Dimethyl Sulfide Oxidation Products Research Articles

Gas-Phase Formation of Sulfurous Acid (H2SO3) in the Atmosphere.

Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical-initiated gas-phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295±0.5 K and 1 bar of air with a molar yield of %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH+CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O+H2SO3) <3×10-18 cm3 molecule-1 s-1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

Gasphasenbildung von Schwefliger Säure (H2SO3) in der Atmosphäre

AbstractSchweflige Säure (H2SO3) ist dafür bekannt, dass sie thermodynamisch instabil ist und in SO2 und H2O zerfällt. Alle Versuche, diese schwer zugängliche Säure in Lösung nachzuweisen, sind bisher gescheitert. Berichte über die Bildung von H2SO3 ausgehend von Experimenten in einem Massenspektrometer sowie Ergebnisse aus theoretischen Berechnungen deuten jedoch auf eine mögliche kinetische Stabilität in der Gasphase hin. Hier wird experimentell gezeigt, dass H2SO3 bei der OH Radikal initiierten Gasphasenoxidation von Methansulfinsäure (CH3S(O)OH) bei 295±0,5 K und 1 bar Luft mit einer molaren Ausbeute von % entsteht. Weitere Hauptprodukte sind SO2, SO3 und Methansulfonsäure. CH3S(O)OH ist ein wichtiges Zwischenprodukt bei der Oxidation von Dimethylsulfid in der Atmosphäre. Globale Modellierungen zeigen eine jährliche H2SO3 Produktion von ∼8 Millionen Tonnen aus der Reaktion OH+CH3S(O)OH. Der untersuchte H2SO3 Zerfall in Anwesenheit von Wasserdampf ergab k(H2O+H2SO3) &lt;3×10−18 cm3 Molekül−1 s−1, was auf eine Lebensdauer von mindestens einer Sekunde für atmosphärische Feuchtebedingungen hinweist. Diese Arbeit liefert den experimentellen Beweis dafür, dass H2SO3 nach seiner Bildung in der Gasphase kinetisch ausreichend stabil ist, um seine Charakterisierung und nachfolgende Reaktionen zu gestatten.

Contribution of expanded marine sulfur chemistry to the seasonal variability of dimethyl sulfide oxidation products and size-resolved sulfate aerosol

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.

Extension, development, and evaluation of the representation of the OH-initiated dimethyl sulfide (DMS) oxidation mechanism in the Master Chemical Mechanism (MCM) v3.3.1 framework

Abstract. Understanding dimethyl sulfide (DMS) oxidation can help us constrain its contribution to Earth's radiative balance. Following the discovery of hydroperoxymethyl thioformate (HPMTF) as a DMS oxidation product, a range of new experimental chamber studies have since improved our knowledge of the oxidation mechanism of DMS and delivered detailed chemical mechanisms. However, these mechanisms have not undergone formal intercomparisons to evaluate their performance. This study aimed to synthesise the recent experimental studies and develop a new, near-explicit, DMS mechanism, through a thorough literature review. A simple box model was then used with the mechanism to simulate a series of chamber experiments and evaluated through comparison with four published mechanisms. Our modelling shows that the mechanism developed in this work outperformed the other mechanisms on average when compared to the experimental chamber data, having the lowest fractional gross error for 8 out of the 14 DMS oxidation products studied. A box model of a marine boundary layer was also run, demonstrating that the deviations in the mechanisms seen when comparing them against chamber data are also prominent under more atmospherically relevant conditions. Although this work demonstrates the need for further experimental work, the mechanism developed in this work has been evaluated against a range of experiments, which validate the mechanism and reduce the bias from individual experiments. Our mechanism provides a good basis for a near-explicit DMS oxidation mechanism that would include other initiation reactions (e.g. halogens) and can be used to compare the performance of reduced mechanisms used in global models.

Atmospheric Gas-Phase Formation of Methanesulfonic Acid.

