Oxidation Of Dimethyl Sulfide Research Articles

•OH oxidation of methionine in the presence of discrete water molecules: DFT, QTAIM and valence bond analyses

The first steps of the oxidation process of amino acid methionine (Met, CAS 63-68-3) by •OH radicals, leading to Met-OH• adduct and then to Met radical cation, were investigated theoretically over the last few years considering the aqueous environment as a continuum. In this work, following the same procedure that we used for the oxidation of dimethyl sulfide as reported by Domin et al. (J Phys Chem B, 121:9321), discrete water molecules, as well as relative positions, of the •OH radical to Met were taken from molecular dynamics calculations. The presence of water molecules strongly modifies the relative energies of Met-OH adducts and cations when water is properly modeled. Depending on the terminal functional groups and on the position of the •OH radical, several stable structures were found; however, the most stable radical is the N-centered or the S∴N radical cation. QTAIM analysis and valence bond (VB) treatment allowed for the characterization of the 2c∴3e nature of S∴N and S∴OH bonds. VB analysis estimated the probability of the heterolytic rupture of the •OH adduct that is modified by the presence of water molecules.

Significant Underestimation of Gaseous Methanesulfonic Acid (MSA) over Southern Ocean.

Methanesulfonic acid (MSA), derived from the oxidation of dimethylsulfide (DMS), has a significant impact on biogenic sulfur cycle and climate. Gaseous MSA (MSAg) has been often ignored in previous studies due to its quick conversion to particulate MSA (MSAp) and low concentrations. MSAg, MSAp, and nss-SO42- were observed simultaneously for the first time with high-time-resolution (1 h) in the Southern Ocean (SO). The mean MSAg level reached up to 3.3 ± 1.6 pptv, ranging from ∼24.5 pptv in the SO, contributing to 31% ± 3% to the total MSA (MSAT). A reduction of the MSA to nss-SO42- ratios by about 30% was obtained when MSAg was not accounted for in the calculation, indicating that MSAg was very important in the assessment of the biogenic sulfur contributions in the atmosphere. Mass ratios of MSA to nss-SO42- increased first and then decreased with the temperature from -10 to 5 °C, with a maximum value at the temperature of -3 °C. Positive correlations between MSAg to MSAT ratios and temperature were presented, when the temperature was higher than 5 °C. This study highlights the importance of MSAg for understanding the atmospheric DMS oxidation mechanism and extends the knowledge of MSA formation in the marine atmosphere.

Hypobromous Acid as an Unaccounted Sink for Marine Dimethyl Sulfide?

Marine emissions of dimethyl sulfide (DMS) to the atmosphere play a fundamental role in the global sulfur (S) cycle and have important consequences for the Earth's radiative balance. In the ocean, DMS is mainly produced by marine algae and bacteria via cleavage of the precursor compound dimethylsulfoniopropionate (DMSP). Here, we studied the reaction between DMS and the strong oxidant hypobromous acid (HOBr), which is also produced by marine algae. Further, reactions between DMS oxidation products and HOBr were studied. The second-order rate constants were determined in competition kinetic experiments using sulfite as a competitor. In addition, we developed a new HPLC-ICP-MS/MS method to identify and quantify the oxidation products of DMS and related compounds. We found that HOBr reacts very fast with DMS to dimethyl sulfoxide (DMSO), with a second-order rate constant of 1.6 × 109 M-1 s-1, while the subsequent oxidation of DMSO to dimethyl sulfone (DMSO2) is much slower (0.4 M-1 s-1). Concentrations of DMSP, DMSO2, and methanesulfonic acid (MSA) did not decrease when exposed to excess concentrations of HOBr, implying that these S-containing compounds are not or only slightly reactive toward HOBr. A quantitative comparison of known DMS sinks shows that HOBr may be an important, hitherto neglected sink for marine DMS that needs to be considered in ocean-atmosphere chemistry models.

