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Particle size distributions from TRACER-MAP

Particle size distributions measured using a custom scanning mobility analyzer (SMPS) and a TSI, Inc. aerodynamic particle sizer (APS). The size distributions measured with the two instruments were merged during data inversion to produce a single distribution spanning a diameter range from approximately 19 nanometers to 15 micrometers. Size-dependent cloud condensation nuclei (CCN) activity measured with a CCN counter operated in parallel to the condensation particle counter in the SMPS are reported separately. The measurements were made from the Baylor University/University of Houston Mobile Air Quality Laboratory (MAQL) between July 5 and August 30, 2022 during the TRACER-MAP project. The trailer moved between five sites in the Houston regions as follows: Aldine: 7/5-7/8, 7/21-7/26, 8/15-8/24 University of Houston: 7/8-7/16, 8/8-8/15 San Jacinto monument: 7/16-7/21 Jones State Forest: 7/26-8/1; 8/24-8/30 AMF site in La Porte: 8/1-8/8

54 ENVIRONMENTAL SCIENCES↗

aoscpcf

ARM Instrument: Condensation Particle Counter

54 ENVIRONMENTAL SCIENCES↗

Operation of the Airmodus A11 nano Condensation Nucleus Counter at various inlet pressures and various operation temperatures, and design of a new inlet system

Measuring sub-3 nm particles outside of controlled laboratory conditions is a challenging task, as many of the instruments are operated at their limits and are subject to changing ambient conditions. In this study, we advance the current understanding of the operation of the Airmodus A11 nano Condensation Nucleus Counter (nCNC), which consists of an A10 Particle Size Magnifier (PSM) and an A20 Condensation Particle Counter (CPC). The effect of the inlet line pressure on the measured particle concentration was measured, and two separate regions inside the A10, where supersaturation of working fluid can take place, were identified. The possibility of varying the lower cut-off diameter of the nCNC was investigated; by scanning the growth tube temperature, the range of the lower cut-off was extended from 1–2.5 to 1–6 nm. Here we present a new inlet system, which allows automated measurement of the background concentration of homogeneously nucleated droplets, minimizes the diffusion losses in the sampling line and is equipped with an electrostatic filter to remove ions smaller than approximately 4.5 nm. Lastly, our view of the guidelines for the optimal use of the Airmodus nCNC is provided.

54 ENVIRONMENTAL SCIENCES↗

Particle Size Distributions Measured in the B757 Engine Plume During EXCAVATE

The Experiment to Characterize Aircraft Volatile Aerosols and Trace Species Emissions (EXCAVATE) took place at NASA Langley Research Center during January 2002. This ground based study was conducted to examine the role of fuel sulfur content on particulate emissions. Size distributions as a function of engine operating conditions were measured in the exhaust plume of a B-757 at four downstream axial locations (1 m, 10 m, 25 m and 35 m). The engine was run on JP-5 with three different sulfur concentrations, 810 ppm, 1050 ppm, 1820 ppm; and was operated over a range of power settings from idle to near-full power. Zalabsky differential-mobility analyzers DMAS), Met One condensation-nuclei counters (CNCs), and a TSI 3022 condensation-particle counter (CPC) were used to measure the size distributions. The total number-count (particle concentration), number-based Emissions Index (EInumber) and mass-based Emissions Index (E1-J increased with fuel sulfur-content and engine pressure ratio (EPR). Count Mean Diameter (Ch4D) also increased with EPR yet remained fairly constant with fuel sulfur-content for a fixed location in the exhaust plume. Also the mode and CMD both increased with distance in the plume.

Sanders, Terry↗

CPC_ACEENA

The condensation particle counter (CPC 3772 or 3010, TSI) measures the number concentration of aerosols from 10 nm to 3 microns. On the G1, it was operated using an external pump and maintained at 1 LPM using a critical orifice. CPC_CVI was installed after CVI inlet, and CVI inlet was operated between two modes: under-kinetic mode and CVI mode. CPC_Isok (3772) and CPC3025 were installed after iso-kinetic inlet and CPC_TD was after the thermal denuder (TD). The infomation about the TD can be found from FIMS dataset.

