Sub-Antarctic marine aerosol: dominant contributions from biogenic sources

J. Schmale; J. Schneider; E. Nemitz; Y. S. Tang; U. Dragosits; T. D. Blackall; P. N. Trathan; G. J. Phillips; M. Sutton; C. F. Braban

doi:10.5194/acp-13-8669-2013

Sub-Antarctic marine aerosol: significant contributions from biogenic sources

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-13-8261-2013 ◽

2013 ◽

Vol 13 (3) ◽

pp. 8261-8332 ◽

Cited By ~ 1

Author(s):

J. Schmale ◽

J. Schneider ◽

E. Nemitz ◽

Y. S. Tang ◽

U. Dragosits ◽

...

Keyword(s):

Methanesulfonic Acid ◽

Sea Salt ◽

Submicron Particles ◽

Local Fauna ◽

Aerosol Mass Spectrometer ◽

Sea Salt Aerosol ◽

Aerosol Mass ◽

Antarctic Marine ◽

Organic Factor ◽

Highly Correlated

Abstract. Biogenic influences on the composition and characteristics of aerosol were investigated on Bird Island (54°00' S, 38°03' W) in the South Atlantic during November and December 2010. This remote marine environment is characterised by large seabird and seal colonies. The chemical composition of the submicron particles, measured by an aerosol mass spectrometer (AMS), was 21% non-sea salt sulfate 2% nitrate, 7% ammonium, 22% organics and 47% sea salt including sea salt sulfate. A new method to isolate the sea salt signature from the high-resolution AMS data was applied. Generally, the aerosol was found to be less acidic than in other marine environments due to the high availability of ammonia, from local fauna emissions. By positive matrix factorisation five different organic aerosol (OA) profiles could be isolated: an amino acids/amine factor (AA-OA, 18% of OA mass), a methanesulfonic acid OA factor (MSA-OA, 25%), a marine oxygenated OA factor (M-OOA, 40%), a sea salt OA fraction (SS-OA, 7%) and locally produced hydrocarbon-like OA (HOA, 9%). The AA-OA was dominant during the first two weeks of November and found to be related with the hatching of penguins in a nearby colony. This factor, rich in nitrogen (C : N ratio = 0.13), has implications for the biogeochemical cycling of nitrogen in the area as particulate matter is often transported over longer distances than gaseous N-rich compounds. The MSA-OA was mainly transported from more southerly latitudes where phytoplankton bloomed. The bloom was identified as one of three sources for particulate sulfate on Bird Island, next to sea salt sulfate and sulfate transported from South America. M-OOA was the dominant organic factor and found to be similar to marine OA observed at Mace Head, Ireland. An additional OA factor highly correlated with sea salt aerosol was identified (SS-OA). However, based on the available data the type of mixture, internal or external, could not be determined. Potassium was not associated to sea salt particles during 19% of the time, indicating the presence of biogenic particles in addition to the MSA-OA and AA-OA factors.

Linking variations in sea spray aerosol particle hygroscopicity to composition during two microcosm experiments

10.5194/acp-2016-36 ◽

2016 ◽

Author(s):

Sara D. Forestieri ◽

Gavin C. Cornwell ◽

Taylor M. Helgestad ◽

Kathryn A. Moore ◽

Christopher Lee ◽

...

Keyword(s):

Light Scattering ◽

Relative Humidity ◽

Salt Content ◽

Sea Salt ◽

Sea Spray ◽

Hygroscopic Growth ◽

Phytoplankton Blooms ◽

Aerosol Composition ◽

Sea Spray Aerosol ◽

Indoor And Outdoor

Abstract. The extent to which water uptake influences the light scattering ability of marine sea spray aerosol (SSA) particles depends critically on SSA chemical composition. The organic fraction of SSA can increase during phytoplankton blooms, decreasing the salt content and therefore the hygroscopicity of the particles. In this study, subsaturated hygroscopic growth factors at 85 % relative humidity (GF(85 %)) of SSA particles were quantified during two induced phytoplankton blooms in marine aerosol reference tanks (MARTs). One MART was illuminated with fluorescent lights and the other was illuminated with sunlight, referred to as the "indoor" and "outdoor" MARTs, respectively. GF(85 %) values for SSA particles were derived from measurements of light scattering and particle size distributions, concurrently with online single particle and bulk aerosol composition measurements. During both microcosm experiments, the observed bulk average GF(85 %) values were depressed substantially relative to pure, inorganic sea salt, by 10 to 19 %, with a one (indoor MART) and six (outdoor MART) day lag between GF(85 %) depression and the peak chlorophyll-a concentrations. The fraction of organiccontaining SSA particles generally increased after the peak of the phytoplankton blooms. The GF(85 %) values were inversely correlated with the fraction of particles containing organic or other biological markers. This indicates these particles were less hygroscopic than the particles identified as predominately sea salt containing and demonstrates a clear relationship between SSA particle composition and the sensitivity of light scattering to variations in relative humidity. The implications of these observations to the direct climate effects of SSA particles are discussed.