Decadal increase in Arctic dimethylsulfide emission

Dimethylsulfide (DMS), a gas produced by marine microbial food webs, promotes aerosol formation in pristine atmospheres, altering cloud radiative forcing and precipitation. Recent studies suggest that DMS controls aerosol formation in the summertime Arctic atmosphere and call for an assessment of pan-Arctic DMS emission (EDMS) in a context of dramatic ecosystem changes. Using a remote sensing algorithm, we show that summertime EDMS from ice-free waters increased at a mean rate of 13.3 ± 6.7 Gg S decade-1 (∼33% decade-1) north of 70°N between 1998 and 2016. This trend, mostly explained by the reduction in sea-ice extent, is consistent with independent atmospheric measurements showing an increasing trend of methane sulfonic acid, a DMS oxidation product. Extrapolation to an ice-free Arctic summer could imply a 2.4-fold (±1.2) increase in EDMS compared to present emission. However, unexpected regime shifts in Arctic geo- and ecosystems could result in future EDMS departure from the predicted range. Superimposed on the positive trend, EDMS shows substantial interannual changes and nonmonotonic multiyear trends, reflecting the interplay between physical forcing, ice retreat patterns, and phytoplankton productivity. Our results provide key constraints to determine whether increasing marine sulfur emissions, and resulting aerosol-cloud interactions, will moderate or accelerate Arctic warming in the context of sea-ice retreat and increasing low-level cloud cover.

Characterization of aerosol growth events over Ellesmere Island during the summers of 2015 and 2016

Abstract. The occurrence of frequent aerosol nucleation and growth events in the Arctic during summertime may impact the region's climate through increasing the number of cloud condensation nuclei in the Arctic atmosphere. Measurements of aerosol size distributions and aerosol composition were taken during the summers of 2015 and 2016 at Eureka and Alert on Ellesmere Island in Nunavut, Canada. These results provide a better understanding of the frequency and spatial extent of elevated Aitken mode aerosol concentrations as well as of the composition and sources of aerosol mass during particle growth. Frequent appearances of small particles followed by growth occurred throughout the summer. These particle growth events were observed beginning in June with the melting of the sea ice rather than with the polar sunrise, which strongly suggests that influence from the marine boundary layer was the primary cause of the events. Correlated particle growth events at the two sites, separated by 480 km, indicate conditions existing over large scales play a key role in determining the timing and the characteristics of the events. In addition, aerosol mass spectrometry measurements were used to analyze the size-resolved chemical composition of aerosols during two selected growth events. It was found that particles with diameters between 50 and 80 nm (physical diameter) during these growth events were predominately organic with only a small sulfate contribution. The oxidation of the organics also changed with particle size, with the fraction of organic acids increasing with diameter from 80 to 400 nm. The growth events at Eureka were observed most often when the temperature inversion between the sea and the measurement site (at 610 m a.s.l.) was non-existent or weak, presumably creating conditions with low aerosol condensation sink and allowing fresh marine emissions to be mixed upward to the observatory's altitude. While the nature of the gaseous precursors responsible for the growth events is still poorly understood, oxidation of dimethyl sulfide alone to produce particle-phase sulfate or methanesulfonic acid was inconsistent with the measured aerosol composition, suggesting the importance of other gas-phase organic compounds condensing for particle growth.

Abatement of dimethyl sulfide using anoxic biotrickling filter

AbstractBACKGROUNDThis study aimed to use a lab‐scale anoxic biotrickling filter (ABTF) for the bioconversion of dimethyl sulfide (DMS) gas to produce less harmful byproducts, i.e. elemental sulfur and/or sulfate. It examined the exploitation of nitrate as an electron acceptor in the oxidation of malodorous DMS‐containing gas in combination with other parameters: gas/liquid (G/L) ratio (40, 60, 80, 100, 150), empty bed residence time (EBRT) (10, 30, 60, 90, 120 s) and inlet loading (IL) (9, 18, 48, 90 g m−3 h−1).RESULTSThermodynamic analysis and half‐reactions showed that at DMS/NO3− molar yield ratios 0.75 and 0.34, elemental sulfur and sulfate were the main metabolic products respectively. Overall, 58% of the sulfur element in DMS was bioconverted to elemental sulfur. Mass balance calculations revealed high denitrification efficiency, i.e. 52.7% of inlet NO3− was converted to N2. The optimal EBRT was found as 30 s (corresponding to removal efficiency (RE) 89%) for inlet concentration 150 mg m−3 and as 60 s (corresponding to RE 78%) for inlet concentration 1500 mg m−3. However, the maximum elimination capacity (EC) was 70.3 g m−3 h−1 at EBRT 60 s and G/L ratio 80. The relative abundance of bacterial communities was dominated by Proteobacteria (56.1%) and Alphaproteobacteria (27.3%) at phylum and class levels respectively.CONCLUSIONThe study revealed that ABTF has a reliable biodegradation capacity in DMS oxidation under anoxic conditions; however, process improvement on mass transfer enhancement for low waste gas concentrations is still required. © 2019 Society of Chemical Industry

