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At least 19 records
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Atmospheric measurements of carbonyl sulfide, dimethyl sulfide, and carbon disulfide using the electron capture sulfur detector

Measurements of atmospheric dimethyl sulfide (DMS), carbonyl sulfide (COS), and carbon disulfide (CS2) were conducted over the Atlantic Ocean on board the NASA Electra aircraft during the Chemical Instrumentation Test and Evaluation (CITE 3) project using the electron capture sulfur detector (ECD-S). The system employed cryogenic preconcentration of air samples, gas chromatographic separation, catalytic fluorination, and electron capture detection. Samples collected for DMS analysis were scrubbed of oxidants with NaOH impregnated glass fiber filters to preconcentration. The detection limits (DL) of the system for COS, DMS, and CS2 were 5, 5, and 2 ppt, respectively. COS concentrations ranged from 404 to 603 ppt with a mean of 489 ppt for measurements over the North Atlantic Ocean (31 deg N to 41 deg N), and from 395 to 437 ppt with a mean of 419 ppt for measurements over the Tropical Atlantic Ocean (11 deg S to 2 deg N). DMS concentrations in the lower marine boundary layer, below 600-m altitude, ranged from below DL to 150 ppt from flights over the North Atlantic, and from 9 to 104 ppt over the Tropical Atlantic. CS2 concentrations ranged from below DL to 29 ppt over the North Atlantic. Almost all CS2 measurements over the Tropical Atlantic were below DL.

Johnson, James E.↗
NASA NTRS1993

Operational overview of the NASA GTE/CITE 3 airborne instrument intercomparisons for sulfur dioxide, hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, and carbon disulfide

This paper reports the overall experimental design and gives a brief overview of results from the third airborne Chemical Instrumentation Test and Evaluation (CITE 3) mission conducted as part of the National Aeronautics and Space Administration's Global Tropospheric Experiment. The primary objective of CITE 3 was to evaluate the capability of instrumentation for airborne measurements of ambient concentrations of SO2, H2S, CS, dimethyl sulfide, and carbonyl sulfide. Ancillary measurements augmented the intercomparison data in order to address the secondary objective of CITE 3 which was to address specific issues related to the budget and photochemistry of tropospheric sulfur species. The CITE 3 mission was conducted on NASA's Wallops Flight Center Electra aircraft and included a ground-based intercomparison of sulfur standards and intercomparison/sulfur science flights conducted from the NASA Wallops Flight Facility, Wallops Island, Virginia, followed by flights from Natal, Brazil. Including the transit flights, CITE 3 included 16 flights encompassing approximately 96 flight hours.

Hoell, James M., Jr.↗
NASA NTRS2020

Global Airborne Sampling Reveals a Previously Unobserved Dimethyl Sulfide Oxidation Mechanism in the Marine Atmosphere

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.

DMS gas-phase oxidation product↗
NASA NTRS1976

Absolute rate parameters for the reaction of ground state atomic oxygen with dimethyl sulfide and episulfide

It is pointed out that the investigated reaction of oxygen with dimethyl sulfide may play an important role in photochemical smog formation and in the chemical evolution of dense interstellar clouds. Kinetic data were obtained with the aid of the flash photolysis-resonance fluorescence method. The photodecomposition of molecular oxygen provided the oxygen atoms for the experiments. The decay of atomic oxygen was studied on the basis of resonance fluorescence observations. Both reactions investigated were found to be fast processes. A negative temperature dependence of the rate constants for reactions with dimethyl sulfide was observed.

Lee, J. H.↗
DOE OSTI2024

Chamber studies of OH + dimethyl sulfoxide and dimethyl disulfide: insights into the dimethyl sulfide oxidation mechanism

