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SummaryManual facemask ventilation, a core component of elective and emergency airway management, is classified as an aerosol generating procedure. This designation is based on a single epidemiological study suggesting an association between facemask ventilation and transmission from the SARS 2003 outbreak. There is no direct evidence to indicate whether facemask ventilation is a high-risk procedure for aerosol generation. We conducted aerosol monitoring during routine facemask ventilation, and facemask ventilation with an intentionally generated leak, in anaesthetised patients with neuromuscular blockade. Recordings were made in ultraclean theatres and compared against the aerosol generated by the patient’s own tidal breathing and coughs. Respiratory aerosol from tidal breathing was reliably detected above the very low background particle concentrations (191 (77-486 [3.8-1313]) versus 2.1 (0.7-4.6 [0-12.9] particles.l-1 median(IQR)[range], n=11, p=0.002). The average aerosol concentration detected during facemask ventilation both without a leak (3.0 particles.l-1 (0 – 9 [0-43])) and with an intentional leak (11 particles.l-1 (7.0 – 26 [1-62])) was 64-fold and 17-fold lower than that of tidal breathing (p=0.001 and p=0.002 respectively). The peak particle concentration during facemask ventilation both without a leak (60 particles.l-1 (0 – 60 [0-120])) and with a leak (120 particles.l-1 (60 – 180 [60-480]) were respectively 20-fold and 10-fold lower than a cough (1260 particles (800 – 3242 [100-3682]), p=0.002 and p=0.001 respectively). This study demonstrates that facemask ventilation, even performed with an intentional leak, does not generate high levels of bioaerosol. On the basis of this evidence, facemask ventilation should not be considered an aerosol generating procedure.

ObjectiveTo determine if oesophago-gastro-duodenoscopy (OGD) generates increased levels of aerosol in conscious patients and identify the source events.DesignA prospective, environmental aerosol monitoring study, undertaken in an ultraclean environment, on patients undergoing OGD. Sampling was performed 20 cm away from the patient’s mouth using an optical particle sizer. Aerosol levels during OGD were compared with tidal breathing and voluntary coughs within subject.ResultsPatients undergoing bariatric surgical assessment were recruited (mean body mass index 44 and mean age 40 years, n=15). A low background particle concentration in theatres (3 L−1) enabled detection of aerosol generation by tidal breathing (mean particle concentration 118 L−1). Aerosol recording during OGD showed an average particle number concentration of 595 L−1with a wide range (3–4320 L−1). Bioaerosol-generating events, namely, coughing or burping, were common. Coughing was evoked in 60% of the endoscopies, with a greater peak concentration and a greater total number of sampled particles than the patient’s reference voluntary coughs (11 710 vs 2320 L−1and 780 vs 191 particles, n=9 and p=0.008). Endoscopies with coughs generated a higher level of aerosol than tidal breathing, whereas those without coughs were not different to the background. Burps also generated increased aerosol concentration, similar to those recorded during voluntary coughs. The insertion and removal of the endoscope were not aerosol generating unless a cough was triggered.ConclusionCoughing evoked during OGD is the main source of the increased aerosol levels, and therefore, OGD should be regarded as a procedure with high risk of producing respiratory aerosols. OGD should be conducted with airborne personal protective equipment and appropriate precautions in those patients who are at risk of having COVID-19 or other respiratory pathogens.

Pulmonary function tests are fundamental to the diagnosis and monitoring of respiratory diseases. There is uncertainty around whether potentially infectious aerosols are produced during testing and there are limited data on mitigation strategies to reduce risk to staff. Healthy volunteers and patients with lung disease underwent standardised spirometry, peak flow and FENO assessments. Aerosol number concentration was sampled using an aerodynamic particle sizer and an optical particle sizer. Measured aerosol concentrations were compared with breathing, speaking and voluntary coughing. Mitigation strategies included a standard viral filter and a full-face mask normally used for exercise testing (to mitigate induced coughing). 147 measures were collected from 33 healthy volunteers and 10 patients with lung disease. The aerosol number concentration was highest in coughs (1.45–1.61 particles/cm3), followed by unfiltered peak flow (0.37–0.76 particles/cm3). Addition of a viral filter to peak flow reduced aerosol emission by a factor of 10 without affecting the results. On average, coughs produced 22 times more aerosols than standard spirometry (with filter) in patients and 56 times more aerosols in healthy volunteers. FENO measurement produced negligible aerosols. Cardiopulmonary exercise test (CPET) masks reduced aerosol emission when breathing, speaking and coughing significantly. Lung function testing produces less aerosols than voluntary coughing. CPET masks may be used to reduce aerosol emission from induced coughing. Standard viral filters are sufficiently effective to allow guidelines to remove lung function testing from the list of aerosol-generating procedures.

Organic aerosol can adopt a wide range of viscosities, from liquid to glass, depending on the local humidity. In highly viscous droplets, the evaporation rates of organic components are suppressed to varying degrees, yet water evaporation remains fast. Here, we examine the coevaporation of semivolatile organic compounds (SVOCs), along with their solvating water, from aerosol particles levitated in a humidity-controlled environment. To better replicate the composition of secondary aerosol, nonvolatile organics were also present, creating a three-component diffusion problem. Kinetic modeling reproduced the evaporation accurately when the SVOCs were assumed to obey the Stokes-Einstein relation, and water was not. Crucially, our methodology uses previously collected data to constrain the time-dependent viscosity, as well as water diffusion coefficients, allowing it to be predictive rather than postdictive. Throughout the study, evaporation rates were found to decrease as SVOCs deplete from the particle, suggesting path function type behavior.

Aerosols are highly dynamic, non-equilibrium systems exhibiting unique microphysical properties relative to bulk systems. Here the authors discuss the roles aerosols play in (bio)chemical transformations and identify open questions in aerosol-mediated reaction rate accelerations, aerosol optical properties, and microorganism survival. Aerosols are highly dynamic, non-equilibrium systems exhibiting unique microphysical properties relative to bulk systems. Here the authors discuss the roles aerosols play in (bio)chemical transformations and identify open questions in aerosol-mediated reaction rate accelerations, aerosol optical properties, and microorganism survival.

The evaporation of liquid solution droplets and solute crystallization can be highly complex and is an important problem, particularly in spray drying where powdered products are produced from sprayed liquid droplets, such as in the food or pharmaceutical industries. In this work, we study the relationship between the evaporation rates of single levitated NaNO

Significance Atmospheric aerosol particles cool Earth’s climate by serving as cloud droplet seeds. This cooling effect represents both the single most uncertain and the largest negative radiative forcing. Cloud droplet activation is strongly influenced by aerosol particle surface tension, which in climate models is assumed equivalent to that of pure water. We directly measure the surface tensions of surfactant-coated, high surface-to-volume ratio droplets, demonstrating that their surface tensions are significantly lower than pure water but do not match the surface tension of the solution from which they were produced and depend on finite droplet size. These results suggest surfactants could potentially significantly modify radiative forcing and highlight the need for a better understanding of atmospheric surfactant concentrations and properties., Surface tension influences the fraction of atmospheric particles that become cloud droplets. Although surfactants are an important component of aerosol mass, the surface tension of activating aerosol particles is still unresolved, with most climate models assuming activating particles have a surface tension equal to that of water. By studying picoliter droplet coalescence, we demonstrate that surfactants can significantly reduce the surface tension of finite-sized droplets below the value for water, consistent with recent field measurements. Significantly, this surface tension reduction is droplet size-dependent and does not correspond exactly to the macroscopic solution value. A fully independent monolayer partitioning model confirms the observed finite-size-dependent surface tension arises from the high surface-to-volume ratio in finite-sized droplets and enables predictions of aerosol hygroscopic growth. This model, constrained by the laboratory measurements, is consistent with a reduction in critical supersaturation for activation, potentially substantially increasing cloud droplet number concentration and modifying radiative cooling relative to current estimates assuming a water surface tension. The results highlight the need for improved constraints on the identities, properties, and concentrations of atmospheric aerosol surfactants in multiple environments and are broadly applicable to any discipline where finite volume effects are operative, such as studies of the competition between reaction rates within the bulk and at the surface of confined volumes and explorations of the influence of surfactants on dried particle morphology from spray driers.