54 ENVIRONMENTAL SCIENCES↗

Deployment of ARM Aerial Facility Scanning Mobility Particle Sizer Field Campaign Report

Atmospheric aerosols influence global climate by scattering and absorbing sunlight (direct effects) and by changing the microphysical structure, lifetime, and coverage of clouds (indirect effects). While it is widely accepted that aerosol indirect effects cool the Earth-atmosphere system by increasing cloud reflectivity and coverage, the magnitudes of the indirect effects are poorly quantified. One key aerosol property for understanding aerosol indirect effects is the ability of aerosol particles to form cloud droplets at atmospheric relevant supersaturations—i.e., cloud condensation Nuclei (CCN) activity. For particles consisting of typical atmospheric inorganic compounds, their CCN activity is well understood and can be effectively predicted using Köhler theory based on physicochemical properties of the solute, such as its mass, molar volume, and activity coefficient. However, atmospheric aerosols often consist of hundreds of organic species, which can contribute ~20-90% to the total fine aerosol mass. Depending on their properties, organic species can significantly influence the ability of aerosol particles to act as CCN and form cloud droplets. This project focuses on the CCN activity of secondary organic aerosol (SOA) compounds formed from key biogenic volatile organic compounds (VOCs) under representative conditions, and the relationship between the hygroscopicity and composition of organic aerosols. The U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility Aerial Facility (AAF) scanning mobility particles sizer (SMPS) was deployed during a ~ 2-week intensive measurement campaign, taking place February 10-February 23, 2016 at the Pacific Northwest National Laboratory (PNNL) Environmental Simulation Chamber. The SMPS was operated with a CCN counter (CCNc). Aerosol particles were first classified by the differential mobility analyzer inside the SMPS; the classified aerosol will then be simultaneously characterized by a condensation particle counter (CPC) (part of the SMPS) and the CCNc.

54 ENVIRONMENTAL SCIENCES↗

Deployment of ARM Aerial Facility Scanning Mobility Particle Sizer Field Campaign Report

Atmospheric aerosols influence global climate by scattering and absorbing sunlight (direct effects) and by changing the microphysical structure, lifetime, and coverage of clouds (indirect effects). While it is widely accepted that aerosol indirect effects cool the Earth-atmosphere system by increasing cloud reflectivity and coverage, the magnitudes of the indirect effects are poorly quantified. One key aerosol property for understanding aerosol indirect effects is the ability of aerosol particles to form cloud droplets at atmospheric relevant supersaturations—i.e., cloud condensation Nuclei (CCN) activity. For particles consisting of typical atmospheric inorganic compounds, their CCN activity is well understood and can be effectively predicted using Köhler theory based on physicochemical properties of the solute, such as its mass, molar volume, and activity coefficient. However, atmospheric aerosols often consist of hundreds of organic species, which can contribute ~20-90% to the total fine aerosol mass. Depending on their properties, organic species can significantly influence the ability of aerosol particles to act as CCN and form cloud droplets. This project focuses on the CCN activity of secondary organic aerosol (SOA) compounds formed from key biogenic volatile organic compounds (VOCs) under representative conditions, and the relationship between the hygroscopicity and composition of organic aerosols. The U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility Aerial Facility (AAF) scanning mobility particles sizer (SMPS) was deployed during a ~ 2-week intensive measurement campaign, taking place February 10-February 23, 2016 at the Pacific Northwest National Laboratory (PNNL) Environmental Simulation Chamber. The SMPS was operated with a CCN counter (CCNc). Aerosol particles were first classified by the differential mobility analyzer inside the SMPS; the classified aerosol will then be simultaneously characterized by a condensation particle counter (CPC) (part of the SMPS) and the CCNc.

