OH Radical-initiated Reactions Research Articles

Insights into the variations of polycyclic aromatic hydrocarbons and their nitrated and oxygenated derivatives in urban airborne PM2.5

Polycyclic aromatic hydrocarbons (PAHs) can be transformed into more toxic species in the atmosphere, but field evidence for their transformation remains rare. Here, polycyclic aromatic compounds (PACs), including PAHs and their nitrated and oxygenated derivatives (NPAHs and OPAHs), in fine particulate matter (PM2.5) were measured in the seasons at multiple locations in a megacity (Guangzhou, China). Molecular diagnostic ratios (MDRs), meteorological factors, and atmospheric oxidant measurements were employed to understand the atmospheric behaviors of PM2.5-bound PACs. The results indicated that similarities/differences in the short-term variations of PAC concentrations between the locations depended on their sources and seasons. The temporal trends in MDRs were more distinct than those in concentrations among the locations. Meteorological factors affected PAC concentrations through a similar pathway (demodulating loadings on PM). Their influence on the ratios can be explained by compounds’ atmospheric half-life, vapor pressure, or particle-size distribution. Temperature was the most powerful factor for both the concentrations and MDRs. Relative humidity was minor, but its positive influence on the reaction to OH radicals was appreciable. The dependence on PM2.5 concentrations suggests that PM plays a more significant role in the sorption or formation of N/OPAHs than in their parent compounds. The OH radical-initiated reaction is the major formation mechanism of N/OPAHs throughout the year, but substantial reactions to NO3 radical in autumn were observed due to high ozone levels. Multiple linear regression revealed that parent PAHs, NO2, and/or O3 are significant contributing factors to the secondary formation of N/OPAHs. Partial least squares-discriminant analysis showed the distinguishing characteristics of summer and autumn PM2.5-bound PACs. This study provides field evidence for the gaseous and heterogeneous reactions of PAHs.

Investigating the Atmospheric Fate and Kinetics of OH Radical-Initiated Oxidation Reactions for Epoxybutane Isomers: Theoretical Insight.

Epoxides, which belong to the category of oxygenated volatile organic compounds (OVOCs), are emitted into the atmosphere by an array of sources and can impact both human and environmental well-being significantly. This study involves comprehensive computational analyses aimed at investigating the mechanism, thermodynamic aspects, and reaction kinetics associated with hydrogen abstraction reactions of cis-2,3-epoxybutane, trans-2,3-epoxybutane, and 1,2-epoxybutane by OH radicals. The potential energy diagrams involving all of the species for each specific pathway were constructed at the CCSD(T)/aug-cc-pVTZ//M06-2X/cc-pVTZ level of theory. The rate coefficients for all possible pathways were calculated using the Rice-Ramsperger-Kassel-Marcus master equation (RRKM-ME) corrected by Eckart tunneling within the 200-350 K temperature range and 1 atm pressure. The overall rate coefficients of the reaction of cis-2,3-epoxybutane, trans-2,3-epoxybutane, and 1,2-epoxybutane with OH radicals at 298.15 K were found to be 0.32 × 10-12, 0.33 × 10-12, and 0.66 × 10-12 cm3 molecule-1 s-1, respectively. We also studied the atmospheric lifetime and photochemical ozone creation potential (POCP) of all three compounds. In addition, we have provided extensive degradation pathways for the product radicals formed from the initial reaction with OH radicals in the presence of O2 and NO. The study showed that the product radicals can result in various harmful end products, including grade 1 and grade 2 carcinogens, as listed by the World Health Organization (WHO).

