Rapid cloud removal of dimethyl sulfide oxidation products limits SO2 and cloud condensation nuclei production in the marine atmosphere

2021 ◽  
Vol 118 (42) ◽  
pp. e2110472118
Author(s):  
Gordon A. Novak ◽  
Charles H. Fite ◽  
Christopher D. Holmes ◽  
Patrick R. Veres ◽  
J. Andrew Neuman ◽  
...  
Keyword(s):  
Radiative Forcing ◽  
Dimethyl Sulfide ◽  
Cloud Condensation Nuclei ◽  
Sulfide Oxidation ◽  
Radiation Balance ◽  
Marine Atmosphere ◽  
Condensation Nuclei ◽  
Near Surface ◽  
Loss Process ◽  
The Impact

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth’s radiation balance and climate. The quantitative assessment of the impact of DMS emissions on CCN concentrations necessitates a detailed description of the oxidation of DMS in the presence of existing aerosol particles and clouds. In the unpolluted marine atmosphere, DMS is efficiently oxidized to hydroperoxymethyl thioformate (HPMTF), a stable intermediate in the chemical trajectory toward sulfur dioxide (SO2) and ultimately sulfate aerosol. Using direct airborne flux measurements, we demonstrate that the irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τHPMTF < 2 h) and terminates DMS oxidation to SO2. When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for the conversion of DMS to sulfate while limiting new particle formation in the marine atmosphere and changing the dynamics of aerosol growth. This loss process potentially reduces the spatial scale over which DMS emissions contribute to aerosol production and growth and weakens the link between DMS emission and marine CCN production with subsequent implications for cloud formation, radiative forcing, and climate.

scholarly journals Global airborne sampling reveals a previously unobserved dimethyl sulfide oxidation mechanism in the marine atmosphere

2020 ◽  
Vol 117 (9) ◽  
pp. 4505-4510 ◽  
Author(s):  
Patrick R. Veres ◽  
J. Andrew Neuman ◽  
Timothy H. Bertram ◽  
Emmanuel Assaf ◽  
Glenn M. Wolfe ◽  
...  
Keyword(s):  
Dimethyl Sulfide ◽  
Cloud Condensation Nuclei ◽  
Sulfide Oxidation ◽  
Oxidation Mechanism ◽  
Global Scale ◽  
Marine Atmosphere ◽  
Aerosol Formation ◽  
Radiative Balance ◽  
Biological Source ◽  
Secondary Aerosols

Dimethyl sulfide (DMS), emitted from the oceans, is the most abundant biological source of sulfur to the marine atmosphere. Atmospheric DMS is oxidized to condensable products that form secondary aerosols that affect Earth’s radiative balance by scattering solar radiation and serving as cloud condensation nuclei. We report the atmospheric discovery of a previously unquantified DMS oxidation product, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), identified through global-scale airborne observations that demonstrate it to be a major reservoir of marine sulfur. Observationally constrained model results show that more than 30% of oceanic DMS emitted to the atmosphere forms HPMTF. Coincident particle measurements suggest a strong link between HPMTF concentration and new particle formation and growth. Analyses of these observations show that HPMTF chemistry must be included in atmospheric models to improve representation of key linkages between the biogeochemistry of the ocean, marine aerosol formation and growth, and their combined effects on climate.

New Directions: The impact of oceanic iron fertilisation on cloud condensation nuclei

2008 ◽  
Vol 42 (22) ◽  
pp. 5728-5730 ◽  
Author(s):  
Matthew T. Woodhouse ◽  
Graham W. Mann ◽  
Kenneth S. Carslaw ◽  
Olivier Boucher
Keyword(s):  
Cloud Condensation Nuclei ◽  
Condensation Nuclei ◽  
New Directions ◽  
The Impact

scholarly journals Black carbon vertical profiles strongly affect its radiative forcing uncertainty

2013 ◽  
Vol 13 (5) ◽  
pp. 2423-2434 ◽  
Author(s):  
B. H. Samset ◽  
G. Myhre ◽  
M. Schulz ◽  
Y. Balkanski ◽  
S. Bauer ◽  
...  
Keyword(s):  
Black Carbon ◽  
Vertical Profile ◽  
Radiative Forcing ◽  
Global Radiation ◽  
Radiation Balance ◽  
Upper Troposphere ◽  
Aerosol Model ◽  
Intercomparison Project ◽  
To Come ◽  
The Impact

