Insight into the formation of organosulfur compounds from the reaction of methyl vinyl ketone with sulfite radical in atmospheric aqueous phase

2021 ◽  
Vol 774 ◽  
pp. 145817
Author(s):  
Guochun Lv ◽  
Heng Zhang ◽  
Xiaomin Sun
Keyword(s):  
Aqueous Phase ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Organosulfur Compounds ◽  
Methyl Vinyl ◽  
Insight Into

scholarly journals Radical mechanisms of methyl vinyl ketone oligomerization through aqueous phase OH-oxidation: on the paradoxical role of dissolved molecular oxygen

2013 ◽  
Vol 13 (1) ◽  
pp. 2913-2954 ◽  
Author(s):  
P. Renard ◽  
F. Siekmann ◽  
A. Gandolfo ◽  
J. Socorro ◽  
G. Salque ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
High Resolution Mass Spectrometry ◽  
Organic Aerosol ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Chemical Mechanism ◽  
Methyl Vinyl ◽  
Phase Chemistry ◽  
Dissolved O2

Abstract. It is now accepted that one of the important pathways of Secondary Organic Aerosol (SOA) formation occurs through aqueous phase chemistry in the atmosphere. However, the liquid phase chemical mechanisms leading to macromolecules are still not well understood. For α-dicarbonyl precursors, such as methylglyoxal and glyoxal, radical reactions through OH-oxidation produce oligomers, irreversibly and faster than accretion reactions. Methyl vinyl ketone (MVK) was chosen in the present study as it is an α, β-unsaturated carbonyl that can undergo such reaction pathways in the aqueous phase and forms even high molecular weight oligomers. We present here experiments on the aqueous phase OH-oxidation of MVK, performed under atmospheric relevant conditions. Using NMR and UV absorption spectroscopy, high and ultra-high resolution mass spectrometry, we show that the fast formation of oligomers up to 1800 Da is due to radical oligomerization of MVK, and 13 series of oligomers (out of a total of 26 series) are identified. The influence of atmospherically relevant parameters such as temperature, initial concentrations of MVK and dissolved oxygen are presented and discussed. In agreement with the experimental observations, we propose a chemical mechanism of OH-oxidation of MVK in the aqueous phase that proceeds via radical oligomerization of MVK on the olefin part of the molecule. This mechanism highlights the paradoxical role of dissolved O2: while it inhibits oligomerization reactions, it contributes to produce oligomerization initiator radicals, which rapidly consume O2, thus leading to the supremacy of oligomerization reactions after several minutes of reaction. These processes, together with the large ranges of initial concentrations investigated (60–656 μM of dissolved O2 and 0.2–20 mM of MVK) show the fundamental role that O2 likely plays in atmospheric organic aerosol.

Development of DNPH/HPLC method for the measurement of carbonyl compounds in the aqueous phase: applications to laboratory simulation and field measurement

2009 ◽  
Vol 6 (5) ◽  
pp. 389 ◽  
Author(s):  
Hongli Wang ◽  
Xuan Zhang ◽  
Zhongming Chen
Keyword(s):  
Aqueous Phase ◽  
Carbonyl Compounds ◽  
Global Climate ◽  
Water Solution ◽  
Field Measurements ◽  
Hplc Method ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Laboratory Simulation ◽  
Methyl Vinyl

Environmental context. Carbonyl compounds, a class of oxygenated organic matter, are crucial participants in atmospheric processes. Recently, studies have shown that the aqueous-phase processes of carbonyls have an important contribution to the formation of secondary organic aerosol (SOA), which is considered to have a significant impact on global climate change and human health. We developed the classical DNPH/HPLC method to characterise the aqueous-phase carbonyls, especially methacrolein, methyl vinyl ketone, glyoxal, and methylglyoxal, which are important precursors of SOA, in order to better understand the pathways of SOA formation in the atmosphere. Abstract. The DNPH/HPLC method for characterising monocarbonyls and dicarbonyls in the aqueous phase has been developed. A series of experiments have been carried out using eight atmospheric ubiquitous carbonyl compounds as model dissolved compounds in both acetonitrile and water solution to obtain the optimal derivatisation and analysis qualifications. Compared with the analysis of carbonyls dissolved in acetonitrile, the influence of acidity on the derivatisation efficiency should be carefully considered in determining carbonyls in water and the optimal acidity is pH 2.0. We find that methyl vinyl ketone (MVK) transforms to crotonaldehyde during the derivatisation reaction. This transformation can be controlled to a minor degree by increasing the mixing ratio of DNPH to MVK up to 100 : 1. This improved method has been satisfactorily applied to laboratory simulations and field measurements for better understanding the carbonyl chemistry in the atmosphere.

