Kinetic and product studies of the reactions of NO3 with a series of unsaturated organic compounds.

Rate coefficients for the reaction of NO3 radicals with 6 unsaturated volatile organic compounds (VOCs) in a 7300 L simulation chamber at ambient temperature and pressure have been determined by the relative rate method. The resulting rate coefficients were determined for isoprene, 2-carene, 3-carene, methyl vinyl ketone (MVK), methacrolein (MACR) and crotonaldehyde (CA), as (6.6 ± 0.8) × 10-13, (1.8 ± 0.6) × 10-11, (8.7 ± 0.5) × 10-12, (1.24 ± 1.04) × 10-16, (3.3 ± 0.9) × 10-15 and (5.7 ± 1.2) × 10-15 cm3/(molecule•sec), respectively. The experiments indicate that NO3 radical reactions with all the studied unsaturated VOCs proceed through addition to the olefinic bond, however, it indicates that the introduction of a carbonyl group into unsaturated VOCs can deactivate the neighboring olefinic bond towards reaction with the NO3 radical, which is to be expected since the presence of these electron-withdrawing substituents will reduce the electron density in the π orbitals of the alkenes, and will therefore reduce the rate coefficient of these electrophilic addition reactions. In addition, we investigated the product formation from the reactions of 2-carene and 3-carene with the NO3 radical. Qualitative identification of an epoxide (C10H16OH+), caronaldehyde (C10H16O2H+) and nitrooxy-ketone (C10H16O4NH+) was achieved using a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) and a reaction mechanism is proposed.

Reactive uptake of NO2 on volcanic particles: A possible source of HONO in the atmosphere.

The heterogeneous degradation of nitrogen dioxide (NO2) on five samples of natural Icelandic volcanic particles has been investigated. Laboratory experiments were carried out under simulated atmospheric conditions using a coated wall flow tube (CWFT). The CWFT reactor was coupled to a blue light nitrogen oxides analyzer (NOx analyzer), and a long path absorption photometer (LOPAP) to monitor in real time the concentrations of NO2, NO and HONO, respectively. Under dark and ambient relative humidity conditions, the steady state uptake coefficients of NO2 varied significantly between the volcanic samples probably due to differences in magma composition and morphological variation related with the density of surface OH groups. The irradiation of the surface with simulated sunlight enhanced the uptake coefficients by a factor of three indicating that photo-induced processes on the surface of the dust occur. Furthermore, the product yields of NO and HONO were determined under both dark and simulated sunlight conditions. The relative humidity was found to influence the distribution of gaseous products, promoting the formation of gaseous HONO. A detailed reaction mechanism is proposed that supports our experimental observations. Regarding the atmospheric implications, our results suggest that the NO2 degradation on volcanic particles and the corresponding formation of HONO is expected to be significant during volcanic dust storms or after a volcanic eruption.

Atmospheric Fate and Impact of Perfluorinated Butanone and Pentanone.

Perfluoroketones, used as replacement to halons and CFCs, are excluded from the Montreal Protocol because they are considered as nonozone depleting substances. However, their chemical structure makes them possible greenhouse gases if their atmospheric lifetimes are long enough. To assess that possibility, we investigated the photolysis of perfluoro-2-methyl-3-pentanone (PF-2M3P), and perfluoro-3-methyl-2-butanone (PF-3M2B) using outdoor atmospheric simulation chambers. In addition, the photolysis of a non fluorinated pentanone (2-methyl-3-pentanone, 2M3P) was studied. The results showed that photolysis is the dominant loss pathway of PF-2M3P and PF-3M2B in the troposphere whereas 2M3P is lost by both photolysis and gas phase reaction with atmospheric oxidants. The photolysis effective quantum yields of PF-2M3P, PF-3M2B, and 2M3P were estimated and some of the main products identified. The photolysis of PF-2M3P and PF-3M2B was found to have a minor impact on the atmospheric burden of fluorinated acids. The atmospheric lifetimes of PF-2M3P, PF-3M2B, and 2M3P were estimated to 3-11 days, ∼13 days, and 1-2 days, respectively. Combining the obtained data, it has been concluded that with 100-year time horizon global warming potentials (GWP100) equivalent to <0.21, ∼0.29, and ≤1.3 × 10-7 for PF-2M3P, PF-3M2B, and 2M3P, respectively, these compounds will have a negligible impact on global warming.