Despite its impact on the climate, the mechanism of methanesulfonic acid (MSA) formation in the oxidation of dimethyl sulfide (DMS) remains unclear. The DMS + OH reaction is known to form methanesulfinic acid (MSIA), methane sulfenic acid (MSEA), the methylthio radical (CH3S), and hydroperoxymethyl thioformate (HPMTF). Among them, HPMTF reacts further to form SO2 and OCS, while the other three form the CH3SO2 radical. Based on theoretical calculations, we find that the CH3SO2 radical can add O2 to form CH3S(O)2OO, which can react further to form MSA. The branching ratio is highly temperature sensitive, and the MSA yield increases with decreasing temperature. In warmer regions, SO2 is the dominant product of DMS oxidation, while in colder regions, large amounts of MSA can form. Global modeling indicates that the proposed temperature-sensitive MSA formation mechanism leads to a substantial increase in the simulated global atmospheric MSA formation and burden.

Industrial-era decline in Arctic methanesulfonic acid is offset by increased biogenic sulfate aerosol.

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-1 over 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.

Occurrence and emissions of biogenic dimethylated sulfur compounds and their responses to mesoscale eddies and typhoon Yutu in the western tropical Pacific Ocean

The western tropical Pacific Ocean (WTPO) plays a vital role in the global sulfur biogeochemical cycle. Here, an investigation was conducted to explore the spatial variations in biogenic dimethylated sulfur compounds (BDSCs) and their controlling factors in the WTPO in 2018. Dimethylsulfide (DMS) sea-to-air fluxes and the contribution of DMS emissions to the atmospheric sulfate burden were estimated. The concentrations of BDSCs in the surface seawater were low compared to the marginal seas of the western Pacific Ocean, attributed to a limited supply of nutrients and low primary production. Besides, higher values of the BDSCs were observed in surface and subsurface water. The nanophytoplankton was the main dimethylsulfoniopropionate (DMSP) producer, and the abundance of low DMSP and dimethylsulfoxide (DMSO) producers determined the DMSP/O concentrations in the oligotrophic WTPO. Moreover, mixed layer depth might be the crucial factor affecting DMS values. DMS fluxes were low in the WTPO, but they still contributed substantially to global DMS emissions, given the vast areas of the Pacific Ocean. The contribution of biogenic non-sea-salt sulfate (nss-SO42-) to total SO42- reached 25.87%, which showed the oxidation products of DMS were the crucial sources of SO42- in aerosols. Responses of BDSCs to mesoscale eddies and a typhoon were investigated for the first time. The warm eddy increased the concentrations of chlorophyll a (Chl-a) and BDSCs. Nevertheless, no effect of a mesoscale cold eddy on Chl-a or BDSCs was evident. The values of Chl-a, DMS, DMSP, biogenic nss-SO42-, and the DMS fluxes increased after Typhoon Yutu passed, indicating that typhoons play a prominent role in DMS emissions and the global sulfur cycles.

Measurement report: Carbonyl sulfide production during dimethyl sulfide oxidation in the atmospheric simulation chamber SAPHIR

Abstract. Carbonyl sulfide (OCS), the most abundant sulfur gas in the Earth's atmosphere, is a greenhouse gas, a precursor to stratospheric sulfate aerosol, and a proxy for terrestrial CO2 uptake. Estimates of important OCS sources and sinks still have significant uncertainties and the global budget is not considered closed. One particularly uncertain source term, the OCS production during the atmospheric oxidation of dimethyl sulfide (DMS) emitted by the oceans, is addressed by a series of experiments in the atmospheric simulation chamber SAPHIR in conditions comparable to the remote marine atmosphere. DMS oxidation was initiated with OH and/or Cl radicals and DMS, OCS, and several oxidation products and intermediates were measured, including hydroperoxymethyl thioformate (HPMTF), which was recently found to play a key role in DMS oxidation in the marine atmosphere. One important finding is that the onset of HPMTF and OCS formation occurred faster than expected from the current chemical mechanisms. In agreement with other recent studies, OCS yields between 9 % and 12 % were observed in our experiments. Such yields are substantially higher than the 0.7 % yield measured in laboratory experiments in the 1990s, which is generally used to estimate the indirect OCS source from DMS in global budget estimates. However, we do not expect the higher yields found in our experiments to directly translate into a substantially higher OCS source from DMS oxidation in the real atmosphere, where conditions are highly variable, and, as pointed out in recent work, heterogeneous HPMTF loss is expected to effectively limit OCS production via this pathway. Together with other experimental studies, our results will be helpful to further elucidate the DMS oxidation chemical mechanism and in particular the paths leading to OCS formation.

