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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.
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Marine dimethyl sulfide (DMS) emissions are the dominant source of natural sulfur in the atmosphere. DMS oxidizes to produce low-volatility acids that potentially nucleate to form particles that may grow into climatically important cloud condensation nuclei (CCN). In this work, we utilize the chemistry transport model ADCHEM to demonstrate that DMS emissions are likely to contribute to the majority of CCN during the biological active period (May-August) at three different forest stations in the Nordic countries. DMS increases CCN concentrations by forming nucleation and Aitken mode particles over the ocean and land, which eventually grow into the accumulation mode by condensation of low-volatility organic compounds from continental vegetation. Our findings provide a new understanding of the exchange of marine precursors between the ocean and land, highlighting their influence as one of the dominant sources of CCN particles over the boreal forest.
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Atmosfera , Atmosfera/químicaRESUMO
OBJECTIVES: Patients with metabolic dysfunction-associated steatotic liver disease (MASLD) exhibit varying degrees of halitosis. The author speculated that small intestinal bacterial overgrowth (SIBO) might lead to MASLD and subsequent extra-oral halitosis and aimed to test this hypothesis. METHODS: This retrospective cross-sectional study reviewed 885 extra-oral halitosis patients. Halitosis and exhaled dimethyl sulfide (DMS) were measured by organoleptic score (OLS) (0-5) and OralChroma, respectively. SIBO and MASLD were diagnosed by hydrogen breath test and Fibroscan combined with cardiometabolic criteria. RESULTS: In this study, 133/885 (15.05%) of the halitosis patients otherwise healthy had MASLD, while 87/133 (65.41%) of the MASLD patients were SIBO-positive. No significant differences were observed in physical parameters such as age, serum biochemical parameters such as lipids, or Fibroscan parameters between the SIBO-positive and SIBO-negative patients. However, the OLS was 4 (interquartile range: 3-4) and exhaled DMS level was 56 (43-75) parts per billion (ppb) in the SIBO-positive patients, significantly greater than 2 (2-3) and 43 (25-51) ppb in the SIBO-negative patients (both p < 0.001). Exhaled hydrogen levels positively correlated with the OLS and exhaled DMS levels (r = 0.774, r = 0.740, both p < 0.001). CONCLUSION: MASLD can cause halitosis by SIBO.
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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.
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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.
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Sulfetos , Oxirredução , TemperaturaRESUMO
The Pacific Ocean plays an important role in regulating the budget of climatically active gases and the burden of sulfate aerosols. Here, a field investigation was conducted to clarify the key processes and factors controlling climatically active gases, including dimethyl sulfide (DMS), carbonyl sulfide (OCS), carbon disulfide (CS2), and carbon dioxide (CO2), in both surface seawater and the lower atmosphere of the western Pacific. In addition, the relative contributions of different sources to atmospheric sulfate aerosols were quantitatively estimated, and their causes were explored. The maximum concentrations of DMS, OCS and CS2 and the minimum partial pressure of CO2 (pCO2) were observed in the Kuroshio-Oyashio Extension. Kuroshio-induced mesoscale eddies brought abundant nutrients and organic matter from the subsurface layer of Oyashio into the euphotic layer, thus enhancing primary productivity and accelerating the photoreaction of organic matter. These processes led to higher concentrations of DMS, OCS and CS2 and lower pCO2. However, the oligotrophic subsurface layer in the subtropical gyre and the strong barrier layer in the equatorial waters suppressed the upward fluxes of nutrients and organic matter, resulting in lower surface concentrations of DMS, OCS, and CS2 in these areas. Being far from the continents, atmospheric concentrations of DMS, OCS and CS2 and pCO2 in the western Pacific generally were observed to depend on the local sea-to-air exchange and may be regulated by atmospheric oxidation and mixing of air masses. In general, oceanic DMS emissions played an important role in the formation of sulfate aerosols in the western Pacific (accounting for â¼19.5% of total sulfate aerosols), especially in the Kuroshio-Oyashio Extension (â¼32.3%). These processes in seawater may also determine the variations and emissions of other climatically active gases from biogenic and photochemical sources.
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Dióxido de Carbono , Gases , Sulfatos , Oceano Pacífico , AerossóisRESUMO
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.
