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Article
Limononic acid oxidation by hydroxyl
radicals and ozone in the aqueous phase
Bartlomiej Witkowski, sara jurdana, and Tomasz Gierczak
Environ. Sci. Technol., Just Accepted Manuscript • DOI: 10.1021/acs.est.7b04867 • Publication Date (Web): 14 Feb 2018
Downloaded from http://pubs.acs.org on February 20, 2018

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1 Limononic acid oxidation by hydroxyl radicals and ozone in the

2 aqueous phase

3 Bartłomiej Witkowski, 1* Sara Jurdana, 1,2 Tomasz Gierczak 1

1
4 University of Warsaw, Faculty of Chemistry,
5 Al. Żwirki i Wigury 101, 02-089 Warsaw, Poland

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19 Keywords: Limononic acid, limonene, secondary organic aerosol, hydroxyl radicals, ozone, relative
20 rate, tandem mass spectrometry

21 *Corresponding author e-mail: bwitk@chem.uw.edu.pl

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22 Permanent address: University of Rijeka, Department of Biotechnology, Radmile Matejčić 2, 51000
23 Rijeka, Croatia

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24 Abstract
25 Kinetics and mechanism of limononic acid, (3-isopropenyl-6-oxoheptanoic acid, LA) oxidation
26 by hydroxyl radicals (OH) and ozone (O3) were studied in the aqueous phase at 298±2 K. These
27 reactions were investigated using liquid chromatography coupled to the electrospray ionization and
28 quadrupole tandem mass spectrometry (LC-ESI/MS/MS). The rate coefficients determined for LA +
29 OH reaction were: 1.3 ± 0.3 × 1010 M-1s-1 at pH=2 and 5.7 ± 0.6 × 109 M-1s-1 at pH=10. The rate
30 coefficient determined for LA ozonolysis was 4.2 ± 0.2 × 104 M-1s-1 at pH=2. Calculated Henry’s Law
31 constant (H) for LA was ca. 6.3 × 106 M × atm-1 thereby indicating that in fogs and clouds with LWC =
32 0.3-0.5 g × m-3 LA will reside entirely in the aqueous-phase. Calculated atmospheric lifetimes due to
33 reaction with OH and O3 strongly indicate that aqueous-phase oxidation can be important for LA
34 under realistic atmospheric conditions. Under acidic conditions, the aqueous-phase oxidation of LA
35 by OH will dominate over reaction with O3, whereas the opposite is more likely when pH ≥ 4.5. The
36 aqueous-phase oxidation of LA produced keto-limononic acid and a number of low-volatility
37 products, such as hydroperoxy-LA and α-hydroxyhydroperoxides.

