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<article xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:oasis="http://docs.oasis-open.org/ns/oasis-exchange/table" xml:lang="en" dtd-version="3.0" article-type="research-article"><?xmltex \makeatother\@nolinetrue\makeatletter?>
  <front>
    <journal-meta><journal-id journal-id-type="publisher">ACP</journal-id><journal-title-group>
    <journal-title>Atmospheric Chemistry and Physics</journal-title>
    <abbrev-journal-title abbrev-type="publisher">ACP</abbrev-journal-title><abbrev-journal-title abbrev-type="nlm-ta">Atmos. Chem. Phys.</abbrev-journal-title>
  </journal-title-group><issn pub-type="epub">1680-7324</issn><publisher>
    <publisher-name>Copernicus Publications</publisher-name>
    <publisher-loc>Göttingen, Germany</publisher-loc>
  </publisher></journal-meta>
    <article-meta>
      <article-id pub-id-type="doi">10.5194/acp-21-11467-2021</article-id><title-group><article-title>Using GECKO-A to derive mechanistic understanding of secondary organic aerosol formation from the
ubiquitous but understudied camphene</article-title><alt-title>Mechanistic modeling of camphene using GECKO-A</alt-title>
      </title-group><?xmltex \runningtitle{Mechanistic modeling of camphene using GECKO-A}?><?xmltex \runningauthor{I.~K.~Afreh et~al.}?>
      <contrib-group>
        <contrib contrib-type="author" corresp="no" rid="aff1">
          <name><surname>Afreh</surname><given-names>Isaac Kwadjo</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Aumont</surname><given-names>Bernard</given-names></name>
          
        <ext-link>https://orcid.org/0000-0002-2781-0877</ext-link></contrib>
        <contrib contrib-type="author" corresp="no" rid="aff2">
          <name><surname>Camredon</surname><given-names>Marie</given-names></name>
          
        </contrib>
        <contrib contrib-type="author" corresp="yes" rid="aff1">
          <name><surname>Barsanti</surname><given-names>Kelley Claire</given-names></name>
          <email>kbarsanti@engr.ucr.edu</email>
        <ext-link>https://orcid.org/0000-0002-6065-8643</ext-link></contrib>
        <aff id="aff1"><label>1</label><institution>Department of Chemical and Environmental Engineering and College of
Engineering-Center for Environmental Research and Technology (CE-CERT),
University of California-Riverside, Riverside, California 92507, United
States</institution>
        </aff>
        <aff id="aff2"><label>2</label><institution>Université Paris Est Creteil and Université de Paris, CNRS, LISA, 94010 Créteil, France</institution>
        </aff>
      </contrib-group>
      <author-notes><corresp id="corr1">Kelley Claire Barsanti (kbarsanti@engr.ucr.edu)</corresp></author-notes><pub-date><day>30</day><month>July</month><year>2021</year></pub-date>
      
      <volume>21</volume>
      <issue>14</issue>
      <fpage>11467</fpage><lpage>11487</lpage>
      <history>
        <date date-type="received"><day>6</day><month>August</month><year>2020</year></date>
           <date date-type="rev-request"><day>11</day><month>September</month><year>2020</year></date>
           <date date-type="rev-recd"><day>27</day><month>April</month><year>2021</year></date>
           <date date-type="accepted"><day>5</day><month>May</month><year>2021</year></date>
      </history>
      <permissions>
        <copyright-statement>Copyright: © 2021 </copyright-statement>
        <copyright-year>2021</copyright-year>
      <license license-type="open-access"><license-p>This work is licensed under the Creative Commons Attribution 4.0 International License. To view a copy of this licence, visit <ext-link ext-link-type="uri" xlink:href="https://creativecommons.org/licenses/by/4.0/">https://creativecommons.org/licenses/by/4.0/</ext-link></license-p></license></permissions><self-uri xlink:href="https://acp.copernicus.org/articles/.html">This article is available from https://acp.copernicus.org/articles/.html</self-uri><self-uri xlink:href="https://acp.copernicus.org/articles/.pdf">The full text article is available as a PDF file from https://acp.copernicus.org/articles/.pdf</self-uri>
      <abstract><title>Abstract</title>
    <p id="d1e114">Camphene, a dominant monoterpene emitted from both biogenic and pyrogenic
sources, has been significantly understudied, particularly in regard to
secondary organic aerosol (SOA) formation. When camphene represents a
significant fraction of emissions, the lack of model parameterizations for
camphene can result in inadequate representation of gas-phase chemistry and
underprediction of SOA formation. In this work, the first mechanistic study of SOA formation from camphene was performed using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A).  GECKO-A was used to generate gas-phase chemical mechanisms for camphene and two well-studied monoterpenes, <inline-formula><mml:math id="M1" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, as well as to predict SOA
mass formation and composition based on gas/particle partitioning theory. The
model simulations represented observed trends in published gas-phase reaction
pathways and SOA yields well under chamber-relevant photooxidation and dark
ozonolysis conditions. For photooxidation conditions, 70 % of the
simulated <inline-formula><mml:math id="M2" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene oxidation products remained in the gas phase
compared to 50 % for limonene, supporting model predictions and
observations of limonene having higher SOA yields than <inline-formula><mml:math id="M3" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene under
equivalent conditions. The top 10 simulated particle-phase products in the
<inline-formula><mml:math id="M4" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene simulations represented 37 %–50 % of
the SOA mass formed and 6 %–27 % of the hydrocarbon mass reacted. To
facilitate comparison of camphene with <inline-formula><mml:math id="M5" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, model
simulations were run under idealized atmospheric conditions, wherein the
gas-phase oxidant levels were controlled, and peroxy radicals reacted equally
with <inline-formula><mml:math id="M6" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and NO. Metrics for comparison included gas-phase
reactivity profiles, time-evolution of SOA mass and yields, and
physicochemical property distributions of gas- and particle-phase
products. The controlled-reactivity simulations demonstrated that (1)
in the early stages of oxidation, camphene is predicted to form very low-volatility products, lower than <inline-formula><mml:math id="M7" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, which condense
at low mass loadings; and (2) the final simulated SOA yield for camphene
(46 %) was relatively high, in between <inline-formula><mml:math id="M8" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (25 %) and
limonene (74 %). A 50 % <inline-formula><mml:math id="M9" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M10" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene mixture was then used as a surrogate to represent SOA formation from camphene; while simulated SOA mass and yield were well represented, the volatility distribution of the particle-phase products was not. To demonstrate the potential importance of including a parameterized representation of SOA formation by camphene in air quality models, SOA mass and yield were predicted for three wildland fire fuels based on measured monoterpene distributions and published SOA parameterizations for <inline-formula><mml:math id="M11" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene. Using the <inline-formula><mml:math id="M12" display="inline"><mml:mrow><mml:mn mathvariant="normal">50</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> surrogate mixture to represent camphene increased predicted SOA mass by 43 %–50 % for black spruce and by 56 %–108 % for Douglas fir. This first detailed modeling study of the gas-phase oxidation of camphene and subsequent SOA formation highlights opportunities for future measurement–model comparisons and lays a foundation for developing chemical mechanisms and SOA parameterizations for camphene that are suitable for air quality modeling.</p>
  </abstract>
    </article-meta>
  </front>
<body>
      

      <?xmltex \hack{\newpage}?>
<?pagebreak page11468?><sec id="Ch1.S1" sec-type="intro">
  <label>1</label><title>Introduction</title>
      <p id="d1e223">Sources of atmospheric monoterpene (<inline-formula><mml:math id="M13" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">10</mml:mn></mml:msub><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">16</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) emissions are
diverse and include biogenic sources (Geron et al., 2000; Guenther et al.,
1995; Hayward et al., 2001; Kesselmeier and Staudt, 1999; Kim et al., 2010;
Ludley et al., 2009; Maleknia et al., 2007; Rinne et al., 2000; Steinbrecher
et al., 1999; Tani et al., 2003; White et al., 2008), as well as pyrogenic
sources (Akagi et al., 2011, 2013; Gilman et al., 2015; Hatch et al., 2015;
Simpson et al., 2011). Monoterpenes account for an estimated one fifth of
total global biogenic volatile organic compound (BVOC) emissions (Guenther et
al., 1995; Hallquist et al., 1999). Quantities and identities of monoterpenes
emitted from biogenic sources primarily depend on plant species and
temperature or light (Geron et al., 2000; Hayward et al., 2001;
Yáñez-Serrano et al., 2018). Studies across biogenic source types
(e.g., terrestrial vegetation, soil, and marine) typically include up to 14
individual monoterpenes, with <inline-formula><mml:math id="M14" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, <inline-formula><mml:math id="M15" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>-pinene, camphene,
3-carene, limonene, myrcene, p-ocimene, and sabinene being the most widely
reported and having the highest emissions (Ambrose et al., 2010; Bäck
et al., 2012; Fehsenfeld et al., 1992; Geron et al., 2000; Hayward et al.,
2001; Rinne et al., 2000; White et al., 2008; Yassaa et al., 2008). As with
biogenic sources, the identities and quantities of monoterpenes from pyrogenic
sources (e.g., biomass burning) vary as a function of plant species and fuel
component (Hatch et al., 2019). Approximately 30 monoterpene isomers have been
observed from biomass burning sources, with <inline-formula><mml:math id="M16" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, <inline-formula><mml:math id="M17" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>-pinene,
camphene, 3-carene, limonene, and myrcene being commonly detected (Akagi
et al., 2013; Gilman et al., 2015; Hatch et al., 2015).</p>
      <p id="d1e270">Monoterpenes have a wide range of molecular structures, atmospheric
lifetimes, and secondary organic aerosol (SOA) formation potentials. The
molecular structures of monoterpenes can be acyclic or cyclic (with
variability in the size and number of rings) and can include one to three
<inline-formula><mml:math id="M18" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>=</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> double bonds (Atkinson and Arey, 2003b; Calogirou et al., 1999;
Jacobson et al., 2000; Lee et al., 2006a). The reaction rate constants of
monoterpenes with atmospheric oxidants vary by orders of magnitude (Atkinson
and Arey, 2003a; Geron et al., 2000), and their atmospheric lifetimes vary
from minutes to days (Atkinson and Arey, 2003b). Monoterpenes can react with
atmospheric oxidants to form less-volatile oxidation products leading to the
formation of SOA. SOA composes a significant fraction of atmospheric fine
particulate matter (<inline-formula><mml:math id="M19" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">PM</mml:mi><mml:mn mathvariant="normal">2.5</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) which adversely affects air quality and
has an impact on climate (Almatarneh et al., 2018; Hallquist et al., 1999; Jacobson
et al., 2000; Kanakidou et al., 2005). The extent of SOA formation from
monoterpenes can vary significantly due to the differences in their
structures, reaction rates, and volatility of their oxidation products and
propensity to form accretion products (Barsanti et al., 2017; Griffin et al., 1999; Ng et al., 2007; Zhang et al., 2015).</p>
      <p id="d1e296"><?xmltex \hack{\newpage}?>Over the past two decades, laboratory studies have been performed using
monoterpene precursors to elucidate their potential to form SOA under
conditions approximating atmospheric relevance. For example, Griffin
et al. (1999) used a series of outdoor chamber experiments to establish the
SOA formation potential of 14 biogenic compounds, including nine monoterpenes.
Since then, several chamber studies under varying experimental conditions have
been conducted for individual monoterpenes including <inline-formula><mml:math id="M20" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, <inline-formula><mml:math id="M21" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>-pinene, 3-carene, limonene, and myrcene (e.g., Amin et al., 2013; Boyd
et al., 2017; Fry et al., 2014; Hatfield and Huff Hartz, 2011; Lee et al.,
2006a; Ng et al., 2007; Presto et al., 2005; Presto and Donahue, 2006; Zhao
et al., 2018). Additionally, other studies have been conducted to investigate
gas-phase reaction pathways and major products from the reactions of
monoterpenes with hydroxyl radical (OH), ozone (<inline-formula><mml:math id="M22" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>), and nitrate
radical (<inline-formula><mml:math id="M23" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) (e.g., Draper et al., 2015; Friedman and Farmer, 2018;
Kundu et al., 2012; Zhang et al., 2015). While some monoterpenes have been
well studied in chambers or other laboratory reactors, other monoterpenes are
relatively under-studied, including some that are commonly measured in
non-negligible quantities in the atmosphere.</p>
      <p id="d1e336">Parameterizations used in air quality models are largely based on laboratory
studies; thus widely studied monoterpenes (e.g., <inline-formula><mml:math id="M24" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and
limonene) are often used as surrogates to represent the gas-phase chemistry
and SOA formation of all terpenes (e.g., Carter, 2010; Saha and Grieshop,
2016; Stockwell et al., 1997). The lack of monoterpene-specific laboratory
data can result in inadequate representation of monoterpene chemistry,
including SOA formation, particularly where a diversity of unrepresented
monoterpenes make a large contribution to total emissions. Camphene is one
monoterpene that has been observed in the atmosphere but has little to no
published data regarding SOA formation. Previous experimental and theoretical
studies of camphene focused on the gas-phase reactions of camphene and product
identification (e.g., Atkinson et al., 1990; Gaona-Colmán et al., 2017;
Hakola et al., 1994). Recently, a density functional theory (DFT) approach was
also used to investigate the oxidation of camphene and the fate of product
radicals under atmospherically relevant conditions (Baruah et al.,
2018). While this approach identified plausible reaction pathways of camphene
photooxidation and associated gas-phase products, formation of SOA was not
considered.</p>
      <p id="d1e347">In this work, a mechanistic study of SOA formation from camphene was conducted
using the Generator for Explicit Chemistry and Kinetics of Organics in the
Atmosphere (GECKO-A). GECKO-A has been previously used to study SOA formation
from a number of precursors (e.g., Camredon et al., 2007; La et al., 2016;
McVay et al., 2016; Valorso et al., 2011). GECKO-A was used here to generate
nearly explicit mechanisms for camphene and the well-studied monoterpenes
<inline-formula><mml:math id="M25" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene. Model simulations were run under
chamber-relevant conditions (“chamber reactivity simulations”) to capture
trends in simulated SOA mass and<?pagebreak page11469?> composition and compared with published
observations using commonly reported metrics including SOA yields and
oxygen <inline-formula><mml:math id="M26" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> carbon (<inline-formula><mml:math id="M27" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>) ratios. Model simulations were also run under idealized atmospheric conditions (“controlled reactivity simulations”) to facilitate a direct comparison of camphene with <inline-formula><mml:math id="M28" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, including comparisons of gas-phase oxidation pathways, gas-phase reactivity profiles, time-evolution of SOA mass and yields, and physicochemical property distributions of gas- and particle-phase products. Based on these analyses, the feasibility of using <inline-formula><mml:math id="M29" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene or limonene as a surrogate for camphene was assessed, and implications for air quality model predictions and opportunities for future studies were identified.</p>
</sec>
<sec id="Ch1.S2">
  <label>2</label><title>Methods</title>
<sec id="Ch1.S2.SS1">
  <label>2.1</label><title>GECKO-A model description</title>
      <p id="d1e405">SOA formation from three monoterpene precursors (<inline-formula><mml:math id="M30" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, limonene,
and camphene) was modeled using GECKO-A. A description of GECKO-A is given by
Aumont et al. (2005). GECKO-A is a modeling tool that generates nearly
explicit gas-phase oxidation mechanisms for individual or multiple organic
compounds under general atmospheric conditions (Aumont et al., 2005, 2012;
Camredon et al., 2007), as well as the properties to represent the
gas/particle partitioning of the stable organic compounds present in the
mechanisms (Camredon et al., 2007; Valorso et al., 2011). The nearly explicit
chemical mechanism is generated using experimental data and a predefined
protocol (Aumont et al., 2005, 2012; Camredon et al., 2007). The protocol is
described in Aumont et al. (2005) and includes updates described in Aumont
et al. (2013), La et al. (2016), McVay et al. (2016), and Valorso et
al. (2011). In the absence of experimental data, reaction rate constants and
products, as well as their physicochemical properties, are estimated based on
structure-activity relationships (SARs) (Aumont et al., 2005).  Autoxidation
leading to the formation of highly oxygenated molecules (HOM) in the gas phase
(e.g., Bianchi et al., 2019; Ehn et al., 2014) is not currently represented
in GECKO-A. A SAR to predict the rate coefficients of peroxy radical
(<inline-formula><mml:math id="M31" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) H migration reactions (H-shifts) that lead to the formation of
HOM was recently published by Vereecken and Nozière (2020).  The straight
implementation of this SAR into GECKO-A would lead to a non-manageable number
of species and reactions. Therefore, reduction protocols are currently under
development to consider the autoxidation reactions in subsequent model
versions. For the application presented herein, limitations and implications
of the absence of HOM formation via <inline-formula><mml:math id="M32" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> autoxidation are discussed
where relevant.</p>
      <p id="d1e437">Some simplifications were applied during the mechanism generation to reduce
the size of the gas-phase chemical mechanisms: (1) the maximum generations of
oxidation for each mechanism was set at six based on prior GECKO-A modeling
results for <inline-formula><mml:math id="M33" display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula>-alkanes (Aumont et al., 2012), and sensitivity studies were
performed in this work for <inline-formula><mml:math id="M34" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene oxidation, in which increasing the
number of generations beyond six did not result in significant changes in the
evolution of the gas or particle phases; (2) species with vapor pressure
below 10<inline-formula><mml:math id="M35" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">13</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> atm (equivalent to <inline-formula><mml:math id="M36" display="inline"><mml:mrow><mml:msup><mml:mi>C</mml:mi><mml:mo>*</mml:mo></mml:msup></mml:mrow></mml:math></inline-formula> of <inline-formula><mml:math id="M37" display="inline"><mml:mrow><mml:mn mathvariant="normal">1.02</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M38" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for species with a mean molecular weight of
250 <inline-formula><mml:math id="M39" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">mol</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) were considered non-volatile and therefore treated as
end products during gas-phase mechanism generation (Valorso et al., 2011); and (3)
position isomers were lumped if the production yield of a species was lower
than 10<inline-formula><mml:math id="M40" display="inline"><mml:msup><mml:mi/><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:math></inline-formula> (Valorso et al., 2011). The chemical mechanisms generated for
this study included <inline-formula><mml:math id="M41" display="inline"><mml:mrow><mml:mn mathvariant="normal">1.4</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> reactions and <inline-formula><mml:math id="M42" display="inline"><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">5</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> oxidation products for <inline-formula><mml:math id="M43" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene; <inline-formula><mml:math id="M44" display="inline"><mml:mrow><mml:mn mathvariant="normal">6.5</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">5</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> reactions and
<inline-formula><mml:math id="M45" display="inline"><mml:mrow><mml:mn mathvariant="normal">9.3</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">4</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> oxidation products for limonene; and <inline-formula><mml:math id="M46" display="inline"><mml:mrow><mml:mn mathvariant="normal">1.3</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> reactions and <inline-formula><mml:math id="M47" display="inline"><mml:mrow><mml:mn mathvariant="normal">1.8</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">5</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> oxidation products for camphene. These
mechanisms were then implemented in a box model to simulate the evolution of
gaseous organic compounds and SOA formation (Aumont et al., 2005, 2012;
Camredon et al., 2007). Gas/particle partitioning of stable organic compounds
was calculated according to the saturation vapor pressure of each organic
compound and assuming thermodynamic equilibrium between the gas and an ideal
(activity coefficients <inline-formula><mml:math id="M48" display="inline"><mml:mrow><mml:mo>=</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:math></inline-formula>), homogeneous, and inert condensed phase. The
saturation vapor pressures were estimated using the Nannoolal method
(Nannoolal et al., 2008), which performs relatively well compared to other
estimation methods when used to simulate SOA formation during <inline-formula><mml:math id="M49" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
oxidation experiments (Valorso et al., 2011). Condensed-phase reactions are
not currently represented in GECKO-A; the limitations and implications of
which are discussed where relevant.</p>
</sec>
<sec id="Ch1.S2.SS2">
  <label>2.2</label><title>GECKO-A-generated oxidation mechanisms</title>
      <p id="d1e667">The monoterpene reaction schemes are generated by GECKO-A using established
protocols, as described in Aumont et al. (2005). First, the mechanism
generator analyzes the structure of the compound to determine the reactive
sites and the plausible reaction pathways. Reaction products and initial
branching ratios are based on experimental data when available. Otherwise, the
reaction products and rate constants are estimated based on structure-activity
relationships (SARs). The initial reaction rate constants of the monoterpenes
with OH, <inline-formula><mml:math id="M50" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M51" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> were based on data from Atkinson and
Arey (2003a). For <inline-formula><mml:math id="M52" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M53" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> OH, the initial branching ratios are
based on data from Peeters et al. (2001). For subsequent reaction steps
with <inline-formula><mml:math id="M54" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M55" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> OH, and for the limonene and camphene mechanisms,
reaction products and branching ratios are based on SARs.</p>
<sec id="Ch1.S2.SS2.SSS1">
  <label>2.2.1</label><title>OH reaction scheme</title>
      <p id="d1e728">The reaction pathways of OH-initiated oxidation of <inline-formula><mml:math id="M56" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, limonene,
and camphene up to the formation of<?pagebreak page11470?> first-generation stable products are shown
in Figs. 1–3, respectively. For figure clarity, inorganic species formed
(including OH) are not shown. The initial reaction steps proceed mainly by the
addition of OH to the <inline-formula><mml:math id="M57" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>=</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> double bond or by hydrogen abstraction. This
leads to the formation of hydroxyalkyl radicals (<inline-formula><mml:math id="M58" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) which react
rapidly with <inline-formula><mml:math id="M59" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form peroxy radicals (<inline-formula><mml:math id="M60" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>). The peroxy
radicals can combine with NO, <inline-formula><mml:math id="M61" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M62" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form stable
products. The peroxy radicals can also lose an oxygen atom through reaction
with NO to form alkoxy radicals, which is consistent with observations
reported by Atkinson and Arey (1998) and Calogirou et al. (1999). For <inline-formula><mml:math id="M63" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene oxidation, the hydroxyalkyl radicals primarily react with
<inline-formula><mml:math id="M64" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form peroxy radicals which then react with NO, <inline-formula><mml:math id="M65" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M66" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form stable products, many with a four-membered ring, or
lose an oxygen atom to form alkoxy radicals. As observed by Lee
et al. (2006b), the alkoxy radicals undergo subsequent reactions leading to
the formation of formaldehyde, acetone, and multifunctional products including
pinonaldehyde. For limonene oxidation, reaction of the peroxy radicals with
<inline-formula><mml:math id="M67" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M68" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M69" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> followed by <inline-formula><mml:math id="M70" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> addition and NO to
<inline-formula><mml:math id="M71" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> conversion leads to the formation of limononaldehyde or
limonaketone and formaldehyde, which is consistent with observations reported
by Lee et al. (2006b). Alternatively, the peroxy radicals react with
<inline-formula><mml:math id="M72" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M73" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M74" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>  to form ring-opened peroxy radicals which further
react to form multifunctional products. For camphene, the hydroxyalkyl
radicals react rapidly with <inline-formula><mml:math id="M75" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form hydroxyalkyl peroxy
radicals. The hydroxyalkyl peroxy radicals subsequently react with NO,
<inline-formula><mml:math id="M76" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and <inline-formula><mml:math id="M77" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form stable products or react with
<inline-formula><mml:math id="M78" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M79" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M80" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form hydroxyalkoxy radicals. The hydroxyalkoxy
radicals then either decompose to form camphenilone (a bicyclic product) and
formaldehyde or react with <inline-formula><mml:math id="M81" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form five-membered ring
hydroxyperoxy radicals which further react to form multifunctional
products. The reaction pathway of OH addition to the exocyclic double bond of
camphene as represented in GECKO-A is in agreement with the observations made
by Gaona-Colmán et al. (2017) and Reissell et al. (1999), as well as by
Baruah et al. (2018) in their DFT study of OH-initiated oxidation of
camphene. While camphene and <inline-formula><mml:math id="M82" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene are structurally bicyclic, their
first-generation products resulting from the decomposition of the bicyclic
hydroxyalkoxy radicals differ; camphene primarily forms five-membered ring first-generation products, while <inline-formula><mml:math id="M83" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene primarily forms four-membered ring
first-generation products. Limonene, which is monocyclic, primarily forms
ring-opened first-generation products when its monocyclic hydroxyalkoxy radicals
decompose.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F1" specific-use="star"><?xmltex \currentcnt{1}?><?xmltex \def\figurename{Figure}?><label>Figure 1</label><caption><p id="d1e1021">Initial oxidation
pathways of <inline-formula><mml:math id="M84" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene oxidation with OH as represented in GECKO-A
(inorganic products are not shown).</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f01.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F2" specific-use="star"><?xmltex \currentcnt{2}?><?xmltex \def\figurename{Figure}?><label>Figure 2</label><caption><p id="d1e1039">Initial oxidation pathways of limonene oxidation with OH
as represented in GECKO-A (inorganic products are not shown).</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f02.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F3" specific-use="star"><?xmltex \currentcnt{3}?><?xmltex \def\figurename{Figure}?><label>Figure 3</label><caption><p id="d1e1051">Initial oxidation pathways of camphene oxidation with OH
as represented in GECKO-A (inorganic products are not shown).</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f03.png"/>

