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Atmos. Chem. Phys.

, 15, 41454159, 2015
Author(s) 2015. CC Attribution 3.0 License.

Elemental composition and clustering behaviour of -pinene

oxidation products for different oxidation conditions
A. P. Praplan1 , S. Schobesberger1,* , F. Bianchi2,3 , M. P. Rissanen1 , M. Ehn1 , T. Jokinen1 , H. Junninen1 , A. Adamov1 ,
A. Amorim4 , J. Dommen2 , J. Duplissy5 , J. Hakala1 , A. Hansel6,7 , M. Heinritzi8,6 , J. Kangasluoma1 , J. Kirkby9,8 ,
M. Krapf2 , A. Krten8 , K. Lehtipalo1 , F. Riccobono2 , L. Rondo8 , N. Sarnela1 , M. Simon8 , A. Tom4 , J. Trstl2 ,
P. M. Winkler10 , C. Williamson8 , P. Ye11 , J. Curtius8 , U. Baltensperger2 , N. M. Donahue11 , M. Kulmala1,5 , and
D. R. Worsnop1,12
1 Department of Physics, P.O. Box 64, 00014 University of Helsinki, Helsinki, Finland
2 Laboratory of Atmospheric Chemistry, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland
3 Institute for Atmospheric and Climate Science, ETH Zurich, 8092 Zurich, Switzerland
4 Laboratory for Systems, Instrumentation, and Modeling in Science and Technology for Space and the Environment (SIM),

University of Lisbon and University of Beira Interior, 1749-016 Lisbon, Portugal

5 Helsinki Institute of Physics, University of Helsinki, Helsinki, Finland
6 University of Innsbruck, Institute for Ion Physics and Applied Physics, Technikerstrasse 25, 6020 Innsbruck, Austria
7 Ionicon Analytik, Eduard Bodem Gasse 3, 6020 Innsbruck, Austria
8 Institute for Atmospheric and Environmental Sciences, Goethe University Frankfurt am Main, Altenhferallee 1, 60438

Frankfurt am Main, Germany

9 CERN, CH1211, Geneva, Switzerland
10 Faculty of Physics, University of Vienna, Boltzmanngasse 5, 1090 Vienna, Austria
11 Center for Atmospheric Particle Studies, Carnegie Mellon University, 5000 Frobes Ave, Pittsburgh, PA 15213, USA
12 Aerodyne Research Incorporated, Billerica, MA 01821, USA
* now at: University of Washington, Department of Atmospheric Sciences, Box 351640, Seattle, WA 98195, USA

Correspondence to: A. P. Praplan (

Received: 7 November 2014 Published in Atmos. Chem. Phys. Discuss.: 9 December 2014
Revised: 16 March 2015 Accepted: 17 March 2015 Published: 22 April 2015

Abstract. This study presents the difference between oxi- dised organic compounds with low molar mass and ions, so
dised organic compounds formed by -pinene oxidation un- that in order to obtain a comprehensive picture of the ele-
der various conditions in the CLOUD environmental cham- mental composition of oxidation products and their cluster-
ber: (1) pure ozonolysis (in the presence of hydrogen as hy- ing behaviour, several instruments must be used. We compare
droxyl radical (OH) scavenger) and (2) OH oxidation (initi- oxidation products containing 10 and 20 carbon atoms and
ated by nitrous acid (HONO) photolysis by ultraviolet light) show that highly oxidised organic compounds are formed in
in the absence of ozone. the early stages of the oxidation.
We discuss results from three Atmospheric Pressure in-
terface Time-of-Flight (APi-TOF) mass spectrometers mea-
suring simultaneously the composition of naturally charged
as well as neutral species (via chemical ionisation with ni- 1 Introduction
trate). Natural chemical ionisation takes place in the CLOUD
chamber and organic oxidised compounds form clusters with Oxidation of organic vapours in the atmosphere and the sub-
nitrate, bisulfate, bisulfate/sulfuric acid clusters, ammonium, sequent condensation of their products is a source of sec-
and dimethylaminium, or get protonated. The results from ondary organic aerosol (SOA, see e.g. Kanakidou et al.,
this study show that this process is selective for various oxi- 2005; Fuzzi et al., 2006; Hallquist et al., 2009, and references
therein). Because of the vast number of different compounds

Published by Copernicus Publications on behalf of the European Geosciences Union.

