Search

During summer, the Southern Ocean is largely unaffected by anthropogenic emissions, which makes this region an ideal place to investigate marine natural aerosol sources and processes. A better understanding of natural aerosol is key to constrain the preindustrial aerosol state and reduce the aerosol radiative forcing uncertainty in global climate models. We report the concentrations of gaseous sulfuric acid, iodic acid, and methanesulfonic acid (MSA) together with a characterization of new particle formation (NPF) events over a large stretch of the Southern Ocean. Measurements were conducted on board the Russian icebreaker Akademik Tryoshnikov from January to March 2017. Iodic acid is characterized by a particular diurnal cycle with reduced concentration around noon, suggesting a lower formation yield when solar irradiance is higher. Gaseous MSA does not have a diurnal cycle and measured concentrations in gas and condensed phase are compatible with this species being primarily produced via heterogeneous oxidation of dimethyl sulfide and subsequent partitioning into the gas phase. We also found that NPF in the boundary layer is mainly driven by sulfuric acid but it occurred very rarely over the vast geographical area probed and did not contribute to the cloud condensation nuclei budget in a directly observable manner. Despite the near absence of NPF events in the boundary layer, Aitken mode particles were frequently measured, supporting the hypothesis of a free tropospheric source. Iodic acid and MSA were not found to participate in nucleation, however, MSA may contribute to aerosol growth via heterogeneous formation in the aqueous phase.

Aerosol particles acting as cloud condensation nuclei (CCN) or ice nucleating particles (INP) play a major role in the formation and glaciation of clouds. Thereby they exert a strong impact on the radiation budget of the Earth. Data on abundance and properties of both types of particles are sparse, especially for remote areas of the world, such as the Southern Ocean (SO). In this work, we present unique results from ship-borne aerosol-particle-related in situ measurements and filter sampling in the SO region, carried out during the Antarctic Circumnavigation Expedition (ACE) in the Austral summer of 2016/17. An overview of CCN and INP concentrations on the Southern Ocean is provided and using additional quantities, insights regarding possible CCN and INP sources and origins are presented. CCN number concentrations spanned 2 orders of magnitude, e.g., for a supersaturation of 0.3 % values ranged roughly from 3 to 590 cm⁻³. CCN showed variable contributions of organic and inorganic material (inter-quartile range of hygroscopicity parameter κ from 0.2 to 0.9). No distinct size-dependence of κ was apparent, indicating homogeneous composition across sizes (critical dry diameter on average between 37 and 123 nm). The contribution of sea spray aerosol (SSA) to the CCN number concentration was on average small. Ambient INP number concentrations were measured in the temperature range from −5 to −27°C. Concentrations spanned up to 3 orders of magnitude, e.g., at −16°C from 0.2 to 100 m⁻³. Elevated values (above 10 m⁻³ at −16°C) were measured when the research vessel was in the vicinity of land, with lower and more constant concentrations when at sea. This hints towards terrestrial and/or coastal INP sources being dominant close to land. In pristine marine areas INP may originate from both oceanic sources and/or long range transport. Sampled aerosol particles (PM10) were analysed for sodium and methanesulfonic acid (MSA). Resulting mass concentrations were used as tracers for primary marine and secondary aerosol particles, respectively. Sodium, with an average concentration around 2.8 μg m⁻³, was found to dominate the sampled particle mass. MSA was highly variable over the SO, with concentrations up to 0.5 μg m⁻³ near the sea ice edge. A correlation analysis yielded strong correlations between sodium mass concentration and particle number concentration in the coarse mode, unsurprisingly indicating a significant contribution of SSA to that mode. CCN number concentration was highly correlated with the number concentration of Aitken and accumulation mode particles. This, together with a lack of correlation between sodium mass and Aitken and accumulation mode number concentrations, underlines the important contribution of non-SSA, probably secondarily formed particles, to the CCN population. INP number concentrations did not significantly correlate with any other measured aerosol physico-chemical parameter.

Understanding the sources of light-absorbing organic (brown) carbon (BrC) and its interaction with black carbon (BC) and other non-refractory particulate matter (NR-PM) fractions is important for reducing uncertainties in the aerosol direct radiative forcing. In this study, we combine multiple filter-based techniques to achieve long-term, spectrally resolved, source- and species-specific atmospheric absorption closure. We determine the mass absorption efficiency (MAE) in dilute bulk solutions at 370 nm to be equal to 1.4 m2 g−1 for fresh biomass smoke, 0.7 m2 g−1 for winter-oxygenated organic aerosol (OA), and 0.13 m2 g−1 for other less absorbing OA. We apply Mie calculations to estimate the contributions of these fractions to total aerosol absorption. While enhanced absorption in the near-UV has been traditionally attributed to primary biomass smoke, here we show that anthropogenic oxygenated OA may be equally important for BrC absorption during winter, especially at an urban background site. We demonstrate that insoluble tar balls are negligible in residential biomass burning atmospheric samples of this study and thus could attribute the totality of the NR-PM absorption at shorter wavelengths to methanol-extractable BrC. As for BC, we show that the mass absorption cross-section (MAC) of this fraction is independent of its source, while we observe evidence for a filter-based lensing effect associated with the presence of NR-PM components. We find that bare BC has a MAC of 6.3 m2 g−1 at 660 nm and an absorption Ångström exponent of 0.93 ± 0.16, while in the presence of coatings its absorption is enhanced by a factor of ∼ 1.4. Based on Mie calculations of closure between observed and predicted total light absorption, we provide an indication for a suppression of the filter-based lensing effect by BrC. The total absorption reduction remains modest, ∼ 10 %–20 % at 370 nm, and is restricted to shorter wavelengths, where BrC absorption is significant. Overall, our results allow an assessment of the relative importance of the different aerosol fractions to the total absorption for aerosols from a wide range of sources and atmospheric ages. When integrated with the solar spectrum at 300–900 nm, bare BC is found to contribute around two-thirds of the solar radiation absorption by total carbonaceous aerosols, amplified by the filter-based lensing effect (with an interquartile range, IQR, of 8 %–27 %), while the IQR of the contributions by particulate BrC is 6 %–13 % (13 %–20 % at the rural site during winter). Future studies that will directly benefit from these results include (a) optical modelling aiming at understanding the absorption profiles of a complex aerosol composed of BrC, BC and lensing-inducing coatings; (b) source apportionment aiming at understanding the sources of BC and BrC from the aerosol absorption profiles; (c) global modelling aiming at quantifying the most important aerosol absorbers., Atmospheric Chemistry and Physics, 21 (17), ISSN:1680-7375, ISSN:1680-7367

