Characterization of the South Atlantic marine boundary layer aerosol using an aerodyne aerosol mass spectrometer

Abstract. Measurements of the submicron fraction of the atmospheric aerosol in the marine boundary layer were performed from January to March 2007 (Southern Hemisphere summer) onboard the French research vessel Marion Dufresne in the Southern Atlantic and Indian Ocean (20° S–60° S, 70° W–60° E). We used an Aerodyne High-Resolution-Time-of-Flight AMS to characterize the chemical composition and to measure species-resolved size distributions of non-refractory aerosol components in the submicron range. Within the "standard" AMS compounds (ammonium, chloride, nitrate, sulfate, organics) "sulfate" is the dominant species in the marine boundary layer with concentrations ranging between 50 ng m−3 and 3 μg m−3. Furthermore, what is seen as "sulfate" by the AMS is likely comprised mostly of sulfuric acid. Another sulfur containing species that is produced in marine environments is methanesulfonic acid (MSA). There have been previously measurements of MSA using an Aerodyne AMS. However, due to the use of an instrument equipped with a quadrupole detector with unit mass resolution it was not possible to physically separate MSA from other contributions to the same m/z. In order to identify MSA within the HR-ToF-AMS raw data and to extract mass concentrations for MSA from the field measurements the standard high-resolution MSA fragmentation patterns for the measurement conditions during the ship campaign (e.g. vaporizer temperature) needed to be determined. To identify characteristic air masses and their source regions backwards trajectories were used and averaged concentrations for AMS standard compounds were calculated for each air mass type. Sulfate mass size distributions were measured for these periods showing a distinct difference between oceanic air masses and those from African outflow. While the peak in the mass distribution was roughly at 250 nm (vacuum aerodynamic diameter) in marine air masses, it was shifted to 470 nm in African outflow air. Correlations between the mass concentrations of sulfate, organics and MSA show a narrow correlation for MSA with sulfate/sulfuric acid coming from the ocean, but not with continental sulfate.

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Characterization of the South Atlantic marine boundary layer aerosol using an Aerodyne Aerosol Mass Spectrometer

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-8-4831-2008 ◽

2008 ◽

Vol 8 (2) ◽

pp. 4831-4876 ◽

Cited By ~ 5

Author(s):

S. R. Zorn ◽

F. Drewnick ◽

M. Schott ◽

T. Hoffmann ◽

S. Borrmann

Keyword(s):

Boundary Layer ◽

Sulfuric Acid ◽

Marine Boundary Layer ◽

Methanesulfonic Acid ◽

Field Measurements ◽

Size Distributions ◽

Air Masses ◽

Aerosol Mass ◽

Mass Size ◽

Mass Concentrations

Abstract. Measurements of the submicron fraction of the atmospheric aerosol in the marine boundary layer were performed from January to March 2007 (Southern Hemisphere summer) onboard the French research vessel Marion Dufresne in the Southern Atlantic and Indian Ocean (20° S–60° S, 70° W–60° E). For chemical composition measurements an Aerodyne High-Resolution-Time-of-Flight AMS was used to measure mass concentrations and species-resolved size distributions of non-refractory aerosol components in the submicron range. Within the "standard" AMS compounds (ammonium, chloride, nitrate, sulfate, organics) "sulfate" is the dominating species in the marine boundary layer reaching concentrations between 50 ng m−3 and 3 μg m−3. Furthermore, what is seen as "sulfate" by the AMS seems to be mostly sulfuric acid. Another sulfur containing species that can ubiquitously be found in marine environments is methanesulfonic acid (MSA). Since MSA has not been directly measured before with an AMS, and is not part of the standard AMS analysis, laboratory experiments needed to be performed in order to be able to identify it within the AMS raw data and to extract mass concentrations for MSA from the field measurements. To identify characteristic air masses and their source regions backwards trajectories were used and averaged concentrations for AMS standard compounds were calculated for each air mass type. Sulfate mass size distributions were measured for these periods showing a distinct difference between oceanic air masses and those from African outflow. While the peak size in the mass distribution was roughly 250 nm in marine air masses it was shifted to 470 nm in African outflow air. Correlations between the mass concentrations of sulfate, organics and MSA were calculated which show a narrow correlation for MSA with sulfate/sulfuric acid coming from the ocean but not with continental sulfate.