4146 A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products

in the atmosphere, with various structures and functionali- et al., 2012a, b; Winkler et al., 2012). Products such as
ties, detailed oxidation mechanisms are usually insufficiently the dicarboxylic acid cis-pinic acid (C9 H14 O4 , Christof-
understood and poorly represented in atmospheric chemical fersen et al., 1998), the tricarboxylic acid 3-methyl-1,2,3-
models, especially for larger and complex molecules (Gold- butanetricarboxylic acid (MBTCA, C8 H12 O6 , Szmigielski
stein and Galbally, 2007; Kroll and Seinfeld, 2008). Tradi- et al., 2007) and oligomeric compounds (Tolocka et al., 2004;
tionally, oxidised organic compounds have been considered Mller et al., 2009) have been identified. Ehn et al. (2012,
condensing on small pre-existing particles (few nanometres 2014) and Schobesberger et al. (2013) have recently ob-
in diameter) to make them grow up to cloud condensation served highly oxidised multifunctional organic compounds
nuclei sizes (larger than 50 to 100 nm diameter). In gen- (i.e. extremely low volatility organic compounds (ELVOCs),
eral, the more oxidised these products, the lower is their already predicted by Kulmala et al., 1998) based on labo-
volatility; therefore, they can condense on smaller particles, ratory experiments and ambient measurements in Hyytil,
contributing to SOA (Pankow, 1994; Seinfeld and Pankow, Finland, with oxygen-to-carbon ratios (O : C) exceeding 1.
2003; Donahue et al., 2006, 2011). However, new studies As an alternative to O : C, Kroll et al. (2011) suggested the
have shown that -pinene oxidation products (and oxidised average oxidation state of carbon OSC as a metric for the de-
organic compounds in general) not only participate in parti- gree of oxidation of atmospheric organic compounds. It can
cle growth but also directly influence particle formation (Ric- be estimated by OSC 2(O : C) H : C.
cobono et al., 2012; Kulmala et al., 2013). It has been shown As the formation of newly observed compounds from
that sulfuric acid forms clusters, which are stabilised by oxi- field studies or from laboratory experiments could not be
dised organic compounds participating directly in the nucle- explained with traditional atmospheric chemistry (Atkin-
ation process (Metzger et al., 2010; Riccobono et al., 2014). son, 2000), new suggestions for mechanisms have been pub-
Other compounds such as ammonia (Kirkby et al., 2011; lished. Intramolecular reactions seem to play an especially
Schobesberger et al., 2015) or amines (Almeida et al., 2013; important role in the formation of highly oxidised com-
Krten et al., 2014) can promote sulfuric acid nucleation as pounds (Peeters et al., 2001; Vereecken and Peeters, 2004;
well due to an efficient acidbase stabilisation mechanism. Ma et al., 2008; Ehn et al., 2014). However, current at-
Monoterpenes (C10 H16 ) are a family of biogenic volatile mospheric chemical models include only few such non-
organic compounds. In boreal forests, -pinene is the most traditional oxidation mechanisms (e.g. intramolecular reac-
abundant monoterpene. It has been extensively studied in tions).
laboratory experiments during the past decades due to its Building on this knowledge, experiments have been con-
large SOA formation potential (Hoppel et al., 2001; Lee and ducted within the CLOUD project at CERN to investigate the
Kamens, 2005; Eddingsaas et al., 2012a). Several oxidation formation of new particles from organic vapours under var-
pathways are known (see Fig. 1). ious oxidation regimes (ozone and hydroxyl radical oxida-
tion). The CLOUD chamber (described in more detail in the
One pathway is ozonolysis, in which ozone (O3 ) re- next section) has extremely low background contamination
acts with the -pinene double bond, forming a primary levels, and therefore provides excellent conditions for un-
ozonide, which will decompose in Criegee intermedi- perturbed nucleation experiments (Schnitzhofer et al., 2014).
ates (Ma et al., 2008; Novelli et al., 2014). These can Additionally, CLOUD makes use of CERNs Proton Syn-
form carboxylic acids (via rearrangement of dioxiranes) chrotron (PS) facility in order to simulate various galactic
or vinylhydroperoxides, which, upon hydroxyl radical cosmic ray (GCR) intensities (increased ion pair concentra-
(OH) elimination, lead to carbonyl compounds. tion).
Another pathway is OH or nitrate radical (NO3 ) oxida- The results presented in this paper focus on the underly-
tion, in which the radical adds to the -pinene double ing chemistry of -pinene oxidation, based on mass spec-
bond (or, alternatively, abstracts a hydrogen atom from trometry measurements. The study investigates positive, neg-
-pinene in the case of OH) resulting in the formation ative and neutral species observed in the CLOUD chamber
of an alkyl radical. Under atmospheric conditions this during -pinene oxidation at a given relative humidity and
radical reacts immediately with molecular oxygen (O2 ) temperature. Two different oxidation pathways have been in-
forming a peroxy radical (RO2 ). This peroxy radical can vestigated: ozonolysis in the presence of an OH scavenger
react with various species including other peroxy radi- and OH oxidation with only background levels of ozone. We
cals. first present the general differences between both systems be-
fore focussing on a subset of oxidised organic compounds, to
Figure 1 is discussed more extensively in Sect. 3.3. show how the elemental composition of oxidation products
Both gas phase and particulate -pinene oxidation prod- varies. The interactions of these various compounds with in-
ucts have been investigated, and more detailed chemi- organic ions and clusters are discussed, and their temporal
cal analyses have become available as analytical meth- evolution is presented in order to investigate formation mech-
ods have progressed recently (Hatakeyama et al., 1989; anisms.
Kamens et al., 1999; Claeys et al., 2009; Eddingsaas

Atmos. Chem. Phys., 15, 41454159, 2015

Discussion Paper
A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products 4147

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Figure 1. Non-exhaustive summary of -pinene ozonolysis (left) and OH oxidation (right) reaction pathways. Oxidation by NO3 has been
1.theNon-exhaustive summary 26
Figure it is notof -pinene ozonolysis
study. Not(left) andreaction
OH oxidation (right) reaction

Discussion Paper
left out for sake of clarity and because relevant to the present all possible pathways and final products are
displayed but Oxidation by NO
only representative 3 hasProducts
examples. been (either
left out fororthe
stable sake ofhave
intermediates) clarity
been and because
grouped in boxes toitindicate
is notthat
the present study. Not all possible reaction pathways and final products are displayed, but only
may arise from the same reaction. The green box marked with a star (*) corresponds to products formed from (acyl)peroxy radicals
(red arrow marked with a star). See main text and discussion for details.
representative examples. Products (either stable or intermediates) have been grouped in boxes to
indicate that several products may arise from the same reaction. The green box marked with a star
2 corresponds
(*) Experimental to products formed from (acyl)peroxy gases, such as water,
radicals sulfur dioxide
(red arrow marked (SO2with
), O3 ,aand -pinene
star). See
are carefully injected to desired levels and monitored. Time
main text and discussion for details.
The CLOUD (Cosmics Leaving Outdoor Droplets) facility resolutions vary from seconds to minutes. An optical fibre
is located at CERN (Meyrin, Switzerland) and consists of ultraviolet (UV) irradiation setup (Kupc et al., 2011) pro-