24 pages, 8 figures, supporting information https://doi.org/10.1029/2021JD034811.-- Data Availability Statement: The data set used in this study are available in (1) Antoine et al. (2019) available at https://doi.org/10.5281/zenodo.3406983; (2) Chen et al. (2019) available at https://doi.org/10.5281/zenodo.3559982; (3) Landwehr et al. (2020) available at https://doi.org/10.5281/zenodo.3836439; (4) Landwehr, Thurnherr et al. (2020) available at https://doi.org/10.5194/amt-13-3487-2020; (5) Schmale et al. (2019) available at https://doi.org/10.5281/zenodo.2636709; (6) Tatzelt et al. (2020) available at https://doi.org/10.5281/zenodo.3922147; (7) Thomalla et al., (2020) available at https://doi.org/10.5281/zenodo.3859515; (8) Thurnherr et al. (2020) available at https://doi.org/10.5281/zenodo.4031705; In addition, the fluorescent aerosol and gel–like POM measurements have been uploading as supplementary information supporting this article, In this study, we investigate the occurrence of primary biological aerosol particles (PBAP) over all sectors of the Southern Ocean (SO) based on a 90-day data set collected during the Antarctic Circumnavigation Expedition (ACE) in austral summer 2016–2017. Super-micrometer PBAP (1–16 µm diameter) were measured by a wide band integrated bioaerosol sensor (WIBS-4). Low (3σ) and high (9σ) fluorescence thresholds are used to obtain statistics on fluorescent and hyper-fluorescent PBAP, respectively. Our focus is on data obtained over the pristine ocean, that is, more than 200 km away from land. The results indicate that (hyper-)fluorescent PBAP are correlated to atmospheric variables associated with sea spray aerosol (SSA) particles (wind speed, total super-micrometer aerosol number concentration, chloride and sodium concentrations). This suggests that a main source of PBAP over the SO is SSA. The median percentage contribution of fluorescent and hyper-fluorescent PBAP to super-micrometer SSA was 1.6% and 0.13%, respectively. We demonstrate that the fraction of (hyper-)fluorescent PBAP to total super-micrometer particles positively correlates with concentrations of bacteria and several taxa of pythoplankton measured in seawater, indicating that marine biota concentrations modulate the PBAP source flux. We investigate the fluorescent properties of (hyper-)fluorescent PBAP for several events that occurred near land masses. We find that the fluorescence signal characteristics of particles near land is much more variable than over the pristine ocean. We conclude that the source and concentration of fluorescent PBAP over the open ocean is similar across all sampled sectors of the SO, The authors acknowledge funding for ACE-SPACE, ACE-SORPASSO by the Swiss Polar Institute, and Ferring Pharmaceuticals. ACE-SPACE was carried out with additional support from the European FP7 project BACCHUS (Grant Agreement 49603445). Gang Chen received funding from the cost action of Chemical On-Line cOmpoSition and Source Apportionment of fine aerosol (COLOSSAL, CA16109), a COST related project of the Swiss National Science Foundation, Source apportionment using long-term Aerosol Mass Spectrometry and Aethalometer Measurements (SAMSAM, IZCOZ0_177063). Sebastian Landwehr received funding from the Swiss Data Science Center project c17-02. Andrea Baccarin received funding from the Swiss National Science Foundation (Grant 200021_169090). Julia Schmale holds the Ingvar Kamprad Chair. Martin Gysel-Beer received funding from the ERC under Grant ERC-CoG-615922-BLACARAT. Charlotte Robinson received funding from the Australian Research Council (Grand ARC DP160103387), With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

Aerosol characteristics over the Southern Ocean are surprisingly heterogeneous because of the distinct regional dynamics and marine microbial regimes. Satellite observations and model simulations underestimate the abundance of cloud condensation nuclei. Uncertainty in radiative forcing caused by aerosol-cloud interactions is about twice as large as for CO2 and remains the least well-understood anthropogenic contribution to climate change. A major cause of uncertainty is the poorly-quantified state of aerosols in the pristine-preindustrial atmosphere, which defines the baseline against which anthropogenic effects are calculated. The Southern Ocean is one of the few remaining near-pristine aerosol environments on Earth, but there are very few measurements to evaluate models. The Antarctic Circumnavigation Expedition: Study of Preindustrial-like Aerosols and their Climate Effects (ACE-SPACE) took place between December 2016 and March 2017 and covered the entire Southern Ocean region (Indian, Pacific and Atlantic Oceans, ship track > 33,000 km) including previously unexplored areas. In situ measurements covered aerosol characteristics (e.g., chemical composition, size distributions, and cloud condensation nuclei (CCN) number concentrations), trace gases and meteorological variables. Remote sensing observations of cloud properties, the physical and microbial ocean state, as well as back trajectory analyses are used to interpret the in situ data. The contribution of sea spray to CCN in the westerly wind belt can be larger than 50%. The abundance of methanesulfonic acid indicates local and regional microbial influence on CCN abundance in Antarctic coastal waters and in the open ocean. We use the in situ data to evaluate simulated CCN concentrations from a global aerosol model. The extensive, available ACE-SPACE dataset (https://zenodo.org/communities/spi-ace?page=1&size=20) provides an unprecedented opportunity to evaluate models and to reduce the uncertainty in radiative forcing associated with the natural processes of aerosol emission, formation, transport and processing occurring over the pristine Southern Ocean.

