Reactive Uptake of NO3, N2O5, NO2, HNO3, and O3on Three Types of Polycyclic Aromatic Hydrocarbon Surfaces

Gross, Simone; Bertram, Allan K.

doi:10.1021/jp7107544

Cited by 101 publications

(155 citation statements)

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“…According to eq 3, the uptake coefficients for NO 3 radicals on BaA, Ch, Py, 1-NP, and 1-OHP particles are 2.4, 1.5, 3.1, 0.5, and 4.8, respectively, which are much larger than the reported data. 12,27 Lambe et al 44 reported that evaporation followed by gas-phase oxidation was the main reason resulting in the uptake coefficients greater than unity observed in their experiment. In this experiment, the vapor pressures of the 4-ring PAHs are less than 6 × 10 −4 Pa and their gas-phase reaction rates with NO 3 radicals are on the order of 10 −17 − 10 −16 cm 3 ·molecule −1 ·s −1 .…”

Section: ■ Results and Discussionmentioning

confidence: 87%

“…12 Considering that the maximum acquisition time of the kinetic data in the experiment is less than 300 s, the direct loss of PAH aerosols due to the reaction with NO 2 is neglected in this study. Kamens et al 35 have reported that the heterogeneous rate constants for reactions of PAHs with N 2 O 5 (∼2.5 × 10 14 molecules·cm −3 ) are on the order of 10 −18 cm 3 ·molecule −1 ·s −1 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Besides, the reported reactive uptake coefficients of N 2 O 5 on PAH surfaces were 4 orders of magnitude lower than those of NO 3 radicals. 12 Therefore, the effects of N 2 O 5 on the loss of PAHs are also ignored in the experiment.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO₃Radicals

Liu

Zhang

Yang

et al. 2012

Environ. Sci. Technol.

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Polycyclic aromatic hydrocarbons (PAHs) and their derivates are mutagenic and carcinogenic substances widely distributed in the atmospheric environment. In this study, effective rate constants for heterogeneous reactions of NO 3 radicals with five 4-ring PAHs [benzo [a]anthracene (BaA), chrysene (Ch), pyrene (Py), 1-nitropyrene (1-NP), and 1-hydroxypyrene (1-OHP)] adsorbed on suspended azelaic acid particles are investigated by a mixed-phase relative rate method with gas-phase isoprene as the reference substance. The concentrations of suspended PAH particles and gas-phase isoprene are monitored concurrently by a real-time vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and an online atmospheric gas analysis mass spectrometer, respectively. The obtained effective rate constants for the reactions of BaA, Ch, Py, 1-NP, and 1-OHP particles with NO 3 radicals are 4.3 × 10 −12 , 4.0 × 10 −12 , 6.4 × 10 −12 , 1.3 × 10 −12 , and 1.0 × 10 −11 cm 3 ·molecule −1 ·s −1 , respectively, and their corresponding atmospheric lifetimes range from several minutes to half an hour at the NO 3 radical concentration of 5 × 10 8 molecules·cm −3 . In addition, the NO 3 uptake coefficients on particulate PAHs are estimated according to the consumption of PAHs under the exposure of NO 3 radicals. The experimental results of these heterogeneous reactions in the aerosol state provide supplementary knowledge for kinetic behaviors of airborne PAHs particles.

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Section: ■ Results and Discussionmentioning

confidence: 87%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO₃Radicals

Liu

Zhang

Yang

et al. 2012

Environ. Sci. Technol.

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“…The PAH nitroderivatives also cause concern for their direct mutagenicity. In addition to direct emission [9][10][11] , some nitro-PAHs are formed in the atmospheric liquid and gas phases via photochemical and dark nitration [12][13][14] . Concerning the inorganic composition of the atmospheric aqueous phase, halides (mainly chloride) are among the most abundant water-soluble anions.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry of 1-Nitronaphthalene: A Potential Source of Singlet Oxygen and Radical Species in Atmospheric Waters

et al. 2010

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Abstract1-Nitronaphthalene (1NN) was used as a model of nitro-PAHs to investigate photosensitized reactions in aqueous solution in the presence of oxygen and halides. Laser Flash Photolysis (LFP) was employed to investigate electron transfer between halide anions and the triplet state of 1NN, leading to the formation of dihalogen radical anions (X 2 •-) in solution. The experiments were performed in the absence or presence of oxygen, showing a bimolecular quenching rate constant for the triplet state of 1NN ( 3 1NN) by oxygen of (1.95 ± 0.05) × 10 9 M -1 s -1 . The decay of 3 1NN was observed to strongly depend on the pH of the medium. At pH > 2, 3 1NN decayed with a pseudo-first order rate constant close to 6.0 × 10 5 s -1 . The rate constant was markedly enhanced at lower pHs, reaching 2.0 × 10 6 s -1 at pH ~ 0.1, which suggests formation of the protonated triplet state ( 3 1NNH + ) at low pHs. Furthermore, we showed that the photoreactions of 3 1NN in the presence of oxygen are potential sources of HO 2 • , 1 O 2 and possibly • OH in aqueous media. In Milli-Q water (pH ~ 6.5) and in the presence of halide anions the quenching rate constant of 3 1NN was evaluated to be (2.9 ± 0.4) × 10 4 M -1 s -1 for chloride, (7.5 ± 0.2) × 10 8 M -1 s -1 for bromide, and (1.1 ± 0.1) × 10 10 M -1 s -1 for iodide. Also in this case a pH-dependent reactivity was evidenced, and the quenching rate constant was (7.7 ± 1.2) × 10 5 M -1 s -1 with chloride at pH 1.1.