a 26.1 m3 stainless steel reactor in a temperature-controlled 29 duces hydroxyl radicals from nitrous acid (HONO) photol-
enclosure. The facility is described in more detail by Kirkby ysis for the OH oxidation experiments (Cox, 1974). HONO
et al. (2011). Thorough cleaning with ultra-pure water and is generated continuously from sodium nitrite and sulfuric
heat (373 K) decreases contaminant levels such as ammonia acid solutions according to the method described in Taira and
and amines to a few pptv, and volatile organic compounds to Kanda (1990). An additional strong UV source a Philips
below 1 ppbv (Praplan et al., 2012; Schnitzhofer et al., 2014). TUV 130W XPT lamp producing 50W power, essentially
However, only heating and flushing with the ultra-pure air of monochromatic at 253.7 nm, and installed in a quartz tube
the chamber has been performed between experiments with inserted into the chamber (called UV sabre) is used to
ammonia and dimethyl amine and the experiments presented increase OH levels in the OH experiment presented in this
in this paper, which is somewhat less efficient than the use of paper. The use of a pion beam ( + ) from CERNs Proton
water. Synchrotron increases the concentration of ions present in
The chamber is used as a continuously stirred reactor. It the chamber up to ca. 4000 ion pairs cm3 for the experi-
is constantly flushed with ultra-pure air produced from cryo- ments presented in this study.
genic molecular nitrogen (N2 ) and O2 in a 79 : 21 ratio. Trace Atmos. Chem. Phys., 15, 41454159, 2015

4148 A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products

Table 1. Conditions of selected runs. The given values correspond The difference between the exact mass and the integer (nom-
to the period with constant [H2 SO4 ]. inal) mass of a detected compound (i.e. its mass defect) is
plotted against its exact mass. Figure 2 presents the mass de-
Run -pinene O3 SO2 HONO H2 UV [H2 SO4 ] fect plots from three different instruments (positive and neg-
(pptv) (ppbv) (ppbv) (ppbv) (%) cm3
ative APi-TOFs, as well as nitrate CI-APi-TOF) for the two
1070.02 660 22 69 0 0.1 no 1.91 107
different oxidation conditions. The mass spectra have been
1100.02 1250 0.8 1.1 2.1 0.2 0 yes 1.03 107
averaged over the time periods when sulfuric acid reached
a stable concentration.
All plots show a similar structure, as the signals tend to
The CLOUD7 campaign was conducted between Septem- be organised in bands, resembling clouds of markers ori-
ber and December 2012. Table 1 summarises the condi- ented diagonally (from upper left to lower right). The bands
tions of representative experiments for ozonolysis and OH are most pronounced in mass defect plots for anions (b and
oxidation used in this analysis. For the ozonolysis exper- e). The first band is located on the left with lower mass defect
iment, ozone was set to about 22 ppbv and the oxidation values and the following bands are located more to the right
was triggered by the injection of -pinene. Hydrogen (H2 ) and higher on the mass defect axis. The size of the mark-
was used as an OH scavenger (0.1 %). For the OH oxida- ers is proportional to the natural logarithm of the peak area
tion experiment HONO and -pinene were introduced until in the mass spectra (> 0.01 s1 in this study) and they have
they reached stable concentrations (about 1.9 0.7 ppbv and been coloured according to the retrieved elemental composi-
1250 pptv, respectively). In this case, the oxidation was trig- tion (grey points have unidentified composition). The organic
gered by turning on the UV lights. A model estimation based compounds in the first band are predominantly species with
on the Master Chemical Mechanism (v3.2) and parametrisa- 10 carbon atoms (C10 ), while in the second band they are
tion of the UV sabre estimated the OH concentration to vary mainly compounds with 20 carbon atoms (C20 ), but also
between 8 and 9.3 105 cm3 . In both experiments, sulfu- compounds with a different number of carbon atoms are de-
ric acid (H2 SO4 ) is formed by oxidation of SO2 . Despite the tected (C8 , C9 , C19 , etc.).
cleanliness of the chamber, ammonia (NH3 ) and dimethy- Attributing unambiguous elemental composition based
lamine (C2 H7 N) are present as trace contaminants. solely on the negative spectra is challenging, as O6 and SO4
State-of-the-art particle counters and sizers were de- have nearly identical masses (95.969 and 95.952 u, respec-
ployed, as well as recently developed mass spectrometers. tively). Higher mass resolution would be required to distin-
The instrumentation is described in detail in Almeida et al. guish between them. Nevertheless, based on previous studies
(2013). We present in this paper results from three high- (Ehn et al., 2010, 2012; Junninen et al., 2010; Jokinen et al.,
resolution mass spectrometers: 2012; Schobesberger et al., 2013), isotopic patterns, and as-
an Atmospheric Pressure interface Time-of-Flight (APi- sumptions on chemical reactions and clustering behaviour,
TOF) mass spectrometer in positive mode the elemental composition of most compounds could be re-
trieved. For instance we assume that no organonitrate com-
an APi-TOF mass spectrometer in negative mode (Jun- pound would form in the ozonolysis-only experiment. For
ninen et al., 2010) signals with low intensity, the elemental composition could
sometimes be inferred by extending a pattern (e.g. increasing
and a chemical ionisation APi-TOF (CI-APi-TOF) us- or decreasing the number of oxygen atoms or adding sulfuric
ing nitrate (NO
3 ) as ionising reagent (Jokinen et al., acid molecules to (C10 Hb Oc )HSO 4 ). In the present study,
2012). the comparison with positive and neutral spectra has been
the key for the unambiguous attribution of elemental compo-
Both APi-TOF mass spectrometers measure ions and charged
sition (see Sect. 3.3). The composition (C20 H30 O12 )HSO 4
molecular clusters as present in the chamber, whereas the CI-
was for example selected over (C20 H28 O6 )(H2 SO4 )HSO 4
APi-TOF measures neutral molecules and clusters charged
as no C20 H28 O6 compound was measured with the other in-
by NO 3 (either by proton transfer or by forming an adduct). struments.
High-resolution spectra acquired with these instruments
In the mass defect plots from negative (b and e) and neu-
were analysed using the tofTools data analysis software (Jun-
tral (c and f) species the red markers represent the clusters
ninen et al., 2010).
containing only sulfuric acid molecules ((H2 SO4 )n HSO 4
(n = 1, 2)) and blue points represent nitric acid clusters
3 Results and discussion ((HNO3 )n NO 3 (n = 1, 2)). Ammoniasulfuric acid clusters
are present in the negative spectra. They are the points
3.1 Mass defect plots marked in pink with mass-to-charge ratio larger than 400 Th
and mass defect smaller than 0.1 (Bianchi et al., 2014).
Mass defect plots are a convenient way to visualise high- Some compounds are deprotonated (dark green) and, because
resolution mass spectral data (Kendrick, 1963; Sleno, 2012).