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A global off-line model of size-resolved aerosol microphysics: I. Model development and prediction of aerosol properties

Atmospheric Chemistry and Physics ◽

10.5194/acp-5-2227-2005 ◽

2005 ◽

Vol 5 (8) ◽

pp. 2227-2252 ◽

Cited By ~ 213

Author(s):

D. V. Spracklen ◽

K. J. Pringle ◽

K. S. Carslaw ◽

M. P. Chipperfield ◽

G. W. Mann

Keyword(s):

Boundary Layer ◽

Sulfuric Acid ◽

Size Distribution ◽

Marine Boundary Layer ◽

Transport Model ◽

Model Development ◽

Aerosol Size Distribution ◽

Chemical Transport Model ◽

Cloud Processing ◽

Nucleation Mechanisms

Abstract. A GLObal Model of Aerosol Processes (GLOMAP) has been developed as an extension to the TOMCAT 3-D Eulerian off-line chemical transport model. GLOMAP simulates the evolution of the global aerosol size distribution using a sectional two-moment scheme and includes the processes of aerosol nucleation, condensation, growth, coagulation, wet and dry deposition and cloud processing. We describe the results of a global simulation of sulfuric acid and sea spray aerosol. The model captures features of the aerosol size distribution that are well established from observations in the marine boundary layer and free troposphere. Modelled condensation nuclei (CN>3nm) vary between about 250–500 cm-3 in remote marine boundary layer regions and are generally in good agreement with observations. Modelled continental CN concentrations are lower than observed, which may be due to lack of some primary aerosol sources or the neglect of nucleation mechanisms other than binary homogeneous nucleation of sulfuric acid-water particles. Remote marine CN concentrations increase to around 2000–10 000 cm

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Particle size distributions in the Eastern Mediterranean troposphere

Atmospheric Chemistry and Physics ◽

10.5194/acp-8-6729-2008 ◽

2008 ◽

Vol 8 (22) ◽

pp. 6729-6738 ◽

Cited By ~ 29

Author(s):

N. Kalivitis ◽

W. Birmili ◽

M. Stock ◽

B. Wehner ◽

A. Massling ◽

...

Keyword(s):

Boundary Layer ◽

Particle Size ◽

Eastern Mediterranean ◽

Particle Formation ◽

Particle Nucleation ◽

Size Distributions ◽

Particle Size Distributions ◽

Air Masses ◽

Crete Island ◽

Particle Sizer

Abstract. Atmospheric particle size distributions were measured on Crete island, Greece in the Eastern Mediterranean during an intensive field campaign between 28 August and 20 October, 2005. Our instrumentation combined a differential mobility particle sizer (DMPS) and an aerodynamic particle sizer (APS) and measured number size distributions in the size range 0.018 μm–10 μm. Four time periods with distinct aerosol characteristics were discriminated, two corresponding to marine and polluted air masses, respectively. In marine air, the sub-μm size distributions showed two particle modes centered at 67 nm and 195 nm having total number concentrations between 900 and 2000 cm−3. In polluted air masses, the size distributions were mainly unimodal with a mode typically centered at 140 nm, with number concentrations varying between 1800 and 2900 cm−3. Super-μm particles showed number concentrations in the range from 0.01 to 2.5 cm−3 without any clear relation to air mass origin. A small number of short-lived particle nucleation events were recorded, where the calculated particle formation rates ranged between 1.1–1.7 cm−3 s−1. However, no particle nucleation and growth events comparable to those typical for the continental boundary layer were observed. Particles concentrations (Diameter <50 nm) were low compared to continental boundary layer conditions with an average concentration of 300 cm−3. The production of sulfuric acid and its subsequently condensation on preexisting particles was examined with the use of a simplistic box model. These calculations suggested that the day-time evolution of the Aitken particle population was governed mainly by coagulation and that particle formation was absent during most days.