Quantum chemical study of the mechanisms, kinetics, and ecotoxicity assessment of OH radical-initiated reactions of 2,2′,4,4′,5,5′ -hexabrominated diphenyl ether (BDE-153) in atmosphere and wastewater

2,2′,4,4′,5,5′-hexabrominated diphenyl ether (BDE-153) and its OH radical addition products are considered potentially harmful to ecological systems. Therefore, the oxidation reactions mechanisms of BDE-153 initiated by OH radical, the reaction kinetics and the ecotoxicity of BDE-153 assessment in the gas and the aqueous phase were investigated using quantum chemical methods. It is more feasible for the OH radical to add at the nonbromine substituted carbon atoms of the aromatic ring in the BDE-153 molecule to create OH addition intermediates. The secondary reactions involving OH addition intermediates in the presence of O2/NO would generate preferred tribromophenol and OH-addition products. Most of the transformation products are still toxic to aquatic organisms. The total and individual rate constants were evaluated by using the KiSThelP program in a suitable temperature range (198–338 K) and a pressure of 1 atm. At 298 K and 1 atm, the total rate constants in atmosphere and wastewater are 2.90 × 10-13 cm3 molecule-1 s−1 and 9.61 × 106 M−1 s−1, and the half-lives are 39.9 days and 72.1–7.21 × 1010 s, respectively. The implicit and explicit solvent models were used to examine the solvent effect on the total reaction. These results clarify the transformation mechanism, atmospheric fate, and ecotoxicity of BDE-153 in advanced oxidation processes. The calculations provided a basis for designing experimental and industrial applications of BDE-153.

Atmospheric Occurrence of Particle-associated Nitrotriphenylenes via Gas-phase Radical-initiated Reactions Observed in South Osaka, Japan

Nitrotriphenylenes (NTPs), which include the highly mutagenic isomer 2-nitrotriphenylene (2-NTP), have been detected in airborne particles. From a public hygienic point of view, it is necessary to study the environmental occurrence of NTPs in detail. In this study, concentrations of five nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) including NTPs in airborne particles and of nitrogen oxides (NOx; NO+NO2) and carbon monoxide (CO), at a location in South Osaka, Japan, were measured at 3 h intervals. It was found that the diurnal variations in the concentrations of 1-nitropyrene (1-NP), NOx, and CO were similar, being high early in the morning and late in the evening. This finding indicates that the occurrence of 1-NP is affected significantly by primary emissions, particularly by automotive emissions. The concentration change in 1-nitrotriphenylene was similar to that of 2-nitropyrene produced by an atmospheric OH radicalinitiated reaction. On the contrary, the variations in the concentrations of 2-nitrofluoranthene (2-NF) and 2-NTP were significantly different from those of the other nitro-PAHs, i.e., their concentrations increased during the nighttime, suggesting that neither 2-NF nor 2-NTP was emitted from the primary sources, but were formed via the NO3 radicalinitiated nitration of the parent fluoranthene and triphenylene (TP) in the atmosphere. Based on the ambient concentration of 2-NTP and the reported rate constant for the reaction of TP with NO3 radicals, the yield of 2-NTP from the gas-phase NO3 radical-initiated reaction of TP was estimated to be 23%.

Characteristics and unique sources of polycyclic aromatic hydrocarbons and nitro-polycyclic aromatic hydrocarbons in PM2.5at a highland background site in northwestern China☆.

Polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in PM2.5 were first observed at a background site (Yuzhong site: YZ site) in the northwestern highlands of China in five seasonal campaigns. Compared with major northwestern cities, PAHs and NPAHs at the YZ site were at a lower level but showed consistent seasonal differences. The PAH and NPAH concentrations peaked in the winter campaigns, which were 36.11±6.54ng/m3 and 418.11±123.55pg/m3, respectively, in winter campaign 1 and 28.97±10.07ng/m3 and 226.89±133.54pg/m3, respectively, in winter campaign 2. These values were approximately a dozen times larger those in other campaigns. The diagnostic ratios indicate that vehicle emissions were the primary source of the PAHs throughout the five campaigns, and coal and biomass combustion also contributed during the winter, summer, and fall campaigns. Among NPAHs, 2-nitrofluoranthene and 2-nitropyrene were generated through OH radical-initiated reactions during atmospheric transport, while 1-nitropyrene came from combustion sources. There is an observation worth pondering, which is that the ratio between pyrene and fluoranthene increased abnormally in the spring and fall campaigns, which is presumably caused by the burning of Tibetan barley straw in the northwestern highlands. The backward trajectories over Tibetan areas in Qinghai and southwestern Gansu are consistent with this hypothesis. In addition, this study reported for the first time that the burning of Tibetan barley straw has become a seasonal contributor to air pollution in northwestern China and is participating in the atmospheric transport of air pollutants driven by the monsoon in East Asia, which urgently requires further research.