          </fig>

</sec>
<sec id="Ch1.S2.SS2.SSS2">
  <label>2.2.2</label><?xmltex \opttitle{{$\protect\chem{O_{{3}}}$} reaction scheme}?><title><inline-formula><mml:math id="M85" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> reaction scheme</title>
      <p id="d1e1079">The initial oxidation pathways of <inline-formula><mml:math id="M86" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>-initiated oxidation of <inline-formula><mml:math id="M87" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, limonene, and camphene are shown in Figs. S1–S3 in the Supplement,
respectively. The reaction starts with the addition of <inline-formula><mml:math id="M88" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to the
<inline-formula><mml:math id="M89" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>=</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> double bond of the parent compound to form an ozonide which
rapidly undergoes bond cleavage to form either a biradical Criegee intermediate
bearing a carbonyl substituent for terpenes with an endocyclic double bond or
a biradical Criegee intermediate and a carbonyl for terpenes with an exocyclic
double bond. The Criegee intermediate can stabilize by collisions and/or
decompose (after possible rearrangement) to form peroxy radicals. The
stabilized Criegee intermediates (SCI) undergo bimolecular reactions with
<inline-formula><mml:math id="M90" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>, CO, NO, and/or <inline-formula><mml:math id="M91" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. The peroxy radicals then react
with <inline-formula><mml:math id="M92" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M93" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M94" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form stable products or react with <inline-formula><mml:math id="M95" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M96" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M97" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form alkoxy radicals. For <inline-formula><mml:math id="M98" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, the
alkoxy radicals either react with <inline-formula><mml:math id="M99" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> or decompose to form
formaldehyde and peroxy radicals. The peroxy radicals further react to form
peroxy acid, carboxylic acid, and <inline-formula><mml:math id="M100" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. For limonene, the alkoxy
radical reactions primarily lead to the formation of organic nitrates, organic
hydroperoxides, carboxylic acids, and peroxy acids. For camphene, the ozonide
decomposes to form (1) camphenilone, a stable bicyclic product that has been
observed experimentally by Calogirou et al. (1999) and Hakola et al. (1994),
and (2) a bicyclic peroxy radical and formaldehyde, consistent with the
camphene <inline-formula><mml:math id="M101" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M102" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> mechanism reported by Gaona-Colmán
et al. (2017). The bicyclic peroxy radical reacts with <inline-formula><mml:math id="M103" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M104" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M105" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
to form stable products or reacts with <inline-formula><mml:math id="M106" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M107" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M108" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form alkoxy
radical which then further reacts to form five-membered ring products.</p>
</sec>
<sec id="Ch1.S2.SS2.SSS3">
  <label>2.2.3</label><?xmltex \opttitle{{$\protect\chem{NO_{{3}}}$} reaction scheme}?><title><inline-formula><mml:math id="M109" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> reaction scheme</title>
      <p id="d1e1336">The initial oxidation pathways of <inline-formula><mml:math id="M110" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>-initiated oxidation of <inline-formula><mml:math id="M111" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, limonene, and camphene are shown in Figs. S4–S6,
respectively. The <inline-formula><mml:math id="M112" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> radical attacks the <inline-formula><mml:math id="M113" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">C</mml:mi><mml:mo>=</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> double bond to
form a nitratoalkyl radical which undergoes rapid reaction with <inline-formula><mml:math id="M114" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
to form a nitratoalkylperoxy radical. The nitratoalkylperoxy radicals of all
three compounds react similarly in three ways: (1) with NO to form dinitrates;
(2) with <inline-formula><mml:math id="M115" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> or <inline-formula><mml:math id="M116" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form nitratocarbonyls,
nitratoalcohols, and nitratoperoxides (Calogirou et al., 1999); and (3) with
<inline-formula><mml:math id="M117" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M118" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M119" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> to form nitratoalkoxy radicals, which react further to
form multifunctional products.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T1" specific-use="star"><?xmltex \currentcnt{1}?><label>Table 1</label><caption><p id="d1e1447">Initial conditions for <inline-formula><mml:math id="M120" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene chamber reactivity simulations.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="7">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="right"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="center"/>
     <oasis:colspec colnum="6" colname="col6" align="center"/>
     <oasis:colspec colnum="7" colname="col7" align="center"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">Abbreviation</oasis:entry>
         <oasis:entry colname="col2">Description</oasis:entry>
         <oasis:entry colname="col3">HC</oasis:entry>
         <oasis:entry colname="col4">NO</oasis:entry>
         <oasis:entry colname="col5">HONO</oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M121" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col7">Organic seed</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(ppb)</oasis:entry>
         <oasis:entry colname="col4">(ppb)</oasis:entry>
         <oasis:entry colname="col5">(ppb)</oasis:entry>
         <oasis:entry colname="col6">(ppb)</oasis:entry>
         <oasis:entry colname="col7">(<inline-formula><mml:math id="M122" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">P_LHC</oasis:entry>
         <oasis:entry colname="col2">Photooxidation</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6"/>
         <oasis:entry colname="col7"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Lower hydrocarbon</oasis:entry>
         <oasis:entry colname="col3">50</oasis:entry>
         <oasis:entry colname="col4">110</oasis:entry>
         <oasis:entry colname="col5">10</oasis:entry>
         <oasis:entry colname="col6"/>
         <oasis:entry colname="col7">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">P_HHC</oasis:entry>
         <oasis:entry colname="col2">Photooxidation</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6"/>
         <oasis:entry colname="col7"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Higher hydrocarbon</oasis:entry>
         <oasis:entry colname="col3">150</oasis:entry>
         <oasis:entry colname="col4">110</oasis:entry>
         <oasis:entry colname="col5">10</oasis:entry>
         <oasis:entry colname="col6"/>
         <oasis:entry colname="col7">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">DO_LHC</oasis:entry>
         <oasis:entry colname="col2">Dark ozonolysis</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6"/>
         <oasis:entry colname="col7"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Lower hydrocarbon</oasis:entry>
         <oasis:entry colname="col3">50</oasis:entry>
         <oasis:entry colname="col4">16</oasis:entry>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6">500</oasis:entry>
         <oasis:entry colname="col7">1</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">DO_HHC</oasis:entry>
         <oasis:entry colname="col2">Dark ozonolysis</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6"/>
         <oasis:entry colname="col7"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Higher hydrocarbon</oasis:entry>
         <oasis:entry colname="col3">150</oasis:entry>
         <oasis:entry colname="col4">16</oasis:entry>
         <oasis:entry colname="col5"/>
         <oasis:entry colname="col6">500</oasis:entry>
         <oasis:entry colname="col7">1</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

</sec>
</sec>
<sec id="Ch1.S2.SS3">
  <label>2.3</label><title>Simulation conditions</title>
      <?pagebreak page11472?><p id="d1e1741">The objective of the chamber reactivity simulations was to compare GECKO-A
model output with published SOA chamber data (Table 1). No attempt was made to
strictly reproduce the conditions of a given chamber experiment. Since the
first objective of this study focuses on the ability of the model to capture
the major trends observed in chamber data (e.g., SOA yields and major
oxidation products), the simulation conditions were set to mimic (or be
representative of) typical chamber conditions. Comparative analyses were
performed for the precursors <inline-formula><mml:math id="M123" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene since they are
among the well-studied monoterpenes in environmental chambers, and sufficient
data exist for measurement–model comparison. These chamber reactivity
simulations included photooxidation (P) and dark ozonolysis (DO) conditions
which were differentiated by the initial concentrations of NO, HONO, and
<inline-formula><mml:math id="M124" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> as shown in Table 1. For both the P and DO conditions, the
initial hydrocarbon mixing ratios were set at a relatively low
(50 <inline-formula><mml:math id="M125" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula>) and a relatively high (150 <inline-formula><mml:math id="M126" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula>) level as compared
with published chamber studies.  This resulted in a total of four chamber
reactivity simulations for each monoterpene precursor. It is noted that the
simulations are unable to capture HOM formation via <inline-formula><mml:math id="M127" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> autoxidation
and subsequent dimerization (Ehn et al., 2014) that may have occurred in the
chamber studies, particularly under DO conditions. In each simulation,
1 <inline-formula><mml:math id="M128" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> of organic seed with a molecular weight of
250 <inline-formula><mml:math id="M129" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">mol</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">1</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> was added to initiate gas/particle partitioning.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T2" specific-use="star"><?xmltex \currentcnt{2}?><label>Table 2</label><caption><p id="d1e1829">Initial conditions for camphene, <inline-formula><mml:math id="M130" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene,
and limonene controlled reactivity simulations. The levels of
<inline-formula><mml:math id="M131" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M132" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula><inline-formula><mml:math id="M133" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula> were fixed during these simulations.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="8">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="center"/>
     <oasis:colspec colnum="4" colname="col4" align="center"/>
     <oasis:colspec colnum="5" colname="col5" align="center"/>
     <oasis:colspec colnum="6" colname="col6" align="center"/>
     <oasis:colspec colnum="7" colname="col7" align="center"/>
     <oasis:colspec colnum="8" colname="col8" align="center"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1">Abbreviation</oasis:entry>
         <oasis:entry colname="col2">Description</oasis:entry>
         <oasis:entry colname="col3">HC</oasis:entry>
         <oasis:entry colname="col4">NO</oasis:entry>
         <oasis:entry colname="col5"><inline-formula><mml:math id="M134" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col6"><inline-formula><mml:math id="M135" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">6</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col7"><inline-formula><mml:math id="M136" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CH</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col8">Organic seed</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">(ppb)</oasis:entry>
         <oasis:entry colname="col4">(ppb)</oasis:entry>
         <oasis:entry colname="col5">(ppb)</oasis:entry>
         <oasis:entry colname="col6">(ppm)</oasis:entry>
         <oasis:entry colname="col7">(ppb)</oasis:entry>
         <oasis:entry colname="col8">(<inline-formula><mml:math id="M137" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1">CR</oasis:entry>
         <oasis:entry colname="col2">Controlled reactivity</oasis:entry>
         <oasis:entry colname="col3">0.1</oasis:entry>
         <oasis:entry colname="col4">1</oasis:entry>
         <oasis:entry colname="col5">30</oasis:entry>
         <oasis:entry colname="col6">10</oasis:entry>
         <oasis:entry colname="col7">50</oasis:entry>
         <oasis:entry colname="col8">10</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e2029">The objective of the controlled reactivity simulations was to examine SOA
formation by camphene in the context of well-studied monoterpenes,
specifically <inline-formula><mml:math id="M138" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, under controlled conditions
(Table 2). In these simulations, the gas-phase chemistry was not controlled by
the individual precursors but by other organic compounds as occurs in the
ambient atmosphere, allowing for a straightforward comparison of terpene oxidation
mechanisms under the controlled reactivity conditions. A mixture of ethane
(10 <inline-formula><mml:math id="M139" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula>) and formaldehyde (50 <inline-formula><mml:math id="M140" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula>) was used to buffer (i.e.,
control) the gas-phase reactivity. The <inline-formula><mml:math id="M141" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M142" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> mixing ratios
were held constant at values of 1 and 30 <inline-formula><mml:math id="M143" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula>, respectively, throughout
the simulation. Hence, <inline-formula><mml:math id="M144" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> reacted equally with <inline-formula><mml:math id="M145" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2<?pagebreak page11473?></mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and
NO, and the levels of the oxidants did not change when relatively small
amounts of precursor were added. The controlled reactivity simulations
included 0.1 <inline-formula><mml:math id="M146" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula> of initial precursor and 10 <inline-formula><mml:math id="M147" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> of
organic seed.</p>
      <p id="d1e2136">All box-model simulations were performed under fixed conditions: temperature
was held at 298 <inline-formula><mml:math id="M148" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">K</mml:mi></mml:mrow></mml:math></inline-formula> and relative humidity at 5 <inline-formula><mml:math id="M149" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">%</mml:mi></mml:mrow></mml:math></inline-formula> to represent
mean chamber conditions, and the solar zenith angle, required to calculate
photolysis frequencies, was set at 50<inline-formula><mml:math id="M150" display="inline"><mml:msup><mml:mi/><mml:mo>∘</mml:mo></mml:msup></mml:math></inline-formula> to represent mean daytime solar
spectra except for dark ozonolysis conditions where no photolysis was
considered.</p>
</sec>
</sec>
<sec id="Ch1.S3">
  <label>3</label><title>Results</title>
<sec id="Ch1.S3.SS1">
  <label>3.1</label><title>Chamber reactivity simulations</title>
<sec id="Ch1.S3.SS1.SSS1">
  <label>3.1.1</label><title>Measurement–model comparison</title>
      <p id="d1e2187">In Fig. 4, SOA yields from the chamber reactivity simulations are shown with
measured SOA yields from chamber studies. SOA data (see Table S1 in the
Supplement) were compiled from 12 published chamber studies (e.g., Chen
et al., 2017; Griffin et al., 1999; Kim and Paulson, 2013; Kourtchev et al.,
2014; Nah et al., 2016; Ng et al., 2007; Yu et al., 1999) in which <inline-formula><mml:math id="M151" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene or limonene
was used as a precursor, and final SOA mass, SOA yield, and reacted hydrocarbon
concentration (<inline-formula><mml:math id="M152" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>HC) were reported (at least two of the three
quantities). For the <inline-formula><mml:math id="M153" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation data, there is an
apparent cluster around an SOA yield of 0.2 for SOA mass <inline-formula><mml:math id="M154" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">150</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M155" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> with which the model agrees (Fig. 4a). The scatter
in the data is due to differences in experimental conditions (e.g.,
temperature and <inline-formula><mml:math id="M156" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> mixing ratios). As previously observed, SOA yields of
<inline-formula><mml:math id="M157" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene tend to be higher at lower temperatures and lower <inline-formula><mml:math id="M158" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
conditions (higher initial VOC<inline-formula><mml:math id="M159" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula><inline-formula><mml:math id="M160" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> ratios) (Kim and Paulson, 2013;
Pathak et al., 2007b). For example, the two relatively high SOA yields (0.38
at 29.3 <inline-formula><mml:math id="M161" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> and 0.46 at 121.3 <inline-formula><mml:math id="M162" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) had
relatively low initial <inline-formula><mml:math id="M163" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> concentrations (Ng et al., 2007), while the
two relatively low SOA yields (0.059 at 44 <inline-formula><mml:math id="M164" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> and 0.06 at
4.5 <inline-formula><mml:math id="M165" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) had relatively high initial <inline-formula><mml:math id="M166" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>
concentrations (Kim and Paulson, 2013; Ng et al., 2007). For mass loadings <inline-formula><mml:math id="M167" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">150</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M168" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M169" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation SOA yield data
plateau at approximately 0.3, which also is captured by the model. In
contrast, for limonene photooxidation, experimental data show a linear trend
in the SOA yield as a function of SOA mass (for SOA mass <inline-formula><mml:math id="M170" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">25</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M171" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>), and the SOA yield does not plateau at higher SOA
mass loadings.  The observed linear trend in SOA yield as a function of SOA
mass is reflected in the model simulations (Fig. 4c). For <inline-formula><mml:math id="M172" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
ozonolysis (Fig. 4b), there is an apparent cluster around an SOA yield of 0.2
for SOA mass <inline-formula><mml:math id="M173" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M174" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>. At SOA mass <inline-formula><mml:math id="M175" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M176" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, the modeled SOA yield is within range of the
observations, towards the lowest values; between SOA mass <inline-formula><mml:math id="M177" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">100</mml:mn></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M178" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M179" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, the modeled
SOA yield is lower than the observations (two data points). The SOA yield
plateaus at approximately 0.4 for SOA mass <inline-formula><mml:math id="M180" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M181" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>; the
model simulations do not extend to this high mass range precluding
comparison. For limonene ozonolysis, Fig. 4d shows the chamber SOA yield
plateauing at approximately 0.8 (for mass loadings <inline-formula><mml:math id="M182" display="inline"><mml:mrow><mml:mo>&gt;</mml:mo><mml:mn mathvariant="normal">200</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M183" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) which is captured by the model simulations.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F4" specific-use="star"><?xmltex \currentcnt{4}?><?xmltex \def\figurename{Figure}?><label>Figure 4</label><caption><p id="d1e2618">GECKO-A SOA yields are represented by blue (<inline-formula><mml:math id="M184" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene) and red (limonene) markers; chamber SOA yields are
represented by grey markers. The initial hydrocarbon mixing ratios are
differentiated by shape: squares represent the simulation using the lower
hydrocarbon (LHC) mixing ratio and diamonds the simulation using the higher
hydrocarbon (HHC) mixing ratio.</p></caption>
            <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f04.png"/>

          </fig>

      <p id="d1e2634">Overall, the model simulations agree well with the observed trends in SOA
yield as a function of SOA mass. The largest discrepancies are for <inline-formula><mml:math id="M185" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis, in which SOA mass is underpredicted relative to the
observations. The contribution of HOM formation from <inline-formula><mml:math id="M186" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
autoxidation is expected to be more important under such conditions, in which the
lifetime of <inline-formula><mml:math id="M187" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is sufficiently long for autoxidation to compete
with bimolecular reactions, and monoterpene oxidation by <inline-formula><mml:math id="M188" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is
greater than by OH leading to higher HOM yields (Ehn et al., 2014; Jokinen
et al., 2015).  The inclusion of HOM formation and subsequent dimerization
would lead to an increase in predicted SOA mass in both the <inline-formula><mml:math id="M189" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
and limonene ozonolysis simulations. An increase in SOA mass due to HOM
formation and subsequent dimerization would improve the measurement–model
agreement for <inline-formula><mml:math id="M190" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene but would also lead to an overprediction of
SOA mass for limonene. In addition, a non-negligible contribution of HOM
monomers and dimers to the particle phase would increase the calculated average oxygen <inline-formula><mml:math id="M191" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> carbon (<inline-formula><mml:math id="M192" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>) ratio and increase the measurement–model discrepancy further, as is discussed
below. McVay et al. (2016) reported similar conclusions for <inline-formula><mml:math id="M193" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
photolysis experiments; a parameterized representation of <inline-formula><mml:math id="M194" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
autoxidation in GECKO-A increased predicted SOA mass for low UV conditions,
improving measurement–model agreement at the end of the experiment and
resulted in no change for high UV conditions.</p>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T3" specific-use="star"><?xmltex \currentcnt{3}?><label>Table 3</label><caption><p id="d1e2733">Simulation-based OH exposure, simulated average
mass-weighted <inline-formula><mml:math id="M195" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio, and chamber average mass-weighted <inline-formula><mml:math id="M196" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio for <inline-formula><mml:math id="M197" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene under photooxidation and ozonolysis
conditions.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="4">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="center"/>
     <oasis:colspec colnum="3" colname="col3" align="center"/>
     <oasis:colspec colnum="4" colname="col4" align="left"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Simulated OH exposure</oasis:entry>
         <oasis:entry colname="col3">Simulated average <inline-formula><mml:math id="M198" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4">Chamber average <inline-formula><mml:math id="M199" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula></oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">(<inline-formula><mml:math id="M200" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">molec</mml:mi><mml:mo>.</mml:mo><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup><mml:mspace linebreak="nobreak" width="0.125em"/><mml:mi mathvariant="normal">s</mml:mi></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row>
         <oasis:entry colname="col1"><inline-formula><mml:math id="M201" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-Pinene photooxidation</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M202" display="inline"><mml:mrow><mml:mn mathvariant="normal">6.7</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">10</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.94</oasis:entry>
         <oasis:entry colname="col4">0.3 to 0.65</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"><inline-formula><mml:math id="M203" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-Pinene ozonolysis</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M204" display="inline"><mml:mrow><mml:mn mathvariant="normal">1.5</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">10</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.64</oasis:entry>
         <oasis:entry colname="col4">0.22 to 0.55</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Limonene photooxidation</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M205" display="inline"><mml:mrow><mml:mn mathvariant="normal">9.1</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">10</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.97</oasis:entry>
         <oasis:entry colname="col4">NA</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Limonene ozonolysis</oasis:entry>
         <oasis:entry colname="col2"><inline-formula><mml:math id="M206" display="inline"><mml:mrow><mml:mn mathvariant="normal">1.7</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">10</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col3">0.67</oasis:entry>
         <oasis:entry colname="col4">0.23 to 0.5</oasis:entry>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table><table-wrap-foot><p id="d1e2767">NA: not available.</p></table-wrap-foot></table-wrap>

      <p id="d1e2984">Table 3 shows the simulated SOA mass-weighted average <inline-formula><mml:math id="M207" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>
ratios for <inline-formula><mml:math id="M208" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation (<inline-formula><mml:math id="M209" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M210" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.94), <inline-formula><mml:math id="M211" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis (<inline-formula><mml:math id="M212" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M213" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.64), limonene photooxidation
(<inline-formula><mml:math id="M214" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M215" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.97), and limonene ozonolysis (<inline-formula><mml:math id="M216" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M217" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 0.67). For <inline-formula><mml:math id="M218" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, the simulated SOA from photooxidation had higher average <inline-formula><mml:math id="M219" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> than
from ozonolysis. This is consistent with experiments by Kourtchev
et al. (2015) in which the reported <inline-formula><mml:math id="M220" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> for OH-initiated <inline-formula><mml:math id="M221" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
SOA was higher than for <inline-formula><mml:math id="M222" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene SOA initiated by ozonolysis. The same
trend was predicted for limonene. Generally, the simulated <inline-formula><mml:math id="M223" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values were
high relative to values reported from chamber studies. Reported average <inline-formula><mml:math id="M224" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula>
values from chamber studies range from 0.3 to 0.65 for <inline-formula><mml:math id="M225" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
photooxidation (e.g., Lambe et al., 2015; Pfaffenberger et al., 2013), 0.22 to
0.55 for <inline-formula><mml:math id="M226" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis (e.g., Chen et al., 2011; Chhabra et al.,
2010; Kourtchev et al., 2015), and 0.23 to 0.5 for limonene ozonolysis (e.g.,
Draper et al., 2015; Heaton et al., 2007; Walser et al., 2008). Factors known
to affect <inline-formula><mml:math id="M227" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratios include mass loading, OH exposure (defined as the
integral of OH concentration and residence time; Lambe et al., 2015), and
accretion product formation (Chhabra et al., 2010; Reinhardt et al., 2007).
Shilling et al. (2009) showed the dependency of <inline-formula><mml:math id="M228" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratios on mass loadings
for <inline-formula><mml:math id="M229" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, in which <inline-formula><mml:math id="M230" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratio decreased from 0.45 to 0.38 as mass
loading increased from 0.5 to 15 <inline-formula><mml:math id="M231" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>. Mass loading is not
likely driving the differences between simulations and observations here
since the simulated mass loadings were similar to the mass loadings of the
chamber experiments (e.g., Chhabra et al., 2011; Shilling et al., 2009) with
which the <inline-formula><mml:math id="M232" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> ratios were compared. Regarding OH exposure, calculated OH
exposures for the photooxidation simulations<?pagebreak page11475?> (Table 3) were within the
typically reported OH exposure ranges (<inline-formula><mml:math id="M233" display="inline"><mml:mrow><mml:mn mathvariant="normal">5.4</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">10</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula>–<inline-formula><mml:math id="M234" display="inline"><mml:mrow><mml:mn mathvariant="normal">4.0</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">11</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M235" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">molec</mml:mi><mml:mo>.</mml:mo><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup><mml:mspace width="0.125em" linebreak="nobreak"/><mml:mi mathvariant="normal">s</mml:mi></mml:mrow></mml:math></inline-formula>) from the chamber photooxidation
experiments (e.g., Lambe et al., 2015; Pfaffenberger et al., 2013). The lower
observed <inline-formula><mml:math id="M236" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> values may be partially explained by the loss of <inline-formula><mml:math id="M237" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">H</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mi mathvariant="normal">O</mml:mi></mml:mrow></mml:math></inline-formula>
in condensed-phase reactions (Claflin et al., 2018; Ziemann and Atkinson,
2012), which were likely occurring in the experiments (e.g., Bakker-Arkema and
Ziemann, 2020; Kenseth et al., 2018) but were not represented in the GECKO-A
simulations.</p>
</sec>
<sec id="Ch1.S3.SS1.SSS2">
  <label>3.1.2</label><?xmltex \opttitle{Major products simulated for $\alpha$-pinene and limonene}?><title>Major products simulated for <inline-formula><mml:math id="M238" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene</title>
      <p id="d1e3344">The results from the simulations using the lower hydrocarbon mixing ratio
(LHC) and higher hydrocarbon mixing ratio (HHC) were qualitatively similar.
Thus, here and in subsequent sections, only the results for the LHC
simulations are shown and discussed; the corresponding figures for the HHC
simulations are provided in the Supplement. Figure 5a and b show the chemical
structures and molecular formulae of the top 10 products by mass in the gas and particle phases at the end of the <inline-formula><mml:math id="M239" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation
simulation. The top 10 gas-phase products (dominated by carbonyl, carboxyl,
and nitrate functional groups) account for 46 % of the reacted <inline-formula><mml:math id="M240" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene carbon mass, with acetone being the top contributor. A total of 2 of the top 10 gas-phase products, pinonic acid (i.e.,
(3-acetyl-2,2-dimethylcyclobutyl)acetic acid) and pinonaldehyde (i.e.,
(3-acetyl-2,2-dimethylcyclobutyl)acetaldehyde), are among the most commonly
reported products in experimental studies (e.g., Lee et al., 2006b). The top
10 particle-phase products (dominated by carbonyl, carboxyl, hydroxyl,
hydroperoxide, and nitrate functional groups) account for 42 % of the SOA
mass and 7 % of the reacted <inline-formula><mml:math id="M241" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene carbon mass. For limonene
photooxidation (Figs. S10 and S11), the top 10 gas-phase
products account for 34 % of reacted limonene, while the top 10
particle-phase products account for 50 % of the SOA mass and 20 % of
the reacted limonene carbon mass. The top 10 particle-phase products are
dominated by dinitrate and carbonyl functional groups, indicating the possible
influence of multigenerational products from peroxy radicals <inline-formula><mml:math id="M242" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> NO reactions.</p>

