scholarly journals Secondary aerosol formation from dimethyl sulfide – improved mechanistic understanding based on smog chamber experiments and modelling

2021 ◽  
Vol 21 (13) ◽  
pp. 9955-9976
Author(s):  
Robin Wollesen de Jonge ◽  
Jonas Elm ◽  
Bernadette Rosati ◽  
Sigurd Christiansen ◽  
Noora Hyttinen ◽  
...  
Keyword(s):  
Dimethyl Sulfide ◽  
Sea Spray ◽  
Smog Chamber ◽  
Marine Atmosphere ◽  
Mass Yield ◽  
Particle Phase ◽  
Secondary Aerosol ◽  
Dms Oxidation ◽  
Aerosol Mass ◽  
Phase Chemistry

Abstract. Dimethyl sulfide (DMS) is the dominant biogenic sulfur compound in the ambient marine atmosphere. Low-volatility acids from DMS oxidation promote the formation and growth of sulfur aerosols and ultimately alter cloud properties and Earth's climate. We studied the OH-initiated oxidation of DMS in the Aarhus University Research on Aerosol (AURA) smog chamber and the marine boundary layer (MBL) with the aerosol dynamics and gas- and particle-phase chemistry kinetic multilayer model ADCHAM. Our work involved the development of a revised and comprehensive multiphase DMS oxidation mechanism, capable of both reproducing smog chamber and atmospheric relevant conditions. The secondary aerosol mass yield in the AURA chamber was found to have a strong dependence on the reaction of methyl sulfinic acid (MSIA) and OH, causing a 82.8 % increase in the total PM at low relative humidity (RH), while the autoxidation of the intermediate radical CH3SCH2OO forming hydroperoxymethyl thioformate (HPMTF) proved important at high temperature and RH, decreasing the total PM by 55.8 %. The observations and modelling strongly support the finding that a liquid water film existed on the Teflon surface of the chamber bag, which enhanced the wall loss of water-soluble intermediates and oxidants dimethyl sulfoxide (DMSO), MSIA, HPMTF, SO2, methanesulfonic acid (MSA), sulfuric acid (SA) and H2O2. The effect caused a 64.8 % and 91.7 % decrease in the secondary aerosol mass yield obtained at both dry (0 % RH–12 % RH) and humid (50 % RH–80 % RH) conditions, respectively. Model runs reproducing the ambient marine atmosphere indicate that OH comprises a strong sink of DMS in the MBL (accounting for 31.1 % of the total sink flux of DMS) although less important than the combined effect of halogen species Cl and BrO (accounting for 24.3 % and 38.7 %, respectively). Cloudy conditions promote the production of SO42- particular mass (PM) from SO2 accumulated in the gas phase, while cloud-free periods facilitate MSA formation in the deliquesced particles. The exclusion of aqueous-phase chemistry lowers the DMS sink as no halogens are activated in the sea spray particles and underestimates the secondary aerosol mass yield by neglecting SO42- and MSA PM production in the particle phase. Overall, this study demonstrated that the current DMS oxidation mechanisms reported in literature are inadequate in reproducing the results obtained in the AURA chamber, whereas the revised chemistry captured the formation, growth and chemical composition of the formed aerosol particles well. Furthermore, we emphasize the importance of OH-initiated oxidation of DMS in the ambient marine atmosphere during conditions with low sea spray emissions.

scholarly journals Secondary aerosol formation from dimethyl sulfide – improved mechanistic understanding based on smog chamber experiments and modelling

2021 ◽  
Author(s):  
Robin Wollesen de Jonge ◽  
Jonas Elm ◽  
Bernadette Rosati ◽  
Sigurd Christiansen ◽  
Noora Hyttinen ◽  
...  
Keyword(s):  
Dimethyl Sulfide ◽  
Sea Spray ◽  
Smog Chamber ◽  
Marine Atmosphere ◽  
Mass Yield ◽  
Particle Phase ◽  
Secondary Aerosol ◽  
Dms Oxidation ◽  
Aerosol Mass ◽  
Phase Chemistry

