FT-IR product study of the photo-oxidation of dimethyl sulfide: Temperature and O2 partial pressure dependence

Arsene, Cecilia; Barnes, Ian; Becker, K. H.

doi:10.1039/a907211j

Cited by 85 publications

(114 citation statements)

References 23 publications

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“…During January-February 2004 and 2005 the average R b of 0.65±0.13 was higher than the peak value for Halley of 0.49 ±0.05 reported for January 1992 and also substantially higher than the annual peak values of 0.46±0.17 (Neumeyer, January 1983-1995 and of 0.28±0.05 (Dumont d'Urville, March 1983-1995 , implying a dominance in the addition pathway for these measurements of DMS at Halley. In addition it is commonly thought that the addition channel is faster at low temperatures (<285 K) (Arsene et al, 1999) which could explain the higher ratios observed in this study.…”

Section: Oxidation Of Dms By Ohsupporting

confidence: 65%

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

et al. 2008

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Abstract. In situ measurements of dimethyl sulphide (DMS) and methane sulphonic acid (MSA) with a minimum in sea extent. Whilst seasonal variability and interannual variability can be attributed to a number of factors, short term variability appeared strongly dependent on air mass origin and trajectory pressure height. The MSA and derived non-sea salt sulphate (nss-SO 2− 4 ) measurements showed no correlation with those of DMS (regression R 2 =0.039, and R 2 =0.001 respectively) in-line with the complexity of DMS fluxes, alternative oxidation routes, transport of air masses and variable spatial coverage of both sea-ice and phytoplankton. MSA was generally low throughout the year, with an annual average of 42 ng m −3 (9.8±13.2 pptV), however MSA: nss-SO 2− 4 ratios were high implying a dominance of the addition oxidation route for DMS. Including BrO measurements into MSA production calculations demonstrated the significance of BrO on DMS oxidation within this region of the atmosphere in austral summer. Assuming an 80% yield of DMSO from the reaction of DMS+BrO, an atmospheric concentration of BrO equal to 3 pptV increased the calculated MSA production from DMS by a factor of 9 above that obtained when considering only Correspondence to: K. A. Read (km519@york.ac.uk) reaction with the hydroxyl radical. These findings have significant atmospheric implications, but may also impact on the interpretation of ice cores which previously relied on the understanding of MSA and nss-SO 2− 4 chemistry to provide information on environmental conditions such as sea ice extent and the origins of sulphur within the ice.

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Section: Oxidation Of Dms By Ohsupporting

confidence: 65%

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

et al. 2008

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“…The production of OCS from the oxidation of DMS by OH has been observed in several chamber experiments, all of which used the same technique and experimental chamber (Barnes et al, 1994(Barnes et al, , 25 1996Patroescu et al, 1998;Arsene et al, 1999Arsene et al, , 2001) with a molar yield of 0.7 ± 0.2%. These studies were carried out at precursor levels far exceeding those in the atmosphere (ppm), so the potential exists for radical-radical reactions that do not occur in nature.…”

Section: Indirect Marine Emissionsmentioning

confidence: 99%

Reviews and Syntheses: Carbonyl Sulfide as a Multi-scale Tracer for Carbon and Water Cycles

Whelan¹,

Lennartz²,

Gimeno³

et al. 2017

Preprint

113

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Abstract. For the past decade, observations of carbonyl sulfide (OCS or COS) have been investigated as a proxy for carbon uptake by plants. OCS is destroyed by enzymes that interact with CO 2 during 25 photosynthesis, namely carbonic anhydrase (CA) and RuBisCO, where CA is the more important. The majority of sources of OCS to the atmosphere are geographically separated from this large plant sink, whereas the sources and sinks of CO 2 are co-located in ecosystems. The drawdown of OCS can therefore be related to the uptake of CO 2 without the added complication of co-located emissions comparable in magnitude. Here we review the state of our understanding of the global OCS cycle and 30 its applications to ecosystem carbon cycle science. OCS uptake is correlated well to plant carbon uptake, especially at the regional scale. OCS can be used in conjunction with other independent measures of ecosystem function, like solar-induced fluorescence and carbon and water isotope studies.More work needs to be done to generate global coverage for OCS observations and to link this powerful Biogeosciences Discuss., https://doi