      <?xmltex \floatpos{p}?><fig id="Ch1.F5" specific-use="star"><?xmltex \currentcnt{5}?><?xmltex \def\figurename{Figure}?><label>Figure 5</label><caption><p id="d1e3377"><bold>(a)</bold> Top 10 gas-phase products and <bold>(b)</bold> top 10
particle-phase products from <inline-formula><mml:math id="M243" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation at the
end of the low hydrocarbon (P_LHC) simulation.</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f05.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F6" specific-use="star"><?xmltex \currentcnt{6}?><?xmltex \def\figurename{Figure}?><label>Figure 6</label><caption><p id="d1e3401"><bold>(a)</bold> Top 10 gas-phase products and <bold>(b)</bold> top 10
particle-phase products from <inline-formula><mml:math id="M244" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene dark ozonolysis at
the end of the low hydrocarbon (DO_LHC) simulation.</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f06.png"/>

          </fig>

      <p id="d1e3422">The top 10 gas- and particle-phase products from the <inline-formula><mml:math id="M245" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
ozonolysis simulation are shown in Fig. 6a and b. The top 10 gas-phase
products account for 62 % of the reacted <inline-formula><mml:math id="M246" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene carbon mass,
while the top 10 particle-phase products account for 42 % of the SOA mass
and 6 % of the reacted <inline-formula><mml:math id="M247" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene carbon mass. A total of 3 of the top 10
products have been previously reported in experimental product studies of
<inline-formula><mml:math id="M248" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis (e.g., Jang and Kamens, 1999; Larsen et al., 2001;
Yu et al., 1999). They include one particle-phase product, pinic acid
(3-(carboxymethyl)-2,2-dimethylcyclobutane-1-carboxylic acid), and two
gas-phase products, pinonic acid (i.e.,
(3-acetyl-2,2-dimethylcyclobutyl)acetic acid) and pinonaldehyde (i.e.,
(3-acetyl-2,2-dimethylcyclobutyl)acetaldehyde). For limonene ozonolysis
(Figs. S12 and S13), the top 10 gas-phase products account
for 24 % of reacted limonene, while the top 10 particle-phase products
account for 37 % of the SOA mass and 27 % of the reacted limonene
carbon mass. The top 10 particle-phase products were dominated by carbonyl,
carboxyl, hydroxyl, and hydroperoxide, indicating the influence of
multi-generational products via peroxy radicals <inline-formula><mml:math id="M249" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M250" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>.</p>
</sec>
<sec id="Ch1.S3.SS1.SSS3">
  <label>3.1.3</label><title>Modeled SOA yield and carbon budget</title>
      <p id="d1e3487">Given the skill of the model in representing published chamber data at both
macroscopic and molecular levels, the model was used to explore the carbon
budget during photooxidation and ozonolysis simulations. The time evolution of
SOA yields for <inline-formula><mml:math id="M251" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene during photooxidation and
ozonolysis, as simulated by GECKO-A, is shown in Fig. 7a and b,
respectively. Also shown are the corresponding final SOA mass
concentrations. As has been previously reported (Lee et al., 2006b), limonene
had a higher SOA yield than <inline-formula><mml:math id="M252" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene under both photooxidation and
ozonolysis conditions.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F7" specific-use="star"><?xmltex \currentcnt{7}?><?xmltex \def\figurename{Figure}?><label>Figure 7</label><caption><p id="d1e3506">Simulated SOA yield <bold>(a, b)</bold> and carbon budget <bold>(c–f)</bold> as a function of time for <inline-formula><mml:math id="M253" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene during
photooxidation <bold>(a, c, e)</bold> and dark ozonolysis <bold>(b, d, f)</bold>. The SOA yield curve
for <inline-formula><mml:math id="M254" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene is represented by a blue line; limonene is
represented by a red line. For the carbon budget plots, the mixing ratios of
the precursor (black line), particle-phase organics (magenta line),
gas-phase organics (green line), and
<inline-formula><mml:math id="M255" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (blue line) are expressed as carbon
atom ratios (ppbC <inline-formula><mml:math id="M256" display="inline"><mml:mo>/</mml:mo></mml:math></inline-formula> initial precursor in ppbC; ppbC signifies parts per billion carbon). The results shown are for the
low hydrocarbon mixing ratio (50 <inline-formula><mml:math id="M257" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula>) simulations.</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f07.png"/>

          </fig>

      <?pagebreak page11477?><p id="d1e3572">The time evolution of the carbon budget during the photooxidation and
ozonolysis simulations is shown in Fig. 7c to f. During photooxidation
(Fig. 7c), the precursors were oxidized largely by OH and <inline-formula><mml:math id="M258" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (see
Fig. S7 for the relative fractions of precursor reacting
with each oxidant), forming organic oxidation products in the gas phase. These
gaseous oxidation products partitioned into the particle phase if their
volatility was low enough. Oxidation products that remained in the gas phase
reacted with OH, <inline-formula><mml:math id="M259" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and/or <inline-formula><mml:math id="M260" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> or were photolyzed if a
chromophore was present; these subsequent gas-phase reactions formed
additional oxidation products that partitioned to the particle phase or
continued to react in the gas phase. At the end of 12 <inline-formula><mml:math id="M261" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">h</mml:mi></mml:mrow></mml:math></inline-formula> of
photooxidation, the <inline-formula><mml:math id="M262" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene system was dominated by organic oxidation
products in the gas phase (70 %), with the remaining fractions being
organic oxidation products in the particle phase (8 %) and
<inline-formula><mml:math id="M263" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> (22 %). The high yield of gas-phase organics is largely
influenced by the high concentrations of acetone and volatile C8 to C10
species (see Fig. 5a for top gas-phase products and Fig. S9a for the gas- and particle-phase product distribution). As shown in the <inline-formula><mml:math id="M264" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M265" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> OH reaction scheme (Fig. 1) acetone is formed when the monocyclic
alkoxy radical decomposes via <inline-formula><mml:math id="M266" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> addition. For limonene
photooxidation (Fig. 7e), the concentration of acetone is lower than for
<inline-formula><mml:math id="M267" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and more of the C8 to C10 species are further oxidized and
partitioned into the particle phase (Fig. S9c). This resulted in a final
distribution of 50 % gas-phase organic products, 20 % particle-phase
organic products, and 30 % <inline-formula><mml:math id="M268" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. The simulated acetone yields
are qualitatively consistent with experimental data that have shown yields of
acetone from <inline-formula><mml:math id="M269" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation (Lee et al., 2006b; Wisthaler
et al., 2001) can be up to 4 orders of magnitude higher than from limonene
photooxidation (Lee et al., 2006b; Reissell et al., 1999).</p>
      <p id="d1e3695">For the <inline-formula><mml:math id="M270" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis system (Fig. 7d), at the end of the
simulation 88 % of the carbon is gas-phase organic products, 7 %
particle-phase organic products, and 5 % <inline-formula><mml:math id="M271" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. For limonene
ozonolysis (Fig. 7f), 50 % of the carbon fraction is gas-phase organics,
43 % particle-phase organics, and 7 % <inline-formula><mml:math id="M272" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">CO</mml:mi><mml:mo>+</mml:mo><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>. The higher
particle-phase fraction for limonene ozonolysis is a result of the C8 and C10
organic products of limonene being more highly functionalized and thus
partitioned to the particle phase (Figs. S9d and S13), whereas the C8 and C10
organic products of <inline-formula><mml:math id="M273" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene are<?pagebreak page11478?> more volatile and partitioned to the
gas phase (Figs. 6a and S9b).</p>
</sec>
</sec>
<sec id="Ch1.S3.SS2">
  <label>3.2</label><title>Controlled reactivity simulations</title>
      <p id="d1e3751">The GECKO-A simulations captured trends (e.g., SOA yields and major products)
observed in chamber studies (Sect. 3.1) for <inline-formula><mml:math id="M274" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, two
common terpene model surrogates. The GECKO-A model was then used to perform a
detailed study of SOA formation from camphene under idealized (“controlled
reactivity”) atmospheric conditions which were compared with analogous
simulations for <inline-formula><mml:math id="M275" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene.</p>
<sec id="Ch1.S3.SS2.SSS1">
  <label>3.2.1</label><title>Gas-phase chemistry</title>
      <p id="d1e3775">Time-dependent mixing ratios of <inline-formula><mml:math id="M276" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, OH, and <inline-formula><mml:math id="M277" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> are shown
in Fig. 8 for the controlled reactivity simulations performed at
0.1 <inline-formula><mml:math id="M278" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula> of HC<inline-formula><mml:math id="M279" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">o</mml:mi></mml:msub></mml:math></inline-formula> (camphene, <inline-formula><mml:math id="M280" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, or limonene)
and 10 <inline-formula><mml:math id="M281" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> of organic seed. The <inline-formula><mml:math id="M282" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and total
<inline-formula><mml:math id="M283" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> levels were fixed so that the oxidant (OH, <inline-formula><mml:math id="M284" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, and
<inline-formula><mml:math id="M285" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>) levels remained stable during the simulations. The reaction
rate of camphene with <inline-formula><mml:math id="M286" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> is extremely slow (2 and 3 orders of
magnitude lower than the rate constants for <inline-formula><mml:math id="M287" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M288" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M289" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> and limonene <inline-formula><mml:math id="M290" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> <inline-formula><mml:math id="M291" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, respectively; Atkinson and Arey, 2003a); thus, camphene predominately reacts with OH in
the simulations, while <inline-formula><mml:math id="M292" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene react with <inline-formula><mml:math id="M293" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>
and OH (see Fig. S30 for relative fractions). The time
profiles of <inline-formula><mml:math id="M294" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, OH, and <inline-formula><mml:math id="M295" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> were independent of the
precursor, confirming that the gas-phase oxidant levels were controlled by the
added ethane and formaldehyde. This allows for a comparative assessment of the
monoterpenes. The calculated lifetime of <inline-formula><mml:math id="M296" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> with <inline-formula><mml:math id="M297" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub><mml:mo>/</mml:mo><mml:mi mathvariant="normal">NO</mml:mi></mml:mrow></mml:math></inline-formula>
was <inline-formula><mml:math id="M298" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mn mathvariant="normal">60</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M299" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">s</mml:mi></mml:mrow></mml:math></inline-formula>, and thus it was assumed that these bimolecular
<inline-formula><mml:math id="M300" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> reactions would be dominant, and the absence of HOM formation
via <inline-formula><mml:math id="M301" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> autoxidation in GECKO-A did not significantly have an impact on the
results and conclusions derived from these simulations.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F8" specific-use="star"><?xmltex \currentcnt{8}?><?xmltex \def\figurename{Figure}?><label>Figure 8</label><caption><p id="d1e4053">Mixing ratios of <inline-formula><mml:math id="M302" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">HO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, OH, and
<inline-formula><mml:math id="M303" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> as a function of time for limonene (red line),
camphene (black line), and <inline-formula><mml:math id="M304" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (blue line) during the
controlled reactivity simulations with 0.1 <inline-formula><mml:math id="M305" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula> of HC<inline-formula><mml:math id="M306" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">o</mml:mi></mml:msub></mml:math></inline-formula> and 10 <inline-formula><mml:math id="M307" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> of organic seed. By design, the
profiles of the mixing ratios for each precursor overlap except for at the
very beginning of the <inline-formula><mml:math id="M308" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> profile.</p></caption>
            <?xmltex \igopts{width=426.791339pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f08.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F9" specific-use="star"><?xmltex \currentcnt{9}?><?xmltex \def\figurename{Figure}?><label>Figure 9</label><caption><p id="d1e4141"><bold>(a)</bold> Simulated SOA mass as a function of atmospheric aging
time (reaction with OH) and <bold>(b)</bold> simulated SOA yield as a function of reacted
hydrocarbon concentration (<inline-formula><mml:math id="M309" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>HC) during the controlled
reactivity simulation at 0.1 <inline-formula><mml:math id="M310" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula> HC<inline-formula><mml:math id="M311" display="inline"><mml:msub><mml:mi/><mml:mi mathvariant="normal">o</mml:mi></mml:msub></mml:math></inline-formula> with 10 <inline-formula><mml:math id="M312" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> seed for limonene (red line), camphene (black
line), and <inline-formula><mml:math id="M313" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (blue line).</p></caption>
            <?xmltex \igopts{width=341.433071pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f09.png"/>

          </fig>

</sec>
<sec id="Ch1.S3.SS2.SSS2">
  <label>3.2.2</label><title>Simulated SOA formation</title>
      <p id="d1e4214">Figure 9 illustrates the simulated SOA yields as a function of atmospheric
aging time (Fig. 9a) and the SOA yield as function of reacted HC concentration
(Fig. 9b) for the controlled reactivity simulations. The atmospheric aging
time, <inline-formula><mml:math id="M314" display="inline"><mml:mi mathvariant="italic">τ</mml:mi></mml:math></inline-formula> is defined as
              <disp-formula id="Ch1.E1" content-type="numbered"><label>1</label><mml:math id="M315" display="block"><mml:mrow><mml:mi mathvariant="italic">τ</mml:mi><mml:mo>=</mml:mo><mml:mstyle displaystyle="true"><mml:mfrac style="display"><mml:mn mathvariant="normal">1</mml:mn><mml:mrow class="chem"><mml:mo>[</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mi mathvariant="normal">atm</mml:mi></mml:msub></mml:mrow></mml:mfrac></mml:mstyle><mml:msubsup><mml:mo>∫</mml:mo><mml:mn mathvariant="normal">0</mml:mn><mml:mi>t</mml:mi></mml:msubsup><mml:mrow class="chem"><mml:mo>[</mml:mo><mml:mi mathvariant="normal">OH</mml:mi><mml:msub><mml:mo>]</mml:mo><mml:mi mathvariant="normal">sim</mml:mi></mml:msub></mml:mrow><mml:mi mathvariant="normal">d</mml:mi><mml:mi>t</mml:mi><mml:mo>,</mml:mo></mml:mrow></mml:math></disp-formula>
            where [OH]<inline-formula><mml:math id="M316" display="inline"><mml:msub><mml:mi/><mml:mtext>atm</mml:mtext></mml:msub></mml:math></inline-formula> is the atmospheric OH concentration (<inline-formula><mml:math id="M317" display="inline"><mml:mrow><mml:mn mathvariant="normal">2</mml:mn><mml:mo>×</mml:mo><mml:msup><mml:mn mathvariant="normal">10</mml:mn><mml:mn mathvariant="normal">6</mml:mn></mml:msup></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M318" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">molec</mml:mi><mml:mo>.</mml:mo><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">cm</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> was assumed), and [OH]<inline-formula><mml:math id="M319" display="inline"><mml:msub><mml:mi/><mml:mtext>sim</mml:mtext></mml:msub></mml:math></inline-formula> is the
simulated OH concentration. Camphene was predicted to form more SOA
(0.26 <inline-formula><mml:math id="M320" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) than <inline-formula><mml:math id="M321" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
(0.14 <inline-formula><mml:math id="M322" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) but less than limonene
(0.42 <inline-formula><mml:math id="M323" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>) after 14.5 <inline-formula><mml:math id="M324" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">h</mml:mi></mml:mrow></mml:math></inline-formula> of aging time (Fig. 9a).
The simulation results in Fig. 9b show that<?pagebreak page11479?> camphene, which reacts
predominantly with OH (Fig. S30), forms low-volatility products (more SOA at
lower <inline-formula><mml:math id="M325" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>HC) at the start of the reaction than <inline-formula><mml:math id="M326" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and
limonene. However, after the precursor is completely consumed, the SOA yield
of limonene exceeds that of camphene. The shorter lifetime and chemical
structure, including the presence of two double bonds, contribute to the
relatively high SOA yield of limonene. As previously reported (Lee et al.,
2006b), and as simulated herein, limonene had the highest SOA yield among well-studied monoterpenes. However, the final SOA yield of camphene was relatively
high, approximately twice that of <inline-formula><mml:math id="M327" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene.</p>
</sec>
<sec id="Ch1.S3.SS2.SSS3">
  <label>3.2.3</label><title>Gas- and particle-phase product distribution</title>
      <p id="d1e4426">Figure 10 shows the product distribution in the gas and particle phases after
72 <inline-formula><mml:math id="M328" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">h</mml:mi></mml:mrow></mml:math></inline-formula> (equivalent to 14.5 <inline-formula><mml:math id="M329" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">h</mml:mi></mml:mrow></mml:math></inline-formula> of atmospheric OH aging time) for
the controlled reactivity simulations. While thousands of secondary species
are formed during the oxidation of a given monoterpene, only species that
contribute <inline-formula><mml:math id="M330" display="inline"><mml:mrow><mml:mo>≥</mml:mo><mml:mn mathvariant="normal">0.01</mml:mn></mml:mrow></mml:math></inline-formula> % of the total gas- or particle-phase mass were
included in Fig. 10. Also, all C1 species, as well as seven of the C2
gas-phase products (whose concentrations were largely a direct result of
ethane chemistry) were omitted from Fig. 10. For camphene (Fig. 10a), the
particle phase is largely dominated by C10 species with three to five functional
groups, followed by highly functionalized C7 species (typically with four to five
functional groups). Similarly, for limonene (Fig. 10b), the particle phase is
dominated by C10 species with four to five functional groups, followed by C7 to C9
species with four to five functional groups. However, for <inline-formula><mml:math id="M331" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
(Fig. 10c), there is a broad distribution of C8 to C10 products (with three to four functional groups) contributing to the particle phase. Generally, the
volatility of particle-phase products from camphene and limonene was lower
than from <inline-formula><mml:math id="M332" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene. As shown in Fig. 10a, a large fraction of
gas-phase products from camphene, as compared to limonene, is composed of C9
and C10 products whose volatility was not low enough to partition to the
particle phase. This further explains the SOA yields shown in Fig. 9b, in which
limonene SOA yield exceeded camphene SOA yield at the end of the simulation.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F10" specific-use="star"><?xmltex \currentcnt{10}?><?xmltex \def\figurename{Figure}?><label>Figure 10</label><caption><p id="d1e4471">Number of functional groups associated with gas- and
particle-phase species as a function of carbon number. Results are shown for
camphene, <inline-formula><mml:math id="M333" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, and limonene after 72 <inline-formula><mml:math id="M334" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">h</mml:mi></mml:mrow></mml:math></inline-formula> of
oxidation under controlled reactivity conditions. The markers are sized by
the ratio of their mixing ratio (in ppbC) to the initial mixing ratio of the
precursor (in ppbC). The colors of the markers are scaled by volatility
(represented by saturation concentration, <inline-formula><mml:math id="M335" display="inline"><mml:mrow><mml:msup><mml:mi>C</mml:mi><mml:mo>*</mml:mo></mml:msup></mml:mrow></mml:math></inline-formula>). </p></caption>
            <?xmltex \igopts{width=426.791339pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f10.png"/>

          </fig>

      <?xmltex \floatpos{t}?><fig id="Ch1.F11"><?xmltex \currentcnt{11}?><?xmltex \def\figurename{Figure}?><label>Figure 11</label><caption><p id="d1e4508">Mass percentage of four volatility categories in the
particle phase at the end of the controlled reactivity simulations for
<inline-formula><mml:math id="M336" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, camphene, and limonene.</p></caption>
            <?xmltex \igopts{width=179.252362pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f11.png"/>

          </fig>

      <?pagebreak page11481?><p id="d1e4525">Figure 11 shows the final mass percentages of <inline-formula><mml:math id="M337" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene, camphene, and
limonene particle-phase oxidation products grouped into three volatility
categories. The volatility categories were assigned based on the calculated
mass saturation concentrations (<inline-formula><mml:math id="M338" display="inline"><mml:mrow><mml:msup><mml:mi>C</mml:mi><mml:mo>*</mml:mo></mml:msup></mml:mrow></mml:math></inline-formula>) of the simulated products. <inline-formula><mml:math id="M339" display="inline"><mml:mrow><mml:msup><mml:mi>C</mml:mi><mml:mo>*</mml:mo></mml:msup></mml:mrow></mml:math></inline-formula> was
calculated based on the equilibrium absorption coefficient equation, as
defined by Odum et al. (1996) and Pankow (1994). Log <inline-formula><mml:math id="M340" display="inline"><mml:mrow><mml:msup><mml:mi>C</mml:mi><mml:mo>*</mml:mo></mml:msup></mml:mrow></mml:math></inline-formula> values in the
range of <inline-formula><mml:math id="M341" display="inline"><mml:mrow><mml:mo>&lt;</mml:mo><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3.5</mml:mn></mml:mrow></mml:math></inline-formula>, <inline-formula><mml:math id="M342" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>3.5 to <inline-formula><mml:math id="M343" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.5, and <inline-formula><mml:math id="M344" display="inline"><mml:mo>-</mml:mo></mml:math></inline-formula>0.5 to 2.5 were assigned
respectively as extremely low-volatility, low-volatility, and semi-volatile
organic compounds (ELVOCs, LVOCs, and SVOCs) (Chuang and Donahue, 2016; Zhang
et al., 2015). Limonene, which had the highest simulated SOA yield among the
three studied monoterpenes, was largely LVOCs (59 %), followed by ELVOCs
(24 %) and then SVOCs (17 %). Camphene SOA was also largely LVOCs
(67 %), followed by SVOCs (28 %) and then a significantly lower
fraction of ELVOCs (4 %) than limonene. In contrast, <inline-formula><mml:math id="M345" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene SOA
was dominated by SVOCs (50 %), followed by LVOCs (48 %) and then
ELVOCs (2 %). For experimental studies of <inline-formula><mml:math id="M346" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis,
Zhang et al. (2015) reported a fractional contribution of <inline-formula><mml:math id="M347" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">68</mml:mn></mml:mrow></mml:math></inline-formula> %
SVOCs to final SOA mass, which is similar to the contribution predicted using
GECKO-A. For <inline-formula><mml:math id="M348" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and camphene, intermediate-volatility organic
compounds (IVOCs) were less than 1 % of the SOA mass. Product volatility
distributions can be influenced by gas-phase <inline-formula><mml:math id="M349" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> autoxidation and
condensed-phase reactions, which were not considered here.  While HOM
formation likely played a minor role in these controlled reactivity
simulations, the monomer building blocks of known accretion reactions were
predicted for all monoterpenes studied. Thus, it is expected that accretion
product formation could occur under these conditions, leading to changes in
the simulated volatility distributions.</p>
</sec>
<sec id="Ch1.S3.SS2.SSS4">
  <label>3.2.4</label><?xmltex \opttitle{Using $\alpha$-pinene limonene as a surrogate for camphene}?><title>Using <inline-formula><mml:math id="M350" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene limonene as a surrogate for camphene</title>
      <p id="d1e4662">For the controlled reactivity simulations, the final SOA mass and yield of
camphene (0.26 <inline-formula><mml:math id="M351" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, 0.46) were between the final SOA mass
and yield of <inline-formula><mml:math id="M352" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (0.14 <inline-formula><mml:math id="M353" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, 0.25) and limonene
(0.42 <inline-formula><mml:math id="M354" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>, 0.74). This suggests that camphene could
potentially be represented in models as a <inline-formula><mml:math id="M355" display="inline"><mml:mrow><mml:mn mathvariant="normal">50</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> mixture of <inline-formula><mml:math id="M356" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M357" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> limonene, for which SOA parameterizations currently are available (Griffin
et al., 1999; Pathak et al., 2007a; Zhang et al., 2006). To test this, a
controlled reactivity simulation was run with 50 <inline-formula><mml:math id="M358" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppt</mml:mi></mml:mrow></mml:math></inline-formula> (parts per thousand) <inline-formula><mml:math id="M359" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M360" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 <inline-formula><mml:math id="M361" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppt</mml:mi></mml:mrow></mml:math></inline-formula> limonene; simulation results were then compared with the
simulation results for 0.1 <inline-formula><mml:math id="M362" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula> of camphene. Figure 12a shows that
while the slopes of the SOA yield curves differ over the course of the
reaction, the SOA masses (0.26 <inline-formula><mml:math id="M363" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for 50 % <inline-formula><mml:math id="M364" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M365" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene and 0.26 <inline-formula><mml:math id="M366" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> for camphene)
and yields (0.46 for 50 % <inline-formula><mml:math id="M367" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M368" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene and 0.47
for camphene) were approximately equal at the end of the simulation. However,
the end of simulation particle-phase volatility distributions (Fig. 12b) are
notably different. The 50 % <inline-formula><mml:math id="M369" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M370" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene
simulation had a significantly higher fraction (25 %) of ELVOCs,
influenced by the low-volatility limonene products, than the camphene
simulation (4 %). These results suggest that while the final SOA mass and
yield of the <inline-formula><mml:math id="M371" display="inline"><mml:mrow><mml:mn mathvariant="normal">50</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M372" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M373" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> limonene mixture were representative
of camphene, the properties (e.g., volatility) of the particle-phase products
were not. The volatility distributions will influence the formation of SOA at
the lowest mass loadings and will also influence changes in SOA mass as a
function of dilution, with the surrogate mixture (50 % <inline-formula><mml:math id="M374" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M375" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene) producing less volatile SOA than predicted for
camphene. Thus, the extent to which camphene can be represented by <inline-formula><mml:math id="M376" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M377" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> limonene will depend on the application. To improve the
representation of camphene, a second simulation was run with 50 <inline-formula><mml:math id="M378" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppt</mml:mi></mml:mrow></mml:math></inline-formula>
<inline-formula><mml:math id="M379" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M380" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 <inline-formula><mml:math id="M381" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppt</mml:mi></mml:mrow></mml:math></inline-formula> limonene, in which the rate constants of
<inline-formula><mml:math id="M382" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene were replaced with the rate constants of
camphene during the chemical mechanism generation. However, the representation
of camphene SOA by the <inline-formula><mml:math id="M383" display="inline"><mml:mrow><mml:mn mathvariant="normal">50</mml:mn><mml:mo>/</mml:mo><mml:mn mathvariant="normal">50</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M384" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M385" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> limonene mixture did not
improve (resulted in higher final SOA yield of 0.51) when the rate constants
of <inline-formula><mml:math id="M386" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene were replaced with those of camphene
(Fig. 12a). Also, representing camphene by the limonene mechanism with
camphene rate constants did not improve the representation of camphene SOA
(see Fig. S33). This illustrates the importance of both the
reaction rate constants and structure on SOA formation from monoterpenes.</p>

