scholarly journals DMS oxidation and sulfur aerosol formation in the marine troposphere: a focus on reactive halogen and multiphase chemistry

2018 ◽  
Author(s):  
Qianjie Chen ◽  
Tomás Sherwen ◽  
Mathew Evans ◽  
Becky Alexander
Keyword(s):  
Gas Phase ◽  
Southern Hemisphere ◽  
Dimethyl Sulfide ◽  
Transport Model ◽  
Sulfur Cycle ◽  
Phase Reaction ◽  
Aerosol Formation ◽  
Cloud Droplets ◽  
Sulfur Chemistry ◽  
Marine Troposphere

Abstract. The oxidation of dimethyl sulfide (DMS) in the troposphere and subsequent chemical conversion into sulfur dioxide (SO2) and methane sulfonic acid (MSA) are key processes for the formation and growth of sulfur-containing aerosol and cloud condensation nuclei (CCN), but is highly simplified in large-scale models of the atmosphere. In this study, we implement a series of gas-phase and multiphase sulfur oxidation mechanisms into the GEOS-Chem global chemical transport model, including two important intermediates dimethyl sulfoxide (DMSO) and methane sulphinic acid (MSIA), to investigate the sulfur cycle in the global marine troposphere. We found that DMS is mainly oxidized in the gas phase by OH (66 %), NO3 (16 %) and BrO (12 %) globally. DMS+BrO is important for the model's ability to reproduce the observed seasonality of surface DMS mixing ratio in the Southern Hemisphere. MSA is mainly produced from multiphase oxidation of MSIA by O3(aq) (69 %) and OH(aq) (25 %) in cloud droplets and aerosols. Aqueous-phase reaction with OH accounts for 38 % of MSA removal globally and is important for the model's ability to reproduce observations of MSA/nssSO42– ratio in the Southern Hemisphere. The modeled conversion yield of DMS into SO2 and MSA is 78 % and 13 %, respectively, compared to 91 % and 9 % in the standard model run that includes only gas-phase oxidation of DMS by OH and NO3. The largest uncertainties for modeling sulfur chemistry in the marine boundary layer (MBL) are unknown concentrations of reactive halogens (BrO and Cl) and OH(aq) concentrations in cloud droplets and aerosols. To reduce uncertainties in MBL sulfur chemistry, we should prioritize observations of reactive halogens and OH(aq).

scholarly journals DMS oxidation and sulfur aerosol formation in the marine troposphere: a focus on reactive halogen and multiphase chemistry

2018 ◽  
Vol 18 (18) ◽  
pp. 13617-13637 ◽  
Author(s):  
Qianjie Chen ◽  
Tomás Sherwen ◽  
Mathew Evans ◽  
Becky Alexander
Keyword(s):  
Gas Phase ◽  
Dimethyl Sulfide ◽  
Transport Model ◽  
Removal Rate ◽  
Sulfur Cycle ◽  
Phase Reaction ◽  
Aerosol Formation ◽  
Cloud Droplets ◽  
Sulfur Chemistry ◽  
Marine Troposphere

Abstract. The oxidation of dimethyl sulfide (DMS) in the troposphere and subsequent chemical conversion into sulfur dioxide (SO2) and methane sulfonic acid (MSA) are key processes for the formation and growth of sulfur-containing aerosol and cloud condensation nuclei (CCN), but are highly simplified in large-scale models of the atmosphere. In this study, we implement a series of gas-phase and multiphase sulfur oxidation mechanisms into the Goddard Earth Observing System-Chemistry (GEOS-Chem) global chemical transport model – including two important intermediates, dimethyl sulfoxide (DMSO) and methane sulphinic acid (MSIA) – to investigate the sulfur cycle in the global marine troposphere. We found that DMS is mainly oxidized in the gas phase by OH (66 %), NO3 (16 %) and BrO (12 %) globally. DMS + BrO is important for the model's ability to reproduce the observed seasonality of surface DMS mixing ratio in the Southern Hemisphere. MSA is mainly produced from multiphase oxidation of MSIA by OH(aq) (66 %) and O3(aq) (30 %) in cloud droplets and aerosols. Aqueous-phase reaction with OH accounts for only 12 % of MSA removal globally, and a higher MSA removal rate is needed to reproduce observations of the MSA ∕ nssSO42- ratio. The modeled conversion yield of DMS into SO2 and MSA is 75 % and 15 %, respectively, compared to 91 % and 9 % in the standard model run that includes only gas-phase oxidation of DMS by OH and NO3. The remaining 10 % of DMS is lost via deposition of intermediates DMSO and MSIA. The largest uncertainties for modeling sulfur chemistry in the marine boundary layer (MBL) are unknown concentrations of reactive halogens (BrO and Cl) and OH(aq) concentrations in cloud droplets and aerosols. To reduce uncertainties in MBL sulfur chemistry, we should prioritize observations of reactive halogens and OH(aq).