Respiratory particles produced by breathing, coughing, and speaking or generated during medical procedures serve as important routes for disease transmission. Characterising the number of particles generated as well as their size distribution is fundamental for guiding policy on infection control. However, sampling such particles carries inherent challenges. Respiratory particles are polydisperse in size, temporally and spatially variable, and emitted in very low concentrations, usually lower than the pre-existing aerosol concentration in indoor environments. In addition, they are typically emitted in a highly dynamic, warm and humid jet, leading to further rapid processes, such as dispersion and evaporation. Here, we discuss important considerations for sampling respiratory aerosol, focusing on sampling particles < 20 µm in diameter. Instruments capable of counting single-particles within this size range are commercially available. We provide recommendations for experimental protocols and demonstrate the limitations behind such approaches. We highlight the importance of a measurement space with as low a background aerosol concentration as possible, and of sampling for as long as possible to enable accurate quantitation of the size distribution of an aerosol plume. This is particularly important for the larger particles (> 5µm diameter) that are so low in concentration that they may require hours of sampling time to be accurately quantified. We explore the relationship between the flow rates of the exhalation and the sampling instrument and the consequent quantification of particle flux. We also discuss the transport and evaporation dynamics of liquid particles within respiratory jets, and their impacts on conducting aerosol sampling studies.

Gas-particle equilibrium partitioning is a fundamental concept used to describe the growth and loss of secondary organic aerosol (SOA). However, recent literature has suggested that gas-particle partitioning may be kinetically limited, preventing volatilization from the aerosol phase as a result of the physical state of the aerosol (e.g. glassy, viscous). Experimental measurements of diffusion constants within viscous aerosol are limited and do not represent the complex chemical composition observed in SOA (i.e. multicomponent mixtures). Motivated by the need to address fundamental questions regarding the effect of the physical state and chemical composition of a particle on gas-particle partitioning, we present the design and operation of a newly built 0.3 m3 continuous-flow reactor (CFR), which can be used as a tool to gain considerable insights into the composition and physical state of SOA. The CFR was used to generate SOA from the photo-oxidation of α-pinene, limonene, β-caryophyllene and toluene under different experimental conditions (i.e. relative humidity, VOC and VOC∕NOx ratios). Up to 102 mg of SOA mass was collected per experiment, allowing the use of highly accurate compositional- and single-particle analysis techniques, which are not usually accessible due to the large quantity of organic aerosol mass required for analysis. A suite of offline analytical techniques was used to determine the chemical composition and physical state of the generated SOA, including attenuated total reflectance infrared spectroscopy; carbon, hydrogen, nitrogen, and sulfur (CHNS) elemental analysis; 1H and 1H-13C nuclear magnetic resonance spectroscopy (NMR); ultra-performance liquid chromatography ultra-high-resolution mass spectrometry (UHRMS); high-performance liquid chromatography ion-trap mass spectrometry (HPLC-ITMS); and an electrodynamic balance (EDB). The oxygen-to-carbon (O∕C) and hydrogen-to-carbon (H∕C) ratios of generated SOA samples (determined using a CHNS elemental analyser) displayed good agreement with literature values and were consistent with the characteristic Van Krevelen diagram trajectory, with an observed slope of −0.41. The elemental composition of two SOA samples formed in separate replicate experiments displayed excellent reproducibility, with the O∕C and H∕C ratios of the SOA samples observed to be within error of the analytical instrumentation (instrument accuracy ±0.15 % to a reference standard). The ability to use a highly accurate CHNS elemental analyser to determine the elemental composition of the SOA samples allowed us to evaluate the accuracy of reported SOA elemental compositions using UHRMS (a commonly used technique). In all of the experiments investigated, the SOA O∕C ratios obtained for each SOA sample using UHRMS were lower than the O∕C ratios obtained from the CHNS analyser (the more accurate and non-selective technique). The average difference in the ΔO∕C ratios ranged from 19 % to 45 % depending on the SOA precursor and formation conditions. α-pinene SOA standards were generated from the collected SOA mass using semi-preparative HPLC-ITMS coupled to an automated fraction collector, followed by 1H NMR spectroscopy. Up to 35.8±1.6 % (propagated error of the uncertainty in the slope of the calibrations graphs) of α-pinene SOA was quantified using this method; a considerable improvement from most previous studies. Single aerosol droplets were generated from the collected SOA samples and trapped within an EDB at different temperatures and relative humidities to investigate the dynamic changes in their physiochemical properties. The volatilization of organic components from toluene and β-caryophyllene SOA particles at 0 % relative humidity was found to be kinetically limited, owing to particle viscosity. The unconventional use of a newly built CFR, combined with comprehensive offline chemical characterization and single-particle measurements, offers a unique approach to further our understanding of the relationship between SOA formation conditions, chemical composition and physiochemical properties.

The validation of approaches to predict the hygroscopicity of complex mixtures of organic components in aerosol is important for understanding the hygroscopic response of organic aerosol in the atmosphere. We report new measurements of the hygroscopicity of mixtures of dicarboxylic acids and amino acids using a comparative kinetic electrodynamic balance (CK-EDB) approach, inferring the equilibrium water content of the aerosol from close to a saturation relative humidity (100%) down to 80%. We show that the solution densities and refractive indices of the mixtures can be estimated with an accuracy of better than ±2% using the molar refractive index mixing rule and densities and refractive indices for the individual binary organic-aqueous solutions. Further, we show that the often-used mass-, volume-, and mole-weighted mixing rules to estimate the hygroscopicity parameter κ can overestimate the hygroscopic parameter by a factor of as much as 3, highlighting the need to understand the specific nonideal interactions that may arise synergistically in mixtures and cannot be represented by simple models. Indeed, in some extreme cases the hygroscopicity of a multicomponent mixture can be very close to that for the least hygroscopic component. For mixtures of similar components for which no additional synergistic interactions need be considered, the hygroscopicity of the mixed component aerosol can be estimated with high accuracy from the hygroscopic response of the binary aqueous-organic aerosol. In conclusion, we suggest that the hygroscopicity of multicomponent organic aerosol can be highly nonadditive and that simple correlations of hygroscopicity with composition may often misrepresent the level of complexity essential to interpreting aerosol hygroscopicity.

Aerosol generating procedures (AGPs) are defined as any procedure releasing airborne particles σ)) and peak positions (DP,C)). The aerosol size distribution provided a robust fingerprint of aerosol emission from a source. 41 patients underwent fifteen different dental procedures. For nine procedures, no aerosol was detected above background. Where aerosol was detected, the percentage of procedure time that aerosol was observed above background ranged from 12.7% for ultrasonic scaling, to 42.9% for 3-in-1 air + water syringe. For ultrasonic scaling, 3-in-1 syringe use and surgical drilling, the aerosol size distribution matched the non-salivary contaminated instrument source, with no unexplained aerosol. High and slow speed drilling produced aerosol from patient procedures with different size distributions to those measured from the phantom head controls (mode widths log(σ)) and peaks (DP,C), p< 0.002) and, therefore, may pose a greater risk of salivary contamination. This study provides evidence for sources of aerosol generation during common dental procedures, enabling more informed evaluation of risk and appropriate mitigation strategies.

