Decreases in Epoxide-Driven Secondary Organic Aerosol Production under Highly Acidic Conditions: The Importance of Acid-Base Equilibria.

Isoprene has the highest atmospheric emissions of any nonmethane hydrocarbon, and isoprene epoxydiols (IEPOX) are well-established oxidation products and the primary contributors forming isoprene-derived secondary organic aerosol (SOA). Highly acidic particles (pH 0-3) widespread across the lower troposphere enable acid-driven multiphase chemistry of IEPOX, such as epoxide ring-opening reactions forming methyltetrol sulfates through nucleophilic attack of sulfate (SO42-). Herein, we systematically demonstrate an unexpected decrease in SOA formation from IEPOX on highly acidic particles (pH < 1). While IEPOX-SOA formation is commonly assumed to increase at low pH when more [H+] is available to protonate epoxides, we observe maximum SOA formation at pH 1 and less SOA formation at pH 0.0 and 0.4. This is attributed to limited availability of SO42- at pH values below the acid dissociation constant (pKa) of SO42- and bisulfate (HSO4-). The nucleophilicity of HSO4- is 100× lower than SO42-, decreasing SOA formation and shifting particulate products from low-volatility organosulfates to higher-volatility polyols. Current model parameterizations predicting SOA yields for IEPOX-SOA do not properly account for the SO42-/HSO4- equilibrium, leading to overpredictions of SOA formation at low pH. Accounting for this underexplored acidity-dependent behavior is critical for accurately predicting SOA concentrations and resolving SOA impacts on air quality.

Numerical Simulations of Synthetic Ester Hydrolysis in the Indoor Environment.

The hydrolysis of synthetic esters (SEs), including phthalates and adipates, in damp indoor environments can lead to the release of volatile organic compounds implicated in poor air quality and acute health impacts, known as "sick building syndrome" (SBS). We have adapted the multiphase atmospheric chemistry box model, GAMMA, to simulate SE hydrolysis occurring in surface films in the indoor environment, along with multilayer boundary layer mass transfer and ventilation, in order to investigate this phenomenon on a process level. We then applied the model to analyze three scenarios in which hydrolysis has been hypothesized to have a significant impact on indoor air quality. Simulation results suggest that (1) alkaline hydrolysis of bis(2-ethylhexyl) adipate (DEHA) and bis(2-ethylhexyl) phthalate (DEHP) from PVC flooring on damp surfaces alone is not sufficient to explain the levels of 2-ethylhexanol reported in indoor air during episodes of SBS; (2) acute exposure to 2,2,4-trimethyl-1,3-pentanediol (TMPD) may be of concern during and shortly after the application of latex paint on an alkaline surface; and (3) alkaline hydrolysis of SEs following their airborne uptake in aqueous films is not expected to generate considerable amounts of alcohols associated with SBS.

Airborne Transmission of SARS-CoV-2: Evidence and Implications for Engineering Controls.

Since late 2019, severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has spread globally, causing a pandemic (coronavirus disease 2019, or COVID-19) with dire consequences, including widespread death, long-term illness, and societal and economic disruption. Although initially uncertain, evidence is now overwhelming that SARS-CoV-2 is transmitted primarily through small respiratory droplets and aerosols emitted by infected individuals. As a result, many effective nonpharmaceutical interventions for slowing virus transmission operate by blocking, filtering, or diluting respiratory aerosol, particularly in indoor environments. In this review, we discuss the evidence for airborne transmission of SARS-CoV-2 and implications for engineering solutions to reduce transmission risk.

Room-level ventilation in schools and universities.

Ventilation is of primary concern for maintaining healthy indoor air quality and reducing the spread of airborne infectious disease, including COVID-19. In addition to building-level guidelines, increased attention is being placed on room-level ventilation. However, for many universities and schools, ventilation data on a room-by-room basis are not available for classrooms and other key spaces. We present an overview of approaches for measuring ventilation along with their advantages and disadvantages. We also present data from recent case studies for a variety of institutions across the United States, with various building ages, types, locations, and climates, highlighting their commonalities and differences, and examples of the use of this data to support decision making.