Atmos. Chem. Phys., 15, 41454159, 2015

Discussion Paper
A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products 4149

Positive Negative Neutral

0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
(a) (b) (c)
0.4 Unknown
OxOrg only

Ozonolysis only
Mass defect [Th]

0.2 (OxOrg)HSO4

Discussion Paper
Unknown (OxOrg)(H2SO4)2HSO4
OxOrg only
(OxOrg)NH+4 or (OxOrg)NO3
0.1 (OxOrg)(HNO3)NO3
OxOrg with more
than 1 base

(d) (e) (f)


Discussion Paper
Mass defect [Th]
OH oxidation





0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Mass/charge [Th] Mass/charge [Th] Mass/charge [Th]

Discussion Paper
Figure 2. Mass defect plots derived from detected cations (positive APi-TOF, a and d), anions (negative APi-TOF, b and e), and neutral
Figure 2. Mass defect plots derived from detected cations (positive APi-TOF, a and d), anions (neg-
molecular clusters (CI-APi-TOF, c and f) of -pinene ozonolysis with OH scavenger (ac) and -pinene oxidation by OH only (df). The
legend in APi-TOF,
(a) applies b and
to panel (d) ase), andwhile
well, neutral molecular
the legend clusters
in (b) applies (CI-APi-TOF,
to (c), c and f) of -pinene ozonolysis
(e), and (f) as well.
with OH scavenger (ac) and -pinene oxidation by OH only (df).The legend in panel a applies to
panel d as well, while the legend in panel b applies to panels c, e, and f as well.
of the presence of NOx in the OH oxidation experiment, a first-generation oxidation product of -pinene). This sug-
some compounds are organonitrates (bound to NO 3 , light gests that OH oxidation of first-generation products of -
blue). In the CI-APi-TOF spectra, such compounds share the pinene ozonolysis is conducive to the binding of H2 SO4 for

same elemental composition with oxidised organics bound to 30 the compounds of the third and fourth band in the nega-
(HNO3 )NO 3 from the CI. Even if they have been labelled so, tive spectra. Nevertheless, C30 and C40 bands are seen
one may not totally exclude the detection of organonitrates in spectra of positive clusters (a and d) in both cases with
bound to NO 3 by the CI-APi-TOF. a weaker signal for the third and fourth bands compared to
At higher masses, the bands contain clusters of or- the first two. However, as none of these bands is observed for
ganic molecules and inorganic ions ((H2 SO4 )n HSO 4 (n = the neutral clusters (c and f) for either oxidation conditions,
0, 1, 2) or NO 3 ). The binding to sulfuric acid clusters these large compounds evidently do not form stable clusters
((H2 SO4 )n HSO (n = 1, 2)) is more pronounced for the with NO 3 . This means that if large oxidised organic com-
ozonolysis-only experiment, even though H2 SO4 levels are pounds are formed in the gas phase before being protonated
similar in both experiments (within a factor of 2). or binding to ions, their functionalities favour binding with
Clusters detected in the positive spectra (a and d) almost NH+ +
4 or C2 H8 N rather than with NO3 or (H2 SO4 )n HSO4

exclusively consist of an -pinene oxidation product and (n = 0, 1, 2), pointing towards compounds with acidic (car-
a cation (either a proton (H+ ), an ammonium (NH+ 4 ), or boxylic) functionalities.
a dimethylaminium (C2 H8 N+ )), even for the higher masses.
They rarely contain neutral ammonia (NH3 ) or dimethy- 3.2 Average carbon oxidation state, OSC
lamine (C2 H7 N) molecules. In Fig. 2, no distinction is made
between NH+ + The average carbon oxidation state (OSC ) of the identified
4 and C2 H8 N containing clusters.
The third band (C30 ) is not evident in spectra of an- oxidised organic compounds in the clusters for both oxida-
ions (b and e) and the fourth band (C40 ) is absent. These tion conditions is presented in Fig. 3 (dark grey symbols and
have been observed by Schobesberger et al. (2013), though lines). OSC has been derived by averaging all peaks with re-
in a different reaction system (OH oxidation of pinanediol, trieved elemental composition, weighted by signal intensity,
for groups of compounds (e.g. C10 , C20 ) and for each instru- Atmos. Chem. Phys., 15, 41454159, 2015

4150 A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products

Discussion Paper
3 slightly more oxidised. These values converge (decreasing
(a) Positive
2.5 Neutral (with NO3) for negative and neutral species and increasing for positive
2 Negative species) and are about the same for the C20 band. Averaged
1.5 OSC for the C20 band is about 0.3 in the ozonolysis-only
Ozonolysis only

1 experiment and about 0.7 in the OH oxidation experiment,

independent of which ions the oxidised organic compounds


0 are bound to.
Note that the operationally defined OSC neglects the effect

Discussion Paper

1 of peroxide functionalities (OOH), which one expects to be

1.5 abundant for low NOx levels as it is the case in the present ex-
2 periments. We derived a formula to estimate the lowest value
40 30 20 10 0
# Carbon of OSC , maximising the number of hydroperoxide func-
tional groups for compounds with exactly n10 carbon atoms
2.5 Neutral (with NO3) (n = 1, 2, 3, 4): OSC,max(OOH) n0.8+O : C1.5(H : C).
2 Negative It derives from the minimum number of carbonyl (C = O)

