Development and validation of a thermally regulated atmospheric simulation chamber (THALAMOS): A versatile tool to simulate atmospheric processes.

Atmospheric simulation chambers, are unique tools for investigating atmospheric processes in the gas and heterogeneous phases. They can provide a controlled yet realistic environment that simulates atmospheric conditions. In the current study, a Teflon atmospheric simulation chamber of 600 L, named THALAMOS (thermally regulated atmospheric simulation chamber) has been developed and cross-validated. THALAMOS can be operated over the temperature range 233 to 373 K under both static and flow conditions. It is equipped with state of the art instrumentation (selective ion flow tube mass spectrometry (SIFT-MS), long path Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectrometry (GC-MS), various analyzers) for the in-line monitoring of both reactants and products. THALAMOS was validated by measuring the rate coefficients of well documented reactions, i.e. the reaction of ethanol with OH radicals and the reaction of dichloromethane with Cl atoms, in a wide temperature range. Two different detection techniques were used in parallel, FTIR and SIFT-MS, to internally cross-validate the obtained results. The measured rate coefficients are in excellent agreement, both between each other and with the literature recommended values. Furthermore, the gas phase oxidation of toluene by Cl atoms (kinetics and product yields) was studied in the temperature range of 253 to 333 K. To the best of our knowledge, THALAMOS is a unique facility on national level and among a few smog chambers internationally that can be operated in such a wide temperature range providing the scientific community with a versatile tool to simulate both outdoor and indoor physicochemical processes.

Particulate metal bioaccessibility in physiological fluids and cell culture media: Toxicological perspectives.

According to the literature, tiny amounts of transition metals in airborne fine particles (PM2.5) may induce proinflammatory cell response through reactive oxygen species production. The solubility of particle-bound metals in physiological fluids, i.e. the metal bioaccessibility is driven by factors such as the solution chemical composition, the contact time with the particles, and the solid-to-liquid phase ratio (S/L). In this work, PM2.5-bound metal bioaccessibility was assessed in various physiological-like solutions including cell culture media in order to evidence the potential impact on normal human bronchial epithelial cells (NHBE) when studying the cytotoxicity and inflammatory responses of PM2.5 towards the target bronchial compartment. Different fluids (H2O, PBS, LHC-9 culture medium, Gamble and human respiratory mucus collected from COPD patients), various S/L conditions (from 1/6000 to 1/100,000) and exposure times (6, 24 and 72h) were tested on urban PM2.5 samples. In addition, metals' total, soluble and insoluble fractions from PM2.5 in LHC-9 were deposited on NHBE cells (BEAS-2B) to measure their cytotoxicity and inflammatory potential (i.e., G6PDH activity, secretion of IL-6 and IL-8). The bioaccessibility is solution-dependent. A higher salinity or organic content may increase or inhibit the bioaccessibiliy according to the element, as observed in the complex mucus matrix. Decreasing the S/L ratio also affect the bioaccessibility depending on the solution tested while the exposure time appears less critical. The LHC-9 culture medium appears to be a good physiological proxy as it induces metal bioaccessibilities close to the mucus values and is little affected by S/L ratios or exposure time. Only the insoluble fraction can be linked to the PM2.5-induced cytotoxicity. By contrast, both soluble and insoluble fractions can be related to the secretion of cytokines. The metal bioaccessibility in LHC-9 of the total, soluble, and insoluble fractions of the PM2.5 under study did not explain alone, the cytotoxicity nor the inflammatory response observed in BEAS-2B cells. These findings confirm the urgent need to perform further toxicological studies to better evaluate the synergistic effect of both bioaccessible particle-bound metals and organic species.

Investigation of the Gas-Phase Photolysis and Temperature-Dependent OH Reaction Kinetics of 4-Hydroxy-2-butanone.