The potential role of methanesulfonic acid (MSA) in aerosol formation and growth and the associated radiative forcings

Abstract. Atmospheric marine aerosol particles impact Earth's albedo and climate. These particles can be primary or secondary and come from a variety of sources, including sea salt, dissolved organic matter, volatile organic compounds, and sulfur-containing compounds. Dimethylsulfide (DMS) marine emissions contribute greatly to the global biogenic sulfur budget, and its oxidation products can contribute to aerosol mass, specifically as sulfuric acid and methanesulfonic acid (MSA). Further, sulfuric acid is a known nucleating compound, and MSA may be able to participate in nucleation when bases are available. As DMS emissions, and thus MSA and sulfuric acid from DMS oxidation, may have changed since pre-industrial times and may change in a warming climate, it is important to characterize and constrain the climate impacts of both species. Currently, global models that simulate aerosol size distributions include contributions of sulfate and sulfuric acid from DMS oxidation, but to our knowledge, global models typically neglect the impact of MSA on size distributions. In this study, we use the GEOS-Chem-TOMAS (GC-TOMAS) global aerosol microphysics model to determine the impact on aerosol size distributions and subsequent aerosol radiative effects from including MSA in the size-resolved portion of the model. The effective equilibrium vapor pressure of MSA is currently uncertain, and we use the Extended Aerosol Inorganics Model (E-AIM) to build a parameterization for GC-TOMAS of MSA's effective volatility as a function of temperature, relative humidity, and available gas-phase bases, allowing MSA to condense as an ideally nonvolatile or semivolatile species or too volatile to condense. We also present two limiting cases for MSA's volatility, assuming that MSA is always ideally nonvolatile (irreversible condensation) or that MSA is always ideally semivolatile (quasi-equilibrium condensation but still irreversible condensation). We further present simulations in which MSA participates in binary and ternary nucleation with the same efficacy as sulfuric acid whenever MSA is treated as ideally nonvolatile. When using the volatility parameterization described above (both with and without nucleation), including MSA in the model changes the global annual averages at 900 hPa of submicron aerosol mass by 1.2 %, N3 (number concentration of particles greater than 3 nm in diameter) by −3.9 % (non-nucleating) or 112.5 % (nucleating), N80 by 0.8 % (non-nucleating) or 2.1 % (nucleating), the cloud-albedo aerosol indirect effect (AIE) by −8.6 mW m−2 (non-nucleating) or −26 mW m−2 (nucleating), and the direct radiative effect (DRE) by −15 mW m−2 (non-nucleating) or −14 mW m−2 (nucleating). The sulfate and sulfuric acid from DMS oxidation produces 4–6 times more submicron mass than MSA does, leading to an ∼10 times stronger cooling effect in the DRE. But the changes in N80 are comparable between the contributions from MSA and from DMS-derived sulfate/sulfuric acid, leading to comparable changes in the cloud-albedo AIE. Model–measurement comparisons with the Heintzenberg et al. (2000) dataset over the Southern Ocean indicate that the default model has a missing source or sources of ultrafine particles: the cases in which MSA participates in nucleation (thus increasing ultrafine number) most closely match the Heintzenberg distributions, but we cannot conclude nucleation from MSA is the correct reason for improvement. Model–measurement comparisons with particle-phase MSA observed with a customized Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS) from the ATom campaign show that cases with the MSA volatility parameterizations (both with and without nucleation) tend to fit the measurements the best (as this is the first use of MSA measurements from ATom, we provide a detailed description of these measurements and their calibration). However, no one model sensitivity case shows the best model–measurement agreement for both Heintzenberg and the ATom campaigns. As there are uncertainties in both MSA's behavior (nucleation and condensation) and the DMS emissions inventory, further studies on both fronts are needed to better constrain MSA's past, current, and future impacts upon the global aerosol size distribution and radiative forcing.