Yearly variation in characteristics and health risk of polycyclic aromatic hydrocarbons and nitro-PAHs in urban shanghai from 2010–2018

This study encompassed the regular observation of nine polycyclic aromatic hydrocarbons (PAHs) and three nitro-PAHs (NPAHs) in particulate matter (PM) in Shanghai in summer and winter from 2010 to 2018. The results showed that the mean concentrations of ƩPAHs in summer decreased by 24.7% in 2013 and 18.1% in 2017 but increased by 10.2% in 2015 compared to the data in 2010. However, the mean concentrations of ƩPAHs in winter decreased by 39.7% from 2010 (12.8 ± 4.55 ng/m3) to 2018 (7.72 ± 3.33 ng/m3), and the mean concentrations of 1-nitropyrene in winter decreased by 79.0% from 2010 (42.3 ± 16.1 pg/m3) to 2018 (8.90 ± 2.09 pg/m3). Correlation analysis with meteorological conditions revealed that the PAH and NPAH concentrations were both influenced by ambient temperature. The diagnostic ratios of PAHs and factor analysis showed that they were mainly affected by traffic emissions with some coal and/or biomass combustion. The ratio of 2-nitrofluoranthene to 2-nitropyrene was near 10, which indicated that the OH radical-initiated reaction was the main pathway leading to their secondary formation. Moreover, backward trajectories revealed different air mass routes in each sampling period, indicating a high possibility of source effects from the northern area in winter in addition to local and surrounding influences. Meanwhile, the mean total benzo[a]pyrene-equivalent concentrations in Shanghai in winter decreased by 50.8% from 2010 (1860 ± 645 pg/m3) to 2018 (916 ± 363 pg/m3). These results indicated the positive effects of the various policies and regulations issued by Chinese authorities.

Branching Ratios and Rate Constants for Decomposition and Isomerization of β-Hydroxyalkoxy Radicals Formed from OH Radical-Initiated Reactions of C6-C13 2-Methyl-1-Alkenes in the Presence of NOx.

A series of C6-C13 2-methyl-1-alkenes were reacted with OH radicals in the presence of NOx in a Teflon environmental chamber, and molar yields of the 2-ketone products were measured using gas chromatography. Yields were corrected for secondary reactions with OH radicals and for gas-wall partitioning of the 2-methyl-1-alkene and 2-ketone, with the latter correction being determined from measurements of gas-wall partitioning of 2-ketone standards. Molar yields of 2-ketones decreased with increasing 2-methyl-1-alkene carbon number from a maximum of 0.82 for C6 to a minimum of 0.34 ± 0.02 for C9-C13, which after normalization for the fraction of reaction that occurred by OH radical addition to the C═C double bond (with the rest occurring by H atom abstraction) were 0.86 and 0.39 ± 0.01. These yields were combined with branching ratios determined previously for site-specific OH radical addition to the C═C double bond and for formation of β-hydroxynitrates to determine branching ratios for decomposition and isomerization of β-hydroxyalkoxy radicals. Branching ratios for decomposition decreased with increasing 2-methyl-1-alkene carbon number from a maximum of 0.97 for C6 to a minimum of 0.49 ± 0.01 for C9-C13, while the corresponding values for isomerization increased from 0.03 to 0.51 ± 0.01. The results were used to estimate absolute rate constants and activation energies for decomposition and isomerization and were also combined with previously measured yields of β-hydroxynitrates, dihydroxynitrates, trihydroxynitrates, and H atom abstraction products to obtain yields of ∼75% for the C9-C13 reaction products, with the remainder likely being mostly dihydroxycarbonyls and trihydroxycarbonyls.