Abstract. The impact of black carbon (BC) aerosols on the global radiation balance is not well constrained. Here twelve global aerosol models are used to show that at least 20% of the present uncertainty in modeled BC direct radiative forcing (RF) is due to diversity in the simulated vertical profile of BC mass. Results are from phases 1 and 2 of the global aerosol model intercomparison project (AeroCom). Additionally, a significant fraction of the variability is shown to come from high altitudes, as, globally, more than 40% of the total BC RF is exerted above 5 km. BC emission regions and areas with transported BC are found to have differing characteristics. These insights into the importance of the vertical profile of BC lead us to suggest that observational studies are needed to better characterize the global distribution of BC, including in the upper troposphere.

scholarly journals Global source attribution of sulfate concentration and direct and indirect radiative forcing

2017 ◽  
Vol 17 (14) ◽  
pp. 8903-8922 ◽  
Author(s):  
Yang Yang ◽  
Hailong Wang ◽  
Steven J. Smith ◽  
Richard Easter ◽  
Po-Lun Ma ◽  
...  
Keyword(s):  
Southern Hemisphere ◽  
Northern Hemisphere ◽  
Radiative Forcing ◽  
Dimethyl Sulfide ◽  
Sulfur Source ◽  
Atmospheric Conditions ◽  
So2 Emissions ◽  
Near Surface ◽  
Indirect Radiative Forcing ◽  
Global Source

Abstract. The global source–receptor relationships of sulfate concentrations, and direct and indirect radiative forcing (DRF and IRF) from 16 regions/sectors for years 2010–2014 are examined in this study through utilizing a sulfur source-tagging capability implemented in the Community Earth System Model (CESM) with winds nudged to reanalysis data. Sulfate concentrations are mostly contributed by local emissions in regions with high emissions, while over regions with relatively low SO2 emissions, the near-surface sulfate concentrations are primarily attributed to non-local sources from long-range transport. Regional source efficiencies of sulfate concentrations are higher over regions with dry atmospheric conditions and less export, suggesting that lifetime of aerosols, together with regional export, is important in determining regional air quality. The simulated global total sulfate DRF is −0.42 W m−2, with −0.31 W m−2 contributed by anthropogenic sulfate and −0.11 W m−2 contributed by natural sulfate, relative to a state with no sulfur emissions. In the Southern Hemisphere tropics, dimethyl sulfide (DMS) contributes 17–84 % to the total DRF. East Asia has the largest contribution of 20–30 % over the Northern Hemisphere mid- and high latitudes. A 20 % perturbation of sulfate and its precursor emissions gives a sulfate incremental IRF of −0.44 W m−2. DMS has the largest contribution, explaining −0.23 W m−2 of the global sulfate incremental IRF. Incremental IRF over regions in the Southern Hemisphere with low background aerosols is more sensitive to emission perturbation than that over the polluted Northern Hemisphere.

scholarly journals Measured and modelled Cloud Condensation Nuclei (CCN) concentration in São Paulo, Brazil: the importance of aerosol size-resolved chemical composition on CCN concentration prediction

2013 ◽  
Vol 13 (12) ◽  
pp. 32353-32389 ◽  
Author(s):  
G. P. Almeida ◽  
J. Brito ◽  
C. A. Morales ◽  
M. F. Andrade ◽  
P. Artaxo
Keyword(s):  
Chemical Composition ◽  
Real Time ◽  
Cloud Condensation Nuclei ◽  
Bulk Composition ◽  
Sao Paulo ◽  
Aerosol Size Distribution ◽  
São Paulo ◽  
Condensation Nuclei ◽  
Aerosol Composition ◽  
The Impact