scholarly journals Influence of Water on the Gas-Phase Reaction of Dimethyl Sulfide with BrO in the Marine Boundary Layer

ACS Omega ◽  
2021 ◽  
Vol 6 (3) ◽  
pp. 2410-2419
Author(s):  
Junyao Li ◽  
Narcisse T. Tsona ◽  
Shanshan Tang ◽  
Xiuhui Zhang ◽  
Lin Du
Keyword(s):  
Boundary Layer ◽  
Gas Phase ◽  
Dimethyl Sulfide ◽  
Marine Boundary Layer ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Influence Of Water

scholarly journals Description and evaluation of a detailed gas-phase chemistry scheme in the TM5-MP global chemistry transport model (r112)

2020 ◽  
Author(s):  
Stelios Myriokefalitakis ◽  
Nikos Daskalakis ◽  
Angelos Gkouvousis ◽  
Andreas Hilboll ◽  
Twan van Noije ◽  
...  
Keyword(s):  
Gas Phase ◽  
Transport Model ◽  
Vertical Mixing ◽  
Three Dimensional ◽  
Chemical Mechanism ◽  
Aerosol Formation ◽  
Chemistry Transport Model ◽  
Mixing Ratios ◽  
Time Requirements ◽  
Phase Chemistry

Abstract. This work documents and evaluates the tropospheric gas-phase chemical mechanism MOGUNTIA in the three-dimensional chemistry transport model TM5-MP. Compared to the modified CB05 chemical mechanism previously used in the model, the MOGUNTIA includes a detailed representation of the light hydrocarbons (C1-C4) and isoprene, along with a simplified chemistry representation of terpenes and aromatics. Another feature implemented in TM5-MP for this work is the use of the Rosenbrock solver in the chemistry code, which can replace the classical Euler Backward Integration method of the model. Global budgets of ozone (O3), carbon monoxide (CO), hydroxyl radicals (OH), nitrogen oxides (NOX) and volatile organic compounds (VOCs) are here analyzed and their mixing ratios are compared with a series of surface, aircraft and satellite observations for the year 2006. Both mechanisms appear to be able to represent satisfactorily observed mixing ratios of important trace gases, with the MOGUNTIA chemistry configuration yielding lower biases compared to measurements in most of the cases. However, the two chemical mechanisms fail to reproduce the observed mixing ratios of light VOCs, indicating insufficient primary emission source strengths, too weak vertical mixing in the boundary layer, and/or a low bias in the secondary contribution of C2-C3 organics via VOC atmospheric oxidation. Relative computational memory and time requirements of the different model configurations are also compared and discussed. Overall, compared to other chemistry schemes in use in global CTMs, the MOGUNTIA scheme simulates a large suite of oxygenated VOCs that are observed in the atmosphere at significant levels and are involved in aerosol formation, expanding, thus, the applications of TM5-MP.

scholarly journals Dimethyl sulfide in the summertime Arctic atmosphere: measurements and source sensitivity simulations

2016 ◽  
Vol 16 (11) ◽  
pp. 6665-6680 ◽  
Author(s):  
Emma L. Mungall ◽  
Betty Croft ◽  
Martine Lizotte ◽  
Jennie L. Thomas ◽  
Jennifer G. Murphy ◽  
...  
Keyword(s):  
Dimethyl Sulfide ◽  
Transport Model ◽  
Sulfur Cycle ◽  
Oxidation Products ◽  
The Arctic ◽  
High Time Resolution ◽  
Study Region ◽  
Baffin Bay ◽  
Mixing Ratios ◽  
Arctic Atmosphere

