An official website of the United States government
Abstract. Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methanesulfonic acid (MSA) and sulfuric acid (H2SO4) are well-known natural precursors of atmospheric aerosols, contributing to particle mass and cloud formation over ocean and coastal regions. Despite a long-recognized and well-studied role in the marine troposphere, DMS oxidation chemistry remains a work in progress within many current air quality and climate models, with recent advances exploring heterogeneous chemistry and uncovering previously unknown intermediate species. With the identification of additional DMS oxidation pathways and intermediate species that influence the eventual fate of DMS, it is important to understand the impact of these pathways on the overall sulfate aerosol budget and aerosol size distribution. In this work, we update and evaluate the DMS oxidation mechanism of the chemical transport model GEOS-Chem by implementing expanded DMS oxidation pathways in the model. These updates include gas- and aqueous-phase reactions, the formation of the intermediates dimethyl sulfoxide (DMSO) and methanesulfinic acid (MSIA), and cloud loss and aerosol uptake of the recently quantified intermediate hydroperoxymethyl thioformate (HPMTF). We find that this updated mechanism collectively decreases the global mean surface-layer gas-phase sulfur dioxide (SO2) mixing ratio by 40 % and enhances the sulfate aerosol (SO42-) mixing ratio by 17 %. We further perform sensitivity analyses exploring the contribution of cloud loss and aerosol uptake of HPMTF to the overall sulfur budget. Comparing modeled concentrations to available observations, we find improved biases relative to previous studies. To quantify the impacts of these chemistry updates on global particle size distributions and the mass concentration, we use the TwO-Moment Aerosol Sectional (TOMAS) aerosol microphysics module coupled to GEOS-Chem and find that changes in particle formation and growth affect the size distribution of aerosol. With this new DMS-oxidation scheme, the global annual mean surface-layer number concentration of particles with diameters smaller than 80 nm decreases by 16.8 %, with cloud loss processes related to HPMTF being mostly responsible for this reduction. However, the global annual mean number of particles larger than 80 nm (corresponding to particles capable of acting as cloud condensation nuclei, CCN) increases by 3.8 %, suggesting that the new scheme promotes seasonal particle growth to these sizes.
more »
« less
Impacts of DMS Emissions and Chemistry on E3SMv2 Simulated Cloud Droplet Numbers and Aerosol Concentrations Over the Southern Ocean
Abstract The accurate representation of cloud droplet number concentration (Nd) is crucial for predicting future climate. However, models often underestimate Ndover the Southern Ocean (SO), where natural sources dominate, and aerosols are composed primarily of marine biogenic sulfate and sea spray. This study uses a range of diverse data sets to evaluate and untangle biases in Energy Exascale Earth System Model version 2 (E3SMv2) simulated clouds, aerosols, and sulfur species. The default E3SMv2 underestimates Ndover SO by a factor of 2 when compared with observations in 3 km‐resolution simulations. Updating the dimethyl sulfide (DMS) emission and chemistry leads to a better agreement between the model and the observations in Ndand boundary layer aerosols, but low biases persist in the free tropospheric aerosol concentrations larger than 70 nm, possibly attributable to insufficient particle growth. Furthermore, updates to DMS emissions and chemistry resulted in reduced vertical DMS concentrations and improved the overall agreement between simulated and observed DMS vertical profiles. Preliminary evaluation also reveals remaining biases in simulated sulfur species, including overestimation in DMS at high latitudes, and in simulated sulfate mass concentration, highlighting the necessity for further efforts to improve the model treatment of relevant processes.
more »
« less
- Award ID(s):
- 2124993
- PAR ID:
- 10593780
- Publisher / Repository:
- DOI PREFIX: 10.1029
- Date Published:
- Journal Name:
- Journal of Advances in Modeling Earth Systems
- Volume:
- 17
- Issue:
- 5
- ISSN:
- 1942-2466
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Marine phytoplankton are primary producers in ocean ecosystems and emit dimethyl sulfide (DMS) into the atmosphere. DMS emissions are the largest biological source of atmospheric sulfur and are one of the largest uncertainties in global climate modeling. DMS is oxidized to methanesulfonic acid (MSA), sulfur dioxide, and hydroperoxymethyl thioformate, all of which can be oxidized to sulfate. Ice core records of MSA are used to investigate past DMS emissions but rely on the implicit assumption that the relative yield of oxidation products from DMS remains constant. However, this assumption is uncertain because there are no long-term records that compare MSA to other DMS oxidation products. Here, we share the first long-term record of both MSA and DMS-derived biogenic sulfate concentration in Greenland ice core samples from 1200 to 2006 CE. While MSA declines on average by 0.2 µg S kg–1over the industrial era, biogenic sulfate from DMS increases by 0.8 µg S kg–1. This increasing biogenic sulfate contradicts previous assertions of declining North Atlantic primary productivity inferred from decreasing MSA concentrations in Greenland ice cores over the industrial era. The changing ratio of MSA to biogenic sulfate suggests that trends in MSA could be caused by time-varying atmospheric chemistry and that MSA concentrations alone should not be used to infer past primary productivity.more » « less
-
null (Ed.)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 (SO 2 ) 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 ( τ HPMTF < 2 h) and terminates DMS oxidation to SO 2 . When accounting for HPMTF cloud loss in a global chemical transport model, we show that SO 2 production from DMS is reduced by 35% globally and near-surface (0 to 3 km) SO 2 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.more » « less
-
Abstract Controls on pristine aerosol over the Southern Ocean (SO) are critical for constraining the strength of global aerosol indirect forcing. Observations of summertime SO clouds and aerosols in synoptically varied conditions during the 2018 SOCRATES aircraft campaign reveal novel mechanisms influencing pristine aerosol‐cloud interactions. The SO free troposphere (3–6 km) is characterized by widespread, frequent new particle formation events contributing to much larger concentrations (≥1,000 mg−1) of condensation nuclei (diameters > 0.01 μm) than in typical sub‐tropical regions. Synoptic‐scale uplift in warm conveyor belts and sub‐polar vortices lifts marine biogenic sulfur‐containing gases to free‐tropospheric environments favorable for generating Aitken‐mode aerosol particles (0.01–0.1 μm). Free‐tropospheric Aitken particles subside into the boundary layer, where they grow in size to dominate the sulfur‐based cloud condensation nuclei (CCN) driving SO cloud droplet number concentrations (Nd ∼ 60–100 cm−3). Evidence is presented for a hypothesized Aitken‐buffering mechanism which maintains persistently high summertime SONdagainst precipitation removal through CCN replenishment from activation and growth of boundary layer Aitken particles. Nudged hindcasts from the Community Atmosphere Model (CAM6) are found to underpredict Aitken and accumulation mode aerosols andNd, impacting summertime cloud brightness and aerosol‐cloud interactions and indicating incomplete representations of aerosol mechanisms associated with ocean biology.more » « less
-
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, HOOCH 2 SCHO), 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.more » « less