Effect of the Hydroxyl Group on Yields and Composition of Organic Aerosol Formed from OH Radical-Initiated Reactions of Alcohols in the Presence of NOx

The effect of a hydroxyl group and its position on the yields of secondary organic aerosol (SOA) formed from OH radical-initiated reactions of the 1- to 5-decanol isomers, 1- and 2-undecanol isomer...

Theoretical and Kinetic Properties of OH Radical-Initiated Oxidation of Galaxolide in the Atmosphere.

Galaxolide (HHCB), an important emerging contaminant, has attracted great environmental concern owing to its widespread occurrence and potential toxicity. In this study, the detailed multichannel mechanism of OH radical-initiated atmospheric degradation reactions of HHCB has been investigated by employing density functional theory (DFT). The reactants, transition states, intermediates, and products were optimized at the MPWB1K/6-31+G(d,p) level, and single-point energies were further refined at the MPWB1K/6-311+G(3df,2p) level of theory. The canonical variational transition-state (CVT) theory combined with the small curvature tunneling (SCT) was performed to evaluate the Arrhenius expressions and rate constants of key elementary reactions over a suitable range of 180-370 K. The thermodynamic and kinetic calculation results show that OH addition and hydrogen abstraction reactions are competitive pathways for HHCB. The dominant products in the presence of O2/NO are epoxide, dialdehyde, alcohol ketone, cyclolactone compounds, and HO2 radicals. At 298 K, the total rate constant of OH-initiated degradation of HHCB is 2.71 × 10-11 cm3 molecule-1 s-1. The atmospheric lifetime of HHCB determined by OH-initiated reactions is 10.09 h, which is in favor of the phenomenon of medium-range transport for HHCB in the atmosphere.

Atmospheric chemistry of perfluorocyclopentene (cyc-CF2CF2CF2CF=CF−): Kinetics, products and mechanism of gas-phase reactions with OH radicals, and atmospheric implications

As a high-profile etching gas, perfluorocyclopentene (cyc-CF2CF2CF2CF=CF−) should be assessed for its atmospheric chemistry and environmental impact prior to expanding its industrial applications. However, the corresponding studies have been limited. In this study, the rate constants for the gas-phase reactions of cyc-CF2CF2CF2CF=CF− with OH radicals were determined by a relative rate method, and shown to be consistent with a theoretical computational results: k1-exp.(298 K) = (4.43 ± 0.10) × 10−14, k1-cal.(298 K) = 4.3 × 10−14, and k1-exp.(253–328 K) = (3.39 ± 0.86) × 10−13 exp(–(616 ± 78)/T) cm3 molecule−1 s−1. The atmospheric lifetime of cyc-CF2CF2CF2CF=CF− is 0.715 year, and its photochemical ozone creation potential is 0.48. Furthermore, the products and mechanism of the OH radical-initiated oxidation reactions were studied for the first time. The major products COF2, CO2, CO, and FC(O)OH are considered to have a negligible environmental effect. The radiative efficiency was determined as 0.246 W m−2 ppb−1, and the global warming potentials (GWPs) with 20-, 100-, and 500- year time horizon were estimated as 188, 51, and 15, respectively. The GWP100 value is significantly lower than those of the replacing targets (6630, 11100, 16 100, 23 500, and 9540 for CF4, C2F6, NF3, SF6, and c-C4F8, respectively).

Photo-degradation ibuprofen by UV/H2O2 process: response surface analysis and degradation mechanism

The removal of ibuprofen (IBP) in aqueous solution using UV/H2O2 process was evaluated. The response surface methodology (RSM) and Box-Behnken design were employed to investigate the effects of process parameters on IBP removal, including the initial IBP concentration, H2O2 dosage, UV light intensity, and initial pH value of solution. The RSM model developed herein fits well with the experiments, and provides a good insight into the OH radical irritated degradation mechanisms and kinetics. High resolution accurate mass spectrometry coupled with liquid chromatography was used to identify the degradation intermediates. A total of 23 degradation products were identified, including mono-hydroxylated products and dihydroxylated products. A series of OH radical-initiated reactions, including hydroxylation, dihydroxylation, decarboxylation, demethylation, ring break, lead to the final mineralization of IBP to CO2 and H2O. UV/H2O2 technology could be a promising technology for IBP removal in aqueous solution.