1.5 functionalities required based on the number of hydrogen
OH oxidation

Discussion Paper
1 atoms, knowing that the elemental composition of -pinene,
the starting material is C10 H16 . Therefore, this approach


0 cannot be generalised, and it remains an approximation, as

0.5 one cannot precisely derive OSC without knowing the exact
1 structure of the analysed compounds. This is represented in
Fig. 3 by light grey bars, symbols, and dashed lines. These
values vary marginally from operationally defined OSC val-
40 30 20 10 0
# Carbon ues for ozonolysis. The variation is slightly higher from com-

pounds with 20 and 40 carbon atoms in the OH oxidation

Discussion Paper
3. Mean carbonFigure 3. Mean
oxidation carbon
state (OSoxidation state (OSC ) for pure ozonoly-
C ) for pure ozonolysis (a) and OH oxidation (b) as a func-
sis (a) and OH oxidation (b) as a function of the number of car-
he number of carbons for each identified oxidised organic compound in clusters Thefornext
all three
sections focus on the differences in elemental
bon atoms for each identified oxidised organic compound in clus-
ents. The shape of the markers indicate which type of clusters is depicted and the colorsand
ters for the three instruments. The shapes of the markers indicate
composition areclustering behaviour of newly formed com-
me as in Fig. 2.which
The type
weighted means
of clusters and standard
is depicted, deviations
and the colours are thefor theasvarious
same in bands of positive oxidation conditions. For the sake of clar-
pounds for either
gative APi-TOF Fig.(C2.< 8, weighted
The C = 812, meansC =and1820,
standard C =deviations
2830, and C=
for the 3840) are
various ity, indicated with analysis of clusters containing C10 and
only a detailed
ray symbols andbandsbars. See main
of positive text forAPi-TOF
and negative detailed(C discussion.
< 8, C = 812, C = 18 C 20 oxidised organic compounds is presented.
20, C = 2830, and C = 3840) are indicated with large grey sym-
3.3 Elemental composition of selected oxidised organics

bols and bars. See main text for detailed discussion.

The identified C10 and C20 oxidised organic compounds from
ment separately. Weighted averages and standard deviations the clusters with highest signal were grouped regardless of
for bands for each instrument are shown as large grey sym- which inorganic ions they were bound to (Figs. 4 and 5).
bols and bars, respectively. Bands are defined as following: These stacked bars represent the clusters peak area in the
C0 for C < 8, C10 for C = 812, C20 for C = 1820, mass spectra in which the oxidised organic compounds were
C30 for C = 2830, and C40 for C = 3840. The sensi- identified. No quantitative comparison is made. From both
tivity of each ion does not change dramatically within a band overview figures, charged species are discussed first, and
so that it is assumed to be similar for all signals used for each later compared to neutral species, comparing both oxidation
average. pathways. In the end, time series of some clusters are pre-
Note that weighted averages for the CI-APi-TOF instru- sented in order to understand their temporal evolution.
ment are not representative of the whole population of neu-
tral molecules (see discussion in the next section). However, 3.3.1 Ions
because NO 3 is an important atmospheric ion, CI-APi-TOF
results are also discussed in this section. Ehn et al. (2012) The differences in compound distribution between pure
observed that oxidised compounds bind naturally to NO 3 at ozonolysis using an OH scavenger (ac) and OH oxida-
low levels of sulfuric acid, for instance during night-time. tion (df) for positively (a and d) and negatively (b and e)
The OSC trends are similar for both oxidation condi- charged clusters containing a C10 oxidised compound are
tions. The values for the C0 band are high (i.e. compounds illustrated in Fig. 4. The range of compounds measured is
are more oxidised) for negative and neutral species but be- similar for both experiments, but their distribution patterns
low zero (i.e. compounds are less oxidised) for the positive differ. For positively charged species (a and d), elemental
species. The compounds detected in the neutral channel are compositions C10 H14 O17 , and C10 H16 O28 have been iden-

Atmos. Chem. Phys., 15, 41454159, 2015

A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products 4151

Discussion Paper
Positive Negative Neutral
1 1 1
Signal (s ) Signal (s ) Signal (s )
0 10 20 30 0 5 10 15 0 50 100 150
(a) (b) (c)
Ozonolysis only


...12 C H O
...13 x (y1) z
C10H15O8 NO3

Discussion Paper
...11 CxH(y1)Oz
...18 HSO4
...3 (H2SO4)HSO4
...4 H+
...6 NH+ (H SO ) HSO
...7 4 2 4 2 4
...9 C H N+ NO
...10 2 8 3

0 1 2 3 4 0 5 10 15 0 20 40 60

(d) (e) (f)

Discussion Paper
OH oxidation

...11 H+ CxH(y1)Oz
...13 NH+
...10 + NO3
C10H16O C2H8N

...11 CxH(y1)Oz
...14 HSO4

Discussion Paper
...3 (H2SO4)HSO4
...6 (H2SO4)2HSO4
...9 NO3

Figure 4. Stacked peak area for observed clusters containing C10 Hb Oc according to core ion(s) of positive (a and d), negative (b and e), and
neutral 4.f) Stacked
(c and peakfrom
clusters obtained area for observed
-pinene clusters
ozonolysis with containing
OH scavenger c according
C10 Hb Ooxidation
(ac) and -pinene to (df).
by OH only core ion(s)
of positive (a and d), negative (b and e), and neutral (c and f) clusters obtained from -pinene
ozonolysis with OH scavenger (ac) and -pinene oxidation by OH only (df).
tified in both experiments, whereas the elemental composi- gen atoms in the positive spectra (a), whereas OH oxidation

