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Direct measurements of gas/particle partitioning and mass accommodation coefficients in environmental chambers Jordan Edward Krechmer, Douglas A. Day, Paul J. Ziemann, and Jose L. Jimenez Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b02144 • Publication Date (Web): 31 Aug 2017 Downloaded from http://pubs.acs.org on September 3, 2017

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Environmental Science & Technology

Direct measurements of gas/particle partitioning and mass accommodation coefficients in environmental chambers Jordan E. Krechmer%, Douglas A. Day, Paul J. Ziemann, Jose L. Jimenez* Cooperative Institute for Research in Environmental Sciences (CIRES) and Department of Chemistry and Biochemistry, Boulder, Colorado 80309, United States Corresponding author: * Jose-Luis Jimenez University of Colorado; UCB 216, Boulder, CO 80309-0216 Phone: 303-492-3557 Fax: 303-492-1149 [email protected] Keywords: Aerosols, SOA, environmental chambers, gas/particle partitioning Abstract Secondary organic aerosols (SOA) are a major contributor to fine particulate mass and wield substantial influences on the Earth’s climate and human health. Despite extensive research in recent years, many of the fundamental processes of SOA formation and evolution remain poorly understood. Most atmospheric aerosol models use gas/particle equilibrium partitioning theory as a default treatment of gas-aerosol transfer, despite questions about potentially large kinetic effects. We have conducted fundamental SOA formation experiments in a Teflon environmental chamber using a novel method. A simple chemical system produces a very fast burst of lowvolatility gas-phase products, which are competitively taken up by liquid organic seed particles and Teflon chamber walls. Clear changes in the species time evolution with differing amounts of seed allow us to quantify the particle uptake processes. We reproduce gas- and aerosol-phase observations using a kinetic box model, from which we quantify the aerosol mass accommodation coefficient (α) as 0.7 on average, with values near unity especially for low volatility species. α appears to decrease as volatility increases. α has historically been a very difficult parameter to measure with reported values varying over three orders of magnitude. We use the experimentally-constrained model to evaluate the correction factor (Φ) needed for chamber SOA mass yields due to losses of vapors to walls as a function of species volatility and particle condensational sink. Φ ranges from 1 – 4.

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Introduction

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Gas/particle partitioning (GPP) is a fundamental physical process describing the interaction

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between atmospheric organic gases and particles. Originally treated as an adsorptive process,1,2

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most atmospheric models currently treat GPP of organic compounds as an absorptive process.3–5

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In this interpretation, semivolatile organic gases condense into and evaporate from particles until

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quickly reaching a volatility- and available organic aerosol mass-dependent equilibrium.3,4

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Semivolatile equilibrium partitioning is often parameterized using a volatility basis set, which

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lumps the amount of condensable material in the air in multiple bins spaced typically by a decade

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of the saturation mass concentration of the compound.5 GPP has been incorporated into

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numerous box, regional, and global models6–10 as a default treatment of organic aerosol

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formation and evolution.

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Still, modeling of GPP by rapid absorptive equilibrium remains controversial. There are

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now several real-time analysis techniques capable of measuring the gas/particle distribution of

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trace organic compounds at relatively high time resolution in the field.11–14 Many of these

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measurements have shown substantial disagreements with semivolatile equilibrium partitioning

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theory and one another, however.15,16 Some recent works have even suggested that semivolatile

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equilibrium partitioning is not reached under certain conditions due to strong kinetic limitations,

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and more detailed treatments are required to match atmospheric observations.17–21 GPP model treatment is expected to have a large influence on secondary organic aerosol

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(SOA)

mass

concentrations

predicted

by

atmospheric

models.

Most

models

use

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parameterizations of the SOA yield, i.e. the mass of SOA formed per unit mass of volatile

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organic compound (VOC) precursor reacted.22 Almost all experiments quantifying SOA mass

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yields that have been used in models were performed in Teflon-walled environmental


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chambers.22–26 However, it has recently been reported that Teflon chambers suffer from losses of

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semivolatile gaseous compounds to chamber walls.27–30 Wall losses can have strong effects on

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aerosol mass yields,30 and could also affect conclusions about chemical composition and

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processes gleaned from chamber experiments. The question even arises: if wall losses are

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substantial for a certain range of compounds, and fast enough to be on similar time scales as the

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approach to equilibrium GPP, is it possible to observe and accurately characterize GPP kinetics

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and equilibrium in environmental chambers?

