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The investigation of hydroxyl radical (OH) chemistry during intensive field campaigns has led to the development of several techniques dedicated to ambient measurements of total OH reactivity, which is the inverse of the OH lifetime. Three techniques are currently used during field campaigns, including the total OH loss rate method, the pump–probe method, and the comparative reactivity method. However, no formal intercomparison of these techniques has been published so far, and there is a need to ensure that measurements of total OH reactivity are consistent among the different techniques. An intercomparison of two OH reactivity instruments, one based on the comparative reactivity method (CRM) and the other based on the pump–probe method, was performed in October 2012 in a NOx-rich environment, which is known to be challenging for the CRM technique. This study presents an extensive description of the two instruments, the CRM instrument from Mines Douai (MD-CRM) and the pump–probe instrument from the University of Lille (UL-FAGE), and highlights instrumental issues associated with the two techniques. It was found that the CRM instrument used in this study underestimates ambient OH reactivity by approximately 20 % due to the photolysis of volatile organic compounds (VOCs) inside the sampling reactor; this value is dependent on the position of the lamp within the reactor. However, this issue can easily be fixed, and the photolysis of VOCs was successfully reduced to a negligible level after this intercomparison campaign. The UL-FAGE instrument may also underestimate ambient OH reactivity due to the difficulty to accurately measure the instrumental zero. It was found that the measurements are likely biased by approximately 2 s-1, due to impurities in humid zero air. Two weeks of ambient sampling indicate that the measurements performed by the two OH reactivity instruments are in agreement, within the measurement uncertainties for each instrument, for NOx mixing ratios up to 100 ppbv. The CRM technique has hitherto mainly been used in low-NOx environments, i.e. environments with ambient NOx mixing ratios lower than a few ppbv, due to a measurement artifact generated by ambient NO inside the sampling reactor. However, this study shows that this technique can also be used under NOx-rich conditions if a NOx-dependent correction is carefully applied on the OH reactivity measurements. A full suite of 52 VOCs, NOx, and other inorganic species were monitored during this intercomparison. An investigation of the OH reactivity budget for this urban site suggests that this suite of trace gases can account for the measured total OH reactivity.

Rationale: This study has developed a data processing protocol based on mass defect analysis for the automatic construction of unique peak lists addressing the need for the fast and efficient treatment of databases of mass spectra with limited mass resolution., Methods: The data processing protocol, implemented in MATLAB, is tested on a database of 126 mass spectra obtained from time-of-flight secondary ion mass spectrometry analysis of the exhaust of a laboratory diesel miniCAST burner deposited on Ti substrates., Results: The data processing protocol converts the mass spectra into a data matrix suitable for chemometrics (peak list) by combining mass defect analysis and multivariate analysis. In particular, the role of the mass defect analysis is expanded to improve mass calibration and automate the construction of the peak list., Conclusions: In this context, mass defect analysis becomes an invaluable technique for the efficient processing of databases of mass spectra with limited mass resolution by allowing the fast and automated construction of a peak list common to all mass spectra, by improving the mass calibration, and finally by reducing the number of molecular formulae consistent with a given accurate mass, thus facilitating the identification of unknown ions., (© 2024 John Wiley & Sons Ltd.)

Soot particles released in the atmosphere have long been investigated for their ability to affect the radiative forcing. Although freshly emitted soot particles are generally considered to yield only positive contributions to the radiative forcing, atmospheric aging can activate them into efficient cloud condensation or ice nuclei, which can trigger the formation of persistent clouds and ultimately provide a negative contribution to the radiative forcing. Depending on their residence time in the atmosphere, soot particles can undergo several physical and chemical aging processes that affect their chemical composition, particle size distribution and morphology, and ultimately their optical and hygroscopic properties. The impact of the physical-chemical aging on the properties of soot particles is still difficult to quantify, as well as their effect on the radiative forcing of the atmosphere. This work investigates the hygroscopic properties of chemically aged soot particles obtained from the combustion of aviation fuel, and in particular the interplay between aging mechanisms initiated by two widespread atmospheric oxidizers (O 3 and SO 2 ). Activation is measured in water supersaturation conditions using a cloud condensation nuclei counter. Once particle morphology and size distribution are taken into account, the hygroscopicity parameter κ is derived using κ-Köhler theory and correlated to the change of the chemical composition of the particles aged in a simulation chamber. While fresh soot particles are poor cloud condensation nuclei (κ < 10 -4 ) and are not significantly affected by either O 3 or SO 2 at the timescale of the experiments, rapid activation is observed when they are simultaneously exposed to both oxidizers. Activated particles become efficient cloud condensation nuclei, comparable to the highly hygroscopic particulate matter typically found in the atmosphere (κ = 0.2-0.6 at RH = 20 %). Statistical analysis reveals a correlation between the activation and sulfur-containing ions detected on the chemically aged particles that are absent from the fresh particles., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A novel instrument based on broadband cavity-enhanced absorption spectroscopy has been developed using a supercontinuum broadband light source, which showcases its ability in simultaneous measurements of the concentration of NO 2 and the extinction of particulate matter. Side-by-side intercomparison was carried out with the reference NOx analyzer for NO 2 and OPC-N2 particle counter for particulate matter, which shows a good linear correlation with r 2 > 0.90. The measurement limits (1σ) of the developed instrument were experimentally determined to be 230 pptv in 40 s for NO 2 and 1.24 Mm -1 for the extinction of particulate matter in 15 s. This work provides a promising method in simultaneously monitoring atmospheric gaseous compounds and particulate matter, which would further advance our understanding on gas-particle heterogeneous interactions in the context of climate change and air quality.

