OH Radical-Initiated Chemistry of Isoprene in Aqueous Media. Atmospheric Implications

Kameel, F. R.; Hoffmann, Michael R.; Colussi, A. J.

doi:10.1021/jp4026267

Cited by 24 publications

(36 citation statements)

References 61 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is a result of using the default elemental analysis correction factors, which have been determined empirically for an ensemble of species rather than individual compounds (Aiken et al, 2008); however, errors in the absolute elemental ratios are not expected to affect the observed trends in H / C and O / C, nor the overall conclusions of this work. The rapid oxidation of dissolved organic species observed here is broadly consistent with the findings of other bulk oxidation studies (Altieri et al, 2006(Altieri et al, , 2008Carlton et al, 2007;Kirkland et al, 2013;Lee et al, 2011a, b;Liu et al, 2012a;Perri et al, 2009;Sun et al, 2010;Tan et al, 2009Tan et al, , 2010Zhang et al, 2010;Zhao et al, 2012).…”

Section: Bulk Oxidation Of Erythritolsupporting

confidence: 92%

“…Aqueous-phase oxidation has received considerable attention as a potential formation pathway for highly oxidized organic aerosol (Ervens et al, 2011;Lim et al, 2010). The oxidation of organic species in the aqueous phase has recently been investigated in the laboratory for a range of water-soluble species, including small carbonyls (Altieri et al, 2008;Carlton et al, 2007;Kirkland et al, 2013;Perri et al, 2009Perri et al, , 2010Tan et al, 2009Tan et al, , 2010, isoprene and its oxidation products (Altieri et al, 2006;Kameel et al, 2013;Liu et al, 2012a;Renard et al, 2013;Zhang et al, 2010), and phenolic compounds (Smith et al, 2014;Sun et al, 2010). Such bulk-phase studies have clearly demonstrated that aqueous-phase oxidation, when it occurs, can lead to the rapid formation of highly oxidized organic species.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

Daumit¹,

Carrasquillo²,

Hunter³

et al. 2014

Preprint

View full text Add to dashboard Cite

Abstract. Oxidation in the atmospheric aqueous phase (cloud droplets and deliquesced particles) has received recent attention as a potential pathway for the formation of highly oxidized organic aerosol. Most laboratory studies of aqueous-phase oxidation, however, are carried out in bulk solutions rather than aqueous droplets. Here we describe experiments in which aqueous oxidation of polyols (water-soluble species with chemical formula CnH2n+2On) is carried out within submicron particles in an environmental chamber, allowing for significant gas-particle partitioning of reactants, intermediates, and products. Dark Fenton chemistry is used as a source of hydroxyl radicals, and oxidation is monitored using a high-resolution aerosol mass spectrometer (AMS). Aqueous oxidation is rapid, and results in the formation of particulate oxalate; this is accompanied by substantial loss of carbon to the gas phase, indicating the formation of volatile products. Results are compared to those from analogous oxidation reactions carried out in bulk solution. The bulk-phase chemistry is similar to that in the particles, but with substantially less carbon loss. This is likely due to differences in partitioning of early-generation products, which evaporate out of the aqueous phase under chamber conditions (in which liquid water content is low), but remain in solution for further aqueous processing in the bulk phase. This work suggests that the product distributions from oxidation in aqueous aerosol may be substantially different from those in bulk oxidation experiments. This highlights the need for aqueous oxidation studies to be carried out under atmospherically relevant partitioning conditions, with liquid water contents mimicking those of cloud droplets or aqueous aerosol.

show abstract

Section: Bulk Oxidation Of Erythritolsupporting

confidence: 92%

Section: Introductionmentioning

confidence: 99%

Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

Daumit¹,

Carrasquillo²,

Hunter³

et al. 2014

Preprint

View full text Add to dashboard Cite

show abstract

“…The •OH radical is the most representative active oxygen-free radical during the metabolic process in cells. It was found that the •OH radical plays an important role in a series of biological phenomena such as aging, radiation damage, cancer and cytophagy (Kameel et al 2013). The •OH radical is generated in a "FeSO 4 -H 2 O 2 " system and neutralized by antioxidant molecules present in mixed juice scum extracts.…”

Section: Hydroxyl Radical Scavenging Activitymentioning

confidence: 99%

Assessment of the Bioactive Capacity of Mixed Juice Scum Extracts from Sugarcane Mills

An-gen

Zou

et al. 2015

J Food Process Engineering

View full text Add to dashboard Cite

The scum is a semisolid by-product in canesugar mills where flotation technology is used for mixed juice clarification. To evaluate its potential bioactive properties, an aqueous extract, a 70% ethanol extract and a 100% ethanol extract from the scum were obtained and used for antioxidant activity assessment. Chemical assays of 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2 0 -azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) diammonium salt (ABTS) were used to determine the total antioxidant activity, and a chemiluminescence assay was conducted to assess the hydroxyl (•OH) and superoxide anion (O 2•2 ) radicals' scavenging activity. Results showed that all extracts had high antioxidant activity, of which the 100% ethanol extract was more powerful in DPPH, ABTS and •OH assays. Potential antioxidants in ethanol extracts could be associated with sugarcane wax, polyphenols and flavonoids, while in the aqueous extract, it could be water-soluble vitamins and proteins which resulted in the highest (O 2•2 ) scavenging activity. This study suggested that the scum has potential bioactive application.

show abstract

“…More generally, "conjugation of the C = C with substituents such as the benzene ring (styrene and αmethylstyrene), and alkene double bond (butadiene and iso-prene), the carbonyl linkage (acrylic acid, methyl acrylate, methyl methacrylate), and the nitrile group (acrylonitrile) similarly leads to stabilization of the monomer and decreases enthalpies of polymerization" (Odian, 2004). It is thus likely that a large number of atmospherically relevant molecules can follow the same process either in the bulk or at the wet aerosol interface (Kameel et al, 2013(Kameel et al, , 2014. In this context, our results suggest that this class of compounds can impact the aerosol composition, and contribute to aqSOA formation upon water evaporation.…”

Section: Atmospheric Implicationsmentioning

confidence: 99%

“…The photooxidation of carbonyl compounds has been studied in the aqueous phase, and their ability to form oligomers and potentially aqSOA was shown Carlton et al, 2006 andPerri et al, 2009;El Haddad et al, 2009;Tan et al, 2009Tan et al, , 2010Tan et al, and 2012Zhang et al, 2010;Zhao et al, 2012;Liu et al, 2012;Ortiz-Montalvo et al, 2012;Lim et al, 2013;Renard et al, 2013;Kameel et al, 2013;Kameel et al, 2014;Daumit et al, 2014). In particular, Renard et al (2013) showed that • OH oxidation of MVK in the aqueous phase proceeds via a radical mechanism leading to oligomers which molecular masses up to 1800 Da, with the precursor initial concentration from 2 to 20 mM.…”

Section: Introductionmentioning

confidence: 99%

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

Renard¹,

Siekmann²,

Salque³

et al. 2014

Preprint

View full text Add to dashboard Cite

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.

show abstract

OH Radical-Initiated Chemistry of Isoprene in Aqueous Media. Atmospheric Implications

Abstract: Figure

Cited by 24 publications

References 61 publications

Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

Laboratory studies of the aqueous-phase oxidation of polyols: submicron particles vs. bulk aqueous solution

Assessment of the Bioactive Capacity of Mixed Juice Scum Extracts from Sugarcane Mills

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

Contact Info

Product

Resources

About