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Particle size distributions in the Eastern Mediterranean troposphere

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-8-6571-2008 ◽

2008 ◽

Vol 8 (2) ◽

pp. 6571-6601

Author(s):

N. Kalivitis ◽

W. Birmili ◽

M. Stock ◽

B. Wehner ◽

A. Massling ◽

...

Keyword(s):

Boundary Layer ◽

Particle Size ◽

Eastern Mediterranean ◽

Particle Formation ◽

Particle Nucleation ◽

Size Distributions ◽

Particle Size Distributions ◽

Air Masses ◽

Crete Island ◽

Particle Sizer

Abstract. Atmospheric particle size distributions were measured on Crete island, Greece in the Eastern Mediterranean during an intensive field campaign between 28 August and 20 October 2005. Our instrumentation combined a differential mobility particle sizer (DMPS) and an aerodynamic particle sizer (APS) and measured number size distributions in the size range 0.018 μm–10 μm. Four time periods with distinct aerosol characteristics were discriminated, two corresponding to marine and polluted air masses, respectively. In marine air, the sub-μm size distributions showed two particle modes centered at 67 nm and 195 nm having total number concentrations between 900 and 2000 cm−3. In polluted air masses, the size distributions were mainly unimodal with a mode typically centered at 140 nm, with number concentrations varying between 1800 and 2900 cm−3. Super-μm particles showed number concentrations in the range from 0.01 to 2.5 cm−3 without any clear relation to air mass origin. A small number of short-lived particle nucleation events were recorded, where the calculated particle formation rates ranged between 1.1–1.7 cm−3 s−1. However, no particle nucleation and growth events comparable to those typical for the continental boundary layer were observed. Particles concentrations (Diameter <50 nm) were low compared to continental boundary layer conditions with an average concentration of 300 cm−3. The production of sulfuric acid and its subsequently condensation on preexisting particles was examined with the use of a simplistic box model. These calculations suggested that the day-time evolution of the Aitken particle population was governed mainly by coagulation and that particle formation was absent during most days.

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On the relationship between acetone and carbon monoxide in air masses of different origin

Atmospheric Chemistry and Physics Discussions ◽

10.5194/acpd-3-1017-2003 ◽

2003 ◽

Vol 3 (1) ◽

pp. 1017-1049

Author(s):

M. de Reus ◽

H. Fischer ◽

F. Arnold ◽

J. de Gouw ◽

R. Holzinger ◽

...

Keyword(s):

Boundary Layer ◽

Carbon Monoxide ◽

Field Experiments ◽

Marine Boundary Layer ◽

Biogenic Emissions ◽

Model Calculations ◽

Single Observation ◽

Tropical Regions ◽

Air Masses ◽

Clean Air

Abstract. Carbon monoxide and acetone measurements are presented for five aircraft measurement campaigns at mid-latitudes, polar and tropical regions in the northern hemisphere. Throughout all campaigns, free tropospheric air masses, which were influenced by anthropogenic emissions, showed a similar linear relation between CO and acetone, with a slope of 21–25 pptv acetone/ppbv CO. Measurements in the anthropogenically influenced marine boundary layer revealed a slope of 13–16 pptv acetone/ppbv CO. The different slopes observed in the marine boundary layer and the free troposphere indicate that acetone is emitted by the ocean in relatively clean air masses and taken up by the ocean in polluted air masses. In the lowermost stratosphere, a good correlation between CO and acetone was observed as well, however, with a much smaller slope (~5 pptv acetone/ppbv CO) compared to the troposphere. This is caused by the longer photochemical lifetime of CO compared to acetone in the lower stratosphere, due to the increasing photolytic loss of acetone and the decreasing OH concentration with altitude. No significant correlation between CO and acetone was observed over the tropical rain forest due to the large direct and indirect biogenic emissions of acetone. The common slopes of the linear acetone-CO relation in various layers of the atmosphere, during five field experiments, makes them useful for model calculations. Often a single observation of the CO-acetone correlation, determined from stratospheric measurements, has been used in box model applications. This study shows that different slopes have to be considered for marine boundary layer, free tropospheric and stratospheric air masses, and that the CO-acetone relation cannot be used for air masses which are strongly influenced by biogenic emissions.

