OH and HO2 measurements in a forested region of north-western Greece

Boundary layer concentrations of hydroxyl (OH) and hydroperoxyl (HO₂) radicals were measured at 1180 m elevation in a mountainous, forested region of north-western Greece during the AEROsols formation from BIogenic organic Carbon (AEROBIC) field campaign held in July–August 1997. In situ measurements of OH radicals were made by laser-induced fluorescence (LIF) at low pressure, exciting in the (0, 0) band of the A–X system at 308 nm. HO₂ radicals were monitored by chemical titration to OH upon the addition of NO, with subsequent detection by LIF. The instrument was calibrated regularly during the field campaign, and demonstrated a sensitivity towards OH and HO₂ of 5.2×10⁵ and 2.4×10⁶ molecule cm⁻³, respectively, for a signal integration period of 2.5 min and a signal-to-noise ratio of 1. Diurnal cycles of OH and HO₂ were measured on 10 days within a small clearing of a forest of Greek Fir (Abies Borisi-Regis). In total 4165 OH data points and 1501 HO₂ data points were collected at 30 s intervals. Noon-time OH and HO₂ concentrations were between 4–12×10⁶ and 0.4–9×10⁸ molecule cm⁻³, respectively. The performance of the instrument is evaluated, and the data are interpreted in terms of correlations with controlling variables. A significant correlation (r²=0.66) is observed between the OH concentration and the rate of photolysis of ozone, J(O¹D). However, OH persisted into the early evening when J(O¹D) had fallen to very low values, consistent with the modelling study presented in the following paper (Carslaw et al., 2001, OH and HO₂ radical chemistry in a forest region of north-western Greece. Atmospheric Environment 35, 4725–4737) that predicts a significant radical source from the ozonolysis of biogenic alkenes. Normalisation of the OH concentrations for variations in J(O¹D) revealed a bell-shaped dependence of OH upon NO_x (NO+NO₂), which peaked at [NO_x] ∼1.75 ppbv. The diurnal variation of HO₂ was found to be less correlated with J(O¹D) compared to OH.     

Kinetics of the gas-phase reactions of alkylnaphthalenes with O3, N2O5 and OH radicals at 298 ± 2 K

Rate constants for the gas-phase reactions of the OH radical with 1-methylnaphthalene and of N₂O₅ with 1- and 2-methylnaphthalene and 2,3-dimethylnaphthalene have been determined at 298 ± 2 K by use of relative rate techniques. The rate constants determined were: for the reaction of OH radicals with 1-methylnaphthalene, (5.30 ± 0.48) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹; for the reaction of N₂O₅ with 1-methylnaphthalene, 2-methylnaphthalene and 2,3-dimethylnaphthalene, (3.3 ± 0.7) × 10⁻¹⁷, (4.2 ± 0.9) × 10⁻¹⁷ and (5.7 ± 1.9) × 10⁻¹⁷ cm³ molecule⁻¹ s⁻¹, respectively. In addition, an upper limit to the rate constant of 1.3 × 10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ was measured for the reaction of O₃ with 1-methylnaphthalene at 298 ± 2 K. These data, when combined with data from previous literature, allow the atmospheric gas-phase removal processes of these alkylnaphthalenes to be quantified.     

Rate constants for the gas phase reactions of OH radicals and O3 with pyrrole at 295 ± 1 K and atmospheric pressure

As part of a program to investigate the atmospheric chemistry and lifetimes of heteroatom-containing organics, rate constants have been determined for the reaction of OH radicals and O₃ with pyrrole in one atmosphere of air at 295 ± 1 K. The rate constants obtained were 1.20 × 10⁻¹⁰ and 1.57 × 10⁻¹⁷ cm³ molecule ⁻¹s⁻¹ for reaction with OH radicals and O₃, respectively. With these rate constants, it can be calculated that under atmospheric conditions the major loss process of pyrrole will be via reaction with the OH radical, with a lifetime due to reaction with OH radicals of ~ 2 h at an OH radical concentration of l × 10⁶ molecule cm⁻³.     