Effect of the Keto Group on Yields and Composition of Organic Aerosol Formed from OH Radical-Initiated Reactions of Ketones in the Presence of NOx.

Yields of secondary organic aerosol (SOA) were measured for OH radical-initiated reactions of the 2- through 6-dodecanone positional isomers and also n-dodecane and n-tetradecane in the presence of NOx. Yields decreased in the order n-tetradecane > dodecanone isomer average > n-dodecane, and the dodecanone isomer yields decreased as the keto group moved toward the center of the molecule, with 6-dodecanone being an exception. Trends in the yields can be explained by the effect of carbon number and keto group presence and position on product vapor pressures, and by the isomer-specific effects of the keto group on branching ratios for keto alkoxy radical isomerization, decomposition, and reaction with O2. Most importantly, results indicate that isomerization of keto alkoxy radicals via 1,5- and 1,6-H shifts are significantly hindered by the presence of a keto group whereas decomposition is enhanced. Analysis of particle composition indicates that the SOA products are similar for all isomers, and that compared to those formed from the corresponding reactions of alkanes the presence of a pre-existing keto group opens up additional heterogeneous/multiphase reaction pathways that can lead to the formation of new products. The results demonstrate that the presence of a keto group alters gas and particle phase chemistry and provide new insights into the potential effects of molecular structure on the products of the atmospheric oxidation of volatile organic compounds and subsequent formation of SOA.

Estimation of Rate Constants for Gas-Phase Reactions of Chrysene, Benz[a]anthracene, and Benzanthrone with OH and NO3 Radicals via a Relative Rate Method in CCl4 Liquid Phase-System

ABSTRACTCCl4 liquid-phase reaction kinetics of polycyclic aromatic compounds (PACs), including chrysene (CHRY), benz[a]anthracene (BaA), and benzanthrone (BA), with NO3 radicals were investigated at 273 K using a relative rate method with naphthalene (NA) as the reference compound. The obtained relative reaction rates of CHRY, BaA, and BA to NA were 1.76 ± 0.08, 2.27 ± 0.20, 0.75 ± 0.01, respectively. CHRY, BaA, and BA are semi-volatile PACs with four aromatic rings. They are chemically modified into mutagenic nitropolycyclic aromatic compounds via gas-phase OH or NO3 radical-initiated reactions. Based on the PACs relative reactivity in the CCl4 liquid phase-system, the rate constants at 298 K for the gas-phase reaction of CHRY, BaA, and BA with OH radicals and those of CHRY, BaA, and BA with NO3 radicals were estimated to be (in cm3molecule−1s−1): CHRY, (4.4 ± 0.3) × 10−11 and (9.2 ± 3.2) × 10−28 [NO2]; BaA, (5.3 ± 0.5) × 10−11 and (1.3 ± 0.5) × 10−27 [NO2]; BA, (2.3 ± 0.1) × 10−11 and (3.1 ± 1.1) × 10−28 [NO2].

Impact of OH Radical-Initiated H2CO3 Degradation in the Earth's Atmosphere via Proton-Coupled Electron Transfer Mechanism.

The decomposition of isolated carbonic acid (H2CO3) molecule into CO2 and H2O (H2CO3 → CO2 + H2O) is prevented by a large activation barrier (>35 kcal/mol). Nevertheless, it is surprising that the detection of the H2CO3 molecule has not been possible yet, and the hunt for the free H2CO3 molecule has become challenging not only in the Earth's atmosphere but also on Mars. In view of this fact, we report here the high levels of quantum chemistry calculations investigating both the energetics and kinetics of the OH radical-initiated H2CO3 degradation reaction to interpret the loss of the H2CO3 molecule in the Earth's atmosphere. It is seen from our study that proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) are the two mechanisms by which the OH radical initiates the degradation of the H2CO3 molecule. Moreover, the PCET mechanism is potentially the important one, as the effective barrier, defined as the difference between the zero point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, for the PCET mechanism at the CCSD(T)/6-311++G(3df,3pd) level of theory is ∼3 to 4 kcal/mol lower than the effective barrier height associated with the HAT mechanism. The CCSD(T)/6-311++G(3df,3pd) level predicted effective barrier heights for the degradations of the two most stable conformers of H2CO3 molecule via the PCET mechanism are only ∼2.7 and 4.3 kcal/mol. A comparative reaction rate analysis at the CCSD(T)/6-311++G(3df,3pd) level of theory has also been carried out to explore the potential impact of the OH radical-initiated H2CO3 degradation relative to that from water (H2O), formic acid (FA), acetic acid (AA) and sulfuric acid (SA) assisted H2CO3 → CO2 + H2O decomposition reactions in both the Earth's troposphere and stratosphere. The comparison of the reaction rates reveals that, although the atmospheric concentration of the OH radical is substantially lower than the concentrations of the H2O, FA, AA in the Earth's atmosphere, nevertheless, the OH radical-initiated H2CO3 degradation reaction has significant impact, especially toward the loss of the H2CO3 molecule in the Earth's atmosphere. In clean environments, which exist in greater numbers in comparison to the polluted environments of the Earth's atmosphere, the impact of the OH radical-initiated H2CO3 degradation reaction is seen to be comparable to that from a competing pathway which utilizes hydrogen bonded molecules such as H2O, FA or AA to catalyze the H2CO3 decomposition. Similarly, in the polluted environments, and especially in the Earth's troposphere, although the reactions rates for the OH radical-initiated H2CO3 degradation and FA-assisted H2CO3 decomposition are comparable within a factor of ∼15, nevertheless, the AA-assisted H2CO3 decomposition reaction is appeared to be the dominant channel. This follows only because of slightly greater catalytic efficiency of the AA over FA upon the H2CO3 → CO2 + H2O decomposition reaction. In contrary, although the catalytic efficiencies of SA, FA, and AA upon the H2CO3 decomposition reaction are similar to each other and the concentrations of both the SA and OH radical in the Earth's atmosphere are more-or-less equal to each other, but nevertheless, the SA-assisted H2CO3 decomposition reaction cannot compete with the OH radical-initiated H2CO3 degradation reaction.

Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications

Oxidation products of monoterpenes and isoprene have a major influence on the global secondary organic aerosol (SOA) burden and the production of atmospheric nanoparticles and cloud condensation nuclei (CCN). Here, we investigate the formation of extremely low volatility organic compounds (ELVOC) from O3 and OH radical oxidation of several monoterpenes and isoprene in a series of laboratory experiments. We show that ELVOC from all precursors are formed within the first minute after the initial attack of an oxidant. We demonstrate that under atmospherically relevant concentrations, species with an endocyclic double bond efficiently produce ELVOC from ozonolysis, whereas the yields from OH radical-initiated reactions are smaller. If the double bond is exocyclic or the compound itself is acyclic, ozonolysis produces less ELVOC and the role of the OH radical-initiated ELVOC formation is increased. Isoprene oxidation produces marginal quantities of ELVOC regardless of the oxidant. Implementing our laboratory findings into a global modeling framework shows that biogenic SOA formation in general, and ELVOC in particular, play crucial roles in atmospheric CCN production. Monoterpene oxidation products enhance atmospheric new particle formation and growth in most continental regions, thereby increasing CCN concentrations, especially at high values of cloud supersaturation. Isoprene-derived SOA tends to suppress atmospheric new particle formation, yet it assists the growth of sub-CCN-size primary particles to CCN. Taking into account compound specific monoterpene emissions has a moderate effect on the modeled global CCN budget.

Heterogeneous reactions of particulate matter-bound PAHs and NPAHs with NO3/N2O5, OH radicals, and O3 under simulated long-range atmospheric transport conditions: reactivity and mutagenicity.