54 ENVIRONMENTAL SCIENCES↗

aoscpcu1m (b1)

The condensation particle counter (CPC) measures sub-micron aerosol particle number concentration by condensing fluid onto particles and causing them to grow to sizes that are easily detectable by optical scattering. The condensing liquid is typically an alcohol (e.g., butanol) or water. Depending on the CPC type, typical CPC instruments can count particles with sizes that range from 3 to 3000 nanometers (ultrafine CPC) or from 10 to 3000 nanometers (fine CPC). The CPC is part of the aerosol observing system (AOS).

54 ENVIRONMENTAL SCIENCES↗

aoscpcf (01)

The condensation particle counter (CPC) measures sub-micron aerosol particle number concentration by condensing fluid onto particles and causing them to grow to sizes that are easily detectable by optical scattering. The condensing liquid is typically an alcohol (e.g., butanol) or water. Depending on the CPC type, typical CPC instruments can count particles with sizes that range from 3 to 3000 nanometers (ultrafine CPC) or from 10 to 3000 nanometers (fine CPC). The CPC is part of the aerosol observing system (AOS).

54 ENVIRONMENTAL SCIENCES↗

aoscpc (a1)

The condensation particle counter (CPC) measures sub-micron aerosol particle number concentration by condensing fluid onto particles and causing them to grow to sizes that are easily detectable by optical scattering. The condensing liquid is typically an alcohol (e.g., butanol) or water. Depending on the CPC type, typical CPC instruments can count particles with sizes that range from 3 to 3000 nanometers (ultrafine CPC) or from 10 to 3000 nanometers (fine CPC). The CPC is part of the aerosol observing system (AOS).

54 ENVIRONMENTAL SCIENCES↗

Ice nucleation measurements from DRUM impactors during TRACER campaign in the Houston TX region from July to September 2022