A data set of concurrent measurements of sea spray aerosol concentration, wind speed, sea state, and air and water temperature was acquired across all sectors of the S...

The mass concentration of black carbon (BC) particles in the atmosphere has traditionally been quantified with two methods: as elemental carbon (EC) concentrations measured by thermal-optical analysis and as equivalent black carbon (eBC) concentrations when BC mass is derived from particle light absorption coefficient measurements. Over the last decade, ambient measurements of refractory black carbon (rBC) mass concentrations based on laser-induced incandescence (LII) have become more common, mostly due to the development of the Single-Particle Soot Photometer (SP2) instrument. In this work, EC and rBC mass concentration measurements from field campaigns across several background European sites (Paris, Bologna, Cabauw and Melpitz) have been collated and examined to identify the similarities and differences between BC mass concentrations measured by the two techniques. All EC concentration measurements in PM2.5 were performed with the EUSAAR-2 thermal-optical protocol. All rBC concentration measurements were performed with SP2s calibrated with the same calibration material as recommended in the literature. The median ratio between observed rBC and EC mass concentrations was 0.92, when considering all data points from all five campaigns, and the corresponding geometric standard deviation (GSD) was 1.5. The minimal and maximal observed values of median rBC to EC mass concentration ratios on single campaign level were 0.53 and 1.29, respectively. This shows that substantial systematic bias between these two quantities occurred during some campaigns, which also contributes to the large overall GSD. On single campaign level, the relative spread of individual rBC to EC mass concentration ratios was typically between a factor of 1.2 and 1.3 (1 GSD), which indicates fairly good precision of both methods. Despite considerable variability of BC properties and sources across the whole data set, it was not possible to clearly assign reasons for discrepancies to one or the other method, both known to have their own specific limitations and uncertainties. However, differences in the particle size range covered by these two methods were identified as one likely reason for discrepancies. In particular, rBC to EC mass concentration ratios were found to be systematically less than unity, despite applying a correction for small BC cores that remain undetected by the SP2. This was observed when the rBC mass size distribution was shifted towards smaller modal diameter, which occurred during traffic emission dominated episodes. Overall, the high correlation between rBC and EC mass concentrations indicates that both methods essentially quantify the same property of atmospheric aerosols, whereas systematic differences in measured absolute values by up to a factor of 2 can occur. This finding for the level of agreement between two current state-of-the-art techniques has important implications for studies based on BC mass concentration measurements, for example for the interpretation of uncertainties of inferred BC mass absorption coefficient values, which are required for modelling the radiative forcing of BC. Homogeneity between BC mass determination techniques is very important also towards a routine BC mass measurement for air quality or human health regulations.

Accounting for the wavelength- and source-dependent optical absorption properties of the abundant light-absorbing organic (brown) carbon (BrC) and the mixing state of atmospheric black carbon (BC) are essential to reduce the large uncertainty in aerosol radiative forcing. Estimation of BrC absorption online by subtraction is highly uncertain and may be biased if not decoupled from the potential BC absorption enhancement (lensing) due to non-refractory (organic and inorganic) coating acquisition.Here, the reported total particulate absorption is based on long-term, filter-based seven-wavelength Aethalometer (AE33 model) data, corrected for multiple scattering effects with Multi-Wavelength Absorbance Analyzer (5λ MWAA) measurements. Using ultraviolet-visible spectroscopy absorbance measurements along with particle size distributions obtained by a scanning mobility particle sizer, we have conducted Mie calculations to assess the importance of source-specific extractable particulate BrC (Moschos et al., 2018) versus BC absorption.For the species-specific optical closure, the wavelength dependence of bare BC absorption is estimated using MWAA measurements upon successive filter extractions to remove the influence of BrC/coatings. The lensing contribution, supported by observations from field-emission scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, is estimated at longer wavelengths using a refined proxy for the BC coating thickness. The approach is validated independently by applying a novel positive matrix factorization-based approach on the calibrated total AE33 absorption data.Based on the observational constraints established in this study, we demonstrate for various distinct case studies that the interplay between lensing and BrC absorption results in lower than expected BC absorption at shorter wavelengths. This indicates that the volume additivity assumption is not valid for particulate absorption by internally mixed heterogeneous atmospheric aerosol populations. These comprehensive experimental analyses verify the BC lensing suppression predicted for simplified core-shell structures containing moderately absorbing BrC (Lack & Cappa, 2010). The implications discussed in this work are relevant for co-emitted species from biomass burning or aged plumes with high BrC to BC mass/absorption ratio. ReferencesMoschos, V., Kumar, N. K., Daellenbach, K. R., Baltensperger, U., Prévôt, A. S. H., and El Haddad, I.: Source apportionment of brown carbon absorption by coupling ultraviolet-visible spectroscopy with aerosol mass spectrometry, Environ. Sci. Tech. Lett., 5, 302-308, https://doi.org/10.1021/acs.estlett.8b00118, 2018.Lack, D. A. and Cappa, C. D.: Impact of brown and clear carbon on light absorption enhancement, single scatter albedo and absorption wavelength dependence of black carbon, Atmos. Chem. Phys., 10, 4207–4220, https://doi.org/10.5194/acp-10-4207-2010, 2010.