Hydroxyketones are key secondary reaction products in the atmospheric oxidation of volatile organic compounds (VOCs). The fate of these oxygenated VOCs is however poorly understood and scarcely taken into account in atmospheric chemistry modeling. In this work, a combined investigation of the photolysis and temperature-dependent OH radical reaction of 4-hydroxy-2-butanone (4H2B) is presented. The objective was to evaluate the importance of the photolysis process relative to OH oxidation in the atmospheric degradation of 4H2B. A photolysis lifetime of about 26 days was estimated with an effective quantum yield of 0.08. For the first time, the occurrence of a Norrish II mechanism was hypothesized following the observation of acetone among photolysis products. The OH reaction rate coefficient follows the Arrhenius trend (280-358 K) and could be modeled through the following expression: k4H2B(T) = (1.26 ± 0.40) × 10(-12) × exp((398 ± 87)/T) in cm(3) molecule(-1) s(-1). An atmospheric lifetime of 2.4 days regarding the OH + 4H2B reaction was evaluated, indicating that OH oxidation is by far the major degradation channel. The present work underlines the need for further studies on the atmospheric fate of oxygenated VOCs.

Low-Pressure Photolysis of 2,3-Pentanedione in Air: Quantum Yields and Reaction Mechanism.

Dicarbonyls in the atmosphere mainly arise from secondary sources as reaction products in the degradation of a large number of volatile organic compounds (VOC). Because of their sensitivity to solar radiation, photodissociation of dicarbonyls can dominate the fate of these VOC and impact the atmospheric radical budget. The photolysis of 2,3-pentanedione (PTD) has been investigated for the first time as a function of pressure in a static reactor equipped with continuous wave cavity ring-down spectroscopy to measure the HO2 radical photostationary concentrations along with stable species. We showed that (i) Stern-Volmer plots are consistent with low OH-radical formation yields in RCO + O2 reactions, (ii) the decrease of the photodissociation rate due to pressure increase from 26 to 1000 mbar is of about 30%, (iii) similarly to other dicarbonyls, the Stern-Volmer analysis shows a curvature at the lower pressure investigated, which may be assigned to the existence of excited singlet and triplet PTD states, (iv) PTD photolysis at 66 mbar leads to CO2, CH2O and CO with yields of (1.16 ± 0.04), (0.33 ± 0.02) and (0.070 ± 0.005), respectively, with CH2O yield independent of pressure up to 132 mbar and CO yield in agreement with that obtained at atmospheric pressure by Bouzidi et al. (2014), and (v) the PTD photolysis mechanism remains unchanged between atmospheric pressure and 66 mbar. As a part of this work, the O2 broadening coefficient for the absorption line of HO2 radicals at 6638.21 cm(-1) has been determined (γO2 = 0.0289 cm(-1) atm(-1)).

Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.

The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K.

Experimental factors influencing the bioaccessibility and the oxidative potential of transition metals from welding fumes.

Inhalation of welding fumes (WFs) containing high levels of transition metals (Cr, Cu, Fe, Mn, Ni…) is associated with numerous health effects including oxidative stress. However, the measurements of the oxidative potential (OP) and bioaccessibility of WF transition metals depend on several physicochemical parameters and may be subject to several experimental artifacts. In this work, we investigated the influence of the experimental conditions that may affect the bioaccessibility of transition metals and their OP on stainless-steel WF extracts. WFs were produced using a generation bench and sampled on filters. The soluble fraction of the metals was analysed. Two different extraction fluids mimicking physiological pulmonary conditions were studied: phosphate buffer and Hatch's solution. Three extraction times were tested to determine the optimal time for a significant OPDTT using the dithiothreitol (DTT) method. The storage conditions of WFs after filter sampling such as duration, temperature and atmospheric conditions were investigated. The results indicate that experimental conditions can significantly affect the OPDTT and metal bioaccessibility analyses. Cr, Cu and Ni show higher solubility in Hatch's solution than in the phosphate buffer. Mn is highly sensitive to DTT and shows close solubility in the two fluids. An extraction time of 0.5 h in phosphate buffer allows a better sensitivity to OPDTT, probably by limiting complexations, interactions between metals and precipitation. Storage time and temperature can influence the physical or chemical evolution of the WFs, which can affect their OPDTT and Mn solubility. However, storage under N2(g) limits these changes. On-line measurements of OPDTT could provide an alternative to filter sampling to overcome these artifacts.

Development of a new flow reactor for kinetic studies. Application to the ozonolysis of a series of alkenes.