The nosocomial spread of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) has focused attention on the risk of aerosol generating procedures (AGPs) in healthcare [1]. SARS-CoV-2 has been isolated from pleural fluid, which has the potential to infect staff or patients if viraemic fluid is aerosolised during procedures [2, 3]. However, evidence for aerosol generation from pleural procedures is very limited. Current guidelines for appropriate use of personal protective equipment (PPE) while performing pleural procedures are based on expert opinion and application of the precautionary principle [4]. We set out to quantify if pleural procedures generated appreciable aerosol (aerosolised liquid particles that have the potential to carry virus) compared to aerosol sampled during normal respiratory activities of breathing and coughing., Percutaneous pleural procedures should not be considered aerosol generating. This study should inform future iterations of guidelines on the appropriate use of PPE when performing these procedures. https://bit.ly/3xFF71d

IntroductionLung function tests are fundamental diagnostic and monitoring tools for patients with respiratory symptoms. There is significant uncertainty around whether potentially infectious aerosol is produced during different lung function testing modalities; and limited data on possible mitigation strategies to reduce risk to staff and limit fallow time.MethodsHealthy volunteers were recruited in an ultraclean, laminar flow theatre and had standardised spirometry as per ERS/ATS guidance, as well as peak flow measurement and FENO assessment of airway inflammation. Aerosol emission was sampled minimum once each second using both an Aerodynamic Particle Sizer (APS) and Optical Particle Sizer (OPS), and compared to breathing, speaking and coughing. Mitigation strategies such as a peak flow viral filter and a CPET facemask (to mitigate induced coughing) were tested.Results33 healthy volunteers were recruited. Aerosol emission was highest in cough (1.61 particles/cm3/sample), followed by unfiltered peak flow (0.76 particles/cm3/sample). Filtered spirometry produced lower peak aerosol emission (0.11 particles/ cm3/sample) than that of a voluntary cough, and addition of a viral filter to the mouthpiece reduced peak flow aerosol emission to similar levels. The filter made little difference to recorded FEV peak flow values. Peak aerosol FENO measurement produced negligible aerosol. Reusable CPET masks with filter reduced aerosol emission when breathing, speaking, and coughing significantly.ConclusionsCompared to voluntary coughing, all lung function testing produced fewer aerosol particles. Filtered spirometry produces lower peak aerosol emission than peak voluntary coughing, and should not be deemed an aerosol generating procedure. The use of viral filters reduces aerosol emission in peak flow by > 10 times, and has little impact on recorded peak flow values. CPET masks are a useful option to reduce aerosol emission from induced coughing while performing spirometry.

The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic has resulted in an unprecedented shutdown in social and economic activity, with the cultural sector particularly severely affected. Restrictions on musical performances have arisen from a perception that there is a significantly higher risk of aerosol production from singing than speaking, based upon high-profile examples of clusters of COVID-19 following choral rehearsals. However, comparing aerosol generation from different types of vocalization, including singing, across a range of volumes is a rapidly evolving area of research. Here, we measured aerosols from singing, speaking and breathing from a large cohort of 25 professional singers in a range of musical genres in a zero-background environment, allowing unequivocal attribution of aerosol production to specific vocalizations. We do not assess the relative volumes at which people speak and sing. However, both showed steep increases in mass concentration with increase in loudness (spanning a factor of 20–30 across the dynamic range measured, p < 0.001). At the quietest volume (50 to 60 dBA), neither singing (p = 0.19) nor speaking (p = 0.20) were significantly different to breathing. At the loudest volume (90 to 100 dBA), a statistically significant difference (p < 0.001) was observed between singing and speaking, but with singing only generating a factor of between 1.5 and 3.4 more aerosol mass. Guidelines for musical performances should be based on the loudness and duration of the vocalization, the number of participants and the environment in which the activity occurs, rather than the type of vocalization. Mitigations such as the use of amplification and increased attention to ventilation should be employed where practicable. Copyright © 2021 American Association for Aerosol Research

BackgroundRisk of aerosolisation of SARS-CoV-2 directly informs organisation of acute healthcare and PPE guidance. Continuous positive airways pressure (CPAP) and high-flow nasal oxygen (HFNO) are widely used modes of oxygen delivery and respiratory support for patients with severe COVID-19, with both considered as high risk aerosol generating procedures. However, there are limited high quality experimental data characterising aerosolisation during oxygen delivery and respiratory support.MethodsHealthy volunteers were recruited to breathe, speak, and cough in ultra-clean, laminar flow theatres followed by using oxygen and respiratory support systems. Aerosol emission was measured using two discrete methodologies, simultaneously. Hospitalised patients with COVID-19 were also recruited and had aerosol emissions measured during breathing, speaking, and coughing.FindingsIn healthy volunteers (n = 25 subjects; 531 measures), CPAP (with exhalation port filter) produced less aerosols than breathing, speaking and coughing (even with large >50L/m facemask leaks). HFNO did emit aerosols, but the majority of these particles were generated from the HFNO machine, not the patient. HFNO-generated particles were small (InterpretationIn healthy volunteers, CPAP is associated with less aerosol emission than breathing, speaking or coughing. Aerosol emission from the respiratory tract does not appear to be increased by HFNO. Although direct comparisons are complex, cough appears to generate significant aerosols in a size range compatible with airborne transmission of SARS-CoV-2. As a consequence, the risk of SARS-CoV-2 aerosolisation is likely to be high in all areas where patients with Covid-19 are coughing. Guidance on personal protective equipment policy should reflect these updated risks.FundingNIHR-UKRI Rapid COVID call (COV003), Wellcome Trust GW4-CAT Doctoral Training Scheme (FH), MRC CARP Fellowship(JD, MR/T005114/1). Natural Environment Research Council grant (BB, NE/P018459/1)Research in contextEvidence before this studyPubMed was searched from inception until 10/1/21 using the terms ‘aerosol’, and variations of ‘non-invasive positive pressure ventilation’ and ‘high-flow nasal oxygen therapy’. Studies were included if they measured aerosol generated from volunteers or patients receiving non-invasive positive pressure ventilation (NIV) or high flow nasal oxygen therapy (HFNO), or provided experimental evidence on a simulated human setting. One study was identified (Gaeckle et al, 2020) which measured aerosol emission with one methodology (APS) but was limited by high background concentration of aerosol and a low number of participants (n = 10).Added value of this studyThis study used multiple methodologies to measure aerosol emission from the respiratory tract before and during CPAP and high-flow nasal oxygen, in an ultra-clean, laminar flow theatre with near-zero background aerosol and recruited patients with COVID-19 to ensure similar aerosol distributions. We conclude that there is negligible aerosol generation with CPAP, that aerosol emission from HFNO is from the machine and not the patient, coughing emits aerosols consistent with airborne transmission of SARS CoV2 and that healthy volunteers are a reasonable proxy for COVID-19 patients.Implications of all the available evidenceCPAP and HFNO should not be considered high risk aerosol generating procedures, based on our study and that of Gaeckle et al. Recorded aerosol emission from HFNO stems from the machine. Cough remains a significant aerosol risk. PPE guidance should be updated to ensure medical staff are protected with appropriate PPE in situations when patients with suspected or proven COVID-19 are likely to cough.

