Organic peroxy radicals (RO₂) are important intermediates in aerobic systems such as Earth's atmosphere. The existence of a channel producing dialkyl peroxides (ROOR) in their self- and cross-reactions (i.e., between the same or different radicals) has long been debated and considered a theoretical “key problem in the atmospheric chemistry of peroxy radicals”. Over the past decade, observations have suggested that this channel could be an important source of condensable compounds and, ultimately, new aerosol particles in Earth's atmosphere. However, experimental evidence for specific RO₂ reactions is scarce. In this work, the formation of ROOR in the self- and cross-reactions of eight RO₂ (CH₃O₂ ¹³CH₃O₂, CD₃O₂, C₂H₅O₂, 1- and iso-C₃H₇O₂, 1- and tert-C₄H₉O₂) could be observed by modifying the ionisation conditions on a proton transfer mass spectrometer. The ROOR formation channel was confirmed to be in competition with the other product channels rather than precede them. For six of the RO₂ studied, the branching ratio, γ, for the ROOR channel of the self-reaction was quantified relative to these other channels. The results allowed for the first time to identify some trends in γ with respect to the RO₂ structure: γ decreases with increasing RO₂ chain length for the linear/primary radicals, ranging from (14.1 ± 7)% for CH₃O₂ to (1.1 ± 0.5)% for 1-C₄H₉O₂, while branched radicals exhibit much higher γ than their linear counterparts, with γ = (17.2 ± 8.6)% for iso-C₃H₇O₂ and (46.6 ± 23.2)% for tert-C₄H₉O₂. The formation of ROOR products from RO₂ reactions in the atmosphere should thus be strongly dependent on the RO₂ structure.

Road traffic is an important source of urban air pollutants. Due to increasingly strict controls of exhaust emissions from road traffic, their contribution to the total emissions has strongly decreased over time in high-income countries. In contrast, non-exhaust emissions from road vehicles are not yet legislated and now make up the major proportion of road traffic emissions in many countries. Brake wear, which occurs due to friction between brake linings and their rotating counterpart, is one of the main non-exhaust sources contributing to particle emissions. Since the focus of brake wear emission has largely been on particulate pollutants, little is currently known about gaseous emissions such as volatile organic compounds from braking and their fate in the atmosphere. This study investigates the oxidative ageing of gaseous brake wear emissions generated with a pin-on-disc tribometer, using an oxidation flow reactor. The results demonstrate, for the first time, that the photooxidation of gaseous brake wear emissions can lead to formation of secondary particulate matter, which could amplify the environmental impact of brake wear emissions.

The autoxidation of alkylperoxy radicals (RO2, where R is organic) is an important degradation pathway for organic compounds in a wide range of chemical systems including Earth's atmosphere. It is thought to proceed by internal H-shift reactions and, for unsaturated radicals, cyclization. However, experimental data on specific reactions steps for unsaturated RO2 is scarce. This work investigates the unimolecular reactions of 1-butenyl-O2, 1-pentenyl-O2, 1-hexenyl-O2, and 2-methyl-2-pentenyl-O2 radicals near room temperature (302 ± 3 K) experimentally, by monitoring the radicals directly, and theoretically. The experimental rate coefficients are in good agreement with those determined with high-level quantum calculations, confirming that cyclization can be competitive with H-shift in some cases. However, the products observed experimentally with two different mass spectrometers suggest that all the peroxy radicals studied lead to fast decomposition (k > 1 s−1) after the isomerization step. While the mechanisms for these decompositions could not be fully elucidated theoretically, they question whether these channels contribute to propagation or to termination of the autoxidation chains.

Aerosol and aqueous particles are ubiquitous in Earth’s atmosphere and play key roles in geochemical processes such as natural chemical cycles, cloud and fog formation, air pollution, visibility, climate forcing, etc. The surface tension of atmospheric particles can affect their size distribution, condensational growth, evaporation, and exchange of chemicals with the atmosphere, which, in turn, are important in the above-mentioned geochemical processes. However, because measuring this quantity is challenging, its role in atmospheric processes was dismissed for decades. Over the last 15 years, this field of research has seen some tremendous developments and is rapidly evolving. This review presents the state-of-the-art of this subject focusing on the experimental approaches. It also presents a unique inventory of experimental adsorption isotherms for over 130 mixtures of organic compounds in water of relevance for model development and validation. Potential future areas of research seeking to better determine the surface tension of atmospheric particles, better constrain laboratory investigations, or better understand the role of surface tension in various atmospheric processes, are discussed. We hope that this review appeals not only to atmospheric scientists but also to researchers from other fields, who could help identify new approaches and solutions to the current challenges.