tion C10 H18 O29 , for instance, is only seen in the OH oxida- 32 leads to C20 H30,32,34 Oc without preference for compounds
tion experiment. For the negatively charged species (b and with even numbers of oxygen atoms (d). In the negative
e) the C10 H12 O512 , C10 H14 O213 and C10 H16 O611 com- spectra (b and e), the preference for compounds with even
positions are present in both experiments, whereas com- number is less evident, and the range of O : C is broader.
positions C10 H16 O15 are typical for OH oxidation. Due In the ozonolysis experiment (b), it remains ambiguous if
to the previously addressed issue with O6 and SO4 hav- (C20 Hb Oc )(H2 SO4 )n HSO4 (n = 1, 2) are formed by aggre-
ing very close masses, the attribution in the negative spec- gation of two C10 containing clusters (neutral and negative,
tra of composition such as (C10 Hb Oc )(H2 SO4 )n HSO 4 re- Eq. 1), or by the reaction of a formed C20 compound with
mains ambiguous as their signal is small and interferes with a sulfuric acid cluster (Eq. 2). The addition of a sulfuric acid
(C10 Hb+2 Oc+6 )(H2 SO4 )n1 HSO 4 (n = 1, 2). molecule to an existing bisulfate cluster (Eq. 3) is also pos-
The corresponding analysis for the second band (C20 com- sible. The reaction pathways do not exclude each other and
pounds) reveals clear differences between ozonolysis and might coexist (see also Sect. 4).
OH oxidation in the formation of ion clusters (Fig. 5).
Pure ozonolysis leads to mostly C20 H30 Oc products, with
higher signals for compounds with an even number of oxy- Atmos. Chem. Phys., 15, 41454159, 2015

4152 A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products

Discussion Paper
Positive Negative Neutral
Signal (s1) Signal (s1) Signal (s1)
0 50 100 150 0 2 4 6 8 0 5 10 15 20
...4 (a) (b) (c)
Ozonolysis only


...3 H+ HSO4


...5 NH+

Discussion Paper
...7 + 2 4 4 3
...8 C2H8N

0 5 10 15 0 1 2 3 0 2 4 6 8

...4 (d) (e) (f)

Discussion Paper
OH oxidation

...3 NH+
...7 C2H8N+


Discussion Paper

Figure 5. Stacked peak area for observed clusters containing C20 Hb Oc according to core ion(s) of positive (a and d), negative (b and e), and
neutral 5.f)Stacked
(c and peakfrom
clusters obtained area for observed
-pinene clusters
ozonolysis with containing
OH scavenger c according
C20 Hb Ooxidation
(ac) and -pinene to (df).
by OH only core ion(s)
of positive (a and d), negative (b and e), and neutral (c and f) clusters obtained from -pinene
ozonolysis with OH scavenger (ac) and -pinene oxidation by OH only (df).
These results illustrate how the oxidation processes mod-

33 ify the proton affinity and the clustering behaviour of the
(C10 Hb Oc )HSO
4 + (C10 Hd Oe )H2 SO4
oxidation products of -pinene. The addition of functional
groups modifies the interaction with protons, ions and ionic
(C20 Hb+d Oc+e )(H2 SO4 )HSO4 (1)
clusters. Figure 1 presents an overview of both oxidation
C20 Hb Oc + (H2 SO4 )HSO 4 pathways (with examples of possible structures for the ob-
(C20 Hb Oc )(H2 SO4 )HSO (2) served products). Despite different mechanisms in the early
steps, peroxy radicals are produced under both oxidation
(C20 Hb Oc )HSO4 + (H2 SO4 ) conditions and will react in a similar way with various avail-
(C20 Hb Oc )(H2 SO4 )HSO 4 (3) able reaction partners independent of their formation path-
way (Fig. 1, Reactions 1 to 5 in the green box). The de-
It remains unclear why such clusters with additional neutral composition reaction of alkyloxy radicals (from reaction 4)
molecules are not observed in the OH oxidation experiment. and intramolecular H-abstractions followed by reaction with
This may be due to the lower concentration of H2 SO4 in this O2 (reaction 5) lead again to peroxy radicals (and acylper-
experiment, or because their signals are low and hidden by oxy radicals), which can again react via reactions 1 to 5 in
isobaric clusters of a different composition. an iterative manner (red arrows). Terminal reactions lead to

