Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles

Ziemann, Paul J.

doi:10.1039/b417502f

Cited by 202 publications

(428 citation statements)

References 32 publications

(61 reference statements)

Supporting

Mentioning

391

Contrasting

Order By: Relevance

“…A large body of literature on this laboratory model system is available (Rudich 2003;Rudich et al 2007;Zahardis and Petrucci 2007). The reaction has been found to be in general agreement with the Criegee mechanism and the first-generation products have been identified (Hearn and Smith 2004;Hung et al 2005;Ziemann 2005). However, the atmospheric lifetime of oleic acid inferred from field observations (days) was markedly longer than the laboratory measurements (in seconds) (Rudich et al 2007).…”

Section: Introductionmentioning

confidence: 56%

Roles of the Phase State and Water Content in Ozonolysis of Internal Mixtures of Maleic Acid and Ammonium Sulfate Particles

Chan

2012

Aerosol Science and Technology

View full text Add to dashboard Cite

The ozonolysis of maleic acid/ammonium sulfate (MA/AS, 30/70 wt%) internal mixtures was investigated at various relative humidities (RHs) (80%, 55%, 30%, and <5%) and physical states (aqueous and crystalline solid). Complementary laboratory techniques-an electrodynamic balance coupled with in situ Raman spectroscopy and a reaction flow cell coupled with offline ion chromatography (IC)-were employed to probe the mass changes, spectroscopic changes, product identities, and post-reaction hygroscopic changes in ozone-processed MA/AS mixed particles. The rate of ozonolysis was highly dependent on the physical state and the water content of the particles. Crystalline solid particles underwent negligible changes even after exposure to 10-ppm ozone for six days. Aqueous particles reacted much faster and the rate was related to the RH during reaction. It took 23 h to reduce MA to 50% of its initial mass at 80% RH, whereas it took 87 h to do the same at 55% RH or lower. We believe that the salting-out of ozone in concentrated droplets at 55% RH may have contributed to the reduced ozonolysis rate. The molar conversion of MA to glyoxylic acid was about unity in both the 55% RH and the 80% RH experiments. Exposed particles may have formed amorphous solids when dried and their hygroscopicity was different from that of the corresponding parent particles. Early deliquescence of reacted particles was observed, suggesting the strong influence of aging on aerosol hygroscopicity.

show abstract

Section: Introductionmentioning

confidence: 56%

Roles of the Phase State and Water Content in Ozonolysis of Internal Mixtures of Maleic Acid and Ammonium Sulfate Particles

Chan

2012

Aerosol Science and Technology

View full text Add to dashboard Cite

show abstract

“…This method was already applied in other studies to measure the peroxide content of aerosols (Docherty et al, 2005;Ziemann, 2005;Surratt et al, 2006;Nguyen et al, 2010). Herein peroxy-groups oxidize iodide ions (I − ) to molecular iodine (I 2 ) in solution which subsequently forms yellow coloured triiodide ions (I − 3 ).…”

Section: Introductionmentioning

confidence: 99%

“…Surratt et al, 2006). Peroxide mass fractions from 20 % to over 100 % were reported in SOA from various precursors assuming a molecular weight of 300 g mol −1 for peroxides (Docherty et al, 2005;Ziemann, 2005;Surratt et al, 2006;Nguyen et al, 2010). To enhance the sensitivity we developed a long path absorption spectroscopy system.…”

Section: Introductionmentioning

confidence: 99%

Development of a sensitive long path absorption photometer to quantify peroxides in aerosol particles (Peroxide-LOPAP)

et al. 2012

View full text Add to dashboard Cite

Abstract.A new off-line instrument to quantify peroxides in aerosol particles using iodometry in long path absorption spectroscopy has been developed and is called peroxide long path absorption photometer (Peroxide-LOPAP). The new analytical setup features important technical innovations compared to hitherto published iodometric peroxide measurements. Firstly, the extraction, chemical conversion and measurement of the aerosol samples are performed in a closed oxygen-free (∼ 1 ppb) environment. Secondly, a 50-cm optical detection cell is used for an increased photometric sensitivity. The limit of detection was 0.1 µM peroxide in solution or 0.25 nmol m −3 with respect to an aerosol sample volume of 1 m 3 . The test reaction was done at a constant elevated temperature of 40 • C and the reaction time was 60 min.Calibration experiments showed that the test reaction with all reactive peroxides, i.e. hydrogen peroxide (H 2 O 2 ), peracids and peroxides with vicinal carbonyl groups (e.g. lauroyl peroxide) goes to completion and their sensitivity (slope of calibration curve) varies by only ±5 %. However, very inert peroxides have a lower sensitivity. For example, tert-butyl hydroperoxide shows only 37 % sensitivity compared to H 2 O 2 after 1 h. A kinetic study revealed that even after 5 h only 85 % of this inert compound had reacted.The time trends of the peroxide content in secondary organic aerosol (SOA) from the ozonolysis and photooxidation of α-pinene in smog chamber experiments were measured. The highest mass fraction of peroxides with 34 % (assuming a molecular weight of 300 g mol −1 ) was found in freshly generated SOA from α-pinene ozonolysis. Mass fractions decreased with increasing NO levels in the photooxidation experiments. A decrease of the peroxide content was also observed with aging of the aerosol, indicating a decomposition of peroxides in the particles.

