Ice-nucleating agents in sea spray aerosol identified and quantified with a holistic multimodal freezing model.

Sea spray aerosol (SSA) is a widely recognized important source of ice-nucleating particles (INPs) in the atmosphere. However, composition-specific identification, nucleation processes, and ice nucleation rates of SSA-INPs have not been well constrained. Microspectroscopic characterization of ambient and laboratory-generated SSA confirms that water-borne exudates from planktonic microorganisms composed of a mixture of proteinaceous and polysaccharidic compounds act as ice-nucleating agents (INAs). These data and data from previously published mesocosm and wave channel studies are subsequently used to further develop the stochastic freezing model (SFM) producing ice nucleation rate coefficients for SSA-INPs. The SFM simultaneously predicts immersion freezing and deposition and homogeneous ice nucleation by SSA particles under tropospheric conditions. Predicted INP concentrations agree with ambient and laboratory measurements. In addition, this holistic freezing model is independent of the source and exact composition of the SSA particles, making it well suited for implementation in cloud and climate models.

Dry heat sterilization as a method to recycle N95 respirator masks: The importance of fit.

In times of crisis, including the current COVID-19 pandemic, the supply chain of filtering facepiece respirators, such as N95 respirators, are disrupted. To combat shortages of N95 respirators, many institutions were forced to decontaminate and reuse respirators. While several reports have evaluated the impact on filtration as a measurement of preservation of respirator function after decontamination, the equally important fact of maintaining proper fit to the users' face has been understudied. In the current study, we demonstrate the complete inactivation of SARS-CoV-2 and preservation of fit test performance of N95 respirators following treatment with dry heat. We apply scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), X-ray diffraction (XRD) measurements, Raman spectroscopy, and contact angle measurements to analyze filter material changes as a consequence of different decontamination treatments. We further compared the integrity of the respirator after autoclaving versus dry heat treatment via quantitative fit testing and found that autoclaving, but not dry heat, causes the fit of the respirator onto the users face to fail, thereby rendering the decontaminated respirator unusable. Our findings highlight the importance to account for both efficacy of disinfection and mask fit when reprocessing respirators to for clinical redeployment.

Representation of Multiphase OH Oxidation of Amorphous Organic Aerosol for Tropospheric Conditions.

Organic aerosol (OA) is ubiquitous in the atmosphere and, during transport, can experience chemical transformation with consequences for air quality and climate. Prediction of the chemical evolution of OA depends on its reactivity with atmospheric oxidants such as the OH radical. OA particles undergo amorphous phase transitions from liquid to solid (glassy) states in response to temperature changes, which, in turn, will impact its reactivity toward OH oxidation. To improve the predictability of OA reactivity toward OH oxidation, the reactive uptake coefficients (γ) of OH radicals reacting with triacontane and squalane serving as amorphous OA surrogates were measured at temperatures from 213-293 K. γ increases strongest with temperature when the organic species is in the liquid phase, compared to when being in the semisolid or solid phase. The resistor model is applied, accounting for the amorphous phase state changes using the organic species' glass transition temperature and fragility, to evaluate the physicochemical parameters of the temperature dependent OH uptake process. This allows for the derivation of a semiempirical formula, applicable to models, to predict the degree of oxidation and chemical lifetime of the condensed-phase organic species for typical tropospheric temperature and humidity when OA particle viscosity is known.

Stochastic nucleation processes and substrate abundance explain time-dependent freezing in supercooled droplets.

Atmospheric immersion freezing (IF), a heterogeneous ice nucleation process where an ice nucleating particle (INP) is immersed in supercooled water, is a dominant ice formation pathway impacting the hydrological cycle and climate. Implementation of IF derived from field and laboratory data in cloud and climate models is difficult due to the high variability in spatio-temporal scales, INP composition, and morphological complexity. We demonstrate that IF can be consistently described by a stochastic nucleation process accounting for uncertainties in the INP surface area. This approach accounts for time-dependent freezing, a wide range of surface areas and challenges phenomenological descriptions typically used to interpret IF. The results have an immediate impact on the current description, interpretation, and experiments of IF and its implementation in models. The findings are in accord with nucleation theory, and thus should hold for any supercooled liquid material that nucleates in contact with a substrate.

Chemical evolution of atmospheric organic carbon over multiple generations of oxidation.

