Kinetics and Oligomer Products of the Multiphase Reactions of Hydroxyacetone with Atmospheric Amines, Ammonium Sulfate, and Cloud Processing.

Hydroxyacetone (HA) is an atmospheric oxidation product of isoprene and other organic precursors that can form brown carbon (BrC). Measured bulk aqueous-phase reaction rates of HA with ammonium sulfate, methylamine, and glycine suggest that these reactions cannot compete with aqueous-phase hydroxyl radical oxidation. In cloud chamber photooxidation experiments with either gaseous or particulate HA in the presence of the same N-containing species, BrC formation was minor, with similar mass absorption coefficients at 365 nm (<0.

On the correlation between hygroscopic properties and chemical composition of cloud condensation nuclei obtained from the chemical aging of soot particles with O and SO.

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.

Infrared optical signature reveals the source-dependency and along-transport evolution of dust mineralogy as shown by laboratory study.

Advancing knowledge of the mineralogical composition of dust is key for understanding and predicting its climate and environmental impacts. The variability of dust mineralogy from one source to another and its evolution during atmospheric transport is not measured at large scale. In this study we use laboratory measurements to demonstrate that the extinction signature of suspended dust aerosols in the 740 - 1250 cm atmospheric window can be used to derive dust mineralogy in terms of the main infrared - active minerals, namely quartz, clays, feldspars and calcite.

Complex urban atmosphere alters alveolar stem cells niche properties and drives lung fibrosis.

There is growing evidence suggesting that urban pollution has adverse effects on lung health. However, how urban pollution affects alveolar mesenchymal and epithelial stem cell niches remains unknown. This study aimed to determine how complex representative urban atmospheres alter alveolar stem cell niche properties.

Correction to Brown Carbon from Photo-Oxidation of Glyoxal and SO in Aqueous Aerosol.

[This corrects the article DOI: 10.1021/acsearthspacechem.3c00035.

Brown Carbon from Photo-Oxidation of Glyoxal and SO in Aqueous Aerosol.

Aqueous-phase dark reactions during the co-oxidation of glyoxal and S(IV) were recently identified as a potential source of brown carbon (BrC). Here, we explore the effects of sunlight and oxidants on aqueous solutions of glyoxal and S(IV), and on aqueous aerosol exposed to glyoxal and SO. We find that BrC is able to form in sunlit, bulk-phase, sulfite-containing solutions, albeit more slowly than in the dark.

Kinetic and Mechanistic Study of the Reactions of NO Radicals with Unsaturated Aldehydes: 2-Butenal, 2-Methyl-2-butenal, and 3-Methyl-2-butenal.

The kinetics and mechanisms of the gas-phase reactions of NO radical with two branched unsaturated aldehydes, 2-methyl-2-butenal (also called 2-methyl-crotonaldehyde) and 3-methyl-2-butenal (or 3-methyl-crotonaldehyde), have been investigated by experimental and theoretical approaches. Kinetic data were also provided, for comparison, for 2-butenal (or crotonaldehyde). Experiments were performed in a simulation chamber at 295 ± 3 K and atmospheric pressure.

Kinetics, Products, and Brown Carbon Formation by Aqueous-Phase Reactions of Glycolaldehyde with Atmospheric Amines and Ammonium Sulfate.

Glycolaldehyde (GAld) is a C water-soluble aldehyde produced during the atmospheric oxidation of isoprene and many other species and is commonly found in cloudwater. Previous work has established that glycolaldehyde evaporates more readily from drying aerosol droplets containing ammonium sulfate (AS) than does glyoxal, methylglyoxal, or hydroxyacetone, which implies that it does not oligomerize as quickly as these other species. Here, we report NMR measurements of glycolaldehyde's aqueous-phase reactions with AS, methylamine, and glycine.

Chemistry and Photochemistry of Pyruvic Acid at the Air-Water Interface.