Kinetics of the reactions of NO3 radical with alkanes.

The rate coefficients for the reactions of NO3 radicals with methane (CH4), ethane (C2H6), propane (C3H8), n-butane (n-C4H10), iso-butane (iso-C4H10), 2,3-dimethylbutane (C6H14), cyclopentane (C5H10) and cyclohexane (C6H12) at atmosphere pressure (1000 ± 5 hPa) and room temperature (298 ± 1.5 K) were measured using an absolute method. Careful attention was paid to the role of secondary reactions and impurities. The upper limits of rate coefficients for methane and ethane at 298 K are <4 × 10-20 and <5 × 10-19 cm3 molecule-1 s-1, respectively. The rate coefficients at 298 K for propane, n-butane, iso-butane, 2,3-dimethybutane, cyclopentane and cyclohexane are, (9.2 ± 2.9) × 10-18, (1.5 ± 0.4) × 10-17, (8.2 ± 2.2) × 10-17, (5.8 ± 2.4) × 10-16, (1.5 ± 0.6) × 10-16 and (1.3 ± 0.4) × 10-16 cm3 molecule-1 s-1, respectively. Rate coefficients for the reactions of NO3 radical with two deuterated n-butanes (butane-D10 and butane-1,1,1,4,4,4-D6) are also reported. We show that the rate coefficients for NO3 reactions correlate with the enthalpy change for the reaction, thereby suggesting that the mechanism for NO3 reactions with alkanes is through H atom abstraction. The measured rate coefficients are compared with available literature values. This study increases the number of available rate coefficients for the reactions of NO3 with alkanes and sets significantly lower upper limits for reaction of NO3 with ethane and methane. The atmospheric significance of our reported rate coefficients is briefly discussed.

Atmospheric loss of nitrous oxide (N2O) is not influenced by its potential reactions with OH and NO3 radicals.

The rate coefficient for the possible reaction of OH radical with N2O was determined to be k1 < 1 × 10-17 cm3 molecule-1 s-1 between 253 and 372 K using pulsed laser photolysis to generate OH radicals and pulsed laser induced fluorescence to detect them. The rate coefficient for the reaction of NO3 radical with N2O was measured to be k2 < 5 × 10-20 cm3 molecule-1 s-1 at 298 K using a direct method that involves a large reaction chamber equipped with cavity ring down spectroscopic detection of NO3 and N2O5. Various tests were carried out ensure the accuracy of our measurements. Based on our measured upper limits, we suggest that these two reactions alter the atmospheric lifetime of N2O of ∼120 years by less than 4%.

Kinetic and product studies of Cl atoms reactions with a series of branched Ketones.

The rate constants for the Cl atom reaction with three branched ketones have been measured at 298±2K and 760Torr using the relative rate method in the absence of NO. The rate constants values obtained (in units of 10-10cm3/(molecule·sec)) are: k(2-methyl-3-pentanone)=1.07±0.26, k(3-methyl-2-pentanone)=1.21±0.26, and k(4-methyl-2-pentanone)=1.35±0.27. Combining the chemical kinetic data obtained by this study with those reported for other ketones, a revised Structure Activity Relationship (SAR) parameter and R group reactivity (kR) of R(O)R' and CHx (x=1, 2, 3) group reactivity (kCHx) toward Cl atoms were proposed. In addition, the products from the three reactions in the presence of NO were also identified and quantified by using PTR-ToF-MS and GC-FID, and the yields of the identified products are: acetone (39%±8%)+ethanal (78%±12%), 2-butanone (22%±2%)+ethanal (75%±10%)+propanal (14%±1%) and acetone (26%±3%)+2-methylpropanal (24%±2%), for Cl atoms reaction with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone, respectively. Based on the obtained results, the reaction mechanisms of Cl atoms with these three ketones are proposed.

Investigation of the reaction of ozone with isoprene, methacrolein and methyl vinyl ketone using the HELIOS chamber.