The heterogeneous reactions of ambient particulate matter (PM)-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) with NO3/N2O5, OH radicals, and O3 were studied in a laboratory photochemical chamber. Ambient PM2.5 and PM10 samples were collected from Beijing, China, and Riverside, California, and exposed under simulated atmospheric long-range transport conditions for O3 and OH and NO3 radicals. Changes in the masses of 23 PAHs and 20 NPAHs, as well as the direct and indirect-acting mutagenicity of the PM (determined using the Salmonella mutagenicity assay with TA98 strain), were measured prior to and after exposure to NO3/N2O5, OH radicals, and O3. In general, O3 exposure resulted in the highest relative degradation of PM-bound PAHs with more than four rings (benzo[a]pyrene was degraded equally well by O3 and NO3/N2O5). However, NPAHs were most effectively formed during the Beijing PM exposure to NO3/N2O5. In ambient air, 2-nitrofluoranthene (2-NF) is formed from the gas-phase NO3 radical- and OH radical-initiated reactions of fluoranthene, and 2-nitropyrene (2-NP) is formed from the gas-phase OH radical-initiated reaction of pyrene. There was no formation of 2-NF or 2-NP in any of the heterogeneous exposures, suggesting that gas-phase formation of NPAHs did not play an important role during chamber exposures. Exposure of Beijing PM to NO3/N2O5 resulted in an increase in direct-acting mutagenic activity which was associated with the formation of mutagenic NPAHs. No NPAH formation was observed in any of the exposures of the Riverside PM. This was likely due to the accumulation of atmospheric degradation products from gas-phase reactions of volatile species onto the surface of PM collected in Riverside prior to exposure in the chamber, thus decreasing the availability of PAHs for reaction.

Atmospheric Oxidation Mechanism and Kinetic Studies for OH and NO3 Radical-Initiated Reaction of Methyl Methacrylate

The mechanism for OH and NO3 radical-initiated oxidation reactions of methyl methacrylate (MMA) was investigated by using density functional theory (DFT) molecular orbital theory. Geometrical parameters of the reactants, intermediates, transition states, and products were fully optimized at the B3LYP/6-31G(d,p) level. Detailed oxidation pathways were presented and discussed. The rate constants were deduced by the canonical variational transition-state (CVT) theory with the small-curvature tunneling (SCT) correction and the multichannel Rice-Ramspergere-Kassele-Marcus (RRKM) theory, based on the potential energy surface profiles over the general atmospheric temperature range of 180–370 K. The calculated results were in reasonable agreement with experimental measurement.

Products of the OH Radical-Initiated Reactions of Furan, 2- and 3-Methylfuran, and 2,3- and 2,5-Dimethylfuran in the Presence of NO

Products of the gas-phase reactions of OH radicals with furan, furan-d4, 2- and 3-methylfuran, and 2,3- and 2,5-dimethylfuran have been investigated in the presence of NO using direct air sampling atmospheric pressure ionization tandem mass spectrometry (API-MS and API-MS/MS), and gas chromatography with flame ionization and mass spectrometric detectors (GC-FID and GC-MS) to analyze samples collected onto annular denuders coated with XAD solid adsorbent and further coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for derivatization of carbonyl-containing compounds to their oximes. The products observed were unsaturated 1,4-dicarbonyls, unsaturated carbonyl-acids and/or hydroxy-furanones, and from 2,5-dimethylfuran, an unsaturated carbonyl-ester. Quantification of the unsaturated 1,4-dicarbonyls was carried out by GC-FID using 2,5-hexanedione as an internal standard, and the measured molar formation yields were: HC(O)CH═CHCHO (dominantly the E-isomer) from OH + furan, 75 ± 5%; CH3C(O)CH═CHCHO (dominantly the E-isomer) from OH + 2-methylfuran, 31 ± 5%; HC(O)C(CH3)═CHCHO (a E-/Z-mixture) from OH + 3-methylfuran, 38 ± 2%; and CH3C(O)C(CH3)═CHCHO from OH + 2,3-dimethylfuran, 8 ± 2%. In addition, a formation yield of 3-hexene-2,5-dione from OH + 2,5-dimethylfuran of 27% was obtained from a single experiment, in good agreement with a previous value of 24 ± 3% from GC-FID analyses of samples collected onto Tenax solid adsorbent without derivatization.

