Youfeng Wang

Kinetic Studies of Heterogeneous Reactions of Polycyclic Aromatic Hydrocarbon Aerosols with NO3 Radicals

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.

Heterogeneous Reactions of Particulate Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms

Methoxyphenols, tracers for wood smoke, are emitted into the atmosphere in large quantities, but their chemical degradation in the atmosphere has not been well characterized. In this study, heterogeneous kinetics of particulate syringaldehyde (SA), vanillic acid (VA), and coniferyl aldehyde (CA) with NO₃ radicals is investigated with a mixed-phase relative rate method. A vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer and an atmospheric gas analysis mass spectrometer are used to monitor online the decays of particulate methoxyphenols and gas-phase isoprene synchronously. The reactive uptake coefficients of NO₃ radicals on SA, VA, and CA particles are calculated to be 0.33, 0.31, and 0.28, respectively, according to the measured methoxyphenol loss ratios and the average NO₃ concentrations. The effective rate constants for heterogeneous reactions of particulate SA, VA, and CA with NO₃ radicals measured under experimental conditions are 5.7 × 10⁻¹², 5.2 × 10⁻¹², and 3.5 × 10⁻¹² cm³ molecule⁻¹ s⁻¹, respectively. In addition, oxalic acid, 2,6-dimethoxybenzoquinone, 5-nitro-VA, 4,6-dinitrogaiacol, protocatechuic acid, vanillin, 5-nitrovanillin, VA, and 5-nitro-CA are identified as the reaction products by gas chromatography-mass spectrometry analysis. On the basis of the identified products, the reaction mechanisms of methoxyphenols with NO₃ radicals are proposed. The main transformation pathway of methoxyphenols is the NO₃ electrophilic addition, followed by H-abstraction and nitro-substituted processes. The experimental results might shed light on the chemical behaviors of methoxyphenols at night.

Effects of humidity and [NO3]/[N2O5] ratio on the heterogeneous reaction of fluoranthene and pyrene with N2O5/NO3/NO2.

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 (Ramdahl et al., 1986). In previous studies, these two products were observed in the gas-phase reaction between N2O5/NO3/NO2 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 [NO3]/[N2O5] ratios were carried out. Under low humidity (0.5% RH) or a relatively high ratio of [NO3]/[N2O5], 2-NFL and 2-NPY were observed as the major nitro-FL isomers for the first time in the heterogeneous reaction. Decreasing the humidity or increasing the [NO3]/[N2O5] ratio in the reaction essentially increases the concentration radio of [NO3(g)]/[NO2(+)(aq)] on the particle surface (NO2(+) is derived from the ionization of N2O5). Thus, it can be concluded that under different atmospheric conditions, the change of [NO3(g)]/[NO2(+)(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.

Heterogeneous Reactions of Pirimiphos-Methyl and Pirimicarb with NO3 Radicals

Pirimiphos-methyl (PMM) and pirimicarb (PM) are two typical N,N-dialkyl substituted pyrimidine pesticides. The heterogeneous reactions of suspended PMM and PM particles with NO(3) radicals are investigated using an online aerosol time-of-flight mass spectrometer and a real-time atmospheric gas analysis mass spectrometer. Three products for PMM and five products for PM are observed and assigned with the aid of GC/MS. Phosphoric acid 2-diethylamino-6-methyl-4-pyrimidinyl dimethyl ester and 2-(dimethylamino)-5,6-dimethyl-4-hydroxy-pyrimidine are the main reaction products observed for PMM and PM, respectively. The effective rate constants for the reactions of PMM and PM particles with NO(3) radicals are (9.9 ± 0.3) × 10(-12) and (7.5 ± 0.3) × 10(-13) cm(3) molecule(-1) s(-1), respectively, obtained using a mixed-phase relative rate method. Geometries and energies of transition states (TS) and intermediates (IM) are obtained by DFT calculation to elucidate the detailed mechanism of the P═S group oxidation into the P═O group for PMM. The theoretical studies present the reasonable intermediates including the S-oxide and the diradical (IM1(a) and IM2(a)). The mechanism explanation may provide useful information for understanding the degradation mechanism of organothionophosphorus compounds in the environment.