Determining the link between hygroscopicity and composition for semi-volatile aerosol species

Atmospheric Measurement Techniques ◽

10.5194/amt-11-4361-2018 ◽

2018 ◽

Vol 11 (7) ◽

pp. 4361-4372 ◽

Cited By ~ 1

Author(s):

Joel Alroe ◽

Luke T. Cravigan ◽

Marc D. Mallet ◽

Zoran D. Ristovski ◽

Branka Miljevic ◽

...

Keyword(s):

Sampling Technique ◽

Organic Aerosol ◽

Marine Aerosol ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass ◽

Coastal Marine ◽

Bypass Line ◽

Sea Spray Aerosol ◽

Aerosol Properties ◽

Cape Grim

Abstract. Internally and externally mixed aerosols present significant challenges in assessing the hygroscopicity of each aerosol component. This study presents a new sampling technique which uses differences in volatility to separate mixtures and directly examine their respective composition and hygroscopic contribution. A shared thermodenuder and unheated bypass line are continuously cycled between an aerosol mass spectrometer and a volatility and hygroscopicity tandem differential mobility analyser, allowing real-time comparative analysis of heated and unheated aerosol properties. Measurements have been taken of both chamber-generated secondary organic aerosol and coastal marine aerosol at Cape Grim, Australia, to investigate system performance under diverse conditions. Despite rapidly changing aerosol properties and the need to restrict analysis to a narrow size range, the former experiment separated the hygroscopic influences of ammonium sulfate and two distinct organic components with similar oxygen to carbon ratios but different volatilities. Analysis of the marine aerosol revealed an external mixture of non-sea-salt sulfates and sea spray aerosol, which likely shared similar volatile fractions composed of sulfuric acid and a non-hygroscopic organic component.

Effect of primary organic sea spray emissions on cloud condensation nuclei concentrations

Atmospheric Chemistry and Physics ◽

10.5194/acp-12-89-2012 ◽

2012 ◽

Vol 12 (1) ◽

pp. 89-101 ◽

Cited By ~ 46

Author(s):

D. M. Westervelt ◽

R. H. Moore ◽

A. Nenes ◽

P. J. Adams

Keyword(s):

Surface Tension ◽

Southern Ocean ◽

Source Function ◽

Cloud Condensation Nuclei ◽

Organic Aerosol ◽

Sea Salt ◽

Sea Spray ◽

Aerosol Emission ◽

Sea Spray Aerosol ◽

Surfactant Effects

Abstract. This work estimates the primary marine organic aerosol global emission source and its impact on cloud condensation nuclei (CCN) concentrations by implementing an organic sea spray source function into a series of global aerosol simulations. The source function assumes that a fraction of the sea spray emissions, depending on the local chlorophyll concentration, is organic matter in place of sea salt. Effect on CCN concentrations (at 0.2% supersaturation) is modeled using the Two-Moment Aerosol Sectional (TOMAS) microphysics algorithm coupled to the GISS II-prime general circulation model. The presence of organics affects CCN activity in competing ways: by reducing the amount of solute available in the particle and decreasing surface tension of CCN. To model surfactant effects, surface tension depression data from seawater samples taken near the Georgia coast were applied as a function of carbon concentrations. A global marine organic aerosol emission rate of 17.7 Tg C yr−1 is estimated from the simulations. Marine organics exert a localized influence on CCN(0.2%) concentrations, decreasing regional concentrations by no more than 5% and by less than 0.5% over most of the globe, assuming direct replacement of sea salt aerosol with organic aerosol. The decrease in CCN concentrations results from the fact that the decrease in particle solute concentration outweighs the organic surfactant effects. The low sensitivity of CCN(0.2%) to the marine organic emissions is likely due to the small compositional changes: the mass fraction of OA in accumulation mode aerosol increases by only ~15% in a biologically active region of the Southern Ocean. To test the sensitivity to uncertainty in the sea spray emissions process, we relax the assumption that sea spray aerosol number and mass remain fixed and instead can add to sea spray emissions rather than replace existing sea salt. In these simulations, we find that marine organic aerosol can increase CCN by up to 50% in the Southern Ocean and 3.7% globally during the austral summer. This vast difference in CCN impact highlights the need for further observational exploration of the sea spray aerosol emission process as well as evaluation and development of model parameterizations.