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“…1,27,31,33 Alternatively, some recent studies suggested that high concentrations of N 2 O 5 and NO 2 in the ambient atmosphere may block the accommodation and reaction of the NO 3 radical on the particle surfaces. 27,30,36 Unfortunately, these speculations have not yet been scientifically proven.…”

Section: ■ Introductionmentioning

confidence: 99%

Effects of Humidity and [NO₃]/[N₂O₅] Ratio on the Heterogeneous Reaction of Fluoranthene and Pyrene with N₂O₅/NO₃/NO₂

Zhang

Sun

et al. 2014

Environ. Sci. Technol.

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Atmospheric 2-nitrofluoranthene (2-NFL) and 2-nitropyrene (2-NPY) were two important nitro-polycyclic aromatic hydrocarbons (NPAHs). Especially, 2-NFL was recognized to be the most abundant particle-associated NPAH . In previous studies, these two products were observed in the gas-phase reaction between N 2 O 5 /NO 3 /NO 2 and their parent polycyclic aromatic hydrocarbons (PAHs), while the heterogeneous reaction generated other nitro-PAH isomers (1, 3, 7, 8-NFL and 1-NPY) (Atkinson et al. 1990). To clarify the possible reasons for this difference, the heterogeneous reactions of suspended fluoranthene (FL) and pyrene (PY) particles under different relative humidity (RH; 0.5%−43%) and [NO 3 + (aq)] in the particle surface has an influence on the product distribution of FL and PY in the atmosphere. The experimental results provide evidence for the heterogeneous formations of particle-bound 2-NFL and 2-NPY. However, relative to the gas-phase formation, they will be negligible in the real atmosphere. 2-NFL and 2-NPY observed in the ambient particles should mainly derive from deposition of gas-phase reactions. Additionally, this study also clarifies the reason for different nitro-PAHs isomers observed between gas and particulate reactions. ■ INTRODUCTIONThe atmospheric chemistry between polycyclic aromatic hydrocarbons (PAHs) and gas-phase oxidants (O 3 , OH, NO 3 , and NO 2 ) is the most important source of toxic and mutagenic PAH derivatives (nitro-PAHs and oxy-PAHs) in the atmosphere. 1−6 Nitro-PAHs (NPAHs) have mutagenic potencies up to 100 000 times greater than PAHs 7−10 and constitute 10% of the total mutagenicity of inhalable particles in the ambient atmosphere. 11,12 Additionally, these nitrated species especially have strong narrow band adsorption bands in the UV−visible range, which may enhance the radiative forcing in the atmosphere and therefore contribute to significant climate effects. 13,14 Both 2-nitrofluoranthene (2-NFL) and 2-nitropyrene (2-NPY) are two ubiquitous nitro-PAH pollutants and ambient 2-NFL/2-NPY ratio is generally used to assess the contribution of the NO 3 radical chemistry for NPAHs formation. 15−18 Considering that neither 2-NFL nor 2-NPY have been directly observed from combustion emissions, 19−21 most research has focused on the contribution of the atmospheric reactions of FL and PY with gas-phase oxidants (OH or NO 3 radicals in the presence of NO 2 ). Some studies have suggested that these two nitro-PAHs were formed exclusively via atmospheric gas-phase reactions of FL and PY. 22,23 The production of 2-NFL involves the gas-phase reaction between FL and either OH or NO 3 radicals in the presence of NO 2 , whereas the production of 2-NPY mainly involves the gas-phase reaction of PY initiated by OH radical. 24−27 The formation of both 2-NFL and 2-NPY in the gas phase is a multistep addition−elimination reaction initiated by OH or NO 3 radical species. This radical-initiated reaction is postulated to proceed by an initiated-addition of OH radical (present during the day...

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Reactive Uptake of NO₃, N₂O₅, NO₂, HNO₃, and O₃on Three Types of Polycyclic Aromatic Hydrocarbon Surfaces

Cited by 101 publications

References 51 publications

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO₃Radicals

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO₃Radicals

Photochemistry of 1-Nitronaphthalene: A Potential Source of Singlet Oxygen and Radical Species in Atmospheric Waters

Effects of Humidity and [NO₃]/[N₂O₅] Ratio on the Heterogeneous Reaction of Fluoranthene and Pyrene with N₂O₅/NO₃/NO₂

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Reactive Uptake of NO3, N2O5, NO2, HNO3, and O3on Three Types of Polycyclic Aromatic Hydrocarbon Surfaces

Cited by 101 publications

References 51 publications

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO3Radicals

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO3Radicals

Photochemistry of 1-Nitronaphthalene: A Potential Source of Singlet Oxygen and Radical Species in Atmospheric Waters

Effects of Humidity and [NO3]/[N2O5] Ratio on the Heterogeneous Reaction of Fluoranthene and Pyrene with N2O5/NO3/NO2

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Reactive Uptake of NO₃, N₂O₅, NO₂, HNO₃, and O₃on Three Types of Polycyclic Aromatic Hydrocarbon Surfaces

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO₃Radicals

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO₃Radicals

Effects of Humidity and [NO₃]/[N₂O₅] Ratio on the Heterogeneous Reaction of Fluoranthene and Pyrene with N₂O₅/NO₃/NO₂