Kinetics of the oxidation of hydrogen sulfite by hydrogen peroxide in aqueous solution:: ionic strength effects and temperature dependence

Conductometry was used to study the kinetics of the oxidation of hydrogen sulfite, HSO⁻₃, by hydrogen peroxide in aqueous non-buffered solution at the low concentration level of 10⁻⁵–10⁻⁶ M, typically found in cloud water. The kinetic data confirm that the rate law reported for the pH range 3–6 at higher concentration levels, rate=k_H·[H⁺]·[HSO⁻₃]·[H₂O₂], is valid at the low concentration level and at low ionic strength I_c. At 298 K and I_c=1.5×10⁻⁴ M, third-order rate constant k_H was found to be k_H=(9.1±0.5)×10⁷ M⁻² s⁻¹. The temperature dependence of k_H led to an activation energy of E_a=29.7±0.9 kJ mol⁻¹. The effect of the ionic strength (adjusted with NaCl) on rate constant k_H was studied in the range I_c=2×10⁻⁴–5.0 M at pH=4.5–5.2 by conductometry and stopped-flow spectrophotometry. The dependence of k_H on I_c can be described with a semi-empirical relationship, which is useful for the purpose of comparison and extrapolation. The kinetic data obtained are critically compared with those reported earlier.     

Rate constant for the reaction of ozone with diethyl sulfide

The rate constant for the reaction of diethyl sulfide (DES; C₂H₅SC₂H₅) with ozone was determined for the first time, which was (2.77±0.27)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ under a room temperature of (289±1) K. Experiments were conducted under supposedly pseudo-first-order decay conditions, keeping [DES]₀>50[O₃]₀, but having different combinations of [DES]₀ and [O₃]₀. Cyclohexane was added into the reactor to eliminate the effect of OH radicals. The wall decay of ozone and the role of cyclohexane were also discussed in the present work.     

Night-time tropospheric chemistry of the unsaturated alcohols (Z)-pent-2-en-1-ol and pent-1-en-3-ol: Kinetic studies of reactions of NO3 and N2O5 with stress-induced plant emissions

The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO₃) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO₃ in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO₃. The rate coefficients were determined to be (1.53±0.23)×10⁻¹³ and (1.39±0.19)×10⁻¹⁴ cm³ molecule⁻¹ s⁻¹ for reactions of NO₃ with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N₂O₅ as source of NO₃ resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO₂ allowed us to determine the rate coefficients for the N₂O₅ reactions to be (5.0±2.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for (Z)-pent-2-en-1-ol, and (9.1±5.8)×10⁻¹⁹ cm³ molecule⁻¹ s⁻¹ for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.     

FT-IR kinetic and product study of the Br-radical initiated oxidation of α, β-unsaturated organic carbonyl compounds

Using the relative kinetic technique the kinetics of the gas-phase reactions of Br radicals with acrolein, methacrolein and methylvinyl ketone have been investigated at (301±3) K in 1013 mbar of (N₂+O₂) bath gas at varying proportions. In 1013 mbar of synthetic air the following rate coefficients have been obtained (in units of cm³ molecule⁻¹ s⁻¹): acrolein (3.21±0.11)×10⁻¹²; methacrolein (2.33±0.08)×10⁻¹¹; methyl vinyl ketone (1.87±0.06)×10⁻¹¹. This study represents the first determination of the rate coefficients for these compounds. As for other unsaturated hydrocarbons the rate coefficient with Br was found to increase with increasing partial pressure of O₂. From the product studies of the reactions it has been established that addition of Br radicals to the terminal C-atom is the major pathway in all three cases. However, for acrolein H atom abstraction from the -CO–H group is also significant. Mechanisms are proposed to explain the observed products, mainly β-brominated carbonyl compounds.     

Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were J_MHP=4.5 (±1.0)×10⁻⁵ s⁻¹ and J_EHP=3.8 (±1.0)×10⁻⁵ s⁻¹ for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10⁸ M⁻¹ s⁻¹ and 5.8 (±1.9)×10⁸ M⁻¹ s⁻¹ relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10⁹ M⁻¹ s⁻¹ relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Atmospheric fate of acrylic acid and acrylonitrile: Rate constants with Cl atoms and OH radicals in the gas phase