The evolution of atmospheric organic carbon as it undergoes oxidation has a controlling influence on concentrations of key atmospheric species, including particulate matter, ozone and oxidants. However, full characterization of organic carbon over hours to days of atmospheric processing has been stymied by its extreme chemical complexity. Here we study the multigenerational oxidation of α-pinene in the laboratory, characterizing products with several state-of-the-art analytical techniques. Although quantification of some early generation products remains elusive, full carbon closure is achieved (within measurement uncertainty) by the end of the experiments. These results provide new insights into the effects of oxidation on organic carbon properties (volatility, oxidation state and reactivity) and the atmospheric lifecycle of organic carbon. Following an initial period characterized by functionalization reactions and particle growth, fragmentation reactions dominate, forming smaller species. After approximately one day of atmospheric aging, most carbon is sequestered in two long-lived reservoirs-volatile oxidized gases and low-volatility particulate matter.

Condensed-phase biogenic-anthropogenic interactions with implications for cold cloud formation.

Anthropogenic and biogenic gas emissions contribute to the formation of secondary organic aerosol (SOA). When present, soot particles from fossil fuel combustion can acquire a coating of SOA. We investigate SOA-soot biogenic-anthropogenic interactions and their impact on ice nucleation in relation to the particles' organic phase state. SOA particles were generated from the OH oxidation of naphthalene, α-pinene, longifolene, or isoprene, with or without the presence of sulfate or soot particles. Corresponding particle glass transition (Tg) and full deliquescence relative humidity (FDRH) were estimated using a numerical diffusion model. Longifolene SOA particles are solid-like and all biogenic SOA sulfate mixtures exhibit a core-shell configuration (i.e. a sulfate-rich core coated with SOA). Biogenic SOA with or without sulfate formed ice at conditions expected for homogeneous ice nucleation, in agreement with respective Tg and FDRH. α-pinene SOA coated soot particles nucleated ice above the homogeneous freezing temperature with soot acting as ice nuclei (IN). At lower temperatures the α-pinene SOA coating can be semisolid, inducing ice nucleation. Naphthalene SOA coated soot particles acted as ice nuclei above and below the homogeneous freezing limit, which can be explained by the presence of a highly viscous SOA phase. Our results suggest that biogenic SOA does not play a significant role in mixed-phase cloud formation and the presence of sulfate renders this even less likely. However, anthropogenic SOA may have an enhancing effect on cloud glaciation under mixed-phase and cirrus cloud conditions compared to biogenic SOA that dominate during pre-industrial times or in pristine areas.

Direct observation of ice nucleation events on individual atmospheric particles.

Heterogeneous ice nucleation is a physical chemistry process of critical relevance to a range of topics in the fundamental and applied sciences and technologies. Heterogeneous ice nucleation remains insufficiently understood, partially due to the lack of experimental methods capable of obtaining in situ microscopic details of ice formation over nucleating substrates or particles. We present microscopic observations of ice nucleation events on kaolinite particles at the nanoscale and demonstrate the capability of direct tracking and micro-spectroscopic characterization of individual ice nucleating particles (INPs) in an authentic atmospheric sample. This approach utilizes a custom-built ice nucleation cell, interfaced with an Environmental Scanning Electron Microscope (IN-ESEM platform) operated at temperatures and relative humidities relevant for heterogeneous ice nucleation. The IN-ESEM platform allows dynamic observations of individual ice formation events over particles in isobaric and isothermal experiments. Isothermal experiments on individual kaolinite particles demonstrate that ice crystals preferably nucleate at the edges of the stacked kaolinite platelets, rather than on their basal planes. These experimental observations of the location of ice nucleation provide direct information for further theoretical chemistry predictions of ice formation on kaolinite.

Progress in the Analysis of Complex Atmospheric Particles.

This article presents an overview of recent advances in field and laboratory studies of atmospheric particles formed in processes of environmental air-surface interactions. The overarching goal of these studies is to advance predictive understanding of atmospheric particle composition, particle chemistry during aging, and their environmental impacts. The diversity between chemical constituents and lateral heterogeneity within individual particles adds to the chemical complexity of particles and their surfaces. Once emitted, particles undergo transformation via atmospheric aging processes that further modify their complex composition. We highlight a range of modern analytical approaches that enable multimodal chemical characterization of particles with both molecular and lateral specificity. When combined, these approaches provide a comprehensive arsenal of tools for understanding the nature of particles at air-surface interactions and their reactivity and transformations with atmospheric aging. We discuss applications of these novel approaches in recent studies and highlight additional research areas to explore the environmental effects of air-surface interactions.

Ice-nucleating bacteria control the order and dynamics of interfacial water.