The performing arts have been significantly restricted due to the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic. We report measurements of aerosol and droplet concentrations generated when playing woodwind and brass instruments and comparisons with breathing, speaking, and singing. These measurements were conducted in a room with zero number concentration aerosol background in the 0.5-20 µm diameter size range, allowing clear attribution of detected particles to specific activities. A total of 13 instruments were examined across 9 participants. Respirable particle number concentrations and size distributions for playing instruments are consistent with those from the participant when breathing, based on measurements with multiple participants playing the flute and piccolo as well as measurements across the entire cohort. Due to substantial interparticipant variability, we do not provide a comparative assessment of the aerosol generated by playing different instruments, instead considering only the variation in aerosol yield across all instruments studied. Both particle number and mass concentrations from playing instruments are lower than those from speaking and singing at high volume, and no large droplets >20 µm diameter are detected. Combined, these observations suggest that playing instruments generates less aerosol than speaking or singing at high volumes. Moreover, there is no difference between the aerosol concentrations generated by professional and amateur performers while breathing, speaking, or singing, suggesting conclusions for professional singers may also apply to amateurs.

Optical trapping is a well-established technique to manipulate and levitate micro- and nanoscale particles and droplets. However, optical traps for single aerosol studies are most often limited to trapping spherical non-absorbing droplets and a universal optical trap for the stable confinement of particles regardless of their absorption strength and morphology is not established. Instead, new opportunities arise from levitating droplets using electrodynamic traps. Here, using a combined Electrodynamic Linear Quadrupole trap and a Cavity Ring-Down Spectrometer, we demonstrate that it is possible to trap single droplets and simultaneously measure their extinction cross sections and elastic scattering phase functions over extended periods of time. To test the novel setup, we evaluated the evaporation of 1,2,6-hexanetriol under low humidity conditions, and the evolution of aqueous (NH4)2SO4 and NaCl droplets experiencing changing environmental conditions. Our studies extended beyond spherical droplets and we measured particle extinction cross sections after the efflorescence (crystallisation) of the inorganic salt particles. Comparison of measured cross sections for crystallised particles with light scattering model predictions (using Mie theory or T-Matrix/Extended Boundary-Condition Method (EBCM) implementations for random orientation, with either the spheroid or superellipsoid parameterisations) enables information on particle shape to be inferred. Specifically, we find that cross sections for dry (NH4)2SO4 particles are accounted by Mie theory and, thus, particle shape is represented well by a sphere. Conversely, the cross sections for dry NaCl particles are only reconciled with light scattering models pertaining to non-spherical shapes. These results will have implications for accurate remote sensing retrievals of dry salt optical properties and for parameterisations implemented in radiative forcing calculations with changing humidity. Moreover, our new platform for precise and accurate measurement of optical properties of micron-scale and sub-micron particles has potential applications in a range of areas of atmospheric science, such as precise light scattering measurements for ice crystals and mineral dusts. It represents a promising step towards accurate characterisations of the optical properties for non-spherical and light absorbing aerosols.

Emerging outbreaks of airborne pathogenic infections worldwide, such as the current severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic, have raised the need to understand parameters affecting the airborne survival of microbes in order to develop measures for effective infection control. We report a novel experimental strategy, TAMBAS (tandem approach for microphysical and biological assessment of airborne microorganism survival), to explore the synergistic interactions between the physicochemical and biological processes that impact airborne microbe survival in aerosol droplets. This innovative approach provides a unique and detailed understanding of the processes taking place from aerosol droplet generation through to equilibration and viability decay in the local environment, elucidating decay mechanisms not previously described. The impact of evaporation kinetics, solute hygroscopicity and concentration, particle morphology, and equilibrium particle size on airborne survival are reported, using Escherichia coli MRE162 as a benchmark system. For this system, we report that (i) particle crystallization does not directly impact microbe longevity, (ii) bacteria act as crystallization nuclei during droplet drying and equilibration, and (iii) the kinetics of size and compositional change appear to have a larger effect on microbe longevity than the equilibrium solute concentration. IMPORTANCE A transformative approach to identify the physicochemical processes that impact the biological decay rates of bacteria in aerosol droplets is described. It is shown that the evaporation process and changes in the phase and morphology of the aerosol particle during evaporation impact microorganism viability. The equilibrium droplet size was found to affect airborne bacterial viability. Furthermore, the presence of Escherichia coli MRE162 in a droplet does not affect aerosol growth/evaporation but influences the dynamic behavior of the aerosol by processing the culture medium prior to aerosolization, affecting the hygroscopicity of the culture medium; this highlights the importance of the inorganic and organic chemical composition within the aerosolized droplets that impact hygroscopicity. Bacteria also act as crystallization nuclei. The novel approach and data have implications for increased mechanistic understanding of aerosol survival and infectivity in bioaerosol studies spanning the medical, veterinary, farming, and agricultural fields, including the role of microorganisms in atmospheric processing and cloud formation.

The potential aerosolised transmission of severe acute respiratory syndrome coronavirus-2 is of global concern. Airborne precaution personal protective equipment and preventative measures are universally mandated for medical procedures deemed to be aerosol generating. The implementation of these measures is having a huge impact on healthcare provision. There is currently a lack of quantitative evidence on the number and size of airborne particles produced during aerosol-generating procedures to inform risk assessments. To address this evidence gap, we conducted real-time, high-resolution environmental monitoring in ultraclean ventilation operating theatres during tracheal intubation and extubation sequences. Continuous sampling with an optical particle sizer allowed characterisation of aerosol generation within the zone between the patient and anaesthetist. Aerosol monitoring showed a very low background particle count (0.4 particles.l−1) allowing resolution of transient increases in airborne particles associated with airway management. As a positive reference control, we quantitated the aerosol produced in the same setting by a volitional cough (average concentration, 732 (418) particles.l−1, n = 38). Tracheal intubation including facemask ventilation produced very low quantities of aerosolised particles (average concentration, 1.4 (1.4) particles.l−1, n = 14, p < 0.0001 vs. cough). Tracheal extubation, particularly when the patient coughed, produced a detectable aerosol (21 (18) l−1, n = 10) which was 15-fold greater than intubation (p = 0.0004) but 35-fold less than a volitional cough (p < 0.0001). The study does not support the designation of elective tracheal intubation as an aerosol-generating procedure. Extubation generates more detectable aerosol than intubation but falls below the current criterion for designation as a high-risk aerosol-generating procedure. These novel findings from real-time aerosol detection in a routine healthcare setting provide a quantitative methodology for risk assessment that can be extended to other airway management techniques and clinical settings. They also indicate the need for reappraisal of what constitutes an aerosol-generating procedure and the associated precautions for routine anaesthetic airway management.

Background: Transmission of SARS-CoV-2 by bioaerosols is of increasing concern. The enhanced levels of personal protective equipment (PPE) and preventative measures to attenuate viral transmission during aerosol generating procedures (AGPs) are having a huge impact on healthcare provision. There is no quantitative evidence on the number and size of airborne particles produced during AGPs to inform risk assessments. Methods: Real-time, high-resolution environmental monitoring was conducted in ultraclean ventilation operating theatres. Continuous sampling with an optical particle sizer allowed characterisation of aerosol generation within the airway management zone during endotracheal intubation and extubation for urgent orthopaedic trauma or neuro-surgery. Findings: Aerosol monitoring showed a very low background particle count allowing resolution of the transient airborne particle plume produced by reference volitional coughs (maximum concentration, 1,690±140 particles.L‑1,n=38). By comparison, endotracheal intubation including mask ventilation produced negligible quantities of aerosolised particles (maximum concentration, 80±10 L‑1,n=14, P

The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic has resulted in an unprecedented shutdown in social and economic activity with the cultural sector particularly severely affected. Restrictions on performance have arisen from a perception that there is a significantly higher risk of aerosol production from singing than speaking based upon high-profile examples of clusters of COVID-19 following choral rehearsals. However, no direct comparison of aerosol generation from singing and speaking has been reported. Here, we measure aerosols from singing, speaking and breathing in a zero-background environment, allowing unequivocal attribution of aerosol production to specific vocalisations. Speaking and singing show steep increases in mass concentration with increase in volume (spanning a factor of 20-30 across the dynamic range measured, p-5). At the quietest volume (50 to 60 dB), neither singing (p=0.19) or speaking (p=0.20) were significantly different to breathing. At the loudest volume (90 to 100 dB), a statistically significant difference (p-5) is observed between singing and speaking, but with singing only generating a factor of between 1.5 and 3.4 more aerosol mass. Guidelines should create recommendations based on the volume and duration of the vocalisation, the number of participants and the environment in which the activity occurs, rather than the type of vocalisation. Mitigations such as the use of amplification and increased attention to ventilation should be employed where practicable.