During TRACER, three Davis Rotating Uniform size-cut Monitors (DRUM; DRUMAir 4-DRUM) were used to collect aerosols for ice nucleation measurements in the Brooks laboratory at Texas A&M University. The three instruments were located at AMF1 in La Porte, Ancillary site in Guy (ANC), and onboard the Texas A&M Rapid Onsite Atmospheric Measurements Van (ROAM-V). ROAM-V was deployed to capture airmasses behind (maritime) and ahead (continental) of the passage of the sea-breeze front through Houston. On select sampling days, ROAM-V sampled in the morning/mid-day on the coast and then transited to a second inland site for the afternoon/evening. The suite of instruments deployed on ROAM-V included a Condensation Particle Counter (CPC; GRIMM Model 5.403 CPC), Scanning Mobility Particle Sizer (SMPS; TSI 3750 detector, TSI 3082 classifier, TSI 3088 neutralizer, TSI 3081A Differential Mobility Analyzer), Cloud Condensation Nuclei counter (Droplet Measurement Technologies CCN Counter), micro pulse lidar (Droplet Measurement Technologies Micro Pulse LiDAR (miniMPL)), and one of the Davis Rotating Uniform size-cut Monitors (DRUM; DRUMAir 4-DRUM). Before sampling at each location, the latitude and longitude were recorded using the GPS on the phone application “My Altitude”. Each DRUM sampler was operated at a flow rate of 23 LPM. Each DRUM has four stages where the aerodynamic diameter size cuts are as follows: stage 1 larger than 3 μm, stage 2 from 3 to 1.2 μm, stage 3 from 1.2 to 0.34 μm, and stage 4 from 0.34 to 0.15 μm. Pretreated aluminum foil was used as a substrate on all stages. At AMF1 and ANC sites, the DRUMs were operated on the shared aerosol inlet, with generous support of the DOE ARM site staff. These instruments rotated 24 mm per day and only contained aluminum foil substrates. Substrates were changed weekly and transported to Texas A&M for storage in -80C freezer until analysis. The DRUM onboard ROAM-V was operated at a faster rotation rate of 150 mm per day to clearly separate the multiple deployment locations for ROAM-V. For the ROAM-V DRUM, substrates were changed every deployment and transported to Texas A&M for storage in -80C freezer until analysis. At Texas A&M, ice nucleation experiments were conducted to measure the ice nucleation temperature of the ambient aerosol samples collected from the three DRUMs using our previously established procedures (Alsante et al., 2023; Fornea et al., 2009; Matthews et al., 2023). For ice nucleation, only samples collected on stage 3 were analyzed, given that these are the most relevant size (1.2 to 0.34 μm diameter) for potential ice nucleating particles. For the AMF1 and ANC sites, we cut and analyzed 2 mm (2-hour) samples. We analyzed the time periods of the AMF1 site instrument when the ROAM-V was deployed. A 72-hour period from July 11th at 23:49 through July 15th at 1:49 was analyzed from the ANC site instrument. For the ROAM-V instrument, we separated the daily samples by site location. Between 1- and 6-hour independent samples were analyzed at each location. We also cut the ROAM-V samples in half to allow for compositional analysis of the aerosol on the other half of the substrate. All viable samples from the ROAM-V were analyzed. Analysis was done using a custom-built ice nucleation apparatus, recently updated to include an array of 16 individual samples (Matthews et al., 2023). On our experimental setup, we used 100 μL of Ultra-High-Performance Liquid Chromatography (UHPLC) water (Sigma Aldrich, >99.9% purity) to wash off the aerosol from the DRUM substrate. Then, we micropipetted 2 μL droplet samples into each of the 16 wells of the array, using hydrophobically coated microscope slides. Experiments would cycle 28 times from 10 C to -40C over a 20-hour period. During analysis of the TRACER samples, nine experiments were conducted with UHPLC water process blanks that followed an identical preparation procedure. The average freezing temperature and standard deviation for these process blanks is -27.7±2.4 C. This data was collected for ARM Field Campaign AFC07023 and supported by DOE ASR grant DE-SC0021047. For any further questions, please feel free to contact the instrument PI, Sarah D. Brooks, sbrooks@tamu.edu. Alsante, A. N., Thornton, D. C., & Brooks, S. D. (2023). Ice nucleation catalyzed by the photosynthesis enzyme RuBisCO and other abundant biomolecules. Communications Earth & Environment, 4(1), 51. Fornea, A. P., Brooks, S. D., Dooley, J. B., & Saha, A. (2009). Heterogeneous freezing of ice on atmospheric aerosols containing ash, soot, and soil. Journal of Geophysical Research: Atmospheres, 114(D13). DOI:10.1029/2009JD011958 Matthews, B. H., Alsante, A. N., & Brooks, S. D. (2023). Pollen Emissions of Subpollen Particles and Ice Nucleating Particles. ACS Earth and Space Chemistry.

54 ENVIRONMENTAL SCIENCES↗

Texas A&M University Mobile Facility Measurements during TRACER (Field Campaign Report)