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52 1. Introduction

53 Secondary organic aerosols (SOA) are formed due to nucleation or partitioning of the semi-
1, 2
54 volatile oxidation products of VOCs in accordance with the partitioning theory. Globally, non-
55 methane VOCs budget is dominated by biogenic emission of isoprene and monoterpenes: α, β-
3, 4
56 pinene, and limonene. Gas-phase oxidation of these atmospherically abundant biogenic VOC
5
57 (BVOC) contributes significantly to the secondary organic aerosols (SOA) formation. However,
58 because of our limited understanding of the SOA formation mechanisms, impact of the terpene
59 biogenic emission on the climate is still uncertain. 5-10
60 Limonene is a more efficient secondary organic aerosol (SOA) precusor than α and β-pinene
61 because it possess two carbon-carbon double bonds. 11-15 A significant fraction of the first generation
11, 12, 16 17-20
62 oxidation products of limonene will retain the less reactive, exocyclic double bond.
63 Consequently, these unsaturated, semi-volatile compounds can undergo further oxidation in the gas,
64 particle or aqueous phase thereby increasing the overall SOA yield. 14, 15
65 Recently, it has been recognized that the aqueous-phase processing of the semi-volatile
7, 21-23
66 monoterpene derivatives can contribute to SOA but these processes are very poorly
10, 21, 22, 24
67 characterized. Also, little attention has been directed to the investigation of the aqueous-
25
68 phase processing of limonene oxidation products. The unsaturated, first-generation oxidation
69 products of limonene can react with ozone (O3) and hydroxyl radicals (OH) in the aqueous-phase. If
70 relevant under atmospheric conditions, these aqueous-phase reaction may lead to aqueous-phase
7, 14, 21-23
71 SOA (aqSOA). However, to-date, most studies of the terpene derived aqSOA precursors have
72 been focused on the less reactive, saturated cis-pinonic acid (CPA) and other saturated derivatives of
73 α-pinene. 26-29
74 Limononic acid (3-isopropenyl-6-oxoheptanoic acid, LA) is a first-generation product of limonene
12, 17, 30 28
75 oxidation in the gas-phase and also a major product of CPA photolysis. LA has a exocyclic
76 double bond and the estimated Henry's law constant (H) for this compound is 6.3 × 106 M × atm-1. 31
77 In fog and clouds with LWC = 0.3-0.5 g × m-3 LA will reside entirely in the aqueous-phase. Thus, LA is a
78 good model compound for studying aqSOA formation due to oxidation of the unsaturated, semi-
79 volatile derivatives of monoterpenes. In the gas-phase LA reacts with O3 (k≈5 × 10-19 cm3 × molecule-1
80 s-1) 11, 12, 15, 16
and OH (k=7 × 1011 cm3 × molecule-1 s-1) 32, 33
but the rate coefficients for these two
81 reactions in the aqueous-phase are currently unknown.
82 The aim of this work is to investigate the kinetics and mechanism of LA reaction with OH
83 (reaction 1) and with O3 (reaction 2) in the aqueous-phase. These reactions were studied in a batch
84 reactor using liquid chromatography coupled to the electrospray ionization tandem mass
85 spectrometry (LC-ESI/MS/MS).

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86 2. Experimental
87 List of reagents is provided in section S1 of the Supplementary Information (SI).
88 2.1. Limononic acid synthesis and purification

89 LA was synthesized by irradiating CPA solution in deionized (DI) water/MeOH with a 254 nm
90 mercury Pen-Ray lamp. To confirm the structure of LA as the major product of CPA Norrish-II
28 1
91 isomerization, H NMR spectrum was acquired. LA 1H NMR spectrum obtained is in a good
92 agreement with the previously published data. 28 Details of this synthesis are provided in section S2.

93 2.2. Kinetics of limononic acid reaction with OH and O3

94 The rate coefficients for reaction (1) reaction (2) in the aqueous-phase were obtained using
95 competition kinetics by monitoring the relative loss of LA and the reference compound.

Limononic acid + OH → products 1

Limononic acid + O → products 2

96 If LA and the reference compound are lost only due to reaction with OH or O3, the kLA can be
97 calculated using eq. (I)

[Limononic acid] k ! [Reference]

Ln  = Ln   I
[Limononic acid] k "#$ [Reference]

98 [Limononic acid] and [Reference] are the initial (0) and intermediate (t) concentrations, kLA
99 and kref are the bimolecular rate coefficients for LA and reference compound.

100 Caffeine (kOH=6.9 ± 0.7 × 109 M−1 s−1 at pH=2), phenylalanine (kOH=9 ± 1 × 109 M−1 s−1 at pH=10
101 and 5.7 ± 0.5 × 109 M−1 s−1 at pH=2), p-toluic acid (kOH= 8 ± 0.8 × 109 M−1 s−1 at pH=10) 34 were chosen
102 as the reference compounds to study kinetics of reaction (1) – k1. Gallic acid (kozone= 9.7 × 104 M−1 s−1
103 at pH =2) 27, 38 was used to study kinetics of reaction (2) – k2. It was assumed that one molecule of O3
104 reacts with one molecule of gallic acid and LA. 35

105 2.3. Oxidation of limononic acid by OH

36
106 The aqueous-phase photo-reactor was described in our previous study. Briefly, the photo-
107 reactor consisted of a 50 ml Pyrex vessel and the reaction mixture was stirred with magnetic stirrer.
108 The reaction solution was irradiated with a UVAHAND 250 GS H1/BL lamp (Honle UV technology, 310
109 W) to generate OH by H2O2 photolysis.