The simultaneous evaporation and condensation of multiple volatile components from multicomponent aerosol droplets leads to changes in droplet size, composition and temperature. Measurements and models that capture and predict these dynamic aerosol processes are key to understanding aerosol microphysics in a broad range of contexts. We report measurements of the evaporation kinetics of droplets (initially ∼25 μm radius) formed from mixtures of ethanol and water levitated within a electrodynamic balance over timescales spanning 500 ms to 6 s. Measurements of evaporation into a gas phase of varied relative humidity and temperature are shown to compare well with predictions from a numerical model. We show that water condensation from the gas phase can occur concurrently with ethanol evaporation from aqueous-ethanol droplets. Indeed, water can condense so rapidly during the evaporation of a pure ethanol droplet in a humid environment, driven by the evaporative cooling the droplet experiences, that the droplet becomes pure water within 0.4 s.

A quantitative understanding of the evaporative drying kinetics and nucleation rates of aqueous based aerosol droplets is important for a wide range of applications, from atmospheric aerosols to industrial processes such as spray drying. Here, we introduce a numerical model for interpreting measurements of the evaporation rate and phase change of drying free droplets made using a single particle approach. We explore the evaporation of aqueous sodium chloride and sodium nitrate solution droplets. Although the chloride salt is observed to reproducibly crystallize at all drying rates, the nitrate salt solution can lose virtually all of its water content without crystallizing. The latter phenomenon has implications for our understanding of the competition between the drying rate and nucleation kinetics in these two systems. The nucleation model is used in combination with the measurements of crystallization events to infer nucleation rates at varying equilibrium state points, showing that classical nucleation theory provides a good description of the crystallization of the chloride salt but not the nitrate salt solution droplets. The reasons for this difference are considered.

Mass transfer between the gas and condensed phases in aerosols can be limited by slow bulk diffusion within viscous particles. During the heterogeneous and multiphase reactions of viscous organic aerosol particles, it is necessary to consider the interplay of numerous mass transfer processes and how they are impacted by viscosity, including the partitioning kinetics of semi-volatile organic reactants, water and oxidants. To constrain kinetic models of the heterogeneous chemistry, measurements must provide information on as many observables as possible. Here, the ozonolysis kinetics of maleic acid (MA) in ternary aerosol particles containing water and sucrose is used as a model system. By varying the mass ratio of sucrose to MA and by performing reactions at a wide range of relative humidity, direct measurements show that the viscosity of the particle can be varied over 7 orders of magnitude. Measurements of the volatilisation kinetics of MA show that this range in viscosity leads to a suppression in the effective vapour pressure of MA of 3-4 orders of magnitude. The inferred values of the diffusion coefficient of MA in the particle phase closely mirror the expected change in diffusion coefficient from the Stokes-Einstein equation and the change in viscosity. The kinetics of ozonolysis show a similar dependence on particle viscosity that can be further investigated using the kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB). Two scenarios, one constraining the diffusion coefficients for MA to those expected based on the Stokes-Einstein equation and the other including the diffusion coefficients as a fit parameter, yield similarly adequate representations of the ozonolysis kinetics, as inferred from the experimental decay in the signature of the vinylic C-H stretching vibration of MA. However, these two scenarios provide very different parameterisations of the compositional dependence of the diffusion coefficients of ozone within the condensed phase, yielding qualitatively different time-dependent internal concentration profiles. We suggest that this highlights the importance of providing additional experimental observables (e.g. particle size, heterogeneity in composition) if measurements and models are to be universally reconciled.

This work was supported by the UK Natural Environment Research Council (NERC grant NE/I528277/1) and the European Research Council (ERC starting grant 279405 and the Atmospheric Chemistry Climate Interactions (ACCI) project, grant 267760). PTG thanks NCAS Climate for support.

Measurements of the water activity-dependent viscosity of aerosol particles from two techniques are compared, specifically from the coalescence of two droplets in holographic optical tweezers (HOT) and poke-and-flow experiments on particles deposited onto a glass substrate. These new data are also compared with the fitting of dimer coagulation, isolation, and coalescence (DCIC) measurements. The aerosol system considered in this work are ternary mixtures of sucrose-citric acid-water and sucrose-NaNO 3 -water, at varying solute mass ratios. Results from HOT and poke-and-flow are in excellent agreement over their overlapping range of applicability (â10 3 -10 7 Pa s); fitted curves from DCIC data show variable agreement with the other two techniques because of the sensitivity of the applied modeling framework to the representation of water content in the particles. Further, two modeling approaches for the predictions of the water activity-dependent viscosity of these ternary systems are evaluated. We show that it is possible to represent their viscosity with relatively simple mixing rules applied to the subcooled viscosity values of each component or to the viscosity of the corresponding binary mixtures.

The airborne transmission of infection relies on the ability of pathogens to survive aerosol transport as they transit between hosts. Understanding the parameters that determine the survival of airborne microorganisms is critical to mitigating the impact of disease outbreaks. Conventional techniques for investigating bioaerosol longevity in vitro have systemic limitations that prevent the accurate representation of conditions that these particles would experience in the natural environment. Here, we report a new approach that enables the robust study of bioaerosol survival as a function of relevant environmental conditions. The methodology uses droplet-on-demand technology for the generation of bioaerosol droplets (1 to greater than 100 per trial) with tailored chemical and biological composition. These arrays of droplets are captured in an electrodynamic trap and levitated within a controlled environmental chamber. Droplets are then deposited on a substrate after a desired levitation period (less than 5 s to greater than 24 h). The response of bacteria to aerosolization can subsequently be determined by counting colony forming units, 24 h after deposition. In a first study, droplets formed from a suspension of Escherichia coli MRE162 cells (10 8 ml −1 ) with initial radii of 27.8 ± 0.08 µm were created and levitated for extended periods of time at 30% relative humidity. The time-dependence of the survival rate was measured over a time period extending to 1 h. We demonstrate that this approach can enable direct studies at the interface between aerobiology, atmospheric chemistry and aerosol physics to identify the factors that may affect the survival of airborne pathogens with the aim of developing infection control strategies for public health and biodefence applications.

As pulmonary drug deposition is a function of aerosol particle size distribution, it is critical that the dynamics of particle formation and maturation in pMDI sprays in the interim between generation and inhalation are fully understood. This paper presents an approach to measure the evaporative and condensational fluxes of volatile components and water from and to solution pMDI droplets following generation using a novel technique referred to as the Single Particle Electrodynamic Lung (SPEL). In doing so, evaporating aerosol droplets are shown capable of acting as condensation nuclei for water. Indeed, we show that the rapid vaporisation of volatile components from a volatile droplet is directly correlated to the volume of water taken up by condensation. Furthermore, a significant volume of water is shown to condense on droplets of a model pMDI formulation (hydrofluoroalkane (HFA), ethanol and glycerol) during evaporative droplet ageing, displaying a dramatic shift from a core composition of a volatile species to that of predominantly water (non-volatile glycerol remained in this case). This yields a droplet with a water activity of 0.98 at the instance of inhalation. The implications of these results on regional and total pulmonary drug deposition are explored using the International Commission of Radiological Protection (ICRP) deposition model, with an integrated semi-analytical treatment of hygroscopic growth. Through this, droplets with water activity of 0.98 upon inhalation are shown to produce markedly different dose deposition profiles to those with lower water activities at the point of inspiration.