One of the main goals of the U.S Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Tracking Aerosol Convection Interactions Experiment (TRACER) near Houston, Texas is to improve understanding of how meteorology and aerosols impact storm dynamical and microphysical processes in deep convection to better constrain and improve their model representation. The Houston area is strongly influenced by sea- and bay-breeze circulations that generate convergence and help to initiate and organize deep convection. To properly isolate and understand the roles of varied meteorological conditions and cloud condensation nuclei (CCN) and ice nucleation particles (INP) distributions in different air masses, co-located thermodynamic, kinematic, and aerosol vertical profile observations are needed. The focus of this campaign was to provide key measurements in air masses both in front of and behind sea/bay breeze fronts moving through the greater Houston area to sample the airmass heterogeneity. The overarching scientific goal of this campaign is to understand how the vertical distributions of both CCN and INP correspond to the inflow layer of deep convection in maritime, background continental, and polluted continental air masses, and how these variations influence deep convection. To fully sample the heterogeneity in both meteorological conditions and aerosols across the sea-breeze front (SBF), Texas A&M University (TAMU) deployed a InterMet 3050A 403 MHz mobile unit launching iMet-4 radiosondes and the new Rapid Onsite Atmospheric Measurement Van (ROAM-V) for aerosol sampling during the TRACER intensive operational period (IOP) from June to September 2022. The suite of instruments deployed on ROAM-V included a condensation particle counter (CPC; GRIMM Model 5.403 CPC), scanning mobility particle sizer (SMPS; TSI 3750 detector, TSI 3082 classifier, TSI 3088 neutralizer, TSI 3081A differential mobility analyzer), cloud condensation nuclei counter (Droplet Measurement Technologies CCN counter), micropulse lidar (Droplet Measurement Technologies micropulse lidar [miniMPL]), and a Davis Rotating Uniform size-cut Monitor (DRUM; DRUMAir 4-DRUM). Before sampling at each location, the latitude and longitude were recorded using the Global Positioning System (GPS) on the phone application “My Altitude”. The DRUM data were collected as part of a closely related ARM field campaign and also supported by DOE Atmospheric System Research grant DE-SC0021047. The TAMU team sampled these airmass heterogeneities by strategically choosing deployment sites in a different airmass than the ARM fixed sites in La Porte and Guy, Texas. On days when the sea/bay breeze boundary was pushing inland, the TAMU team would usually sample the airmass on the maritime side of the SBF at a coastal site in Galveston, Texas in the early afternoon (1730-1900 UTC) and then move inland ahead of the SBF to sample the airmass on the continental side during late afternoon (2030-2230). Figure 1 shows the Galveston maritime site and the array of sites for the late afternoon continental measurements.

54 ENVIRONMENTAL SCIENCES↗

Mini-Micropulse Lidar data from TAMU TRACER campaign in the Houston TX region from July to September 2022

During TRACER, the Texas A&M Rapid Onsite Atmospheric Measurements Van (ROAM-V) was deployed to capture airmasses behind (maritime) and ahead (continental) of the passage of the sea-breeze front through Houston. On select sampling days, ROAM-V sampled in the morning/mid-day on the coast and then transited to a second inland site for the afternoon/evening. The suite of instruments deployed on ROAM-V included a Condensation Particle Counter (CPC; GRIMM Model 5.403 CPC), Scanning Mobility Particle Sizer (SMPS; TSI 3750 detector, TSI 3082 classifier, TSI 3088 neutralizer, TSI 3081A Differential Mobility Analyzer), Cloud Condensation Nuclei counter (Droplet Measurement Technologies CCN Counter), micro pulse lidar (Droplet Measurement Technologies Micro Pulse LiDAR (mini-MPL)), and a Davis Rotating Uniform size-cut Monitor (DRUM; DRUMAir 4-DRUM). Before sampling at each location, the latitude and longitude were recorded using the GPS on the phone application “My Altitude”. The mini-MPL deployed with ROAM-V is a 532 nm elastic and polarization lidar. The mini-MPL outputs normalized relative backscatter (NRB) derived from raw signal after after-pulse, overlap, and dead-time correction calibration. The depolarization ratio is calculated from the co-polarized and cross-polarized NRB (Flynna et al., 2007). The NRB and depolarization ratio data are resampled from the original data at 1-minute intervals. The vertical resolution of the mini-MPL data is 15 meters. The mini-MPL data can be used to determine the boundary layer, cloud top, and cloud bottom height and can be used to retrieve aerosol type and concentration profile. This data was collected for ARM Field Campaign AFC07055 and supported by DOE ASR grant DE-SC0021047. For any further questions, please feel free to contact the instrument PI, Sarah D. Brooks, sbrooks@tamu.edu . Flynna, C. J., Mendozaa, A., Zhengb, Y., & Mathurb, S. (2007). Novel polarization-sensitive micropulse lidar measurement technique. Optics express, 15(6), 2785-2790.

54 ENVIRONMENTAL SCIENCES↗

Miniaturized Optical Particle Counter (MOPC) Instrument Handbook

The U.S. Department of Energy Atmospheric Radiation Measurement (ARM) aerosol counting, composition, extinction, and sizing system (ACCESS) includes a base module (9400), a filter sampler (9401), an advanced mixing condensation particle counter (MCPC, 9403), a miniaturized optical particle counter (mOPC, 9405), and a single-channel tricolor absorption photometer (STAP, 9406). This handbook focuses on the mOPC, which measures the aerosol particle size distribution between 0.19 and 3 μm.

