Advanced aerosol optical tweezers chamber design to facilitate phase-separation and equilibration timescale experiments on complex droplets

<p>The phase-separation of mixed aerosol particles and the resulting morphology plays an important role in determining the interactions of liquid aerosols with their gas-phase environment. We present the application of a new aerosol optical tweezers chamber for delivering a uniformly mixed aerosol flow to the trapped droplet's position for performing experiments that determine the phase-separation and resulting properties of complex mixed droplets. This facilitates stable trapping when adding additional phases through aerosol coagulation, and reproducible measurements of the droplet's equilibration timescale. We demonstrate the trapping of pure organic carbon droplets, which allows us to study the morphology of droplets containing pure hydrocarbon phases to which a second phase is added by coagulation. A series of experiments using simple compounds are presented to establish our ability to use the cavity enhanced Raman spectra to distinguish between homogeneous single-phase, and phase-separated core–shell or partially engulfed morphologies. The core–shell morphology is distinguished by the pattern of the whispering gallery modes (WGMs) in the Raman spectra where the WGMs are influenced by refraction through both phases. A core–shell optimization algorithm was developed to provide a more accurate and detailed analysis of the WGMs than is possible using the homogeneous Mie scattering solution. The unique analytical capabilities of the aerosol optical tweezers provide a new approach for advancing our understanding of the chemical and physical evolution of complex atmospheric particulate matter, and the important environmental impacts of aerosols on atmospheric chemistry, air quality, human health, and climate change.</p> <p>Copyright © 2016 American Association for Aerosol Research</p

Aerosol Measurements in the Free Troposphere at the North Atlantic Pico Mountain Observatory in the Azores.

3th Atmospheric Science Research (ASR), Science Team Meeting. Arlington, Virginia, March 12-16, 2012.Pico is a small island (447 km2) in the archipelago of the Azores, Portugal, in the North Atlantic Ocean. The island has a very steep inactive volcano. An atmospheric monitoring station (Pico Mountain Observatory) was established close to the summit of the volcano by the late Dr. Richard Honrath and colleagues in 2001. The station, far from persistent local sources, is located near the northern cliff of the summit caldera at an altitude of 2225 meters. The station altitude is typically well above the boundary layer during summertime, when average marine boundary-layer heights are below 1200 meters and rarely exceed 1300 meters. Air masses reaching the station are often transported from North America and seldom from Europe or North Africa. The station’s uniqueness and significance lie in its location that allows study of the transport and evolution of gases and aerosols from North America in the free troposphere. Until recently, the focus was on the measurement and analysis of trace gases (ozone, carbon monoxide, non-methane hydrocarbons, nitrogen oxides) and light-absorbing aerosol (black carbon and iron oxide). Aerosol light attenuation has been measured at the site since 2001 using a seven-wavelengths aethalometer. An optical particle sizer was installed at the site in 2010 and has been running in parallel to the aethalometer for two seasons. A three-wavelength nephelometer, to measure the aerosol total- and back-scattering, and aerosol samplers for morphological and chemical analysis will be installed at the site in 2012. Our goal is to enhance the observatory monitoring capabilities for aerosol research. The objectives of this new research program are to: (a) assess background as well as specific event tropospheric aerosol properties, (b) compare aerosol and gases measurements with model outputs, and (c) use the data collected to provide satellite validation. This research is anticipated to enhance our understanding of the interactions between tropospheric aerosols, clouds, and climate by allowing, for example, the analysis of North American outflows and seasonal changes, the assessment of different source regions, the estimation of aerosol radiative forcing above marine clouds and in clear sky, and the study of the relative contribution of anthropogenic versus biomass burning emissions. In this poster we present a preliminary analysis of the black carbon and aerosol size data in conjunction with retroplume model analysis

Extensive Soot Compaction by Cloud Processing from Laboratory and Field Observations

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models.Peer reviewe

Extensive soot compaction by cloud processing from laboratory and field observations

Soot particles form during combustion of carbonaceous materials and impact climate and air quality. When freshly emitted, they are typically fractal-like aggregates. After atmospheric aging, they can act as cloud condensation nuclei, and water condensation or evaporation restructure them to more compact aggregates, affecting their optical, aerodynamic, and surface properties. Here we survey the morphology of ambient soot particles from various locations and different environmental and aging conditions. We used electron microscopy and show extensive soot compaction after cloud processing. We further performed laboratory experiments to simulate atmospheric cloud processing under controlled conditions. We find that soot particles sampled after evaporating the cloud droplets, are significantly more compact than freshly emitted and interstitial soot, confirming that cloud processing, not just exposure to high humidity, compacts soot. Our findings have implications for how the radiative, surface, and aerodynamic properties, and the fate of soot particles are represented in numerical models

The Morphology and Equilibration of Levitated Secondary Organic Particles Under Controlled Conditions