Recent large wildfires, such as those in Portugal in 2017, have devastating impacts on societies, economy, ecosystems and environments. However, wildfires are a natural phenomenon, which has been exacerbated by land use during the past millennia. Ice cores are one of the archives preserving information on fire occurrences over these timescales. A difficulty is that emission sensitivity of ice cores is often unknown, which constitutes a source of uncertainty in the interpretation of such archives. Information from specific and well-documented case studies is therefore useful to better understand the spatial representation of ice-core burning records. The wildfires near Pedrógão Grande in central Portugal in 2017 provided a test bed to link a fire event to its footprint left in a high-alpine snowpack considered a surrogate for high-alpine ice-core sites. Here, we (1) analysed black carbon (BC) and microscopic charcoal particles deposited in the snowpack close to the high-alpine research station Jungfraujoch in the Swiss Alps; (2) calculated backward trajectories based on ERA-Interim reanalysis data and simulated the transport of these carbonaceous particles using a global aerosol-climate model; and (3) analysed the fire spread, its spatial and temporal extent, and its intensity with remote-sensing (e.g. MODIS) Active Fire and Burned Area products. According to modelled emissions of the FINN v1.6 database, the fire emitted a total amount of 203.5 t BC from a total burned area of 501 km2 as observed on the basis of satellite fire products. Backward trajectories unambiguously linked a peak of atmospheric-equivalent BC observed at the Jungfraujoch research station on 22 June – with elevated levels until 25 June – with the highly intensive fires in Portugal. The atmospheric signal is in correspondence with an outstanding peak in microscopic charcoal observed in the snow layer, depositing nearly as many charcoal particles as during an average year in other ice archives. In contrast to charcoal, the amount of atmospheric BC deposited during the fire episode was minor due to a lack of precipitation. Simulations with a global aerosol-climate model suggest that the observed microscopic charcoal particles originated from the fires in Portugal and that their contribution to the BC signal in snow was negligible. Our study revealed that microscopic charcoal can be transported over long distances (1500 km) and that snow and ice archives are much more sensitive to distant events than sedimentary archives, for which the signal is dominated by local fires. The findings are important for future ice-core studies as they document that, for BC as a fire tracer, the signal preservation depends on precipitation. Single events, like this example, might not be preserved due to unfavourable meteorological conditions., The Cryosphere, 14 (11), ISSN:1994-0416, ISSN:1994-0424

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.

Meteorology and microphysics affect cloud formation, cloud droplet distributions, and shortwave reflectance. The Eastern Pacific Emitted Aerosol Cloud Experiment and the Stratocumulus Observations of Los-Angeles Emissions Derived Aerosol-Droplets studies provided measurements in six case studies of cloud thermodynamic properties, initial particle number distribution and composition, and cloud drop distribution. In this study, we use simulations from a chemical and microphysical aerosol-cloud parcel (ACP) model with explicit kinetic drop activation to reproduce observed cloud droplet distributions of the case studies. Four cases had subadiabatic lapse rates, resulting in fewer activated droplets, lower liquid water content, and higher cloud base height than an adiabatic lapse rate. A weighted ensemble of simulations that reflect measured variation in updraft velocity and cloud base height was used to reproduce observed droplet distributions. Simulations show that organic hygroscopicity in internally mixed cases causes small effects on cloud reflectivity (CR) (

Volatility-hygroscopicity tandem differential mobility analyzer measurements were used to infer the composition of sub-100 nm diameter Southern Ocean marine aerosols at Cape Grim in November and December 2007. This study focuses on a short-lived high sea spray aerosol (SSA) event on 7–8 December with two externally mixed modes in the Hygroscopic Growth Factor (HGF) distributions (90% relative humidity (RH)), one at HGF > 2 and another at HGF~1.5. The particles with HGF > 2 displayed a deliquescent transition at 73–75% RH and were nonvolatile up to 280°C, which identified them as SSA particles with a large inorganic sea-salt fraction. SSA HGFs were 3–13% below those for pure sea-salt particles, indicating an organic volume fraction (OVF) of up to 11–46%. Observed high inorganic fractions in sub-100 nm SSA is contrary to similar, earlier studies. HGFs increased with decreasing particle diameter over the range 16–97 nm, suggesting a decreased OVF, again contrary to earlier studies. SSA comprised up to 69% of the sub-100 nm particle number, corresponding to concentrations of 110–290 cm−3. Air mass back trajectories indicate that SSA particles were produced 1500 km, 20–40 h upwind of Cape Grim. Transmission electron microscopy (TEM) and X-ray spectrometry measurements of sub-100 nm aerosols collected from the same location, and at the same time, displayed a distinct lack of sea salt. Results herein highlight the potential for biases in TEM analysis of the chemical composition of marine aerosols.

Size-resolved observations of aerosol particles and cloud droplet residuals were studied at a marine boundary layer site (251 m a.m.s.l.) in La Jolla, San Diego, California, during 2012. A counterflow virtual impactor (CVI) was used as the inlet to sample cloud residuals while a total inlet was used to sample both cloud residuals and interstitial particles. Two cloud events totaling 10 h of in-cloud sampling were analyzed. Based on bulk aerosol particle concentrations, mass concentrations of refractory black carbon (rBC), and back trajectories, the two air masses sampled were classified as polluted marine air. Since the fraction of cloud droplets sampled by the CVI was less than 100%, the measured activated fractions of rBC should be considered as lower limits to the total fraction of rBC activated during the two cloud events. Size distributions of rBC and a coating analysis showed that sub-100 nm rBC cores with relatively thick coatings were incorporated into the cloud droplets (i.e., 95 nm rBC cores with median coating thicknesses of at least 65 nm were incorporated into the cloud droplets). Measurements also show that the coating volume fraction of rBC cores is relatively large for sub-100 nm rBC cores. For example, the median coating volume fraction of 95 nm rBC cores incorporated into cloud droplets was at least 0.9, a result that is consistent with κ-Köhler theory. Measurements of the total diameter of the rBC-containing particles (rBC core and coating) suggest that the total diameter of rBC-containing particles needed to be at least 165 nm to be incorporated into cloud droplets when the core rBC diameter is ≥ 85 nm. This result is consistent with previous work that has shown that particle diameter is important for activation of non-rBC particles. The activated fractions of rBC determined from the measurements ranged from 0.01 to 0.1 for core rBC diameters ranging from 70 to 220 nm. This type of data is useful for constraining models used for predicting rBC concentrations in the atmosphere.