Abstract. Dimethyl sulfide (DMS) plays a major role in the global sulfur cycle. In addition, its atmospheric oxidation products contribute to the formation and growth of atmospheric aerosol particles, thereby influencing cloud condensation nuclei (CCN) populations and thus cloud formation. The pristine summertime Arctic atmosphere is strongly influenced by DMS. However, atmospheric DMS mixing ratios have only rarely been measured in the summertime Arctic. During July–August, 2014, we conducted the first high time resolution (10 Hz) DMS mixing ratio measurements for the eastern Canadian Archipelago and Baffin Bay as one component of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments (NETCARE). DMS mixing ratios ranged from below the detection limit of 4 to 1155 pptv (median 186 pptv) during the 21-day shipboard campaign. A transfer velocity parameterization from the literature coupled with coincident atmospheric and seawater DMS measurements yielded air–sea DMS flux estimates ranging from 0.02 to 12 µmol m−2 d−1. Air-mass trajectory analysis using FLEXPART-WRF and sensitivity simulations with the GEOS-Chem chemical transport model indicated that local sources (Lancaster Sound and Baffin Bay) were the dominant contributors to the DMS measured along the 21-day ship track, with episodic transport from the Hudson Bay System. After adjusting GEOS-Chem oceanic DMS values in the region to match measurements, GEOS-Chem reproduced the major features of the measured time series but was biased low overall (2–1006 pptv, median 72 pptv), although within the range of uncertainty of the seawater DMS source. However, during some 1–2 day periods the model underpredicted the measurements by more than an order of magnitude. Sensitivity tests indicated that non-marine sources (lakes, biomass burning, melt ponds, and coastal tundra) could make additional episodic contributions to atmospheric DMS in the study region, although local marine sources of DMS dominated. Our results highlight the need for both atmospheric and seawater DMS data sets with greater spatial and temporal resolution, combined with further investigation of non-marine DMS sources for the Arctic.

scholarly journals Investigating the composition of organic aerosol resulting from cyclohexene ozonolysis: low molecular weight and heterogeneous reaction products

2006 ◽  
Vol 6 (12) ◽  
pp. 4973-4984 ◽  
Author(s):  
J. F. Hamilton ◽  
A. C. Lewis ◽  
J. C. Reynolds ◽  
L. J. Carpenter ◽  
A. Lubben
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Ion Trap ◽  
High Resolution Mass Spectrometry ◽  
Heterogeneous Reaction ◽  
Organic Aerosol ◽  
Tandem Mass ◽  
Phase Reaction ◽  
Reaction Products ◽  
Aerosol Formation

Abstract. The composition of organic aerosol formed from the gas phase ozonolysis of cyclohexene has been investigated in a smog chamber experiment. Comprehensive gas chromatography with time of flight mass spectrometric detection was used to determine that dicarboxylic acids and corresponding cyclic anhydrides dominated the small gas phase reaction products found in aerosol sampled during the first hour after initial aerosol formation. Structural analysis of larger more polar molecules was performed using liquid chromatography with ion trap tandem mass spectrometry. This indicated that the majority of identified organic mass was in dimer form, built up from combinations of the most abundant small acid molecules, with frequent indication of the inclusion of adipic acid. Trimers and tetramers potentially formed via similar acid combinations were also observed in lower abundances. Tandem mass spectral data indicated dimers with either acid anhydride or ester functionalities as the linkage between monomers. High-resolution mass spectrometry identified the molecular formulae of the most abundant dimer species to be C10H16O6, C11H18O6, C10H14O8 and C11H16O8 and could be used in some cases to reduce uncertainty in exact chemical structure determination by tandem MS.

scholarly journals Attribution of modeled atmospheric sulfate and SO<sub>2</sub> in the Northern Hemisphere for June–July 1997

2006 ◽  
Vol 6 (12) ◽  
pp. 4723-4738 ◽  
Author(s):  
C. M. Benkovitz ◽  
S. E. Schwartz ◽  
M. P. Jensen ◽  
M. A. Miller
Keyword(s):  
Gas Phase ◽  
Aqueous Phase ◽  
Northern Hemisphere ◽  
Radiative Forcing ◽  
Transport Model ◽  
Atmospheric Particulate Matter ◽  
Phase Reaction ◽  
Formation Pathway ◽  
Cloud Properties ◽  
June July

Abstract. Anthropogenic sulfate aerosol is a major contributor to shortwave radiative forcing of climate change by direct light scattering and by perturbing cloud properties and to local concentrations of atmospheric particulate matter. Here we analyze results from previously published calculations with an Eulerian transport model for atmospheric sulfur species in the Northern Hemisphere in June–July, 1997 to quantify the absolute and relative contributions of specific source regions (North America, Europe, and Asia) and SO2-to-sulfate conversion mechanisms (gas-phase, aqueous-phase and primary sulfate) to sulfate and SO2 column burdens as a function of location and time. Although material emitted within a given region dominates the sulfate and SO2 column burden in that region, examination of time series at specific locations shows that material imported from outside can make a substantial and occasionally dominant contribution. Frequently the major fraction of these exogenous contributions to the sulfate column burden was present aloft, thus minimally impacting air quality at the surface, but contributing substantially to the burden and, by implication, to radiative forcing and diminution of surface irradiance. Although the dominant sulfate formation pathway in the domain as a whole is aqueous-phase reaction in clouds (62%), in regions with minimum opportunity for aqueous-phase reaction gas-phase oxidation is dominant, albeit with considerable temporal variability depending on meteorological conditions. These calculations highlight the importance of transoceanic transport of sulfate, especially at the western margins of continents under the influence of predominantly westerly transport winds.

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