Rate coefficients for the reactions of hydroxyl radicals and chlorine atoms with acrylic acid and acrylonitrile have been determined at 298 K and atmospheric pressure. The decay of the organics was followed using a gas chromatograph with a flame ionization detector (GC-FID) and the rate constants were determined using a relative rate method with different reference compounds. Room temperature rate constants are found to be (in cm³ molecule⁻¹ s⁻¹): k₁(OH+CH₂CHC(O)OH)=(1.75±0.47)×10⁻¹¹, k₂(Cl+CH₂CHC(O)OH)=(3.99±0.84)×10⁻¹⁰, k₃(OH+CH₂CHCN)=(1.11±0.33)×10⁻¹¹ and k₄(Cl+CH₂CHCN)=(1.11±0.23)×10⁻¹⁰ with uncertainties representing ±2σ. This is the first kinetic study for these reactions under atmospheric pressure. The rate coefficients are compared with previous determinations taking into account the effect of pressure on the rate constants. The effect of substituent atoms or groups on the overall rate constants is analyzed in comparison with other unsaturated compounds in the literature. In addition, atmospheric lifetimes based on the homogeneous sinks of acrylic acid and acrylonitrile are estimated and compared with other tropospheric sinks for these compounds.     

Carbon monoxide photoproduction from rice and maize leaves

We investigated CO photoproduction from intact leaves of rice (Oryza sativa L.) and maize (Zea mays L.) by laboratory experiments. CO photoproduction showed positive correlation with light intensity and was positively dependent on oxygen concentration. The average CO photoproduction was 2.6±0.3×10¹⁰ molecules cm⁻² s⁻¹ from rice leaves and 2.2±0.1×10¹⁰ molecules cm⁻² s⁻¹ from maize leaves (n=5) at a radiation intensity of 49 mW cm⁻². CO photoproduction from senescent rice leaves was 9 times greater (25.7±1.5×10¹⁰ molecules cm⁻² s⁻¹, n=2) at the same radiation intensity than from live leaves, and responded slowly to changes in oxygen concentration and light intensity. CO photoproduction showed no correlation with CO₂ concentration or humidity. This indicates that CO photoproduction in leaves is not directly controlled by carbon metabolism or stomatal conductance. The lack of dependence on stomatal conductance leads to the conclusion that the diffusion of CO from inside the leaves to the atmosphere is not a controlling factor for CO photoproduction from rice and maize leaves.     

Heterogeneous reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on particles

This work deals with the kinetic study of the reactions of ozone with pyrene, 1-hydroxypyrene and 1-nitropyrene, adsorbed on model particles. Experiments were performed at room temperature and atmospheric pressure, using a quasi-static flow reactor in the absence of light. Compounds were extracted from particles using pressurized fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different O₃ concentrations from which second order rate constants were calculated. The following rate constant values were obtained at 293 K: k(O₃ + Pyrene) = (3.2 ± 0.7) × 10^?16 cm³ molecule^?1 s^?1; k(O₃ + 1OHP) = (7.7 ± 1.4) ×10 ^?16 cm³ molecule^?1 s^?1; and k(O₃ + 1NP) = (2.2 ± 0.5) × 10^?17 cm³ molecule^?1 s^?1, for pyrene, 1-hydroxypyrene and 1-nitropyrene adsorbed on silica particles. The variation in the rate constants demonstrates the strong influence of the substituent (OH or NO₂) on the heterogeneous reactivity of pyrene. The pyrene particulate concentration was also varied in order to check how this parameter may influence the experiments. Finally, oxidation products were investigated for all reactions and some were detected and identified for the first time for ozone heterogeneous reaction with pyrene adsorbed on particles.     

Atmospheric degradation of fluoroesters (FESs): Gas-phase reactivity study towards OH radicals at 298 K

Using the relative technique, rate coefficients have been measured for the gas phase reactions of hydroxyl radicals with four fluoroacetates, methyl trifluoroacetate (CF₃COOCH₃), ethyl trifluoroacetate (CF₃COOCH₂CH₃), methyl difluoroacetate (CF₂HCOOCH₃) and 2,2,2-trifluoroethyl trifluoroacetate (CF₃COOCH₂CF₃). Experiments were carried out at 296±2 K and atmospheric pressure (∼750 Torr) using nitrogen or synthetic air as bath gases. The following rate coefficients were derived for the reaction of OH radicals (in units of cm³ mol⁻¹ s⁻¹) with CF₃COOCH₃, k=(4.97±1.04)×10⁻¹⁴, CF₃COOCH₂CH₃, k=(2.64±0.59)×10⁻¹³, CF₂HCOOCH₃, k=(1.48±0.34)×10⁻¹³ and CF₃COOCH₂CF₃, (1.05±0.23)×10⁻¹³. The rate constants obtained are compared with previous literature data of other volatile organic compounds to establish reactivity trends. Atmospheric implications are discussed in terms of lifetimes and fates of the fluoroacetates in the troposphere.     