Abstract. Dimethyl sulfide (DMS) is the dominant biogenic sulphur compound in the ambient atmosphere. Low volatile acids from DMS oxidation promote the formation and growth of sulphur aerosols, and ultimately alter cloud properties and Earth's climate. We studied the OH-initiated oxidation of DMS in the Aarhus University research on aerosols (AURA) smog chamber and the marine boundary layer (MBL) with the aerosol dynamics, gas- and particle-phase chemistry kinetic multilayer model ADCHAM. Our work involved the development of a revised and comprehensive multiphase DMS oxidation mechanism, both capable of reproducing smog chamber and atmospheric relevant conditions. The secondary aerosol mass yield in the AURA chamber was found to have a strong dependence on the reaction of methyl sulfinic acid (MSIA) and OH at low relative humidity (RH), while the autoxidation of the intermediate radical CH3SCH2OO forming hydroperoxymethyl thioformate (HPMTF) proved important at high RH. The observations and modelling strongly support that a liquid water film existed on the Teflon surface of the chamber bag, which enhanced the wall loss of water soluble intermediates and oxidants DMSO, MSIA, HPMTF, SO2, MSA, SA and H2O2. The effect caused a decrease in the secondary aerosol mass yield obtained at both dry (0–12 % RH) and humid (50–80 % RH) conditions. Model runs reproducing the ambient marine atmosphere indicate that OH comprise a strong sink of DMS in the MBL, although less important than halogen species Cl and BrO. Cloudy conditions promote the production of SO42− particular mass (PM) from SO2 accumulated in the gas-phase, while cloud-free periods facilitate MSA formation in the deliquesced particles. The exclusion of aqueous-phase chemistry lowers the DMS sink as no halogens are activated in the sea spray particles, and underestimates the secondary aerosol mass yield by neglecting SO42− and MSA PM production in the particle phase. Overall, this study demonstrated that the current DMS oxidation mechanisms reported in literature are inadequate in reproducing the results obtained in the AURA chamber, whereas the revised chemistry captured the formation, growth and chemical composition of the formed aerosol particles well. Furthermore, we emphasise the importance of OH-initiated oxidation of DMS in the ambient marine atmosphere during conditions with low sea spray emissions.

scholarly journals In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007: implications for gas- and particle-phase chemistry

2009 ◽  
Vol 9 (15) ◽  
pp. 5505-5518 ◽  
Author(s):  
N. C. Bouvier-Brown ◽  
A. H. Goldstein ◽  
J. B. Gilman ◽  
W. C. Kuster ◽  
J. A. de Gouw
Keyword(s):  
Sierra Nevada ◽  
Atmospheric Chemistry ◽  
Ponderosa Pine ◽  
Forest Canopy ◽  
Loss Rate ◽  
Weather Conditions ◽  
Particle Phase ◽  
Aerosol Mass ◽  
Phase Chemistry

Abstract. We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 7.6% to the overall ozone-olefin loss rate above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 6–32% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.1% to the total ozone-olefin loss rate above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.

scholarly journals An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

2016 ◽  
Vol 113 (42) ◽  
pp. 11776-11781 ◽  
Author(s):  
Erik Hans Hoffmann ◽  
Andreas Tilgner ◽  
Roland Schrödner ◽  
Peter Bräuer ◽  
Ralf Wolke ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Dimethyl Sulfide ◽  
Oxidation Products ◽  
Radical Mechanism ◽  
Sulfur Source ◽  
Aerosol Formation ◽  
Detailed Model ◽  
Model Studies ◽  
Dms Oxidation ◽  
Phase Chemistry

Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42−) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions.

scholarly journals In-situ ambient quantification of monoterpenes, sesquiterpenes, and related oxygenated compounds during BEARPEX 2007 – implications for gas- and particle-phase chemistry

2009 ◽  
Vol 9 (2) ◽  
pp. 10235-10269 ◽  
Author(s):  
N. C. Bouvier-Brown ◽  
A. H. Goldstein ◽  
J. B. Gilman ◽  
W. C. Kuster ◽  
J. A. de Gouw
Keyword(s):  
Sierra Nevada ◽  
Atmospheric Chemistry ◽  
Ponderosa Pine ◽  
Forest Canopy ◽  
Weather Conditions ◽  
Particle Phase ◽  
Aerosol Mass ◽  
Phase Chemistry ◽  
Ozone Reactivity