show abstract

“…As of late, a great deal of effort has gone into understanding the secondary chemistry resulting from the ozonolysis of unsaturated fatty acids (Zahardis et al, 2005;Ziemann, 2005;Hearn et al, 2005;Reynolds et al, 2006;Hung et al, 2005;Gross et al, 2006) and OL has emerged as a model compound for describing the heterogeneous ozonolysis of particulate rich in fatty acid content (for example, see review by Zahardis and Petrucci, 2007). The products of this secondary chemistry generally stem from the high reactivity of stabilized Criegee intermediates (SCI) and include high molecular weight, peroxidic oligomers (Reynolds et al, 2006;Hung and Ariya, 2007;Zahardis et al, 2006a;Katrib et al, 2005;Hung et al, 2005;Gross et al, 2006;Hearn et al, 2005;Ziemann, 2005). These types of products may have a role in the experimentally observed increase in hygroscopicity and CCN activation of fine organic particles with ozonation (Broekhuizen et al, 2004;Shilling et al, 2007;King et al, 2004;Hung and Ariya, 2007).…”

Section: Introductionmentioning

confidence: 99%

“…Conversely, DOS and similar high molecular weight esters (i.e. dioctyl adipate) are common constituents in studies of organic particles (Ziemann, 2005;Mochida et al, 2006) that are not a source of SCI and inert to ozone (Mochida et al, 2006); hence, DOS serves as an excellent negative control for comparison to the studies of ozonized mixed particles of amines with OL.…”

Section: Introductionmentioning

confidence: 99%

The ozonolysis of primary aliphatic amines in fine particles

2008

View full text Add to dashboard Cite

Abstract. The oxidative processing by ozone of the particulate amines octadecylamine (ODA) and hexadecylamine (HDA) is reported. Ozonolysis of these amines resulted in strong NO − 2 and NO − 3 ion signals that increased with ozone exposure as monitored by photoelectron resonance capture ionization aerosol mass spectrometry. These products suggest a mechanism of progressive oxidation of the particulate amines to nitroalkanes. Additionally, a strong ion signal at 125 m/z is assigned to the ion NO − 3 (HNO 3 ). For ozonized mixed particles containing ODA or HDA + oleic acid (OL), with p O 3 ≥3×10 −7 atm, imine, secondary amide, and tertiary amide products were measured. These products most likely arise from reactions of amines with aldehydes (for imines) and stabilized Criegee intermediates (SCI) or secondary ozonides (for amides) from the fatty acid. The routes to amides via SCI and/or secondary ozonides were shown to be more important than comparable amide forming reactions between amines and organic acids, using azelaic acid as a test compound. Finally, direct evidence is provided for the formation of a surface barrier in the ODA + OL reaction system that resulted in the retention of OL at high ozone exposures (up to 10 −3 atm for 17 s). This effect was not observed in HDA + OL or single component OL particles, suggesting that it may be a species-specific surfactant effect from an in situ generated amide or imine. Implications to tropospheric chemistry, including particle bound amines as sources of oxidized gas phase nitrogen species (e.g. NO 2 , NO 3 ), formation of nitrogen enriched HULIS via ozonolysis of amines and source apportionment are discussed.

show abstract

Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles

Cited by 202 publications

References 32 publications

Roles of the Phase State and Water Content in Ozonolysis of Internal Mixtures of Maleic Acid and Ammonium Sulfate Particles

Roles of the Phase State and Water Content in Ozonolysis of Internal Mixtures of Maleic Acid and Ammonium Sulfate Particles

Development of a sensitive long path absorption photometer to quantify peroxides in aerosol particles (Peroxide-LOPAP)

The ozonolysis of primary aliphatic amines in fine particles

Contact Info

Product

Resources

About