      <?xmltex \floatpos{t}?><fig id="Ch1.F12" specific-use="star"><?xmltex \currentcnt{12}?><?xmltex \def\figurename{Figure}?><label>Figure 12</label><caption><p id="d1e5005"><bold>(a)</bold> Simulated SOA yield as a function of atmospheric
aging time for camphene (black line), 50 % <inline-formula><mml:math id="M387" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M388" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 %
limonene (magenta line), and 50 % <inline-formula><mml:math id="M389" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M390" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene
in which the rate constants of <inline-formula><mml:math id="M391" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene were replaced with the rate constants
of camphene (green line); and <bold>(b)</bold> mass percentage of four volatility
categories in the particle phase at the end of the controlled reactivity
simulations for camphene, 50 % <inline-formula><mml:math id="M392" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M393" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene, and limonene, and 50 % <inline-formula><mml:math id="M394" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M395" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene in which the rate constants of <inline-formula><mml:math id="M396" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene were replaced with the rate constants of
camphene.</p></caption>
            <?xmltex \igopts{width=497.923228pt}?><graphic xlink:href="https://acp.copernicus.org/articles/21/11467/2021/acp-21-11467-2021-f12.png"/>

          </fig>

<?xmltex \floatpos{t}?><table-wrap id="Ch1.T4" specific-use="star"><?xmltex \currentcnt{4}?><label>Table 4</label><caption><p id="d1e5094">SOA yield and mass predicted using two-product and VBS
parameters for the top five monoterpenes by emission factor (EF) from black
spruce, Douglas fir, and lodgepole pine. For each fire fuel, the
monoterpenes were represented using two different surrogate assignments. In
Assignment 1, <inline-formula><mml:math id="M397" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene is used to represent all
monoterpenes except limonene. In Assignment 2, camphene is represented as 50 % <inline-formula><mml:math id="M398" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M399" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene. There is no Assignment
2 for lodgepole pine because camphene is not one of the top five
monoterpenes by EF. The percentage (%) increase in SOA was calculated
based on the difference between the total SOA of assignments 1 and 2. The
EFs of assignments 1 and 2, the two-product SOA parameters, and the VBS
parameters are provided in Tables S2–S4, respectively.</p></caption><oasis:table frame="topbot"><oasis:tgroup cols="8">
     <oasis:colspec colnum="1" colname="col1" align="left"/>
     <oasis:colspec colnum="2" colname="col2" align="left"/>
     <oasis:colspec colnum="3" colname="col3" align="center"/>
     <oasis:colspec colnum="4" colname="col4" align="right"/>
     <oasis:colspec colnum="5" colname="col5" align="right"/>
     <oasis:colspec colnum="6" colname="col6" align="right"/>
     <oasis:colspec colnum="7" colname="col7" align="right"/>
     <oasis:colspec colnum="8" colname="col8" align="right"/>
     <oasis:thead>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3">Yield<inline-formula><mml:math id="M400" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mtext>pin</mml:mtext></mml:mrow></mml:msub></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col4">Yield<inline-formula><mml:math id="M401" display="inline"><mml:msub><mml:mi/><mml:mtext>lim</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col5">SOA<inline-formula><mml:math id="M402" display="inline"><mml:msub><mml:mi/><mml:mrow><mml:mi mathvariant="italic">α</mml:mi><mml:mtext>pin</mml:mtext></mml:mrow></mml:msub></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col6">SOA<inline-formula><mml:math id="M403" display="inline"><mml:msub><mml:mi/><mml:mtext>lim</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col7">SOA<inline-formula><mml:math id="M404" display="inline"><mml:msub><mml:mi/><mml:mtext>total</mml:mtext></mml:msub></mml:math></inline-formula></oasis:entry>
         <oasis:entry colname="col8">% increase</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2"/>
         <oasis:entry colname="col3"/>
         <oasis:entry colname="col4"/>
         <oasis:entry colname="col5">(<inline-formula><mml:math id="M405" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col6">(<inline-formula><mml:math id="M406" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col7">(<inline-formula><mml:math id="M407" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace width="0.125em" linebreak="nobreak"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula>)</oasis:entry>
         <oasis:entry colname="col8">in SOA</oasis:entry>
       </oasis:row>
     </oasis:thead>
     <oasis:tbody>
       <oasis:row rowsep="1">
         <oasis:entry namest="col1" nameend="col8">Black Spruce </oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Two-product</oasis:entry>
         <oasis:entry colname="col2">Assignment 1</oasis:entry>
         <oasis:entry colname="col3">0.099</oasis:entry>
         <oasis:entry colname="col4">0.6</oasis:entry>
         <oasis:entry colname="col5">4.5</oasis:entry>
         <oasis:entry colname="col6">6.4</oasis:entry>
         <oasis:entry colname="col7">10.9</oasis:entry>
         <oasis:entry colname="col8">50 %</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry rowsep="1" colname="col2">Assignment 2</oasis:entry>
         <oasis:entry rowsep="1" colname="col3">0.103</oasis:entry>
         <oasis:entry rowsep="1" colname="col4">0.6</oasis:entry>
         <oasis:entry rowsep="1" colname="col5">3.6</oasis:entry>
         <oasis:entry rowsep="1" colname="col6">12.8</oasis:entry>
         <oasis:entry rowsep="1" colname="col7">16.4</oasis:entry>
         <oasis:entry rowsep="1" colname="col8"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">VBS</oasis:entry>
         <oasis:entry colname="col2">Assignment 1</oasis:entry>
         <oasis:entry colname="col3">0.194</oasis:entry>
         <oasis:entry colname="col4">0.93</oasis:entry>
         <oasis:entry colname="col5">8.8</oasis:entry>
         <oasis:entry colname="col6">9.9</oasis:entry>
         <oasis:entry colname="col7">18.7</oasis:entry>
         <oasis:entry colname="col8">43 %</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Assignment 2</oasis:entry>
         <oasis:entry colname="col3">0.202</oasis:entry>
         <oasis:entry colname="col4">0.93</oasis:entry>
         <oasis:entry colname="col5">7</oasis:entry>
         <oasis:entry colname="col6">19.7</oasis:entry>
         <oasis:entry colname="col7">26.7</oasis:entry>
         <oasis:entry colname="col8"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry namest="col1" nameend="col8">Douglas fir </oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Two-product</oasis:entry>
         <oasis:entry colname="col2">Assignment 1</oasis:entry>
         <oasis:entry colname="col3">0.098</oasis:entry>
         <oasis:entry colname="col4">0.6</oasis:entry>
         <oasis:entry colname="col5">4.5</oasis:entry>
         <oasis:entry colname="col6">6.1</oasis:entry>
         <oasis:entry colname="col7">10.6</oasis:entry>
         <oasis:entry colname="col8">108 %</oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1"/>
         <oasis:entry rowsep="1" colname="col2">Assignment 2</oasis:entry>
         <oasis:entry rowsep="1" colname="col3">0.108</oasis:entry>
         <oasis:entry rowsep="1" colname="col4">0.6</oasis:entry>
         <oasis:entry rowsep="1" colname="col5">2.5</oasis:entry>
         <oasis:entry rowsep="1" colname="col6">19.6</oasis:entry>
         <oasis:entry rowsep="1" colname="col7">22.1</oasis:entry>
         <oasis:entry rowsep="1" colname="col8"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">VBS</oasis:entry>
         <oasis:entry colname="col2">Assignment 1</oasis:entry>
         <oasis:entry colname="col3">0.194</oasis:entry>
         <oasis:entry colname="col4">0.93</oasis:entry>
         <oasis:entry colname="col5">8.9</oasis:entry>
         <oasis:entry colname="col6">9.4</oasis:entry>
         <oasis:entry colname="col7">18.3</oasis:entry>
         <oasis:entry colname="col8">56 %</oasis:entry>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry colname="col1"/>
         <oasis:entry colname="col2">Assignment 2</oasis:entry>
         <oasis:entry colname="col3">0.203</oasis:entry>
         <oasis:entry colname="col4">0.93</oasis:entry>
         <oasis:entry colname="col5">6.6</oasis:entry>
         <oasis:entry colname="col6">21.9</oasis:entry>
         <oasis:entry colname="col7">28.5</oasis:entry>
         <oasis:entry colname="col8"/>
       </oasis:row>
       <oasis:row rowsep="1">
         <oasis:entry namest="col1" nameend="col8">Lodgepole pine </oasis:entry>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">Two-product</oasis:entry>
         <oasis:entry rowsep="1" colname="col2">Assignment 1</oasis:entry>
         <oasis:entry rowsep="1" colname="col3">0.097</oasis:entry>
         <oasis:entry rowsep="1" colname="col4">0.6</oasis:entry>
         <oasis:entry rowsep="1" colname="col5">4.7</oasis:entry>
         <oasis:entry rowsep="1" colname="col6">4.6</oasis:entry>
         <oasis:entry rowsep="1" colname="col7">9.3</oasis:entry>
         <oasis:entry rowsep="1" colname="col8"/>
       </oasis:row>
       <oasis:row>
         <oasis:entry colname="col1">VBS</oasis:entry>
         <oasis:entry colname="col2">Assignment 1</oasis:entry>
         <oasis:entry colname="col3">0.192</oasis:entry>
         <oasis:entry colname="col4">0.93</oasis:entry>
         <oasis:entry colname="col5">9.3</oasis:entry>
         <oasis:entry colname="col6">7.1</oasis:entry>
         <oasis:entry colname="col7">16.4</oasis:entry>
         <oasis:entry colname="col8"/>
       </oasis:row>
     </oasis:tbody>
   </oasis:tgroup></oasis:table></table-wrap>

      <p id="d1e5589">To demonstrate the potential impact of including a parameterized
representation of SOA formation by camphene in air quality models, SOA mass
and yields were predicted for three wildland fire fuels based on the measured
monoterpene distributions in Hatch et al. (2015) for black spruce, and Hatch
et al. (2019) for Douglas fir and lodgepole pine. The top five monoterpenes by
emissions factor (mass of compound emitted per mass of fuel burned) represent <inline-formula><mml:math id="M408" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">70</mml:mn></mml:mrow></mml:math></inline-formula> %–80 % of the total monoterpene emission factor (EF) for each of
these fuels. These top five monoterpenes were used to represent SOA formation
from monoterpenes for each fuel by normalizing the monoterpene EF for each
fuel, assigning <inline-formula><mml:math id="M409" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene as the model surrogate for all measured
compounds except limonene, including camphene, and then reassigning camphene
as 50 % <inline-formula><mml:math id="M410" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M411" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene. SOA mass concentrations
and yields were predicted assuming a background PM level of
50 <inline-formula><mml:math id="M412" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">µ</mml:mi><mml:mi mathvariant="normal">g</mml:mi><mml:mspace linebreak="nobreak" width="0.125em"/><mml:msup><mml:mi mathvariant="normal">m</mml:mi><mml:mrow><mml:mo>-</mml:mo><mml:mn mathvariant="normal">3</mml:mn></mml:mrow></mml:msup></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M413" display="inline"><mml:mi mathvariant="normal">Δ</mml:mi></mml:math></inline-formula>HC <inline-formula><mml:math id="M414" display="inline"><mml:mo>=</mml:mo></mml:math></inline-formula> 10 <inline-formula><mml:math id="M415" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">ppb</mml:mi></mml:mrow></mml:math></inline-formula> and using
published two-product SOA parameters based on Griffin et al. (1999) (Table S3) and volatility basis set (VBS) parameters (low <inline-formula><mml:math id="M416" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>,
dry) based on Pathak et al. (2007b) (for <inline-formula><mml:math id="M417" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene) and Zhang
et al. (2006) (for limonene) (Table S4). The two model
parameterizations were used to represent a range of potential outcomes. The
SOA yields using the two-product parameters were lower than predicted here for
<inline-formula><mml:math id="M418" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (<inline-formula><mml:math id="M419" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">0.1</mml:mn></mml:mrow></mml:math></inline-formula>) but similar for camphene (<inline-formula><mml:math id="M420" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">0.6</mml:mn></mml:mrow></mml:math></inline-formula>); using
the VBS parameters, the yields were similar for <inline-formula><mml:math id="M421" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (<inline-formula><mml:math id="M422" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">0.2</mml:mn></mml:mrow></mml:math></inline-formula>)
but higher than predicted here for camphene (<inline-formula><mml:math id="M423" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">0.9</mml:mn></mml:mrow></mml:math></inline-formula>). The total OA mass
loadings in the parameterized SOA calculations were a factor of 3–6 higher
than in the GECKO-A controlled<?pagebreak page11482?> reactivity simulations, which is consistent
with the higher SOA yield for camphene predicted using the VBS parameters. The
results of the SOA calculations are summarized in Table 4. For lodgepole pine,
there is no change in SOA mass because camphene is not one of the top five
monoterpenes by EF. However, for fuels in which camphene contributed
significantly to the measured monoterpene EF, SOA mass increased by
43 %–50 % for black spruce and by 56 %–108 % for Douglas
fir.</p>
</sec>
</sec>
</sec>
<?pagebreak page11483?><sec id="Ch1.S4" sec-type="conclusions">
  <label>4</label><title>Conclusions</title>
      <p id="d1e5749">While camphene is a ubiquitous monoterpene measured in significant quantities
from both biogenic and pyrogenic sources, little is known about SOA formation
from camphene, and there are no published parameterizations to represent
camphene SOA in air quality models. GECKO-A simulations suggest that the
initial organic oxidation products of camphene are of low volatility and can
condense at low OA mass loadings – lower than oxidation products predicted for
<inline-formula><mml:math id="M424" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene. Predicted final SOA yields for camphene in the
controlled reactivity simulations (<inline-formula><mml:math id="M425" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">45</mml:mn></mml:mrow></mml:math></inline-formula> %) were in between those
predicted for <inline-formula><mml:math id="M426" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene (25 %) and limonene (<inline-formula><mml:math id="M427" display="inline"><mml:mrow><mml:mo>∼</mml:mo><mml:mn mathvariant="normal">75</mml:mn></mml:mrow></mml:math></inline-formula> %),
suggesting that SOA formation from camphene can be represented in air quality
models assuming a 50 % <inline-formula><mml:math id="M428" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M429" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> 50 % limonene surrogate mixture. The
predicted SOA yields do not account for condensed-phase accretion reactions,
which could occur under the simulation conditions. Calculations based on
measured monoterpene distributions for three wildland fire fuels illustrate
that accounting for camphene, in this case using the surrogate mixture and
published SOA parameterizations for <inline-formula><mml:math id="M430" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, increased
predicted SOA mass from monoterpenes by 43 %–108 %. This demonstrates
the potential impact of representing SOA formation from camphene in air
quality models and the need for an appropriate parameterization. The
surrogate mixture appears to represent the SOA mass and yield of camphene
well but not necessarily the volatility distribution of the products. The SOA
mass, yields, and product volatility distributions can be influenced by
gas-phase HOM formation and subsequent dimerization, as well as condensed-phase accretion reactions, which were not considered here. Further modeling and/or experimental studies are needed to develop and test a suitable parameterization for representing camphene SOA formation in air quality models; this includes robust assessments of changes in SOA composition and yields associated with gas-phase HOM formation via <inline-formula><mml:math id="M431" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">RO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> autoxidation and condensed-phase accretion reactions under a range of atmospherically relevant conditions.</p>
</sec>

      
      </body>
    <back><notes notes-type="codeavailability"><title>Code availability</title>

      <p id="d1e5823">The GECKO-A codes are not publicly accessible since the developers of the GECKO-A model want to completely evaluate the model prior to its release to the public. Please contact authors Bernard Aumont and Marie Camredon for questions regarding the GECKO-A model codes.</p>
  </notes><notes notes-type="dataavailability"><title>Data availability</title>

      <p id="d1e5829">The GECKO-A simulation dataset is available on Zenodo: <ext-link xlink:href="https://doi.org/10.5281/zenodo.5059693" ext-link-type="DOI">10.5281/zenodo.5059693</ext-link> (Afreh et al., 2021). Please contact authors Isaac Kwadjo Afreh and Kelley Claire Barsanti for questions regarding the GECKO-A simulation data.</p>
  </notes><?xmltex \hack{\newpage}?><app-group>
        <supplementary-material position="anchor"><p id="d1e5836">The supplement related to this article is available online at: <inline-supplementary-material xlink:href="https://doi.org/10.5194/acp-21-11467-2021-supplement" xlink:title="pdf">https://doi.org/10.5194/acp-21-11467-2021-supplement</inline-supplementary-material>.</p></supplementary-material>
        </app-group><notes notes-type="authorcontribution"><title>Author contributions</title>

      <p id="d1e5845">IKA performed the model simulations and led analysis and visualization efforts. KCB conceptualized, administered, and supervised the project. BA and MC developed the software and methodology, including the model, and supported the research design and interpretation of the results. IKA prepared the manuscript with review and editing contributions from KCB, BA, and MC.</p>
  </notes><notes notes-type="competinginterests"><title>Competing interests</title>

      <p id="d1e5851">The authors declare that they have no conflict of interest.</p>
  </notes><notes notes-type="disclaimer"><title>Disclaimer</title>

      <p id="d1e5857">Publisher’s note: Copernicus Publications remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.</p>
  </notes><ack><title>Acknowledgements</title><p id="d1e5863">The authors would like to thank Richard Valorso for the training given in
the use of GECKO-A modeling tools. Isaac Kwadjo Afreh and Kelley Claire Barsanti acknowledge support from the National Oceanic and Atmospheric Administration (NOAA) and the National Science Foundation (NSF).</p></ack><notes notes-type="financialsupport"><title>Financial support</title>

      <p id="d1e5868">This research has been supported by the National Oceanic and Atmospheric Administration (grant no. AC4 NA16OAR4310103) and the National Science Foundation (NSF) (grant no. AGS-1753364).</p>
  </notes><notes notes-type="reviewstatement"><title>Review statement</title>

      <p id="d1e5875">This paper was edited by Delphine Farmer and reviewed by three anonymous referees.</p>
  </notes><ref-list>
    <title>References</title>