Atmos. Chem. Phys., 15, 41454159, 2015

A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products 4153

(extremely) low volatility organic compounds ((E)LVOCs). ments and the authors claimed that the composition of neu-
In our experiments, NOx is only relevant for the OH ox- tral clusters was similar to that of negatively charged clusters.
idation pathway. No explicit structure is given for prod- Even though this statement may be true, it cannot be shown
ucts of intramolecular H-abstraction, as it is not yet known with only one type of chemical ionisation.
which H atom would be abstracted first. Termination reac- While the distribution of clusters in the neutral spectra
tion branching ratios leading to the various functionalities are compared to the positive and negative spectra is different for
influenced by HO2 , RO2 and NOx levels. Therefore, there C10 compounds, it is almost identical for the C20 compounds.
is a minor difference in functional groups for species with Therefore, C20 compounds independently of their forma-
a lower number of oxygen atoms: ozonolysis favours car- tion pathways display a similar reactivity towards NH+ 4,
bonyl functional groups (ketones, aldehydes), while OH oxi- C2 H8 N+ , HSO 4 and NO
3 , even though the distribution is
dation produces hydroxyl (alcohols) functionalities (Atkin- shifted towards slightly more oxidised compounds in the
son, 2000; Vereecken et al., 2012; Taatjes et al., 2013). neutral spectra, especially for C20 H30,32 Oc . In our experi-
However, for multifunctional species (more than five oxygen ments, the negative spectra are sensitive to a broader range
atoms, ELVOCs), no particular functional group is dominant. of O : C, in particular for C20 H30 Oc .
Bipolar charging probabilities determined for aerosol par-
ticles are sometimes extrapolated down to 1 nm diameters
(e.g. Jiang et al., 2011) ignoring the role of chemical compo- 4 Time series of clusters
sition. Although the present results do not necessarily apply
to all types of clusters, they do suggest that this extrapolation Normalised time series have been derived for all three instru-
is valid down to around 1.5 nm in mobility diameter, which is ments to investigate formation mechanisms. The time reso-
roughly the size of the detected C20 containing clusters (Ehn lution is 2 min except for positive data (1 min) and negative
et al., 2011). Below this size, compounds clearly behave dif- OH oxidation data (5 min). These have been set in order to
ferently depending on polarity and charger ion composition optimise the signal-to-noise ratio in each of the spectra.
due to the limited type and number of functional groups, so Analysis of positive C20 containing clusters in the ozonol-
that they bind selectively to specific ions. ysis experiment shows that most oxidised compounds (up to
Ehn et al. (2012) identified C10 H14 O711,13 , O18 , not shown) appear almost immediately after the begin-
C10 H16 O711 , C20 H30 O1216,18 , and C20 H32 O11,13,15 ning of the experiment (vertical black line) and reach their
in -pinene ozonolysis chamber experiments (and a subset maximum concentration the earliest (Fig. 6). This is observed
of these in the boreal forest site in Hyytil, Finland). All for clusters of C20 H30 Oc with either NH+ +
4 or C2 H8 N . The
of these were also identified during our study in either signals of the clusters containing the most oxidised com-
experiment. pounds decrease after reaching their maximum, whereas the
signals of the other clusters level off. This is due to the
3.3.2 Neutral species change in -pinene : O3 ratio, as the O3 level is kept con-
stant during the experiment, while the -pinene mixing ra-
The clusters containing C10 and C20 oxidised compounds tio slowly increases (no steady-state conditions). Therefore,
from the ozonolysis only experiment (c) and the OH oxida- when -pinene is very low, formation rates of the various ox-
tion (f) are depicted in Figs. 4 and 5. idation products change because fewer termination reactions
C10 H15 O8,10 (bound to NO 3 ) are seen in the neutral spec- (with RO2 ) happen, allowing further oxidation by successive
tra of the OH oxidation experiment (Fig. 4f). They are also intramolecular H-shifts as suggested by Ehn et al. (2014);
seen in the negative spectra (Fig. 4e). see Fig. 1. This observation is in line with chamber exper-
Comparing the mass spectra of the neutral species with iments (Shilling et al., 2009; Ng et al., 2010; Pfaffenberger
the previously discussed plots from the negative clusters, it et al., 2013), showing that higher O : C of SOA is achieved
appears that the natural ionisation happening in the cham- with low -pinene levels. This result contrasts with the view
ber with HSO 4 is less selective than the chemical ionisa- that the most oxidised organic compounds are formed only
tion with NO 3 in the CI-APi-TOF ion source. Therefore, not after long oxidants exposure time (e.g. Jimenez et al., 2009;
all the neutral species appear in the spectra of the neutral Andreae, 2009; Kang et al., 2011). Highly oxidised organic
clusters. The detected compounds represent ELVOCs though compounds can also be formed very quickly, depending on
and were shown to be proportional to the (total) concentra- the oxidation conditions. The different behaviour of oxidised
tion of oxidised compounds (Ehn et al., 2014). Therefore, for organic compounds with the same elemental composition
a comprehensive detection of -pinene oxidation products bound to NH+ +
4 and C2 H8 N can be explained by either the
and their mechanistic interpretation, HSO 4 seems to perform different formation rates of these clusters (both cations com-
better than NO 3 as an ionisation reagent. peting and NH+ 4 seemingly forming more stable clusters) or
Schobesberger et al. (2013) presented a similar analysis by the fact that there can be various compounds with the
for oxidation reactions of pinanediol with OH (and high same elemental composition but different chemical proper-
H2 SO4 levels). No CI-APi-TOF was used for those experi- ties. Atmos. Chem. Phys., 15, 41454159, 2015

Discussion Paper
4154 A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products

1 1
(a) (b)
0.9 0.9

0.8 0.8
(C20H30O10)NH+4 (C20H30O10)C2H8N+
0.7 0.7

Ozonolysis only
Normalised signal

Normalised signal
0.6 (C20H30O12)NH+4 0.6 (C20H30O12)C2H8N+

0.5 0.5
(C20H30O14)NH+4 (C20H30O14)C2H8N+

Discussion Paper
0.4 0.4
(C20H30O16)NH+4 (C20H30O16)C2H8N+
0.3 0.3

0.2 0.2

0.1 0.1

0 0
23:00 00:00 01:00 23:00 00:00 01:00
Time Time

1 1
(c) (d)
0.9 0.9

0.8 0.8

Discussion Paper
(C20H32O9)NH+4 (C20H32O9)C2H8N+
0.7 0.7
Normalised signal

Normalised signal
OH oxidation

0.6 (C20H32O10)NH+4 0.6 (C20H32O10)C2H8N+

0.5 0.5
(C H O )NH+ (C20H32O11)C2H8N+
20 32 11 4
0.4 0.4
(C20H32O12)NH+4 (C20H32O12)C2H8N+
0.3 0.3

0.2 0.2

0.1 0.1

0 0
10:00 11:00 12:00 13:00 10:00 11:00 12:00 13:00

Discussion Paper
Time Time

Figure 6. Time series of observed

Figure positive
6. Time clusters
series containing
of observed C20clusters
positive H30,32 Ocontaining
c oxidisedCcompounds NH+
bound tocompounds
20 H30,32 Oz oxidised
4 (a and c) and C2 H8 N (b
and d) for -pinene pure to NH+
ozonolysis4 (a and
(ab) c)
and and
2 8 N +
(b and
oxidation d) for
(cd). -pinene
vertical ozonolysis
black line (ab)
marks and
the pure OH
beginning of the experiment.
oxidation (cd). The vertical black line marks the beginning of the experiment.