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Dimethyl sulfide (DMS) influences climate via cloud condensation nuclei (CCN) formation resulting from its oxidation products (mainly methanesulfonic acid, MSA, and sulfuric acid, H2SO4). Despite their importance, accurate prediction of MSA and H2SO4 from DMS oxidation remains challenging. With comprehensive experiments carried out in the Cosmics Leaving Outdoor Droplets (CLOUD) chamber at CERN, we show that decreasing the temperature from +25 to -10 °C enhances the gas-phase MSA production by an order of magnitude from OH-initiated DMS oxidation, while H2SO4 production is modestly affected. This leads to a gas-phase H2SO4-to-MSA ratio (H2SO4/MSA) smaller than one at low temperatures, consistent with field observations in polar regions. With an updated DMS oxidation mechanism, we find that methanesulfinic acid, CH3S(O)OH, MSIA, forms large amounts of MSA. Overall, our results reveal that MSA yields are a factor of 2-10 higher than those predicted by the widely used Master Chemical Mechanism (MCMv3.3.1), and the NOx effect is less significant than that of temperature. Our updated mechanism explains the high MSA production rates observed in field observations, especially at low temperatures, thus, substantiating the greater importance of MSA in the natural sulfur cycle and natural CCN formation. Our mechanism will improve the interpretation of present-day and historical gas-phase H2SO4/MSA measurements.
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Dimethylsulfoniopropionate (DMSP) is widespread in the oceans, and its biological metabolite, dimethyl sulfide (DMS), plays an important role in the atmosphere. The Antarctic region has become a hotspot in DMS studies due to the high spatial and temporal variability in DMS(P) concentration, but the level of bacterial DMS production remains unclear. In this study, a bacterium isolated from Antarctic floating ice, Rhodococcus sp. NJ-530, was found to metabolize DMSP into DMS, and the rate of DMS production was measured as 3.96 pmol·mg protein-1 ·h-1 . Rhodococcus sp. NJ-530 had a DddD-Rh enzyme containing two CaiB domains, which belonged to the CoA-transferase III superfamily. However, the DddD-Rh had a molecular weight of 73.21 kDa, which was very different from previously characterized DddD enzymes in sequence and evolution. In vitro assays showed that DddD-Rh was functional in the presence of acetyl-CoA. This was the first functional DddD from Gram-positive Actinobacteria. Moreover, a quantitative real-time polymerase chain reaction revealed that high temperature facilitated the expression of dddD-Rh, and changes of salinity had little effect on it. This study adds new evidence to the bacterial DMS production in the Southern Ocean and provides a basis for investigating the metabolic mechanism of DMSP in extreme environments.
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Coenzima A-Transferases/metabolismo , Rhodococcus/metabolismo , Sulfetos/metabolismo , Compostos de Sulfônio/metabolismo , Acetilcoenzima A/química , Regiões Antárticas , Coenzima A-Transferases/genética , Desmetilação , TemperaturaRESUMO
Dimethyl sulfoxide (DMSO) is used as a cryoprotectant for peripheral blood stem cells (PBSC) preservation. Dimethyl sulfide (DMS) is a metabolite of DMSO secreted through patients' breath after PBSC infusion. It possesses malodor causing an unpleasant environment. We evaluated the efficacy of a photocatalyst environment purifier, which has the potential to lyse toxic substances, in reducing DMS malodor. High DMS concentration in the air after PBSC infusion rapidly decreased after operating the device. Our results suggest that photocatalytic reaction has the potential to reduce the DMS odor associated with PBSC infusion.
