, which could be responsible for the observed reduction in condensing ability.

Comparison between summertime and wintertime Arctic Ocean primary marine aerosol properties

Abstract. Primary marine aerosols (PMAs) are an important source of cloud condensation nuclei, and one of the key elements of the remote marine radiative budget. Changes occurring in the rapidly warming Arctic, most importantly the decreasing sea ice extent, will alter PMA production and hence the Arctic climate through a set of feedback processes. In light of this, laboratory experiments with Arctic Ocean water during both Arctic winter and summer were conducted and focused on PMA emissions as a function of season and water properties. Total particle number concentrations and particle number size distributions were used to characterize the PMA population. A comprehensive data set from the Arctic summer and winter showed a decrease in PMA concentrations for the covered water temperature (Tw) range between −1°C and 15°C. A sharp decrease in PMA emissions for a Tw increase from −1°C to 4°C was followed by a lower rate of change in PMA emissions for Tw up to about 6°C. Near constant number concentrations for water temperatures between 6°C to 10°C and higher were recorded. Even though the total particle number concentration changes for overlapping Tw ranges were consistent between the summer and winter measurements, the distribution of particle number concentrations among the different sizes varied between the seasons. Median particle number concentrations for a dry diameter (Dp&lt; 0.125μm measured during winter conditions were similar (deviation of up to 3%), or lower (up to 70%) than the ones measured during summer conditions (for the same water temperature range). For Dp &gt; 0.125μm, the particle number concentrations during winter were mostly higher than in summer (up to 50%). The normalized particle number size distribution as a function of water temperature was examined for both winter and summer measurements. An increase in Tw from −1°C to 10°C during winter measurements showed a decrease in the peak of relative particle number concentration at about a Dp of 0.180μm, while an increase was observed for particles with Dp &gt; 1μm. Summer measurements exhibited a relative shift to smaller particle sizes for an increase of Tw in the range 7–11°C. The differences in the shape of the number size distributions between winter and summer may be caused by different production of organic material in water, different local processes modifying the water masses within the fjord (for example sea ice production in winter and increased glacial meltwater inflow during summer) and different origin of the dominant sea water mass. Further research is needed regarding the contribution of these factors to the PMA production.

Ship impacts on the marine atmosphere: insights into the contribution of shipping emissions to the properties of marine aerosol and clouds

Abstract. We report properties of marine aerosol and clouds measured in the shipping lanes between Monterey Bay and San Francisco off the coast of Central California. Using a suite of aerosol instrumentation onboard the CIRPAS Twin Otter aircraft, these measurements represent a unique set of data contrasting the properties of clean and ship-impacted marine air masses in dry aerosol and cloud droplet residuals. Below-cloud aerosol exhibited average mass and number concentrations of 2 μg m−3 and 510 cm−3, respectively, which are consistent with previous studies performed off the coast of California. Enhancements in vanadium and cloud droplet number concentrations are observed concurrently with a decrease in cloud water pH, suggesting that periods of high aerosol loading are primarily linked to increased ship influence. Mass spectra from a compact time-of-flight Aerodyne aerosol mass spectrometer reveal an enhancement in the fraction of organic at m/z 42 (f42) and 99 (f99) in ship-impacted clouds. These ions are well correlated to each other (R2&gt;0.64) both in and out of cloud and constitute 14% (f44) and 3% (f99) of organic mass during periods of enhanced sulfate. High-resolution mass spectral analysis of these masses from ship measurements suggests that the ions responsible for this variation were oxidized, possibly due to cloud processing. We propose that the organic fractions of these ions be used as a metric for determining the extent to which cloud-processed ship emissions impact the marine atmosphere where (f42 &gt; 0.15; f99 &gt; 0.04) would imply heavy influence from shipping emissions, (0.05 &lt; f42 &lt; 0.15; 0.01 &lt; f99 &lt; 0.04) would imply moderate, but persistent, influences from ships, and (f42 &lt; 0.05; f99 &lt; 0.01) would imply clean, non-ship-influenced air.

