Role of Hydrogen Migrations in Carbonyl Peroxy Radicals in the Atmosphere

Carbonyl peroxy radicals (RC(O)O2) are the ubiquitous radical intermediates in the atmospheric oxidation of volatile organic compounds. In this work, theoretical studies are carried out to explore the role of the unimolecular H-migration in the carbonyl peroxy radicals by using quantum chemistry and kinetics calculations. The results showed that H-migration could be significant in the atmosphere at least in CH3CH2CH2C(O)O2 and (CH3)2CHCH2C(O)O2 with rates of ∽0.012 and -0.58^-1 at 298 K. Subsequent reactions of CH3CHCH2C(O)OOH would lead to the products with multi-functional groups, which might affect the aerosol formation process;while (CH3)2CCH2C(O)OOH would transform to formaldehyde and acetone in a few steps. These processes would be important for the atmospheric modelling of volatile organic compounds under low-NOx conditions.

Theoretical investigation on reaction mechanism and kinetics of m-xylene bicyclic peroxy radical with HO_(2)

M-xylene bicyclic peroxy radical(M-BPR)is an important atmospheric intermediate formed by the oxidation of m-xylene,which plays an important role in the new particle formation and growth of secondary organic aerosol.In this work,the reaction mechanism,thermodynamic analysis,and kinetics of the reaction between M-BPR and HO_(2)were investigated at the CCSD(T)/cc-pVDZ//B3LYP/6-311G(d,p)level of theory coupled with transition state theory.The calculated results indicate that the title reaction can occur on both singlet and triplet potential energy surfaces,and the formation of hydroperoxides and 3O_(2)via triplet state is the main reaction channel,while the other four singlet product channels are negligible due to the higher barrier heights.Additionally,the reaction rate constants are estimated by using the transition state theory over the temperature range of 258 K to 378 K,and reaction rate constants arc found to be negatively correlated with temperature.At 298 K,the total rate constant for the title reaction is 1.86×10^(-11)cm^(3)·molecule^(-1)·s^(-1).The calculated rate constants over the studied temperature range were used to fit the data and the three-parameter Arrhenius ex-studied is obtainted to be k(T)=4.22×10^(-15)·(T/300)^(1.44)·exp(2505/T)⁠.

Field measurement of the organic peroxy radicals by the low-pressure reactor plus laser-induced fluorescence spectroscopy

A low-pressure reactor(LPR) was developed for the measurement of ambient organic peroxy(RO2)radicals with the use of the laser-induced fluorescence(LIF) instrument.The reactor converts all the RO_(x)(=RO2+HO2+RO+OH) radicals into HO2 radicals.It can conduct different measurement modes through altering the reagent gases,achieving the speciated measurement of RO2 and RO2^#(RO2 radicals derived from the long-chain alkane,alkene and aromatic hydrocarbon).An example of field measurement results was given,with a maximum concentration of 1.88 × 10^(8) molecule/cm^(3) for RO2 and 1.18×10^(8) molecule/cm^(3) for RO2^(#).Also,this instrument quantifies the local ozone production rates directly,which can help to deduce the regional ozone control strategy from an experimental perspective.The new device can se rve as a potent tool for both the explo ration of frontier chemistry and the diagnosis of the control strategies.

Nighttime peroxy radicals chemistry at Rishiri Island during the campaign RISFEX 2003

Peroxy radicals （ROx） concentrations were measured by Peroxy Radical Chemical Amplifier （PERCA） technique during the field campaign RISFEX 2003 （RiShifi Fall Experiment 2003）, which was performed in September 2003 at Rishiri island （45.07 N, 141.12 E, and 35 m asl） in the sea of Japan. The concentrations of nighttime ROx radicals had temporal variations around an average of 7.9±5.8 （1σ） pptv and showed a positive correlation with the summed mixing ratio of four monoterpene species. Model calculations suggested that local nighttime ROx radicals were dominated by the reactions of monoterpene with ozone （03） and nitrate radical （NO3）, contributing ca. 76% and 19%, respectively. The comparisons between the observed ROx and ones modeled had implied that the current model may be overestimated the yields of peroxy radicals from the reactions of monoterpenes with ozone and an important source of peroxy radicals was possibly missed. Abnormal high concentrations of observed ROx radicals were found during high relative humidity （RH） period （especially 〉 95%）, and the possible explanation was that the humidity correction of ROx radicals under high RH conditions may be inaccurate and overestimates ROx concen-

Photochemical Method to Evaluate Oxidation Levels in Heat-Treated Vegetable Oil： Comparison with Peroxide-Value and Acid-Value

To determine the degree of oxidation in vegetable oil, a photochemical method using the electron spin resonance （ESR） spin trapping technique was developed, and the results were compared with those obtained using conventional peroxide-value （PV） and acid-value （AV） methods. Vegetable oil heat-treated were subjected to short UV illumination, and the produced alkyl-oxyl radicals were identified and quantified using the ESR spin trapping technique. ESR signal intensity was used as an indicator of oil oxidation, which monotonically increased as a function of the heat-treatment time. Commercially, available oils were selected and analyzed. The results were compared with those obtained using the PV and AV methods. The present method displayed some analogies with the PV method at least in the early stage of heating. Overall, the present method had highly sensitive and capable of detecting early-stage oxidation in vegetable oil.

Oxidation Mechanism and Toxicity Evolution of Linalool,a Typical Indoor Volatile Chemical Product

Linalool,a high-reactivity volatile chemical product(VCP)commonly found in cleaning products and disinfectants,is increasingly recognized as an emerging contaminant,especially in indoor air.Understanding the gas-phase oxidation mechanism of linalool is crucial for assessing its impact on atmospheric chemistry and human health.Using quantum chemical calculations and computational toxicology simulations,we investigated the atmospheric transformation and toxicity evolution of linalool under low and high NO/HO_(2)·levels,representing indoor and outdoor environments.Our findings reveal that linalool can undergo the novel mechanisms involving concerted peroxy(RO_(2)·)and alkoxy radical(RO·)modulated autoxidation,particularly emphasizing the importance of cyclization reactions indoors.This expands the widely known RO_(2)·-dominated H-shift-driven autoxidation and proposes a generalized autoxidation mechanism that leads to the formation of low-volatility secondary organic aerosol(SOA)precursors.Toxicological analysis shows that over half of transformation products(TPs)exhibited higher carcinogenicity and respiratory toxicity compared to linalool.We also propose time-dependent toxic effects of TPs to assess their long-term toxicity.Our results indicate that the strong indoor emission coupled with slow consumption rates lead to significant health risks under an indoor environment.The results highlight complex indoor air chemistry and health concerns regarding persistent toxic products during indoor cleaning,which involves the use of linalool or other VCPs.

The production of formaldehyde and hydroxyacetone in methacrolein photooxidation: New insights into mechanism and effects of water vapor

Methacrolein（MACR） is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios（0 to 4.04） and relative humidities（＆lt; 3% to80%） using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde（HCHO） were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH3-UC（=CH2）OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NOx level, while lower at high-NOxlevel. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NOx level is that water vapor promotes the production of Umethacrolein nitrate in the reaction of HOCH2 C（CH3）（OO）CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89 × 10 （-18） cm3/molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor.