Reactive processing of formaldehyde and acetaldehyde in aqueous aerosol mimics: Surface tension depression and secondary organic products

The reactive uptake of carbonyl-containing volatile organic compounds (cVOCs) by aqueous atmospheric aerosols is a likely source of particulate organic material. The aqueous-phase secondary organic products of some cVOCs are surface-active. Therefore, cVOC uptake can lead to organic film formation at the gas-aerosol interface and changes in aerosol surface tension. We examined the chemical reactions of two abundant cVOCs, formaldehyde and acetaldehyde, in water and aqueous ammonium sulfate (AS) solutions mimicking tropospheric aerosols. Secondary organic products were identified using Aerosol Chemical Ionization Mass Spectrometry (Aerosol-CIMS), and changes in surface tension were monitored using pendant drop tensiometry. Hemiacetal oligomers and aldol condensation products were identified using Aerosol-CIMS. Acetaldehyde depresses surface tension to 65(\pm2) dyn/cm in pure water (a 10% surface tension reduction from that of pure water) and 62(\pm1) dyn/cm in AS solutions (a 20.6% reduction from that of a 3.1 M AS solution). Surface tension depression by formaldehyde in pure water is negligible; in AS solutions, a 9% reduction in surface tension is observed. Mixtures of these species were also studied in combination with methylglyoxal in order to evaluate the influence of cross-reactions on surface tension depression and product formation in these systems. We find that surface tension depression in the solutions containing mixed cVOCs exceeds that predicted by an additive model based on the single-species isotherms.Comment: Published in Atmospheric Chemistry and Physics 22 November 201

Influence of trans-Pacific pollution transport on acyl peroxy nitrate abundances and speciation at Mount Bachelor Observatory during INTEX-B

International audienceWe present month-long observations of speciated acyl peroxy nitrates (APNs), including PAN, PPN, MPAN, APAN, and the sum of PiBN and PnBN, measured at the Mount Bachelor Observatory (MBO) as part of the INTEX-B collaborative field campaign during spring 2006. APN abundances, measured by thermal dissociation-chemical ionization mass spectrometry (TD-CIMS), are discussed in terms of differing contributions from the boundary layer and the free troposphere and in the context of previous APN measurements in the NE Pacific region. PAN mixing ratios range from 11 to 3955 pptv, with a mean value of 334 pptv for the full measurement period. PPN is linearly correlated with PAN (r2=0.96), with an average abundance of 6.5% relative to PAN; other APNs are generally <1% of PAN. Diurnal cycles and relationships of APNs with ozone reveal a gradient in hydrocarbon chemistry between the boundary layer and the free troposphere. On average, the highest levels of APNs, ozone and PPN/PAN are found in free tropospheric air masses, suggesting that this site is strongly influenced by distant pollution sources. To estimate the impact of long-range transport of Asian pollution on atmospheric composition at MBO, we perform a detailed analysis utilizing HYSPLIT back trajectories. This analysis suggests that trans-Pacific transport of Asian pollution leads to substantial increases in APN and ozone mixing ratios at MBO, especially when transport occurs via the free troposphere. The ensemble of trajectories indicate that Asian-influenced free tropospheric air was sampled in ~16% of our data and contained a median PAN mixing ratio double that of the full dataset

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume VII-Criegee intermediates

This article, the seventh in the series, presents kinetic and photochemical data sheets evaluated by the IUPAC Task Group on Atmospheric Chemical Kinetic Data Evaluation. It covers an extension of the gas-phase and photochemical reactions related to Criegee intermediates previously published in Atmospheric Chemistry and Physics (ACP) in 2006 and implemented on the IUPAC website up to 2020. The article consists of an introduction, description of laboratory measurements, a discussion of rate coefficients for reactions of O3 with alkenes producing Criegee intermediates, rate coefficients of unimolecular and bimolecular reactions and photochemical data for reactions of Criegee intermediates, and an overview of the atmospheric chemistry of Criegee intermediates. Summary tables of the recommended kinetic and mechanistic parameters for the evaluated reactions are provided. Data sheets summarizing information upon which the recommendations are based are given in two files, provided as a Supplement to this article. © Author(s) 2020

The acidity of atmospheric particles and clouds

Acidity, defined as pH, is a central component of aqueous chemistry. In the atmosphere, the acidity of condensed phases (aerosol particles, cloud water, and fog droplets) governs the phase partitioning of semivolatile gases such as HNO3, NH3, HCl, and organic acids and bases as well as chemical reaction rates. It has implications for the atmospheric lifetime of pollutants, deposition, and human health. Despite its fundamental role in atmospheric processes, only recently has this field seen a growth in the number of studies on particle acidity. Even with this growth, many fine-particle pH estimates must be based on thermodynamic model calculations since no operational techniques exist for direct measurements. Current information indicates acidic fine particles are ubiquitous, but observationally constrained pH estimates are limited in spatial and temporal coverage. Clouds and fogs are also generally acidic, but to a lesser degree than particles, and have a range of pH that is quite sensitive to anthropogenic emissions of sulfur and nitrogen oxides, as well as ambient ammonia. Historical measurements indicate that cloud and fog droplet pH has changed in recent decades in response to controls on anthropogenic emissions, while the limited trend data for aerosol particles indicate acidity may be relatively constant due to the semivolatile nature of the key acids and bases and buffering in particles. This paper reviews and synthesizes the current state of knowledge on the acidity of atmospheric condensed phases, specifically particles and cloud droplets. It includes recommendations for estimating acidity and pH, standard nomenclature, a synthesis of current pH estimates based on observations, and new model calculations on the local and global scale. © 2020 Author(s)

Low-Cost Investigation into Sources of PM2.5 in Kinshasa, Democratic Republic of the Congo

peer reviewe

The Essential Role for Laboratory Studies in Atmospheric Chemistry

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines

The Essential Role for Laboratory Studies in Atmospheric Chemistry

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This article highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines

Action to protect the independence and integrity of global health research

Storeng KT, Abimbola S, Balabanova D, et al. Action to protect the independence and integrity of global health research. BMJ GLOBAL HEALTH. 2019;4(3): e001746