The process of water evaporation, although deeply studied, does not enjoy a kinetic description that captures known physics and can be integrated with other detailed processes such as drying of catalytic membranes embedded in vapor-fed devices and chemical reactions in aerosol whose volumes are changing dynamically. In this work, we present a simple, three-step kinetic model for water evaporation that is based on theory and validated by using well-established thermodynamic models of droplet size as a function of time, temperature, and relative humidity as well as data from time-resolved measurements of evaporating droplet size. The kinetic mechanism for evaporation is a combination of two limiting processes occurring in the highly dynamic liquid-vapor interfacial region: direct first order desorption of a single water molecule and desorption resulting from a local fluctuation, described using third order kinetics. The model reproduces data over a range of relative humidities and temperatures only if the interface that separates bulk water from gas phase water has a finite width, consistent with previous experimental and theoretical studies. The influence of droplet cooling during rapid evaporation on the kinetics is discussed; discrepancies between the various models point to the need for additional experimental data to identify their origin.

The physicochemical changes experienced by organic aerosol particles undergoing dehydration into the surrounding gas phase can be drastic, forcing rapid vitrification of the particle and suppressing internal diffusion. Until recently, experimental studies have concentrated on quantifying diffusional mixing of either water or non-volatile components, while relatively little attention has been paid to the role of semivolatile organic component (SVOC) diffusion and volatilisation in maintaining the equilibrium between the gas and particle phases. Here we present methods to simultaneously investigate diffusivities and volatilities in studies of evolving single ternary aerosol particle size and composition. Analysing particles of ternary composition must account for the multiple chemical species that volatilise in response to a step change in gas phase water activity. In addition, treatments of diffusion in multicomponent mixtures are necessary to represent evolving heterogeneities in particle composition. We find that the contributions to observed size behaviour from volatilisation of water and a SVOC can be decoupled and treated separately. Employing Fickian diffusion modelling, we extract the compositional dependence of the diffusion constant of water and compare the results to recently published parametrisations in binary aerosol particles. The treatment of ideality and activity in each case is discussed, with reference to use in multicomponent core shell models. Meanwhile, the evaporation of an SVOC into an unsaturated gas flow may be treated by Maxwell's equation, with slow diffusional transport manifesting as a suppression in the extracted vapour pressure.

The surface composition and tensions of aqueous aerosols govern a set of processes that largely determine the fate of particles in the atmosphere. Predictive modeling of surface tension can provide significant contributions to studies of atmospheric aerosol effects on climate and human health. A previously derived surface tension model for single solute aqueous solutions used adsorption isotherms and statistical mechanics to enable surface tension predictions across the entire concentration range as a function of solute activity. Here, we extend the model derivation to address multicomponent solutions and demonstrate its accuracy with systems containing mixtures of electrolytes and organic solutes. Binary model parameters are applied to the multicomponent model, requiring no further parametrization for mixtures. Five ternary systems are studied here and represent three types of solute combinations: organic–organic (glycerol–ethanol), electrolyte–organic (NaCl–succinic acid, NaCl–glutaric acid), and electrolyte–electrolyte (NaCl–KCl and NH4NO3–(NH4)2SO4). For the NaCl-glutaric acid system, experimental measurements of picoliter droplet surface tension using aerosol optical tweezers show excellent agreement with the model predictions.

Cavity ring-down spectroscopy (CRDS) of single, optically manipulated aerosol particles affords quantitative retrieval of refractive indices for particles of fixed or evolving composition with high precision. Here, we quantify the accuracy with which refractive index determinations can be made by CRDS for single particles confined within the core of a Bessel laser beam and how that accuracy is degraded as the particle size is progressively reduced from the coarse mode (>1 μm radius) to the accumulation mode (n, and imaginary, κ, components of the refractive index can be determined for a single aerosol particle. Published with license by American Association for Aerosol Research Read the transcript Watch the video on Vimeo

The physical, chemical, and biological properties of an aerosol droplet/particle are dependent on the morphology of the droplet/particle itself; for example, a liquid droplet will be processed by oxidants in the gas phase in a fundamentally different way than a solid particle. Additionally, given their small size, aerosol droplets may change phase over timescales in the order of milliseconds (e.g., deliquescence or crystallisation). Thus, ability to rapidly and easily estimate the morphology of a droplet/particle is critical, especially in the interpretation of complex aerosol processes such as spray drying and dissolution. To be reported here is a novel method that uses the forward scattered light (∼32° < θ < ∼58°) passed through a droplet to determine the droplet/particles morphology. The algorithm was developed through the qualitative analysis of over one million individual phase functions of various particle morphologies. The algorithm can differentiate between four different morphologies: homogeneous, core/shell, with inclusions, and non-spherical/inhomogeneous. The algorithm is applicable to droplets between ∼5 to ∼30 microns in radius. The rate of phase analysis is dependent on the rate in which the light scatter can be collected, in the data presented here a particle’s morphology is reported every 10 milliseconds. The accuracy of the phase identification with the algorithm proposed in this work is very high (>90%); its utility is strengthened by the high frequency of the collection of scattered light, which allows an individual droplet to be probed upwards of over 100 times per second. Although not absolute on every phase function analysis, when coupled with repetition and high throughput, the algorithm presented here can be a valuable tool to easily and readily determine particle morphology in dynamic aerosol systems. Copyright © 2019 American Association for Aerosol Research

Drying and crystallization of solution droplets is a problem of broad relevance, determining the microstructures of particles formed in spray-drying, the phase of particles delivered by, for example, aerosol formulations for inhalation therapies, and the impact of aerosols on radiative forcing and climate. The ephemeral nature of free droplets, particularly when considering the drying kinetics of droplets with highly volatile constituents, has often precluded the accurate measurement of transient properties such as droplet size and composition, preventing the robust assessment of predictive models of droplet-drying rates, nucleation, and crystallization. Here, we report novel measurements of the drying kinetics of individual aqueous sodium chloride solution droplets using an electrodynamic balance to isolate and trap single aerosol droplets (radius ≈ 25 μm). The initial solution droplet size and composition are shown to be highly reproducible in terms of drying rate and crystallization time when examined over hundreds of identical evaporating droplets. We introduce a numerical model that determines the concentration gradient across the radial profile of the droplet as it dries, considering both the surface recession because of evaporation and the diffusion of components within the droplet. Drying-induced crystallization is shown to be fully determined for this system, with nucleation and instantaneous crystallization occurring once a critical supersaturation level of 2.04 ± 0.02 is achieved at the surface of the evaporating droplet. This phenomenological model provides a consistent account of the timescale and surface concentration of free-droplet crystallization on drying for the different drying conditions studied, a necessary step in progress toward achieving control over rates of crystallization and the competitive formation of amorphous particles.

Numerous analytical models have been applied to describe the evaporation/condensation kinetics of volatile components from aerosol particles for use in many applications. However, the applicability of these models for treating cases that lead to substantial and rapid changes in particle temperature due to, for example, evaporative cooling remain to be compared with measurements. We consider three typical treatments, comparing predictions of the evaporation rates of pure water droplets over a wide range in gas phase relative humidity (RH) and exploring the sensitivity of the predictions to uncertainties in the thermophysical gas and condensed-phase parameters. We also compare predictions from the three treatments to measurements of the evaporation rates of pure water droplets with varying RH using an electrodynamic balance (EDB), concluding that only two of the model treatments are sufficiently able to account for the level of evaporative cooling (typically as high as 12 K). Finally, we show that the RH can be inferred accurately from the evaporation rate of pure water droplets over the full range in accessible RH and comparison with the model predictions (within absolute uncertainties of 2.5% RH over the range 20% to 95% RH), considering the level of agreement with independent measurements made through determining the equilibrated size of aqueous sodium chloride and sodium nitrate droplets.