Interfacial regions are unique chemical reaction environments that can promote chemistry not found elsewhere. The air-water interface is ubiquitous in the natural environment in the form of ocean surfaces and aqueous atmospheric aerosols. Here we investigate the chemistry and photochemistry of pyruvic acid (PA), a common environmental species, at the air-water interface and compare it to its aqueous bulk chemistry using two different experimental setups: (1) a Langmuir-Blodgett trough, which models natural water surfaces and provides a direct comparison between the two reaction environments, and (2) an atmospheric simulation chamber (CESAM) to monitor the chemical processing of nebulized aqueous PA droplets.

Conformer-Specific Photolysis of Pyruvic Acid and the Effect of Water.

The conformer-specific reactivity of gas-phase pyruvic acid following the S(nπ*) ← S excitation at λ = 350 nm (290-380 nm) and the effect of water are investigated for the two lowest energy conformers. Conformer-specific gas-phase pyruvic acid photolysis rate constants and their respective populations are measured by monitoring their distinct vibrational OH-stretching frequencies. The geometry, relative energies, fundamental vibrational frequencies, and electronic transitions of the pyruvic acid conformers and their monohydrated complexes are calculated with density functional theory and ab initio methods.

Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. 2. Time Evolution and Effect of Particle Acidity.

The present work is an extensive laboratory study of organosulfate (OS) formation from the reaction of α-pinene oxidation products or proxies with acidified ammonium sulfate aerosols in three different acidity conditions ((NH)SO 0.06 M; (NH)SO/HSO 0.06 M/0.

Kinetic Study of the Temperature Dependence of OH-Initiated Oxidation of -Dodecane.

Reaction rate constants for the reaction of -dodecane with hydroxyl radicals were measured as a function of temperature between 283 and 303 K, using the relative rate method in the CESAM chamber (French acronym for "experimental multiphasic atmospheric simulation chamber"). The rate constants obtained at 283, 293, and 303 K are (1.27 ± 0.

Water content of limestones submitted to realistic wet deposition: a CIME2 chamber simulation.

An experimental chamber (CIME2) has been specially designed to simulate wet atmospheric deposition on limestones used in Paris cultural heritage. This instrument is a complementary tool to CIME, a previously developed chamber dedicated to the simulation of dry atmospheric deposition on monuments and artifacts. The aim of this paper is to describe CIME2 and characterize the wet deposits produced inside it.

Methylglyoxal Uptake Coefficients on Aqueous Aerosol Surfaces.

In order to predict the amount of secondary organic aerosol formed by heterogeneous processing of methylglyoxal, uptake coefficients (γ) and estimates of uptake reversibility are needed. Here, uptake coefficients are extracted from chamber studies involving ammonium sulfate and glycine seed aerosol at high relative humidity (RH ≥ 72%). Methylglyoxal uptake coefficients on prereacted glycine aerosol particles had a strong dependence on RH, increasing from γ = 0.

Nitrogen-Containing, Light-Absorbing Oligomers Produced in Aerosol Particles Exposed to Methylglyoxal, Photolysis, and Cloud Cycling.

Aqueous methylglyoxal chemistry has often been implicated as an important source of oligomers in atmospheric aerosol. Here we report on chemical analysis of brown carbon aerosol particles collected from cloud cycling/photolysis chamber experiments, where gaseous methylglyoxal and methylamine interacted with glycine, ammonium, or methylammonium sulfate seed particles. Eighteen N-containing oligomers were identified in the particulate phase by liquid chromatography/diode array detection/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry.

Atmospheric Simulation Chamber Studies of the Gas-Phase Photolysis of Pyruvic Acid.

Pyruvic acid is an atmospherically abundant α-keto-acid that degrades efficiently from the troposphere via gas-phase photolysis. To explore conditions relevant to the environment, 2-12 ppm pyruvic acid is irradiated by a solar simulator in the environmental simulation chamber, CESAM. The combination of the long path length available in the chamber and its low surface area to volume ratio allows us to quantitatively examine the quantum yield and photochemical products of pyruvic acid.