Understanding the oxidation mechanism of methanesulfinic acid by ozone in the atmosphere

Methanesulfinic acid (MSIA) is an important intermediate in the oxidation of dimethyl sulfide (DMS) in the marine boundary layer. The oxidation of MSIA by ozone in the gas phase to form methanesulfonic acid (MSA) was investigated using theoretical calculations in this paper. Three pathways can be found for the reaction of MSIA with ozone. The highest energy barrier is 13.02 kcal mol−1 in the most favorable pathway. By comparing the reaction rate of MSIA + O3 with that of MSIA + OH, it can be concluded that the oxidation of MSIA by O3 to form MSA is of minor significance relative to its oxidation by OH radical in the gas phase. This study can provide some information for the theoretical and experimental studies in the significantly heterogeneous and aqueous-phase oxidation of MSIA by O3.

The Flux and Emission of Dimethylsulfide From the Great Barrier Reef Region and Potential Influence on the Climate of NE Australia

AbstractConcentrations of dimethylsulfoniopropionate (DMSP), dimethylsulfide (DMS), and DMS flux are reported for the Great Barrier Reef (GBR), Great Barrier Reef Lagoon (GBRL), and Coral Sea. Generally higher concentrations of dimethylsulfoniopropionate and DMS occurred in coral reef waters, compared with GBRL concentrations. DMS flux from GBR coral reefs in summer ranged from nondetectable to 153 μmol m−2 d−1 (mean 6.4), while winter fluxes ranged from 0.02 to 15 μmol m−2 d−1 (mean 2.4). No significant seasonal difference in DMS flux occurred for the GBRL. High DMSw concentrations and DMS fluxes periodically occur at coral reefs during very low tides and elevated sea surface temperatures (SSTs). For the GBRL and GBR coral reefs there was a significant correlation between seawater DMSw concentrations and SST (p < 0.001), up to temperatures of 30 °C. During coral bleaching DMS flux from reefs almost completely shuts down when SSTs are >30 °C. The GBRL and associated coral reefs emit 439 and 32 MmolS per year, respectively. Cyclones on average produce 170 MmolS to the GBR atmosphere in summer. This amount can markedly increase during severe cyclones such as severe tropical Cyclone Debbie in March 2017. Overall, the annual DMS emission estimate from the GBRL and coral reefs in the GBR is 0.64 GmolS, with cyclones contributing 27% or greater of the annual emission estimate, depending on the cyclone intensity. Oxidation of atmospheric DMS can potentially affect solar radiation, SSTs, low‐level cloud cover, and rainfall causing cooling and warming of the climate in the GBR region as recent modeling predicts.

Source apportionment of the organic aerosol over the Atlantic Ocean from 53° N to 53° S: significant contributions from marine emissions and long-range transport

Abstract. Marine aerosol particles are an important part of the natural aerosol systems and might have a significant impact on the global climate and biological cycle. It is widely accepted that truly pristine marine conditions are difficult to find over the ocean. However, the influence of continental and anthropogenic emissions on the marine boundary layer (MBL) aerosol is still less understood and non-quantitative, causing uncertainties in the estimation of the climate effect of marine aerosols. This study presents a detailed chemical characterization of the MBL aerosol as well as the source apportionment of the organic aerosol (OA) composition. The data set covers the Atlantic Ocean from 53∘ N to 53∘ S, based on four open-ocean cruises in 2011 and 2012. The aerosol particle composition was measured with a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which indicated that sub-micrometer aerosol particles over the Atlantic Ocean are mainly composed of sulfates (50 % of the particle mass concentration), organics (21 %) and sea salt (12 %). OA has been apportioned into five factors, including three factors linked to marine sources and two with continental and/or anthropogenic origins. The marine oxygenated OA (MOOA, 16 % of the total OA mass) and marine nitrogen-containing OA (MNOA, 16 %) are identified as marine secondary products with gaseous biogenic precursors dimethyl sulfide (DMS) or amines. Marine hydrocarbon-like OA (MHOA, 19 %) was attributed to the primary emissions from the Atlantic Ocean. The factor for the anthropogenic oxygenated OA (Anth-OOA, 19 %) is related to continental long-range transport. Represented by the combustion oxygenated OA (Comb-OOA), aged combustion emissions from maritime traffic and wild fires in Africa contributed, on average, a large fraction to the total OA mass (30 %). This study provides the important finding that long-range transport was found to contribute averagely 49 % of the submicron OA mass over the Atlantic Ocean. This is almost equal to that from marine sources (51 %). Furthermore, a detailed latitudinal distribution of OA source contributions showed that DMS oxidation contributed markedly to the OA over the South Atlantic during spring, while continental-related long-range transport largely influenced the marine atmosphere near Europe and western and central Africa (15∘ N to 15∘ S). In addition, supported by a solid correlation between marine tracer methanesulfonic acid (MSA) and the DMS-oxidation OA (MOOA, R2>0.85), this study suggests that the DMS-related secondary organic aerosol (SOA) over the Atlantic Ocean could be estimated by MSA and a scaling factor of 1.79, especially in spring.

