Fluorescence spectroscopic study of reactions between gaseous ozone and surface-adsorbed polycyclic aromatic hydrocarbons

Wu, C. H.; Salmeen, Irving T.; Niki, H.

doi:10.1021/es00126a007

Cited by 54 publications

(75 citation statements)

References 10 publications

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“…The kinetics of the heterogeneous reaction between gaseous ozone and PAHs bound on various substrates have been investigated in several laboratory studies (Wu et al, 1984;Alebic-Juretic et al, 1990;Pöschl et al, 2001;Ammann et al, 2003;Mmereki and Donaldson, 2003;Kwamena et al, 45 Figure 3. 2004; Mmereki et al, 2004;Donaldson et al, 2005;Kahan et al, 2006;Kwamena et al, 2006Kwamena et al, , 2007.…”

Section: Pah-o 3 -H 2 O Systemmentioning

confidence: 99%

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3

2009

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Abstract. We present a kinetic double-layer surface model (K2-SURF) that describes the degradation of polycyclic aromatic hydrocarbons (PAHs) on aerosol particles exposed to ozone, nitrogen dioxide, water vapor, hydroxyl and nitrate radicals. The model is based on multiple experimental studies of PAH degradation and on the PRA framework (Pöschl-Rudich-Ammann, 2007) for aerosol and cloud surface chemistry and gas-particle interactions.For a wide range of substrates, including solid and liquid organic and inorganic substances (soot, silica, sodium chloride, octanol/decanol, organic acids, etc.), the concentrationand time-dependence of the heterogeneous reaction between PAHs and O 3 can be efficiently described with a LangmuirHinshelwood-type mechanism. Depending on the substrate material, the Langmuir adsorption constants for O 3 vary over three orders of magnitude (K ads,O3 ≈ 10 −15 -10 −13 cm 3 ), and the second-order rate coefficients for the surface layer reaction of O 3 with different PAH vary over two orders of magnitude (k SLR,PAH,O3 ≈ 10 −18 -10 −17 cm 2 s −1 ). The available data indicate that the Langmuir adsorption constants for NO 2 are similar to those of O 3 , while those of H 2 O are several orders of magnitude smaller (K ads,H2O ≈ 10 −18 -10 −17 cm 3 ). The desorption lifetimes and adsorption enthalpies inferred from the Langmuir adsorption constants suggest chemisorption of NO 2 and O 3 and physisorption of H 2 O. Note, however, that the exact reaction mechanisms, rate limiting steps and possible intermediates still remain to be resolved (e.g., surface diffusion and formation of O atoms or O − 3 ions at the surface).Correspondence to: M. Shiraiwa (m.shiraiwa@mpic.de)The K2-SURF model enables the calculation of ozone uptake coefficients, γ O3 , and of PAH concentrations in the quasi-static particle surface layer. Competitive adsorption and chemical transformation of the surface (aging) lead to a strong non-linear dependence of γ O3 on time and gas phase composition, with different characteristics under dilute atmospheric and concentrated laboratory conditions. Under typical ambient conditions, γ O3 of PAH-coated aerosol particles are expected to be in the range of 10 −6 -10 −5 .At ambient temperatures, NO 2 alone does not efficiently degrade PAHs, but it was found to accelerate the degradation of PAHs exposed to O 3 . The accelerating effect can be attributed to highly reactive NO 3 radicals formed in the gas phase or on the surface. Estimated second-order rate coefficients for O 3 -NO 2 and PAH-NO 3 surface layer reactions are in the range of 10 −17 -10 −16 cm 2 s −1 and 10 −15 -10 −12 cm 2 s −1 , respectively.The chemical half-life of PAHs is expected to range from a few minutes on the surface of soot to multiple hours on organic and inorganic solid particles and days on liquid particles. On soot, the degradation of particle-bound PAHs in the atmosphere appears to be dominated by a surface layer reaction with adsorbed ozone. On other substrates, it is likely dominated by gas-surface reactions wit...

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Section: Pah-o 3 -H 2 O Systemmentioning

confidence: 99%

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O3, NO2, H2O, OH and NO3

2009

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“…Only one stack sampling campaign was performed since the process conditions and materials did not change over the course of the study. Ten stack samples were collected in one stack over a period of 10 days (April [15][16][17][18][19][20][21][22][23][24][25][26]1996).…”

Section: Stack Sampling Methods and Strategymentioning

confidence: 99%

“…B[a]P RAR differences between sampling periods (during the same calendar time frame) are significant for many PAHs, and comparisons between chimney and urban sampling station B[a]P RARs indicate that B[a]P may be removed or transformed at a greater rate that most of the other PAHs. Although the stack sampling time frame (April [16][17][18][19][20][21][22][23][24][25][26]1996) differs in comparison with the urban sampling station time frame (December-May), it is believed that the source profile should not change significantly from one season to another as long as the process conditions and materials remain the same. Therefore, based on the study results, B[a]P appears to be less stable than most of the other PAHs, suggesting that it may be a poor marker of urban exposure for the eight PAHs considered in this study.…”