During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE), a plume of organic aerosol was produced by a smoke generator and emitted into the marine atmosphere from aboard the R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, the plume particles had very low hygroscopic growth factors (GFs): between 1.05 and 1.09 for 30 nm and between 1.02 and 1.1 for 150 nm dry size at a relative humidity (RH) of 92%, contrasted by an average marine background GF of 1.6. New particles were produced in large quantities (several 10 000 cm−3), which lead to substantially increased cloud condensation nuclei (CCN) concentrations at supersaturations between 0.07 and 0.88%. Ratios of oxygen to carbon (O : C) and water-soluble organic mass (WSOM) increased with plume age: from < 0.001 to 0.2, and from 2.42 to 4.96 μg m−3, respectively, while organic mass fractions decreased slightly (~ 0.97 to ~ 0.94). High-resolution aerosol mass spectrometer (AMS) spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small, new particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions: an average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, and a GF of 1.04 for an organic mass fraction of 0.35.

The effect of soluble surfactant on the persistence of salt-water bubbles and their ability to produce aerosol particles upon bursting was investigated. Ensembles of individual, millimetric bubbles were produced in NaCl solutions of varying surfactant concentration. Aerosol production efficiency-a fundamental property of single bubbles defined as the number of particles produced per bubble film cap area-decreased by 79% to 98% following the addition of surfactant and increase in solution film pressure from 1-2 to 7-27 mN m(-1). The generated particle size distributions (0.01-10 mu m dry diameter) contained up to three modes and did not change much for film pressures up to 13.8 mN m(-1). The persistence of the bubbles at the water surface and the thickness of their film caps were investigated with high-speed videography. Addition of soluble surfactant increased average bubble persistence providing more time for the bubbles to drain and thin out with the aid of marginal regeneration flows. Bubble film cap thicknesses ranged from around 1 mu m for relatively clean, short-lived bubbles to less than 0.1 mu m for surfactant-stabilized, persistent bubbles. The suppression of aerosol production from the surfactant-stabilized bubbles may have resulted from the dramatic thinning of their caps or reduced surface forces at high film pressure. Previously reported Sea Spray Aerosol source functions were compared to measured aerosol production efficiencies and found to be significantly greater in magnitude, suggesting that there is a source of particles from whitecaps that was not captured in these single-bubble experiments.

A 4 week intensive measurement campaign was conducted in March–April 2007 at Agnes Water, a remote coastal site on the east coast of Australia. A Volatility-Hygroscopicity-Tandem Differential Mobility Analyser (VH-TDMA) was used to investigate changes in the hygroscopic properties of ambient particles as volatile components were progressively evaporated. Nine out of 18 VH-TDMA volatility scans detected internally mixed multi-component particles in the nucleation and Aitken modes in clean marine air. Evaporation of a volatile, organic-like component in the VH-TDMA caused significant increases in particle hygroscopicity. In 3 scans the increase in hygroscopicity was so large it was explained by an increase in the absolute volume of water uptake by the particle residuals, and not merely an increase in their relative hygroscopicity. This indicates the presence of organic components that were suppressing the hygroscopic growth of mixed particles on the timescale of humidification in the VH-TDMA (6.5 secs). This observation was supported by ZSR calculations for one scan, which showed that the measured growth factors of mixed particles were up to 18% below those predicted assuming independent water uptake of the individual particle components. The observed suppression of water uptake could be due to a reduced rate of hygroscopic growth caused by the presence of organic films or organic-inorganic interactions in solution droplets that had a negative effect on hygroscopicity.

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (∼30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.

The complexity of a typical hygroscopicity tandem differential mobility analyser (H-TDMA) can make it an awkward instrument for fieldwork. An improved design is presented here which is both light-weight, portable and permits very precise, reliable hygroscopic growth, deliquescence and efflorescence measurements for aerosols over a continuous relative humidity range from 10% to 95% without reconfiguration. The method achieves this through three significant advances in H-TDMA design: Firstly, the approach efficiently regulates the humidity by rapidly alternating the air flow between a dryer and a saturator, with the time spent in each path controlled by a feedback loop connected to the humidity sensor. Secondly, the temperature of the aerosol humidifier is directly coupled to that of the wet DMA by enveloping the humidifier in the wet DMAs excess air flow. Thirdly, a novel arrangement of two Nafion™ tubes in the humidifier allows for high humidities without needing to pre-wet the aerosol flow.

Although isocyanic acid (HNCO) may cause a variety of health issues via protein carbamylation and has been proposed as a key compound in smoke-related health issues, our understanding of the atmospheric sources and fate of this toxic compound is currently incomplete. To address these issues, a field study was conducted at Mount Soledad, La Jolla, CA, to investigate partitioning of HNCO to clouds and fogs using an Acetate Chemical Ionization Mass Spectrometer coupled to a ground-based counterflow virtual impactor. The first field evidence of cloud partitioning of HNCO is presented, demonstrating that HNCO is dissolved in cloudwater more efficiently than expected based on the effective Henry's law solubility. The measurements also indicate evidence for a secondary, photochemical source of HNCO in ambient air at this site. Key PointsThe first field observation of cloud scavenging of isocyanic acid (HNCO)HNCO may be partitioning to clouds more efficiently than expectedA secondary, photochemical source of HNCO is observed