The aerosol properties of Mount Etna's passive degassing plume and its short-term processes and radiative impact were studied in detail during the EPL-RADIO campaigns (summer 2016-2017), using a synergistic combination of observations and radiative transfer modelling. Summit observations show extremely high particulate matter concentrations. Using portable photometers, the first mapping of small-scale (within [Formula: see text] from the degassing craters) spatial variability of the average size and coarse-to-fine burden proportion of volcanic aerosols is obtained. A substantial variability of the plume properties is found at these spatial scales, revealing that processes (e.g. new particle formation and/or coarse aerosols sedimentation) are at play, which are not represented with current regional scale modelling and satellite observations. Statistically significant progressively smaller particles and decreasing coarse-to-fine particles burden proportion are found along plume dispersion. Vertical structures of typical passive degassing plumes are also obtained using observations from a fixed LiDAR station constrained with quasi-simultaneous photometric observations. These observations are used as input to radiative transfer calculations, to obtain the shortwave top of the atmosphere (TOA) and surface radiative effect of the plume. For a plume with an ultraviolet aerosol optical depth of 0.12-0.14, daily average radiative forcings of [Formula: see text] and [Formula: see text], at TOA and surface, are found at a fixed location [Formula: see text] downwind the degassing craters. This is the first available estimation in the literature of the local radiative impact of a passive degassing volcanic plume.

The rapid industrialization and urbanization of intra- and peri-urban areas at the world scale are responsible for the degradation of the quality of edible crops, because of their contamination with airborne pollutants. Their consumption could lead to serious health risks. In this work, we aim to investigate the phytotoxicity induced by foliar transfer of atmospheric particles of industrial/urban origin. Leaves of cabbage plants (Brassica oleracea var. Prover) were contaminated with metal-rich particles (PbSO 4 CuO and CdO) of micrometer size. A trichloroacetic acid (TCA) treatment was used to inhibit the synthesis of the epicuticular waxes in order to investigate their protective role against metallic particles toxicity. Besides the location of the particles on/in the leaves by microscopic techniques, photosynthetic activity measurements, genotoxicity assessment, and quantification of the gene expression have been studied for several durations of exposure (5, 10, and 15 days). The results show that the depletion of epicuticular waxes has a limited effect on the particle penetration in the leaf tissues. The stomatal openings appear to be the main pathway of particles entry inside the leaf tissues, as demonstrated by the overexpression of the BolC.CHLI1 gene. The effects of particles on the photosynthetic activity are limited, considering only the photosynthetic F v /F m parameter. The genotoxic effects were significant for the contaminated TCA-treated plants, especially after 10 days of exposure. Still, the cabbage plants are able to implement repair mechanisms quickly, and to thwart the physiological effects induced by the particles. Finally, the foliar contamination by metallic particles induces no serious damage to DNA, as observed by monitoring the BolC.OGG1 gene.

Indoor air quality was characterized in 10 recently built energy-efficient French schools during two periods of 4.5 days. Carbon dioxide time-resolved measurements during occupancy clearly highlight the key role of the ventilation rate (scheduled or occupancy indexed), especially in this type of building, which was tightly sealed and equipped with a dual-flow ventilation system to provide air refreshment. Volatile organic compounds (VOCs) and inorganic gases (ozone and NO2 ) were measured indoors and outdoors by passive techniques during the occupied and the unoccupied periods. Over 150 VOC species were identified. Among them, 27 species were selected for quantification, based on their occurrence. High concentrations were found for acetone, 2-butanone, formaldehyde, toluene, and hexaldehyde. However, these concentrations are lower than those previously observed in conventional school buildings. The indoor/outdoor and unoccupied/occupied ratios are informative regarding emission sources. Except for benzene, ozone, and NO2 , all the pollutants in these buildings have an indoor source. Occupancy is associated with increased levels of acetone, 2-butanone, pentanal, butyl acetate, and alkanes., (© 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.)