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation.

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth's changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments.

Brown Carbon Production in Ammonium- or Amine-Containing Aerosol Particles by Reactive Uptake of Methylglyoxal and Photolytic Cloud Cycling.

The effects of methylglyoxal uptake on the physical and optical properties of aerosol containing amines or ammonium sulfate were determined before and after cloud processing in a temperature- and RH-controlled chamber. The formation of brown carbon was observed upon methylglyoxal addition, detected as an increase in water-soluble organic carbon mass absorption coefficients below 370 nm and as a drop in single-scattering albedo at 450 nm. The imaginary refractive index component k reached a maximum value of 0.

Multiphase Photochemistry of Pyruvic Acid under Atmospheric Conditions.

Aerosol and molecular processing in the atmosphere occurs in a complex and variable environment consisting of multiple phases and interfacial regions. To explore the effects of such conditions on the reactivity of chemical systems, we employ an environmental simulation chamber to investigate the multiphase photolysis of pyruvic acid, which photoreacts in the troposphere in aqueous particles and in the gas phase. Upon irradiation of nebulized pyruvic acid, acetic acid and carbon dioxide are rapidly generated, which is consistent with previous literature on the bulk phase photolysis reactions.

High-NO Photooxidation of n-Dodecane: Temperature Dependence of SOA Formation.

The temperature and concentration dependence of secondary organic aerosol (SOA) yields has been investigated for the first time for the photooxidation of n-dodecane (CH) in the presence of NO in the CESAM chamber (French acronym for "Chamber for Atmospheric Multiphase Experimental Simulation"). Experiments were performed with and without seed aerosol between 283 and 304.5 K.

Experimental Study of the Formation of Organosulfates from α-Pinene Oxidation. Part I: Product Identification, Formation Mechanisms and Effect of Relative Humidity.

In the present study, quasi-static reactor and atmospheric simulation chamber experiments were performed to investigate the formation of α-pinene-derived organosulfates. Organosulfates (R-OSOH) were examined for the reactions between acidified ammonium sulfate particles exposed to an individual gaseous volatile organic compound, such as α-pinene and oxidized products (α-pinene oxide, isopinocampheol, pinanediol and myrtenal). Molecular structures were elucidated by liquid chromatography interfaced to high-resolution quadrupole time-of-flight mass spectrometry equipped with electrospray ionization (LC/ESI-HR-QTOFMS).

Characterisation of CIME, an experimental chamber for simulating interactions between materials of the cultural heritage and the environment.

An approach consisting in combining in situ and laboratory experiments is often favoured for investigating the mechanisms involved in the weathering of the materials of the cultural heritage. However, the realistic simulation in the laboratory of the environmental conditions ruling the interactions of atmospheric compounds with materials is a very complex task. The aim of this work is to characterise CIME, a new chamber specially built to simulate the interactions between materials of the cultural heritage and the environment.

Variable-length cell for studies of gas spectra with extremely short optical paths.

We present a cell for studies of light transmission through very strongly absorbing gases. It uses a fixed window and a mirror, parallel to the latter and attached to a micrometric linear motion feedthrough monitoring mirror-window distances from 0 to a couple of centimeters. This device is tested by recording CO2 gas spectra near 4.

Atmospheric fate of a series of carbonyl nitrates: photolysis frequencies and OH-oxidation rate constants.

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air.

[Uterine leiomyosarcoma. Nine case reports, review of the literature].

Object Of The Study: To evaluate management and outcome of the treatment of uterine leiomyosarcoma.

Patients And Methods: Retrospective study of a series of 9 patients treated for uterine leiomyosarcoma in this hospital from 1982 to 1994.

Results: The condition is rarely suspected preoperatively, diagnosis is usually made on histological examination of the operative specimen.