      <ref id="bib1.bib1"><label>1</label><?label 1?><mixed-citation>Afreh, I. K., Barsanti, K. C., Bernard, A., and Camredon, M.: Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene, Zenodo [data set], <ext-link xlink:href="https://doi.org/10.5281/zenodo.5059693" ext-link-type="DOI">10.5281/zenodo.5059693</ext-link>, 2021.</mixed-citation></ref>
      <ref id="bib1.bib2"><label>2</label><?label 1?><mixed-citation>Akagi, S. K., Yokelson, R. J., Wiedinmyer, C., Alvarado, M. J., Reid, J. S., Karl, T., Crounse, J. D., and Wennberg, P. O.: Emission factors for open and domestic biomass burning for use in atmospheric models, Atmos. Chem. Phys., 11, 4039–4072,  <ext-link xlink:href="https://doi.org/10.5194/acp-11-4039-2011" ext-link-type="DOI">10.5194/acp-11-4039-2011</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib3"><label>3</label><?label 2?><mixed-citation>Akagi, S. K., Yokelson, R. J., Burling, I. R., Meinardi, S., Simpson, I., Blake, D. R., McMeeking, G. R., Sullivan, A., Lee, T., Kreidenweis, S., Urbanski, S., Reardon, J., Griffith, D. W. T., Johnson, T. J., and Weise, D. R.: Measurements of reactive trace gases and variable <inline-formula><mml:math id="M432" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> formation rates in some South Carolina biomass burning plumes, Atmos. Chem. Phys., 13, 1141–1165,  <ext-link xlink:href="https://doi.org/10.5194/acp-13-1141-2013" ext-link-type="DOI">10.5194/acp-13-1141-2013</ext-link>, 2013.</mixed-citation></ref>
      <?pagebreak page11484?><ref id="bib1.bib4"><label>4</label><?label 3?><mixed-citation>Almatarneh, M. H., Elayan, I. A., Poirier, R. A., and Altarawneh, M.: The ozonolysis of cyclic monoterpenes: A computational review, Can. J. Chem., 96, 281–292,  <ext-link xlink:href="https://doi.org/10.1139/cjc-2017-0587" ext-link-type="DOI">10.1139/cjc-2017-0587</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib5"><label>5</label><?label 4?><mixed-citation>Ambrose, J. L., Haase, K., Russo, R. S., Zhou, Y., White, M. L.,
Frinak, E. K., Jordan, C., Mayne, H. R., Talbot, R., and Sive, B. C.: A
comparison of GC-FID and PTR-MS toluene measurements in ambient air under
conditions of enhanced monoterpene loading, Atmos. Meas. Tech., 3, 959–980, <ext-link xlink:href="https://doi.org/10.5194/amt-3-959-2010" ext-link-type="DOI">10.5194/amt-3-959-2010</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib6"><label>6</label><?label 5?><mixed-citation>Amin, H. S., Hatfield, M. L., and Huff Hartz, K. E.: Characterization of secondary organic aerosol generated from ozonolysis of <inline-formula><mml:math id="M433" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene mixtures, Atmos. Environ., 67, 323–330,  <ext-link xlink:href="https://doi.org/10.1016/j.atmosenv.2012.10.063" ext-link-type="DOI">10.1016/j.atmosenv.2012.10.063</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib7"><label>7</label><?label 6?><mixed-citation>Atkinson, R. and Arey, J.: Atmospheric chemistry of biogenic Organic Compounds, Accounts Chem. Res., 31, 574–583,  <ext-link xlink:href="https://doi.org/10.1021/ar970143z" ext-link-type="DOI">10.1021/ar970143z</ext-link>, 1998.</mixed-citation></ref>
      <ref id="bib1.bib8"><label>8</label><?label 7?><mixed-citation>Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638,  <ext-link xlink:href="https://doi.org/10.1021/cr0206420" ext-link-type="DOI">10.1021/cr0206420</ext-link>, 2003a.</mixed-citation></ref>
      <ref id="bib1.bib9"><label>9</label><?label 8?><mixed-citation>Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: A review, Atmos. Environ., 37, 197–219,  <ext-link xlink:href="https://doi.org/10.1016/S1352-2310(03)00391-1" ext-link-type="DOI">10.1016/S1352-2310(03)00391-1</ext-link>, 2003b.</mixed-citation></ref>
      <ref id="bib1.bib10"><label>10</label><?label 9?><mixed-citation>Atkinson, R., Aschmann, S. M., and Arey, J.: Rate constants for the gas-phase reactions of OH and <inline-formula><mml:math id="M434" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> radicals and <inline-formula><mml:math id="M435" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> with sabinene and camphene at <inline-formula><mml:math id="M436" display="inline"><mml:mrow><mml:mn mathvariant="normal">296</mml:mn><mml:mo>±</mml:mo><mml:mn mathvariant="normal">2</mml:mn></mml:mrow></mml:math></inline-formula> <inline-formula><mml:math id="M437" display="inline"><mml:mrow class="unit"><mml:mi mathvariant="normal">K</mml:mi></mml:mrow></mml:math></inline-formula>, Atmos. Environ. A-Gen., 24, 2647–2654,  <ext-link xlink:href="https://doi.org/10.1016/0960-1686(90)90144-C" ext-link-type="DOI">10.1016/0960-1686(90)90144-C</ext-link>, 1990.</mixed-citation></ref>
      <ref id="bib1.bib11"><label>11</label><?label 10?><mixed-citation>Aumont, B., Szopa, S., and Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach, Atmos. Chem. Phys., 5, 2497–2517,  <ext-link xlink:href="https://doi.org/10.5194/acp-5-2497-2005" ext-link-type="DOI">10.5194/acp-5-2497-2005</ext-link>, 2005.</mixed-citation></ref>
      <ref id="bib1.bib12"><label>12</label><?label 11?><mixed-citation>Aumont, B., Valorso, R., Mouchel-Vallon, C., Camredon, M., Lee-Taylor, J., and Madronich, S.: Modeling SOA formation from the oxidation of intermediate volatility <inline-formula><mml:math id="M438" display="inline"><mml:mi>n</mml:mi></mml:math></inline-formula>-alkanes, Atmos. Chem. Phys., 12, 7577–7589,  <ext-link xlink:href="https://doi.org/10.5194/acp-12-7577-2012" ext-link-type="DOI">10.5194/acp-12-7577-2012</ext-link>, 2012.</mixed-citation></ref>
      <ref id="bib1.bib13"><label>13</label><?label 12?><mixed-citation>Aumont, B., Camredon, M., Mouchel-Vallon, C., La, S., Ouzebidour, F., Valorso, R., Lee-Taylor, J., and Madronich, S.: Modeling the influence of alkane molecular structure on secondary organic aerosol formation, Faraday Discuss., 165, 105–122,  <ext-link xlink:href="https://doi.org/10.1039/c3fd00029j" ext-link-type="DOI">10.1039/c3fd00029j</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib14"><label>14</label><?label 13?><mixed-citation>Bäck, J., Aalto, J., Henriksson, M., Hakola, H., He, Q., and Boy, M.: Chemodiversity of a Scots pine stand and implications for terpene air concentrations, Biogeosciences, 9, 689–702,  <ext-link xlink:href="https://doi.org/10.5194/bg-9-689-2012" ext-link-type="DOI">10.5194/bg-9-689-2012</ext-link>, 2012.</mixed-citation></ref>
      <ref id="bib1.bib15"><label>15</label><?label 14?><mixed-citation>Bakker-Arkema, J. G., and Ziemann, P. J.: Measurements of kinetics and equilibria for the condensed phase reactions of hydroperoxides with carbonyls to form peroxyhemiacetals, ACS Earth Space Chem., 4, 467–475,  <ext-link xlink:href="https://doi.org/10.1021/acsearthspacechem.0c00008" ext-link-type="DOI">10.1021/acsearthspacechem.0c00008</ext-link>, 2020.</mixed-citation></ref>
      <ref id="bib1.bib16"><label>16</label><?label 15?><mixed-citation>Barsanti, K. C., Kroll, J. H., and Thornton, J. A.: Formation of Low-Volatility Organic Compounds in the Atmosphere: Recent Advancements and Insights, J. Phys. Chem. Lett., 8, 1503–1511,  <ext-link xlink:href="https://doi.org/10.1021/acs.jpclett.6b02969" ext-link-type="DOI">10.1021/acs.jpclett.6b02969</ext-link>, 2017.</mixed-citation></ref>
      <ref id="bib1.bib17"><label>17</label><?label 16?><mixed-citation>Baruah, S. D., Gour, N. K., Sarma, P. J., and Deka, R. C.: OH-initiated mechanistic pathways and kinetics of camphene and fate of product radical: a DFT approach. Environ, Sci. Pollut. R., 25, 2147–2156,  <ext-link xlink:href="https://doi.org/10.1007/s11356-017-0646-2" ext-link-type="DOI">10.1007/s11356-017-0646-2</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib18"><label>18</label><?label 17?><mixed-citation>Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin, P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A., Donahue, N., Kjaergaard, H. G., and Ehn, M.: Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol, Chem. Rev., 119, 3472–3509,  <ext-link xlink:href="https://doi.org/10.1021/acs.chemrev.8b00395" ext-link-type="DOI">10.1021/acs.chemrev.8b00395</ext-link>, 2019.</mixed-citation></ref>
      <ref id="bib1.bib19"><label>19</label><?label 18?><mixed-citation>Boyd, C. M., Nah, T., Xu, L., Berkemeier, T., and Ng, N. L.: Secondary organic aerosol (SOA) from nitrate radical oxidation of monoterpenes: Effects of temperature, dilution, and humidity on aerosol formation, mixing, and evaporation, Environ. Sci. Technol., 51, 7831–7841,  <ext-link xlink:href="https://doi.org/10.1021/acs.est.7b01460" ext-link-type="DOI">10.1021/acs.est.7b01460</ext-link>, 2017.</mixed-citation></ref>
      <ref id="bib1.bib20"><label>20</label><?label 19?><mixed-citation>Calogirou, A., Larsen, B. R., and Kotzias, D.: Gas-phase terpene oxidation products: A review, Atmos. Environ., 33, 1423–1439,  <ext-link xlink:href="https://doi.org/10.1016/S1352-2310(98)00277-5" ext-link-type="DOI">10.1016/S1352-2310(98)00277-5</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib21"><label>21</label><?label 20?><mixed-citation>Camredon, M., Aumont, B., Lee-Taylor, J., and Madronich, S.: The <inline-formula><mml:math id="M439" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">SOA</mml:mi><mml:mo>/</mml:mo><mml:mi mathvariant="normal">VOC</mml:mi><mml:mo>/</mml:mo><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi mathvariant="normal">x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> system: an explicit model of secondary organic aerosol formation, Atmos. Chem. Phys., 7, 5599–5610,  <ext-link xlink:href="https://doi.org/10.5194/acp-7-5599-2007" ext-link-type="DOI">10.5194/acp-7-5599-2007</ext-link>, 2007.</mixed-citation></ref>
      <ref id="bib1.bib22"><label>22</label><?label 21?><mixed-citation>Carter, W. P. L.: Development of a condensed SAPRC-07 chemical mechanism, Atmos. Environ., 44, 5336–5345,  <ext-link xlink:href="https://doi.org/10.1016/j.atmosenv.2010.01.024" ext-link-type="DOI">10.1016/j.atmosenv.2010.01.024</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib23"><label>23</label><?label 22?><mixed-citation>Chen, F., Zhou, H., Gao, J., and Hopke, P. K.: A chamber study of secondary organic aerosol (SOA) formed by ozonolysis of d-limonene in the presence of NO, Aerosol Air Qual. Res., 17, 59–68,  <ext-link xlink:href="https://doi.org/10.4209/aaqr.2016.01.0029" ext-link-type="DOI">10.4209/aaqr.2016.01.0029</ext-link>, 2017.</mixed-citation></ref>
      <ref id="bib1.bib24"><label>24</label><?label 23?><mixed-citation>Chen, Q., Liu, Y., Donahue, N. M., Shilling, J. E., and Martin, S. T.: Particle-phase chemistry of secondary organic material: Modeled compared to measured <inline-formula><mml:math id="M440" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">O</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> and <inline-formula><mml:math id="M441" display="inline"><mml:mrow class="chem"><mml:mi mathvariant="normal">H</mml:mi><mml:mo>:</mml:mo><mml:mi mathvariant="normal">C</mml:mi></mml:mrow></mml:math></inline-formula> elemental ratios provide constraints, Environ. Sci. Technol., 45, 4763–4770,  <ext-link xlink:href="https://doi.org/10.1021/es104398s" ext-link-type="DOI">10.1021/es104398s</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib25"><label>25</label><?label 24?><mixed-citation>Chhabra, P. S., Flagan, R. C., and Seinfeld, J. H.: Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer, Atmos. Chem. Phys., 10, 4111–4131,  <ext-link xlink:href="https://doi.org/10.5194/acp-10-4111-2010" ext-link-type="DOI">10.5194/acp-10-4111-2010</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib26"><label>26</label><?label 25?><mixed-citation>Chhabra, P. S., Ng, N. L., Canagaratna, M. R., Corrigan, A. L., Russell, L. M., Worsnop, D. R., Flagan, R. C., and Seinfeld, J. H.: Elemental composition and oxidation of chamber organic aerosol, Atmos. Chem. Phys., 11, 8827–8845,  <ext-link xlink:href="https://doi.org/10.5194/acp-11-8827-2011" ext-link-type="DOI">10.5194/acp-11-8827-2011</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib27"><label>27</label><?label 26?><mixed-citation>Chuang, W. K. and Donahue, N. M.: A two-dimensional volatility basis set – Part 3: Prognostic modeling and NO<inline-formula><mml:math id="M442" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula> dependence, Atmos. Chem. Phys., 16, 123–134,  <ext-link xlink:href="https://doi.org/10.5194/acp-16-123-2016" ext-link-type="DOI">10.5194/acp-16-123-2016</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib28"><label>28</label><?label 27?><mixed-citation>Claflin, M. S., Krechmer, J. E., Hu, W., Jimenez, J. L., and Ziemann, P. J.: Functional group composition of secondary organic aerosol formed from ozonolysis of <inline-formula><mml:math id="M443" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene under high VOC and autoxidation conditions, ACS Earth Space Chem., 2, 1196–1210,  <ext-link xlink:href="https://doi.org/10.1021/acsearthspacechem.8b00117" ext-link-type="DOI">10.1021/acsearthspacechem.8b00117</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib29"><label>29</label><?label 28?><mixed-citation>Draper, D. C., Farmer, D. K., Desyaterik, Y., and Fry, J. L.: A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of <inline-formula><mml:math id="M444" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, Atmos. Chem. Phys., 15, 12267–12281,  <ext-link xlink:href="https://doi.org/10.5194/acp-15-12267-2015" ext-link-type="DOI">10.5194/acp-15-12267-2015</ext-link>, 2015.</mixed-citation></ref>
      <?pagebreak page11485?><ref id="bib1.bib30"><label>30</label><?label 29?><mixed-citation>Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén, T., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., Canagaratna M., Maso, M. D., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt, J., Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476–479, <ext-link xlink:href="https://doi.org/10.1038/nature13032" ext-link-type="DOI">10.1038/nature13032</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib31"><label>31</label><?label 30?><mixed-citation>Fehsenfeld, F., Calvert, J., Fall, R., Goldan, P., Guenther, A. B., Hewitt, C. N., Lamb, B., Liu, S., Trainer, M., Westberg, H., and Zimmerman, P.: Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry, Global Biogeochem. Cy., 6, 389–430,  <ext-link xlink:href="https://doi.org/10.1029/92GB02125" ext-link-type="DOI">10.1029/92GB02125</ext-link>, 1992.</mixed-citation></ref>
      <ref id="bib1.bib32"><label>32</label><?label 31?><mixed-citation>Friedman, B. and Farmer, D. K.: SOA and gas phase organic acid yields from the sequential photooxidation of seven monoterpenes, Atmos. Environ., 187, 335–345,  <ext-link xlink:href="https://doi.org/10.1016/j.atmosenv.2018.06.003" ext-link-type="DOI">10.1016/j.atmosenv.2018.06.003</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib33"><label>33</label><?label 32?><mixed-citation>Fry, J. L., Draper, D. C., Barsanti, K. C., Smith, J. N., Ortega, J., Winkler, P. M., Lawler, M. J., Brown, S. S., Edwards, P. M., Cohen, R. C., and Lee, L.: Secondary organic aerosol formation and organic nitrate yield from <inline-formula><mml:math id="M445" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> oxidation of biogenic hydrocarbons, Environ. Sci. Technol., 48, 11944–11953,  <ext-link xlink:href="https://doi.org/10.1021/es502204x" ext-link-type="DOI">10.1021/es502204x</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib34"><label>34</label><?label 33?><mixed-citation>Gaona-Colmán, E., Blanco, M. B., Barnes, I., Wiesen, P., and Teruel, M. A.: OH- and <inline-formula><mml:math id="M446" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>-initiated atmospheric degradation of camphene: Temperature dependent rate coefficients, product yields and mechanisms, RSC Adv., 7, 2733–2744,  <ext-link xlink:href="https://doi.org/10.1039/c6ra26656h" ext-link-type="DOI">10.1039/c6ra26656h</ext-link>, 2017.</mixed-citation></ref>
      <ref id="bib1.bib35"><label>35</label><?label 34?><mixed-citation>Geron, C., Rasmussen, R., Arnts, R. R., and Guenther, A.: A review and synthesis of monoterpene speciation from forests in the United States, Atmos. Environ., 34, 1761–1781,  <ext-link xlink:href="https://doi.org/10.1016/S1352-2310(99)00364-7" ext-link-type="DOI">10.1016/S1352-2310(99)00364-7</ext-link>, 2000.</mixed-citation></ref>
      <ref id="bib1.bib36"><label>36</label><?label 35?><mixed-citation>Gilman, J. B., Lerner, B. M., Kuster, W. C., Goldan, P. D., Warneke, C., Veres, P. R., Roberts, J. M., de Gouw, J. A., Burling, I. R., and Yokelson, R. J.: Biomass burning emissions and potential air quality impacts of volatile organic compounds and other trace gases from fuels common in the US, Atmos. Chem. Phys., 15, 13915–13938,  <ext-link xlink:href="https://doi.org/10.5194/acp-15-13915-2015" ext-link-type="DOI">10.5194/acp-15-13915-2015</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib37"><label>37</label><?label 36?><mixed-citation>Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res.-Atmos., 104, 3555–3567,  <ext-link xlink:href="https://doi.org/10.1029/1998JD100049" ext-link-type="DOI">10.1029/1998JD100049</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib38"><label>38</label><?label 37?><mixed-citation>Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., Mckay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A global model of natural volatile organic compound emission, J. Geophys. Res., 100, 8873–8892,  <ext-link xlink:href="https://doi.org/10.1029/94JD02950" ext-link-type="DOI">10.1029/94JD02950</ext-link>, 1995.</mixed-citation></ref>
      <ref id="bib1.bib39"><label>39</label><?label 38?><mixed-citation>Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R.: Product formation from the gas-phase reactions of OH radicals and <inline-formula><mml:math id="M447" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> with a series of monoterpenes, J. Atmos. Chem., 18, 75–102,  <ext-link xlink:href="https://doi.org/10.1007/BF00694375" ext-link-type="DOI">10.1007/BF00694375</ext-link>, 1994.</mixed-citation></ref>
      <ref id="bib1.bib40"><label>40</label><?label 39?><mixed-citation>Hallquist, M., Wängberg, I., Ljungström, E., Barnes, I., and Becker, K. H.: Aerosol and product yields from <inline-formula><mml:math id="M448" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> radical-initiated oxidation of selected monoterpenes, Environ. Sci. Technol., 33, 553–559,  <ext-link xlink:href="https://doi.org/10.1021/es980292s" ext-link-type="DOI">10.1021/es980292s</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib41"><label>41</label><?label 40?><mixed-citation>Hatch, L. E., Luo, W., Pankow, J. F., Yokelson, R. J., Stockwell, C. E., and Barsanti, K. C.: Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography–time-of-flight mass spectrometry, Atmos. Chem. Phys., 15, 1865–1899,  <ext-link xlink:href="https://doi.org/10.5194/acp-15-1865-2015" ext-link-type="DOI">10.5194/acp-15-1865-2015</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib42"><label>42</label><?label 41?><mixed-citation>Hatch, L. E., Jen, C. N., Kreisberg, N. M., Selimovic, V., Yokelson, R. J., Stamatis, C., York, R. A., Foster, D., Stephens, S. L., Goldstein, A. H., and Barsanti, K. C.: Highly speciated measurements of terpenoids emitted from laboratory and mixed-conifer forest prescribed fires, Environ. Sci. Technol., 53, 9418–9428,  <ext-link xlink:href="https://doi.org/10.1021/acs.est.9b02612" ext-link-type="DOI">10.1021/acs.est.9b02612</ext-link>, 2019.</mixed-citation></ref>
      <ref id="bib1.bib43"><label>43</label><?label 42?><mixed-citation>Hatfield, M. L. and Huff Hartz, K. E.: Secondary organic aerosol from biogenic volatile organic compound mixtures, Atmos. Environ., 45, 2211–2219,  <ext-link xlink:href="https://doi.org/10.1016/j.atmosenv.2011.01.065" ext-link-type="DOI">10.1016/j.atmosenv.2011.01.065</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib44"><label>44</label><?label 43?><mixed-citation>Hayward, S., Muncey, R. J., James, A. E., Halsall, C. J., and Hewitt, C. N.: Monoterpene emissions from soil in a Sitka spruce forest, Atmos. Environ., 35, 4081–4087,  <ext-link xlink:href="https://doi.org/10.1016/S1352-2310(01)00213-8" ext-link-type="DOI">10.1016/S1352-2310(01)00213-8</ext-link>, 2001.</mixed-citation></ref>
      <ref id="bib1.bib45"><label>45</label><?label 44?><mixed-citation>Heaton, K. J., Dreyfus, M. A., Wang, S., and Johnston, M. v.: Oligomers in the early stage of biogenic secondary organic aerosol formation and growth, Environ. Sci. Technol., 41, 6129–6136,  <ext-link xlink:href="https://doi.org/10.1021/es070314n" ext-link-type="DOI">10.1021/es070314n</ext-link>, 2007.</mixed-citation></ref>
      <ref id="bib1.bib46"><label>46</label><?label 45?><mixed-citation>Jacobson, M. C., Hansson, H. C., Noone, K. J., and Charlson, R. J.: Organic atmospheric aerosols: Review and state of the science, Rev. Geophys., 38, 267–294,  <ext-link xlink:href="https://doi.org/10.1029/1998RG000045" ext-link-type="DOI">10.1029/1998RG000045</ext-link>, 2000.</mixed-citation></ref>
      <ref id="bib1.bib47"><label>47</label><?label 46?><mixed-citation>Jang, M. and Kamens, R. M.: Newly characterized products and composition of secondary aerosols from the reaction of <inline-formula><mml:math id="M449" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene with ozone, Atmos. Environ., 33, 459–474,  <ext-link xlink:href="https://doi.org/10.1016/S1352-2310(98)00222-2" ext-link-type="DOI">10.1016/S1352-2310(98)00222-2</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib48"><label>48</label><?label 47?><mixed-citation>Jokinen, T., Berndt, T., Makkonen, R., Kerminen, V.-M., Junninen, H., Paasonen, P., Stratmann, F., Herrmann, H., Guenther, A. B., Worsnop, D. R., Kulmala, M., Ehn, M., and Sipilä, M.: Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications, P. Natl. Acad. Sci. USA, 112, 7123–7128,  <ext-link xlink:href="https://doi.org/10.1073/pnas.1423977112" ext-link-type="DOI">10.1073/pnas.1423977112</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib49"><label>49</label><?label 48?><mixed-citation>Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I.,
Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A.,
Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S.,
Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K.,
Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global
climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123,
<ext-link xlink:href="https://doi.org/10.5194/acp-5-1053-2005" ext-link-type="DOI">10.5194/acp-5-1053-2005</ext-link>, 2005.</mixed-citation></ref>