The rate constants for the ozonolysis of isoprene (ISO), methacrolein (MACR) and methyl vinyl ketone (MVK) have been measured using the newly built large volume atmospheric simulation chamber at CNRS-Orleans (France), HELIOS (Chambre de simulation atmosphérique à irradiation naturelle d'Orléans). The OH radical yields from the ozonolysis of isoprene, MACR and MVK have also been determined, as well as the gas phase stable products and their yields. The secondary organic aerosol yield for the ozonolysis of isoprene has been tentatively measured in the presence and absence of an OH radical scavenger. The measurements were performed under different experimental conditions with and without adding cyclohexane (cHX) as an OH radical scavenger. All experiments have been conducted at 760 torr of purified dry air (RH < 1%) and ambient temperature (T = 281-295 K). The data obtained are discussed and compared with those from the literature. The use of the HELIOS facility and its associated analytical equipment enables the derivation of kinetic parameters as well as mechanistic information under near realistic atmospheric conditions.

Kinetics of the Reactions of NO3 Radical with Methacrylate Esters.

Two different experimental methods (relative rate and absolute rate methods) were used to measure the rate coefficients for the reactions of NO3 radical with six methacrylate esters: methyl methacrylate (MMA, k1), ethyl methacrylate (EMA, k2), propyl methacrylate (PMA, k3), isopropyl methacrylate (IPMA, k4), butyl methacrylate (BMA, k5), and isobutyl methacrylate (IBMA, k6). In the relative rate method, the loss of the esters relative to that of a reference compound was followed in a 7300 L Teflon-walled chamber at 298 ± 2 K and 1000 ± 5 hpa. In the absolute method, the temporal profiles of NO3 and N2O5 were followed by using a dual channel cavity ring-down spectrometer in the presence of an excess of ester in the 7300 L chamber. The rate coefficients from these two methods (weighted averages) in the units of 10-15 cm3 molecule-1 s-1 at 298 K are k1 = 2.98 ± 0.35, k2 = 4.67 ± 0.49, k3 = 5.23 ± 0.60, k4 = 7.91 ± 1.00, k5 = 5.91 ± 0.58, and k6 = 6.24 ± 0.66. The quoted uncertainties are at the 2σ level and include estimated systematic errors. Unweighted averages are also reported. In addition, the rate coefficient k7 for the reaction of NO3 radical with deuterated methyl methacrylate (MMA-d8) was measured by using the relative rate method to be essentially the same as k1. The trends in the measured rate coefficient with the length and nature of the alkyl group, along with the equivalence of k1 and k7, strongly suggest that the reaction of NO3 with the methacrylate esters proceeds via addition to the double bond on the methacrylate group. The present results are compared with those from previous studies. Using the measured values of the rate coefficients, along with those for reactions of these esters with OH, O3, and chlorine atoms, we calculated the atmospheric lifetimes of methacrylate esters. We suggest that NO3 radicals do contribute to the atmospheric loss of these unsaturated esters, but to a lesser extent than their reactions with OH and O3.

Atmospheric Degradation Initiated by OH Radicals of the Potential Foam Expansion Agent, CF3(CF2)2CH═CH2 (HFC-1447fz): Kinetics and Formation of Gaseous Products and Secondary Organic Aerosols.

The assessment of the atmospheric impact of the potential foam expansion agent, CF3(CF2)2CH═CH2 (HFC-1447fz), requires the knowledge of its degradation routes, oxidation products, and radiative properties. In this paper, the gas-phase reactivity of HFC-1447fz with OH radicals is presented as a function of temperature, obtaining kOH (T = 263-358 K) = (7.4 ± 0.4) × 10(-13)exp{(161 ± 16)/T} (cm(3)·molecule(-1)·s(-1)) (uncertainties: ±2σ). The formation of gaseous oxidation products and secondary organic aerosols (SOAs) from the OH + HFC-1447fz reaction was investigated in the presence of NOx at 298 K. CF3(CF2)2CHO was observed at low- and high-NOx conditions. Evidence of SOA formation (ultrafine particles in the range 10-100 nm) is reported with yields ranging from 0.12 to 1.79%. In addition, the absolute UV (190-368 nm) and IR (500-4000 cm(-1)) absorption cross-sections of HFC-1447fz were determined at room temperature. No appreciable absorption in the solar actinic region (λ > 290 nm) was observed, leaving the removal by OH radicals as the main atmospheric loss process for HFC-1447fz. The major contribution of the atmospheric loss of HFC-1447fz is due to OH reaction (84%), followed by ozone (10%) and chlorine atoms (6%). Correction of the instantaneous radiative efficiency (0.36 W m(-2)·ppbv(-1)) with the relatively short lifetime of HFC-1447fz (ca. 8 days) implies that its global warming potential at a time horizon of 100 year is negligible (0.19) compared to that of HCFC-141b (782) and to that of modern foam-expansion blowing agents (148, 882, and 804 for HFC-152a, HFC-245fa and HFC-365mfc, respectively).