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Filtros de Ar , Células-Tronco de Sangue Periférico , Criopreservação , Humanos , SulfetosRESUMO
Dimethyl sulfide (DMS) is a volatile sulfur compound produced mainly from the degradation of dimethylsulfoniopropionate (DMSP) in marine environments. DMS undergoes oxidation to form dimethyl sulfoxide (DMSO), dimethyl sulfone (DMSO2), and methanesulfonate (MSA), all of which occur in terrestrial environments and are accessible for consumption by various microorganisms. The purpose of the present study was to determine how the enhancer-binding proteins SfnR1 and SfnR2 contribute to the utilization of DMS and its derivatives in Pseudomonas aeruginosa PAO1. First, results from cell growth experiments showed that deletion of either sfnR2 or sfnG, a gene encoding a DMSO2-monooxygenase, significantly inhibits the ability of P. aeruginosa PAO1 to use DMSP, DMS, DMSO, and DMSO2 as sulfur sources. Deletion of the sfnR1 or msuEDC genes, which encode a MSA desulfurization pathway, did not abolish the growth of P. aeruginosa PAO1 on any sulfur compound tested. Second, data collected from ß-galactosidase assays revealed that the msuEDC-sfnR1 operon and the sfnG gene are induced in response to sulfur limitation or nonpreferred sulfur sources, such as DMSP, DMS, and DMSO, etc. Importantly, SfnR2 (and not SfnR1) is essential for this induction. Expression of sfnR2 is induced under sulfur limitation but independently of SfnR1 or SfnR2. Finally, the results of this study suggest that the main function of SfnR2 is to direct the initial activation of the msuEDC-sfnR1 operon in response to sulfur limitation or nonpreferred sulfur sources. Once expressed, SfnR1 contributes to the expression of msuEDC-sfnR1, sfnG, and other target genes involved in DMS-related metabolism in P. aeruginosa PAO1.IMPORTANCE Dimethyl sulfide (DMS) is an important environmental source of sulfur, carbon, and/or energy for microorganisms. For various bacteria, including Pseudomonas, Xanthomonas, and Azotobacter, DMS utilization is thought to be controlled by the transcriptional regulator SfnR. Adding more complexity, some bacteria, such as Acinetobacter baumannii, Enterobacter cloacae, and Pseudomonas aeruginosa, possess two, nonidentical SfnR proteins. In this study, we demonstrate that SfnR2 and not SfnR1 is the principal regulator of DMS metabolism in P. aeruginosa PAO1. Results suggest that SfnR1 has a supportive but nonessential role in the positive regulation of genes required for DMS utilization. This study not only enhances our understanding of SfnR regulation but, importantly, also provides a framework for addressing gene regulation through dual SfnR proteins in other bacteria.
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Regulação Bacteriana da Expressão Gênica , Pseudomonas aeruginosa/genética , Pseudomonas aeruginosa/metabolismo , Sulfetos/metabolismo , Fatores de Transcrição/metabolismo , Deleção de Genes , Ligação Proteica , Pseudomonas aeruginosa/crescimento & desenvolvimento , Fatores de Transcrição/genéticaRESUMO
Although halogen radicals are recognized to form as products of hydroxyl radical ((â¢)OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM ((3)DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater (â¢)OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark (â¢)OH generation by gamma radiolysis demonstrates that halogen radical production via (â¢)OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl(-) and Br(-) by (3)DOM*, an (â¢)OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters.
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Estuários , Halogênios/química , Radical Hidroxila/química , Ácido Caínico/análogos & derivados , Toxinas Marinhas/química , Carbonatos/química , Água Doce/química , Água Doce/microbiologia , Proliferação Nociva de Algas/efeitos da radiação , Ferro/química , Ácido Caínico/química , Cinética , Luz , Nitratos/química , Fotólise , Água do Mar/química , Água do Mar/microbiologia , Sulfetos/químicaRESUMO
Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42-) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42- aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions.
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Two selected brown algae (Taonia atomaria and Padina pavonica from the family Dictyotaceae, order Dictyotales) growing in the same area (island Vis, central Adriatic Sea) were collected at the same time. Their phytochemical composition of the headspace volatile organic compounds (HS-VOCs; first time report) was determined by headspace solid-phase microextraction (HS-SPME). Hydrodistillation was applied for the isolation of their volatile oils (first report on T. atomaria volatile oil). The isolates were analyzed by gas chromatography (GC-FID) and mass spectrometry (GC-MS). The headspace and oil composition of T. atomaria were quite similar (containing germacrene D, epi-bicyclosesquiphellandrene, ß-cubebene and gleenol as the major compounds). However, P. pavonica headspace and oil composition differed significantly (dimethyl sulfide, octan-1-ol and octanal dominated in the headspace, while the oil contained mainly higher aliphatic alcohols, trans-phytol and pachydictol A). Performed research contributes to the knowledge of the algae chemical biodiversity and reports an array of different compounds (mainly sesquiterpenes, diterpenes and aliphatic compounds); many of them were identified in both algae for the first time. Identified VOCs with distinctive chemical structures could be useful for taxonomic studies of related algae.