Aerosol particles in the marine boundary layer include primary organic and salt particles from sea spray and combustion-derived particles from ships and coastal cities. These particle types serve as nuclei for marine cloud droplet activation, although the particles that activate depend on the particle size and composition as well as the supersaturation that results from cloud updraft velocities. The Eastern Pacific Emitted Aerosol Cloud Experiment (EPEACE) 2011 was a targeted aircraft campaign to assess how different particle types nucleate cloud droplets. As part of E-PEACE 2011, we studied the role of marine particles as cloud droplet nuclei and used emitted particle sources to separate particle-induced feedbacks from dynamical variability. The emitted particle sources included shipboard smoke-generated particles with 0.05-1 μm diameters (which produced tracks measured by satellite and had drop composition characteristic of organic smoke) and combustion particles from container ships with 0.05-0.2 μm diameters (which were measured in a variety of conditions with droplets containing both organic and sulfate components) [1]. Three central aspects of the collaborative E-PEACE results are: (1) the size and chemical composition of the emitted smoke particles compared to ship-track-forming cargo ship emissions as well as background marine particles, with particular attention to the role of organic particles, (2) the characteristics of cloud track formation for smoke and cargo ships, as well as the role of multi-layered low clouds, and (3) the implications of these findings for quantifying aerosol indirect effects. For comparison with the E-PEACE results, the preliminary results of the Stratocumulus Observations of Los-Angeles Emissions Derived Aerosol-Droplets (SOLEDAD) 2012 provided evidence of the cloud-nucleating roles of both marine organic particles and coastal urban pollution, with simultaneous measurements of the effective supersaturations of the clouds in the California coastal region.

The production, size, and chemical composition of sea spray aerosol (SSA) particles strongly depend on seawater chemistry, which is controlled by physical, chemical, and biological processes. Despite decades of studies in marine environments, a direct relationship has yet to be established between ocean biology and the physicochemical properties of SSA. The ability to establish such relationships is hindered by the fact that SSA measurements are typically dominated by overwhelming background aerosol concentrations even in remote marine environments. Herein, we describe a newly developed approach for reproducing the chemical complexity of SSA in a laboratory setting, comprising a unique ocean-atmosphere facility equipped with actual breaking waves. A mesocosm experiment was performed in natural seawater, using controlled phytoplankton and heterotrophic bacteria concentrations, which showed SSA size and chemical mixing state are acutely sensitive to the aerosol production mechanism, as well as to the type of biological species present. The largest reduction in the hygroscopicity of SSA occurred as heterotrophic bacteria concentrations increased, whereas phytoplankton and chlorophyll- a concentrations decreased, directly corresponding to a change in mixing state in the smallest (60–180 nm) size range. Using this newly developed approach to generate realistic SSA, systematic studies can now be performed to advance our fundamental understanding of the impact of ocean biology on SSA chemical mixing state, heterogeneous reactivity, and the resulting climate-relevant properties.

During the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE), a plume of organic aerosol was produced and emitted into the marine atmosphere from aboard the research vessel R/V Point Sur. In this study, the hygroscopic properties and the chemical composition of the plume were studied at plume ages between 0 and 4 h in different meteorological conditions. In sunny conditions, hygroscopic growth factors (GFs) at a relative humidity (RH) of 92% were low, but increased at higher plume ages: from 1.05 to 1.09 for 30 nm and from 1.05 to 1.1 for 150 nm dry size (contrasted by an average marine background GF of 1.6). Simultaneously, ratios of oxygen to carbon (O:C) increased from < 0.001 to 0.2, water-soluble organic mass (WSOM) concentrations increased from 2.42 to 4.96 μg m−3, and organic mass fractions decreased slightly (~ 0.97 to ~ 0.94). New particles were produced in large quantities (several 10 000 cm−3), which lead to substantially increased cloud condensation nuclei (CCN) concentrations at supersaturations between 0.07–0.88%. High-resolution aerosol mass spectrometer (AMS) spectra show that the organic fragment m/z 43 was dominated by C2H3O+ in the small particle mode and by C3H7+ in the large particle mode. In the marine background aerosol, GFs for 150 nm particles at 40% RH were found to be enhanced at higher organic mass fractions. An average GF of 1.06 was observed for aerosols with an organic mass fraction of 0.53, a GF of 1.04 for an organic mass fraction of 0.35.

Aerosol–cloud–radiation interactions are widely held to be the largest single source of uncertainty in climate model projections of future radiative forcing due to increasing anthropogenic emissions. The underlying causes of this uncertainty among modeled predictions of climate are the gaps in our fundamental understanding of cloud processes. There has been significant progress with both observations and models in addressing these important questions but quantifying them correctly is nontrivial, thus limiting our ability to represent them in global climate models. The Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) 2011 was a targeted aircraft campaign with embedded modeling studies, using the Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft and the research vessel Point Sur in July and August 2011 off the central coast of California, with a full payload of instruments to measure particle and cloud number, mass, composition, and water uptake distributions. EPEACE used three emitted particle sources to separate particle-induced feedbacks from dynamical variability, namely 1) shipboard smoke-generated particles with 0.05–1-μm diameters (which produced tracks measured by satellite and had drop composition characteristic of organic smoke), 2) combustion particles from container ships with 0.05–0.2-μm diameters (which were measured in a variety of conditions with droplets containing both organic and sulfate components), and 3) aircraft-based milled salt particles with 3–5-μm diameters (which showed enhanced drizzle rates in some clouds). The aircraft observations were consistent with past large-eddy simulations of deeper clouds in ship tracks and aerosol– cloud parcel modeling of cloud drop number and composition, providing quantitative constraints on aerosol effects on warm-cloud microphysics.