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Exploring microphysical properties of marine boundary layer clouds through network analysis

10.5194/egusphere-egu21-13307 ◽

2021 ◽

Author(s):

Lucile Ricard ◽

Athanasios Nenes ◽

Jakob Runge ◽

Paraskevi Georgakaki

Keyword(s):

Boundary Layer ◽

High Resolution ◽

Network Analysis ◽

Marine Boundary Layer ◽

Large Eddy Simulations ◽

Dynamical Structure ◽

Boundary Layer Clouds ◽

Microphysical Properties ◽

Spatial Coverage ◽

Large Eddy

<p>Aerosol-cloud interactions remain the largest uncertainty in assessments of anthropogenic climate forcing, while the complexity of these interactions require methods that enable abstractions and simplifications that allow their improved treatment in climate models. Marine boundary layer clouds are an important component of the climate system as their large albedo and spatial coverage strongly affect the planetary radiative balance. High resolution simulations of clouds provide an unprecedented understanding of the structure and behavior of these clouds in the marine atmosphere, but the amount of data is often too large and complex to be useful in climate simulations. Data reduction and inference methods provide a way that to reduce the complexity and dimensionality of datasets generated from high-resolution Large Eddy Simulations.</p><p>In this study we use network analysis, (the &#948;-Maps method) to study the complex interaction between liquid water, droplet number and vertical velocity in Large Eddy Simulations of Marine Boundary Layer clouds. &#948;-Maps identifies domains that are spatially contiguous and possibly overlapping and characterizes their connections and temporal interactions. The objective is to better understand microphysical properties of marine boundary layer clouds, and how they are impacted by the variability in aerosols. Here we will capture the dynamical structure of the cloud fields predicted by the MIMICA Large Eddy Simulation (LES) model. The networks inferred from the different simulation fields are compared between them (intra-comparisons) using perturbations in initial conditions and aerosol, using a set of four metrics. The networks are then evaluated for their differences, quantifying how much variability is inherent in the LES simulations versus the robust changes induced by the aerosol fields.&#160;</p>

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Synoptic-scale controls of fog and low-cloud variability in the Namib Desert

Atmospheric Chemistry and Physics ◽

10.5194/acp-20-3415-2020 ◽

2020 ◽

Vol 20 (6) ◽

pp. 3415-3438 ◽

Cited By ~ 1

Author(s):

Hendrik Andersen ◽

Jan Cermak ◽

Julia Fuchs ◽

Peter Knippertz ◽

Marco Gaetani ◽

...

Keyword(s):