Abstract. The oxidation of dimethyl sulfide (DMS) in the marine atmosphere represents an important natural source of non-sea-salt sulfate aerosol, but the chemical mechanisms underlying this process remain uncertain. While recent studies have focused on the role of the peroxy radical isomerization channel in DMS oxidation, this work revisits the impact of the other channels (OH addition and OH abstraction followed by bimolecular RO2 reaction) on aerosol formation from DMS. Due to the presence of common intermediate species, the oxidation of dimethyl sulfoxide (DMSO) and dimethyl disulfide (DMDS) can shed light on these two DMS reaction channels; they are also both atmospherically relevant species in their own right. This work examines the OH oxidation of DMSO and DMDS, using chamber experiments monitored by chemical ionization mass spectrometry and aerosol mass spectrometry to study the full range of sulfur-containing products across a range of NO concentrations. The oxidation of both compounds is found to lead to rapid aerosol formation (which does not involve the intermediate formation of SO2), with a substantial fraction (14 %–47 % S yield for DMSO and 5 %–21 % for DMDS) of reacted sulfur ending up in the particle phase and the highest yields observed under elevated NO conditions. Aerosol is observed to consist mainly of sulfate, methanesulfonic acid, and methanesulfinic acid. In the gas phase, the NOx dependence of several products, including SO2 and S2-containing organosulfur species, suggest reaction pathways not included in current mechanisms. Based on the commonalities with the DMS oxidation mechanism, DMSO and DMDS results are used to reconstruct DMS aerosol yields; these reconstructions roughly match DMS aerosol yield measurements from the literature but differ in composition, underscoring remaining uncertainties in sulfur chemistry. This work indicates that both the abstraction and addition channels contribute to rapid aerosol formation from DMS and highlights the need for more study into the fate of small sulfur radical intermediates (e.g., CH3S, CH3SO2, and CH3SO3) that are thought to play central roles in the DMS oxidation mechanism.

Goss, Matthew B. (ORCID:0000000226885463)↗
DOE OSTI2025

Direct Measurements of Dimethyl Sulfide Oxidation Chemistry: Uncovering the Primary Pathways from Gas Phase to Sulfate Aerosols

We report experimental measurements of dimethyl sulfide oxidation, focusing on a major chemical intermediate, hydroperoxymethyl thioformate (HPMTF). The (photo)chemistry and transport properties of HPMTF, which are critical to accurate modeling of tropospheric sulfur, are not known, partly because current analytical methods are not optimized for elusive chemical intermediates. We investigated dimethyl sulfide oxidation using a custom time-resolved photoionization mass spectrometer, interfaced with pulsed laser photolysis, continuous photolysis, and liquid droplet reactors. We detected and characterized HPMTF (along with other reaction intermediates), quantified its yield, and measured its formation rate coefficient. We also developed a clean, intense, online HPMTF source, suitable for further experimental investigations. Lastly, we measured the mass accommodation coefficient of HPMTF on water droplets – a critical quantity for modeling its atmospheric partitioning between the gas and condensed phases. The experimental platform we developed here enables the exploration of other critical elusive reaction intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Airborne measurements of sulfur dioxide, dimethyl sulfide, carbon disulfide, and carbonyl sulfide by isotope dilution gas chromatography/mass spectrometry

A gas chromatograph/mass spectrometer is described for determining atmospheric sulfur dioxide, carbon disulfide, dimethyl sulfide, and carbonyl sulfide from aircraft and ship platforms. Isotopically labelled variants of each analyte were used as internal standards to achieve high precision. The lower limit of detection for each species for an integration time of 3 min was 1 pptv for sulfur dioxide and dimethyl sulfide and 0.2 pptv for carbon disulfide and carbonyl sulfide. All four species were simultaneously determined with a sample frequency of one sample per 6 min or greater. When only one or two species were determined, a frequency of one sample per 4 min was achieved. Because a calibration is included in each sample, no separate calibration sequence was needed. Instrument warmup was only a few minutes. The instrument was very robust in field deployments, requiring little maintenance.

Bandy, Alan R.↗
NASA NTRS1993

Ocean color and atmospheric dimethyl sulfide: On their mesoscale variability

The mesoscale variability of dimethyl sulfide (DMS) and ocean color is explored to determine the feasibility of a predictive relationship. During NASA's Global Tropospheric Experiment/Chemical Instrumentation Test and Evaluation (GTE/CITE 3), simultaneous shipboard and aircraft studies were carried out in the North Atlantic, followed by aircraft studies in the South Atlantic. Surface concentrations of chlorophyll alpha were measured with an airborne spectroradiometer, the Ocean Data Acquisition System (ODAS), with simultaneous determinations of tropospheric DMS. Shipboard measurements of DMS in air and water as well as in situ chlorophyll alpha were taken in the North Atlantic. No relation was observed between shipboard aquatic DMS and chlorophyll alpha or primary productivity. Higher levels of aqueous DMS were not always reflected by atmospheric DMS, although shipboard and aircraft measurements of atmospheric DMS agreed very well. A significant relationship between atmospheric DMS and ocean color was seen once at low altitudes in both the North and South Atlantic only under clean air conditions. Atmospheric DMS levels during the North Atlantic experiment were probably lowered by the presence of mostly polluted air masses in the study area and were, overall, probably not representative of the in situ sea-to-air flux of DMS. Changes in concentration of aircraft-sensed chlorophyllous pigments were not reflected by atmospheric DMS. If a predictive algorithm is to be found, phytoplankton blooms should probably be the first place to study an ocean color-DMS relationship.