A new flow reactor has been developed to study ozonolysis reactions at ambient pressure and room temperature (297 ± 2 K). The reaction kinetics of O(3) with 4-methyl-1-pentene (4M1P), 2-methyl-2-pentene (2M2P), 2,4,4-trimethyl-1-pentene (tM1P), 2,4,4-trimethyl-2-pentene (tM2P) and α-pinene have been investigated under pseudo-first-order conditions. Absolute measurements of the rate coefficients have been carried out by recording O(3) consumption in excess of organic compound. Alkene concentrations have been determined by sampling adsorbent cartridges that were thermodesorbed and analyzed by gas-chromatography coupled to flame ionization detection. Complementary experimental data have been obtained using a 250 L Teflon smog chamber. The following ozonolysis rate coefficients can be proposed (in cm(3) molecule(-1) s(-1)): k(4M1P) = (8.23 ± 0.50) × 10(-18), k(2M2P) = (4.54 ± 0.96) × 10(-16), k(tM1P) = (1.48 ± 0.11) × 10(-17), k(tM2P) = (1.25 ± 0.10) × 10(-16), and k(α-pinene) = (1.29 ± 0.16) × 10(-16), in very good agreement with literature values. The products of tM2P ozonolysis have been investigated, and branching ratios of (21.4 ± 2.8)% and (73.9 ± 7.3)% have been determined for acetone and 2,2-dimethyl-propanal, respectively. Additionally, a new nonoxidized intermediate, 2-methyl-1-propene, has been identified and quantified. A topological SAR analysis was also performed to strengthen the consistency of the kinetic data obtained with this new flow reactor.

Pesticides in the Indoor Environment of Residential Houses: A Case Study in Strasbourg, France.

Indoor environmental exposure to pesticides has become one of the major concerns that might adversely affect human health and development. People spend most of their lifetime in enclosed indoor environments where they might inhale harmful toxic chemicals, such as pesticides, dispersed either in particulate or in a gas phase. In this study, an assessment of pesticide contamination in indoor environments was conducted. The study covered nine houses during one year, starting from February 2016 and ending in February 2017, in which both air and dust samples were assessed for their potential contamination with 50 pesticides. The results showed that all the assessed houses were contaminated by several pesticides, especially with the allethrin pesticide (detection frequency (DF) = 100%). The highest pesticide contamination was detected in the spring/summer season when it reached an average of around 185 ng g-1 and 186.4 ng sampler-1 in the collected dust and air samples, respectively. The potential contamination of pyrethroid insecticides within all the targeted samples revealed by this study stresses the importance of minimizing the use of such indoor treatments as part of the efficient prevention and control of human exposure to pesticides.

Atmospheric chemistry of 2,3-pentanedione: photolysis and reaction with OH radicals.

The kinetics of the overall reaction between OH radicals and 2,3-pentanedione (1) were studied using both direct and relative kinetic methods at laboratory temperature. The low pressure fast discharge flow experiments coupled with resonance fluorescence detection of OH provided the direct rate coefficient of (2.25 ± 0.44) × 10(-12) cm(3) molecule(-1) s(-1). The relative-rate experiments were carried out both in a collapsible Teflon chamber and a Pyrex reactor in two laboratories using different reference reactions to provide the rate coefficients of 1.95 ± 0.27, 1.95 ± 0.34, and 2.06 ± 0.34, all given in 10(-12) cm(3) molecule(-1) s(-1). The recommended value is the nonweighted average of the four determinations: k(1) (300 K) = (2.09 ± 0.38) × 10(-12) cm(3) molecule(-1) s(-1), given with 2σ accuracy. Absorption cross sections for 2,3-pentanedione were determined: the spectrum is characterized by two wide absorption bands between 220 and 450 nm. Pulsed laser photolysis at 351 nm was used and the depletion of 2,3-pentanedione (2) was measured by GC to determine the photolysis quantum yield of Φ(2) = 0.11 ± 0.02(2σ) at 300 K and 1000 mbar synthetic air. An upper limit was estimated for the effective quantum yield of 2,3-pentanedione applying fluorescent lamps with peak wavelength of 312 nm. Relationships between molecular structure and OH reactivity, as well as the atmospheric fate of 2,3-pentanedione, have been discussed.

Near-surface ozone levels and trends at rural stations in France over the 1995-2003 period.