Observations of hydroxyl and the sum of peroxy radicals at Summit,Greenland during summer 2003

The first measurements of peroxy (HO₂+RO₂) and hydroxyl (OH) radicals above the arctic snowpack were collected during the summer 2003 campaign at Summit, Greenland. The median measured number densities for peroxy and hydroxyl radicals were 2.2×10⁸ mol cm⁻³ and 6.4×10⁶ mol cm⁻³, respectively. The observed peroxy radical values are in excellent agreement ($R^2=0.83$, $\mathrm{M}/\mathrm{O}=1.06$) with highly constrained model predictions. However, calculated hydroxyl number densities are consistently more than a factor of 2 lower than the observed values. These results indicate that our current understanding of radical sources and sinks is in accord with our observations in this environment but that there may be a mechanism that is perturbing the (HO₂+RO₂)/OH ratio. This observed ratio was also found to depend on meteorological conditions especially during periods of high winds accompanied by blowing snow. Backward transport model simulations indicate that these periods of high winds were characterized by rapid transport (1–2 days) of marine boundary layer air to Summit. These data suggest that the boundary layer photochemistry at Summit may be periodically impacted by halogens.     

Relative rate measurements of reactions of unsaturated alcohols with atomic chlorine as a function of temperature

The kinetics of two structurally similar unsaturated alcohols, 3-butene-2-ol and 2-methyl-3-butene-2-ol (MBO232), with Cl atoms have been investigated for the first time, as a function of temperature using a relative method. As far as we know, the present work also provides the first value for 3-buten-2-ol. The coefficient at room temperature was also obtained for 2-propene-1-ol (allyl alcohol). The reactions were investigated using a 400 L Teflon reaction chamber coupled with gas chromatograph-coupled with flame-ionization detection (GC-FID) detection. The experiments were performed at atmospheric pressure and at temperatures between 256 and 298 K in air or nitrogen as the bath gas. The obtained kinetic data were used to derive the Arrhenius expressions, k_MBO232=(2.83±2.50)×10⁻¹⁴ exp (2670±249)/T, k_3-buten-2-ol=(0.65±1.60)×10⁻¹⁵ exp (3656±695)/T (in units of cm³ molecule⁻¹ s⁻¹). Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO₃ radicals.     

A PLP–LIF kinetic study of the atmospheric reactivity of a series of C4–C7 saturated and unsaturated aliphatic aldehydes with OH

Absolute rate coefficients for the reaction of OH radical with a series of saturated and unsaturated aliphatic aldehydes were measured with the pulsed laser photolysis/laser-induced fluorescence technique at room temperature and as a function of total pressure (p_T=100–400 Torr). No pressure dependence of the rate coefficients was observed. The weighted average values obtained, k_OH±2σ, in units of 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, were 2.88±0.26 for n-butanal, 2.48±0.24 for n-pentanal, 2.60±0.21 for n-hexanal, 2.96±0.23 for n-heptanal, 3.51±0.71 for crotonaldehyde, 2.35±0.32 for trans-2-pentenal, 2.95±0.45 for trans-2-hexenal and 2.45±0.30 for trans-2-heptenal, respectively. The results are compared with previous data when available and with the corresponding coefficients for the reactions with NO₃ and O₃. The dominant tropospheric chemical loss process for these aliphatic aldehydes is the daytime reaction with OH, except in the case of trans-2-heptenal where the estimated lifetime for the reaction with NO₃ radical is smaller than the corresponding value for the OH reaction.     

Atmospheric chemistry of 1-methyl-2-pyrrolidinone

Rate constants for the atmospheric reactions of 1-methyl-2-pyrrolidinone with OH radicals, NO₃ radicals and O₃ have been measured at 296±2 K and atmospheric pressure of air, and the products of the OH radical and NO₃ radical reactions investigated. Using relative rate techniques, rate constants for the gas-phase reactions of OH and NO₃ radicals with 1-methyl-2-pyrrolidinone of (2.15±0.36)×10^-11 cm³ molecule^-1 s^-1 and (1.26±0.40)×10^-13 cm³ molecule^-1 s^-1, respectively, were measured, where the indicated errors include the estimated overall uncertainties in the rate constants for the reference compounds. An upper limit to the rate constant for the O₃ reaction of <1×10^-19 cm³ molecule^-1 s^-1 was also determined. These kinetic data lead to a calculated tropospheric lifetime of 1-methyl-2-pyrrolidinone of a few hours, with both the daytime OH radical reaction and the nighttime NO₃ radical reaction being important loss processes. Products of the OH radical and NO₃ radical reactions were analyzed by gas chromatography with flame ionization detection and combined gas chromatography–mass spectrometry. N-methylsuccinimide and (tentatively) 1-formyl-2-pyrrolidinone were identified as products of both of these reactions. The measured formation yields of N-methylsuccinimide and 1-formyl-2-pyrrolidinone were 44±12% and 41±12%, respectively, from the OH radical reaction and 59±16% and ∼4%, respectively, from the NO₃ radical reaction. Reaction mechanisms consistent with formation of these products are presented.     