Oligomer and SOA formation through aqueous phase photooxidation of methacrolein and methyl vinyl ketone

2012 ◽  
Vol 49 ◽  
pp. 123-129 ◽  
Author(s):  
Yao Liu ◽  
Frank Siekmann ◽  
Pascal Renard ◽  
Atallah El Zein ◽  
Guillaume Salque ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Methyl Vinyl

Aqueous Phase Oligomerization of Methyl Vinyl Ketone by Atmospheric Radical Reactions

2014 ◽  
Vol 118 (50) ◽  
pp. 29421-29430 ◽  
Author(s):  
Pascal Renard ◽  
Allison E. Reed Harris ◽  
Rebecca J. Rapf ◽  
Sylvain Ravier ◽  
Carine Demelas ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Radical Reactions ◽  
Methyl Vinyl

scholarly journals Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants

2008 ◽  
Vol 8 (8) ◽  
pp. 2255-2265 ◽  
Author(s):  
Z. M. Chen ◽  
H. L. Wang ◽  
L. H. Zhu ◽  
C. X. Wang ◽  
C. Y. Jie ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Oxidation Products ◽  
Laboratory Simulation ◽  
Aerosol Formation ◽  
Methyl Vinyl ◽  
Gas Phase Oxidation ◽  
Acid Catalyzed ◽  
Catalyzed Oxidation

Abstract. Recent studies indicate that isoprene and its gas-phase oxidation products could contribute a considerable amount of aerosol through aqueous-phase acid-catalyzed oxidation with hydrogen peroxide (H2O2), although the source of H2O2 is unclear. The present study revealed a potentially important route to the formation of aqueous oxidants, including H2O2, from the aqueous-phase ozonolysis of methacrolein (MAC) and methyl vinyl ketone (MVK). Laboratory simulation was used to perform the atmospheric aqueous-phase ozonolysis at different pHs and temperatures. Unexpectedly high molar yields of the products, including hydroxylmethyl hydroperoxide (HMHP), formaldehyde (HCHO) and methylglyoxal (MG), of both of these reaction systems have been seen. Moreover, these yields are almost independent of pH and temperature and are as follows: (i) for MAC–O3, 70.3±6.3% HMHP, 32.3±5.8% HCHO and 98.6±5.4% MG; and (ii) for MVK–O3, 68.9±9.7% HMHP, 13.3±5.8% HCHO and 75.4±7.9% MG. A yield of 24.2±3.6% pyruvic acid has been detected for MVK–O3. HMHP is unstable in the aqueous phase and can transform into H2O2 and HCHO with a yield of 100%. We suggest that the aqueous-phase ozonolysis of MAC and MVK can contribute a considerable amount of oxidants in a direct and indirect mode to the aqueous phase and that these compounds might be the main source of aqueous-phase oxidants. The formation of oxidants in the aqueous-phase ozonolysis of MAC and MVK can lead to substantial aerosol formation from the aqueous-phase acid-catalyzed reaction of H2O2 with MAC, even if there are no other sources of oxidants.

scholarly journals Aqueous-phase oligomerization of methyl vinyl ketone through photooxidation – Part 2: Development of the chemical mechanism and atmospheric implications

2015 ◽  
Vol 15 (16) ◽  
pp. 9109-9127 ◽  
Author(s):  
B. Ervens ◽  
P. Renard ◽  
S. Tlili ◽  
S. Ravier ◽  
J.-L. Clément ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Laboratory Experiments ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Box Model ◽  
Chemical Mechanism ◽  
Oxygen Solubility ◽  
Methyl Vinyl ◽  
Oligomer Formation ◽  
Wide Range

Abstract. Laboratory experiments of efficient oligomerization from methyl vinyl ketone (MVK) in the bulk aqueous phase were simulated in a box model. Kinetic data are applied (if known) or fitted to the observed MVK decay and oligomer mass increase. Upon model sensitivity studies, in which unconstrained rate constants were varied over several orders of magnitude, a set of reaction parameters was found that could reproduce laboratory data over a wide range of experimental conditions. This mechanism is the first that comprehensively describes such radical-initiated oligomer formation. This mechanism was implemented into a multiphase box model that simulates secondary organic aerosol (SOA) formation from isoprene, as a precursor of MVK and methacrolein (MACR) in the aqueous and gas phases. While in laboratory experiments oxygen limitation might occur and lead to accelerated oligomer formation, such conditions are likely not met in the atmosphere. The comparison of predicted oligomer formation shows that MVK and MACR likely do negligibly contribute to total SOA as their solubilities are low and even reduced in aerosol water due to ionic strength effects (Setchenov coefficients). Significant contribution by oligomers to total SOA might only occur if a substantial fraction of particulate carbon acts as oligomer precursors and/or if oxygen solubility in aerosol water is strongly reduced due to salting-out effects.