For the OH oxidation experiment the -pinene concen- 1


tration is high from the beginning of the run and OH is 34 0.9

produced from HONO photolysis by UV light. Note that 0.8

the -pinene concentration decreases during the experiment, 0.7
Normalised signal
Ozonolysis only

so that steady-state conditions are achieved after about 3 h 0.6 (C20H30O12)NO3

of oxidation only. Moreover, various oxidised organic com- 0.5


pounds compete to form stable clusters with the available 0.4

ions. In this case, the signals for the presented positive clus- 0.3

ters containing C20 H32 Oc (with either NH+ +

4 or C2 H7 N ) rise 0.2

almost simultaneously so that it is not possible to tell if one 0.1

of them is formed earlier, even at 1 min time resolution. Try- 0

23:00 00:00 01:00
ing to increase the time resolution to observe which signals Time

increase first would lead to an overly low signal-to-noise ra- (b)
tio. A similar (but less clear) trend is observed as well in the
neutral spectra (Fig. 7). (C20H32O9)NO3
Normalised signal

0.6 (C20H32O10)NO3
OH oxidation

5 Conclusions 0.5

Oxidation of -pinene was conducted in the CLOUD cham- 0.3

ber. The simultaneous use of three different mass spectrom- 0.2

eters provides a unique insight into the chemical reaction 0.1

mechanisms happening in the early stage of -pinene oxi- 0

10:00 11:00 12:00 13:00
dation and molecular cluster formation.
Charged clusters consist of oxidised organic compounds Figure 7. Time series of observed neutral clusters containing
7. Time series
Figure clusters
binding to a core ion (bisulfate or nitrate for negative of observed neutral clusters containing C20 H30 Oz oxidised compoun
C20 H30 Oc oxidised compounds for -pinene pure ozonolysis (a)
-pinene pure ozonolysis (a) and containing C H Oz for pure OH oxidation (b). The vertical
and hydronium, ammonium, or aminium for positive clus- and containing C20 H32 Oc for20pure32OH oxidation (b). The vertical
line marks
ters). Molecular clusters including additional sulfuric acidthe beginning of the experiment.
black line marks the beginning of the experiment.
molecules have also been detected in the negative spectra
for ozonolysis, while in the positive spectra, even clusters
with high masses rarely contain neutral ammonia or dimethy-

Atmos. Chem. Phys., 15, 41454159, 2015

A. P. Praplan et al.: Elemental composition and clustering behaviour of -pinene oxidation products 4155

lamine molecules. The results show the selectivity of this Acknowledgements. We would like to thank CERN for supporting
chemical ionisation process. Especially the difference be- CLOUD with important technical and financial resources, and for
tween ionisation with NO
3 and HSO4 can be seen from the
providing a particle beam from the CERN Proton Synchrotron. We
broader range of C10 oxidised compounds observed in the also thank P. Carrie, L.-P. De Menezes, J. Dumollard, K. Ivanova,
negative spectra compared to the neutral one. The cluster dis- F. Josa, I. Krasin, R. Kristic, A. Laassiri, O. S. Maksumov,
B. Marichy, H. Martinati, S. V. Mizin, R. Sitals, A. Wasem
tribution of the C20 is very similar for all instruments, show-
and M. Wilhelmsson for their important contributions to the
ing that due to the many functional groups of these species, experiment. This research has received funding from the EC
their affinities towards the various ions present are similar. Seventh Framework Programme (Marie Curie Initial Training
This also implies that for the analysis of atmospheric clusters Network CLOUD-ITN no. 215072, MC-ITN CLOUD-TRAIN
containing oxidised organic clusters, the combination of APi- no. 316662, ERC-Starting MOCAPAF grant no. 57360 and
TOF and CI-APi-TOF mass spectrometers with varying ion- ERC-Advanced ATMNUCLE grant no. 227463), PEGASOS
isation reagent is important in order to capture a comprehen- project funded by the European Commission under the Framework
sive picture of formed products, in particular for low molar Programme 7 (FP7-ENV-2010-265148), the German Federal
mass products. Oxidised organic compounds (C20 ) with large Ministry of Education and Research (project nos. 01LK0902A
molar mass can be similarly charged by various ions due to and 01LK1222A), the Swiss National Science Foundation (project
their many functional groups, suggesting that the ionisation nos. 200020_135307 and 206620_141278), the Academy of
Finland (Center of Excellence project no. 1118615), the Academy
starts to be independent of the charging mechanism. Even if
of Finland (135054, 133872, 251427, 139656, 139995, 137749,
the two oxidation mechanisms differ in their first step, they 141217, 141451), the Finnish Funding Agency for Technology
both lead to the formation of peroxy radicals, which pro- and Innovation, the Visl Foundation, the Nessling Foundation,
duce multifunctional oxidised organic compounds. For com- the Austrian Science Fund (FWF; project no. J3198-N21), the
pounds containing a low number of oxygen atoms, ozonol- Portuguese Foundation for Science and Technology (project
ysis products tend to possess more carbonyl functionalities no. CERN/FP/116387/2010), the Swedish Research Council,
while OH oxidation products have more hydroxyl function- Vetenskapsrdet (grant 2011-5120), the Presidium of the Rus-
alities and preferentially get protonated or form clusters with sian Academy of Sciences and Russian Foundation for Basic
cations. However, there is no clear functional group distri- Research (grants 08-02-91006-CERN and 12-02-91522-CERN),
bution for the compounds with a larger degree of oxida- the U.S. National Science Foundation (grants AGS1136479
tion. Their functionalities depend on the termination reac- and CHE1012293), and the Davidow Foundation. We thank the
tofTools team for providing tools for mass spectrometry analysis.
tions with HO2 , RO2 , or NOx and they bind with cations as
well as with anions. Edited by: J. H. Seinfeld
Other differences could be highlighted between the oxi-
dised organic compounds from ozonolysis and OH oxidation
besides their clustering behaviour. For instance, the mean
carbon oxidation state (OSC ) of the oxidised compounds in References
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