Kinetic studies of O3 reactions with 3-bromopropene and 3-iodopropene in the temperature range 288–328 K

The kinetics of the reactions of O₃ with 3-bromopropene and 3-iodopropene has been studied over the temperature range of 288–328 K at atmospheric pressure. The results obtained for the room temperature rate constants are (1.88 ± 0.22) × 10^?18 and (3.52 ± 0.43) × 10^?18 cm³ molecule^?1 s^?1, and the proposed Arrhenius expressions are k = (3.47 ± 1.28) × 10^?15 exp[(?2233 ± 110)/T] and k = (8.17 ± 2.12) × 10^?14 exp[(?2991 ± 80)/T] cm³ molecule^?1 s^?1 for 3-bromopropene and 3-iodopropene, respectively. The atmospheric chemical lifetimes of these two compounds with O₃ were also estimated from these values.     

A photochemical reactor for studies of atmospheric chemistry

A photochemical reactor for studies of atmospheric kinetics and spectroscopy has been built at the Copenhagen Center for Atmospheric Research. The reactor consists of a vacuum FTIR spectrometer coupled to a 100 L quartz cylinder by multipass optics mounted on electropolished stainless steel end flanges, surrounded by UV-A, UV-C and broadband sun lamps in a temperature-controlled housing. The combination of a quartz vessel and UV-C lamps allows higher concentrations of O(¹D) and OH than can be generated by similar chambers. The reactor is able to produce radical concentrations of ca. 8 × 10¹¹ cm^?3 for OH, 3 × 10⁶ cm^?3 for O(¹D), 3.3 × 10¹⁰ cm^?3 for O(³P) and 1.6 × 10¹² cm^?3 for Cl. The reactor can be operated at pressures from 10^?3 to 10³ mbar and temperatures from 240 to 330 K. As a test of the system we have studied the reaction CHCl₃ + Cl using the relative rate technique and find k_CHCl3+Cl/k_CH4+Cl = 1.03 ± 0.11, in good agreement with the accepted value.     

Degradation kinetics of anthracene by ozone on mineral oxides

To further understand the role of substrates on the heterogeneous reactions of polycyclic aromatic hydrocarbons, the reactions of ozone with anthracene adsorbed on different mineral oxides (SiO₂, α-Al₂O₃ and α-Fe₂O₃) and on Teflon disc were investigated in dark at 20 °C. No reaction between ozone and anthracene on Teflon disc was observed when the ozone concentration was ～1.18 × 10¹⁴ molecules cm^?3. The reactions on mineral oxides exhibited pseudo-first-order kinetics for anthracene loss, and the pseudo-first-order rate constant (k_1,obs) displayed a Langmuir–Hinshelwood dependence on the gas-phase ozone concentration. The adsorption equilibrium constants for ozone (K_O3) on SiO₂-1, SiO₂-2, α-Al₂O₃ and α-Fe₂O₃ were (0.81 ± 0.26) × 10^?15 cm³, (2.83 ± 1.17) × 10^?15 cm³, (2.48 ± 0.77) × 10^?15 cm³ and (1.66 ± 0.45) × 10^?15 cm³, respectively; and the maximum pseudo-first-order rate constant (k_1,max) on these oxides were (0.385 ± 0.058) s^?1, (0.101 ± 0.0138) s^?1, (0.0676 ± 0.0086) s^?1 and (0.0457 ± 0.004) s^?1, respectively. Anthraquinone was identified as the main surface product of anthracene reacted with ozone. Comparison with previous research and the results obtained in this study suggest that the reactivity of anthracene with ozone and the lifetimes of anthracene adsorbed on mineral dust in the atmosphere are determined by the nature of the substrate.