Dimethylated Sulfur, Methane and Aerobic Methane Production in the Yellow Sea and Bohai Sea

AbstractThis paper presents a comprehensive study of biogenic dimethylated sulfur compounds and methane (CH4) from 27 March to 16 April 2018 (spring) and from 24 July to 10 August 2018 (summer) in the Yellow Sea and Bohai Sea. The overall distributions of dimethylsulfide (DMS), dimethylsulfoniopropionate (DMSP, precursor of DMS), dimethylsulfoxide (DMSO, oxidation product of DMS) and CH4 in surface waters were characterized by elevated concentrations in summer and in coastal waters, coupled to phytoplankton biomass and terrestrially sourced inputs. Surface waters were oversaturated with CH4. The flux distributions of DMS and CH4 were generally consistent with their concentration distributions. In situ incubation experiments revealed that microbial consumption was the main removal mechanism for DMS, which could remove up to 72.1% of the total DMS compared to sea‐to‐air exchange in the surface layer. High DMS release and enhanced DMS yields (34%–62%) suggested more obvious influence from high DMSP concentrations (1 or 5 μm L−1) on DMS production in oligotrophic waters with lower bacterial sulfur demand in contrast to near‐shore waters. Positive correlations were found between CH4 and DMSP (dissolved) in summer and DMSO (particulate and dissolved) in spring. A DMSP addition experiment suggested that DMSP could act as a precursor for aerobic methanogenesis, and CH4 preferentially occurs under nitrogen‐stressed conditions in the surface layers of the Yellow Sea and Bohai Sea.

Arctic observations of hydroperoxymethyl thioformate (HPMTF) – seasonal behavior and relationship to other oxidation products of dimethyl sulfide at the Zeppelin Observatory, Svalbard

Abstract. Dimethyl sulfide (DMS), a gas produced by phytoplankton, is the largest source of atmospheric sulfur over marine areas. DMS undergoes oxidation in the atmosphere to form a range of oxidation products, out of which sulfuric acid (SA) is well known for participating in the formation and growth of atmospheric aerosol particles, and the same is also presumed for methanesulfonic acid (MSA). Recently, a new oxidation product of DMS, hydroperoxymethyl thioformate (HPMTF), was discovered and later also measured in the atmosphere. Little is still known about the fate of this compound and its potential to partition into the particle phase. In this study, we present a full year (2020) of concurrent gas- and particle-phase observations of HPMTF, MSA, SA and other DMS oxidation products at the Zeppelin Observatory (Ny-Ålesund, Svalbard) located in the Arctic. This is the first time HPMTF has been measured in Svalbard and attempted to be observed in atmospheric particles. The results show that gas-phase HPMTF concentrations largely follow the same pattern as MSA during the sunlit months (April–September), indicating production of HPMTF around Svalbard. However, HPMTF was not observed in significant amounts in the particle phase, despite high gas-phase levels. Particulate MSA and SA were observed during the sunlit months, although the highest median levels of particulate SA were measured in February, coinciding with the highest gaseous SA levels with assumed anthropogenic origin. We further show that gas- and particle-phase MSA and SA are coupled in May–July, whereas HPMTF lies outside of this correlation due to the low particulate concentrations. These results provide more information about the relationship between HPMTF and other DMS oxidation products, in a part of the world where these have not been explored yet, and about HPMTF's ability to contribute to particle growth and cloud formation.