Crystal structure of the dimethylsulfide monooxygenase DmoA from Hyphomicrobium sulfonivorans.

DmoA is a monooxygenase which uses dioxygen (O2) and reduced flavin mononucleotide (FMNH2) to catalyze the oxidation of dimethylsulfide (DMS). Although it has been characterized, the structure of DmoA remains unknown. Here, the crystal structure of DmoA was determined to a resolution of 2.28 Å and was compared with those of its homologues LadA and BdsA. The results showed that their overall structures are similar: they all share a conserved TIM-barrel fold which is composed of eight α-helices and eight β-strands. In addition, they all have five additional insertions. Detailed comparison showed that the structures have notable differences despite their high sequence similarity. The substrate-binding pocket of DmoA is smaller compared with those of LadA and BdsA.

Characterization of submicron aerosol chemical composition and sources in the coastal area of Central Chile

Chemical characteristics and the sources of submicron particles (<1 μm in diameter) were investigated in Valle Alegre, the coastal area of Central Chile. The chemical composition of particles was studied by using a Soot particle Aerosol Mass Spectrometer and Multi-Angle Absorption Photometer. Submicron particles were dominated by organics (42% of mass) and sulfate (39% of mass) while the mass fractions of ammonium, nitrate and black carbon were much smaller (13, 2 and 4% of mass, respectively). Additionally, several metals (V, Zn, Fe, Cd, Cu, K, Na and Mg) were detected in submicron particles and also some of their inorganic salts (e.g. NaCl+, MgCl2+, CaCl2+, KCl+ and KNO3+). The sources of particles were examined by using Positive Matrix Factorization (PMF). Organic aerosol (OA) was divided into five factors by using PMF; hydrocarbon-like OA (HOA), biomass burning OA (BBOA), low-volatility oxygenated OA (LV-OOA), semi-volatile OA (SV-OOA) and marine oxygenated OOA (MOOA). Oxygenated factors (LV-OOA; SV-OOA and MOOA) comprised 75% of total OA with LV-OOA being the dominant factor (38% of OA). Sulfate had two major sources in Valle Alegre; ∼70% of sulfate was related to anthropogenic sources through the oxidation of gas phase SO2 whereas ∼24% of sulfate was associated with biogenic origin related to the oxidation of dimethyl sulfide in the marine environment. Regarding total submicron particle mass (campaign-average 9.5 μg m−3), the contribution of anthropogenic sources was at least as large as that of biogenic origin.

Dissolved and Particulate Dimethylsulfoxide in the South China Sea During Winter

The distributions of particulate and dissolved dimethylsulfoxide (DMSOp, DMSOd) were studied for the first time in the surface water of the South China Sea (SCS) in January 2010. The concentrations of DMSOp ranged from 2.6 to 56.8 nmol L−1 with an average of 11.1 ± 2.2 nmol L−1, and those of DMSOd ranged from 11.8 to 335.1 nmol L−1 with an average of 50.0 ± 16.5 nmol L−1. DMSOd dominated over both dimethylsulfide (DMS) and dissolved dimethylsulfoniopropionate (DMSPd) by 1–3 orders of magnitude and represented the major dissolved dimethyl sulfur pool. In addition, DMSOp/chlorophyll-a ratios varied from 2.7 to 180.7 mmol g−1 with an average of 30.5 ± 9.6 mmol g−1. DMSOd concentrations displayed a significant negative relationship with sea surface temperature (SST) and sea surfaces salinity (SSS) in the whole study area. The distribution of DMSOd in the coastal waters was obviously influenced by the Pearl River discharge, with high concentrations appearing around the river mouth. In the offshore waters, a significant correlation was observed between the DMSOp and DMSOd concentrations, suggesting that DMSOd was mainly from the diffusion of intracellular DMSO rather than from the photochemical and biological oxidation of DMS.