Acidity and the multiphase chemistry of atmospheric aqueous particles and clouds.

The acidity of aqueous atmospheric solutions is a key parameter driving both the partitioning of semi-volatile acidic and basic trace gases and their aqueous-phase chemistry. In addition, the acidity of atmospheric aqueous phases, e.g., deliquesced aerosol particles, cloud, and fog droplets, is also dictated by aqueous-phase chemistry. These feedbacks between acidity and chemistry have crucial implications for the tropospheric lifetime of air pollutants, atmospheric composition, deposition to terrestrial and oceanic ecosystems, visibility, climate, and human health. Atmospheric research has made substantial progress in understanding feedbacks between acidity and multiphase chemistry during recent decades. This paper reviews the current state of knowledge on these feedbacks with a focus on aerosol and cloud systems, which involve both inorganic and organic aqueous-phase chemistry. Here, we describe the impacts of acidity on the phase partitioning of acidic and basic gases and buffering phenomena. Next, we review feedbacks of different acidity regimes on key chemical reaction mechanisms and kinetics, as well as uncertainties and chemical subsystems with incomplete information. Finally, we discuss atmospheric implications and highlight the need for future investigations, particularly with respect to reducing emissions of key acid precursors in a changing world, and the need for advancements in field and laboratory measurements and model tools.

High Pressure Inside Nanometer-Sized Particles Influences the Rate and Products of Chemical Reactions.

The composition of organic aerosol has a pivotal influence on aerosol properties such as toxicity and cloud droplet formation capability, which could affect both climate and air quality. However, a comprehensive and fundamental understanding of the chemical and physical processes that occur in nanometer-sized atmospheric particles remains a challenge that severely limits the quantification and predictive capabilities of aerosol formation pathways. Here, we investigated the effects of a fundamental and hitherto unconsidered physical property of nanoparticles-the Laplace pressure. By studying the reaction of glyoxal with ammonium sulfate, both ubiquitous and important atmospheric constituents, we show that high pressure can significantly affect the chemical processes that occur in atmospheric ultrafine particles (i.e., particles < 100 nm). Using high-resolution mass spectrometry and UV-vis spectroscopy, we demonstrated that the formation of reaction products is strongly (i.e., up to a factor of 2) slowed down under high pressures typical of atmospheric nanoparticles. A size-dependent relative rate constant is determined and numerical simulations illustrate the reduction in the production of the main glyoxal reaction products. These results established that the high pressure inside nanometer-sized aerosols must be considered as a key property that significantly impacts chemical processes that govern atmospheric aerosol growth and evolution.

Indoor Surface Chemistry: Developing a Molecular Picture of Reactions on Indoor Interfaces.

Chemical reactions on indoor surfaces play an important role in air quality in indoor environments, where humans spend 90% of their time. We focus on the challenges of understanding the complex chemistry that takes place on indoor surfaces and identify crucial steps necessary to gain a molecular-level understanding of environmental indoor surface chemistry: (1) elucidate key surface reaction mechanisms and kinetics important to indoor air chemistry, (2) define a range of relevant and representative surfaces to probe, and (3) define the drivers of surface reactivity, particularly with respect to the surface composition, light, and temperature. Within the drivers of surface composition are the roles of adsorbed/absorbed water associated with indoor surfaces and the prevalence, inhomogeneity, and properties of secondary organic films that can impact surface reactivity. By combining laboratory studies, field measurements, and modeling we can gain insights into the molecular processes necessary to further our understanding of the indoor environment.

Heterogeneous Chemistry of CaCO3 Aerosols with HNO3 and HCl.