<p>I advanced the understanding of particle morphology and its implications for the behavior and effects of atmospheric aerosol particles. I have developed new experimental methods for the Aerosol Optical Tweezers (AOT) system and expanded the AOT’s application into studying realistic secondary organic aerosol (SOA) particle phases. The AOT is a highly accurate system developed to study individual particles in real-time for prolonged periods of time. While previous AOT studies have focused on binary or ternary chemical systems, I have investigated complex SOA, and how they interact with other chemical phases, and the surrounding gas-phase. This work has led to new insights into liquid-liquid phase separation and the resulting particle morphology, the surface tension, solubility, and volatility of SOA, and diffusion coefficients of SOA phases. I designed a new aerosol optical tweezers chamber for delivering a uniformly mixed aerosol flow to the trapped droplet’s position. I used this chamber to determine the phase-separation morphology and resulting properties of complex mixed droplets. A series of experiments using simple compounds are presented to establish my ability to use the cavity enhanced Raman spectra to distinguish between homogenous single-phase, and phase-separated core-shell or partially-engulfed morphologies. I have developed a new algorithm for the analysis of whispering gallery modes (WGMs) present in the cavity enhanced Raman spectra retrieved from droplets trapped in the AOT. My algorithm improves the computational scaling when analyzing core-shell droplets (i.e. phase-separated or biphasic droplets) in the AOT, making it computationally practical to analyze spectra collected over many hours at a few Hz. I then demonstrate for the first time the capture and analysis of SOA on a droplet suspended in an AOT. I examined three initial chemical systems of aqueous NaCl, aqueous glycerol, and squalane at ~ 75% relative humidity. For each system I added α-pinene SOA – generated directly in the AOT chamber – to the trapped droplet. The resulting morphology was always observed to be a core of the initial droplet surrounded by a shell of the added SOA. By combining my AOT observations of particle morphology with results from SOA smog chamber experiments, I conclude that the α-pinene SOA shell creates no major diffusion limitations for water, glycerol, and squalane under humid conditions. My AOT experiments highlight the prominence of phase-separated core-shell morphologies for secondary organic aerosols interacting with a range of other chemical phases. The unique analytical capabilities of the aerosol optical tweezers provide a new approach for advancing the understanding of the chemical and physical evolution of complex atmospheric particulate matter, and the important environmental impacts of aerosols on atmospheric chemistry, air quality, human health, and climate change. </p

Emulsified and Liquid–Liquid Phase-Separated States of α‑Pinene Secondary Organic Aerosol Determined Using Aerosol Optical Tweezers

We demonstrate the first capture and analysis of secondary organic aerosol (SOA) on a droplet suspended in an aerosol optical tweezers (AOT). We examine three initial chemical systems of aqueous NaCl, aqueous glycerol, and squalane at ∼75% relative humidity. For each system we added α-pinene SOAgenerated directly in the AOT chamberto the trapped droplet. The resulting morphology was always observed to be a core of the original droplet phase surrounded by a shell of the added SOA. We also observed a stable emulsion of SOA particles when added to an aqueous NaCl core phase, in addition to the shell of SOA. The persistence of the emulsified SOA particles suspended in the aqueous core suggests that this metastable state may persist for a significant fraction of the aerosol lifecycle for mixed SOA/aqueous particle systems. We conclude that the α-pinene SOA shell creates no major diffusion limitations for water, glycerol, and squalane core phases under humid conditions. These experimental results support the current prompt-partitioning framework used to describe organic aerosol in most atmospheric chemical transport models and highlight the prominence of core–shell morphologies for SOA on a range of core chemical phases

Morphology and mixing state of individual freshly emitted wildfire carbonaceous particles

Biomass burning is one of the largest sources of carbonaceous aerosols in the atmosphere, significantly affecting earth\u27s radiation budget and climate. Tar balls, abundant in biomass burning smoke, absorb sunlight and have highly variable optical properties, typically not accounted for in climate models. Here we analyse single biomass burning particles from the Las Conchas fire (New Mexico, 2011) using electron microscopy. We show that the relative abundance of tar balls (80%) is 10 times greater than soot particles (8%). We also report two distinct types of tar balls; one less oxidized than the other. Furthermore, the mixing of soot particles with other material affects their optical, chemical and physical properties. We quantify the morphology of soot particles and classify them into four categories: ∼50% are embedded (heavily coated), ∼34% are partly coated, ∼12% have inclusions and∼4% are bare. Inclusion of these observations should improve climate model performances. © 2013 Macmillan Publishers Limited. All rights reserved

Simulation data supporting the paper Optical properties and radiative forcing of fractal-like tar ball aggregates from biomass burning

Simulations data supporting the paper Optical properties and radiative forcing of fractal-like tar ball aggregates from biomass burning, to be submitted to the Journal of Quantitative Spectroscopy and Radiative Transfer

Physical Properties of Aerosol Internally Mixed With Soot Particles in a Biogenically Dominated Environment in California

©2018. The Authors. Atmospheric soot particles are often internally mixed with organic aerosol. The geometric distribution of the mixing components affects the soot particles\u27 radiative properties. Here we present an electron microscopy analysis of particles collected in a biogenically dominated environment to understand how the viscosity of secondary organic aerosol relates to various soot mixing configurations. The shape of particles impacting on a substrate deforms according to their viscosity. We use the aspect ratio of individual particles determined by tilt angle imaging to classify them into low, intermediate, and high viscosity groups. Ninety percent of the particles partially engulfing soot belong to the intermediate viscosity regime. In contrast, the highly viscous organic aerosol remains externally mixed with or attaches to the surface of soot particles. Our results link the viscosity of organic aerosol with the mixing configuration of soot-containing particles. Including these findings in mixing state models could improve estimates of the soot radiative forcing