Investigating Primary Marine Aerosol Properties: CCN Activity of Sea Salt and Mixed Inorganic–Organic Particles

Sea spray particles ejected as a result of bubbles bursting from artificial seawater containing salt and organic matter in a stainless steel tank were sampled for size distribution, morphology, and cloud condensation nucleus (CCN) activity. Bubbles were generated either by aeration through a diffuser or by water jet impingement on the seawater surface. Three objectives were addressed in this study. First, CCN activities of NaCl and two types of artificial sea salt containing only inorganic components were measured to establish a baseline for further measurements of mixed organic–inorganic particles. Second, the effect of varying bubble residence time in the bulk seawater solution on particle size and CCN activity was investigated and was found to be insignificant for the organic compounds studied. Finally, CCN activities of particles produced from jet impingement were compared with those produced from diffuser aeration. Analyses indicate a considerable amount of organic enrichment in the jet-produced particles relative to the bulk seawater composition when sodium laurate, an organic surfactant, is present in the seawater. In this case, the production of a thick foam layer during impingement may explain the difference in activation and supports hypotheses that particle production from the two methods of generating bubbles is not equal.

Chemical characterization of aerosols over the Atlantic Ocean and the Pacific Ocean during two cruises in 2007 and 2008

To help understand the chemical properties of marine aerosols and the long‐distance transport of continental aerosols to remote oceanic regions, total suspended particulates (TSP) samples were collected over the Atlantic Ocean and the Pacific Ocean during two cruises in September–December 2007 (cruise I) and March–April 2008 (cruise II) aboard the M/V Oceanic II. Data were analyzed and interpreted with the aid of back trajectory, principal component, and multiple linear regression analyses. Compared with the results over the South Pacific from 2 decades ago, the non‐sea‐salt sulfate (NSS‐SO42−) concentrations over the South Pacific have increased by a factor of ∼1.5, while the NO3− concentration has remained constant. On average, NSS‐SO42− accounted for 30–52% of the total SO42− during the two cruises. Chloride deficit was observed in all samples, with NSS‐SO42− being the preferred species for acid displacement over the South Pacific and the Mediterranean Sea. Persistent clean marine air masses were only observed over the northern Atlantic and South Pacific during cruise I, while more frequent impacts of continental air (dust, biomass burning, and industrial plumes) were observed during cruise II. Combined with the NAAPS aerosol maps, these results indicate that during cruise II, (1) southern Atlantic was influenced by Southern Africa and the interhemisphere transport of biomass burning plumes in Central Africa, (2) northern Atlantic was under the combined pollution plumes of Sahara dust intrusion and biomass burning, and (3) the Mediterranean Sea was affected by the mixed pollution from biomass burning and industrial contamination, as well as Saharan dust.

海洋観測船みらいによるPre ACE-Asia航海におけるエアロゾルの化学的特性

海洋観測船みらいによるPre ACE-Asia航海におけるエアロゾルの化学的特性

Optical and chemical properties of marine aerosols over the central equatorial Pacific Ocean during the 2003 R/V Mirai cruise

The optical and chemical properties of atmospheric aerosols were measured over the central equatorial Pacific Ocean (from 150°E to 160°W longitude, near the equator) during the R/V Mirai cruise of January 2003. In the area from 165°E to 160°W along the equator, concentrations of anthropogenic chemical components were low; the average concentration of nonsea salt sulfate was 0.28 μg m−3, that of vanadium was less than the detection limit, and those of elemental carbon and organic carbon were 0.009 and 0.09 μg‐C m−3. The scattering coefficients were low (3.2 × 10−6 m−1 on average), and the absorption coefficients were also extremely low (0.06 × 10−6 m−1 on average). The mean value of single scattering albedo was 0.98, with a standard deviation of 0.01, indicating that the measured aerosols were transparent and had low variability. The measurement results suggest that nonsea salt sulfate and organic carbon were from natural sources. Sea salt particles and nonsea salt sulfate composed a large fraction (94%) of the water‐soluble components of fine particles. Thus the water‐soluble components and organic materials from natural sources were primarily responsible for the scattering of solar radiation. The measurement results give typical values of the optical and chemical properties of aerosols in the unpolluted central equatorial Pacific Ocean.