Sea spray production at the ocean surface is mediated by bubble bursting. A variety of means for producing bubbles in the laboratory have been developed to simulate the production of bubbles by breaking waves but none have made direct comparisons with actual breaking waves in natural seawater. This presentation will discuss the physical and chemical properties of aerosols generated by controlled breaking waves compared with the properties of those generated by a variety of bench-top methods that are more easily reproduced in a laboratory setting.

International audience

Particle emissions, volatility, and the concentration of reactive oxygen species (ROS) were investigated for a pre-Euro I compression ignition engine to study the potential health impacts of employing ethanol fumigation technology. Engine testing was performed in two separate experimental campaigns with most testing performed at intermediate speed with four different load settings and various ethanol substitutions. A scanning mobility particle sizer (SMPS) was used to determine particle size distributions, a volatilization tandem differential mobility analyzer (V-TDMA) was used to explore particle volatility, and a new profluorescent nitroxide probe, BPEAnit, was used to investigate the potential toxicity of particles. The greatest particulate mass reduction was achieved with ethanol fumigation at full load, which contributed to the formation of a nucleation mode. Ethanol fumigation increased the volatility of particles by coating the particles with organic material or by making extra organic material available as an external mixture. In addition, the particle-related ROS concentrations increased with ethanol fumigation and were associated with the formation of a nucleation mode. The smaller particles, the increased volatility, and the increase in potential particle toxicity with ethanol fumigation may provide a substantial barrier for the uptake of fumigation technology using ethanol as a supplementary fuel.

A month-long intensive measurement campaign was conducted in March/April 2007 at Agnes Water, a remote coastal site just south of the Great Barrier Reef on the east coast of Australia. Particle and ion size distributions were continuously measured during the campaign. Coastal nucleation events were observed in clean, marine air masses coming from the south-east on 65% of the days. The events usually began at ~10:00 local time and lasted for 1–4 h. They were characterised by the appearance of a nucleation mode with a peak diameter of ~10 nm. The freshly nucleated particles grew within 1–4 h up to sizes of 20–50 nm. The events occurred when solar intensity was high (~1000 W m−2) and RH was low (~60%). Interestingly, the events were not related to tide height. The volatile and hygroscopic properties of freshly nucleated particles (17–22.5 nm), simultaneously measured with a volatility-hygroscopicity-tandem differential mobility analyser (VH-TDMA), were used to infer chemical composition. The majority of the volume of these particles was attributed to internally mixed sulphate and organic components. After ruling out coagulation as a source of significant particle growth, we conclude that the condensation of sulphate and/or organic vapours was most likely responsible for driving particle growth during the nucleation events. We cannot make any direct conclusions regarding the chemical species that participated in the initial particle nucleation. However, we suggest that nucleation may have resulted from the photo-oxidation products of unknown sulphur or organic vapours emitted from the waters of Hervey Bay, or from the formation of DMS-derived sulphate clusters over the open ocean that were activated to observable particles by condensable vapours emitted from the nutrient rich waters around Fraser Island or Hervey Bay. Furthermore, a unique and particularly strong nucleation event was observed during northerly wind. The event began early one morning (08:00) and lasted almost the entire day resulting in the production of a large number of ~80 nm particles (average modal concentration during the event was 3200 cm−3). The Great Barrier Reef was the most likely source of precursor vapours responsible for this event.

While current research has demonstrated that the operation of some laser printers results in emission of high concentrations of ultrafine particles, fundamental gaps in knowledge in relation to the emissions still remain. In particular, there have been no answers provided to questions such as the following: (1) What is the composition of the particles? (2) What are their formation mechanisms? (3) Why are some printers high emitters, while others are low? Considering the widespread use of printers and human exposure to these particles, understanding the process of particle formation is of critical importance. This study, using state-of-the-art instrumental methods, has addressed these three points. We present experimental evidence that indicates that intense bursts of particles are associated with temperature fluctuations and suggest that the difference between high and low emitters lies in the speed and sophistication of the temperature control. We have also shown, for the first time, that the particles are volatile and are of secondary nature, being formed in the air from VOC originating from both the paper and hot toner. Some of the toner is initially deposited on the fuser roller, after which the organic compounds evaporate and then form particles, through one of two main reaction pathways: homogeneous nucleation or secondary particle formation involving ozone.

J. C. Schroder1, S. J. Hanna1, R. L. Modini2, A. L. Corrigan2, S. M. Kreidenweis6, A. M. Macdonald3, K. J. Noone5, L. M. Russell2, W. R. Leaitch4, and A. K. Bertram1 1Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1, Canada 2Scripps Institute of Oceanography, University of California-San Diego, La Jolla, San Diego, CA, USA 3Air Quality Processes Research Section, Environment Canada, Toronto, ON, Canada 4Climate Chemistry and Measurements Research, Environment Canada, Toronto, ON, Canada 5Department of Applied Environmental Science, Stockholm University, Stockholm, Sweden 6Department of Atmospheric Science, Colorado State University, Fort Collins, CO, USA

An observational study was undertaken to measure odour and dust (PM10 and PM2.5) emission rates and identify non-methane volatile organic compounds (NMVOCs) and odorants in the exhaust air from two tunnel-ventilated layer-chicken sheds that were configured with multi-tiered cages and manure belts. The study sites were located in south-eastern Queensland and the West Gippsland region of Victoria, Australia. Samples were collected in summer and winter on sequential days across the manure-belt cleaning cycle. Odour emissions ranged from 58 to 512 ou/s per 1000 birds (0.03–0.27 ou/s.kg) and dust emission rates ranged 0.014–0.184 mg/s per 1000 birds for PM10 and 0.001–0.190 mg/s per 1000 birds for PM2.5. Twenty NMVOCs were identified, including three that were also identified as odorants using thermal desorption–gas chromatography–mass spectrometry/olfactometry analysis. Odour emission rates were observed to vary with the amount of manure accumulation on the manure belts, being lowest 2–4 days after removing manure. Odour emission rates were also observed to vary with diurnal and seasonal changes in ventilation rate. Dust emissions were observed to increase with ventilation rate but not with manure accumulation. Some NMVOCs were identified at both farms and in different seasons whereas others were observed only at one farm or in one season, indicating that odorant composition was influenced by farm-specific practices and season.