Organic peroxy radicals (ROO•) are key oxidants in a wide range of chemical systems such as living organisms, chemical synthesis and polymerization systems, combustion systems, the natural environment, and the Earth’s atmosphere. Although surfaces are ubiquitous in all of these systems, the interactions of organic peroxy radicals with these surfaces have not been studied until today because of a lack of adequate detection techniques. In this work, the uptake and reaction of gas-phase organic peroxy radicals (CH3OO• and i-C3H7OO•) with solid surfaces was studied by monitoring each radical specifically and in real-time with mass spectrometry. Our results show that the uptake of organic peroxy radicals varies widely with the surface material. While their uptake by borosilicate glass and perfluoroalkoxy alkanes (PFA) was negligible, it was substantial with metals and even dominated over the gas-phase reactions with stainless steel and aluminum. The results also indicate that these uptakes are controlled by redox reactions at the surfaces for which the products were analyzed. Our results show that the reactions of organic peroxy radicals with metal surfaces have to be carefully considered in all the experimental investigations of these radicals as they could directly impact the kinetic and mechanistic knowledge derived from such studies.

The formation of liquid cloud droplets from aerosol particles in the Earth atmosphere is still under debate particularly because of the difficulties to quantify the importance of bulk and surface effects in these processes. Recently, single-particle techniques have been developed to access experimental key parameters at the scale of individual particles. Environmental scanning electron microscopy (ESEM) has the advantage to provide in situ monitoring of the water uptake of individual microscopic particles deposited on solid substrates. In this work, ESEM was used to compare droplet growth on pure ammonium sulfate (NH4)2SO4 and mixed sodium dodecyl sulfate/ammonium sulfate (SDS/(NH4)2SO4) particles and to explore the role of experimental parameters, such as the hydrophobic–hydrophilic character of the substrate, on this growth. With hydrophilic substrates, the growth on pure salt particles was strongly anisotropic, but this anisotropy was suppressed by the presence of SDS. With hydrophobic substrates, it is the wetting behavior of the liquid droplet that is impacted by the presence of SDS. The wetting behavior of the pure (NH4)2SO4 solution on a hydrophobic surface shows a step-by-step mechanism that can be attributed to successive pinning–depinning phenomena at the triple-phase line frontier. Unlike the pure (NH4)2SO4 solution, the mixed SDS/(NH4)2SO4 solution did not show such a mechanism. Therefore, the hydrophobic–hydrophilic character of the substrate plays an important role in the stability and dynamics of the liquid droplets’ nucleation by water vapor condensation. In particular, hydrophilic substrates are not suited for the investigation of the hygroscopic properties (deliquescence relative humidity (DRH) and hygroscopic growth factor (GF)) of particles. Using hydrophobic substrates, data show that the DRH of (NH4)2SO4 particles is measured within 3% accuracy on the RH and their GF could indicate a size-dependent effect in the micrometer range. The presence of SDS does not seem to modify the DRH and GF of (NH4)2SO4 particles. This study shows that the water uptake on deposited particles is a complex process but, once carefully taken into account, ESEM is a suitable technique to study them.

In Earth’s atmosphere, the surface tension of sub-micron aerosol particles is suspected to affect their efficiency in becoming cloud droplets. But this quantity cannot be measured directly and is inferred from the chemical compounds present in aerosols. Amphiphilic surfactants have been evidenced in aerosols but experimental information on the surface properties of their mixtures with other aerosol components is lacking. This work explores experimentally the surface properties of aqueous mixtures of amphiphilic surfactants (SDS, Brij35, TritonX100, TritonX114, and CTAC) with inorganic salts (NaCl, (NH4)2SO4) and soluble organic acids (oxalic and glutaric acid) using pendant droplet tensiometry. Contrary to what could be expected, inorganic salts and organic acids systematically enhanced the efficiency of the surfactants rather than reduced it, by further lowering the surface tension and, in some cases, the CMC. Furthermore, all the mixtures studied were strongly non-ideal, some even displaying some synergism, thus demonstrating that the common assumption of ideality for aerosol mixtures is not valid. The molecular interactions between the mixture components were either in the bulk (salting out), in the mixed surface monolayer (synergy on the surface tension) or in the micelles (synergy on the CMC) and need to be included when describing such aerosol mixtures.

The liquid-air surface tension of aqueous solutions is a fundamental quantity in multi-phase thermodynamics and fluid dynamics and thus relevant in many scientific and engineering fields. Various models have been proposed for its quantitative description. This Perspective gives an overview of the most popular models and their ability to reproduce experimental data of ten binary aqueous solutions of electrolytes and organic molecules chosen to be representative of different solute types. In addition, we propose a new model which reproduces sigmoidal curve shapes (Sigmoid model) to empirically fit experimental surface tension data. The surface tension of weakly surface-active substances is well reproduced by all models. In contrast, only few models successfully model the surface tension of aqueous solutions with strongly surface-active substances. For substances with a solubility limit, usually no experimental data is available for the surface tension of supersaturated solutions and the pure liquid solute. We discuss ways in which these can be estimated and emphasize the need for further research. The newly developed Sigmoid model best reproduces the surface tension of all tested solutions and can be recommended as a model for a broad range of binary mixtures and over the entire concentration range.