      <ref id="bib1.bib50"><label>50</label><?label 49?><mixed-citation>Kenseth, C. M., Huang, Y., Zhao, R., Dalleska, N. F., Hethcox, J. C., Stoltz, B. M., and Seinfeld, J. H.: Synergistic <inline-formula><mml:math id="M450" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mo>+</mml:mo><mml:mi mathvariant="normal">OH</mml:mi></mml:mrow></mml:math></inline-formula> oxidation pathway to extremely low-volatility dimers revealed in <inline-formula><mml:math id="M451" display="inline"><mml:mi mathvariant="italic">β</mml:mi></mml:math></inline-formula>-pinene secondary organic aerosol, P. Natl. Acad. Sci. USA, 115, 8301–8306,  <ext-link xlink:href="https://doi.org/10.1073/pnas.1804671115" ext-link-type="DOI">10.1073/pnas.1804671115</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib51"><label>51</label><?label 50?><mixed-citation>Kesselmeier, J. and Staudt, M.: Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology, J. Atmos. Chem., 33, 23–88,  <ext-link xlink:href="https://doi.org/10.1023/A:1006127516791" ext-link-type="DOI">10.1023/A:1006127516791</ext-link>, 1999.</mixed-citation></ref>
      <?pagebreak page11486?><ref id="bib1.bib52"><label>52</label><?label 51?><mixed-citation>Kim, H. and Paulson, S. E.: Real refractive indices and volatility of secondary organic aerosol generated from photooxidation and ozonolysis of limonene, <inline-formula><mml:math id="M452" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and toluene, Atmos. Chem. Phys., 13, 7711–7723,  <ext-link xlink:href="https://doi.org/10.5194/acp-13-7711-2013" ext-link-type="DOI">10.5194/acp-13-7711-2013</ext-link>, 2013.</mixed-citation></ref>
      <ref id="bib1.bib53"><label>53</label><?label 52?><mixed-citation>Kim, S., Karl, T., Guenther, A., Tyndall, G., Orlando, J., Harley, P., Rasmussen, R., and Apel, E.: Emissions and ambient distributions of Biogenic Volatile Organic Compounds (BVOC) in a ponderosa pine ecosystem: interpretation of PTR-MS mass spectra, Atmos. Chem. Phys., 10, 1759–1771,  <ext-link xlink:href="https://doi.org/10.5194/acp-10-1759-2010" ext-link-type="DOI">10.5194/acp-10-1759-2010</ext-link>, 2010.</mixed-citation></ref>
      <ref id="bib1.bib54"><label>54</label><?label 53?><mixed-citation>Kourtchev, I., Fuller, S. J., Giorio, C., Healy, R. M., Wilson, E., O'Connor, I., Wenger, J. C., McLeod, M., Aalto, J., Ruuskanen, T. M., Maenhaut, W., Jones, R., Venables, D. S., Sodeau, J. R., Kulmala, M., and Kalberer, M.: Molecular composition of biogenic secondary organic aerosols using ultrahigh-resolution mass spectrometry: comparing laboratory and field studies, Atmos. Chem. Phys., 14, 2155–2167,  <ext-link xlink:href="https://doi.org/10.5194/acp-14-2155-2014" ext-link-type="DOI">10.5194/acp-14-2155-2014</ext-link>, 2014.</mixed-citation></ref>
      <ref id="bib1.bib55"><label>55</label><?label 54?><mixed-citation>Kourtchev, I., Doussin, J.-F., Giorio, C., Mahon, B., Wilson, E. M., Maurin, N., Pangui, E., Venables, D. S., Wenger, J. C., and Kalberer, M.: Molecular composition of fresh and aged secondary organic aerosol from a mixture of biogenic volatile compounds: a high-resolution mass spectrometry study, Atmos. Chem. Phys., 15, 5683–5695,  <ext-link xlink:href="https://doi.org/10.5194/acp-15-5683-2015" ext-link-type="DOI">10.5194/acp-15-5683-2015</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib56"><label>56</label><?label 55?><mixed-citation>Kundu, S., Fisseha, R., Putman, A. L., Rahn, T. A., and Mazzoleni, L. R.: High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization, Atmos. Chem. Phys., 12, 5523–5536,  <ext-link xlink:href="https://doi.org/10.5194/acp-12-5523-2012" ext-link-type="DOI">10.5194/acp-12-5523-2012</ext-link>, 2012.</mixed-citation></ref>
      <ref id="bib1.bib57"><label>57</label><?label 56?><mixed-citation>La, Y. S., Camredon, M., Ziemann, P. J., Valorso, R., Matsunaga, A., Lannuque, V., Lee-Taylor, J., Hodzic, A., Madronich, S., and Aumont, B.: Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation, Atmos. Chem. Phys., 16, 1417–1431,  <ext-link xlink:href="https://doi.org/10.5194/acp-16-1417-2016" ext-link-type="DOI">10.5194/acp-16-1417-2016</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib58"><label>58</label><?label 57?><mixed-citation>Lambe, A. T., Chhabra, P. S., Onasch, T. B., Brune, W. H., Hunter, J. F., Kroll, J. H., Cummings, M. J., Brogan, J. F., Parmar, Y., Worsnop, D. R., Kolb, C. E., and Davidovits, P.: Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield, Atmos. Chem. Phys., 15, 3063–3075,  <ext-link xlink:href="https://doi.org/10.5194/acp-15-3063-2015" ext-link-type="DOI">10.5194/acp-15-3063-2015</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib59"><label>59</label><?label 58?><mixed-citation>Larsen, B. R., di Bella, D., Glasius, M., Winterhalter, R., Jensen, N. R., and Hjorth, J.: Gas-phase OH oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 38, 231–276,  <ext-link xlink:href="https://doi.org/10.1023/A:1006487530903" ext-link-type="DOI">10.1023/A:1006487530903</ext-link>, 2001.</mixed-citation></ref>
      <ref id="bib1.bib60"><label>60</label><?label 59?><mixed-citation>Lee, A., Goldstein, A. H., Keywood, M. D., Gao, S., Varutbangkul, V., Bahreini, R., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes, J. Geophys. Res.-Atmos., 111, D07302.  <ext-link xlink:href="https://doi.org/10.1029/2005JD006437" ext-link-type="DOI">10.1029/2005JD006437</ext-link>, 2006a.</mixed-citation></ref>
      <ref id="bib1.bib61"><label>61</label><?label 60?><mixed-citation>Lee, A., Goldstein, A. H., Kroll, J. H., Ng, N. L., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes, J. Geophys. Res.-Atmos., 111, D17305,  <ext-link xlink:href="https://doi.org/10.1029/2006JD007050" ext-link-type="DOI">10.1029/2006JD007050</ext-link>, 2006b.</mixed-citation></ref>
      <ref id="bib1.bib62"><label>62</label><?label 61?><mixed-citation>Ludley, Katherine. E., Jickells, S. M., Chamberlain, P. M., Whitaker, J., and Robinson, C. H.: Distribution of monoterpenes between organic resources in upper soil horizons under monocultures of <italic>Picea abies</italic>, <italic>Picea sitchensis</italic> and <italic>Pinus Sylvestris</italic>, Soil Biol. Biochem., 41, 1050–1059,  <ext-link xlink:href="https://doi.org/10.1016/J.SOILBIO.2009.02.002" ext-link-type="DOI">10.1016/J.SOILBIO.2009.02.002</ext-link>, 2009.</mixed-citation></ref>
      <ref id="bib1.bib63"><label>63</label><?label 62?><mixed-citation>Maleknia, S. D., Bell, T. L., and Adams, M. A.: PTR-MS analysis of reference and plant-emitted volatile organic compounds, Int. J. Mass Spectrom., 262, 203–210,  <ext-link xlink:href="https://doi.org/10.1016/j.ijms.2006.11.010" ext-link-type="DOI">10.1016/j.ijms.2006.11.010</ext-link>, 2007.</mixed-citation></ref>
      <ref id="bib1.bib64"><label>64</label><?label 63?><mixed-citation>McVay, R. C., Zhang, X., Aumont, B., Valorso, R., Camredon, M., La, Y. S., Wennberg, P. O., and Seinfeld, J. H.: SOA formation from the photooxidation of <inline-formula><mml:math id="M453" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene: systematic exploration of the simulation of chamber data, Atmos. Chem. Phys., 16, 2785–2802,  <ext-link xlink:href="https://doi.org/10.5194/acp-16-2785-2016" ext-link-type="DOI">10.5194/acp-16-2785-2016</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib65"><label>65</label><?label 64?><mixed-citation>Nah, T., McVay, R. C., Zhang, X., Boyd, C. M., Seinfeld, J. H.,
and Ng, N. L.: Influence of seed aerosol surface area and oxidation rate on
vapor wall deposition and SOA mass yields: a case study with <inline-formula><mml:math id="M454" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene
ozonolysis, Atmos. Chem. Phys., 16, 9361–9379,
<ext-link xlink:href="https://doi.org/10.5194/acp-16-9361-2016" ext-link-type="DOI">10.5194/acp-16-9361-2016</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib66"><label>66</label><?label 65?><mixed-citation>Nannoolal, Y., Rarey, J., and Ramjugernath, D.: Estimation of pure component properties part 3. Estimation of the vapor pressure of non-electrolyte organic compounds via group contribution and group interactions, Fluid Phase Equilibr., 269, 117–133,  <ext-link xlink:href="https://doi.org/10.1016/j.fluid.2008.04.020" ext-link-type="DOI">10.1016/j.fluid.2008.04.020</ext-link>, 2008.</mixed-citation></ref>
      <ref id="bib1.bib67"><label>67</label><?label 66?><mixed-citation>Ng, N. L., Chhabra, P. S., Chan, A. W. H., Surratt, J. D., Kroll, J. H., Kwan, A. J., McCabe, D. C., Wennberg, P. O., Sorooshian, A., Murphy, S. M., Dalleska, N. F., Flagan, R. C., and Seinfeld, J. H.: Effect of NO<inline-formula><mml:math id="M455" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes, Atmos. Chem. Phys., 7, 5159–5174, <ext-link xlink:href="https://doi.org/10.5194/acp-7-5159-2007" ext-link-type="DOI">10.5194/acp-7-5159-2007</ext-link>, 2007.</mixed-citation></ref>
      <ref id="bib1.bib68"><label>68</label><?label 67?><mixed-citation>Odum Jay, R., Hoffmann, T., Bowman, F., Collins, D., Flagan Richard, C., and Seinfeld John, H.: Gas particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585,  <ext-link xlink:href="https://doi.org/10.1021/es950943+" ext-link-type="DOI">10.1021/es950943+</ext-link>, 1996.</mixed-citation></ref>
      <ref id="bib1.bib69"><label>69</label><?label 68?><mixed-citation>Pankow, J. F.: An absorption model of gas/particle partitioning of organic compounds in the atmosphere, Atmos. Environ., 28, 185–188,  <ext-link xlink:href="https://doi.org/10.1016/1352-2310(94)90093-0" ext-link-type="DOI">10.1016/1352-2310(94)90093-0</ext-link>, 1994.</mixed-citation></ref>
      <ref id="bib1.bib70"><label>70</label><?label 69?><mixed-citation>Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of <inline-formula><mml:math id="M456" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, <ext-link xlink:href="https://doi.org/10.5194/acp-7-3811-2007" ext-link-type="DOI">10.5194/acp-7-3811-2007</ext-link>, 2007a.</mixed-citation></ref>
      <ref id="bib1.bib71"><label>71</label><?label 70?><mixed-citation>Pathak, R. K., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of <inline-formula><mml:math id="M457" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene at atmospherically relevant concentrations: Temperature dependence of aerosol mass fractions (yields), J. Geophys. Res.-Atmos., 112, 1–8,  <ext-link xlink:href="https://doi.org/10.1029/2006JD007436" ext-link-type="DOI">10.1029/2006JD007436</ext-link>, 2007b.</mixed-citation></ref>
      <ref id="bib1.bib72"><label>72</label><?label 1?><mixed-citation>Peeters, J., Vereecken, L., and Fantechi, G.: The detailed mechanism of the OH-initiated atmospheric oxidation of <inline-formula><mml:math id="M458" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene: A theoretical study, Phys. Chem. Chem. Phys., 3, 5489–5504, <ext-link xlink:href="https://doi.org/10.1039/b106555f" ext-link-type="DOI">10.1039/b106555f</ext-link>, 2001.</mixed-citation></ref>
      <ref id="bib1.bib73"><label>73</label><?label 71?><mixed-citation>Pfaffenberger, L., Barmet, P., Slowik, J. G., Praplan, A. P., Dommen, J., Prévôt, A. S. H., and Baltensperger, U.: The link between organic aerosol mass loading and degree of oxygenation: an <inline-formula><mml:math id="M459" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation study, Atmos. Chem. Phys., 13, 6493–6506,  <ext-link xlink:href="https://doi.org/10.5194/acp-13-6493-2013" ext-link-type="DOI">10.5194/acp-13-6493-2013</ext-link>, 2013.</mixed-citation></ref>
      <?pagebreak page11487?><ref id="bib1.bib74"><label>74</label><?label 73?><mixed-citation>Presto, A. A. and Donahue, N. M.: Investigation of <inline-formula><mml:math id="M460" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene <inline-formula><mml:math id="M461" display="inline"><mml:mo>+</mml:mo></mml:math></inline-formula> ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543,  <ext-link xlink:href="https://doi.org/10.1021/es052203z" ext-link-type="DOI">10.1021/es052203z</ext-link>, 2006.</mixed-citation></ref>
      <ref id="bib1.bib75"><label>75</label><?label 72?><mixed-citation>Presto, A. A., Huff Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from terpene ozonolysis. 2. Effect of <inline-formula><mml:math id="M462" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula> concentration, Environ. Sci. Technol., 39, 7046–7054,  <ext-link xlink:href="https://doi.org/10.1021/es050400s" ext-link-type="DOI">10.1021/es050400s</ext-link>, 2005.</mixed-citation></ref>
      <ref id="bib1.bib76"><label>76</label><?label 74?><mixed-citation>Reinhardt, A., Emmenegger, C., Gerrits, B., Panse, C., Dommen, J., Baltensperger, U., Zenobi, R., and Kalberer, M.: Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols, Anal. Chem., 79, 4074–4082,  <ext-link xlink:href="https://doi.org/10.1021/ac062425v" ext-link-type="DOI">10.1021/ac062425v</ext-link>, 2007.</mixed-citation></ref>
      <ref id="bib1.bib77"><label>77</label><?label 75?><mixed-citation>Reissell, A., Harry, C., Aschmann, S. M., Atkinson, R., and Arey, J.: Formation of acetone from the OH radical- and <inline-formula><mml:math id="M463" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">O</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>-initiated reactions of a series of monoterpenes, J. Geophys. Res.-Atmos., 104, 13869–13879,  <ext-link xlink:href="https://doi.org/10.1029/1999JD900198" ext-link-type="DOI">10.1029/1999JD900198</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib78"><label>78</label><?label 76?><mixed-citation>Rinne, J., Tuovinen, J. P., Laurila, T., Hakola, H., Aurela, M., and Hypén, H.: Measurements of hydrocarbon fluxes by a gradient method above a northern boreal forest, Agr. Forest Meteorol., 102, 25–37,  <ext-link xlink:href="https://doi.org/10.1016/S0168-1923(00)00088-5" ext-link-type="DOI">10.1016/S0168-1923(00)00088-5</ext-link>, 2000.</mixed-citation></ref>
      <ref id="bib1.bib79"><label>79</label><?label 77?><mixed-citation>Saha, P. K. and Grieshop, A. P.: Exploring divergent volatility properties from yield and thermodenuder measurements of secondary organic aerosol from <inline-formula><mml:math id="M464" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene ozonolysis, Environ. Sci. Technol., 50, 5740–5749,  <ext-link xlink:href="https://doi.org/10.1021/acs.est.6b00303" ext-link-type="DOI">10.1021/acs.est.6b00303</ext-link>, 2016.</mixed-citation></ref>
      <ref id="bib1.bib80"><label>80</label><?label 78?><mixed-citation>Shilling, J. E., Chen, Q., King, S. M., Rosenoern, T., Kroll, J. H., Worsnop, D. R., DeCarlo, P. F., Aiken, A. C., Sueper, D., Jimenez, J. L., and Martin, S. T.: Loading-dependent elemental composition of <inline-formula><mml:math id="M465" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene SOA particles, Atmos. Chem. Phys., 9, 771–782,  <ext-link xlink:href="https://doi.org/10.5194/acp-9-771-2009" ext-link-type="DOI">10.5194/acp-9-771-2009</ext-link>, 2009.</mixed-citation></ref>
      <ref id="bib1.bib81"><label>81</label><?label 79?><mixed-citation>Simpson, I. J., Akagi, S. K., Barletta, B., Blake, N. J., Choi, Y., Diskin, G. S., Fried, A., Fuelberg, H. E., Meinardi, S., Rowland, F. S., Vay, S. A., Weinheimer, A. J., Wennberg, P. O., Wiebring, P., Wisthaler, A., Yang, M., Yokelson, R. J., and Blake, D. R.: Boreal forest fire emissions in fresh Canadian smoke plumes: <inline-formula><mml:math id="M466" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">1</mml:mn></mml:msub><mml:mo>-</mml:mo><mml:msub><mml:mi mathvariant="normal">C</mml:mi><mml:mn mathvariant="normal">10</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> volatile organic compounds (VOCs), <inline-formula><mml:math id="M467" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, CO, <inline-formula><mml:math id="M468" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula>, NO, HCN and <inline-formula><mml:math id="M469" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">CH</mml:mi><mml:mn mathvariant="normal">3</mml:mn></mml:msub><mml:mi mathvariant="normal">CN</mml:mi></mml:mrow></mml:math></inline-formula>, Atmos. Chem. Phys., 11, 6445–6463,  <ext-link xlink:href="https://doi.org/10.5194/acp-11-6445-2011" ext-link-type="DOI">10.5194/acp-11-6445-2011</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib82"><label>82</label><?label 80?><mixed-citation>Steinbrecher, R., Hauff, K., Rössler, J., Dürr, M., and Seufert, G.: Monoterpene emission from soils in orange plantations of the Valencian Citrus belt, Spain, Phys. Chem. Earth Pt. B, 24, 695–698,  <ext-link xlink:href="https://doi.org/10.1016/S1464-1909(99)00067-2" ext-link-type="DOI">10.1016/S1464-1909(99)00067-2</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib83"><label>83</label><?label 81?><mixed-citation>Stockwell, W. R., Kirchner, F., Kuhn, M., and Seefeld, S.: A new mechanism for regional atmospheric chemistry modeling, J. Geophys. Res.-Atmos., 102, 25847–25879,  <ext-link xlink:href="https://doi.org/10.1029/97jd00849" ext-link-type="DOI">10.1029/97jd00849</ext-link>, 1997.</mixed-citation></ref>
      <ref id="bib1.bib84"><label>84</label><?label 82?><mixed-citation>Tani, A., Hayward, S., and Hewitt, C. N.: Measurement of monoterpenes and related compounds by proton transfer reaction-mass spectrometry (PTR-MS), Int. J. Mass Spectrom., 223–224, 561–578,  <ext-link xlink:href="https://doi.org/10.1016/S1387-3806(02)00880-1" ext-link-type="DOI">10.1016/S1387-3806(02)00880-1</ext-link>, 2003.</mixed-citation></ref>
      <ref id="bib1.bib85"><label>85</label><?label 83?><mixed-citation>Valorso, R., Aumont, B., Camredon, M., Raventos-Duran, T., Mouchel-Vallon, C., Ng, N. L., Seinfeld, J. H., Lee-Taylor, J., and Madronich, S.: Explicit modelling of SOA formation from <inline-formula><mml:math id="M470" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene photooxidation: sensitivity to vapour pressure estimation, Atmos. Chem. Phys., 11, 6895–6910,  <ext-link xlink:href="https://doi.org/10.5194/acp-11-6895-2011" ext-link-type="DOI">10.5194/acp-11-6895-2011</ext-link>, 2011.</mixed-citation></ref>
      <ref id="bib1.bib86"><label>86</label><?label 84?><mixed-citation>Vereecken, L. and Nozière, B.: H migration in peroxy radicals under atmospheric conditions, Atmos. Chem. Phys., 20, 7429–7458,  <ext-link xlink:href="https://doi.org/10.5194/acp-20-7429-2020" ext-link-type="DOI">10.5194/acp-20-7429-2020</ext-link>, 2020.</mixed-citation></ref>
      <ref id="bib1.bib87"><label>87</label><?label 85?><mixed-citation>Walser, M. L., Desyaterik, Y., Laskin, J., Laskin, A., and Nizkorodov, S. A.: High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene, Phys. Chem. Chem. Phys., 10, 1009–1022,  <ext-link xlink:href="https://doi.org/10.1039/b712620d" ext-link-type="DOI">10.1039/b712620d</ext-link>, 2008.</mixed-citation></ref>
      <ref id="bib1.bib88"><label>88</label><?label 86?><mixed-citation>White, M. L., Russo, R. S., Zhou, Y., Mao, H., Varner, R. K., Ambrose, J., Veres, P., Wingenter, O. W., Haase, K., Stutz, J., Talbot, R., and Sive, B. C.: Volatile organic compounds in northern New England marine and continental environments during the ICARTT 2004 campaign, J. Geophys. Res.-Atmos., 113, 1–16,  <ext-link xlink:href="https://doi.org/10.1029/2007JD009161" ext-link-type="DOI">10.1029/2007JD009161</ext-link>, 2008.</mixed-citation></ref>
      <ref id="bib1.bib89"><label>89</label><?label 87?><mixed-citation>Wisthaler, A., Jensen, N. R., Winterhalter, R., Lindinger, W., and Hjorth, J.: Measurements of acetone and other gas phase product yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry (PTR-MS), Atmos. Environ., 35, 6181–6191,  <ext-link xlink:href="https://doi.org/10.1016/S1352-2310(01)00385-5" ext-link-type="DOI">10.1016/S1352-2310(01)00385-5</ext-link>, 2001.</mixed-citation></ref>
      <ref id="bib1.bib90"><label>90</label><?label 88?><mixed-citation>Yáñez-Serrano, A. M., Nölscher, A. C., Bourtsoukidis, E., Gomes Alves, E., Ganzeveld, L., Bonn, B., Wolff, S., Sa, M., Yamasoe, M., Williams, J., Andreae, M. O., and Kesselmeier, J.: Monoterpene chemical speciation in a tropical rainforest:variation with season, height, and time of dayat the Amazon Tall Tower Observatory (ATTO), Atmos. Chem. Phys., 18, 3403–3418,  <ext-link xlink:href="https://doi.org/10.5194/acp-18-3403-2018" ext-link-type="DOI">10.5194/acp-18-3403-2018</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib91"><label>91</label><?label 89?><mixed-citation>Yassaa, N., Peeken, I., Zllner, E., Bluhm, K., Arnold, S., Spracklen, D., and Williams, J.: Evidence for marine production of monoterpenes, Environ. Chem., 5, 391–401,  <ext-link xlink:href="https://doi.org/10.1071/EN08047" ext-link-type="DOI">10.1071/EN08047</ext-link>, 2008.</mixed-citation></ref>
      <ref id="bib1.bib92"><label>92</label><?label 90?><mixed-citation>Yu, J., Cocker III, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products, J. Atmos. Chem., 34, 207–258,  <ext-link xlink:href="https://doi.org/10.1023/A:1006254930583" ext-link-type="DOI">10.1023/A:1006254930583</ext-link>, 1999.</mixed-citation></ref>
      <ref id="bib1.bib93"><label>93</label><?label 91?><mixed-citation>Zhang, J., Huff Hartz, K. E., Pandis, S. N., and Donahue, N. M.: Secondary organic aerosol formation from limonene Ozonolysis: Homogeneous and heterogeneous influences as a function of <inline-formula><mml:math id="M471" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">NO</mml:mi><mml:mi>x</mml:mi></mml:msub></mml:mrow></mml:math></inline-formula>, J. Phys. Chem. A., 110, 11053–11063,  <ext-link xlink:href="https://doi.org/10.1021/jp062836f" ext-link-type="DOI">10.1021/jp062836f</ext-link>, 2006.</mixed-citation></ref>
      <ref id="bib1.bib94"><label>94</label><?label 92?><mixed-citation>Zhang, X, McVay, R. C., Huang, D. D., Dalleska, N. F., Aumont, B., Flagan, R. C., and Seinfeld, J. H.: Formation and evolution of molecular products in alpha-pinene secondary organic aerosol, P. Natl. Acad. Sci. USA, 112, 14168–14173,  <ext-link xlink:href="https://doi.org/10.1073/pnas.1517742112" ext-link-type="DOI">10.1073/pnas.1517742112</ext-link>, 2015.</mixed-citation></ref>
      <ref id="bib1.bib95"><label>95</label><?label 93?><mixed-citation>Zhao, D., Schmitt, S. H., Wang, M., Acir, I.-H., Tillmann, R., Tan, Z., Novelli, A., Fuchs, H., Pullinen, I., Wegener, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A., and Mentel, T. F.: Effects of NO<inline-formula><mml:math id="M472" display="inline"><mml:msub><mml:mi/><mml:mi>x</mml:mi></mml:msub></mml:math></inline-formula> and <inline-formula><mml:math id="M473" display="inline"><mml:mrow class="chem"><mml:msub><mml:mi mathvariant="normal">SO</mml:mi><mml:mn mathvariant="normal">2</mml:mn></mml:msub></mml:mrow></mml:math></inline-formula> on the secondary organic aerosol formation from photooxidation of <inline-formula><mml:math id="M474" display="inline"><mml:mi mathvariant="italic">α</mml:mi></mml:math></inline-formula>-pinene and limonene, Atmos. Chem. Phys., 18, 1611–1628,  <ext-link xlink:href="https://doi.org/10.5194/acp-18-1611-2018" ext-link-type="DOI">10.5194/acp-18-1611-2018</ext-link>, 2018.</mixed-citation></ref>
      <ref id="bib1.bib96"><label>96</label><?label 94?><mixed-citation>Ziemann, P. J. and Atkinson, R.: Kinetics, products, and mechanisms of secondary organic aerosol formation, Chem. Soc. Rev., 41, 6582,  <ext-link xlink:href="https://doi.org/10.1039/c2cs35122f" ext-link-type="DOI">10.1039/c2cs35122f</ext-link>, 2012.</mixed-citation></ref>