Ice-nucleating organisms play important roles in the environment. With their ability to induce ice formation at temperatures just below the ice melting point, bacteria such as Pseudomonas syringae attack plants through frost damage using specialized ice-nucleating proteins. Besides the impact on agriculture and microbial ecology, airborne P. syringae can affect atmospheric glaciation processes, with consequences for cloud evolution, precipitation, and climate. Biogenic ice nucleation is also relevant for artificial snow production and for biomimetic materials for controlled interfacial freezing. We use interface-specific sum frequency generation (SFG) spectroscopy to show that hydrogen bonding at the water-bacteria contact imposes structural ordering on the adjacent water network. Experimental SFG data and molecular dynamics simulations demonstrate that ice-active sites within P. syringae feature unique hydrophilic-hydrophobic patterns to enhance ice nucleation. The freezing transition is further facilitated by the highly effective removal of latent heat from the nucleation site, as apparent from time-resolved SFG spectroscopy.

A marine biogenic source of atmospheric ice-nucleating particles.

The amount of ice present in clouds can affect cloud lifetime, precipitation and radiative properties. The formation of ice in clouds is facilitated by the presence of airborne ice-nucleating particles. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice. Sea-spray aerosol contains large amounts of organic material that is ejected into the atmosphere during bubble bursting at the organically enriched sea-air interface or sea surface microlayer. Here we show that organic material in the sea surface microlayer nucleates ice under conditions relevant for mixed-phase cloud and high-altitude ice cloud formation. The ice-nucleating material is probably biogenic and less than approximately 0.2 micrometres in size. We find that exudates separated from cells of the marine diatom Thalassiosira pseudonana nucleate ice, and propose that organic material associated with phytoplankton cell exudates is a likely candidate for the observed ice-nucleating ability of the microlayer samples. Global model simulations of marine organic aerosol, in combination with our measurements, suggest that marine organic material may be an important source of ice-nucleating particles in remote marine environments such as the Southern Ocean, North Pacific Ocean and North Atlantic Ocean.

Radial diffusion and penetration of gas molecules and aerosol particles through laminar flow reactors, denuders, and sampling tubes.

Flow reactors, denuders, and sampling tubes are essential tools for many applications in analytical and physical chemistry and engineering. We derive a new method for determining radial diffusion effects and the penetration or transmission of gas molecules and aerosol particles through cylindrical tubes under laminar flow conditions using explicit analytical equations. In contrast to the traditional Brown method [Brown, R. L. J. Res. Natl. Bur. Stand. (U. S.) 1978, 83, 1-8] and CKD method (Cooney, D. O.; Kim, S. S.; Davis, E. J. Chem. Eng. Sci. 1974, 29, 1731-1738), the new approximation developed in this study (known as the KPS method) does not require interpolation or numerical techniques. The KPS method agrees well with the CKD method under all experimental conditions and also with the Brown method at low Sherwood numbers. At high Sherwood numbers corresponding to high uptake on the wall, flow entry effects become relevant and are considered in the KPS and CKD methods but not in the Brown method. The practical applicability of the KPS method is demonstrated by analysis of measurement data from experimental studies of rapid OH, intermediate NO3, and slow O3 uptake on various organic substrates. The KPS method also allows determination of the penetration of aerosol particles through a tube, using a single equation to cover both the limiting cases of high and low deposition described by Gormley and Kennedy (Proc. R. Ir. Acad., Sect. A. 1949, 52A, 163-169). We demonstrate that the treatment of gas and particle diffusion converges in the KPS method, thus facilitating prediction of diffusional loss and penetration of gases and particles, analysis of chemical kinetics data, and design of fluid reactors, denuders, and sampling lines.

Multiphase chemical kinetics of OH radical uptake by molecular organic markers of biomass burning aerosols: humidity and temperature dependence, surface reaction, and bulk diffusion.

Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

Heterogeneous OH oxidation of biomass burning organic aerosol surrogate compounds: assessment of volatilisation products and the role of OH concentration on the reactive uptake kinetics.