Abstract. We quantified ambient mixing ratios of 9 monoterpenes, 6 sesquiterpenes, methyl chavicol, the oxygenated terpene linalool, and nopinone using an in-situ gas chromatograph with a quadrupole mass spectrometer (GC-MS). These measurements were a part of the 2007 Biosphere Effects on AeRosols and Photochemistry EXperiment (BEARPEX) at Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. To our knowledge, these observations represent the first direct in-situ ambient quantification of the sesquiterpenes α-bergamotene, longifolene, α-farnesene, and β-farnesene. From average diurnal mixing ratio profiles, we show that α-farnesene emissions are dependent mainly on temperature whereas α-bergamotene and β-farnesene emissions are temperature- and light-dependent. The amount of sesquiterpene mass quantified above the canopy was small (averaging a total of 3.3 ppt during the day), but nevertheless these compounds contributed 8.5% to the overall ozone reactivity above the canopy. Assuming that the monoterpene-to-sesquiterpene emission rate in the canopy is similar to that observed in branch enclosure studies at the site during comparable weather conditions, and the average yield of aerosol mass from these sesquiterpenes is 10–50%, the amount of sesquiterpene mass reacted within the Blodgett Forest canopy alone accounts for 8–38% of the total organic aerosol mass measured during BEARPEX. The oxygenated monoterpene linalool was also quantified for the first time at Blodgett Forest. The linalool mass contribution was small (9.9 ppt and 0.74 ppt within and above the canopy, respectively), but it contributed 1.2% to the total ozone reactivity above the canopy. Reactive and semi-volatile compounds, especially sesquiterpenes, significantly impact the gas- and particle-phase chemistry of the atmosphere at Blodgett Forest and should be included in both biogenic volatile organic carbon emission and atmospheric chemistry models.

scholarly journals Exploring DMS oxidation and implications for global aerosol radiative forcing

2021 ◽  
Author(s):  
Ka Ming Fung ◽  
Colette L. Heald ◽  
Jesse H. Kroll ◽  
Siyuan Wang ◽  
Duseong S. Jo ◽  
...  
Keyword(s):  
Gas Phase ◽  
Radiative Forcing ◽  
Dimethyl Sulfide ◽  
Methanesulfonic Acid ◽  
Atmospheric Model ◽  
Cloud Formation ◽  
Aerosol Formation ◽  
Gas Phase Chemistry ◽  
Dms Oxidation ◽  
Phase Chemistry

Abstract. Aerosol indirect radiative forcing (IRF), which characterizes how aerosols alter cloud formation and properties, is very sensitive to the preindustrial (PI) aerosol burden. Dimethyl sulfide (DMS), emitted from the ocean, is a dominant natural precursor of non-sea-salt sulfate in the PI and pristine present-day (PD) atmospheres. Here we revisit the atmospheric oxidation chemistry of DMS, particularly under pristine conditions, and its impact on aerosol IRF. Based on previous laboratory studies, we expand the simplified DMS oxidation scheme used in the Community Atmospheric Model version 6 with chemistry (CAM6-chem) to capture the OH-addition pathway as well as the H-abstraction pathway and the associated isomerization branch. These additional oxidation channels of DMS produce several stable intermediate compounds, e.g., methanesulfonic acid (MSA) and hydroperoxymethyl thioformate (HPMTF), delay the formation of sulfate, and hence, alter the spatial distribution of sulfate aerosol and radiative impacts. The expanded scheme improves the agreement between modeled and observed concentrations of DMS, MSA, HPMTF, and sulfate over most marine regions based on the NASA Atmospheric Tomography (ATom), the Aerosol and Cloud Experiments in the Eastern North Atlantic (ACE-ENA), and the VAMOS Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden, as well as the burden of sulfate produced from DMS oxidation are relatively insensitive to the assumed isomerization rate, but the burden of HPMTF is very sensitive to a potential additional cloud loss. We find that global sulfate burden under PI and PD emissions increase to 412 Gg-S (+29 %) and 582 Gg-S (+8.8 %), respectively, compared to the standard simplified DMS oxidation scheme. The resulting annual mean global PD direct radiative effect of DMS-derived sulfate alone is −0.11  W m−2. The enhanced PI sulfate produced via the gas-phase chemistry updates alone dampens the aerosol IRF as anticipated (−2.2 W m−2 in standard versus −1.7 W m−2 with updated gas-phase chemistry). However, high clouds in the tropics and low clouds in the Southern Ocean appear particularly sensitive to the additional aqueous-phase pathways, counteracting this change (−2.3 W m−2). This study confirms the sensitivity of aerosol IRF to the PI aerosol loading, as well as the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes.

