Ozonolysis of 2-Methyl-2-pentenal: New Insights from Master Equation Modeling.

Experimental and theoretical studies were carried out to investigate the ozonolysis of trans-2-methyl-2-pentenal. The experiments were conducted in atmospheric simulation chambers coupled to a Fourier transform infrared (FTIR) spectrometer and a gas chromatograph-mass spectrometer at room temperature and atmospheric pressure in the presence of an excess of cyclohexane in dry conditions (RH < 1%). The ozonolysis reaction was investigated theoretically from the results of accurate density functional (M06-2X) and ab initio [CCSD(T)] computations, employing the AVTZ basis set. The sequence of reaction steps was established, and the system of kinetics equations was modeled using MESMER. In the first step, a primary ozonide is formed, which then decomposes along two pathways. The principal ozonolysis products are propanal, methylglyoxal, ethylformate, and a secondary ozonide. An interesting competition between sequential reaction steps and well-skipping is found, which leads to an inversion of the expected methylglyoxal/propanal product ratio at temperatures below 210 K. The mechanism of the "hot ester" reaction channel of the Criegee intermediate was revisited. The computed ozonolysis rate constant and product branching ratio are in excellent agreement with the experimental data that are also reported in the present work.

Method Development for Detecting Low Level Volatile Organic Compounds (VOCs) among Workers and Residents from a Carpentry Work Shop in a Palestinian Village.

Volatile organic compounds (VOCs) are considered a major public health concern in industrial location areas. The presence of exposure to (VOCs) has raised concern regarding the health effects caused by chronic human exposure as this will increase cancer diseases in the village. An analytical method has been developed and modified to help us detect 38 VOCs in the blood of 38 volunteers who are related to a carpentry shop at the parts-per-trillion level. To measure and evaluate the potential risk, several devices, such as portable passive monitors and air-collected samples, in addition to blood concentration, were used to study three different occupational groups. Ten of the volunteers are employees at the shop, 10 volunteers live very close to the shop, and 10 of them are students in an elementary school very close to the shop. In this study, we developed an automated analytical method using headspace (HS) together with solid-phase microextraction (SPME) connected to capillary gas chromatography (GC) equipped with quadrupole mass spectrometry (MS). The detection limits for the method used were measured in the range from 0.001 to 0.15 ng/L, using linear calibration curves that have three orders of magnitude. The detected concentrations ranged from 3 ng L-1 for trichloroethene to 91 ng L-1 for toluene and 270 ng L-1 for 2,4-diisocyanate, which was derived from the paint solvents used for the wood in the carpentry shop and the paints on the walls. More than half of all assessed species (80%) had mean concentration values less than 50 ng L-1, which is the maximum allowed for most VOCs. The major chemical types among the compounds quantified will be those we found in our previous study in the surrounding air of a carpentry workshop in Deir Ballout in Palestine, which were toluene diisocyanate and butyl cyanate. Some were found to be highly present air. Most of the measurements were below the guidelines of the World Health Organization (WHO). Despite the fact that this study only involved a small number of smokers, smoking was found to be connected with several blood and breath components. This group includes unsaturated hydrocarbons (1,3-butadiene, 1,3-pentadiene, 2-butene), furans (2,5-dimethylfuran), and acetonitrile. The proposed classification of measured species into systemic (blood-borne) and exogenous volatiles is strictly hypothetical, as some species may have several origins.

Nickel spreading assessment in New Caledonia by lichen biomonitoring coupled to air mass history.

Lichen biomonitoring and air mass trajectories were used to study the influence of mining activities in the atmospheric dispersion of metallic elements to assess the exposure of the population to dust emitted by mining activities. A map of forward trajectory densities from open mine surfaces throughout New Caledonia was computed and allowed to identify three preferred wind directions (trade wind, bent trade winds and oceanic winds) that could arise in mining particles dispersion all over New Caledonia. Areas where an air quality monitoring would be advisable to evaluate the exposure of the population to the Nickel dusts have been identified. Lichens collected around the industrial mining site KNS and in North Provence of New Caledonia were analysed for their Ni, Co, Cr, Zn and Ti contents. Backward trajectories were simulated from the lichen sampling point using FLEXTRA fed with ECMWF meteorological data, and densities of trajectories having overflown a mine were calculated. Ratio metal/Ti was then plotted as a function of air mass trajectory densities having overflown open pits. A positive correlation between trajectory densities and titanium-normalized metal in lichen for Ni, Co, Cr was highlighted, indicating that mining is a source of dispersion of these metals. For Zn, which is a tracer of fossil fuel or biomass (wood) combustion activity, no correlation was found. Graphical abstract.

Gas-phase UV absorption spectra and OH-oxidation kinetics of 1H-1,2,3-triazole and pyrazole.