The reactive uptake coefficients (γ) of OH by levoglucosan, abietic acid, and nitroguaiacol serving as surrogate compounds for biomass burning aerosol have been determined employing a chemical ionisation mass spectrometer coupled to a rotating-wall flow-tube reactor over a wide range of [OH] ∼10(7)-10(11) molecule cm(-3). Volatilisation products of these organic substrates due to heterogeneous oxidation by OH have been determined at 1 atm using a high resolution proton transfer reaction time-of-flight mass spectrometer (HR-PTR-ToF-MS). γ range within 0.05-1 for [OH] = 2.6 × 10(7)-3 × 10(9) molecule cm(-3) for all investigated organic compounds, but decrease to 0.008-0.034 for [OH] = 4.1 × 10(10)-6.7 × 10(10) molecule cm(-3). γ as a function of [OH] can be described by a Langmuir-Hinshelwood model, neglecting bulk processes, suggesting that despite its strong reactivity, OH is mobile on surfaces prior to reaction. The best fit Langmuir-Hinshelwood parameters on average are K(OH) = 3.81 × 10(-10) cm(3) molecule(-1) and k(s) = 9.71 × 10(-17) cm(2) molecule(-1) s(-1) for all of the investigated organic compounds. Volatilised products have been identified indicating enhancements over background of 50% up to a factor of 15. Amongst the common volatile organic compounds (VOCs) identified between levoglucosan, abietic acid, and nitroguaiacol were methanol, acetaldehyde, formic acid, and acetic acid. VOCs having the greatest enhancement over background were glucic acid from levoglucosan, glycolic acid from abietic acid, and methanol and nitric acid from nitroguaiacol. Reaction mechanisms leading to the formation of glucic acid, glycolic acid, methanol, and nitric acid are proposed. Estimated lower limits of atmospheric lifetimes of biomass burning aerosol particles, 200 nm in diameter, by heterogeneous OH oxidation under fresh biomass burning plume conditions are ∼2 days and up to ∼2 weeks for atmospheric background conditions. However, estimated lifetimes depend crucially on [OH] and corresponding γ, emphasising the need to determine γ under relevant conditions.

A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets.

Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, a(w), which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humidity (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, J(het), to be uniquely expressed by T and a(w), a result we term the a(w) based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, J(het), frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log10(J(het)) values for the various IN types derived exclusively by Tand a(w), provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Lastly, we demonstrate that ABIFM can be used to derive frozen fractions of droplets and ice particle production for atmospheric models of cirrus and mixed phase cloud conditions.

Multiphase chemical kinetics of NO3 radicals reacting with organic aerosol components from biomass burning.

Multiphase reactions with nitrate radicals are among the most important chemical aging processes of organic aerosol particles in the atmosphere especially at nighttime. Reactive uptake of NO(3) by organic compounds has been observed in a number of studies, but the pathways of mass transport and chemical reaction remained unclear. Here we apply kinetic flux models to experimental NO(3) exposure studies. The model accounts for gas phase diffusion within a cylindrical flow tube, reversible adsorption of NO(3), surface-bulk exchange, bulk diffusion, and chemical reactions from the gas-condensed phase interface to the bulk. We resolve the relative contributions of surface and bulk reactions to the uptake of NO(3) by levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). Applying the kinetic flux model, we provide the first estimate of the diffusion coefficient of NO(3) in amorphous solid organic matrices (10(-8)-10(-7) cm(2) s(-1)) and show that molecular markers are well-conserved in the bulk of solid BBA particles but undergo rapid degradation upon deliquescence/liquefaction at high relative humidity, indicating that the observed concentrations and subsequent apportionment of the biomass burning source could be significantly underestimated.

Heterogeneous oxidation kinetics of organic biomass burning aerosol surrogates by O3, NO2, N2O5, and NO3.

The reactive uptake coefficients (γ) of O(3), NO(2), N(2)O(5), and NO(3) by levoglucosan, abietic acid, nitroguaiacol, and an atmospherically relevant mixture of those species serving as surrogates for biomass burning aerosol have been determined employing a chemical ionization mass spectrometer coupled to a rotating-wall flow-tube reactor. γ of O(3), NO(2), N(2)O(5), and NO(3) in the presence of O(2) are in the range of 1-8 × 10(-5), <10(-6)-5 × 10(-5), 4-6 × 10(-5), and 1-26 × 10(-3), respectively, for the investigated organic substrates. Within experimental uncertainties the uptake of NO(3) was not sensitive to the presence of water vapour ( <0.5% relative humidity). [corrected]. NO(3) uptake experiments involving substrates of levoglucosan, abietic acid, and the mixture exhibit an initial strong uptake of NO(3) followed by NO(3) gas-phase recovery as a function of NO(3) exposure. In contrast, the uptake of NO(3) by nitroguaiacol continuously proceeds at the same efficiency for investigated NO(3) exposures. The derived oxidative power, i.e. the product of γ and atmospheric oxidant concentration, for applied oxidants is similar or significantly larger in magnitude than for OH, emphasizing the potential importance of these oxidants for particle oxidation. Estimated atmospheric lifetimes for the topmost organic layer with respect to O(3), NO(2), N(2)O(5), and NO(3) oxidation for typical polluted conditions range between 1-112 min, indicating the potential for significant chemical transformation during atmospheric transport. The contact angles determined prior to, and after heterogeneous oxidation by NO(3), representative of 50 ppt for 1 day, do not decrease and thus do not indicate a significant increase in hygroscopicity with potential impacts on water uptake and cloud formation processes.