Atmospheric Chemistry of 1-Methoxy 2-Propyl Acetate: UV Absorption Cross Sections, Rate Coefficients, and Products of Its Reactions with OH Radicals and Cl Atoms.

The rate coefficients for the reactions of OH and Cl with 1-methoxy 2-propyl acetate (MPA) in the gas phase were measured using absolute and relative methods. The kinetic study on the OH reaction was conducted in the temperature (263-373) K and pressure (1-760) Torr ranges using the pulsed laser photolysis-laser-induced fluorescence technique, a low pressure fast flow tube reactor-quadrupole mass spectrometer, and an atmospheric simulation chamber/GC-FID. The derived Arrhenius expression is kMPA+OH(T) = (2.01 ± 0.02) × 10-12 exp[(588 ± 123/T)] cm3 molecule-1 s-1. The absolute and relative rate coefficients for the reaction of Cl with MPA were measured at room temperature in the flow reactor and the atmospheric simulation chamber, which led to k(Cl+MPA) = (1.98 ± 0.31) × 10-10 cm3 molecule-1 s-1. GC-FID, GC-MS, and FT-IR techniques were used to investigate the reaction mechanism in the presence of NO. The products formed from the reaction of MPA with OH and their yields were methyl formate (80 ± 7.3%), acetic acid (50 ± 4.8%), and acetic anhydride (22 ± 2.4%), while for Cl reaction, the obtained yields were 60 ± 5.4, 41 ± 3.8, and 11 ± 1.2%, respectively, for the same products. The UV absorption cross section spectrum of MPA was determined in the wavelength range 210-370 nm. The study has shown no photolysis of MPA under atmospheric conditions. The obtained results are used to derive the atmospheric implication.

Seasonal, diurnal and nocturnal variations of carbonyl compounds in the semi-urban environment of Orléans, France.

Atmospheric carbonyls were measured at a semi-urban site in Orléans, France, from October 2010 to July 2011. Formaldehyde, acetaldehyde and acetone were found to be the most abundant carbonyls, with average concentrations of 3.1, 1.0, 2.0 ppb, respectively in summer, 2.3, 0.7, 2.2 ppb, respectively in autumn, 2.2, 1.0, 2.1 ppb, respectively in spring, and 1.5, 0.7, 1.1 ppb, respectively in winter. Photo-oxidation of volatile organic compounds (VOCs) was found to make a remarkable contribution to atmospheric carbonyls in the semi-urban site based on the distinct seasonal and diurnal variations of the carbonyls, as well as the significantly positive correlations between the carbonyls and ozone. The significantly negative correlations between NOx and O3 as well as the carbonyls and the positive correlations between wind speed and O3 as well as the carbonyls implied that the carbonyls and O3 at the semi-urban site were probably formed during air mass transport from neighboring cities.

NitroMAC: An instrument for the measurement of HONO and intercomparison with a long-path absorption photometer.

NitroMAC (French acronym for continuous atmospheric measurements of nitrogenous compounds) is an instrument which has been developed for the semi-continuous measurement of atmospheric nitrous acid (HONO). This instrument relies on wet chemical sampling and detection using high performance liquid chromatography (HPLC)-visible absorption at 540 nm. Sampling proceeds by dissolution of gaseous HONO in a phosphate buffer solution followed by derivatization with sulfanilamide/N-(1-naphthyl)-ethylenediamine. The performance of this instrument was found to be as follows: a detection limit of around 3 ppt with measurement uncertainty of 10% over an analysis time of 10 min. Intercomparison was made between the instrument and a long-path absorption photometer (LOPAP) during two experiments in different environments. First, air was sampled in a smog chamber with concentrations up to 18 ppb of nitrous acid. NitroMAC and LOPAP measurements showed very good agreement. Then, in a second experiment, ambient air with HONO concentrations below 250 ppt was sampled. While NitroMAC showed its capability of measuring HONO in moderate and highly polluted environments, the intercomparison results in ambient air highlighted that corrections must be made for minor interferences when low concentrations are measured.