Gas-Phase Reactions of Methoxyphenols with NO3 Radicals: Kinetics, Products, and Mechanisms

Methoxyphenols, a group of important tracers for wood smoke, are emitted to the atmosphere in large quantities, but their transformations are rarely studied. In this study, the kinetics and products of the gas-phase reactions of eugenol and 4-ethylguaiacol with NO3 radicals were investigated online using a vacuum ultraviolet photoionization gas time-of-flight mass spectrometer. The rate coefficients of the gaseous reactions of eugenol and 4-ethylguaiacol with NO3 radicals were (1.6 ± 0.4) × 10(-13) and (1.1 ± 0.2) × 10(-12) cm(3) molecule(-1) s(-1) (at 298 K), indicating that the atmospheric lifetimes of the NO3 radicals were 3.5 and 0.5 h, respectively. With the aid of gas-chromatography-mass-spectrometry analysis, several types of degradation products were identified with nitro derivatives as the major products. The configurations of the nitro-product isomers and their formation mechanisms were determined via theoretical calculations. On the basis of these products, degradation pathways of the methoxyphenols with NO3 radicals were proposed. This study determines the degradation rates and mechanisms of the methoxyphenols at night and implies the significant NO3 nighttime chemistry.

Vacuum Ultraviolet Photoionization Mass Spectra of Typical Organics Contained in Ambient Aerosols

ABSTRACT This paper reports an investigation on typical organics contained in ambient aerosols with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The VUV-ATOFMS utilizes a vacuum ultraviolet krypton lamp as an ionization source. The single- and multi-constituent particles generated with typical atmospheric organics (n-eicosane, n-triacontane, 1-pentadecanol, 1-eicosanol, hexanoic acid, decanoic acid, heptadecanoic acid, oleic acid, succinic acid, pyrene, vanillin, benzoic acid, terephthalic acid, and D-galactose) are analyzed with VUV-ATOFMS. The time-of-flight mass spectra of all organic particles are obtained except hexanoic acid. The mass spectra reveal that the detection efficiencies for a certain compound contained in multi-constituent and single-constituent particles are different. These discrepancies may result from the different evaporation dynamics of aerosols in both atomization and vaporization processes. The pyrene has the strongest signal intensity in single- or multi-constituent aerosols, indicating that the VUV-ATOFMS performs well in detecting polycyclic aromatic hydrocarbons. These experimental results present a view on the VUV-photoionization mass spectra of the 14 typical organics contained in ambient aerosols.

Lipid fingerprinting of Bacillus spp. using online MALDI-TOF mass spectrometry

Rapid identification of Bacillus spores has attracted great interest in the medical and forensic communities due to the highly pathogenic nature of certain Bacillus species and its potential application in bioweapons. In this study, we evaluated the feasibility of rapid and reliable identification of several Bacillus spp. (B. subtilis, B. cereus, B. megaterium, B. pumilus, and B. sphaericus) using online MALDI-TOF mass spectrometry combined with lipid profiling. The bacterial cultures in liquid medium were extracted with methanol and chloroform, and the extracts were aerosolized into droplets and immediately analyzed with an online MALDI-TOF mass spectrometer. Results showed that phosphatidylethanolamine (PE), phosphatidylglycerol (PG), and diglycosyldiacylglycerol (DGDG) were present in the mass spectra, as alkali metal adducts. The unique lipid profiles obtained from these Bacillus spp. allowed us to differentiate between them. The reliability and reproducibility of the rapid identification method for Bacillus were tested under different experimental conditions. An alternative online chemotaxonomic method for bacterial identification is demonstrated.

