Rate constant and branching ratio of the reaction of ethyl peroxy radicals with methyl peroxy radicals.

The cross-reaction of ethyl peroxy radicals (CHO) with methyl peroxy radicals (CHO) (R1) has been studied using laser photolysis coupled to time resolved detection of the two different peroxy radicals by continuous wave cavity ring down spectroscopy (cw-CRDS) in their AÃ-X̃ electronic transition in the near-infrared region, CHO at 7602.25 cm, and CHO at 7488.13 cm.

The "atmosphere" of the human body.

A human-occupied indoor space shares many similarities with Earth and its atmosphere.

A modeling study of the impact of photolysis on indoor air quality.

The importance of photolysis as an initiator of air chemistry outdoors is widely recognized, but its role in chemical processing indoors is often ignored. This paper uses recent experimental data to modify a detailed chemical model, using it to investigate the impacts of glass type, artificial indoor lighting, cloudiness, time of year and latitude on indoor photolysis rates and hence indoor air chemistry. Switching from an LED to an uncovered fluorescent tube light increased predicted indoor hydroxyl radical concentrations by ~13%.

Atmospheric reactivity of biogenic volatile organic compounds in a maritime pine forest during the LANDEX episode 1 field campaign.

Trace gas measurements were performed during the LANDEX (the LANDes EXperiment) Episode 1 field campaign in the summer 2017, in one of the largest European maritime pine forests (> 95% Pinus pinaster) located in southwestern France. Efforts have been focused on obtaining a good speciation of 20 major biogenic volatile organic compounds (BVOCs, including pinenes, carenes, terpinenes, linalool, camphene, etc.).

Water does not catalyze the reaction of OH radicals with ethanol.

Recent experiments suggested that water catalyzes the reaction of OH radicals with alcohols, while another work showed the opposite result. Here, we resolve this disagreement and show that heterogeneous oxidation systematically biased the work showing the catalytic effect and corroborate that water does not catalyze the reaction of OH with alcohols.

Investigation on the near-field evolution of industrial plumes from metalworking activities.

In a context where a significant fraction of the population lives near industrial areas, the main objectives of this study are to provide (a) new data on PM chemical compositions, heavy-metal concentrations and trace gases released by metalworking activities and (b) new information on the near-field evolution (up to about a thousand meters) of such industrial plumes in terms of particle chemical composition and size distribution. For that purpose, a one-month field campaign was performed in an industrial area near the city of Dunkirk (Northern France), combining measurements of atmospheric dynamics and physico-chemical characterization of air masses. Comparisons between several elemental ratios (mainly Mn/Fe), particle size distributions and volatile organic compound (VOC) concentrations at the stacks and at a near-field site suggest that plumes of a ferromanganese alloy plant were quickly mixed with pollutants emitted by other sources (mainly other industries, possibly traffic and sea spray), in particular a neighboring steelworks, before reaching the sampling site.

Water Vapor Does Not Catalyze the Reaction between Methanol and OH Radicals.

Recent reports [Jara-Toro et al., Angew. Chem.

The reaction of hydroxyl and methylperoxy radicals is not a major source of atmospheric methanol.

Methanol is a benchmark for understanding tropospheric oxidation, but is underpredicted by up to 100% in atmospheric models. Recent work has suggested this discrepancy can be reconciled by the rapid reaction of hydroxyl and methylperoxy radicals with a methanol branching fraction of 30%. However, for fractions below 15%, methanol underprediction is exacerbated.

Impact of material emissions and sorption of volatile organic compounds on indoor air quality in a low energy building: Field measurements and modeling.

The assessment of VOC emission rates and sorption coefficients was performed for ten surfaces present within a classroom, using field and laboratory emission cells (FLEC) coupled to online and off-line VOC quantification techniques. A total of 21 identified VOCs were emitted by the different surfaces. VOC emission rates measured using PTR-ToF-MS were compared to gas chromatographic measurements.

The reaction of fluorine atoms with methanol: yield of CHO/CHOH and rate constant of the reactions CHO + CHO and CHO + HO.

Xenondifluoride, XeF2, has been photolysed in the presence of methanol, CH3OH. Two reaction pathways are possible: F + CH3OH → CH2OH + HF and F + CH3OH → CH3O + HF. Both products, CH2OH and CH3O, will be converted to HO2 in the presence of O2.

The Reaction between CHO and OH Radicals: Product Yields and Atmospheric Implications.

The reaction between CHO and OH radicals has been shown to be fast and to play an appreciable role for the removal of CHO radials in remote environments such as the marine boundary layer. Two different experimental techniques have been used here to determine the products of this reaction. The HO yield has been obtained from simultaneous time-resolved measurements of the absolute concentration of CHO, OH, and HO radicals by cw-CRDS.

Rate Constant of the Reaction between CHO Radicals and OH Radicals Revisited.

The reaction between CHO and OH radicals has been studied in a laser photolysis cell using the reaction of F atoms with CH and HO for the simultaneous generation of both radicals, with F atoms generated through 248 nm photolysis of XeF. An experimental setup combining cw-Cavity Ring Down Spectroscopy (cw-CRDS) and high repetition rate laser-induced fluorescence (LIF) to a laser photolysis cell has been used. The absolute concentration of CHO was measured by cw-CRDS, while the relative concentration of OH(v = 0) radicals was determined by LIF.