Responding to changes in the surrounding environment, aerosol particles can grow by water condensation changing rapidly in composition and changing dramatically in viscosity. The timescale for growth is important to establish for particles undergoing hydration processes in the atmosphere or during inhalation. Using an electrodynamic balance, we report direct measurements at -7.5, 0, and 20 °C of timescales for hygroscopic condensational growth on a range of model hygroscopic aerosol systems. These extend from viscous aerosol particles containing a single saccharide solute (sucrose, glucose, raffinose, or trehalose) and a starting viscosity equivalent to a glass of ∼1012 Pa·s, to nonviscous (∼10-2 Pa·s) tetraethylene glycol particles. The condensation timescales observed in this work indicate that water condensation occurs rapidly at all temperatures examined (-2 to 1012 Pa·s. Only a marginal delay (

The importance of organic aerosol particles in the environment has been long established, influencing cloud formation and lifetime, absorbing and scattering sunlight, affecting atmospheric composition and impacting on human health. Conventionally, ambient organic particles were considered to exist as liquids. Recent observations in field measurements and studies in the laboratory suggest that they may instead exist as highly viscous semi-solids or amorphous glassy solids under certain conditions, with important implications for atmospheric chemistry, climate and air quality. This review explores our understanding of aerosol particle phase, particularly as identified by measurements of the viscosity of organic particles, and the atmospheric implications of phase state., The phase state of organic particles in the atmosphere has important consequences for the impact of aerosols on climate, visibility, air quality and health. Here, the authors review the evidence for the formation of amorphous glassy particles and the methods for determining aerosol particle viscosity.

Inhalation of elevated levels of particulate air pollution has been shown to elicit the onset of adverse health effects in humans, where the magnitude of the response is a product of where in the lung the particulate dose is delivered. At any point in time during inhalation the depositional flux of the aerosol is a function of the radius of the droplet, thus a detailed understanding of the rate and magnitude of the mass flux of water to the droplet during inhalation is crucial. In this study, we assess the impact of aerosol hygroscopicity on deposited dose through the inclusion of a detailed treatment of the mass flux of water to account for the dynamics of particle size in a modified version of the standard International Commission on Radiological Protection (ICRP) whole lung deposition model. The ability to account for the role of the relative humidity (RH) of the aerosol prior to, and during, inhalation on the deposition pattern is explored, and found to have a significant effect on the deposition pattern. The model is verified by comparison to previously published measurements, and used to demonstrate that ambient RH affects where in the lung indoor particulate air pollution is delivered.

The effect of gel formation on the mass transfer of water during evaporation or condensation from MgSO4 droplets is studied using aerosol optical tweezers coupled with Raman spectroscopy. In particular, the kinetics of water transport during hydration and dehydration are followed for variable step changes in relative humidity and compared with previous measurements using different methodologies. Slow diffusion of water in the particle bulk is shown to limit water evaporation and condensation from the aerosol. Desorption of water continues over a long time at the very low RH region and this is validated with complementary studies made by FTIR-ATR and measurements of water adsorption isotherms. The observations can be rationalized when considering the possible phase transformation of the gel structure at very low RHs. Finally, the influence of the duration of the drying time (RH ≤ 10%) on the kinetics of condensation during hydration is investigated. Apparent diffusion coefficients of water molecules in the gel are obtained, showing little dependence on the water activity and droplet composition, and are consistent with the slow removal of water during drying from pores formed at the gel transition RH.

Aerosols are found in a wide diversity of contexts and applications, including the atmosphere, pharmaceutics, and industry. Aerosols are dispersions of particles in a gas, and the coupling of the two phases results in highly dynamic systems where chemical and physical properties like size, composition, phase, and refractive index change rapidly in response to environmental perturbations. Aerosol particles span a wide range of sizes from 1 nm to tens of micrometres or from small molecular clusters that may more closely resemble gas phase molecules to large particles that can have similar qualities to bulk materials. However, even large particles with finite volumes exhibit distinct properties from the bulk condensed phase, due in part to their higher surface-to-volume ratio and their ability to easily access supersaturated solute states inaccessible in the bulk. Aerosols represent a major challenge for study because of the facile coupling between the particle and gas, the small amounts of sample available for analysis, and the sheer breadth of operative processes. Time scales of aerosol processes can be as short as nanoseconds or as long as years. Despite their very different impacts and applications, fundamental chemical physics processes serve as a common theme that underpins our understanding of aerosols. This perspective article discusses challenges in the study of aerosols and highlights recent chemical physics advancements that have enabled improved understanding of these complex systems.

Aerosols are dynamic systems, responding to variations in the surrounding environmental conditions by changing in size, composition and phase. Although, widely used in inhalation therapies, details of the processes occurring on aerosol generation and during inhalation have received little attention. Instead, research has focused on improvements to the formulation of the drug prior to aerosolization and the resulting clinical efficacy of the treatment. Here, we highlight the processes that occur during aerosol generation and inhalation, affecting aerosol disposition when deposited and, potentially, impacting total and regional doses. In particular, we examine the response of aerosol particles to the humid environment of the respiratory tract, considering both the capacity of particles to grow by absorbing moisture and the timescale for condensation to occur. [Formula: see text]

We report a new method to investigate water transport kinetics in aerosol particles by using rapid scan FTIR spectroscopy combined with a custom-built pulse relative humidity (RH) control system. From real time in situ measurements of RH and composition using high time resolution infrared spectroscopy (0.12 s for one spectrum), and through achieving a high rate of RH change (as fast as 60% per second), we are able to investigate the competition between the gas and condensed phase diffusive transport limits of water for particles with mean diameter ~3 mm and varying phase and viscosity. The characteristic time (t) for equilibration in particle composition following a step change in RH is measured to quantify dissolution timescales for crystalline particles and to probe the kinetics of water evaporation and condensation in amorphous particles. We show that dissolution kinetics are prompt for crystalline inorganic salt particles following an increase in RH from below to above the deliquescence RH, occurring on a timescale comparable to the timescale of the RH change (1 to 109 Pa s considered here. For amorphous particles, these kinetics are shown to be consistent with previous measurements of mass transfer rates in larger single particles. More specifically, the consistency suggests that fully understanding and modelling the complex microphysical processes and heterogeneities that form in viscous particles may not be necessary for estimating timescales for particle equilibration. A comparison of the kinetics for crystalline and amorphous particles illustrates the interplay of the rates of gas and condensed phase diffusion in determining mass transport rates of water in aerosol.

The interaction of atmospheric aerosols with radiation remains a significant source of uncertainty in modelling radiative forcing. Laboratory measurements of the microphysical properties of atmospherically relevant particles is one approach to reduce this uncertainty. We report a new method to investigate light absorption by a single aerosol particle, inferring changes in the imaginary part of the refractive index with change in environmental conditions (e.g. relative humidity) and inferring the size dependence of the optical extinction cross-section. More specifically, we present measurements of the response of single aerosol particles to near infrared (NIR) laser induced heating at a wavelength 1520 nm. Particles were composed of aqueous NaCl or (NH4)2SO4 and were studied over ranges in relative humidity (40 - 85%), particle radius (1 – 2.2 µm) and NIR laser power. The ensuing size change and real component of the refractive index were extracted from measurements of the angular variation in elastically scattered light. From the heating-induced size change at varying NIR beam intensities, we retrieved the change in the imaginary component of the refractive index. In addition, cavity ring-down spectroscopy measurements monitored the change in extinction cross-section with modulation of the heatinglaser power.