Abstract. Measurements of cloud condensation nuclei (CCN), aerosol size distribution and non-refractory chemical composition were performed from 16 to 31 October 2012 in the São Paulo Metropolitan Area (SPMA), Brazil. CCN measurements were performed at 0.2%, 0.4%, 0.6%, 0.8% and 1.0% water supersaturation and were subsequently compared with Köhler theory, considering the chemical composition. Real-time chemical composition has been obtained deploying for the first time in SPMA an Aerosol Chemical Ionization Monitor (ACSM). CCN closure analyses were performed considering internal mixture. Average aerosol composition during the studied period yielded 4.81 ± 3.05, 3.26 ± 2.10, 0.30 ± 0.27, 0.52 ± 0.32, 0.37 ± 0.21 and 0.04 ± 0.04 μg m−3 for organics, BC, NH4, SO4, NO3 and Cl, respectively. Particle number concentration was 12 813 ± 5350 cm−3, being a large fraction in the nucleation mode. CCN concentrations were on average 1090 ± 328 cm−3 and 3570 ± 1695 cm−3 at SS = 0.2% and SS = 1.0%, respectively. Results show an increase in aerosol hygroscopicity in the afternoon as a result of aerosol photochemical processing, leading to an enhancement of both organic and inorganic secondary aerosols in the atmosphere, as well as an increase in aerosol average diameter. Considering the bulk composition alone, CCN concentrations were substantially overpredicted (29.6 ± 45.1% at 0.2% supersaturation and 57.3 ± 30.0% at 1.0% supersaturation). Overall, the impact of composition on the calculated NCCN decreases with decreasing supersaturation, partially because using bulk composition introduces less bias for large diameters and lower critical supersaturations. Results suggest that the consideration of only inorganic fraction improves the calculated NCCN. Introducing a size-dependent chemical composition based on filter measurements from previous campaigns has considerably improved simulated values for NCCN (average overprediction error 3.0 ± 33.4% at 0.20% supersaturation and average under prediction error 2.4 ± 20.5% at 1.0% supersaturation). This study provides the first insight on aerosol real-time composition and hygroscopicity on a~site strongly impacted by emissions of a unique vehicular fleet due to the extensive biofuel usage.

scholarly journals Structure-Function Analysis Indicates that an Active-Site Water Molecule Participates in Dimethylsulfoniopropionate Cleavage by DddK

2019 ◽  
Vol 85 (8) ◽  
Author(s):  
Ming Peng ◽  
Xiu-Lan Chen ◽  
Dian Zhang ◽  
Xiu-Juan Wang ◽  
Ning Wang ◽  
...  
Keyword(s):  
Water Molecule ◽  
Active Site ◽  
Dimethyl Sulfide ◽  
Catalytic Mechanism ◽  
Heterotrophic Bacteria ◽  
Function Analysis ◽  
Cloud Condensation Nuclei ◽  
Oxidation Products ◽  
Condensation Nuclei ◽  
Marine Heterotrophic Bacteria

ABSTRACT The osmolyte dimethylsulfoniopropionate (DMSP) is produced in petagram quantities in marine environments and has important roles in global sulfur and carbon cycling. Many marine microorganisms catabolize DMSP via DMSP lyases, generating the climate-active gas dimethyl sulfide (DMS). DMS oxidation products participate in forming cloud condensation nuclei and, thus, may influence weather and climate. SAR11 bacteria are the most abundant marine heterotrophic bacteria; many of them contain the DMSP lyase DddK, and their dddK transcripts are relatively abundant in seawater. In a recently described catalytic mechanism for DddK, Tyr64 is predicted to act as the catalytic base initiating the β-elimination reaction of DMSP. Tyr64 was proposed to be deprotonated by coordination to the metal cofactor or its neighboring His96. To further probe this mechanism, we purified and characterized the DddK protein from Pelagibacter ubique strain HTCC1062 and determined the crystal structures of wild-type DddK and its Y64A and Y122A mutants (bearing a change of Y to A at position 64 or 122, respectively), where the Y122A mutant is complexed with DMSP. The structural and mutational analyses largely support the catalytic role of Tyr64, but not the method of its deprotonation. Our data indicate that an active water molecule in the active site of DddK plays an important role in the deprotonation of Tyr64 and that this is far more likely than coordination to the metal or His96. Sequence alignment and phylogenetic analysis suggest that the proposed catalytic mechanism of DddK has universal significance. Our results provide new mechanistic insights into DddK and enrich our understanding of DMS generation by SAR11 bacteria. IMPORTANCE The climate-active gas dimethyl sulfide (DMS) plays an important role in global sulfur cycling and atmospheric chemistry. DMS is mainly produced through the bacterial cleavage of marine dimethylsulfoniopropionate (DMSP). When released into the atmosphere from the oceans, DMS can be photochemically oxidized into DMSO or sulfate aerosols, which form cloud condensation nuclei that influence the reflectivity of clouds and, thereby, global temperature. SAR11 bacteria are the most abundant marine heterotrophic bacteria, and many of them contain DMSP lyase DddK to cleave DMSP, generating DMS. In this study, based on structural analyses and mutational assays, we revealed the catalytic mechanism of DddK, which has universal significance in SAR11 bacteria. This study provides new insights into the catalytic mechanism of DddK, leading to a better understanding of how SAR11 bacteria generate DMS.