Atmospheric chemistry of (CF3)2C=CH2: OH radicals, Cl atoms and O3 rate coefficients, oxidation end-products and IR spectra.

The rate coefficients for the gas phase reactions of OH radicals, k1, Cl atoms, k2, and O3, k3, with 3,3,3-trifluoro-2(trifluoromethyl)-1-propene ((CF3)2C=CH2, hexafluoroisobutylene, HFIB) were determined at room temperature and atmospheric pressure employing the relative rate method and using two atmospheric simulation chambers and a static photochemical reactor. OH and Cl rate coefficients obtained by both techniques were indistinguishable, within experimental precision, and the average values were k1 = (7.82 ± 0.55) × 10(-13) cm(3) molecule(-1) s(-1) and k2 = (3.45 ± 0.24) × 10(-11) cm(3) molecule(-1) s(-1), respectively. The quoted uncertainties are at 95% level of confidence and include the estimated systematic uncertainties. An upper limit for the O3 rate coefficient was determined to be k3 < 9.0 × 10(-22) cm(3) molecule(-1) s(-1). In global warming potential (GWP) calculations, radiative efficiency (RE) was determined from the measured IR absorption cross-sections and treating HFIB both as long (LLC) and short (SLC) lived compounds, including estimated lifetime dependent factors in the SLC case. The HFIB lifetime was estimated from kinetic measurements considering merely the OH reaction, τOH = 14.8 days and including both OH and Cl chemistry, τeff = 10.3 days. Therefore, GWP(HFIB,OH) and GWP(HFIB,eff) were estimated to be 4.1 (LLC) and 0.6 (SLC), as well as 2.8 (LLC) and 0.3 (SLC) for a hundred year time horizon. Moreover, the estimated photochemical ozone creation potential (ε(POCP)) of HFIB was calculated to be 4.60. Finally, HCHO and (CF3)2C(O) were identified as final oxidation products in both OH- and Cl-initiated oxidation, while HC(O)Cl was additionally observed in the Cl-initiated oxidation.

Atmospheric chemistry of benzyl alcohol: kinetics and mechanism of reaction with OH radicals.

The atmospheric oxidation of benzyl alcohol has been investigated using smog chambers at ICARE, FORD, and EUPHORE. The rate coefficient for reaction with OH radicals was measured and an upper limit for the reaction with ozone was established; kOH = (2.8 ± 0.4) × 10(-11) at 297 ± 3 K (averaged value including results from Harrison and Wells) and kO(3) < 2 × 10(-19) cm(3) molecule(-1) s(-1) at 299 K. The products of the OH radical initiated oxidation of benzyl alcohol in the presence of NOX were studied. Benzaldehyde, originating from H-abstraction from the -CH(2)OH group, was identified using in situ FTIR spectroscopy, HPLC-UV/FID, and GC-PID and quantified in a yield of (24 ± 5) %. Ring retaining products originating from OH-addition to the aromatic ring such as o-hydroxybenzylalcohol and o-dihydroxybenzene as well as ring-cleavage products such as glyoxal were also identified and quantified with molar yields of (22 ± 2)%, (10 ± 3)%, and (2.7 ± 0.7)%, respectively. Formaldehyde was observed with a molar yield of (27 ± 10)%. The results are discussed with respect to previous studies and the atmospheric oxidation mechanism of benzyl alcohol.

Reaction of NO(2) with selected conjugated alkenes.

The gas phase reactions of selected alkenes (isoprene, myrcene, ocimene, and 1,3-cyclohexadiene) with NO2 under dark condition have been investigated at T ∼ 298 K and P ∼ 760 Torr of purified air. The kinetic studies were performed under pseudo-first-order conditions using a large excess of NO2 concentration to those of the alkenes. The rate coefficients (in 10(-19) cm(3) molecule(-1) s(-1)) obtained are 1.1 ± 0.2 for isoprene, 2.5 ± 0.3 for myrcene, 8.5 ± 1.2 for ocimene, and 15 ± 1 for 1,3-cyclohexadiene. Several products were identified by using in situ Fourier transform infrared (FT-IR) spectrometry, and acetone was found to be the major product from the reactions of NO2 with myrcene and ocimene, with a formation yield of 22 ± 3% and 26 ± 7%, respectively. The oxidation products from the reactions of NO2 with isoprene and 1,3-cyclohexadiene were found to be mainly nitro compounds identified by FT-IR spectroscopy. Reaction mechanisms were proposed to account for the products observed.