Heterogeneous reactions of particulate benzo[b]fluoranthene and benzo[k]fluoranthene with NO3 radicals

Benzo[b]fluoranthene (B[b]F) and benzo[k]fluoranthene (B[k]F) are widespread priority pollutants of polycyclic aromatic hydrocarbons (PAHs), which can react with atmospheric oxidants during transport in the troposphere and lead to the formation of more toxic compounds. At present, the rates of heterogeneous reactions of B[b]F and B[k]F aerosols with NO3 radicals, an important atmospheric oxidant, are not fully understood. Thus, this study investigated the products and kinetics of heterogeneous reactions of suspended B[b]F and B[k]F particles with NO3 radicals in an aerosol reaction chamber at room temperature (293±2K) under atmospheric pressure. The reactions are monitored online using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and an atmospheric gas analysis mass spectrometer. The mono-nitro-, di-nitro-, tri-nitro-products, and those products containing both nitro and ketone groups are observed with VUV-ATOFMS. The effective rate constants for heterogeneous reactions of particulate B[b]F and B[k]F with NO3 radicals under the experimental conditions are respectively estimated to (1.2±0.1)×10(-12)cm(3)molecule(-1)s(-1) and (5.8±0.3)×10(-13)cm(3)molecule(-1)s(-1) using a mixed-phase relative rate method, and the corresponding effective uptake coefficients are respectively estimated to 0.22 and 0.65. The lifetimes of particulate B[b]F and B[k]F at a typical concentration of NO3 radicals (5×10(8)moleculecm(-3)) in the lower troposphere during the night are estimated to 3.0 and 3.9h, respectively. The experimental results of these heterogeneous reactions in the aerosol state provide supplementary knowledge for kinetic behaviors of airborne PAHs particles.

Kinetic and product study of the heterogeneous reactions of NO3 radicals with suspended resmethrin, phenothrin, and fenvalerate particles

Resmethrin, phenothrin, and fenvalerate are the synthetic pyrethroids that have been used widely against groundling or flying insect pests both indoors and outdoors. In this study, the heterogeneous reactions of the three pyrethroid particles with NO(3) radicals are investigated with a mixed-phase relative rate method. The reactions are performed in a reaction chamber equipped with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and an atmospheric gas analysis mass spectrometer. The uptake coefficients of NO(3) radicals on resmethrin, phenothrin, and fenvalerate particles are ~0.20, 0.04, and 0.03 respectively, calculated with a spherical shell model. And the atmospheric lifetimes of the three pyrethroid particles toward NO(3) radicals are estimated to be ~2.6, 7.5, and 9.3 h, respectively. The molecular structures of reaction products and the reaction pathways are suggested based on the measurements of VUV-ATOFMS and off-line GC-MS.

Theoretical study on the atmospheric transformation mechanism of pirimiphos-methyl initiated by O3

Pirimiphos-methyl (PMM) is a widely used organophosphorus pesticide that can be released into the atmosphere in gas and condensed phases. It possesses a PS bond and an N,N-dialkyl group adjacent to pyrimidine, which are common functional groups for pesticides. Currently, the reaction mechanisms of O3 with these functional groups are poorly understood. In this study, the mechanisms and possible degradation products for O3-initiated atmospheric oxidation of PMM were investigated using the Density Functional Theory (DFT) method. The results show that H abstraction from the alpha carbon of the N,N-diethyl group and its subsequent reactions (hydroxylation, N-dealkylation, and carbonylation reactions), as well as the transformation of the PS bond to the PO oxone form, are the most favorable reaction pathways for PMM and O3. The Gibbs free energy (ΔG) indicates that the subsequent reactions tend to take place more spontaneously once the initial reaction occurs. In addition, theoretical calculations indicate that water can serve as an effective catalyst in the N-dealkylation reaction process. Water-assisted reactions lead to the activation energy decreasing by 20.2 kcal mol(-1) compared with direct reactions, and thus may represent a dominant reaction pathway for the N-dealkylation process in the atmosphere. These theoretical results provide new insights into O3-initiated degradation of PMM and its analogues.