Revealing the chemical characteristics of Arctic low-level cloud residuals – in situ observations from a mountain site

Abstract. The role aerosol chemical composition plays in Arctic low-level cloud formation is still poorly understood. In this study we address this issue by combining in situ observations of the chemical characteristics of cloud residuals (dried liquid cloud droplets or ice crystals) and aerosol particles from the Zeppelin Observatory in Ny-Ålesund, Svalbard (approx. 480 m a.s.l.). These measurements were part of the 1-year-long Ny-Ålesund Aerosol and Cloud Experiment 2019–2020 (NASCENT). To obtain the chemical composition of cloud residuals at molecular level, we deployed a Filter Inlet for Gases and AEROsols coupled to a Chemical Ionization Mass Spectrometer (FIGAERO-CIMS) with iodide as the reagent ion behind a ground-based counterflow virtual impactor (GCVI). The station was enshrouded in clouds roughly 15 % of the time during NASCENT, out of which we analyzed 14 cloud events between December 2019 and December 2020. During the entire year, the composition of the cloud residuals shows contributions from oxygenated organic compounds, including organonitrates, and traces of the biomass burning tracer levoglucosan. In summer, methanesulfonic acid (MSA), an oxidation product of dimethyl sulfide (DMS), shows large contributions to the sampled mass, indicating marine natural sources of cloud condensation nuclei (CCN) and ice nucleating particle (INP) mass during the sunlit part of the year. In addition, we also find contributions of the inorganic acids nitric acid and sulfuric acid, with outstanding high absolute signals of sulfuric acid in one cloud residual sample in spring and one in late summer (21 May and 12 September 2020), probably caused by high anthropogenic sulfur emissions near the Barents Sea and Kara Sea. During one particular cloud event, on 18 May 2020, the air mass origin did not change before, during, or after the cloud. We therefore chose it as a case study to investigate cloud impact on aerosol physicochemical properties. We show that the overall chemical composition of the organic aerosol particles was similar before, during, and after the cloud, indicating that the particles had already undergone one or several cycles of cloud processing before being measured as residuals at the Zeppelin Observatory and/or that, on the timescales of the observed cloud event, cloud processing of the organic fraction can be neglected. Meanwhile, there were on average fewer particles but relatively more in the accumulation mode after the cloud. Comparing the signals of sulfur-containing compounds of cloud residuals with aerosols during cloud-free conditions, we find that sulfuric acid had a higher relative contribution to the cloud residuals than to aerosols during cloud-free conditions, but we did not observe an increase in particulate MSA due to the cloud. Overall, the chemical composition, especially of the organic fraction of the Arctic cloud residuals, reflected the overall composition of the general aerosol population well. Our results thus suggest that most aerosols can serve as seeds for low-level clouds in the Arctic.

Measurement report: Long-range transport and the fate of dimethyl sulfide oxidation products in the free troposphere derived from observations at the high-altitude research station Chacaltaya (5240 m a.s.l.) in the Bolivian Andes

Abstract. Dimethyl sulfide (DMS) is the primary natural contributor to the atmospheric sulfur burden. Observations concerning the fate of DMS oxidation products after long-range transport in the remote free troposphere are, however, sparse. Here we present quantitative chemical ionization mass spectrometric measurements of DMS and its oxidation products sulfuric acid (H2SO4), methanesulfonic acid (MSA), dimethylsulfoxide (DMSO), dimethylsulfone (DMSO2), methanesulfinic acid (MSIA), methyl thioformate (MTF), methanesulfenic acid (MSEA, CH3SOH), and a compound of the likely structure CH3S(O)2OOH in the gas phase, as well as measurements of the sulfate and methanesulfonate aerosol mass fractions. The measurements were performed at the Global Atmosphere Watch (GAW) station Chacaltaya in the Bolivian Andes located at 5240 m above sea level (a.s.l.). DMS and DMS oxidation products are brought to the Andean high-altitude station by Pacific air masses during the dry season after convective lifting over the remote Pacific ocean to 6000–8000 m a.s.l. and subsequent long-range transport in the free troposphere (FT). Most of the DMS reaching the station is already converted to the rather unreactive sulfur reservoirs DMSO2 in the gas phase and methanesulfonate (MS−) in the particle phase, which carried nearly equal amounts of sulfur to the station. The particulate sulfate at Chacaltaya is however dominated by regional volcanic emissions during the time of the measurement and not significantly affected by the marine air masses. In one of the FT events, even some DMS was observed next to reactive intermediates such as methyl thioformate, dimethylsulfoxide, and methanesulfinic acid. Also for this event, back trajectory calculations show that the air masses came from above the ocean (distance &gt;330 km) with no local surface contacts. This study demonstrates the potential impact of marine DMS emissions on the availability of sulfur-containing vapors in the remote free troposphere far away from the ocean.