Atmospheric Chemistry of Methyl and Ethyl N,N,N′,N′-Tetramethylphosphorodiamidate and O,S-Dimethyl Methylphosphonothioate

Rate constants for the reactions of OH radicals with methyl N,N,N',N'-tetramethylphosphorodiamidate [CH3OP(O)[N(CH3)2]2; MTMPDA], ethyl N,N,N',N'-tetramethylphosphorodiamidate [C2H5OP(O)[N(CH3)2]2; ETMPDA], and O,S-dimethyl methylphosphonothioate [CH3OP(O)(CH3)SCH3; OSDMMP] have been measured over the temperature range 281-349 K at atmospheric pressure of air using a relative rate method. The rate expressions obtained were 4.96 × 10(-12) e((1058±71)/T) cm(3) molecule(-1) s(-1) (1.73 × 10(-10) cm(3) molecule(-1) s(-1) at 298 K) for OH + MTMPDA, 4.46 × 10(-12) e((1144±95)/T) cm(3) molecule(-1) s(-1) (2.07 × 10(-10) cm(3) molecule(-1) s(-1) at 298 K) for OH + ETMPDA, and 1.31 × 10(-13) e((1370±229)/T) cm(3) molecule(-1) s(-1) (1.30 × 10(-11) cm(3) molecule(-1) s(-1) at 298 K) for OH + OSDMMP. The rate constant for OH + OSDMMP was independent of O2 content over the range 2.1-71% O2 at 296 ± 2 K. In addition, rate constants for the reactions of NO3 radicals and O3 with MTMPDA, of (1.4 ± 0.1) × 10(-12) cm(3) molecule(-1) s(-1) and <3.5 × 10(-19) cm(3) molecule(-1) s(-1), respectively, were measured at 297 ± 2 K. Products of the OH radical- and, for MTMPDA, NO3 radical-initiated reactions were investigated using gas chromatography and in situ atmospheric pressure ionization mass spectrometry. A product of molecular weight 180 was observed from the OH and NO3 radical-initiated reactions of MTMPDA, and this is attributed to CH3OP(O)[N(CH3)2]N(CH3)CHO. Similarly, a product of molecular weight 194 was observed from the OH + ETMPDA reaction and attributed to C2H5OP(O)[N(CH3)2]N(CH3)CHO. Possible reaction mechanisms are discussed.

Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

In this study, the ozone and OH-radical reactions of myrcene were investigated in an aerosol chamber (at 292–295 K and 50% relative humidity) to examine the gas-phase oxidation products and secondary organic aerosol (SOA) formation. The ozone reaction studies were performed in the presence and absence of CO, which serves as an OH radical scavenger. In the photooxidation experiments OH radicals were generated by photolysis of methyl nitrite. The ozonolysis of myrcene in the presence of CO resulted in a substantial yield of 4-vinyl-4-pentenal (55.3%), measured as m/z 111 plus m/z 93 using proton transfer reaction-mass spectrometry (PTR-MS) and confirmed unambiguously as C7H10O by denuder measurements and HPLC/ESI-TOFMS analysis of its 2,4-dinitrophenylhydrazine (DNPH) derivative. Additionally, the formation of two different organic dicarbonyls with m/z 113 and a molecular formula of C6H8O2 were observed (2.1%). The yields of these dicarbonyls were higher in the ozonolysis experiments without an OH scavenger (5.4%) and even higher (13.8%) in the myrcene OH radical reaction. The formation of hydroxyacetone as a direct product of the myrcene reaction with ozone with a molar yield of 17.6% was also observed. The particle size distribution and volume concentrations were monitored and facilitated the calculation of SOA yields, which ranged from 0 to 0.01 (ozonolysis in the presence of CO) to 0.39 (myrcene OH radical reaction). Terpenylic acid was found in the SOA samples collected from the ozonolysis of myrcene in the absence of an OH scavenger and the OH radical-initiated reaction of myrcene but not in samples collected from the ozonolysis in the presence of CO as an OH radical scavenger, suggesting that terpenylic acid formation involves the reaction of myrcene with an OH radical. A reaction mechanism describing the formation of terpenylic acid is proposed.