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Óleos Voláteis/química , Phaeophyceae/química , Organismos Aquáticos/química , Organismos Aquáticos/metabolismo , Vias Biossintéticas , Destilação , Cromatografia Gasosa-Espectrometria de Massas , Óleos Voláteis/isolamento & purificação , Óleos Voláteis/metabolismo , Phaeophyceae/metabolismo , Microextração em Fase SólidaRESUMO
BACKGROUND: Dimethyl sulfide (DMS) is a small sulfur-containing impact odorant, imparting distinctive positive and / or negative characters to food and beverages. In white wine, the presence of DMS at perception threshold is considered to be a fault, contributing strong odors reminiscent of asparagus, cooked cabbage, and creamed corn. The source of DMS in wine has long been associated with S-methyl-l-methionine (SMM), a derivative of the amino acid methionine, which is thought to break down into DMS through chemical degradation, particularly during wine ageing. RESULTS: We developed and validated a new liquid chromatography-tandem mass spectrometry (LC-MS/MS) method with a stable isotope dilution assay (SIDA) to measure SMM in grape juice and wine. The application of this new method for quantitating SMM, followed by the quantitation of DMS using headspace-solid phase micro-extraction coupled with gas chromatography-mass spectrometry (HS-SPME/GC-MS), confirmed that DMS can be produced in wine via the chemical breakdown of SMM to DMS, with greater degradation observed at 28 °C than at 14 °C. Further investigation into the role of grape juice and yeast strain on DMS formation revealed that the DMS produced from three different Sauvignon blanc grape juices, either from the SMM naturally present or SMM spiked at 50 mmol L-1 , was modulated depending on each of the four strains of Saccharomyces cerevisiae wine yeast used for fermentation. CONCLUSION: This study confirms the existence of a chemical pathway to the formation of DMS and reveals a yeast-mediated mechanism towards the formation of DMS from SMM during alcoholic fermentation. © 2019 Society of Chemical Industry.
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Cromatografia Líquida/métodos , Sucos de Frutas e Vegetais/análise , Saccharomyces cerevisiae/metabolismo , Sulfetos/metabolismo , Espectrometria de Massas em Tandem/métodos , Vitamina U/análise , Vitis/química , Fermentação , Frutas/química , Frutas/metabolismo , Frutas/microbiologia , Sucos de Frutas e Vegetais/microbiologia , Odorantes/análise , Sulfetos/análise , Vitamina U/metabolismo , Vitis/metabolismo , Vitis/microbiologia , Vinho/análiseRESUMO
The ingestion of microplastics by marine species has been at least partially attributed to plastics emitting a dimethyl sulfide signature when exposed to marine conditions. Dimethyl sulfide, a member of the volatile organic sulfur compounds group, is an infochemical that many species rely on to locate and identify prey while foraging. Microplastic ingestion is also observed in freshwater systems; however, this study shows that the same dimethyl sulfide signature is not obtained by three common types of plastic (high-density polyethylene, low-density polyethylene, and polystyrene) in freshwater systems, suggesting that there may be an alternate mechanism driving plastic ingestion by freshwater species.
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Água Doce/química , Microplásticos/química , Sulfetos/química , Animais , Monitoramento Ambiental , Microplásticos/análise , Modelos Químicos , Polietileno/química , Poliestirenos/química , Sulfetos/análise , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/químicaRESUMO
The Southern Ocean is a hotspot of the climate-relevant organic sulfur compound dimethyl sulfide (DMS). Spatial and temporal variability in DMS concentration is higher than in any other oceanic region, especially in the marginal ice zone. During a one-week expedition across the continental shelf of the West Antarctic Peninsula (WAP), from the shelf break into Marguerite Bay, in January 2015, spatial heterogeneity of DMS and its precursor dimethyl sulfoniopropionate (DMSP) was studied and linked with environmental conditions, including sea-ice melt events. Concentrations of sulfur compounds, particulate organic carbon (POC) and chlorophyll a in the surface waters varied by a factor of 5-6 over the entire transect. DMS and DMSP concentrations were an order of magnitude higher than currently inferred in climatologies for the WAP region. Particulate DMSP concentrations were correlated most strongly with POC and the abundance of haptophyte algae within the phytoplankton community, which, in turn, was linked with sea-ice melt. The strong sea-ice signal in the distribution of DMS(P) implies that DMS(P) production is likely to decrease with ongoing reductions in sea-ice cover along the WAP. This has implications for feedback processes on the region's climate system.This article is part of the theme issue 'The marine system of the West Antarctic Peninsula: status and strategy for progress in a region of rapid change'.