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

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).

Effect of Malt-Derived Potential Antioxidants on Dimethyl Sulfide Oxidation.

During malt kilning, dimethyl sulfide (DMS) is partly oxidized to dimethyl sulfoxide (DMSO), which can be reduced by yeast to generate DMS during fermentation. The aim of this study was to test the effect of malt-derived potential antioxidants on DMS oxidation and to assess their applicability for DMSO minimization. In the presence of 18 μM copper, all tested antioxidants (250 μM) catalyzed DMS oxidation to deviating extents (sulfite > ascorbic acid (Asco) > gallic acid (GA) > L-cysteine (Cys) > L-glutathione (GSH)). Hydrogen peroxide was found as primary DMS oxidant for each substance except for sulfite. Electron spin resonance spectroscopy provided evidence for the formation of bisulfite radicals and peroxymonosulfate radicals, which are proposed as being capable of exhaustive DMS oxidation (∼100%) over a wide concentration. The data demonstrate that use of antioxidants per se cannot be suggested for the minimization of DMSO formation in malt and other foodstuffs. Potential shifts from pro- to antioxidative behavior of antioxidants and their implications on malt quality are discussed.

Investigation of reactive oxygen species produced by microwave electrodeless discharge lamp on oxidation of dimethyl sulfide

Microwave electrodeless discharge lamp (MEDL) has been regarded as a powerful light source of photoreaction. Four kinds of chemicals, nitrogen (N2), oxygen (O2), water (H2O) and dimethyl sulfide (DMS), were used as molecular probes to explore the generation process of reactive oxygen species (ROS) and their photo-oxidation performances on the photodegradation of organic pollutants with application of an exterior MEDL system. ROS such as O (3P), O3, O (1D) and 1O2 were generated via irradiation of O2 and H2O except dry N2 by MEDL. They were transformed to other ROS including ·OH and H2O2 with increase of relative humidity. The ROS productivity was inhibited evidently by humidity and ·OH became the major active species at high humidity. An optimal mineralization rate of 23.6% for DMS photodegradation was reached in dry air compared with 8.74% at high humidity, which indicated that O (1D) and 1O2 were more powerful oxidants than O3 and OH. The results showed that the higher mineralization rate of organic pollutants was obtained by increasing the generation efficiency of ROS of O (1D) and 1O2. Furthermore, the results provided an alternative to develop intensification technology on photodegadation of organic pollutants with MEDL system and an optimal operation process including photocatalyst and humidity.

Chemical Transformation of Methanesulfonic Acid and Sodium Methanesulfonate through Heterogeneous OH Oxidation

Methanesulfonic acid (CH3SO3H, MSA) is one of the major organosulfur acids formed from the photochemical oxidation of dimethyl sulfide (DMS) produced by oceanic phytoplankton. MSA can react with metal halides (e.g., sodium chloride) in ambient aerosols to form methanesulfonate salts (e.g., sodium methanesulfonate, CH3SO3Na). While the formation processes of MSA and its salts are reasonably well understood, their subsequent chemical transformations in the atmosphere are not fully resolved. MSA and its salts accumulate near the aerosol surface due to their surface activities, which make them available to heterogeneous oxidation at the gas–aerosol interface by oxidants such as hydroxyl (OH) radicals. In this work, the compositional changes of aerosol comprised of MSA and its sodium salt (CH3SO3Na) are measured following heterogeneous OH oxidation. An aerosol flow tube reactor is coupled with a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART) and a high-resolution mass spectrom...