scholarly journals Oceanic phytoplankton are a potentially important source of benzenoids to the remote marine atmosphere

2021 ◽  
Vol 2 (1) ◽  
Author(s):  
Manon Rocco ◽  
Erin Dunne ◽  
Maija Peltola ◽  
Neill Barr ◽  
Jonathan Williams ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Dimethyl Sulfide ◽  
Laboratory Culture ◽  
Marine Phytoplankton ◽  
Marine Atmosphere ◽  
Aerosol Formation ◽  
Incubation Experiments ◽  
Phytoplankton Communities ◽  
Anthropogenic Air Pollutants ◽  
Benzene Toluene

AbstractBenzene, toluene, ethylbenzene and xylenes can contribute to hydroxyl reactivity and secondary aerosol formation in the atmosphere. These aromatic hydrocarbons are typically classified as anthropogenic air pollutants, but there is growing evidence of biogenic sources, such as emissions from plants and phytoplankton. Here we use a series of shipborne measurements of the remote marine atmosphere, seawater mesocosm incubation experiments and phytoplankton laboratory cultures to investigate potential marine biogenic sources of these compounds in the oceanic atmosphere. Laboratory culture experiments confirmed marine phytoplankton are a source of benzene, toluene, ethylbenzene, xylenes and in mesocosm experiments their sea-air fluxes varied between seawater samples containing differing phytoplankton communities. These fluxes were of a similar magnitude or greater than the fluxes of dimethyl sulfide, which is considered to be the key reactive organic species in the marine atmosphere. Benzene, toluene, ethylbenzene, xylenes fluxes were observed to increase under elevated headspace ozone concentration in the mesocosm incubation experiments, indicating that phytoplankton produce these compounds in response to oxidative stress. Our findings suggest that biogenic sources of these gases may be sufficiently strong to influence atmospheric chemistry in some remote ocean regions.

scholarly journals Mapping gaseous amines, ammonia, and their particulate counterparts in marine atmospheres of China’s marginal seas: Part 1 – Differentiating marine emission from continental transport

2021 ◽  
Author(s):  
Dihui Chen ◽  
Yanjie Shen ◽  
Juntao Wang ◽  
Yang Gao ◽  
Huiwang Gao ◽  
...  
Keyword(s):  
Significant Negative Correlation ◽  
The Yellow Sea ◽  
Sea Spray ◽  
Marine Atmosphere ◽  
Coastal Site ◽  
Marginal Seas ◽  
Range Transport ◽  
Order Of Magnitude ◽  
Using Data ◽  
Set Up