Increased oceanic dimethyl sulfide emissions in areas of sea ice retreat inferred from a Greenland ice core

Ocean phytoplankton are an important source of dimethyl sulfide, which influences marine cloud formation. Model studies suggest that declines in Arctic sea ice may lead to increased dimethyl sulfide emissions, however observational support is lacking. Here, we present a 55-year high-resolution ice core record of methane sulfonic acid flux, an oxidation product of dimethyl sulfide, from the southeast Greenland Ice Sheet. We infer temporal variations in ocean dimethyl sulfide emissions and find that springtime (April–June) fluxes of methane sulfonic acid correlate well with satellite-derived chlorophyll-a concentration in the Irminger Sea. Summertime (July–September) methane sulfonic acid fluxes were 3 to 6 times higher between 2002–2014 than 1972–2001. We attribute this to sea ice retreat day becoming earlier and a coincident increase in chlorophyll-a concentration in the adjacent open coastal waters.

Reactive Uptake of Hydroperoxymethyl Thioformate to Sodium Chloride and Sodium Iodide Aerosol Particles.

The oxidation products of dimethyl sulfide (DMS) contribute to the production and growth of cloud condensation nuclei (CCN) in the marine boundary layer. Recent work demonstrates that DMS is oxidized by OH radicals to the stable intermediate hydroperoxymethyl thioformate (HPMTF), which is both globally ubiquitous and efficiently lost to multiphase processes in the marine atmosphere. At present, there are no experimental measurements of the reactive uptake of HPMTF to aerosol particles, limiting model implementation of multiphase HPMTF chemistry. Using an entrained aerosol flow reactor combined with chemical ionization mass spectrometry (CIMS), we measured the reactive uptake coefficient (γ) of HPMTF to dry sodium chloride (NaCl), wet NaCl, and wet sodium iodide (NaI) particles to be (1.9 ± 1.3) × 10-4, (1.6 ± 0.6) × 10-3, and (9.2 ± 2.3) × 10-1, respectively. While we did not directly measure the condensed-phase products of HPMTF reactive uptake in this experiment, the ionization products observed in the CIMS instrument provide mechanistic insight on the reaction mechanism of HPMTF with halides.

The Potential for Great Barrier Reef Regional Climate Regulation via Dimethylsulfide Atmospheric Oxidation Products

Research related to the potential for coral reef-derived dimethylsulfide (DMS) oxidation products to regulate the regional climate of the Great Barrier Reef (GBR) according to the CLAW hypothesis is summarized in this mini review. The GBR has been indicated as a region of high DMS production where atmospheric emissions may be increased when corals are subject to environmental stresses associated with low tide. During low wind speeds over aerially exposed coral reefs, plumes of atmospheric DMS and new sulfate-containing nano-particle production under photo-oxidative conditions have been detected on the GBR. Hygroscopic growth of these particles in combination with coagulation and condensation processes could potentially provide a coral-mediated mechanism of new aerosol for seeding low-level stratocumulus clouds. Fine mode aerosol optical depth over GBR coral reefs has been correlated with low wind speeds and a coral stress metric formulated as a function of irradiance, water clarity, and tide height. This correlation has been proposed as a possible mechanism by which the GBR might alter the optical properties of the overlying atmosphere to attenuate local insolation leading to regional climate regulation. However, recent regional-scale aerosol-climate modeling indicates that the potential for GBR regional climate regulationviaDMS atmospheric oxidation products is weak under current anthropogenic conditions which have instigated mass coral bleaching events along the entire length of the GBR between 1998 and 2022. This increased bleaching indicates that DMS oxidation products are insufficient to regulate the regional climate of the GBR according to the CLAW hypothesis under current global warming conditions.