Calcite (CaCO3) aerosols often serve as an idealized proxy for calcium-rich mineral dust. Their use has also previously been proposed for stratospheric solar radiation management (SSRM). Little is known about the heterogeneous chemistry of calcite aerosols with trace gases HNO3 and HCl and therefore their potential impact on stratospheric ozone (O3). Here we report the results of an experimental study of the uptake of HNO3 and HCl onto submicron CaCO3 particles in two different flow reactors. Products and reaction kinetics were observed by impacting aerosolized CaCO3 onto ZnSe windows, exposing them to the reagent gases at a wide range of concentrations, at 296 K and under dry conditions, and analyzing the particles before and after trace gas exposure using Fourier transform infrared spectroscopy (FTIR). A Ca(OH)(HCO3) termination layer was detected in the form of a HCO3- peak in the FTIR spectra, indicating a hydrated surface even under dry conditions. The results demonstrate the reaction of HNO3 with Ca(OH)(HCO3) to produce Ca(NO3)2, water, and CO2. HCl reacted with Ca(OH)(HCO3) to produce CaCl2 and also water and CO2. The depletion of the Ca(OH)(HCO3)/Ca(CO3) signal due to reaction with HNO3 or HCl followed pseudo-first-order kinetics. From the FTIR analysis, the reactive uptake coefficient for HNO3 was determined to be in the range of 0.013 ≤ γHNO3 ≤ 0.14, and that for HCl was 0.0011 ≤ γHCl ≤ 0.012 within the reported uncertainty. The reaction of HCl with airborne CaCO3 aerosols was also studied in an aerosol flow tube coupled with a quadrupole chemical ionization mass spectrometer (CIMS) under similar conditions to the FTIR study, and γHCl was determined to be 0.013 ± 0.001. Following previous modeling studies, these results suggest that the reactions of HCl and HNO3 with calcite in the stratosphere could ameliorate the potential for stratospheric solar radiation management to lead to stratospheric ozone depletion.

Impact of Environmental Conditions on Secondary Organic Aerosol Production from Photosensitized Humic Acid.

Recent studies have shown the potential of the photosensitizer chemistry of humic acid, as a proxy for humic-like substances in atmospheric aerosols, to contribute to secondary organic aerosol mass. The mechanism requires particle-phase humic acid to absorb solar radiation and become photoexcited, then directly or indirectly oxidize a volatile organic compound (VOC), resulting in a lower volatility product in the particle phase. We performed experiments in a photochemical chamber, with aerosol-phase humic acid as the photosensitizer and limonene as the VOC. In the presence of 26 ppb limonene and under atmospherically relevant UV-visible irradiation levels, there is no significant change in particle diameter. Calculations show that SOA production via this pathway is highly sensitive to VOC precursor concentrations. Under the assumption that HULIS is equally or less reactive than the humic acid used in these experiments, the results suggest that the photosensitizer chemistry of HULIS in ambient atmospheric aerosols is unlikely to be a significant source of secondary organic aerosol mass.

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 semi-volatile 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 indicates acidity may be relatively constant due to the semi-volatile 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.

Organic Peroxides and Sulfur Dioxide in Aerosol: Source of Particulate Sulfate.

Sulfur oxides (SOx) are important atmospheric trace species in both gas and particulate phases, and sulfate is a major component of atmospheric aerosol. One potentially important source of particulate sulfate formation is the oxidation of dissolved SO2 by organic peroxides, which comprises a major fraction of secondary organic aerosol (SOA). In this study, we investigated the reaction kinetics and mechanisms between SO2 and condensed-phase peroxides. pH-dependent aqueous phase reaction rate constants between S(IV) and organic peroxide standards were measured. Highly oxygenated organic peroxides with O/C > 0.6 in α-pinene SOA react rapidly with S(IV) species in the aqueous phase. The reactions between organic peroxides and S(IV) yield both inorganic sulfate and organosulfates (OS), as observed by electrospray ionization ion mobility mass spectrometry. For the first time, 34S-labeling experiments in this study revealed that dissolved SO2 forms OS via direct reactions without forming inorganic sulfate as a reactive intermediate. Kinetics of OS formation was estimated semiquantitatively, and such reaction was found to account for 30-60% of sulfur reacted. The photochemical box model GAMMA was applied to assess the implications of the measured SO2 consumption and OS formation rates. Our findings indicate that this novel pathway of SO2-peroxide reaction is important for sulfate formation in submicron aerosol.

Urban pollution greatly enhances formation of natural aerosols over the Amazon rainforest.