Dust emissions from large-scale, tunnel-ventilated poultry sheds could have negative health and environmental impacts. Despite this fact, the literature concerning dust emissions from tunnel-ventilated poultry sheds in Australia and overseas is relatively scarce. Dust measurements were conducted during two consecutive production cycles at a single broiler shed on a poultry farm near Ipswich, Queensland. Fresh litter was employed during the first cycle and partially reused litter was employed during the second cycle. This provided an opportunity to study the effect that partial litter reuse has on dust emissions. Dust levels were characterised by the number concentration of suspended particles having a diameter between 0.5 and 20 μm and by the mass concentration of dust particles of less than 10 μm diameter (PM10) and 2.5 μm diameter (PM2.5). In addition, we measured the number size distributions of dust particles. The average concentration and emission rate of dust was higher when partially reused litter was used in the shed than when fresh litter was used. In addition, we found that dust particles emitted from the shed with partially reused litter were finer than the particles emitted with fresh litter. Although the change in litter properties is certainly contributing to this observed variability, other factors such as ventilation rate and litter moisture content are also likely to be involved.

Aerosol particles acting as cloud condensation nuclei (CCN) or ice-nucleating particles (INPs) play a major role in the formation and glaciation of clouds. Thereby they exert a strong impact on the radiation budget of the Earth. Data on abundance and properties of both types of particles are sparse, especially for remote areas of the world, such as the Southern Ocean (SO). In this work, we present unique results from ship-borne aerosol-particle-related in situ measurements and filter sampling in the SO region, carried out during the Antarctic Circumnavigation Expedition (ACE) in the austral summer of 2016–2017. An overview of CCN and INP concentrations over the Southern Ocean is provided and, using additional quantities, insights regarding possible CCN and INP sources and origins are presented. CCN number concentrations spanned 2 orders of magnitude, e.g. for a supersaturation of 0.3 % values ranged roughly from 3 to 590 cm−3. CCN showed variable contributions of organic and inorganic material (inter-quartile range of hygroscopicity parameter κ from 0.2 to 0.9). No distinct size dependence of κ was apparent, indicating homogeneous composition across sizes (critical dry diameter on average between 30 and 110 nm). The contribution of sea spray aerosol (SSA) to the CCN number concentration was on average small. Ambient INP number concentrations were measured in the temperature range from −5 to −27 ∘C using an immersion freezing method. Concentrations spanned up to 3 orders of magnitude, e.g. at −16 ∘C from 0.2 to 100 m−3. Elevated values (above 10 m−3 at −16 ∘C) were measured when the research vessel was in the vicinity of land (excluding Antarctica), with lower and more constant concentrations when at sea. This, along with results of backward-trajectory analyses, hints towards terrestrial and/or coastal INP sources being dominant close to ice-free (non-Antarctic) land. In pristine marine areas INPs may originate from both oceanic sources and/or long-range transport. Sampled aerosol particles (PM10) were analysed for sodium and methanesulfonic acid (MSA). Resulting mass concentrations were used as tracers for primary marine and secondary aerosol particles, respectively. Sodium, with an average mass concentration around 2.8 µg m−3, was found to dominate the sampled, identified particle mass. MSA was highly variable over the SO, with mass concentrations up to 0.5 µg m−3 near the sea ice edge. A correlation analysis yielded strong correlations between sodium mass concentration and particle number concentration in the coarse mode, unsurprisingly indicating a significant contribution of SSA to that mode. CCN number concentration was highly correlated with the number concentration of Aitken and accumulation mode particles. This, together with a lack of correlation between sodium mass and Aitken and accumulation mode number concentrations, underlines the important contribution of non-SSA, probably secondarily formed particles, to the CCN population. INP number concentrations did not significantly correlate with any other measured aerosol physico-chemical parameter.

Primary marine aerosol (PMA)-cloud interactions off the coast of California were investigated using observations of marine aerosol, cloud condensation nuclei (CCN), and stratocumulus clouds during the Eastern Pacific Emitted Aerosol Cloud Experiment (E-PEACE) and the Stratocumulus Observations of Los-Angeles Emissions Derived Aerosol-Droplets (SOLEDAD) studies. Based on recently reportedmeasurements of PMA size distributions, a constrained lognormal-mode-fitting procedure was devised to isolate PMA number size distributions fromtotal aerosol size distributions and applied to E-PEACEmeasurements. During the 12 day E-PEACE cruise on the R/V Point Sur, PMA typically contributed less than 15% of total particle concentrations. PMA number concentrations averaged 12 cm-3 during a relatively calmer period (average wind speed 12m/s1) lasting 8 days, and 71 cm-3 during a period of higher wind speeds (average 16m/s1) lasting 5 days. On average, PMA contributed less than 10% of total CCN at supersaturations up to 0.9% during the calmer period; however, during the higher wind speed period, PMA comprised 5-63% of CCN (average 16-28%) at supersaturations less than 0.3%. Sea salt was measured directly in the dried residuals of cloud droplets during the SOLEDAD study. The mass fractions of sea salt in the residuals averaged 12 to 24% during three cloud events. Comparing the marine stratocumulus clouds sampled in the two campaigns, measured peak supersaturations were 0.2 ± 0.04% during E-PEACE and 0.05-0.1% during SOLEDAD. The availablemeasurements show that cloud droplet number concentrations increased with > 100 nmparticles in E-PEACE but decreased in the three SOLEDAD cloud events. © 2015. American Geophysical Union. All Rights Reserved.