Di(oxymethylene)glycol forms in formaldehyde aqueous solutions by polymerization of methanediol. The structure and hydrogen bond interactions of di(oxymethylene)glycol with water were characterized by performing Car-Parrinello molecular dynamics simulations. The anharmonic vibrational frequencies of di(oxymethylene)glycol in solution were determined with ab initio calculations considering explicitly the hydrogen-bonded water molecules, while other interactions with solvent were described within a polarizable continuum model approach. The calculations allow for a detailed interpretation of the experimental Raman spectrum of formaldehyde aqueous solutions, leading to the assignment of the band at 920 cm(-1) to the symmetric CO stretching mode of di(oxymethylene)glycol.

In recent years, the use of kerosene space heaters as additional or principal heat source has been increasing, because these heaters allow a continuous control on the energy cost. These devices are unvented, and all combustion products are released into the room where the heaters are operated. The indoor air quality of seven private homes using wick-type or electronic injection-type kerosene space heaters was investigated. Concentrations of CO, CO2, NOx, formaldehyde and particulate matter (0.02-10 μm) were measured, using time-resolved instruments when available. All heaters tested are significant sources of submicron particles, NOx and CO2. The average NO2 and CO2 concentrations are determined by the duration of use of the kerosene heaters. These results stress the need to regulate the use of unvented combustion appliances to decrease the exposure of people to air contaminants., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The structural, electronic, and spectroscopic properties of methanediol in aqueous solutions have been studied by a combined approach based on Car-Parrinello molecular dynamics simulations and ab initio calculations. The hydrogen bond interactions between the solute and water have been characterized, showing the important role of the solvent in the stabilization of the methanediol conformers in solution. First insights on the experimental vibrational spectra have been obtained by the analysis of the simulation results, with particular regard to the most prominent band at 1050 cm(-1) that has been attributed to both the symmetric and antisymmetric CO stretching modes. The assignment has been completed adopting both electric and mechanical anharmonic calculations considering the interactions with the solvent using a polarizable continuum model.

Unlabelled: Laboratory measurements of the gaseous emission factors (EF) from two recent kerosene space heaters (wick and injector) with five different fuels have been conducted in an 8-m(3) environmental chamber. The two heaters tested were found to emit mainly CO(2), CO, NO, NO(2), and some volatile organic compounds (VOCs). NO(2) is continuously emitted during use, with an EF of 100-450 μg per g of consumed fuel. CO is normally emitted mainly during the first minutes of use (up to 3 mg/g). Formaldehyde and benzene EFs were quantified at 15 and 16 μg/g, respectively, for the wick heater. Some other VOCs, such as 1,3-butadiene, were detected with lower EFs. We demonstrated the unsuitability of a 'biofuel' containing fatty acid methyl esters for use with the wick heater, and that the accumulation of soot on the same heater, whatever the fuel, leads to a dramatic increase in the CO EF, up to 16 mg/g, which could be responsible for chronic and acute CO intoxications., Practical Implications: Our results show that in spite of new technologies and emission standards for unvented kerosene space heaters, as well as for the fuels, the use of these heaters in indoor environments still leads to NO(x) levels in excess of current health recommendations. Whereas injection heaters generate more nitrogen oxides than wick heaters, prolonged use of the latter leads to a soot buildup, concomitant with high CO emissions, which could be responsible for acute and chronic intoxications. The use of a biofuel in a wick heater is also of concern. Maintenance of the heaters and adequate ventilation of the room during use of kerosene space heaters are therefore of prime importance to reduce personal exposure., (© 2011 John Wiley & Sons A/S.)

Quantitative measurements of the partial vapor pressure of formaldehyde are performed above aqueous H2CO solutions of different concentrations (from 10(-5) to 0.3 molar fraction) using mass spectrometry and IR diode laser spectroscopy. Both experimental techniques allow direct probing of the gas phase concentration collected at equilibrium above the aqueous solutions. A correlation is observed between the polymerization processes occurring in the solution and the partial pressure of H2CO measured at vapor liquid equilibrium (VLE). A similar correlation is observed from total pressure measurements for which the equilibrium vapor pressure decreases as [VLE XH2CO]liq is increased. A saturation regime of the H2CO partial pressure is reached as the dissolved fraction of formaldehyde increases above approximately 0.15 mol frac. Henry's law constants are derived at 295K for the diluted solutions.

A new method for measuring trace concentrations of atmospheric pollutants by infrared diode laser spectroscopy has been devised. This method relies on the increase of the signal as the pressure inside the cell increases, while the frequency of the diode is stabilized on the line, even if it is unresolved. Performances of this method were tested with N2O and with 1,3-butadiene. As an example of application, we measured the butadiene emitted by car exhausts. Sensitivity and rapidity of this method are equivalent to the usual scanning method in which the whole line is described, but this new method benefits from its simplicity and robustness.