Modification of the Conversion of Dimethylsulfide to Methanesulfonic Acid by Anthropogenic Pollution as Revealed by Long-Term Observations

Since the CLAW hypothesis was proposed approximately three decades ago, aerosols derived from dimethylsulfide (DMS) conversion have been intensively investigated. In this study, long-term observations were conducted for methanesulfonic acid (MSA), the oxidation product of DMS, from 2008 to 2016 in the marine boundary layer of the Bering Sea. We found that (1) the increase in sea surface temperatures led to increased DMS emissions and MSA concentrations; however, (2) air masses from different sources caused significant differences in the conversion efficiencies of DMS to MSA; and (3) air masses with high O3 and NO2, low relative humidity, temperature, and cloud liquid water path from the northwest Pacific, which were influenced by anthropogenic activities, together inhibited the conversion of DMS to MSA. Among them, O3, T2M, and RH were the principal factors. Conversely, air masses, with contrasting atmospheric environments, from the Arctic Ocean promoted the conversion of DMS to MSA.

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

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.

Large seasonal and interannual variations of biogenic sulfur compounds in the Arctic atmosphere (Svalbard; 78.9° N, 11.9° E)

Abstract. Seasonal to interannual variations in the concentrations of sulfur aerosols (&lt; 2.5 µm in diameter; non sea-salt sulfate: NSS-SO42-; anthropogenic sulfate: Anth-SO42-; biogenic sulfate: Bio-SO42-; methanesulfonic acid: MSA) in the Arctic atmosphere were investigated using measurements of the chemical composition of aerosols collected at Ny-Ålesund, Svalbard (78.9∘ N, 11.9∘ E) from 2015 to 2019. In all measurement years the concentration of NSS-SO42- was highest during the pre-bloom period and rapidly decreased towards summer. During the pre-bloom period we found a strong correlation between NSS-SO42- (sum of Anth-SO42- and Bio-SO42-) and Anth-SO42-. This was because more than 50 % of the NSS-SO42- measured during this period was Anth-SO42-, which originated in northern Europe and was subsequently transported to the Arctic in Arctic haze. Unexpected increases in the concentration of Bio-SO42- aerosols (an oxidation product of dimethylsulfide: DMS) were occasionally found during the pre-bloom period. These probably originated in regions to the south (the North Atlantic Ocean and the Norwegian Sea) rather than in ocean areas in the proximity of Ny-Ålesund. Another oxidation product of DMS is MSA, and the ratio of MSA to Bio-SO42- is extensively used to estimate the total amount of DMS-derived aerosol particles in remote marine environments. The concentration of MSA during the pre-bloom period remained low, primarily because of the greater loss of MSA relative to Bio-SO42- and the suppression of condensation of gaseous MSA onto particles already present in air masses being transported northwards from distant ocean source regions (existing particles). In addition, the low light intensity during the pre-bloom period resulted in a low concentration of photochemically activated oxidant species including OH radicals and BrO; these conditions favored the oxidation pathway of DMS to Bio-SO42- rather than to MSA, which acted to lower the MSA concentration at Ny-Ålesund. The concentration of MSA peaked in May or June and was positively correlated with phytoplankton biomass in the Greenland and Barents seas around Svalbard. As a result, the mean ratio of MSA to the DMS-derived aerosols was low (0.09 ± 0.07) in the pre-bloom period but high (0.32 ± 0.15) in the bloom and post-bloom periods. There was large interannual variability in the ratio of MSA to Bio-SO42- (i.e., 0.24 ± 0.11 in 2017, 0.40 ± 0.14 in 2018, and 0.36 ± 0.14 in 2019) during the bloom and post-bloom periods. This was probably associated with changes in the chemical properties of existing particles, biological activities surrounding the observation site, and air mass transport patterns. Our results indicate that MSA is not a conservative tracer for predicting DMS-derived particles, and the contribution of MSA to the growth of newly formed particles may be much larger during the bloom and post-bloom periods than during the pre-bloom period.