Section: Intersite Comparisons Of Urban Sampling Station B[a]pmentioning

confidence: 99%

Use of Benzo[a]pyrene Relative Abundance Ratios to Assess Exposure to Polycyclic Aromatic Hydrocarbons in the Ambient Atmosphere in the Vicinity of a Söderberg Aluminum Smelter

Sanderson

Farant

2000

Journal of the Air & Waste Management Association

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The purpose of this study was to investigate the use of benzo [a]pyrene (B[a]P) relative abundance ratios (RARs) to assess exposure to polycyclic aromatic hydrocarbons (PAHs) in the urban atmospheric air in the vicinity of a horizontal stud Söderberg aluminum reduction facility. The B[a]P RARs refer to the concentration of individual PAHs measured in a given sample divided by the concentration of B[a]P found in the same sample. This study compared the B[a]P RARs calculated for the facility stack and three sites near the Söderberg aluminum smelter for three different sampling periods. Interperiod differences were significant for many of the PAHs, and the differences between the stations proved insignificant at p < 0.05. The differences between each individual station and the facility stack were significant for all PAHs. B[a]P RARs increased in value at the stations compared with the stack, indicating that B[a]P may be degraded or removed from the atmosphere at a rate greater than that of the majority of the measured PAHs. It is concluded that B[a]P and B[a]P RARs may be poor markers of exposure to PAHs in the vicinity of this Söderberg aluminum refinery for the entire mixture of PAHs present in the ambient atmosphere.

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“…Previous research indicates that heterogeneous PAH degradation reactions generally follow second order kinetics (Wu et al, 1984;Wu and Niki, 1985).…”

Section: Heterogeneous Reactionsmentioning

confidence: 99%

“…The coated glass fibers then are exposed to air containing near ambient levels of NO, and traces of gaseous HNO,. Other substrates used include glass fiber filters (Pitts et al, 1985) fused silica plates (Wu et al, 1984) fly ash (Korfmacher et al, 1980) alumina, carbon black and silica gel (Behmeyer and Hites, 1985). Although 'many elegant techniques.. .…”

Section: Introductionmentioning

confidence: 99%

An experimental technique for studying heterogeneous reactions of polyaromatic hydrocarbons on particle surfaces

Guo

Kamens

1991

J Atmos Chem

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An experimental technique for studying atmospheric heterogeneous reactions of polyaromatic hydrocarbons (PAH) on particle surfaces is reported. Particle bound organics were reacted in a 200 liter Teflon continuous stirred tank reactor (CSTR), with vapor phase oxidants. To provide a source of chemically stable particles for the CSTR, soot particles from a residential wood stove were first introduced during under darkness into a 25 m' outdoor Teflon chamber. Air containing the particles was then added at a constant flow to the CSTR. The rates of heterogeneous reactions were obtained by comparing reacted particle samples with unreacted ones. The derivation of rate expressions for heterogeneous reactions in the CSTR is described. The use of the technique for a study of the nitration of selected soot particle bound PAH species by NOz and HNO, is demonstrated.

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Fluorescence spectroscopic study of reactions between gaseous ozone and surface-adsorbed polycyclic aromatic hydrocarbons

Cited by 54 publications

References 10 publications

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O<sub>3</sub>, NO<sub>2</sub>, H<sub>2</sub>O, OH and NO<sub>3</sub>

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O<sub>3</sub>, NO<sub>2</sub>, H<sub>2</sub>O, OH and NO<sub>3</sub>

Use of Benzo[a]pyrene Relative Abundance Ratios to Assess Exposure to Polycyclic Aromatic Hydrocarbons in the Ambient Atmosphere in the Vicinity of a Söderberg Aluminum Smelter

An experimental technique for studying heterogeneous reactions of polyaromatic hydrocarbons on particle surfaces

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Fluorescence spectroscopic study of reactions between gaseous ozone and surface-adsorbed polycyclic aromatic hydrocarbons

Cited by 54 publications

References 10 publications

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O&lt;sub&gt;3&lt;/sub&gt;, NO&lt;sub&gt;2&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O, OH and NO&lt;sub&gt;3&lt;/sub&gt;

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O&lt;sub&gt;3&lt;/sub&gt;, NO&lt;sub&gt;2&lt;/sub&gt;, H&lt;sub&gt;2&lt;/sub&gt;O, OH and NO&lt;sub&gt;3&lt;/sub&gt;

Use of Benzo[a]pyrene Relative Abundance Ratios to Assess Exposure to Polycyclic Aromatic Hydrocarbons in the Ambient Atmosphere in the Vicinity of a Söderberg Aluminum Smelter

An experimental technique for studying heterogeneous reactions of polyaromatic hydrocarbons on particle surfaces

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Product

Resources

About

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O<sub>3</sub>, NO<sub>2</sub>, H<sub>2</sub>O, OH and NO<sub>3</sub>

Kinetic double-layer model of aerosol surface chemistry and gas-particle interactions (K2-SURF): Degradation of polycyclic aromatic hydrocarbons exposed to O<sub>3</sub>, NO<sub>2</sub>, H<sub>2</sub>O, OH and NO<sub>3</sub>