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“…4,[7][8][9]15,[19][20][21][22][23] It is thought that this occurs through the formation of a DMS-OH adduct and the subsequent reaction of this complex with O 2 or nitrogen oxides. So, we have explored the potential energy surfaces corresponding to the following reactions which have been proposed to yield DMSO from the DMS-OH adduct:…”

Section: Resultsmentioning

confidence: 99%

“…It is known, for instance, that the addition pathway produces DMSO (CH 3 SOCH 3 ) but discrepancies exist concerning formation yield data for this sulfur-containing product and with respect to the reaction pathways of the DMSO formation mechanism. In fact, the DMS-OH 1 O 2 reaction has been proposed to proceed via the following thermodynamically feasible channels The experimental results of Arsene et al 20 show concentration-time behaviors of DMS and several of its oxidized products monitored in situ using long path FTIR spectroscopy in the absence of NO x . The measured DMSO yield values at 284 and 295 K are approximately the same as the fraction of the DMS 1 OH reaction occurring via the addition pathway II, thus indicating a branching ratio of unity for the DMSO forming channel (a).…”

Section: Introductionmentioning

confidence: 95%

“…In this sense, the experimental divergences concerning the importance of DMSO formation channel may also be due to the variation in the experimental conditions, NO x -free or NO x -containing, employed in the laboratory experiments mentioned in the previous paragraph. 7,19,20 In fact, the relative importance of the reaction pathways and thus the product yields in the DMS degradation scheme has been said to be influenced by the NO x content of chamber experiments. Even the CH 3 SO 3 H(MSA)/SO 2 ratio has been proposed to be NO x -dependent, although there are no direct experimental evidences of this hypothesis.…”

Section: Introductionmentioning

confidence: 98%

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Formation pathways of DMSO from DMS‐OH in the presence of O₂ and NO_x: A theoretical study

2008

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The relative importance of the reaction pathways and thus the product yields in the dimethyl sulfide (DMS) degradation scheme initiated by the hydroxyl (OH) radical has been said to be influenced by the content of nitrogen oxides (NO(x)) in chamber experiments. In this study, ab initio and density functional electronic structure calculations of all the possible reaction pathways corresponding to the reaction process initiated by DMS-OH + oxygen (O(2)), leading to the formation of the dimethyl sulfoxide (DMSO) product in the presence of NO(x) (NO and NO(2)), are carried out for the first time. The results for the different pathways are compared with the objective of inferring their kinetic relevance in the laboratory experiments that measure DMSO formation yields. Our theoretical results clearly show the existence of NO(x)-dependent pathways leading to the formation of DMSO in addition to O(2)-dependent channels. So then, NO(x)-containing conditions would have to modify the relative importance of the addition channel in the DMS oxidation process.

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FT-IR product study of the photo-oxidation of dimethyl sulfide: Temperature and O2 partial pressure dependence

Cited by 85 publications

References 23 publications

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

Reviews and Syntheses: Carbonyl Sulfide as a Multi-scale Tracer for Carbon and Water Cycles

Formation pathways of DMSO from DMS‐OH in the presence of O₂ and NO_x: A theoretical study

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FT-IR product study of the photo-oxidation of dimethyl sulfide: Temperature and O2 partial pressure dependence

Cited by 85 publications

References 23 publications

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

DMS and MSA measurements in the Antarctic Boundary Layer: impact of BrO on MSA production

Reviews and Syntheses: Carbonyl Sulfide as a Multi-scale Tracer for Carbon and Water Cycles

Formation pathways of DMSO from DMS‐OH in the presence of O2 and NOx: A theoretical study

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Formation pathways of DMSO from DMS‐OH in the presence of O₂ and NO_x: A theoretical study