Morphological features and mixing states of soot-containing particles in the marine boundary layer over the Indian and Southern oceans

Abstract. Mixing states of soot-containing aerosol particles constitute important information for the simulation of climatic effects of black carbon in the atmosphere. To elucidate the mixing states and morphological features of soot-containing particles over remote oceans, we conducted on-board observations over the southern Indian Ocean and the Southern Ocean during the TR/V Umitaka-maru UM-08-09 cruise, which started from Benoa, Indonesia, on 1 December 2008 via Cape Town, South Africa, and which terminated in Fremantle, Australia, on 6 February 2009. The light absorption coefficients of size-segregated particles (&lt; 0.5 and &lt; 1.0 µm diameter) and aerosol number concentrations (0.1–0.5 µm diameter) were measured to assist direct aerosol sampling. Size-segregated aerosol particles were collected for chemical analysis using ion chromatography. For transmission electron microscopy (TEM) analyses using water-dialysis methods, dried submicrometer aerosol particles were collected using a cascade impactor. We analyzed 13 TEM samples. Results of water-dialysis analysis demonstrate that most particles were water-soluble. However, for all TEM samples, particles were rarely found (2.1 % of particles on a TEM sample at a maximum) containing insoluble residuals with the characteristic soot shape. For samples collected over the Indian and Southern oceans at latitudes less than 62∘ S, some (20–35 %) soot-containing particles were found as bare soot. For samples collected near the Antarctic coast (65–68∘ S, 38–68∘ E), all soot-containing particles were mixed with water-soluble materials. Furthermore, 56 % of soot-containing particles had a satellite structure formed by the impact of droplets such as sulfuric acid. Chemical analysis of submicrometer particles near the Antarctic coast revealed high concentrations of non-sea-salt (nss) SO42- and CH3SO3-, suggesting that aged soot-containing particles were transformed by soluble materials derived from dimethyl sulfide (DMS) oxidation. The obtained information of soot at various remote ocean areas is expected to be useful to understand long-range transport processes and to improve simulations of global soot concentration.

Response Surface and Kinetic Modeling of Dimethyl Sulfide Oxidation – On the Origin of Dimethyl Sulfoxide in Malt

ABSTRACTDimethyl sulfide (DMS) contributes significantly to beer aroma. Malt contains considerable amounts of its oxidized form dimethyl sulfoxide (DMSO), the precursor of DMS during fermentation. Yet, detailed information regarding mechanisms of DMSO formation in malt is limited. Recently, hydrogen peroxide was suggested as a potential DMS oxidant in malt. The aim of this study was to characterize the reaction of hydrogen peroxide and DMS in buffered model solutions. Initially, hydrogen peroxide was identified in green malt using leuco crystal violet and horseradish peroxidase. Based on these findings the reaction of DMS with H2O2 was investigated in buffered model solutions at varying temperatures and pH using response surface modeling (RSM). Significant amounts of DMSO were formed by H2O2 mediated oxidation of DMS (∼0–41%), which was determined by temperature and hydrogen peroxide concentration (P ≤ 0.003). The effect of the pH was insignificant (P ≥ 0.4). Kinetics of DMS oxidation by H2O2 (DMS:H2O2 = 1:3) at 95°C followed a pseudo first order mechanism (k = 0.0041 min−1). Molecular oxygen was not capable of oxidizing DMS, whereas hydroxyl radical mediated DMS oxidation was faster than DMS oxidation aroused by H2O2. Potential reaction mechanisms and their relevance in DMS oxidation are discussed as a first approach to minimize DMSO levels in malt.

Influence of Water on the Oxidation of Dimethyl Sulfide by the ·OH Radical.

Oxidative stress of sulfur-containing biological molecules in aqueous environments may lead to the formation of adduct intermediates that are too short-lived to be experimentally detectable. In this study we have modeled the simplest of such oxidative reactions: the attack of dimethyl sulfide (DMS) by a hydroxyl radical (·OH) to form a radical adduct, whose subsequent heterolytic dissociation leads to a radical cation (DMS+) that is important for further reactions. We have modeled the aqueous environment with a limited number of discrete water molecules, selected after an original multistep procedure, and further embedded in a polarizable continuum model, to observe the impact of the water configuration on the heterolytic dissociation of the radical adduct. Molecular dynamics and quantum chemical methods (DFT, MP2, and CCSD) were used to elucidate the lowest energy structures resulting from the ·OH attack on DMS. Subsequent high level ab initio valence bond (BOVB) calculations revealed the possibility for the occurrence of subsequent heterolytic dissociation.