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OBJECTIVE: Dimethyl sulfide (DMS, CAS 75-18-3) is an industrial chemical. It is both an irritant and neurotoxicant that may be life-threatening because of accidental release. The effects of DMS on public health and associated public health response depend on the exposure concentration and duration. However, currently, public health advisory information exists for only a 1 h exposure duration, developed by the American Industrial Hygiene Association (AIHA). In the present work, the AIHA-reviewed data were computationally extrapolated to other common short-term durations. METHODS: The extrapolation was carried out using the toxic load equation, Cn × t = TL, where C and t are exposure concentration and duration, TL is toxic load, and n is a chemical-specific toxic load exponent derived in the present work using probit meta-analysis. The developed threshold levels were vetted against the AIHA database of clinical and animal health effects induced by DMS. RESULTS: Tier-1 levels were derived based on human exposures that resulted in an easily detectable odor, because DMS is known to have a disagreeable odor that may cause nausea. Tier-2 levels were derived from the lower 95% confidence bounds on a benchmark concentration that caused 10% incidence (BMCL10) of coma in rats during a 15 min inhalation exposure to DMS. Tier-3 levels were based on a BMCL05 for mortality in rats. CONCLUSION: Emergency responders and health assessors may consider these computationally derived threshold levels as a supplement to traditional chemical risk assessment procedures in instances where AIHA developed public health advisory levels do not exist.
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Poluentes Atmosféricos , Exposição por Inalação , Irritantes , Sulfetos , Níveis Máximos Permitidos , Administração por Inalação , Poluentes Atmosféricos/normas , Poluentes Atmosféricos/toxicidade , Animais , Coma/induzido quimicamente , Humanos , Exposição por Inalação/efeitos adversos , Exposição por Inalação/normas , Irritantes/normas , Irritantes/toxicidade , Odorantes , Medição de Risco , Sulfetos/normas , Sulfetos/toxicidade , Fatores de TempoRESUMO
This paper presents a mid-infrared dimethyl sulfide (CH3SCH3, DMS) sensor based on tunable laser absorption spectroscopy with a distributed feedback interband cascade laser to measure DMS in the atmosphere. Different from previous work, in which only DMS was tested and under pure nitrogen conditions, we measured DMS mixed by common air to establish the actual atmospheric measurement environment. Moreover, we used tunable laser absorption spectroscopy with spectral fitting to enable multi-species (i.e., DMS, CH4, and H2O) measurement simultaneously. Meanwhile, we used empirical mode decomposition and greatly reduced the interference of optical fringes and noise. The sensor performances were evaluated with atmospheric mixture in laboratory conditions. The sensor's measurement uncertainties of DMS, CH4, and H2O were as low as 80 ppb, 20 ppb, and 0.01% with an integration time 1 s, respectively. The sensor possessed a very low detection limit of 9.6 ppb with an integration time of 164 s for DMS, corresponding to an absorbance of 7.4 × 10-6, which showed a good anti-interference ability and stable performance after optical interference removal. We demonstrated that the sensor can be used for DMS measurement, as well as multi-species atmospheric measurements of DMS, H2O, and CH4 simultaneously.
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Volatile Organic Sulfur Compounds (VOSCs) are instrumental in global S-cycling and greenhouse gas production. VOSCs occur across a diversity of inland waters, and with widespread eutrophication and climate change, are increasingly linked with malodours in organic-rich waterbodies and drinking-water supplies. Compared with marine systems, the role of VOSCs in biogeochemical processes is far less well characterized for inland waters, and often involves different physicochemical and biological processes. This review provides an updated synthesis of VOSCs in inland waters, focusing on compounds known to cause malodours. We examine the major limnological and biochemical processes involved in the formation and degradation of alkylthiols, dialkylsulfides, dialkylpolysulfides, and other organosulfur compounds under different oxygen, salinity and mixing regimes, and key phototropic and heterotrophic microbial producers and degraders (bacteria, cyanobacteria, and algae) in these environs. The data show VOSC levels which vary significantly, sometimes far exceeding human odor thresholds, generated by a diversity of biota, biochemical pathways, enzymes and precursors. We also draw attention to major issues in sampling and analytical artifacts which bias and preclude comparisons among studies, and highlight significant knowledge gaps that need addressing with careful, appropriate methods to provide a more robust understanding of the potential effects of continued global development.