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In mathematical representations of the kinetics of GPP, the mass accommodation

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coefficient (α; also known as the sticking coefficient; and equal to the evaporation coefficient at

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equilibrium) is a critical parameter that defines the fraction of gas/particle collisions that result in

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a colliding species being taken up by a particle. α for organic species was historically assumed to

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be 1, mostly from liquid evaporation measurements.31–33 More recent measurements of mass

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accommodation coefficients for aerosol-phase compounds34–36 range across two orders of

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magnitude. A very wide range of values (as low as 0.001) has been used in models and data

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fitting, sometimes as a tuning parameter which might obscure other model structural

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limitations.30,37–40 Comparing these literature values is complicated by the different methods used

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to derive α. Some models34,41 and measurements34,35 conflate particle diffusion kinetics and

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surface accommodation as one effective mass accommodation coefficient. Other models have

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attempted to specifically separate mass accommodation and particle-phase diffusion

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coefficients.36,42,43

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Given the discrepancies that persist between ambient SOA measurements and

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models,44,45 the substantial fraction of organic material in the atmosphere which is thought to be

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semivolatile,46 and the difficulty of quantifying GPP in field studies,16 it is important to closely



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examine in detail the kinetics of approach to equilibrium GPP. . It is also important to further

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evaluate the impact that losses of vapors to Teflon chamber walls may have in SOA yield

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measurements. Herein, we conduct fundamental gas/particle partitioning experiments in an

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environmental chamber with a particular focus on GPP kinetics. A well-characterized simple

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chemical system is used to produce low-volatility organic compounds very rapidly, which are

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taken up by liquid organic seed particles and/or the Teflon chamber walls. We use liquid organic

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seed aerosol specifically to establish an experimental method under which particle-phase kinetic

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limitations are not present. Both gas-phase products and total aerosol volume and surface area

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concentrations are continuously monitored. Analysis of these experiments allow us to thoroughly

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analyze the gas-phase and accommodation kinetics of GPP in the presence of walls for semi- and

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low-volatility gas-phase compounds. A box model is used to quantify c*and α. We use liquid

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aerosol particles as seeds, which removes particle-phase diffusion as a limiting parameter and

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allows us to infer the true value of α. We discuss the implications for quantifying gas/particle

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partitioning under more complex conditions.

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MATERIALS AND METHODS

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Environmental chamber experiments

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A schematic outlining the chamber and instruments used in this work is shown in Figure

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1. We conducted all of our experiments in the one of the two chambers in the CU Environmental

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Chamber (CUEC) Facility. The CUEC bag was constructed of FEP Teflon with a maximum

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volume of 20 m3. The enclosure temperature was maintained at 26 ± 1° C for all experiments.

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The chambers were filled with clean, dry (< 1% RH) air from two AADCO Model 737-15 clean

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air generators (Cleaves, OH, USA). The chambers were equipped with an automated flushing


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system that alternately evacuated and refilled the bag when it was not in use (~5% of full volume

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every 5 minutes), while maintaining the bag volume at ~95% of maximum volume using

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differential pressure between the bag and climate-controlled enclosure. Running the automated

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flushing sequence overnight before each experiment ensured that each experiment started with

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aerosol concentrations of 0 particles cm-3 as measured with an ultrafine condensation particle

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counter (UCPC, TSI model 3776 with a diameter cutoff of 2.5 nm). The experimental procedure is similar to the one detailed in Krechmer et al.27 to measure

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vapor wall losses to Teflon walls, but with the addition of seed aerosol. Dioctyl sebacate (DOS)

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seed was chosen for this set of experiments because it has been shown19 to be reliably liquid

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under the experimental conditions used here and should not impose particle-phase diffusion

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limitations on time scales relevant to the experiment. DOS also has a low vapor pressure (2 × 10-

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6

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reaction, thus not affecting GPP through particle-phase reactions.

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Pa)47 and, as a diester, should be unreactive with any of the products formed in the OH˙

First, we injected dioctyl sebacate (DOS; >97%; Sigma-Aldrich; saturation concentration

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at 298 K (c*) < 0.1 µg m-3)48 liquid seed aerosol into the chamber using an evaporation-

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condensation generator modeled after Sinclair and Lamer.49 The aerosol generator was

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configured to seed the chamber to 100 µg m-3 of DOS in ~15 minutes. Particle-phase wall losses

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occurred on a ~10 hr timescale, but it was not necessary to account for them explicitly in this

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model since the time-dependent aerosol size distribution measurements were used to constrain

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the box model. If needed, we diluted the chamber with clean air until the DOS seed surface area

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reached a desired level. '-condensation generator was tuned to produce aerosol with a lognormal

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surface area distribution centered at 200 nm. A scanning mobility particle sizer (SMPS)

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comprised of a TSI model 3080 electrostatic classifier and model 3775 condensation particle



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counter monitored aerosol number, surface area, and volume concentrations. The SMPS scan

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was programmed to last 120 s, with 15 s to return to the starting voltage, resulting in a time

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resolution of 135 s. We provide a summary of different experiments and seed concentrations in

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Table S1.