scholarly journals Sensitivity Studies on the Impact of Dust and Aerosol Pollution Acting as Cloud Nucleating Aerosol on Orographic Precipitation in the Colorado River Basin

2018 ◽  
Vol 2018 ◽  
pp. 1-15 ◽  
Author(s):  
Vandana Jha ◽  
William R. Cotton ◽  
Gustavo G. Carrió ◽  
Robert Walko
Keyword(s):  
River Basin ◽  
Colorado River ◽  
Cloud Condensation Nuclei ◽  
Winter Season ◽  
Colorado River Basin ◽  
Orographic Precipitation ◽  
Condensation Nuclei ◽  
Aerosol Pollution ◽  
Sensitivity Studies ◽  
The Impact

In this study, we examine the cumulative effect of pollution aerosol and dust acting as cloud nucleating aerosol;cloud condensation nuclei (CCN), giant cloud condensation nuclei, and ice nuclei (IN), on orographic precipitation in the Rocky Mountains. We analyze the results of sensitivity studies for specific cases in 2004-2005 winter season to analyze the relative impact of aerosol pollution and dust acting as CCN and IN on precipitation in the Colorado River Basin. Dust is varied from 3 to 10 times in the experiments, and the response is found to be nonmonotonic and depends on various environmental factors. The sensitivity studies show that adding dust in a wet system increases precipitation when IN effects are dominant. For a relatively dry system high concentrations of dust can result in overseeding the clouds and reductions in precipitation. However, when adding dust to a system with warmer cloud bases where drizzle formation is active, the response is nonmonotonic.

Acoustic Cloud Condensation Nuclei Counter

2005 ◽  
Author(s):  
Abhijit Deshpande ◽  
Marcellin Zahui
Keyword(s):  
Water Surface ◽  
Cloud Condensation Nuclei ◽  
Droplet Diameter ◽  
Bubble Formation ◽  
Maximum Velocity ◽  
Acoustic Energy ◽  
Water Droplets ◽  
Condensation Nuclei ◽  
Micro Scale ◽  
The Impact

Analysis and simulation of an acoustic cloud condensation nuclei counter is presented. The instrument is capable of accurately counting the number of micro scale water droplets impacting a water surface. The sound produced underwater by the water droplets is determined when the droplets strike the water surface with an impact velocity equal to either their terminal or maximum velocity. First, the terminal velocities of the droplets are calculated using Stoke’s law and compared to measured velocities from Gunn and Kinzer. Then the maximum velocities that these droplets can sustain without breaking are calculated as a function of droplet diameter. Second, the sound due to droplet impact is estimated. Due to their size and water surface tension, there is no bubble formation at impact when the droplets are falling with terminal velocities. However conditions for regular bubble entrainments are established and limit velocities are calculated. Assuming that the micro water droplets can be accelerated, the maximum velocities for no bubble entrainments are calculated. The results show that the level of the sound produced by individual micro scale droplet falling with terminal velocity is so small that experimental verification is not possible. However, reasonable level of acoustic energy can be obtained by increasing the impact velocities of the droplets or by measuring the sound radiated by a group of impacting droplets. Finally, the droplets counting process is simulated using a water surface of one centimeter squared and a vertical growth chamber.

scholarly journals The relative impact of cloud condensation nuclei and ice nucleating particle concentrations on phase partitioning in Arctic mixed-phase stratocumulus clouds

2018 ◽  
Vol 18 (23) ◽  
pp. 17047-17059 ◽  
Author(s):  
Amy Solomon ◽  
Gijs de Boer ◽  
Jessie M. Creamean ◽  
Allison McComiskey ◽  
Matthew D. Shupe ◽  
...  
Keyword(s):  
Cloud Condensation Nuclei ◽  
Mixed Phase ◽  
Radiative Properties ◽  
Condensation Nuclei ◽  
Phase Partitioning ◽  
Cloud Dynamics ◽  
Stratocumulus Clouds ◽  
Cloud Ice ◽  
Mixed Phase Clouds ◽  
The Impact