Linking variations in sea spray aerosol particle hygroscopicity to composition during two microcosm experiments

Atmospheric Chemistry and Physics ◽

10.5194/acp-16-9003-2016 ◽

2016 ◽

Vol 16 (14) ◽

pp. 9003-9018 ◽

Cited By ~ 21

Author(s):

Sara D. Forestieri ◽

Gavin C. Cornwell ◽

Taylor M. Helgestad ◽

Kathryn A. Moore ◽

Christopher Lee ◽

...

Keyword(s):

Organic Matter ◽

Light Scattering ◽

Time Lag ◽

Sea Salt ◽

Sea Spray ◽

Phytoplankton Blooms ◽

Chl A ◽

Volume Fractions ◽

Sea Spray Aerosol ◽

Indoor And Outdoor

Abstract. The extent to which water uptake influences the light scattering ability of marine sea spray aerosol (SSA) particles depends critically on SSA chemical composition. The organic fraction of SSA can increase during phytoplankton blooms, decreasing the salt content and therefore the hygroscopicity of the particles. In this study, subsaturated hygroscopic growth factors at 85 % relative humidity (GF(85 %)) of predominately submicron SSA particles were quantified during two induced phytoplankton blooms in marine aerosol reference tanks (MARTs). One MART was illuminated with fluorescent lights and the other was illuminated with sunlight, referred to as the "indoor" and "outdoor" MARTs, respectively. Optically weighted GF(85 %) values for SSA particles were derived from measurements of light scattering and particle size distributions. The mean optically weighted SSA diameters were 530 and 570 nm for the indoor and outdoor MARTs, respectively. The GF(85 %) measurements were made concurrently with online particle composition measurements, including bulk composition (using an Aerodyne high-resolution aerosol mass spectrometer) and single particle (using an aerosol time-of-flight mass spectrometer) measurement, and a variety of water-composition measurements. During both microcosm experiments, the observed optically weighted GF(85 %) values were depressed substantially relative to pure inorganic sea salt by 5 to 15 %. There was also a time lag between GF(85 %) depression and the peak chlorophyll a (Chl a) concentrations by either 1 (indoor MART) or 3-to-6 (outdoor MART) days. The fraction of organic matter in the SSA particles generally increased after the Chl a peaked, also with a time lag, and ranged from about 0.25 to 0.5 by volume. The observed depression in the GF(85 %) values (relative to pure sea salt) is consistent with the large observed volume fractions of non-refractory organic matter (NR-OM) comprising the SSA. The GF(85 %) values exhibited a reasonable negative correlation with the SSA NR-OM volume fractions after the peak of the blooms (i.e., Chl a maxima); i.e., the GF(85 %) values generally decreased when the NR-OM volume fractions increased. The GF(85 %) vs. NR-OM volume fraction relationship was interpreted using the Zdanovskii–Stokes–Robinson (ZSR) mixing rule and used to estimate the GF(85 %) of the organic matter in the nascent SSA. The estimated pure NR-OM GF(85 %) values were 1.16 ± 0.09 and 1.23 ± 0.10 for the indoor and outdoor MARTS, respectively. These measurements demonstrate a clear relationship between SSA particle composition and the sensitivity of light scattering to variations in relative humidity. The implications of these observations to the direct climate effects of SSA particles are discussed.