Nearly five-year continuous atmospheric measurements of black carbon over a suburban area in central France.

Atmospheric black carbon (BC) concentration over a nearly 5 year period (mid-2017-2021) was continuously monitored over a suburban area of Orléans city (France). Annual mean atmospheric BC concentration were 0.75 ± 0.65, 0.58 ± 0.44, 0.54 ± 0.64, 0.48 ± 0.46 and 0.50 ± 0.72 µg m-3, respectively, for the year of 2017, 2018, 2019, 2020 and 2021. Seasonal pattern was also observed with maximum concentration (0.70 ± 0.18 µg m-3) in winter and minimum concentration (0.38 ± 0.04 µg m-3) in summer. We found a different diurnal pattern between cold (winter and fall) and warm (spring and summer) seasons. Further, fossil fuel burning contributed >90 % of atmospheric BC in the summer and biomass burning had a contribution equivalent to that of the fossil fuel in the winter. Significant week days effect on BC concentrations was observed, indicating the important role of local emissions such as car exhaust in BC level at this site. The behavior of atmospheric BC level with COVID-19 lockdown was also analyzed. We found that during the lockdown in warm season (first lockdown: 27 March-10 May 2020 and third lockdown 17 March-3 May 2021) BC concentration were lower than in cold season (second lockdown: 29 October-15 December 2020), which could be mainly related to the BC emission from biomass burning for heating. This study provides a long-term BC measurement database input for air quality and climate models. The analysis of especially weekend and lockdown effect showed implications on future policymaking toward improving local and regional air quality as well.

Studies of the gas phase reactions of linalool, 6-methyl-5-hepten-2-ol and 3-methyl-1-penten-3-ol with O3 and OH radicals.

The reactions of three unsaturated alcohols (linalool, 6-methyl-5-hepten-2-ol, and 3-methyl-1-penten-3-ol) with ozone and OH radicals have been studied using simulation chambers at T ∼ 296 K and P ∼ 760 Torr. The rate coefficient values (in cm(3) molecule(-1) s(-1)) determined for the three compounds are linalool, k(O3) = (4.1 ± 1.0) × 10(-16) and k(OH) = (1.7 ± 0.3) × 10(-10); 6-methyl-5-hepten-2-ol, k(O3) = (3.8 ± 1.2) × 10(-16) and k(OH) = (1.0 ± 0.3) × 10(-10); and 3-methyl-1-penten-3-ol, k(O3) = (5.2 ± 0.6) × 10(-18) and k(OH) = (6.2 ± 1.8) × 10(-11). From the kinetic data it is estimated that, for the reaction of O(3) with linalool, attack at the R-CH═C(CH(3))(2) group represents around (93 ± 52)% (k(6-methyl-5-hepten-2-ol)/k(linalool)) of the overall reaction, with reaction at the R-CH═CH(2) group accounting for about (1.3 ± 0.5)% (k(3-methyl-1-penten-3-ol)/k(linalool)). In a similar manner it has been calculated that for the reaction of OH radicals with linalool, attack of the OH radical at the R-CH═C(CH(3))(2) group represents around (59 ± 18)% (k(6-methyl-5-hepten-2-ol)/k(linalool)) of the total reaction, while addition of OH to the R-CH═CH(2) group is estimated to be around (36 ± 6)% (k(3-methyl-1-penten-3-ol)/k(linalool)). Analysis of the products from the reaction of O(3) with linalool confirmed that addition to the R-CH═C(CH(3))(2) group is the predominant reaction pathway. The presence of formaldehyde and hydroxyacetone in the reaction products together with compelling evidence for the generation of OH radicals in the system indicates that the hydroperoxide channel is important in the loss of the biradical [(CH(3))(2)COO]* formed in the reaction of O(3) with linalool. Studies on the reactions of O(3) with the unsaturated alcohols showed that the yields of secondary organic aerosols (SOAs) are higher in the absence of OH scavengers compared to the yields in their presence. However, even under low-NO(X) concentrations, the reactions of OH radicals with 3-methyl-1-penten-3-ol and 6-methyl-5-hepten-2-ol will make only a minor contribution to SOA formation under atmospheric conditions. Relatively high yields of SOAs were observed in the reactions of OH with linalool, although the initial concentrations of reactants were quite high. The importance of linalool in the formation of SOAs in the atmosphere requires further investigation. The impact following releases of these unsaturated alcohols into the atmosphere are discussed.