Abstract. This study investigates the interactions between cloud dynamics and aerosols in idealized large-eddy simulations (LES) of Arctic mixed-phase stratocumulus clouds (AMPS) observed at Oliktok Point, Alaska, in April 2015. This case was chosen because it allows the cloud to form in response to radiative cooling starting from a cloud-free state, rather than requiring the cloud ice and liquid to adjust to an initial cloudy state. Sensitivity studies are used to identify whether there are buffering feedbacks that limit the impact of aerosol perturbations. The results of this study indicate that perturbations in ice nucleating particles (INPs) dominate over cloud condensation nuclei (CCN) perturbations; i.e., an equivalent fractional decrease in CCN and INPs results in an increase in the cloud-top longwave cooling rate, even though the droplet effective radius increases and the cloud emissivity decreases. The dominant effect of ice in the simulated mixed-phase cloud is a thinning rather than a glaciation, causing the mixed-phase clouds to radiate as a grey body and the radiative properties of the cloud to be more sensitive to aerosol perturbations. It is demonstrated that allowing prognostic CCN and INPs causes a layering of the aerosols, with increased concentrations of CCN above cloud top and increased concentrations of INPs at the base of the cloud-driven mixed layer. This layering contributes to the maintenance of the cloud liquid, which drives the dynamics of the cloud system.

scholarly journals Measured and modelled cloud condensation nuclei (CCN) concentration in São Paulo, Brazil: the importance of aerosol size-resolved chemical composition on CCN concentration prediction

2014 ◽  
Vol 14 (14) ◽  
pp. 7559-7572 ◽  
Author(s):  
G. P. Almeida ◽  
J. Brito ◽  
C. A. Morales ◽  
M. F. Andrade ◽  
P. Artaxo
Keyword(s):  
Chemical Composition ◽  
Real Time ◽  
Cloud Condensation Nuclei ◽  
Bulk Composition ◽  
Sao Paulo ◽  
Aerosol Size Distribution ◽  
São Paulo ◽  
Condensation Nuclei ◽  
Kohler Theory ◽  
The Impact

Abstract. Measurements of cloud condensation nuclei (CCN), aerosol size distribution and non-refractory chemical composition were performed from 16 to 31 October 2012 in the São Paulo Metropolitan Area (SPMA), Brazil. CCN measurements were performed at 0.23, 0.45, 0.68, 0.90 and 1.13% water supersaturation and were subsequently compared with the Köhler theory, considering the chemical composition. Real-time chemical composition has been obtained by deploying, for the first time in the SPMA, an aerosol chemical ionization monitor (ACSM). CCN closure analyses were performed considering internal mixtures. Average aerosol composition during the studied period yielded (arithmetic mean~± standard deviation) 4.81 ± 3.05, 3.26 ± 2.10, 0.30 ± 0.27, 0.52 ± 0.32, 0.37 ± 0.21 and 0.04 ± 0.04 μg m−3 for organics, BC, NH4, SO4, NO3 and Cl, respectively. Particle number concentration was 12 813 ± 5350 cm−3, with a dominant nucleation mode. CCN concentrations were on average 1090 ± 328 and 3570 ± 1695 cm−3 at SS = 0.23% and SS = 1.13%, respectively. Results show an increase in aerosol hygroscopicity in the afternoon as a result of aerosol photochemical processing, leading to an enhancement of both organic and inorganic secondary aerosols in the atmosphere, as well as an increase in aerosol average diameter. Considering the bulk composition alone, observed CCN concentrations were substantially overpredicted when compared with the Köhler theory (44.1 ± 47.9% at 0.23% supersaturation and 91.4 ± 40.3% at 1.13% supersaturation). Overall, the impact of composition on the calculated CCN concentration (NCCN) decreases with decreasing supersaturation, partially because using bulk composition introduces less bias for large diameters and lower critical supersaturations, defined as the supersaturation at which the cloud droplet activation will take place. Results suggest that the consideration of only inorganic fraction improves the calculated NCCN. Introducing a size-dependent chemical composition based on filter measurements from previous campaigns has considerably improved simulated values for NCCN (average overprediction error 14.8 ± 38.6% at 0.23% supersaturation and 3.6 ± 21.6% at 1.13% supersaturation). This study provides the first insight on aerosol real-time composition and hygroscopicity at a site strongly impacted by emissions of a unique vehicular fleet due to the extensive biofuel usage.

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