There is a considerable interest in quantifying near-surface ozone concentrations and associated trends, as they serve to define the impacts on ozone of the anthropogenic precursors reductions and to evaluate the effects of emission control strategies. A statistical test has been used to the ozone air concentrations measured in the French rural monitoring network stations, called MERA, in order to bring out spatio-temporal trends in air quality in France over the 1995-2003 period. The non-parametric Mann-Kendall test has been developed for detecting and estimating monotonic trends in the time series and applied in our study at annual values: mean, 98th percentile and median based on hourly averaged ozone concentrations and applied to daily maxima. In France, when averaged overall 9 stations between 1995 and 2003, a slight increasing trend of the O(3) levels (+0.6 +/- 1.3% year( - 1)) is observed, which is strongly influenced by the concentrations of the high altitude stations. In stations below 1000 m a mean rate of -0.48% year( - 1) from annual average concentrations, of -0.45% year( - 1) for medians and of +0.56% year( - 1) for P.98 over the 1995-2003 period were obtained. In stations above 1,000 m a mean rate of +1.75% year( - 1) from annual averages values, of +4.05% year( - 1) for medians and of +2.55% year( - 1) for P.98 were calculated over the 1997-2003 period. This situation is comparable to the one observed in other countries. In Europe and in France a reduction of precursor emissions is observed whereas a slight increasing trend of the O(3) levels is observed over the 1995-2003 period. One reason is the non-linearity of chemical ozone production with respect to precursor emissions. Possible explanations are an increase in near-surface ozone values caused by a reduced ozone titration by reduced NO( x ), the meteorological parameters change, an increase in bio-geogenic compound concentrations, the intercontinental transport from North America and Asia and the influence of stratospheric-tropospheric exchanges. These possible explanations must be interpreted carefully as on the short time scales considered.

Influence of Dispersed Nanoparticles on the Kinetics of Formation and Molecular Mass of Polyaniline.

Using a combination of the open circuit potential and pH profiles of aniline (An) polymerization and their mathematical treatment, we develop a new convenient semiquantitative approach to determine the influence of the dispersed nanoparticles (e.g., TiO2 nanoparticles) on the kinetic features of this process and molecular mass of the formed polyaniline (PANI). It is revealed that the reciprocal values of the polymerization stages, namely, the duration of the induction period, of homogeneous and heterogeneous pernigraniline (PN) accumulation, and of PN reduction with An, are linear functions of the weight fraction of the nanoparticles. We found that when nanoparticles are added the weight-averaged molecular weight of PANI initially increases from 56 000 to 79 000 and the polydispersity index drops from 3.9 to 1.7. However, at high TiO2 concentrations, the former dramatically decreases, whereas the latter increases. We use the relative proton concentration as a function of time and the different extents of acceleration of the consecutive stages of An polymerization to explain the changes in the molecular weight distribution of PANI with different contents of TiO2 nanoparticles in the polymerization medium.

Characterising sources and sinks of rural VOC in eastern France.

Fifty non-methane hydrocarbons (NMHC) and seventeen carbonyl compounds were measured at a French rural site from 1997 to 2001, as part of the EMEP programme. Data handling was based on an original source-receptor approach. First, the examination of the levels and trends was completed by the comparison of the seasonal distribution of rural and urban VOC/acetylene ambient ratios. This analysis has shown that most of the compounds derived from mixing and photochemical transformation of mid-range transported urban pollutants from the downwind urban area. Then, identified sources and sinks were temporally apportioned. Urban air masses mixing explains, at least, 80% of the wintertime levels of anthropogenic NMHC and isoprene. In summer, photochemistry dominates the day-to-day distribution of anthropogenic NMHC whilst summertime isoprene is also controlled by in-situ biogenic emissions. Then, the results of C(1)-C(3) carbonyls were discussed with respect to their direct biogenic and anthropogenic emissions and photochemical production through the [carbonyl/auto-exhaust tracers] emission ratio. Diluted vehicle exhaust emissions mainly contribute to the total content of lower aldehydes in winter while other processes control lower ketones. Secondary production is predominant in summer with at least a 50% high intensity. Its dependence upon temperature and radiation is also demonstrated. Finally, the importance of the primary and secondary biogenic production of acetone and formaldehyde is assessed. In particular, biogenic contribution would explain 37 +/- 25% of acetone levels in summer.