Boundary Layer ◽

Cloud Cover ◽

Large Scale ◽

Marine Boundary Layer ◽

Synoptic Scale ◽

Namib Desert ◽

Data Set ◽

Air Masses ◽

Low Cloud ◽

Low Cloud Cover

Abstract. Fog is a defining characteristic of the climate of the Namib Desert, and its water and nutrient input are important for local ecosystems. In part due to sparse observation data, the local mechanisms that lead to fog occurrence in the Namib are not yet fully understood, and to date, potential synoptic-scale controls have not been investigated. In this study, a recently established 14-year data set of satellite observations of fog and low clouds in the central Namib is analyzed in conjunction with reanalysis data in order to identify synoptic-scale patterns associated with fog and low-cloud variability in the central Namib during two seasons with different spatial fog occurrence patterns. It is found that during both seasons, mean sea level pressure and geopotential height at 500 hPa differ markedly between fog/low-cloud and clear days, with patterns indicating the presence of synoptic-scale disturbances on fog and low-cloud days. These regularly occurring disturbances increase the probability of fog and low-cloud occurrence in the central Namib in two main ways: (1) an anomalously dry free troposphere in the coastal region of the Namib leads to stronger longwave cooling of the marine boundary layer, increasing low-cloud cover, especially over the ocean where the anomaly is strongest; (2) local wind systems are modulated, leading to an onshore anomaly of marine boundary-layer air masses. This is consistent with air mass back trajectories and a principal component analysis of spatial wind patterns that point to advected marine boundary-layer air masses on fog and low-cloud days, whereas subsiding continental air masses dominate on clear days. Large-scale free-tropospheric moisture transport into southern Africa seems to be a key factor modulating the onshore advection of marine boundary-layer air masses during April, May, and June, as the associated increase in greenhouse gas warming and thus surface heating are observed to contribute to a continental heat low anomaly. A statistical model is trained to discriminate between fog/low-cloud and clear days based on information on large-scale dynamics. The model accurately predicts fog and low-cloud days, illustrating the importance of large-scale pressure modulation and advective processes. It can be concluded that regional fog in the Namib is predominantly of an advective nature and that fog and low-cloud cover is effectively maintained by increased cloud-top radiative cooling. Seasonally different manifestations of synoptic-scale disturbances act to modify its day-to-day variability and the balance of mechanisms leading to its formation and maintenance. The results are the basis for a new conceptual model of the synoptic-scale mechanisms that control fog and low-cloud variability in the Namib Desert and will guide future studies of coastal fog regimes.

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The potential role of methanesulfonic acid (MSA) in aerosol formation and growth and the associated radiative forcings

Atmospheric Chemistry and Physics ◽

10.5194/acp-19-3137-2019 ◽

2019 ◽

Vol 19 (5) ◽

pp. 3137-3160 ◽

Cited By ~ 14

Author(s):

Anna L. Hodshire ◽

Pedro Campuzano-Jost ◽

John K. Kodros ◽

Betty Croft ◽

Benjamin A. Nault ◽

...

Keyword(s):