54 ENVIRONMENTAL SCIENCES↗

Deployment of ARM Aerial Facility (AAF) Scanning Mobility Particle Sizer Field Campaign Report

Atmospheric aerosols influence global climate by scattering and absorbing sunlight (direct effects) and by changing the microphysical structure, lifetime, and coverage of clouds (indirect effects). While it is widely accepted that aerosol indirect effects act to cool the Earth-atmosphere system by increasing cloud reflectivity and coverage, the magnitudes of the indirect effects are poorly quantified. One key aerosol property for understanding aerosol indirect effects is the ability of aerosol particles to form cloud droplets at atmospheric relevant supersaturations—i.e., cloud condensation nuclei (CCN) activity. For particles consisting of typical atmospheric inorganic compounds, their CCN activity is well understood and can be effectively predicted using Köhler theory based on physicochemical properties of the solute, such as its mass, molar volume, and activity coefficient. However, atmospheric aerosols often consist of hundreds of organic species, which can contribute ~20-90% to the total fine aerosol mass. Depending on their properties, organic species can significantly influence the ability of aerosol particles to act as CCN and form cloud droplets. This project focuses on the CCN activity of secondary organic aerosol compounds formed from key biogenic volatile organic compounds (VOCs) under representative conditions, and the relationship between the hygroscopicity and composition of organic aerosols. The ARM Aerial Facility (AAF) scanning mobility particles sizer (SMPS) was deployed during a ~ 6 week intensive measurement campaign, taking place June 15-July 31 2015 at the Pacific Northwest National Laboratory (PNNL) Environmental Simulation Chamber. The SMPS was operated with a CCN counter. Aerosol particles were first classified by the differential mobility analyzer inside the SMPS; the classified aerosol will then be simultaneously characterized by a condensation particle counter (part of the SMPS) and the CCN counter.

54 ENVIRONMENTAL SCIENCES↗

Kinetics of small particle activation in supersaturated vapors

We examine the nucleated (with barrier) activation of perfectly wetting (zero contact angle) particles ranging from bulk size down to one nanometer. Thermodynamic properties of the particles, coated with liquid layers of varying thickness and surrounded by vapor, are analyzed. Nano-size particles are predicted to activate at relative humidity below the Kelvin curve on crossing a nucleation barrier, located at a critical liquid layer thickness such that the total particle size (core + liquid layer) equals the Kelvin radius (Fig. 1). This barrier vanishes precisely as the critical layer thickness approaches the thin layer limit and the Kelvin radius equals the radius of the particle itself. These considerations are similar to those included in Fletcher's theory (Fletcher, 1958) however the present analysis differs in several important respects. Firstly, where Fletcher used the classical prefactor-exponent form for the nucleation rate, requiring separate estimation of the kinetic prefactor, we solve a diffusion-drift equation that is equivalent to including the full Becker-Doering (BD) multi-state kinetics of condensation/evaporation along the growth coordinate. We also determine the mean first passage time (MFPT) for barrier crossing (Wedekind et al., 2007), which is shown to provide a generalization of BD nucleation kinetics especially useful for barrier heights that are considerably lower than those typically encountered in homogeneous vapor-liquid nucleation, and make explicit comparisons between the MFPT and BD kinetic models. Barrier heights for heterogeneous nucleation are computed by a thermo-dynamic area construction introduced recently to model deliquescence and efflorescence of small particles (McGraw and Lewis, 2009). In addition to providing a graphical representation of the activation process that offers new insights, the area construction provides a molecular approach that avoids explicit use of the interfacial tension. Typical barrier profiles for water condensation on particles of different size are shown in Fig. 2. The main emphasis of this paper lies in the computation of these barriers and barrier crossing rates by the various methods described. The present theory is especially relevant to determining the lower size limit for particle detection in condensation particle counters. Recently it has been shown that particles can take on liquid at sizes significantly smaller than predicted from the Kelvin relation in the no-barrier case (Winkler et al., 2008). This implies a detection principle based on the activated nucleation model that is the focus of the present study. Calculations are presented for water, n-propanol, and several other condensable vapors.