We introduce and assess a group contribution scheme by which the refractive index (RI) (λ = 589 nm) of nonabsorbing components common to secondary organic aerosols can be predicted from the molecular formula and chemical functionality. The group contribution method is based on representative values of ratios of the molecular polarizability and molar volume of different functional groups derived from data for a training set of 234 compounds. The training set consists of 106 nonaromatic compounds common to atmospheric aerosols, 64 aromatic compounds, and 64 compounds containing halogens; a separate group contribution model is provided for each of these three classes of compound. The resulting predictive model reproduces the RIs of compounds in the training set with mean errors of ±0.58, ±0.36, and ±0.30% for the nonaromatic, aromatic, and halogen-containing compounds, respectively. We then evaluate predictions from the group contribution model for compounds with no previously reported RI, comparing values with predictions from previous treatments and with measurements from single aerosol particle experiments. We illustrate how such comparisons can be used to further refine the predictive model. We suggest that the accuracy of this model is already sufficient to better constrain the optical properties of organic aerosol of known composition.

Laboratory studies can provide important insights into the processes that occur at the scale of individual particles in ambient aerosol. We examine the accuracies of measurements of core physicochemical properties of aerosols that can be made in single particle studies and explore the impact of these properties on the microscopic processes that occur in ambient aerosol. Presenting new measurements, we examine here the refinements in our understanding of aerosol hygroscopicity, surface tension, viscosity and optical properties that can be gained from detailed laboratory measurements for complex mixtures through to surrogates for secondary organic atmospheric aerosols.

Alkylaminium sulfates originate from the neutralisation reaction between short-chained amines and sulfuric acid and have been detected in atmospheric aerosol particles. Their physicochemical behaviour is less well characterised than their inorganic equivalent, ammonium sulfate, even though they play a role in atmospheric processes such as the nucleation and growth of new particles and cloud droplet formation. In this work, a comparative evaporation kinetics experimental technique using a cylindrical electrodynamic balance is applied to determine the hygroscopic properties of six short-chained alkylaminium sulfates, specifically mono-, di-, and tri-methylaminium sulfate and mono-, di-, and tri-ethyl aminium sulfate. This approach allows for the retrieval of a water-activity-dependent growth curve in less than 10 s, avoiding the uncertainties that can arise from the volatilisation of semi-volatile components. Measurements are made on particles > 5 µm in radius, avoiding the need to correct equilibrium measurements for droplet-surface curvature with assumed values of the droplet-surface tension. Variations in equilibrium solution droplet composition with varying water activity are reported over the range 0.5 to > 0.98, along with accurate parameterisations of solution density and refractive index. The uncertainties in water activities associated with the hygroscopicity measurements are typically 0.9 and ∼ ±1 % below 0.9, with maximum uncertainties in diameter growth factors of ±0.7 %. Comparison with previously reported measurements show deviation across the entire water activity range.

We present a first exploratory study to assess the use of aerosol optical tweezers as an instrument for sampling and detecting accumulation and coarse mode aerosol. A sub-picolitre aqueous aerosol droplet is captured in the optical trap and used as a sampling volume, accreting mass from a free flowing aerosol generated by a medical nebuliser or atomiser. Real-time measurements of the initial stability in size, refractive index and composition of the sampling droplet inferred from Raman spectroscopy confirm that these quantities can be measured with high accuracy and low noise. Typical standard deviations in size and refractive index of the sampling droplet over a period of 200 s are

Evaporation studies of single aqueous sucrose aerosol particles as a function of relative humidity (RH) are presented for coarse and fine mode particles down into the submicron size range (600 nm < r < 3.0 [mu]m). These sucrose particles serve as a proxy for biogenic secondary organic aerosols that have been shown to exist under ambient conditions in an ultraviscous glassy state which can affect the kinetics of water mass transport within the bulk phase and hinder particle response to changes in the gas phase water content. A counter propagating Bessel beams (CPBBs) optical trapping setup is employed to monitor the real time change in the particle radius with RH decreasing from 75 to 5. The slow down of the size change upon each RH step and the deviation from the theoretical equilibrium hygroscopic growth curve indicate the onset of glassy behavior in the RH range of 10 40. Size dependent effects were not observed within the uncertainty of the measurements. The influence of the drying time below the glass transition RH on the timescale of subsequent water condensation and re equilibration for sucrose particles is explored by optical tweezers measurements of micron sized particles (3 [mu]m < r < 6 [mu]m). The timescale for water condensation and re equilibration is shown to increase with increasing drying time i.e. the time over which a viscous particle is dried below 5 RH. These studies demonstrate the importance of the history of the particle conditioning on subsequent water condensation and re equilibration dynamics of ultraviscous and glassy aerosol particles.

We demonstrate that the equilibrium hygroscopic response of an aerosol droplet and the kinetics of water condensation and evaporation can be retrieved with high accuracy, even close to saturation, through comparative measurements of probe and sample aerosol droplets. The experimental methodology is described and is based on an electrodynamic balance with a newly designed trapping chamber. Through use of a probe aerosol, composed of either pure water or a sodium chloride solution of known concentration, the gas-phase relative humidity (RH) can be accurately measured with an uncertainty of typically0.005. By fast manipulation of the airflows into the chamber, a step-change in RH over a time scale of0.5 s can be achieved. Using this approach, the kinetics of mass transfer are studied using the comparative procedure, and results are compared to theoretical mass flux predictions. The time-dependent measured mass fluxes for sodium chloride, ammonium sulfate, sorbitol, and galactose are used to calculate droplet water activities as a function of the droplet growth factor, allowing retrieval of a hygroscopic growth curve in a matter of seconds. Comparisons with both new and established thermodynamic predictions of hygroscopicity, as well as to optical tweezers measurements, are presented, demonstrating good agreement within the experimental uncertainties.

The hygroscopic properties of an aerosol originating from a nebulizer solution can affect the extent of peripheral deposition within the respiratory tract, which in turn affects drug efficacy of drugs delivered to the lungs. Thus, the ability to tailor the degree and rate of hygroscopic growth of an aerosol produced by a nebulizer through modification of the formulation would serve to improve drug efficacy through targeted lung deposition. In this study, the kinetic and thermodynamic hygroscopic properties of sodium chloride aerosol mixed with commercially available Pluronic polymers, specifically F77 and F127, are reported using three complementary single aerosol analysis techniques, specifically aerosol optical tweezers, a double ring electrodynamic balance and a concentric cylinder electrodynamic balance. The F77 polymer is shown to have a predictable effect on the hygroscopic properties of the aerosol: the ability of the droplet to uptake water from the air depends on the solute weight percent of sodium chloride present in a linear dose dependant manner. Unlike the smaller F77, a non-linear relationship was observed for the larger molecular weight F127 polymer, with significant suppression of hygroscopic growth (>50% by mass) for solution aerosol containing even only 1 wt% of the polymer and 99 wt% sodium chloride. The suppression of growth is shown to be consistent with the formation of mixed phase aerosol particles containing hydrophilic inorganic rich domains and hydrophobic polymer rich domains that sequester some of the inorganic component, with the two phases responding to changes in relative humidity independently. This independence of coupling with the gas phase is apparent in both the equilibrium state and the kinetics of water evaporation/condensation. By starting with a saline nebulizer solution with a concentration of F127 ∼10 −2 mM, a 12% reduction in the radius of all aerosol produced at a relative humidity (RH) of 84% is possible. The difference in diameter is RH dependent, and may be much greater at higher humidities. These findings suggest that the addition of μM concentrations of larger Pluronic polymers to nebulizer formulations may greatly reduce the size of aerosols produced.