Photolysis of CH₃CHO at 248 nm: evidence of triple fragmentation from primary quantum yield of CH₃ and HCO radicals and H atoms.

Radical quantum yields have been measured following the 248 nm photolysis of acetaldehyde, CH3CHO. HCO radical and H atom yields have been quantified by time resolved continuous wave Cavity Ring Down Spectroscopy in the near infrared following their conversion to HO2 radicals by reaction with O2. The CH3 radical yield has been determined using the same technique following their conversion into CH3O2.

Quantification of OH and HO2 radicals during the low-temperature oxidation of hydrocarbons by Fluorescence Assay by Gas Expansion technique.

•OH and •HO2 radicals are known to be the key species in the development of ignition. A direct measurement of these radicals under low-temperature oxidation conditions (T = 550-1,000 K) has been achieved by coupling a technique named fluorescence assay by gas expansion, an experimental technique designed for the quantification of these radicals in the free atmosphere, to a jet-stirred reactor, an experimental device designed for the study of low-temperature combustion chemistry. Calibration allows conversion of relative fluorescence signals to absolute mole fractions.

Absorption spectrum and absolute absorption cross sections of CH3O2 radicals and CH3I molecules in the wavelength range 7473-7497 cm(-1).

The absorption spectrum of CH3O2 radicals and CH3I molecules has been measured in the range 7473-7497 cm(-1). CH3O2 radicals have been generated by 248 nm laser photolysis of CH3I in the presence of O2, and the relative absorption has been measured by time-resolved continuous-wave cavity ring-down spectroscopy (cw-CRDS). Calibration of the relative absorption spectrum has been carried out on three distinct wavelengths by carefully measuring CH3O2 decays under different experimental conditions and extracting the initial radical concentration (and with this the absolute absorption cross sections) by using the well-known rate constant for the CH3O2 self-reaction.

Experimental and modeling study of the oxidation of n-butane in a jet stirred reactor using cw-CRDS measurements.

The gas-phase oxidation of n-butane has been studied in an atmospheric jet-stirred reactor (JSR) at temperatures up to 950 K. For the first time, continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared has been used, together with gas chromatography (GC), to analyze the products formed during its oxidation. In addition to the quantification of formaldehyde and water, which is always difficult by GC, cw-CRDS allowed as well the quantification of hydrogen peroxide (H2O2).

Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid.

The hydroxyl (OH) radical is the most important oxidant in the atmosphere since it controls its self-oxidizing capacity. The main sources of OH radicals are the photolysis of ozone and the photolysis of nitrous acid (HONO). Due to the attenuation of solar radiation in the indoor environment, the possibility of OH formation through photolytic pathways indoors has been ignored up to now.

Detection of some stable species during the oxidation of methane by coupling a jet-stirred reactor (JSR) to cw-CRDS.

We present the coupling of a jet-stirred reactor to detection by cw-CRDS in the near infrared and first results obtained during the oxidation of methane. The mixture is rapidly expanded from the jet-stirred reactor into a 80 cm-long cw-CRDS cell maintained at a the pressure around 1.33 kPa, thus freezing the reaction and decreasing pressure broadening of the absorption lines.

Quantification of hydrogen peroxide during the low-temperature oxidation of alkanes.

The first reliable quantification of hydrogen peroxide (H(2)O(2)) formed during the low-temperature oxidation of an organic compound has been achieved thanks to a new system that couples a jet stirred reactor to a detection by continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared. The quantification of this key compound for hydrocarbon low-temperature oxidation regime has been obtained under conditions close to those actually observed before the autoignition. The studied hydrocarbon was n-butane, the smallest alkane which has an oxidation behavior close to that of the species present in gasoline and diesel fuels.

Formation of HO2 radicals from the 248 nm two-photon excitation of different aromatic hydrocarbons in the presence of O2.

The excitation energy dependence of HO(2) radical formation from the 248 nm irradiation of four different aromatic hydrocarbons (benzene, toluene, o-xylene, and mesitylene) in the presence of O(2) has been studied. HO(2) has been monitored at 6638.20 cm(-1) by cw-CRDS, and the formation of a short-lived, unidentified species, showing broad-band absorption around the HO(2) absorption line, has been observed.

Measurement of absolute absorption cross sections for nitrous acid (HONO) in the near-infrared region by the continuous wave cavity ring-down spectroscopy (cw-CRDS) technique coupled to laser photolysis.

Absolute absorption cross sections for selected lines of the OH stretch overtone 2ν(1) of the cis-isomer of nitrous acid HONO have been measured in the range 6623.6-6645.6 cm(-1) using the continuous wave cavity ring-down spectroscopy (cw-CRDS) technique.

HO2 formation from the photoexcitation of benzene/O2 mixtures at 248 nm: an energy dependence study.

The energy dependence of HO(2) radical formation from the irradiation of benzene (C(6)H(6)) in the presence of oxygen (O(2)) at 248 nm is studied. We investigate the origin of the HO(2) radicals, that is, whether they originate from the reaction of O(2) with products obtained by one- or two-photon excitation of C(6)H(6). The concentration-time profiles of HO(2) radicals are monitored by continuous-wave cavity ring-down spectroscopy (cw-CRDS) coupled to a laser photolysis reactor.