Quantitative single particle analysis with the Aerodyne aerosol mass spectrometer: development of a new classification algorithm and its application to field data

Atmospheric Measurement Techniques Discussions ◽

10.5194/amtd-6-5653-2013 ◽

2013 ◽

Vol 6 (3) ◽

pp. 5653-5691 ◽

Cited By ~ 1

Author(s):

F. Freutel ◽

F. Drewnick ◽

J. Schneider ◽

T. Klimach ◽

S. Borrmann

Keyword(s):

Mass Spectrometer ◽

Single Particle ◽

Field Data ◽

Classification Algorithm ◽

Particle Mass ◽

Submicron Particles ◽

Particle Analysis ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass

Abstract. Single particle mass spectrometry has proven a valuable tool for gaining information on the mixing state of aerosol particles. With the Aerodyne aerosol mass spectrometer (AMS) equipped with a light scattering probe, non-refractory components of submicron particles with diameters larger than about 300 nm can even be quantified on a single particle basis. Here, we present a new method for the analysis of AMS single particle mass spectra. The developed algorithm classifies the particles according to their components (e.g., sulphate, nitrate, different types of organics) and simultaneously provides quantitative information about the composition of the single particles. This classification algorithm was validated by applying it to data acquired in laboratory experiments with particles of known composition, and applied to field data acquired during the MEGAPOLI summer campaign (July 2009) in Paris. As shown, it is not only possible to directly measure the mixing state of atmospheric particles, but also to directly observe repartitioning of semi-volatile species between gas and particle phase during the course of the day.

Aerosol physicochemical properties and implication for visibility during an intense haze episode during winter in Beijing

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-14-23375-2014 ◽

2014 ◽

Vol 14 (16) ◽

pp. 23375-23413 ◽

Cited By ~ 5

Author(s):

Y. H. Wang ◽

Z. R. Liu ◽

J. K. Zhang ◽

B. Hu ◽

D. S. Ji ◽

...

Keyword(s):

Light Scattering ◽

Particle Growth ◽

Submicron Particles ◽

Aerosol Mass Spectrometer ◽

Average Mass ◽

Submicron Aerosol ◽

Aerosol Mass ◽

Synoptic Conditions ◽

Haze Episode ◽

Pm2.5 And Pm10

Abstract. The evolution of physical, chemical and optical properties of urban aerosol particles was characterized during an extreme haze episode in Beijing, PRC from 24 January through 31 January 2013 based on in-situ measurements. The average mass concentrations of PM1, PM2.5 and PM10 were 99 ± 67 μg m−3 (average ± stdev), 188 ± 128 μg m−3 and 265 ± 157 μg m−3, respectively. A significant increase in PM1−2.5 fraction was observed during the most heavily polluted periods. The average scattering coefficient (λ = 550 nm) was 877 ± 624 M m−1. An increasing relative amount of coarse particles can be deduced from the variations of backscattering ratios, asymmetry parameter and scattering Ångström exponent. Particle number size distributions between 14 nm and 2500 nm diameter showed high number concentrations, particularly in the nucleation mode and accumulation modes. Size-resolved chemical composition of submicron aerosol from a High Resolution-ToF-Aerosol Mass Spectrometer showed that the mass concentration of organic, sulfate, nitrate, ammonium and chlorine mainly resided on 500 nm to 800 nm (vacuum diameter) particles, and sulfate and ammonium contributed most to particle growth during the most heavily polluted day (28 January). Increasing relative humidity and stable synoptic conditions on 28 January combined with heavy pollution, lead to enhanced water uptake by the hygroscopic submicron particles and formation of secondary aerosol, maybe the main reasons for the severity of the haze episode. Light scattering apportionment showed that organic, ammonium sulfate, ammonium nitrate and ammonium chloride compounds contributed to light scattering fractions of 57%, 23%, 10% and 10%, respectively. This study indicated that the organic component in submicron aerosol plays an important role in visibility degradation in this haze episode in and around Beijing.

Chemically-resolved aerosol volatility measurements from two megacity field studies

Atmospheric Chemistry and Physics ◽

10.5194/acp-9-7161-2009 ◽

2009 ◽

Vol 9 (18) ◽

pp. 7161-7182 ◽

Cited By ~ 226

Author(s):

J. A. Huffman ◽

K. S. Docherty ◽

A. C. Aiken ◽

M. J. Cubison ◽

I. M. Ulbrich ◽

...