  </ref-list></back>
    <!--<article-title-html>Using GECKO-A to derive mechanistic understanding of secondary organic aerosol formation from the ubiquitous but understudied camphene</article-title-html>
<abstract-html><p>Camphene, a dominant monoterpene emitted from both biogenic and pyrogenic
sources, has been significantly understudied, particularly in regard to
secondary organic aerosol (SOA) formation. When camphene represents a
significant fraction of emissions, the lack of model parameterizations for
camphene can result in inadequate representation of gas-phase chemistry and
underprediction of SOA formation. In this work, the first mechanistic study of SOA formation from camphene was performed using the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A).  GECKO-A was used to generate gas-phase chemical mechanisms for camphene and two well-studied monoterpenes, <i>α</i>-pinene and limonene, as well as to predict SOA
mass formation and composition based on gas/particle partitioning theory. The
model simulations represented observed trends in published gas-phase reaction
pathways and SOA yields well under chamber-relevant photooxidation and dark
ozonolysis conditions. For photooxidation conditions, 70&thinsp;% of the
simulated <i>α</i>-pinene oxidation products remained in the gas phase
compared to 50&thinsp;% for limonene, supporting model predictions and
observations of limonene having higher SOA yields than <i>α</i>-pinene under
equivalent conditions. The top 10 simulated particle-phase products in the
<i>α</i>-pinene and limonene simulations represented 37&thinsp;%–50&thinsp;% of
the SOA mass formed and 6&thinsp;%–27&thinsp;% of the hydrocarbon mass reacted. To
facilitate comparison of camphene with <i>α</i>-pinene and limonene, model
simulations were run under idealized atmospheric conditions, wherein the
gas-phase oxidant levels were controlled, and peroxy radicals reacted equally
with HO<sub>2</sub> and NO. Metrics for comparison included gas-phase
reactivity profiles, time-evolution of SOA mass and yields, and
physicochemical property distributions of gas- and particle-phase
products. The controlled-reactivity simulations demonstrated that (1)
in the early stages of oxidation, camphene is predicted to form very low-volatility products, lower than <i>α</i>-pinene and limonene, which condense
at low mass loadings; and (2) the final simulated SOA yield for camphene
(46&thinsp;%) was relatively high, in between <i>α</i>-pinene (25&thinsp;%) and
limonene (74&thinsp;%). A 50&thinsp;% <i>α</i>-pinene&thinsp;+&thinsp;50&thinsp;% limonene mixture was then used as a surrogate to represent SOA formation from camphene; while simulated SOA mass and yield were well represented, the volatility distribution of the particle-phase products was not. To demonstrate the potential importance of including a parameterized representation of SOA formation by camphene in air quality models, SOA mass and yield were predicted for three wildland fire fuels based on measured monoterpene distributions and published SOA parameterizations for <i>α</i>-pinene and limonene. Using the 50∕50 surrogate mixture to represent camphene increased predicted SOA mass by 43&thinsp;%–50&thinsp;% for black spruce and by 56&thinsp;%–108&thinsp;% for Douglas fir. This first detailed modeling study of the gas-phase oxidation of camphene and subsequent SOA formation highlights opportunities for future measurement–model comparisons and lays a foundation for developing chemical mechanisms and SOA parameterizations for camphene that are suitable for air quality modeling.</p></abstract-html>
<ref-html id="bib1.bib1"><label>1</label><mixed-citation>
Afreh, I. K., Barsanti, K. C., Bernard, A., and Camredon, M.: Using GECKO-A to derive mechanistic understanding of SOA formation from the ubiquitous but understudied camphene, Zenodo [data set], <a href="https://doi.org/10.5281/zenodo.5059693" target="_blank">https://doi.org/10.5281/zenodo.5059693</a>, 2021.
</mixed-citation></ref-html>
<ref-html id="bib1.bib2"><label>2</label><mixed-citation>
Akagi, S. K., Yokelson, R. J., Wiedinmyer, C., Alvarado, M. J., Reid, J. S., Karl, T., Crounse, J. D., and Wennberg, P. O.: Emission factors for open and domestic biomass burning for use in atmospheric models, Atmos. Chem. Phys., 11, 4039–4072,  <a href="https://doi.org/10.5194/acp-11-4039-2011" target="_blank">https://doi.org/10.5194/acp-11-4039-2011</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib3"><label>3</label><mixed-citation>
Akagi, S. K., Yokelson, R. J., Burling, I. R., Meinardi, S., Simpson, I., Blake, D. R., McMeeking, G. R., Sullivan, A., Lee, T., Kreidenweis, S., Urbanski, S., Reardon, J., Griffith, D. W. T., Johnson, T. J., and Weise, D. R.: Measurements of reactive trace gases and variable O<sub>3</sub> formation rates in some South Carolina biomass burning plumes, Atmos. Chem. Phys., 13, 1141–1165,  <a href="https://doi.org/10.5194/acp-13-1141-2013" target="_blank">https://doi.org/10.5194/acp-13-1141-2013</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib4"><label>4</label><mixed-citation>
Almatarneh, M. H., Elayan, I. A., Poirier, R. A., and Altarawneh, M.: The ozonolysis of cyclic monoterpenes: A computational review, Can. J. Chem., 96, 281–292,  <a href="https://doi.org/10.1139/cjc-2017-0587" target="_blank">https://doi.org/10.1139/cjc-2017-0587</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib5"><label>5</label><mixed-citation>
Ambrose, J. L., Haase, K., Russo, R. S., Zhou, Y., White, M. L.,
Frinak, E. K., Jordan, C., Mayne, H. R., Talbot, R., and Sive, B. C.: A
comparison of GC-FID and PTR-MS toluene measurements in ambient air under
conditions of enhanced monoterpene loading, Atmos. Meas. Tech., 3, 959–980, <a href="https://doi.org/10.5194/amt-3-959-2010" target="_blank">https://doi.org/10.5194/amt-3-959-2010</a>, 2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib6"><label>6</label><mixed-citation>
Amin, H. S., Hatfield, M. L., and Huff Hartz, K. E.: Characterization of secondary organic aerosol generated from ozonolysis of <i>α</i>-pinene mixtures, Atmos. Environ., 67, 323–330,  <a href="https://doi.org/10.1016/j.atmosenv.2012.10.063" target="_blank">https://doi.org/10.1016/j.atmosenv.2012.10.063</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib7"><label>7</label><mixed-citation>
Atkinson, R. and Arey, J.: Atmospheric chemistry of biogenic Organic Compounds, Accounts Chem. Res., 31, 574–583,  <a href="https://doi.org/10.1021/ar970143z" target="_blank">https://doi.org/10.1021/ar970143z</a>, 1998.
</mixed-citation></ref-html>
<ref-html id="bib1.bib8"><label>8</label><mixed-citation>
Atkinson, R. and Arey, J.: Atmospheric degradation of volatile organic compounds, Chem. Rev., 103, 4605–4638,  <a href="https://doi.org/10.1021/cr0206420" target="_blank">https://doi.org/10.1021/cr0206420</a>, 2003a.
</mixed-citation></ref-html>
<ref-html id="bib1.bib9"><label>9</label><mixed-citation>
Atkinson, R. and Arey, J.: Gas-phase tropospheric chemistry of biogenic volatile organic compounds: A review, Atmos. Environ., 37, 197–219,  <a href="https://doi.org/10.1016/S1352-2310(03)00391-1" target="_blank">https://doi.org/10.1016/S1352-2310(03)00391-1</a>, 2003b.
</mixed-citation></ref-html>
<ref-html id="bib1.bib10"><label>10</label><mixed-citation>
Atkinson, R., Aschmann, S. M., and Arey, J.: Rate constants for the gas-phase reactions of OH and NO<sub>3</sub> radicals and O<sub>3</sub> with sabinene and camphene at 296±2&thinsp;K, Atmos. Environ. A-Gen., 24, 2647–2654,  <a href="https://doi.org/10.1016/0960-1686(90)90144-C" target="_blank">https://doi.org/10.1016/0960-1686(90)90144-C</a>, 1990.
</mixed-citation></ref-html>
<ref-html id="bib1.bib11"><label>11</label><mixed-citation>
Aumont, B., Szopa, S., and Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach, Atmos. Chem. Phys., 5, 2497–2517,  <a href="https://doi.org/10.5194/acp-5-2497-2005" target="_blank">https://doi.org/10.5194/acp-5-2497-2005</a>, 2005.
</mixed-citation></ref-html>
<ref-html id="bib1.bib12"><label>12</label><mixed-citation>
Aumont, B., Valorso, R., Mouchel-Vallon, C., Camredon, M., Lee-Taylor, J., and Madronich, S.: Modeling SOA formation from the oxidation of intermediate volatility <i>n</i>-alkanes, Atmos. Chem. Phys., 12, 7577–7589,  <a href="https://doi.org/10.5194/acp-12-7577-2012" target="_blank">https://doi.org/10.5194/acp-12-7577-2012</a>, 2012.
</mixed-citation></ref-html>
<ref-html id="bib1.bib13"><label>13</label><mixed-citation>
Aumont, B., Camredon, M., Mouchel-Vallon, C., La, S., Ouzebidour, F., Valorso, R., Lee-Taylor, J., and Madronich, S.: Modeling the influence of alkane molecular structure on secondary organic aerosol formation, Faraday Discuss., 165, 105–122,  <a href="https://doi.org/10.1039/c3fd00029j" target="_blank">https://doi.org/10.1039/c3fd00029j</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib14"><label>14</label><mixed-citation>
Bäck, J., Aalto, J., Henriksson, M., Hakola, H., He, Q., and Boy, M.: Chemodiversity of a Scots pine stand and implications for terpene air concentrations, Biogeosciences, 9, 689–702,  <a href="https://doi.org/10.5194/bg-9-689-2012" target="_blank">https://doi.org/10.5194/bg-9-689-2012</a>, 2012.
</mixed-citation></ref-html>
<ref-html id="bib1.bib15"><label>15</label><mixed-citation>
Bakker-Arkema, J. G., and Ziemann, P. J.: Measurements of kinetics and equilibria for the condensed phase reactions of hydroperoxides with carbonyls to form peroxyhemiacetals, ACS Earth Space Chem., 4, 467–475,  <a href="https://doi.org/10.1021/acsearthspacechem.0c00008" target="_blank">https://doi.org/10.1021/acsearthspacechem.0c00008</a>, 2020.
</mixed-citation></ref-html>
<ref-html id="bib1.bib16"><label>16</label><mixed-citation>
Barsanti, K. C., Kroll, J. H., and Thornton, J. A.: Formation of Low-Volatility Organic Compounds in the Atmosphere: Recent Advancements and Insights, J. Phys. Chem. Lett., 8, 1503–1511,  <a href="https://doi.org/10.1021/acs.jpclett.6b02969" target="_blank">https://doi.org/10.1021/acs.jpclett.6b02969</a>, 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib17"><label>17</label><mixed-citation>
Baruah, S. D., Gour, N. K., Sarma, P. J., and Deka, R. C.: OH-initiated mechanistic pathways and kinetics of camphene and fate of product radical: a DFT approach. Environ, Sci. Pollut. R., 25, 2147–2156,  <a href="https://doi.org/10.1007/s11356-017-0646-2" target="_blank">https://doi.org/10.1007/s11356-017-0646-2</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib18"><label>18</label><mixed-citation>
Bianchi, F., Kurtén, T., Riva, M., Mohr, C., Rissanen, M. P., Roldin, P., Berndt, T., Crounse, J. D., Wennberg, P. O., Mentel, T. F., Wildt, J., Junninen, H., Jokinen, T., Kulmala, M., Worsnop, D. R., Thornton, J. A., Donahue, N., Kjaergaard, H. G., and Ehn, M.: Highly Oxygenated Organic Molecules (HOM) from Gas-Phase Autoxidation Involving Peroxy Radicals: A Key Contributor to Atmospheric Aerosol, Chem. Rev., 119, 3472–3509,  <a href="https://doi.org/10.1021/acs.chemrev.8b00395" target="_blank">https://doi.org/10.1021/acs.chemrev.8b00395</a>, 2019.
</mixed-citation></ref-html>
<ref-html id="bib1.bib19"><label>19</label><mixed-citation>
Boyd, C. M., Nah, T., Xu, L., Berkemeier, T., and Ng, N. L.: Secondary organic aerosol (SOA) from nitrate radical oxidation of monoterpenes: Effects of temperature, dilution, and humidity on aerosol formation, mixing, and evaporation, Environ. Sci. Technol., 51, 7831–7841,  <a href="https://doi.org/10.1021/acs.est.7b01460" target="_blank">https://doi.org/10.1021/acs.est.7b01460</a>, 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib20"><label>20</label><mixed-citation>
Calogirou, A., Larsen, B. R., and Kotzias, D.: Gas-phase terpene oxidation products: A review, Atmos. Environ., 33, 1423–1439,  <a href="https://doi.org/10.1016/S1352-2310(98)00277-5" target="_blank">https://doi.org/10.1016/S1352-2310(98)00277-5</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib21"><label>21</label><mixed-citation>
Camredon, M., Aumont, B., Lee-Taylor, J., and Madronich, S.: The SOA∕VOC∕NO<sub>x</sub> system: an explicit model of secondary organic aerosol formation, Atmos. Chem. Phys., 7, 5599–5610,  <a href="https://doi.org/10.5194/acp-7-5599-2007" target="_blank">https://doi.org/10.5194/acp-7-5599-2007</a>, 2007.
</mixed-citation></ref-html>
<ref-html id="bib1.bib22"><label>22</label><mixed-citation>
Carter, W. P. L.: Development of a condensed SAPRC-07 chemical mechanism, Atmos. Environ., 44, 5336–5345,  <a href="https://doi.org/10.1016/j.atmosenv.2010.01.024" target="_blank">https://doi.org/10.1016/j.atmosenv.2010.01.024</a>, 2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib23"><label>23</label><mixed-citation>
Chen, F., Zhou, H., Gao, J., and Hopke, P. K.: A chamber study of secondary organic aerosol (SOA) formed by ozonolysis of d-limonene in the presence of NO, Aerosol Air Qual. Res., 17, 59–68,  <a href="https://doi.org/10.4209/aaqr.2016.01.0029" target="_blank">https://doi.org/10.4209/aaqr.2016.01.0029</a>, 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib24"><label>24</label><mixed-citation>
Chen, Q., Liu, Y., Donahue, N. M., Shilling, J. E., and Martin, S. T.: Particle-phase chemistry of secondary organic material: Modeled compared to measured O : C and H : C elemental ratios provide constraints, Environ. Sci. Technol., 45, 4763–4770,  <a href="https://doi.org/10.1021/es104398s" target="_blank">https://doi.org/10.1021/es104398s</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib25"><label>25</label><mixed-citation>
Chhabra, P. S., Flagan, R. C., and Seinfeld, J. H.: Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer, Atmos. Chem. Phys., 10, 4111–4131,  <a href="https://doi.org/10.5194/acp-10-4111-2010" target="_blank">https://doi.org/10.5194/acp-10-4111-2010</a>, 2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib26"><label>26</label><mixed-citation>
Chhabra, P. S., Ng, N. L., Canagaratna, M. R., Corrigan, A. L., Russell, L. M., Worsnop, D. R., Flagan, R. C., and Seinfeld, J. H.: Elemental composition and oxidation of chamber organic aerosol, Atmos. Chem. Phys., 11, 8827–8845,  <a href="https://doi.org/10.5194/acp-11-8827-2011" target="_blank">https://doi.org/10.5194/acp-11-8827-2011</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib27"><label>27</label><mixed-citation>
Chuang, W. K. and Donahue, N. M.: A two-dimensional volatility basis set – Part 3: Prognostic modeling and NO<sub><i>x</i></sub> dependence, Atmos. Chem. Phys., 16, 123–134,  <a href="https://doi.org/10.5194/acp-16-123-2016" target="_blank">https://doi.org/10.5194/acp-16-123-2016</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib28"><label>28</label><mixed-citation>
Claflin, M. S., Krechmer, J. E., Hu, W., Jimenez, J. L., and Ziemann, P. J.: Functional group composition of secondary organic aerosol formed from ozonolysis of <i>α</i>-pinene under high VOC and autoxidation conditions, ACS Earth Space Chem., 2, 1196–1210,  <a href="https://doi.org/10.1021/acsearthspacechem.8b00117" target="_blank">https://doi.org/10.1021/acsearthspacechem.8b00117</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib29"><label>29</label><mixed-citation>
Draper, D. C., Farmer, D. K., Desyaterik, Y., and Fry, J. L.: A qualitative comparison of secondary organic aerosol yields and composition from ozonolysis of monoterpenes at varying concentrations of NO<sub>2</sub>, Atmos. Chem. Phys., 15, 12267–12281,  <a href="https://doi.org/10.5194/acp-15-12267-2015" target="_blank">https://doi.org/10.5194/acp-15-12267-2015</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib30"><label>30</label><mixed-citation>
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H., Pullinen, I., Springer, M., Rubach, F., Tillmann, R., Lee, B., Lopez-Hilfiker, F., Andres, S., Acir, I. H., Rissanen, M., Jokinen, T., Schobesberger, S., Kangasluoma, J., Kontkanen, J., Nieminen, T., Kurtén, T., Nielsen, L. B., Jørgensen, S., Kjaergaard, H. G., Canagaratna M., Maso, M. D., Berndt, T., Petäjä, T., Wahner, A., Kerminen, V. M., Kulmala, M., Worsnop, D. R., Wildt, J., Mentel, T. F.: A large source of low-volatility secondary organic aerosol, Nature, 506, 476–479, <a href="https://doi.org/10.1038/nature13032" target="_blank">https://doi.org/10.1038/nature13032</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib31"><label>31</label><mixed-citation>
Fehsenfeld, F., Calvert, J., Fall, R., Goldan, P., Guenther, A. B., Hewitt, C. N., Lamb, B., Liu, S., Trainer, M., Westberg, H., and Zimmerman, P.: Emissions of volatile organic compounds from vegetation and the implications for atmospheric chemistry, Global Biogeochem. Cy., 6, 389–430,  <a href="https://doi.org/10.1029/92GB02125" target="_blank">https://doi.org/10.1029/92GB02125</a>, 1992.
</mixed-citation></ref-html>
<ref-html id="bib1.bib32"><label>32</label><mixed-citation>
Friedman, B. and Farmer, D. K.: SOA and gas phase organic acid yields from the sequential photooxidation of seven monoterpenes, Atmos. Environ., 187, 335–345,  <a href="https://doi.org/10.1016/j.atmosenv.2018.06.003" target="_blank">https://doi.org/10.1016/j.atmosenv.2018.06.003</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib33"><label>33</label><mixed-citation>
Fry, J. L., Draper, D. C., Barsanti, K. C., Smith, J. N., Ortega, J., Winkler, P. M., Lawler, M. J., Brown, S. S., Edwards, P. M., Cohen, R. C., and Lee, L.: Secondary organic aerosol formation and organic nitrate yield from NO<sub>3</sub> oxidation of biogenic hydrocarbons, Environ. Sci. Technol., 48, 11944–11953,  <a href="https://doi.org/10.1021/es502204x" target="_blank">https://doi.org/10.1021/es502204x</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib34"><label>34</label><mixed-citation>
Gaona-Colmán, E., Blanco, M. B., Barnes, I., Wiesen, P., and Teruel, M. A.: OH- and O<sub>3</sub>-initiated atmospheric degradation of camphene: Temperature dependent rate coefficients, product yields and mechanisms, RSC Adv., 7, 2733–2744,  <a href="https://doi.org/10.1039/c6ra26656h" target="_blank">https://doi.org/10.1039/c6ra26656h</a>, 2017.
</mixed-citation></ref-html>
<ref-html id="bib1.bib35"><label>35</label><mixed-citation>
Geron, C., Rasmussen, R., Arnts, R. R., and Guenther, A.: A review and synthesis of monoterpene speciation from forests in the United States, Atmos. Environ., 34, 1761–1781,  <a href="https://doi.org/10.1016/S1352-2310(99)00364-7" target="_blank">https://doi.org/10.1016/S1352-2310(99)00364-7</a>, 2000.
</mixed-citation></ref-html>
<ref-html id="bib1.bib36"><label>36</label><mixed-citation>
Gilman, J. B., Lerner, B. M., Kuster, W. C., Goldan, P. D., Warneke, C., Veres, P. R., Roberts, J. M., de Gouw, J. A., Burling, I. R., and Yokelson, R. J.: Biomass burning emissions and potential air quality impacts of volatile organic compounds and other trace gases from fuels common in the US, Atmos. Chem. Phys., 15, 13915–13938,  <a href="https://doi.org/10.5194/acp-15-13915-2015" target="_blank">https://doi.org/10.5194/acp-15-13915-2015</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib37"><label>37</label><mixed-citation>
Griffin, R. J., Cocker, D. R., Flagan, R. C., and Seinfeld, J. H.: Organic aerosol formation from the oxidation of biogenic hydrocarbons, J. Geophys. Res.-Atmos., 104, 3555–3567,  <a href="https://doi.org/10.1029/1998JD100049" target="_blank">https://doi.org/10.1029/1998JD100049</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib38"><label>38</label><mixed-citation>
Guenther, A., Hewitt, C. N., Erickson, D., Fall, R., Geron, C., Graedel, T., Harley, P., Klinger, L., Lerdau, M., Mckay, W. A., Pierce, T., Scholes, B., Steinbrecher, R., Tallamraju, R., Taylor, J., and Zimmerman, P.: A global model of natural volatile organic compound emission, J. Geophys. Res., 100, 8873–8892,  <a href="https://doi.org/10.1029/94JD02950" target="_blank">https://doi.org/10.1029/94JD02950</a>, 1995.
</mixed-citation></ref-html>
<ref-html id="bib1.bib39"><label>39</label><mixed-citation>
Hakola, H., Arey, J., Aschmann, S. M., and Atkinson, R.: Product formation from the gas-phase reactions of OH radicals and O<sub>3</sub> with a series of monoterpenes, J. Atmos. Chem., 18, 75–102,  <a href="https://doi.org/10.1007/BF00694375" target="_blank">https://doi.org/10.1007/BF00694375</a>, 1994.
</mixed-citation></ref-html>
<ref-html id="bib1.bib40"><label>40</label><mixed-citation>
Hallquist, M., Wängberg, I., Ljungström, E., Barnes, I., and Becker, K. H.: Aerosol and product yields from NO<sub>3</sub> radical-initiated oxidation of selected monoterpenes, Environ. Sci. Technol., 33, 553–559,  <a href="https://doi.org/10.1021/es980292s" target="_blank">https://doi.org/10.1021/es980292s</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib41"><label>41</label><mixed-citation>
Hatch, L. E., Luo, W., Pankow, J. F., Yokelson, R. J., Stockwell, C. E., and Barsanti, K. C.: Identification and quantification of gaseous organic compounds emitted from biomass burning using two-dimensional gas chromatography–time-of-flight mass spectrometry, Atmos. Chem. Phys., 15, 1865–1899,  <a href="https://doi.org/10.5194/acp-15-1865-2015" target="_blank">https://doi.org/10.5194/acp-15-1865-2015</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib42"><label>42</label><mixed-citation>
Hatch, L. E., Jen, C. N., Kreisberg, N. M., Selimovic, V., Yokelson, R. J., Stamatis, C., York, R. A., Foster, D., Stephens, S. L., Goldstein, A. H., and Barsanti, K. C.: Highly speciated measurements of terpenoids emitted from laboratory and mixed-conifer forest prescribed fires, Environ. Sci. Technol., 53, 9418–9428,  <a href="https://doi.org/10.1021/acs.est.9b02612" target="_blank">https://doi.org/10.1021/acs.est.9b02612</a>, 2019.
</mixed-citation></ref-html>
<ref-html id="bib1.bib43"><label>43</label><mixed-citation>
Hatfield, M. L. and Huff Hartz, K. E.: Secondary organic aerosol from biogenic volatile organic compound mixtures, Atmos. Environ., 45, 2211–2219,  <a href="https://doi.org/10.1016/j.atmosenv.2011.01.065" target="_blank">https://doi.org/10.1016/j.atmosenv.2011.01.065</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib44"><label>44</label><mixed-citation>
Hayward, S., Muncey, R. J., James, A. E., Halsall, C. J., and Hewitt, C. N.: Monoterpene emissions from soil in a Sitka spruce forest, Atmos. Environ., 35, 4081–4087,  <a href="https://doi.org/10.1016/S1352-2310(01)00213-8" target="_blank">https://doi.org/10.1016/S1352-2310(01)00213-8</a>, 2001.
</mixed-citation></ref-html>
<ref-html id="bib1.bib45"><label>45</label><mixed-citation>
Heaton, K. J., Dreyfus, M. A., Wang, S., and Johnston, M. v.: Oligomers in the early stage of biogenic secondary organic aerosol formation and growth, Environ. Sci. Technol., 41, 6129–6136,  <a href="https://doi.org/10.1021/es070314n" target="_blank">https://doi.org/10.1021/es070314n</a>, 2007.
</mixed-citation></ref-html>