Sulfuric Acid ◽

Methanesulfonic Acid ◽

Aerosol Size Distribution ◽

Size Distributions ◽

Global Models ◽

Cloud Albedo ◽

Dms Oxidation ◽

Aerosol Mass ◽

The Impact ◽

Model Measurement

Abstract. Atmospheric marine aerosol particles impact Earth's albedo and climate. These particles can be primary or secondary and come from a variety of sources, including sea salt, dissolved organic matter, volatile organic compounds, and sulfur-containing compounds. Dimethylsulfide (DMS) marine emissions contribute greatly to the global biogenic sulfur budget, and its oxidation products can contribute to aerosol mass, specifically as sulfuric acid and methanesulfonic acid (MSA). Further, sulfuric acid is a known nucleating compound, and MSA may be able to participate in nucleation when bases are available. As DMS emissions, and thus MSA and sulfuric acid from DMS oxidation, may have changed since pre-industrial times and may change in a warming climate, it is important to characterize and constrain the climate impacts of both species. Currently, global models that simulate aerosol size distributions include contributions of sulfate and sulfuric acid from DMS oxidation, but to our knowledge, global models typically neglect the impact of MSA on size distributions. In this study, we use the GEOS-Chem-TOMAS (GC-TOMAS) global aerosol microphysics model to determine the impact on aerosol size distributions and subsequent aerosol radiative effects from including MSA in the size-resolved portion of the model. The effective equilibrium vapor pressure of MSA is currently uncertain, and we use the Extended Aerosol Inorganics Model (E-AIM) to build a parameterization for GC-TOMAS of MSA's effective volatility as a function of temperature, relative humidity, and available gas-phase bases, allowing MSA to condense as an ideally nonvolatile or semivolatile species or too volatile to condense. We also present two limiting cases for MSA's volatility, assuming that MSA is always ideally nonvolatile (irreversible condensation) or that MSA is always ideally semivolatile (quasi-equilibrium condensation but still irreversible condensation). We further present simulations in which MSA participates in binary and ternary nucleation with the same efficacy as sulfuric acid whenever MSA is treated as ideally nonvolatile. When using the volatility parameterization described above (both with and without nucleation), including MSA in the model changes the global annual averages at 900 hPa of submicron aerosol mass by 1.2 %, N3 (number concentration of particles greater than 3 nm in diameter) by −3.9 % (non-nucleating) or 112.5 % (nucleating), N80 by 0.8 % (non-nucleating) or 2.1 % (nucleating), the cloud-albedo aerosol indirect effect (AIE) by −8.6 mW m−2 (non-nucleating) or −26 mW m−2 (nucleating), and the direct radiative effect (DRE) by −15 mW m−2 (non-nucleating) or −14 mW m−2 (nucleating). The sulfate and sulfuric acid from DMS oxidation produces 4–6 times more submicron mass than MSA does, leading to an ∼10 times stronger cooling effect in the DRE. But the changes in N80 are comparable between the contributions from MSA and from DMS-derived sulfate/sulfuric acid, leading to comparable changes in the cloud-albedo AIE. Model–measurement comparisons with the Heintzenberg et al. (2000) dataset over the Southern Ocean indicate that the default model has a missing source or sources of ultrafine particles: the cases in which MSA participates in nucleation (thus increasing ultrafine number) most closely match the Heintzenberg distributions, but we cannot conclude nucleation from MSA is the correct reason for improvement. Model–measurement comparisons with particle-phase MSA observed with a customized Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) from the ATom campaign show that cases with the MSA volatility parameterizations (both with and without nucleation) tend to fit the measurements the best (as this is the first use of MSA measurements from ATom, we provide a detailed description of these measurements and their calibration). However, no one model sensitivity case shows the best model–measurement agreement for both Heintzenberg and the ATom campaigns. As there are uncertainties in both MSA's behavior (nucleation and condensation) and the DMS emissions inventory, further studies on both fronts are needed to better constrain MSA's past, current, and future impacts upon the global aerosol size distribution and radiative forcing.

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Ozone variability and halogen oxidation within the Arctic and sub-Arctic springtime boundary layer

Atmospheric Chemistry and Physics ◽

10.5194/acp-10-10223-2010 ◽

2010 ◽

Vol 10 (21) ◽

pp. 10223-10236 ◽

Cited By ~ 92

Author(s):

J. B. Gilman ◽

J. F. Burkhart ◽

B. M. Lerner ◽

E. J. Williams ◽

W. C. Kuster ◽

...

Keyword(s):

Boundary Layer ◽

North Atlantic ◽

Marine Boundary Layer ◽

Transport Model ◽

Arctic Basin ◽

The Arctic ◽

Arctic Boundary Layer ◽

Air Masses ◽

The North ◽

The North Atlantic

Abstract. The influence of halogen oxidation on the variabilities of ozone (O3) and volatile organic compounds (VOCs) within the Arctic and sub-Arctic atmospheric boundary layer was investigated using field measurements from multiple campaigns conducted in March and April 2008 as part of the POLARCAT project. For the ship-based measurements, a high degree of correlation (r = 0.98 for 544 data points collected north of 68° N) was observed between the acetylene to benzene ratio, used as a marker for chlorine and bromine oxidation, and O3 signifying the vast influence of halogen oxidation throughout the ice-free regions of the North Atlantic. Concurrent airborne and ground-based measurements in the Alaskan Arctic substantiated this correlation and were used to demonstrate that halogen oxidation influenced O3 variability throughout the Arctic boundary layer during these springtime studies. Measurements aboard the R/V Knorr in the North Atlantic and Arctic Oceans provided a unique view of the transport of O3-poor air masses from the Arctic Basin to latitudes as far south as 52° N. FLEXPART, a Lagrangian transport model, was used to quantitatively determine the exposure of air masses encountered by the ship to first-year ice (FYI), multi-year ice (MYI), and total ICE (FYI+MYI). O3 anti-correlated with the modeled total ICE tracer (r = −0.86) indicating that up to 73% of the O3 variability measured in the Arctic marine boundary layer could be related to sea ice exposure.

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