54 ENVIRONMENTAL SCIENCES↗

Size and time-resolved growth rate measurements of 1 to 5 nm freshly formed atmospheric nuclei

This study presents measurements of size and time-resolved particle diameter growth rates for freshly nucleated particles down to 1 nm geometric diameter. Novel data analysis methods were developed, de-coupling for the first time the size and time-dependence of particle growth rates by fitting the aerosol general dynamic equation to size distributions obtained at an instant in time. Size distributions of freshly nucleated total aerosol (neutral and charged) were measured during two intensive measurement campaigns in different environments (Atlanta, GA and Boulder, CO) using a recently developed electrical mobility spectrometer with a diethylene glycol-based ultrafine condensation particle counter as the particle detector. One new particle formation (NPF) event from each campaign was analyzed in detail. At a given instant in time during the NPF event, size-resolved growth rates were obtained directly from measured size distributions and were found to increase approximately linearly with particle size from {approx}1 to 3 nm geometric diameter, increasing from 5.5 {+-} 0.8 to 7.6 {+-} 0.6 nm h{sup -1} in Atlanta (13:00) and from 5.6 {+-} 2 to 27 {+-} 5 nm h{sup -1} in Boulder (13:00). The resulting growth rate enhancement {Lambda}, defined as the ratio of the observed growth rate to the growth rate due to the condensation of sulfuric acid only, was found to increase approximately linearly with size from {approx}1 to 3 nm geometric diameter. For the presented NPF events, values for {Lambda} had lower limits that approached {approx}1 at 1.2 nm geometric diameter in Atlanta and {approx}3 at 0.8 nm geometric diameter in Boulder, and had upper limits that reached 8.3 at 4.1 nm geometric diameter in Atlanta and 25 at 2.7 nm geometric diameter in Boulder. Nucleated particle survival probability calculations comparing the effects of constant and size-dependent growth indicate that neglecting the strong dependence of growth rate on size from 1 to 3 nm observed in this study could lead to a significant overestimation of CCN survival probability.

54 ENVIRONMENTAL SCIENCES↗

First Measurements of Neutral Atmospheric Cluster and 1–2 nm Particle Number Size Distributions During Nucleation Events

Recent observations throughout the atmosphere have shown that nucleation occurs frequently (Kulmala et al. 2004). Modeling studies and observations have shown that nucleated particles contribute significantly to concentrations of cloud condensation nuclei (Spracklen et al. 2008), thereby affecting climate (IPCC 2007). Size-resolved measurements extending down to molecular dimensions can provide information on processes that lead to nucleation and would enable development and verification of theories for particle nucleation and growth in the atmosphere and other aerosol systems. This article describes measurements of the complete number size distribution, spanning the size range from vapor molecules and molecular clusters to submicrometer particles, during atmospheric nucleation events. The measurements used two new instruments, the cluster chemical ionization mass spectrometer (Cluster CIMS) and the DEG SMPS. The Cluster CIMS measures neutral molecular clusters from 50 to 900 amu. The DEG SMPS is a scanning mobility particle spectrometer (SMPS) equipped with a diethylene glycol (DEG)-based condensation particle counter (CPC) capable of 1.1 nm mobility diameter particle detection, and overlapping the sizes detected by the Cluster CIMS (Iida et al. 2009; Jiang et al. 2011). The Cluster CIMS distinguishes neutral clusters from ions formed by ion-induced clustering by varying the reaction time for ions with the sampled air (Zhao et al. 2010). It distinguishes clusters from high molecular weight gases by measuring the incremental signal at a specified mass detected during nucleation events. The clusters that were measured in this study contain sulfuric acid, which is known to participate in atmospheric nucleation (Kuang et al. 2008).

54 ENVIRONMENTAL SCIENCES↗