scholarly journals Aqueous phase oligomerization of methyl vinyl ketone through photooxidation – Part 1: Aging processes of oligomers

2014 ◽  
Vol 14 (10) ◽  
pp. 15283-15322 ◽  
Author(s):  
P. Renard ◽  
F. Siekmann ◽  
G. Salque ◽  
A. Smaani ◽  
C. Demelas ◽  
...  
Keyword(s):  
Aqueous Phase ◽  
Process Model ◽  
Organic Aerosol ◽  
Companion Paper ◽  
Water Soluble ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Substantial Part ◽  
Methyl Vinyl ◽  
Model Studies

Abstract. Secondary organic aerosol (SOA) represents a substantial part of organic aerosol, which affects climate and human health. It is now accepted that one of the important pathways of SOA formation occurs via aqueous phase chemistry in the atmosphere. Recently, we have shown in a previous study (Renard et al., 2013) the mechanism of oligomerization of MVK (methyl vinyl ketone), and suggested that unsaturated water soluble organic compounds (UWSOC) might efficiently form SOA in wet aerosol particles, even for weakly soluble ones like MVK. The atmospheric relevance of these processes is explored by means of process model studies (in a companion paper). In the present study we investigate the aging of these aqueous phase MVK-oligomers (Part 1). We compared aqueous phase composition and SOA composition after nebulization, mainly by means of UPLC-ESI-MS and AMS, respectively. Both instruments match and show similar trend of oligomer formation and aging. The SMPS analysis performed on the nebulized solutions allow to quantify these SOA and to measure their mass yields. We have highlighted in the current study that MVK •OH-oxidation undergoes kinetic competition between functionalization and oligomerization. The SOA composition and its evolution highly depend on the precursor initial concentration. We determined the threshold of MVK concentration, i.e. 2 mM, from which oligomerization prevails over functionalization. Hence, at these concentrations, •OH-oxidation of MVK forms oligomers that are SV-OOA, with low O / C and high f43. Oligomers are then fragmented, via unidentified intermediates that have the properties of LV-OOA which then end into succinic, malonic and oxalic diacids. For lower initial MVK concentrations, the oligomerization is not the major process, and functionalization dominates, resulting in small carbonyls, dicarbonyls and mainly monoacids. The aging of these oligomers could be an explanation for the presence of a part of the diacids observed in aerosol.

scholarly journals Aqueous-phase ozonolysis of methacrolein and methyl vinyl ketone: a potentially important source of atmospheric aqueous oxidants

2007 ◽  
Vol 7 (6) ◽  
pp. 17599-17623
Author(s):  
Z. M. Chen ◽  
H. L. Wang ◽  
L. H. Zhu ◽  
C. X. Wang ◽  
C. Y. Jie ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Aqueous Phase ◽  
Pyruvic Acid ◽  
Vinyl Ketone ◽  
Methyl Vinyl Ketone ◽  
Laboratory Simulation ◽  
Methyl Vinyl ◽  
Reaction Systems ◽  
Acid Catalyzed ◽  
Catalyzed Oxidation

Abstract. Recent studies indicate that isoprene could contribute a considerable amount of aerosol through aqueous-phase acid-catalyzed oxidation with hydrogen peroxide (H2O2), although the source of H2O2 is unclear. The present study revealed a potentially important route to the formation of aqueous oxidants, including H2O2, from the aqueous-phase ozonolysis of methacrolein (MAC) and methyl vinyl ketone (MVK). Laboratory simulation was used to perform the atmospheric aqueous-phase ozonolysis at different pHs and temperatures. Unexpectedly high molar yields of the products, including hydroxylmethyl hydroperoxide (HMHP), formaldehyde (HCHO) and methylglyoxyl (MG), of both of these reaction systems have been seen. Moreover, these yields are almost independent of pH and temperature and are as follows: (i) for MAC–O3, 70.3±6.3% HMHP, 32.3±5.8% HCHO and 98.6±5.4% MG; and (ii) for MVK–O3, 68.9±9.7% HMHP, 13.3±5.8% HCHO and 75.4±7.9% MG. A yield of 24.2±3.6% pyruvic acid has been detected for MVK–O3. HMHP is unstable in the aqueous phase and can transform into H2O2 and HCHO with a yield of 100%. We suggest that the aqueous-phase ozonolysis of MAC and MVK can contribute a considerable amount of oxidants in a direct and indirect mode to the aqueous phase and that these compounds might be the main source of aqueous-phase oxidants. The formation of oxidants in the aqueous-phase ozonolysis of MAC and MVK effectively confirms the formation of aerosols from the aqueous-phase acid-catalyzed reaction of H2O2 with isoprene, even if there are no other sources of oxidants.

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