Abstract. To study sea-derived gaseous amines, ammonia, and primary particulate aminium ions in the marine atmospheres of China's marginal seas, an onboard URG-9000D Ambient Ion Monitor-Ion chromatography (AIM-IC, Thermo Fisher) was set up on the front deck of the R/V Dongfanghong 3 to semi-continuously measure the spatiotemporal variations in the concentrations of atmospheric trimethylamine (TMAgas), dimethylamine (DMAgas), and ammonia (NH3gas) along with their particulate matter (PM2.5) counterparts. In this study, we differentiated marine emissions of the gas species originating from continental transport using data obtained from December 9 to 22, 2019 during the cruise over the Yellow and Bohai Seas, facilitated by additional measurements collected at a coastal site near the Yellow Sea during summer 2019. The data obtained during the cruise and the coastal site demonstrated that the observed TMAgas and protonated trimethylamine (TMAH+) in PM2.5 over the Yellow and Bohai Seas overwhelmingly originated from marine sources. During the cruise, there was no significant correlation (P > 0.05) between the simultaneously measured TMAH+ and TMAgas concentrations. Additionally, the concentrations of TMAH+ in the marine atmosphere varied around 0.28 ± 0.18 μg m−3 (average  ±  standard deviation), with several episodic hourly average values exceeding 1 μg m−3, which were approximately one order of magnitude larger than those of TMAgas (approximately 0.031 ± 0.009 μg m−3). Moreover, there was a significant negative correlation (P < 0.01) between the concentrations of TMAH+ and NH4+ in PM2.5 during the cruise. Therefore, the observed TMAH+ in PM2.5 was overwhelmingly derived from primary sea-spray aerosols. Using the TMAgas and TMAH+ in PM2.5 as tracers for sea-derived basic gases and sea-spray particulate aminium ions, the values of non-sea-derived DMAgas and NH3gas, as well as non-sea-spray particulate DMAH+ in PM2.5, were estimated, and the estimated average values of each species contributed to 16 %, 34 %, and 65 % of the observed average concentrations, respectively. Uncertainties remained in the estimations as TMAH+ may decompose into smaller molecules in seawater to varying extents. The non-sea-derived gases and non-sea-spray particulate DMAH+ likely originated from long-range transport from the upwind continents, according to the recorded offshore winds and increased concentrations of SO42− and NH4+ in PM2.5. The lack of a detectable increase in the particulate DMAH+, NH4+, and SO42− concentrations in several SO2 plumes did not support the secondary formation of particulate DMAH+ in the marine atmosphere.

scholarly journals Volatility and hygroscopicity of aging secondary organic aerosol in a smog chamber

2011 ◽  
Vol 11 (3) ◽  
pp. 7423-7467 ◽  
Author(s):  
T. Tritscher ◽  
J. Dommen ◽  
P. F. DeCarlo ◽  
P. B. Barmet ◽  
A. P. Praplan ◽  
...  
Keyword(s):  
Volume Fraction ◽  
Organic Aerosol ◽  
Heterogeneous Reactions ◽  
Physical Parameters ◽  
Oh Radicals ◽  
Smog Chamber ◽  
Chemical Aging ◽  
Aerosol Mass ◽  
Gas Phase Oxidation ◽  
Substantial Change

Abstract. The evolution of secondary organic aerosols (SOA) during (photo-)chemical aging processes was investigated in a smog chamber. SOA from 10–40 ppb α-pinene was formed during ozonolysis followed by aging with OH radicals. The particles' volatility and hygroscopicity (expressed as volume fraction remaining (VFR) and hygroscopicity parameter κ) were measured with a volatility and hygroscopicity tandem differential mobility analyzer (V/H-TDMA). These measurements were used as sensitive physical parameters to reveal the possible mechanisms responsible for the chemical changes in the SOA composition during aging: A change of VFR and/or κ during processing of atmospheric aerosol may occur either by addition of SOA mass (by condensation) or by an exchange of molecules in the SOA by other molecules with different properties. The former process increases the SOA mass by definition, while the latter keeps the SOA mass roughly constant and may occur either by heterogeneous reactions on the surface of the SOA particles, by homogeneous reactions like oligomerization or by an evaporation – gas-phase oxidation – recondensation cycle. Thus, when there is a substantial change in the aerosol mass with time, the condensation mechanism may be assumed to be dominant, while, when the mass stays roughly constant the exchange mechanism is likely to be dominant, a process termed ripening here. Depending on the phase of the experiment, an O3 mediated condensation, O3 mediated ripening, OH mediated condensation, and OH mediated ripening could be distinguished. During the O3 mediated condensation the particles volatility decreased (increasing VFR) while the hygroscopicity increased. Thereafter, in the course of O3 mediated ripening volatility continued to decrease, but hygroscopicity stayed roughly constant. After exposing the SOA to OH radicals an OH mediated condensation started with a significant increase of SOA mass. Concurrently, hygroscopicity and volatility increased. This phase was then followed by an OH mediated ripening with a decrease of volatility.

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