Keyword(s):

Chemical Species ◽

Methanesulfonic Acid ◽

Field Studies ◽

Ambient Aerosols ◽

Aerosol Mass Spectrometer ◽

Diurnal Cycles ◽

Aerosol Mass ◽

Rapid Temperature ◽

A New Technique

Abstract. The volatilities of different chemical species in ambient aerosols are important but remain poorly characterized. The coupling of a recently developed rapid temperature-stepping thermodenuder (TD, operated in the range 54–230°C) with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) during field studies in two polluted megacities has enabled the first direct characterization of chemically-resolved urban particle volatility. Measurements in Riverside, CA and Mexico City are generally consistent and show ambient nitrate as having the highest volatility of any AMS standard aerosol species while sulfate showed the lowest volatility. Total organic aerosol (OA) showed volatility intermediate between nitrate and sulfate, with an evaporation rate of 0.6%·K−1 near ambient temperature, although OA dominates the residual species at the highest temperatures. Different types of OA were characterized with marker ions, diurnal cycles, and positive matrix factorization (PMF) and show significant differences in volatility. Reduced hydrocarbon-like OA (HOA, a surrogate for primary OA, POA), oxygenated OA (OOA, a surrogate for secondary OA, SOA), and biomass-burning OA (BBOA) separated with PMF were all determined to be semi-volatile. The most aged OOA-1 and its dominant ion, CO2+, consistently exhibited the lowest volatility, with HOA, BBOA, and associated ions for each among the highest. The similar or higher volatility of HOA/POA compared to OOA/SOA contradicts the current representations of OA volatility in most atmospheric models and has important implications for aerosol growth and lifetime. A new technique using the AMS background signal was demonstrated to quantify the fraction of species up to four orders-of-magnitude less volatile than those detectable in the MS mode, which for OA represent ~5% of the non-refractory (NR) OA signal. Our results strongly imply that all OA types should be considered semivolatile in models. The study in Riverside identified organosulfur species (e.g. CH3HSO3+ ion, likely from methanesulfonic acid), while both studies identified ions indicative of amines (e.g. C5H12N+) with very different volatility behaviors than inorganic-dominated ions. The oxygen-to-carbon ratio of OA in each ambient study was shown to increase both with TD temperature and from morning to afternoon, while the hydrogen-to-carbon ratio showed the opposite trend.

Quantitative single-particle analysis with the Aerodyne aerosol mass spectrometer: development of a new classification algorithm and its application to field data

Atmospheric Measurement Techniques ◽

10.5194/amt-6-3131-2013 ◽

2013 ◽

Vol 6 (11) ◽

pp. 3131-3145 ◽

Cited By ~ 21

Author(s):

F. Freutel ◽

F. Drewnick ◽

J. Schneider ◽

T. Klimach ◽

S. Borrmann

Keyword(s):

Mass Spectrometer ◽

Single Particle ◽

Field Data ◽

Classification Algorithm ◽

Particle Mass ◽

Submicron Particles ◽

Particle Analysis ◽

Mixing State ◽

Aerosol Mass Spectrometer ◽

Aerosol Mass

Abstract. Single-particle mass spectrometry has proven a valuable tool for gaining information on the mixing state of aerosol particles. With the Aerodyne aerosol mass spectrometer (AMS) equipped with a light-scattering probe, non-refractory components of submicron particles with diameters larger than about 300 nm can even be quantified on a single-particle basis. Here, we present a new method for the analysis of AMS single-particle mass spectra. The developed algorithm classifies the particles according to their components (e.g. sulphate, nitrate, different types of organics) and simultaneously provides quantitative information about the composition of the single particles. This classification algorithm was validated by applying it to data acquired in laboratory experiments with particles of known composition, and applied to field data acquired during the MEGAPOLI summer campaign (July 2009) in Paris. As shown, it is not only possible to directly measure the mixing state of atmospheric particles, but also to directly observe repartitioning of semi-volatile species between gas and particle phase during the course of the day.

Global scale emission and distribution of sea-spray aerosol: Sea-salt and organic enrichment

Atmospheric Environment ◽

10.1016/j.atmosenv.2009.11.013 ◽

2010 ◽

Vol 44 (5) ◽

pp. 670-677 ◽

Cited By ~ 148

Author(s):

E. Vignati ◽

M.C. Facchini ◽

M. Rinaldi ◽

C. Scannell ◽

D. Ceburnis ◽

...

Keyword(s):

Global Scale ◽

Sea Salt ◽

Organic Enrichment ◽

Sea Spray ◽

Sea Spray Aerosol