One of the least understood aspects in atmospheric chemistry is how urban emissions influence the formation of natural organic aerosols, which affect Earth's energy budget. The Amazon rainforest, during its wet season, is one of the few remaining places on Earth where atmospheric chemistry transitions between preindustrial and urban-influenced conditions. Here, we integrate insights from several laboratory measurements and simulate the formation of secondary organic aerosols (SOA) in the Amazon using a high-resolution chemical transport model. Simulations show that emissions of nitrogen-oxides from Manaus, a city of ~2 million people, greatly enhance production of biogenic SOA by 60-200% on average with peak enhancements of 400%, through the increased oxidation of gas-phase organic carbon emitted by the forests. Simulated enhancements agree with aircraft measurements, and are much larger than those reported over other locations. The implication is that increasing anthropogenic emissions in the future might substantially enhance biogenic SOA in pristine locations like the Amazon.

Southeast Atmosphere Studies: learning from model-observation syntheses.

Concentrations of atmospheric trace species in the United States have changed dramatically over the past several decades in response to pollution control strategies, shifts in domestic energy policy and economics, and economic development (and resulting emission changes) elsewhere in the world. Reliable projections of the future atmosphere require models to not only accurately describe current atmospheric concentrations, but to do so by representing chemical, physical and biological processes with conceptual and quantitative fidelity. Only through incorporation of the processes controlling emissions and chemical mechanisms that represent the key transformations among reactive molecules can models reliably project the impacts of future policy, energy and climate scenarios. Efforts to properly identify and implement the fundamental and controlling mechanisms in atmospheric models benefit from intensive observation periods, during which collocated measurements of diverse, speciated chemicals in both the gas and condensed phases are obtained. The Southeast Atmosphere Studies (SAS, including SENEX, SOAS, NOMADSS and SEAC4RS) conducted during the summer of 2013 provided an unprecedented opportunity for the atmospheric modeling community to come together to evaluate, diagnose and improve the representation of fundamental climate and air quality processes in models of varying temporal and spatial scales. This paper is aimed at discussing progress in evaluating, diagnosing and improving air quality and climate modeling using comparisons to SAS observations as a guide to thinking about improvements to mechanisms and parameterizations in models. The effort focused primarily on model representation of fundamental atmospheric processes that are essential to the formation of ozone, secondary organic aerosol (SOA) and other trace species in the troposphere, with the ultimate goal of understanding the radiative impacts of these species in the southeast and elsewhere. Here we address questions surrounding four key themes: gas-phase chemistry, aerosol chemistry, regional climate and chemistry interactions, and natural and anthropogenic emissions. We expect this review to serve as a guidance for future modeling efforts.

Insights into the characteristics and sources of primary and secondary organic carbon: High time resolution observation in urban Shanghai.

There is growing evidence suggesting that organic aerosols play an important role in the evolution of severe haze episodes. However, long-term investigations of the different characteristics of carbonaceous aerosols during haze and non-haze days are insufficient. In this work, hourly measurements of organic carbon (OC) and elemental carbon (EC) in PM2.5 were conducted in Shanghai, a megacity in Eastern China, over the course of a year from July 2013 to June 2014. Both OC and EC exhibited a bimodal diel pattern and were highly dependent on the wind speed and direction. The concentration-weighted trajectory (CWT) analysis illustrated that primary OC (POC) and EC were largely associated with regional and long-range transport. Secondary OC (SOC) formation was the strongest during the harvest season owing to significant biomass burning emissions from the adjacent Yangtze River Delta and farther agricultural regions. Compared to OC (6.7 µg m-3) and EC (2.0 µg m-3) in the non-haze days, higher levels of both OC (15.6 µg m-3) and EC (7.7 µg m-3) were observed in the haze days as expected, but with lower OC/EC ratios in the haze days (2.4) than in non-haze days (4.6). The proportion of POC and EC in PM2.5 remained relatively constant as a function of PM2.5 mass loadings, while that of SOC significantly decreased on the highly polluted days. It is concluded that the haze pollution in urban Shanghai was influenced more by the primary emissions (POC and EC), while the role of SOC in triggering haze was limited.