Occurrence and cycle of dimethyl sulfide in the western Pacific Ocean

AbstractOceanic production and occurrence of dimethyl sulfide (DMS) and its subsequent ventilation to the atmosphere significantly contribute to the global sulfur cycle and impact the climate regulation. Spatial distributions of DMS, dimethylsulfoniopropionate (DMSP, precursor of DMS), and dimethyl sulfoxide (DMSO, oxidation product of DMS), production and removal processes of DMS (including biological production, microbial consumption, photo‐degradation, and sea‐to‐air exchange), and biogenic contributions to the atmospheric sulfate burden were simultaneously studied in the western Pacific Ocean during winter. Sea surface DMS, DMSP, and DMSO were strongly correlated and had similar distribution patterns. The DMS photo‐degradation efficiency ratio (normalized using incident photon flux density) for ultraviolet B radiation (UVB): ultraviolet A radiation (UVA): photosynthetically active radiation (PAR) was 391: 36: 1. However, considering the solar spectral composition, the actual contributions of UVB, UVA, and PAR to DMS photo‐degradation in surface waters were 40.6% ± 10.7%, 41.2% ± 15.6%, and 18.2% ± 7.2%, respectively. When integrated across the entire mixed layer, UVA and PAR became the dominant drivers, accounting for 45.2% ± 18.0% and 38.0% ± 17.3% of DMS photo‐degradation, respectively, as UVB was significantly attenuated in seawater. The DMS budget of the entire mixed layer indicated that microbial consumption, photo‐degradation, and ventilation accounted for about 74.3% ± 11.9%, 19.3% ± 9.3%, and 6.5% ± 4.0% of total DMS removal, respectively. Even if ventilation was a minor DMS removal pathway, DMS emissions still contributed approximately 45.2% ± 25.6% of the atmospheric non‐sea‐salt sulfate burden over the western Pacific Ocean.

Long‐Term Trends for Marine Sulfur Aerosol in the Alaskan Arctic and Relationships With Temperature

AbstractMarine aerosol plays a vital role in cloud‐aerosol interactions during summer in the Arctic. The recent rise in temperature and decrease in sea ice extent have the potential to impact marine biogenic sources. Compounds like methanesulfonic acid (MSA) and non‐sea‐salt sulfate (nss‐SO42−), oxidation products of dimethyl sulfide (DMS) emitted by marine primary producers, are likely to increase in concentration. Long‐term studies are vital to understand these changes in marine sulfur aerosol and potential interactions with Arctic climate. Samples were collected over three summers at two coastal sites on the North Slope of Alaska (Utqiaġvik and Oliktok Point). MSA concentrations followed previously reported seasonal trends, with evidence of high marine primary productivity influencing both sites. When added to an additional data set collected at Utqiaġvik, an increase in MSA concentration of + 2.5% per year and an increase in nss‐SO42− of + 2.1% per year are observed for the summer season over the 20‐year record (1998–2017). This study identifies ambient air temperature as a strong factor for MSA, likely related to a combination of interrelated factors including warmer sea surface temperature, reduced sea ice, and temperature‐dependent chemical reactions. Analysis of individual particles at Oliktok Point, within the North Slope of Alaska oil fields, showed evidence of condensation of MSA onto anthropogenic particles, highlighting the connection between marine and oil field emissions and secondary organic aerosol. This study shows the continued importance of understanding MSA in the Arctic while highlighting the need for further research into its seasonal relationship with organic carbon.