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The chemical system used here was the oxidation of long-chain alcohols by the OH

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radical under high-NO conditions. This system is the same used by Krechmer et al.27 because the

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oxidation products are simple and well-characterized (and with consistent chemical functionality

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in a progression of carbon numbers) as opposed to those of other gaseous precursors such as α-

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pinene or isoprene.

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After the seed aerosol concentration stabilized, we injected 50 µL of 1-hexanol, 40 µL of

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1-octanol, 25 µL of 1-nonanol, 18 µL of 1-decanol, and 12 µL of 1-dodecanol (all >99% purity;

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Sigma-Aldrich) into the chamber by gently heating the liquids into a clean nitrogen stream (UHP

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liquid nitrogen evaporate) flowing into the chamber. Injection took ~5 minutes. This resulted in a

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total VOC concentration in the chamber of 1.4 ppm. We fully mixed the bag contents by turning

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on a Teflon-coated fan inside the bag for 1 min to mix the contents. Finally, we injected 4 ppm

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of NO (99%, Matheson Tri-gas) and 4 ppm of methyl nitrite (MeONO, synthesized after the

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method of Taylor et al.50) into the chamber as pure gases using a small glass bulb and mixed the

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contents again for 1 min.

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To initiate chemical production, we turned on the chamber UV black lights (~300-400

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nm) at 100% intensity (JNO2 = 0.01 s-1) for precisely 10 s via computer-control. MeONO formed

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OH radicals, which then oxidized the alkanols forming ppt-levels of several oxidized products,27

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including hydroxynitrates (HN), dihydroxynitrates (DHN), trihydroxynitrates (THN), and

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carbonyl dihydroxynitrates (CDHN). A list of the compounds, along with their exact masses and


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estimated saturation concentrations (c*) is provided in Table S2. We did not observe new particle

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formation. We were able to continuously monitor the latter three types of products with a

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chemical ionization mass spectrometer (CIMS). This “rapid burst” method, developed

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previously,27 is critical to these experiments because it produces compounds over a wide range of

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volatilities over the entire volume of the chamber much faster than the vapors can equilibrate

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with the particles and walls. After each burst, the system was left to come to equilibrium for at

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least 1 hr.

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The amount of aerosol produced by each photooxidation burst comprised an average of

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7% of the total aerosol volume in the chamber (Figure S1). Therefore, the system can be

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modeled assuming that the gas-phase compounds are partitioning into pure DOS particles and

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not into a product compound mixture. The specific molecules studied here are estimated to form

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~ 20 ppt and account for < ~5% of the SOA. The majority of the aerosol formed is likely to be

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semivolatile hydroxynitrates, which are not detectable by the nitrate CIMS.27 The commercial

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iodide CIMS, which would likely detect the majority of aerosol-forming compounds, suffers

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from a significant time delay for semivolatile products due to gas-wall partitioning in the

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instrument source.27 This makes it unsuitable for a study such as this where it is critical to

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measure the gas-phase decays as close to real time as possible.

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NO3-CIMS

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A chemical ionization time-of-flight mass spectrometer equipped with a nitrate ion

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ionization source (NO3-CIMS) monitored gas-phase product concentrations. The instrument51,52

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and nitrate anion source53 have been described extensively in previous works. We used the

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instrument in a configuration similar to the one in Krechmer et al.27. Notably here, we placed the

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instrument inside the CUEC enclosure directly adjacent to the reactor bag. This allowed us to use



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a 0.6 m long electropolished stainless steel inlet to isothermally bring 10 standard L min-1

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(defined as 25° C, 1 Atm) of sample air directly from the bag to the instrument without dilution.

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The short inlet with a sub-sampled center flow minimizes wall losses and results in a residence

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time of sampled air in the instrument inlet and source of < 4 s. The NO3-CIMS acquired spectra

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at 1 Hz. We then processed instrument data using Tofware (Tofwerk, AG and Aerodyne, version

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2.5.8) toolkit within IGOR Pro 6 (Wavemetrics, Inc.) at the same time resolution. Throughout

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this work we report CIMS results in units of ions s-1 because we are only concerned with relative

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changes in gas-phase concentration and the CIMS response has previously been shown to be

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linear.54,55 The NO3-CIMS detected gaseous product molecules as clusters with the nitrate ion,

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but the NO3- prefix has been removed from reported formulas throughout this paper for clarity.

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An example mass spectrum of some of the product compounds is provided in Figure S2.

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Box model

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A chemical kinetic box model was used to simulate the behavior of gas- and aerosol-

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phase compounds, accounting for partitioning and evaporation of each oxidized products to walls

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and particles. A schematic of the model is shown in Figure S3. The model was solved using

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KinSim v3.24 within IGOR Pro.56

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The vapor wall loss or condensation rate coefficient, kc was determined using the

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procedure of Krechmer et al.,27 the results of which are shown in Figure S4. Under these

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conditions (c*

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