<ref-html id="bib1.bib46"><label>46</label><mixed-citation>
Jacobson, M. C., Hansson, H. C., Noone, K. J., and Charlson, R. J.: Organic atmospheric aerosols: Review and state of the science, Rev. Geophys., 38, 267–294,  <a href="https://doi.org/10.1029/1998RG000045" target="_blank">https://doi.org/10.1029/1998RG000045</a>, 2000.
</mixed-citation></ref-html>
<ref-html id="bib1.bib47"><label>47</label><mixed-citation>
Jang, M. and Kamens, R. M.: Newly characterized products and composition of secondary aerosols from the reaction of <i>α</i>-pinene with ozone, Atmos. Environ., 33, 459–474,  <a href="https://doi.org/10.1016/S1352-2310(98)00222-2" target="_blank">https://doi.org/10.1016/S1352-2310(98)00222-2</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib48"><label>48</label><mixed-citation>
Jokinen, T., Berndt, T., Makkonen, R., Kerminen, V.-M., Junninen, H., Paasonen, P., Stratmann, F., Herrmann, H., Guenther, A. B., Worsnop, D. R., Kulmala, M., Ehn, M., and Sipilä, M.: Production of extremely low volatile organic compounds from biogenic emissions: Measured yields and atmospheric implications, P. Natl. Acad. Sci. USA, 112, 7123–7128,  <a href="https://doi.org/10.1073/pnas.1423977112" target="_blank">https://doi.org/10.1073/pnas.1423977112</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib49"><label>49</label><mixed-citation>
Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I.,
Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A.,
Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S.,
Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K.,
Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global
climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123,
<a href="https://doi.org/10.5194/acp-5-1053-2005" target="_blank">https://doi.org/10.5194/acp-5-1053-2005</a>, 2005.
</mixed-citation></ref-html>
<ref-html id="bib1.bib50"><label>50</label><mixed-citation>
Kenseth, C. M., Huang, Y., Zhao, R., Dalleska, N. F., Hethcox, J. C., Stoltz, B. M., and Seinfeld, J. H.: Synergistic O<sub>3</sub> + OH oxidation pathway to extremely low-volatility dimers revealed in <i>β</i>-pinene secondary organic aerosol, P. Natl. Acad. Sci. USA, 115, 8301–8306,  <a href="https://doi.org/10.1073/pnas.1804671115" target="_blank">https://doi.org/10.1073/pnas.1804671115</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib51"><label>51</label><mixed-citation>
Kesselmeier, J. and Staudt, M.: Biogenic volatile organic compounds (VOC): An overview on emission, physiology and ecology, J. Atmos. Chem., 33, 23–88,  <a href="https://doi.org/10.1023/A:1006127516791" target="_blank">https://doi.org/10.1023/A:1006127516791</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib52"><label>52</label><mixed-citation>
Kim, H. and Paulson, S. E.: Real refractive indices and volatility of secondary organic aerosol generated from photooxidation and ozonolysis of limonene, <i>α</i>-pinene and toluene, Atmos. Chem. Phys., 13, 7711–7723,  <a href="https://doi.org/10.5194/acp-13-7711-2013" target="_blank">https://doi.org/10.5194/acp-13-7711-2013</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib53"><label>53</label><mixed-citation>
Kim, S., Karl, T., Guenther, A., Tyndall, G., Orlando, J., Harley, P., Rasmussen, R., and Apel, E.: Emissions and ambient distributions of Biogenic Volatile Organic Compounds (BVOC) in a ponderosa pine ecosystem: interpretation of PTR-MS mass spectra, Atmos. Chem. Phys., 10, 1759–1771,  <a href="https://doi.org/10.5194/acp-10-1759-2010" target="_blank">https://doi.org/10.5194/acp-10-1759-2010</a>, 2010.
</mixed-citation></ref-html>
<ref-html id="bib1.bib54"><label>54</label><mixed-citation>
Kourtchev, I., Fuller, S. J., Giorio, C., Healy, R. M., Wilson, E., O'Connor, I., Wenger, J. C., McLeod, M., Aalto, J., Ruuskanen, T. M., Maenhaut, W., Jones, R., Venables, D. S., Sodeau, J. R., Kulmala, M., and Kalberer, M.: Molecular composition of biogenic secondary organic aerosols using ultrahigh-resolution mass spectrometry: comparing laboratory and field studies, Atmos. Chem. Phys., 14, 2155–2167,  <a href="https://doi.org/10.5194/acp-14-2155-2014" target="_blank">https://doi.org/10.5194/acp-14-2155-2014</a>, 2014.
</mixed-citation></ref-html>
<ref-html id="bib1.bib55"><label>55</label><mixed-citation>
Kourtchev, I., Doussin, J.-F., Giorio, C., Mahon, B., Wilson, E. M., Maurin, N., Pangui, E., Venables, D. S., Wenger, J. C., and Kalberer, M.: Molecular composition of fresh and aged secondary organic aerosol from a mixture of biogenic volatile compounds: a high-resolution mass spectrometry study, Atmos. Chem. Phys., 15, 5683–5695,  <a href="https://doi.org/10.5194/acp-15-5683-2015" target="_blank">https://doi.org/10.5194/acp-15-5683-2015</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib56"><label>56</label><mixed-citation>
Kundu, S., Fisseha, R., Putman, A. L., Rahn, T. A., and Mazzoleni, L. R.: High molecular weight SOA formation during limonene ozonolysis: insights from ultrahigh-resolution FT-ICR mass spectrometry characterization, Atmos. Chem. Phys., 12, 5523–5536,  <a href="https://doi.org/10.5194/acp-12-5523-2012" target="_blank">https://doi.org/10.5194/acp-12-5523-2012</a>, 2012.
</mixed-citation></ref-html>
<ref-html id="bib1.bib57"><label>57</label><mixed-citation>
La, Y. S., Camredon, M., Ziemann, P. J., Valorso, R., Matsunaga, A., Lannuque, V., Lee-Taylor, J., Hodzic, A., Madronich, S., and Aumont, B.: Impact of chamber wall loss of gaseous organic compounds on secondary organic aerosol formation: explicit modeling of SOA formation from alkane and alkene oxidation, Atmos. Chem. Phys., 16, 1417–1431,  <a href="https://doi.org/10.5194/acp-16-1417-2016" target="_blank">https://doi.org/10.5194/acp-16-1417-2016</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib58"><label>58</label><mixed-citation>
Lambe, A. T., Chhabra, P. S., Onasch, T. B., Brune, W. H., Hunter, J. F., Kroll, J. H., Cummings, M. J., Brogan, J. F., Parmar, Y., Worsnop, D. R., Kolb, C. E., and Davidovits, P.: Effect of oxidant concentration, exposure time, and seed particles on secondary organic aerosol chemical composition and yield, Atmos. Chem. Phys., 15, 3063–3075,  <a href="https://doi.org/10.5194/acp-15-3063-2015" target="_blank">https://doi.org/10.5194/acp-15-3063-2015</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib59"><label>59</label><mixed-citation>
Larsen, B. R., di Bella, D., Glasius, M., Winterhalter, R., Jensen, N. R., and Hjorth, J.: Gas-phase OH oxidation of monoterpenes: Gaseous and particulate products, J. Atmos. Chem., 38, 231–276,  <a href="https://doi.org/10.1023/A:1006487530903" target="_blank">https://doi.org/10.1023/A:1006487530903</a>, 2001.
</mixed-citation></ref-html>
<ref-html id="bib1.bib60"><label>60</label><mixed-citation>
Lee, A., Goldstein, A. H., Keywood, M. D., Gao, S., Varutbangkul, V., Bahreini, R., Ng, N. L., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes, J. Geophys. Res.-Atmos., 111, D07302.  <a href="https://doi.org/10.1029/2005JD006437" target="_blank">https://doi.org/10.1029/2005JD006437</a>, 2006a.
</mixed-citation></ref-html>
<ref-html id="bib1.bib61"><label>61</label><mixed-citation>
Lee, A., Goldstein, A. H., Kroll, J. H., Ng, N. L., Varutbangkul, V., Flagan, R. C., and Seinfeld, J. H.: Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes, J. Geophys. Res.-Atmos., 111, D17305,  <a href="https://doi.org/10.1029/2006JD007050" target="_blank">https://doi.org/10.1029/2006JD007050</a>, 2006b.
</mixed-citation></ref-html>
<ref-html id="bib1.bib62"><label>62</label><mixed-citation>
Ludley, Katherine. E., Jickells, S. M., Chamberlain, P. M., Whitaker, J., and Robinson, C. H.: Distribution of monoterpenes between organic resources in upper soil horizons under monocultures of <i>Picea abies</i>, <i>Picea sitchensis</i> and <i>Pinus Sylvestris</i>, Soil Biol. Biochem., 41, 1050–1059,  <a href="https://doi.org/10.1016/J.SOILBIO.2009.02.002" target="_blank">https://doi.org/10.1016/J.SOILBIO.2009.02.002</a>, 2009.
</mixed-citation></ref-html>
<ref-html id="bib1.bib63"><label>63</label><mixed-citation>
Maleknia, S. D., Bell, T. L., and Adams, M. A.: PTR-MS analysis of reference and plant-emitted volatile organic compounds, Int. J. Mass Spectrom., 262, 203–210,  <a href="https://doi.org/10.1016/j.ijms.2006.11.010" target="_blank">https://doi.org/10.1016/j.ijms.2006.11.010</a>, 2007.
</mixed-citation></ref-html>
<ref-html id="bib1.bib64"><label>64</label><mixed-citation>
McVay, R. C., Zhang, X., Aumont, B., Valorso, R., Camredon, M., La, Y. S., Wennberg, P. O., and Seinfeld, J. H.: SOA formation from the photooxidation of <i>α</i>-pinene: systematic exploration of the simulation of chamber data, Atmos. Chem. Phys., 16, 2785–2802,  <a href="https://doi.org/10.5194/acp-16-2785-2016" target="_blank">https://doi.org/10.5194/acp-16-2785-2016</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib65"><label>65</label><mixed-citation>
Nah, T., McVay, R. C., Zhang, X., Boyd, C. M., Seinfeld, J. H.,
and Ng, N. L.: Influence of seed aerosol surface area and oxidation rate on
vapor wall deposition and SOA mass yields: a case study with <i>α</i>-pinene
ozonolysis, Atmos. Chem. Phys., 16, 9361–9379,
<a href="https://doi.org/10.5194/acp-16-9361-2016" target="_blank">https://doi.org/10.5194/acp-16-9361-2016</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib66"><label>66</label><mixed-citation>
Nannoolal, Y., Rarey, J., and Ramjugernath, D.: Estimation of pure component properties part 3. Estimation of the vapor pressure of non-electrolyte organic compounds via group contribution and group interactions, Fluid Phase Equilibr., 269, 117–133,  <a href="https://doi.org/10.1016/j.fluid.2008.04.020" target="_blank">https://doi.org/10.1016/j.fluid.2008.04.020</a>, 2008.
</mixed-citation></ref-html>
<ref-html id="bib1.bib67"><label>67</label><mixed-citation>
Ng, N. L., Chhabra, P. S., Chan, A. W. H., Surratt, J. D., Kroll, J. H., Kwan, A. J., McCabe, D. C., Wennberg, P. O., Sorooshian, A., Murphy, S. M., Dalleska, N. F., Flagan, R. C., and Seinfeld, J. H.: Effect of NO<sub><i>x</i></sub> level on secondary organic aerosol (SOA) formation from the photooxidation of terpenes, Atmos. Chem. Phys., 7, 5159–5174, <a href="https://doi.org/10.5194/acp-7-5159-2007" target="_blank">https://doi.org/10.5194/acp-7-5159-2007</a>, 2007.
</mixed-citation></ref-html>
<ref-html id="bib1.bib68"><label>68</label><mixed-citation>
Odum Jay, R., Hoffmann, T., Bowman, F., Collins, D., Flagan Richard, C., and Seinfeld John, H.: Gas particle partitioning and secondary organic aerosol yields, Environ. Sci. Technol., 30, 2580–2585,  <a href="https://doi.org/10.1021/es950943+" target="_blank">https://doi.org/10.1021/es950943+</a>, 1996.
</mixed-citation></ref-html>
<ref-html id="bib1.bib69"><label>69</label><mixed-citation>
Pankow, J. F.: An absorption model of gas/particle partitioning of organic compounds in the atmosphere, Atmos. Environ., 28, 185–188,  <a href="https://doi.org/10.1016/1352-2310(94)90093-0" target="_blank">https://doi.org/10.1016/1352-2310(94)90093-0</a>, 1994.
</mixed-citation></ref-html>
<ref-html id="bib1.bib70"><label>70</label><mixed-citation>
Pathak, R. K., Presto, A. A., Lane, T. E., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of <i>α</i>-pinene: parameterization of secondary organic aerosol mass fraction, Atmos. Chem. Phys., 7, 3811–3821, <a href="https://doi.org/10.5194/acp-7-3811-2007" target="_blank">https://doi.org/10.5194/acp-7-3811-2007</a>, 2007a.
</mixed-citation></ref-html>
<ref-html id="bib1.bib71"><label>71</label><mixed-citation>
Pathak, R. K., Stanier, C. O., Donahue, N. M., and Pandis, S. N.: Ozonolysis of <i>α</i>-pinene at atmospherically relevant concentrations: Temperature dependence of aerosol mass fractions (yields), J. Geophys. Res.-Atmos., 112, 1–8,  <a href="https://doi.org/10.1029/2006JD007436" target="_blank">https://doi.org/10.1029/2006JD007436</a>, 2007b.
</mixed-citation></ref-html>
<ref-html id="bib1.bib72"><label>72</label><mixed-citation>
Peeters, J., Vereecken, L., and Fantechi, G.: The detailed mechanism of the OH-initiated atmospheric oxidation of <i>α</i>-pinene: A theoretical study, Phys. Chem. Chem. Phys., 3, 5489–5504, <a href="https://doi.org/10.1039/b106555f" target="_blank">https://doi.org/10.1039/b106555f</a>, 2001.
</mixed-citation></ref-html>
<ref-html id="bib1.bib73"><label>73</label><mixed-citation>
Pfaffenberger, L., Barmet, P., Slowik, J. G., Praplan, A. P., Dommen, J., Prévôt, A. S. H., and Baltensperger, U.: The link between organic aerosol mass loading and degree of oxygenation: an <i>α</i>-pinene photooxidation study, Atmos. Chem. Phys., 13, 6493–6506,  <a href="https://doi.org/10.5194/acp-13-6493-2013" target="_blank">https://doi.org/10.5194/acp-13-6493-2013</a>, 2013.
</mixed-citation></ref-html>
<ref-html id="bib1.bib74"><label>74</label><mixed-citation>
Presto, A. A. and Donahue, N. M.: Investigation of <i>α</i>-pinene&thinsp;+&thinsp;ozone secondary organic aerosol formation at low total aerosol mass, Environ. Sci. Technol., 40, 3536–3543,  <a href="https://doi.org/10.1021/es052203z" target="_blank">https://doi.org/10.1021/es052203z</a>, 2006.
</mixed-citation></ref-html>
<ref-html id="bib1.bib75"><label>75</label><mixed-citation>
Presto, A. A., Huff Hartz, K. E., and Donahue, N. M.: Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NO<sub><i>x</i></sub> concentration, Environ. Sci. Technol., 39, 7046–7054,  <a href="https://doi.org/10.1021/es050400s" target="_blank">https://doi.org/10.1021/es050400s</a>, 2005.
</mixed-citation></ref-html>
<ref-html id="bib1.bib76"><label>76</label><mixed-citation>
Reinhardt, A., Emmenegger, C., Gerrits, B., Panse, C., Dommen, J., Baltensperger, U., Zenobi, R., and Kalberer, M.: Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols, Anal. Chem., 79, 4074–4082,  <a href="https://doi.org/10.1021/ac062425v" target="_blank">https://doi.org/10.1021/ac062425v</a>, 2007.
</mixed-citation></ref-html>
<ref-html id="bib1.bib77"><label>77</label><mixed-citation>
Reissell, A., Harry, C., Aschmann, S. M., Atkinson, R., and Arey, J.: Formation of acetone from the OH radical- and O<sub>3</sub>-initiated reactions of a series of monoterpenes, J. Geophys. Res.-Atmos., 104, 13869–13879,  <a href="https://doi.org/10.1029/1999JD900198" target="_blank">https://doi.org/10.1029/1999JD900198</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib78"><label>78</label><mixed-citation>
Rinne, J., Tuovinen, J. P., Laurila, T., Hakola, H., Aurela, M., and Hypén, H.: Measurements of hydrocarbon fluxes by a gradient method above a northern boreal forest, Agr. Forest Meteorol., 102, 25–37,  <a href="https://doi.org/10.1016/S0168-1923(00)00088-5" target="_blank">https://doi.org/10.1016/S0168-1923(00)00088-5</a>, 2000.
</mixed-citation></ref-html>
<ref-html id="bib1.bib79"><label>79</label><mixed-citation>
Saha, P. K. and Grieshop, A. P.: Exploring divergent volatility properties from yield and thermodenuder measurements of secondary organic aerosol from <i>α</i>-pinene ozonolysis, Environ. Sci. Technol., 50, 5740–5749,  <a href="https://doi.org/10.1021/acs.est.6b00303" target="_blank">https://doi.org/10.1021/acs.est.6b00303</a>, 2016.
</mixed-citation></ref-html>
<ref-html id="bib1.bib80"><label>80</label><mixed-citation>
Shilling, J. E., Chen, Q., King, S. M., Rosenoern, T., Kroll, J. H., Worsnop, D. R., DeCarlo, P. F., Aiken, A. C., Sueper, D., Jimenez, J. L., and Martin, S. T.: Loading-dependent elemental composition of <i>α</i>-pinene SOA particles, Atmos. Chem. Phys., 9, 771–782,  <a href="https://doi.org/10.5194/acp-9-771-2009" target="_blank">https://doi.org/10.5194/acp-9-771-2009</a>, 2009.
</mixed-citation></ref-html>
<ref-html id="bib1.bib81"><label>81</label><mixed-citation>
Simpson, I. J., Akagi, S. K., Barletta, B., Blake, N. J., Choi, Y., Diskin, G. S., Fried, A., Fuelberg, H. E., Meinardi, S., Rowland, F. S., Vay, S. A., Weinheimer, A. J., Wennberg, P. O., Wiebring, P., Wisthaler, A., Yang, M., Yokelson, R. J., and Blake, D. R.: Boreal forest fire emissions in fresh Canadian smoke plumes: C<sub>1</sub> − C<sub>10</sub> volatile organic compounds (VOCs), CO<sub>2</sub>, CO, NO<sub>2</sub>, NO, HCN and CH<sub>3</sub>CN, Atmos. Chem. Phys., 11, 6445–6463,  <a href="https://doi.org/10.5194/acp-11-6445-2011" target="_blank">https://doi.org/10.5194/acp-11-6445-2011</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib82"><label>82</label><mixed-citation>
Steinbrecher, R., Hauff, K., Rössler, J., Dürr, M., and Seufert, G.: Monoterpene emission from soils in orange plantations of the Valencian Citrus belt, Spain, Phys. Chem. Earth Pt. B, 24, 695–698,  <a href="https://doi.org/10.1016/S1464-1909(99)00067-2" target="_blank">https://doi.org/10.1016/S1464-1909(99)00067-2</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib83"><label>83</label><mixed-citation>
Stockwell, W. R., Kirchner, F., Kuhn, M., and Seefeld, S.: A new mechanism for regional atmospheric chemistry modeling, J. Geophys. Res.-Atmos., 102, 25847–25879,  <a href="https://doi.org/10.1029/97jd00849" target="_blank">https://doi.org/10.1029/97jd00849</a>, 1997.
</mixed-citation></ref-html>
<ref-html id="bib1.bib84"><label>84</label><mixed-citation>
Tani, A., Hayward, S., and Hewitt, C. N.: Measurement of monoterpenes and related compounds by proton transfer reaction-mass spectrometry (PTR-MS), Int. J. Mass Spectrom., 223–224, 561–578,  <a href="https://doi.org/10.1016/S1387-3806(02)00880-1" target="_blank">https://doi.org/10.1016/S1387-3806(02)00880-1</a>, 2003.
</mixed-citation></ref-html>
<ref-html id="bib1.bib85"><label>85</label><mixed-citation>
Valorso, R., Aumont, B., Camredon, M., Raventos-Duran, T., Mouchel-Vallon, C., Ng, N. L., Seinfeld, J. H., Lee-Taylor, J., and Madronich, S.: Explicit modelling of SOA formation from <i>α</i>-pinene photooxidation: sensitivity to vapour pressure estimation, Atmos. Chem. Phys., 11, 6895–6910,  <a href="https://doi.org/10.5194/acp-11-6895-2011" target="_blank">https://doi.org/10.5194/acp-11-6895-2011</a>, 2011.
</mixed-citation></ref-html>
<ref-html id="bib1.bib86"><label>86</label><mixed-citation>
Vereecken, L. and Nozière, B.: H migration in peroxy radicals under atmospheric conditions, Atmos. Chem. Phys., 20, 7429–7458,  <a href="https://doi.org/10.5194/acp-20-7429-2020" target="_blank">https://doi.org/10.5194/acp-20-7429-2020</a>, 2020.
</mixed-citation></ref-html>
<ref-html id="bib1.bib87"><label>87</label><mixed-citation>
Walser, M. L., Desyaterik, Y., Laskin, J., Laskin, A., and Nizkorodov, S. A.: High-resolution mass spectrometric analysis of secondary organic aerosol produced by ozonation of limonene, Phys. Chem. Chem. Phys., 10, 1009–1022,  <a href="https://doi.org/10.1039/b712620d" target="_blank">https://doi.org/10.1039/b712620d</a>, 2008.
</mixed-citation></ref-html>
<ref-html id="bib1.bib88"><label>88</label><mixed-citation>
White, M. L., Russo, R. S., Zhou, Y., Mao, H., Varner, R. K., Ambrose, J., Veres, P., Wingenter, O. W., Haase, K., Stutz, J., Talbot, R., and Sive, B. C.: Volatile organic compounds in northern New England marine and continental environments during the ICARTT 2004 campaign, J. Geophys. Res.-Atmos., 113, 1–16,  <a href="https://doi.org/10.1029/2007JD009161" target="_blank">https://doi.org/10.1029/2007JD009161</a>, 2008.
</mixed-citation></ref-html>
<ref-html id="bib1.bib89"><label>89</label><mixed-citation>
Wisthaler, A., Jensen, N. R., Winterhalter, R., Lindinger, W., and Hjorth, J.: Measurements of acetone and other gas phase product yields from the OH-initiated oxidation of terpenes by proton-transfer-reaction mass spectrometry (PTR-MS), Atmos. Environ., 35, 6181–6191,  <a href="https://doi.org/10.1016/S1352-2310(01)00385-5" target="_blank">https://doi.org/10.1016/S1352-2310(01)00385-5</a>, 2001.
</mixed-citation></ref-html>
<ref-html id="bib1.bib90"><label>90</label><mixed-citation>
Yáñez-Serrano, A. M., Nölscher, A. C., Bourtsoukidis, E., Gomes Alves, E., Ganzeveld, L., Bonn, B., Wolff, S., Sa, M., Yamasoe, M., Williams, J., Andreae, M. O., and Kesselmeier, J.: Monoterpene chemical speciation in a tropical rainforest:variation with season, height, and time of dayat the Amazon Tall Tower Observatory (ATTO), Atmos. Chem. Phys., 18, 3403–3418,  <a href="https://doi.org/10.5194/acp-18-3403-2018" target="_blank">https://doi.org/10.5194/acp-18-3403-2018</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib91"><label>91</label><mixed-citation>
Yassaa, N., Peeken, I., Zllner, E., Bluhm, K., Arnold, S., Spracklen, D., and Williams, J.: Evidence for marine production of monoterpenes, Environ. Chem., 5, 391–401,  <a href="https://doi.org/10.1071/EN08047" target="_blank">https://doi.org/10.1071/EN08047</a>, 2008.
</mixed-citation></ref-html>
<ref-html id="bib1.bib92"><label>92</label><mixed-citation>
Yu, J., Cocker III, D. R., Griffin, R. J., Flagan, R. C., and Seinfeld, J. H.: Gas-Phase Ozone Oxidation of Monoterpenes: Gaseous and Particulate Products, J. Atmos. Chem., 34, 207–258,  <a href="https://doi.org/10.1023/A:1006254930583" target="_blank">https://doi.org/10.1023/A:1006254930583</a>, 1999.
</mixed-citation></ref-html>
<ref-html id="bib1.bib93"><label>93</label><mixed-citation>
Zhang, J., Huff Hartz, K. E., Pandis, S. N., and Donahue, N. M.: Secondary organic aerosol formation from limonene Ozonolysis: Homogeneous and heterogeneous influences as a function of NO<sub><i>x</i></sub>, J. Phys. Chem. A., 110, 11053–11063,  <a href="https://doi.org/10.1021/jp062836f" target="_blank">https://doi.org/10.1021/jp062836f</a>, 2006.
</mixed-citation></ref-html>
<ref-html id="bib1.bib94"><label>94</label><mixed-citation>
Zhang, X, McVay, R. C., Huang, D. D., Dalleska, N. F., Aumont, B., Flagan, R. C., and Seinfeld, J. H.: Formation and evolution of molecular products in alpha-pinene secondary organic aerosol, P. Natl. Acad. Sci. USA, 112, 14168–14173,  <a href="https://doi.org/10.1073/pnas.1517742112" target="_blank">https://doi.org/10.1073/pnas.1517742112</a>, 2015.
</mixed-citation></ref-html>
<ref-html id="bib1.bib95"><label>95</label><mixed-citation>
Zhao, D., Schmitt, S. H., Wang, M., Acir, I.-H., Tillmann, R., Tan, Z., Novelli, A., Fuchs, H., Pullinen, I., Wegener, R., Rohrer, F., Wildt, J., Kiendler-Scharr, A., Wahner, A., and Mentel, T. F.: Effects of NO<sub><i>x</i></sub> and SO<sub>2</sub> on the secondary organic aerosol formation from photooxidation of <i>α</i>-pinene and limonene, Atmos. Chem. Phys., 18, 1611–1628,  <a href="https://doi.org/10.5194/acp-18-1611-2018" target="_blank">https://doi.org/10.5194/acp-18-1611-2018</a>, 2018.
</mixed-citation></ref-html>
<ref-html id="bib1.bib96"><label>96</label><mixed-citation>
Ziemann, P. J. and Atkinson, R.: Kinetics, products, and mechanisms of secondary organic aerosol formation, Chem. Soc. Rev., 41, 6582,  <a href="https://doi.org/10.1039/c2cs35122f" target="_blank">https://doi.org/10.1039/c2cs35122f</a>, 2012.
</mixed-citation></ref-html>--></article>