Diurnal variation and potential sources of indoor formaldehyde at elementary school, high school and university in the Centre Val de Loire region of France.

Formaldehyde (HCHO) is one of the abundant indoor pollutants and has been classified as a human carcinogen by the International Agency for Research on Cancer (IARC). Indoor HCHO at schools is particularly important due to the high occupancy density and the health effects on children. In this study, high time resolved measurement of formaldehyde concentration was conducted in the classrooms at elementary school, high school and university under normal students' activities in three different locations in the Region Centre Val de Loire-France. Indoor average formaldehyde concentrations at those three educational institutions were observed to be in the range 10.96-17.95 µg/m3, not exceeding the World Health Organization (WHO) guideline value of 100 µg/m3. As expected, ventilation was found playing an important role in the control of indoor formaldehyde concentration. After opening windows for 30 min, formaldehyde level decreased by ~25% and 38% in the classroom at the elementary school and the high school, respectively. In addition to the primary sources, the objective of this study was also to determine potential secondary sources of indoor formaldehyde in these schools by measuring the other volatile organic compounds (VOCs) present in the classrooms by a Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS). The measurements suggest that the release of residue from tobacco smokers is one of the major sources of indoor HCHO at the high school, which increases HCHO by ~55% averagely within 1 h. Moreover, the control experiments conducted in the university suggests that VOCs such as that released from cleaning products like terpenes, can contribute to the increase of indoor formaldehyde levels through chemical reactions with ozone. This study confirms simple recommendations to reduce the indoors HCHO concentration in schools: use ventilation systems, limit the emissions like cigarette smoke or cleaning products. It also points out that the secondary sources of formaldehyde must be also considered in the classroom.

Atmospheric chemistry of ketones: Reaction of OH radicals with 2-methyl-3-pentanone, 3-methyl-2-pentanone and 4-methyl-2-pentanone.

This work reports new kinetic and mechanistic information on the atmospheric chemistry of ketones. Both absolute and relative rate methods were used to determine the rate constants for OH reactions with 2-methyl-3-pentanone (2M3P), 3-methyl-2-pentanone (3M2P) and 4-methyl-2-pentanone (4M2P), three widely used compounds in the industry. This work constitutes the first temperature dependence study of the reactions of OH with 2M3P and 3M2P. The following rate constants values are recommended at 298 K (in 10-12 cm3 molecule-1 s-1): kOH+2M3P = 3.49 ± 0.5; kOH+3M2P = 6.02 ± 0.14 and kOH+4M2P = 11.02 ± 0.42. The following Arrhenius expressions (in units of cm3 molecule-1 s-1) adequately describe the measured rate constants for OH reactions with 2M3P and 3M2P in the temperature range 263-373 K: k2M3P = (2.33 ± 0.06) × 10-12 exp((127.4 ± 18.6)/T) and k3M2P = (1.05 ± 0.14) × 10-12 exp((537 ± 41)/T). Products studies from the reactions of OH with the investigated ketones were conducted in a 7.3 m3 simulation chamber using PTR-ToF-MS, UHPLC-MS and GC-MS. A series of short chain carbonyl compounds including formaldehyde, acetone, acetaldehyde, 2-butanone and 2-methypropanal were observed as products. Combining the yields of carbonyls measured with those estimated from the SAR method, we propose various mechanistic degradation schemes of the investigated ketones initiated by reaction with OH radicals.

Ozone formation from illuminated titanium dioxide surfaces.

The nitrogen oxides (NO(x)) decomposition on illuminated TiO(2) surfaces has been widely studied, but little is known about the subsequent formation of non-nitrogen containing products. In this study, TiO(2) coated glass surfaces and TiO(2) films with nitrate anions (either premixed with TiO(2) as KNO(3) or deposited from gaseous NO(x)) are irradiated with broad-band light. Upon irradiation, detected gas phase products include NO(2), HNO(2), and O(3). To the best of our knowledge, this is the first study that reveals the production of O(3) from TiO(2) surfaces. By surface charge transfer reactions, nitrate anions are oxidized into nitrate radicals and their photochemistry (almost in the visible) leads to O(3) formation, enhancing the oxidizing power of these surfaces.