Matrai, Patricia A.↗
DOE OSTI2022

Product distribution, kinetics, and aerosol formation from the OH oxidation of dimethyl sulfide under different RO 2 regimes

Abstract. The atmospheric oxidation of dimethyl sulfide (DMS) represents a major natural source of atmospheric sulfate aerosols. However, there remain large uncertainties in our understanding of the underlying chemistry that governs the product distribution and sulfate yield from DMS oxidation. Here, chamber experiments were conducted to simulate gas-phase OH-initiated oxidation of DMS under a range of reaction conditions. Most importantly, the bimolecular lifetime (τbi) of the peroxy radical CH3SCH2OO was varied over several orders of magnitude, enabling the examination of the role of peroxy radical isomerization reactions on product formation. An array of analytical instruments was used to measure nearly all sulfur-containing species in the reaction mixture, and results were compared with a near-explicit chemical mechanism. When relative humidity was low, “sulfur closure” was achieved under both high-NO (τbi<0.1 s) and low-NO (τbi>10 s) conditions, though product distributions were substantially different in the two cases. Under high-NO conditions, approximately half the product sulfur was in the particle phase, as methane sulfonic acid (MSA) and sulfate, with most of the remainder as SO2 (which in the atmosphere would eventually oxidize to sulfate or be lost to deposition). Under low-NO conditions, hydroperoxymethyl thioformate (HPMTF, HOOCH2SCHO), formed from CH3SCH2OO isomerization, dominates the sulfur budget over the course of the experiment, suppressing or delaying the formation of SO2 and particulate matter. The isomerization rate constant of CH3SCH2OO at 295 K is found to be 0.13±0.03 s−1, in broad agreement with other recent laboratory measurements. The rate constants for the OH oxidation of key first-generation oxidation products (HPMTF and methyl thioformate, MTF) were also determined (kOH+HPMTF=2.1×10-11 cm3 molec.−1 s−1, kOH+MTF=1.35×10-11 cm3 molec.−1 s−1). Product measurements agree reasonably well with mechanistic predictions in terms of total sulfur distribution and concentrations of most individual species, though the mechanism overpredicts sulfate and underpredicts MSA under high-NO conditions. Lastly, results from high-relative-humidity conditions suggest efficient heterogenous loss of at least some gas-phase products.

Ye, Qing (ORCID:0000000337978988)↗
DOE OSTI2025

Cloud processing of dimethyl sulfide (DMS) oxidation products limits sulfur dioxide (SO 2 ) and carbonyl sulfide (OCS) production in the eastern North Atlantic marine boundary layer

Dimethyl sulfide (DMS) is the major sulfur species emitted from the ocean. The gas-phase oxidation of DMS by hydroxyl radicals proceeds through the stable, soluble intermediate hydroperoxymethyl thioformate (HPMTF), eventually forming carbonyl sulfide (OCS) and sulfur dioxide (SO 2 ). Recent work has shown that HPMTF is efficiently lost to marine boundary layer (MBL) clouds, thus arresting OCS and SO 2 production and their contributions to new-particle formation and growth events. To date, no long-term field studies exist to assess the extent to which frequent cloud processing impacts the fate of HPMTF. Here, we present 6 weeks of measurements of the cloud fraction and the marine sulfur species methanethiol, DMS, and HPMTF made at the Atmospheric Radiation Measurement (ARM) research facility on Graciosa Island, Azores, Portugal. Using an observationally constrained chemical box model, we determine that cloud loss is the dominant sink of HPMTF in this region of the MBL during the study, accounting for 79 %–91 % of HPMTF loss on average. When accounting for HPMTF uptake to clouds, we calculate campaign average reductions in DMS-derived MBL SO 2 and OCS of 52 %–60 % and 80 %–92 % for the study period. Using yearly measurements of the site- and satellite-measured 3D cloud fraction and DMS climatology, we infer that HPMTF cloud loss is the dominant sink of HPMTF in the eastern North Atlantic during all seasons and occurs on timescales faster than what is prescribed in global chemical transport models. Accurately resolving this rapid loss of HPMTF to clouds has important implications for constraining drivers of MBL new-particle formation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Global ocean dimethyl sulfide climatology estimated from observations and an artificial neural network

Marine dimethyl sulfide (DMS) is important to climate due to the ability of DMS to alter Earth's radiation budget. Knowledge of the global-scale distribution, seasonal variability, and sea-to-air flux of DMS is needed in order to improve understanding of atmospheric sulfur, aerosol/cloud dynamics, and albedo. Here we examine the use of an artificial neural network (ANN) to extrapolate available DMS measurements to the global ocean and produce a global climatology with monthly temporal resolution. A global database of 82 996 ship-based DMS measurements in surface waters was used along with a suite of environmental parameters consisting of latitude–longitude coordinates, time of day, time of year, solar radiation, mixed layer depth, sea surface temperature, salinity, nitrate, phosphate, and silicate. Linear regressions of DMS against the environmental parameters show that on a global-scale mixed layer depth and solar radiation are the strongest predictors of DMS. These parameters capture ~9 % and ~7 % of the raw DMS data variance, respectively. Multilinear regression can capture more of the raw data variance (~39 %) but strongly underestimates DMS in high-concentration regions. In contrast, the artificial neural network captures ~66 % of the raw data variance in our database. Like prior climatologies our results show a strong seasonal cycle in surface ocean DMS with the highest concentrations and sea-to-air fluxes in the high-latitude summertime oceans. We estimate a lower global sea-to-air DMS flux (20.12±0.43 Tg S yr –1 ) than the prior estimate based on a map interpolation method when the same gas transfer velocity parameterization is used. Our sensitivity test results show that DMS concentration does not change unidirectionally with each of the environmental parameters, which emphasizes the interactions among these parameters. The ANN model suggests that the flux of DMS from the ocean to the atmosphere will increase with global warming. Given that larger DMS fluxes induce greater cloud albedo, this corresponds to a negative climate feedback.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2021

Rapid Cloud Removal of Dimethyl Sulfide Oxidation Products Limits SO 2 and Cloud Condensation Nuclei Production in the Marine Atmosphere

Oceans emit large quantities of dimethyl sulfide (DMS) to the marine atmosphere. The oxidation of 60 DMS leads to the formation and growth of cloud condensation nuclei (CCN) with consequent effects on Earth’s radiation balance and climate. 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 towards sulfur dioxide (SO 2 ) and ultimately sulfate aerosol (Veres et al. 2020). Using direct airborne flux measurements, we demonstrate that irreversible loss of HPMTF to clouds in the marine boundary layer determines the HPMTF lifetime (τ HPMTF < 2 hours) and terminates DMS oxidation to SO 2 in the cloudy marine boundary layer. 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 (0-3km) SO 2 concentrations over the ocean are lowered by 24%. This large, previously unconsidered loss process for volatile sulfur accelerates the timescale for 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.

dimethyl sulfide↗
DOE OSTI2024

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

Marine emissions of dimethyl sulfide (DMS) and the subsequent formation of its oxidation products methanesulfonic acid (MSA) and sulfuric acid (H 2 SO 4 ) 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 path ways 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 (SO 2 ) mixing ratio by 40 % and enhances the sulfate aerosol ($SO^{2-}_{4}$) 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.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1992

Environmental factors controlling fluxes of dimethyl sulfide in a New Hampshire fen

The major environmental factors controlling fluxes of dimethyl sulfide (DMS) in a Sphagnum-dominated peatland were investigated in a poor fen in New Hampshire. DMS emissions from the surface of the peatland varied greatly over 24 hours and seasonally. Maximum DMS emissions occurred in summer with minima in the late fall. Temperature was the major environmental factor controlling these variabilities. There was also some evidence that the changes in water table height might have contributed to the seasonable variability in DMS emission. The influence of the water table was greater during periods of elevated temperature. DMS and MSH were the most abundant dissolved volatile sulfur compound (VSC) in the surface of the water table. Concentrations of dissolved VSC's varied with time and space throughout the fen. Dissolved MDS, MSH, and OCS in the surface of the water table were supersaturated with respect to their concentrations in the atmosphere suggesting that the peat surface was a source of VSC's in the peatland. VCS in peatlands seemed to be produced primarily by microbial processes in the anoxic surface layers of the peat rich in organic matter and inorganic sulfide. Sphagnum mosses were not a direct source of VSC's. However, they increased transport of DMS from the peat surface to the atmosphere.