In this work, we report the gas phase UV absorption spectra and the kinetics of the OH-oxidation of 1H-1,2,3-triazole and pyrazole. UV spectra were determined between 200 and 250 nm, at 350 ± 2 K and at pressures between 0.09 and 0.3 Torr. The reported maximal UV absorption cross sections are (cm2 per molecule): σ 206 nm, 1H-1H-1,2,3-triazole = 2.04 × 10-18 and σ 203 nm, pyrazole = 5.44 × 10-18. The very low absorption capacity of these compounds beyond 240 nm indicates that their atmospheric photodissociation is negligible. The OH-oxidation of these species was performed in an atmospheric simulation chamber coupled to an FTIR spectrometer and to a GC/MS over the temperature range 298-357 K and at atmospheric pressure. Experiments were conducted in relative mode using benzaldehyde, trans-2-hexenal and heptane as references. The obtained rate constants at 298 K were (×10-11 cm3 per molecule per s): k(OH + 1H-1,2,3-triazole) = 2.16 ± 0.41; k(OH + pyrazole) = 2.94 ± 0.42. These results were compared to those available in the literature and discussed in terms of structure-reactivity and temperature dependency. Their tropospheric lifetimes with respect to reaction with OH radicals were then estimated.

Influence of the coating level on the heterogeneous ozonolysis kinetics and product yields of chlorpyrifos ethyl adsorbed on sand particles.

Heterogeneous oxidation of chlorpyrifos ethyl (CLP) coated sand particles by gaseous ozone was studied. Mono-size sand was coated with CLP at different coating levels between 10 and 100 µg g-1 and exposed to ozone. Results were analyzed thanks to Gas Surface Reaction and Surface Layer Reaction Models. Kinetic parameters derived from these models were analyzed and led to several conclusions. The equilibrium constant of O3 between the gas phase and the CLP-coated sand was independent on the sand contamination level. Ozone seems to have similar affinity for coated or uncoated sand surface. Meanwhile, the kinetic parameters decreased with an increasing coating level. Chlorpyrifos Oxon, (CLPO) has been identified and quantified as an ozonolysis product. The product yield of CLPO remains constant (53 ± 10%) for the different coating level. The key parameter influencing the CLP reactivity towards ozone was the CLP-coating level. This dependence had a great influence on the lifetime of the CLP coated on sand particles, with respect to ozone, which could reach several years at high contamination level.

Heterogeneous ozonolysis of folpet and dimethomorph: a kinetic and mechanistic study.

The research study discussed in this paper concerns determination of the kinetic rate constants for heterogeneous degradation of the pesticides folpet and dimethomorph by ozone at room temperature. The study also involves identification of the degradation products of the analyzed compound in the condensed phase by solid-phase microextraction/gas chromatography/mass spectrometry (SPME/GC/MS). The heterogeneous O3 reactivity of the identified degradation product of dimethomorph, 4-chlorophenyl 3,4-dimethoxyphenyl methanone (CPMPM), is also evaluated experimentally. The obtained results show that the rate constant values of the analytes are (1.7 ± 0.5) × 10(-19), (2.1 ± 0.8) × 10(-19), (2.6 ± 0.2) × 10(-20), and (2.7 ± 0.2) × 10(-20) cm(3)·molecule(-1)·s(-1) for (Z)-dimethomorph, (E)-dimethomorph, folpet, and CPMPM, respectively. Such values implicate heterogeneous ozone lifetimes that vary from a few days to several months, meaning that, depending on their reactivity with respect to other atmospheric oxidants, these compounds might be relatively persistent and may be transported to regions far from their point of application.

Size distributions of fine and ultrafine particles in the city of Strasbourg: correlation between number of particles and concentrations of NO(x) and SO(2) gases and some soluble ions concentration determination.

An Electrical Low Pressure Impactor (ELPI) was used during spring and autumn 2003 in the centre of Strasbourg for the measurement of atmospheric aerosols size distribution. The concentration of NO(x) and SO(2) in air was simultaneously measured with specific analysers. Samples were collected in the range 0.007-10 microm in equivalent aerodynamic diameter size. Number distributions are representative of a pollution originating from urban traffic with a particle size distribution exhibiting a nucleation mode below 29 nm and an accumulation mode around 80 nm in size. A mean particle density equal to 39000+/-35000 total particles per cm(3) with a size ranging from 7 to 10 microm was obtained after a sampling period of 2 weeks in spring. About 86.9% of the number of particles have an aerodynamic diameter below 0.1 microm and 13.1% between 0.1 and 1 microm. Correlation coefficients between the number of particles impacted on each ELPI plate and gas concentrations (SO(2) and NO(x)) showed that the numbers of particles with diameter between 0.10 and 0.62 microm are highly related to the NO(x) concentration. This result indicates that particles are traffic induced since NO(x) is mainly emitted by cars as shown by measurements on various sites. Particles are less clearly correlated to the SO(2) concentration. Particle analysis on different ELPI plates for a sampling period of 2 weeks in autumn showed high level of soluble NO(3)(-), SO(4)(2-) and NH(4)(+) ions. Indeed, up to 90% b.w. of these three species were found in the particle range 0.1-1 microm. The formation of particulate NH(4)NO(3) is favoured by high NO(x) concentration, which induces the formation of gaseous HNO(3).