Demello, William Zamboni↗
NASA NTRS1994

Application of static and dynamic enclosures for determining dimethyl sulfide and carbonyl sulfide exchange in Sphagnum peatlands: Implications for the magnitude and direction of flux

A static enclosure method was applied to determine the exchange of dimethyl sulfide (DMS) and carbonyl sulfide (OCS) between the surface of Sphagnum peatlands and the atmosphere. Measurements were performed concurrently with dynamic (flow through) enclosure measurements with sulfur-free air used as sweep gas. This latter technique has been used to acquire the majority of available data on the exchange of S gases between the atmosphere and the continental surfaces and has been criticized because it is thought to overestimate the true flux of gases by disrupting natural S gas gradients. DMS emission rates determined by both methods were not statistically different between 4 and greater than 400 nmol/sq m/h, indicating that previous data on emissions of at least DMS are probably valid. However, the increase in DMS in static enclosures was not linear, indicating the potential for a negative feedback of enlosure DMS concentrations on efflux. The dynamic enclosure method measured positive OCS flux rates (emission) at all sites, while data using static enclosures indicated that OCS was consumed from the atmosphere at these same sites at rates of 3.7 to 55 nmol/sq m/h. Measurements using both enclosure techniques at a site devoid of vegetation showed that peat was a source of both DMS and OCS. However, the rate of OCS efflux from decomposing peat was more than counterbalanced by OCS consumption by vegetation, including Sphagnum mosses, and net OCS uptake occurred at all sites. We propose that all wetlands are net sinks for OCS.

De Mello, William Z.↗
NASA NTRS1993

Measurements of dimethyl sulfide and SO2 during GTE/CITE 3

As part of NASA's Tropospheric Experiment Chemical Instrumentation Test and Evaluation (GTE/CITE 3) Sulfur Gas Intercomparison, we conducted measurements of dimethyl sulfide (DMS) and SO2 using two techniques well suited for sampling from an aircraft due to their simplicity of design. DMS was collected by preconcentration on gold wire preceded by a KOH-impregnated filter oxidant scrubber, and analyzed by gas chromatography with flame photometric detection. SO2 was collected on K2CO3/glycerol-impregnated filters and analyzed by ion chromatography. In blind tests, both techniques produced excellent agreement with National Institutes of Standards and Technology (NIST) standards. For field measurements, the DMS technique produced excellent correlation with the mean of the six different techniques intercompared. For SO2, the five techniques intercompared were rather poorly correlated, but correlations between the three techniques which passed NIST standards tests were somewhat better. Our SO2 filter measurements exhibited rather large uncertainties due to higher than normal variabiltiy of the filter blanks, which we believe was caused by extended storage in the field. In measurements conducted off the coast of Natal, Brazil, a diurnal afternoon minimum in DMS concentrations accompanied by a corresponding maximum in SO2 concentrations was observed. However, due to rather large uncertainties in the SO2 measurements, any conclusions about the SO2 trend must by considered tentative.

Ferek, Ronald J.↗
NASA NTRS1993

An intercomparison of instrumentation for tropospheric measurements of dimethyl sulfide: Aircraft results for concentrations at the parts-per-trillion level

This paper reports results from NASA's Chemical Instrumentation and Test Evaluation (CITE 3) during which airborne measurements of dimethyl sulfide (DMS) from six instruments were intercompared. Represented by the six instruments are three fundamentally different detection principles (flame photometric, mass spectrometric, and electron capture after fluorination); three collection/preconcentration methods (cryogenic, gold wool absorption, and polymer absorbent); and three types of oxidant scrubbers (solid phase alkaline, aqueous reactor, and cotton). The measurements were made over the Atlantic Ocean in August/September 1989 during flights from NASA's Wallops Flight Center, Virginia, and Natal, Brazil. The majority of the intercomparisons are at DMS mixing ratios less than 50 pptv. Results show that instrument agreement is of the order of a few pptv for mixing ratios less than 50 pptv and to within about 15% above 50 pptv. Statistically significant (95% confidence) measurement biases were noted among some of the techniques. However, in all cases, any bias is small and within the accuracy of the measurements and prepared DMS standards. Thus, we conclude that the techniques intercompared during CITE 3 provide equally valid measurements of DMS in the range of a few pptv to 100 pptv (upper range of the intercomparisons).

Gregory, Gerald L.↗
DOE OSTI2022

Exploring dimethyl sulfide (DMS) oxidation and implications for global aerosol radiative forcing

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 and 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 Variability of the American Monsoon Systems (VAMOS) Ocean-Cloud-Atmosphere-Land Study Regional Experiment (VOCALS-REx) measurements. We find that the global HPMTF burden and 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 and the need to better understand the processes controlling aerosol formation in the PI atmosphere and the cloud response to these changes.

54 ENVIRONMENTAL SCIENCES↗