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110 The reaction mixture consisted of 25 ml of 17 mM H2O2 solution in DI water. Concentrations of

111 LA and the reference compounds were ca. 30 µM. Solution pH was adjusted by adding HCl or NaOH.
112 OH concentration in the absence of other reactants was ca. 5 × 10-12 M. 17
Slightly higher reactants
113 concentrations were used in some experiments to study the mechanism and identify reaction (1)
114 products. Aliquots of the reaction mixture (100 µL) were sampled from the reactor, incubated with
115 the equal volume of the catalase solution (≈ 0.1 mg/ml) and injected into LC/MS.

116 2.4. Ozonolysis of limononic acid

117 Kinetics of reaction (2) was studied by adding different volumes of the ozone solution (ca. 6
118 µM, determined with the indigo method 37) to the aqueous solution of LA and gallic acid (2 µM each).
38
119 Ozone solution was prepared by bubbling the ozone through phosphoric acid solution in DI water
120 (pH=2). 38, 39 The samples always contained excess reactants relative to O3 and the tert-butyl alcohol
121 (t-BuOH) was used as OH scavenger (10-20 mM). 38, 39

122 Mechanism of reaction (2) was studied by slowly bubbling the ozone (≈ 5 ml/min) through
123 solution of LA (50 µM) in DI water. 150 µL aliquots of the reaction mixture were sampled from the
124 bubbler and subjected to the LC/MS analysis.

125 2.5. Liquid chromatography coupled to the mass spectrometry

126 LC/MS analysis were carried out with LC20A liquid chromatograph (Shimadzu) coupled to the
17
127 QTRAP 3200 (AB Sciex) triple quadrupole mass spectrometer as previously described. For the
128 products identification a 55 min gradient elution program was used. Shorter gradient elution
129 program was used for the kinetic analysis (section S3).

130 Mass spectra were acquired in the scan mode in the mass range 50-700 m/z and in the
131 multiple reaction monitoring (MRM) mode. The ESI conditions were as follows: capillary voltage was -
132 4.5 kV and 5.5 kV in the negative and positive ionization modes. Ion source temperature was 450 °C,
133 nitrogen was used as curtain (3 × 105 Pa), auxiliary (3 × 105 Pa) and collision gas. Fragmentation
134 spectra of reactions (1) and (2) products were acquired during chromatographic run, after the
135 analytes were separated by LC. Ion lenses voltages for the MRM mode were adjusted by directly
136 injecting the analytes into the ESI ion source.17

137 2.6. Control experiments and error analysis

17
138 Control experiments were carried out to search for systematic errors. Briefly, UV-vis
139 irradiation, H2O2, phosphoric acid and t-BuOH by themselves did not caused any measureable
140 decomposition of LA and the reference compounds within the time-scale of the experiment as

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141 described in section S4. Unfortunately, reaction (2) kinetics was only investigated under acidic
142 conditions due to some experimental problems (data not shown).

143 It was also impossible to avoid some minor repartitioning of LA into the gas-phase under
144 acidic pH conditions. To account for the non-OH losses of LA under acidic pH conditions, two Pyrex
145 vessels were placed in front of the lamp after carefully adjusting their positions. The reaction mixture
146 volumes and compositions were identical in both bottles but H2O2 was added only to one. During
147 these experiments, the reaction solutions were sampled simultaneously from both bottles. In the
148 second set of control experiments, the reaction vessel without the H2O2 was place at exactly the
149 same distance from the lamp immediately after the photo-oxidation experiment (with the H2O2
150 added to the reaction mixture) was completed. The results from both sets of these control
151 experiments were averaged. During the experiments under acidic conditions, LA was lost due to
152 reaction (1) and also due to repartitioning into the gas phase. Using the first order loss rates (min-1),
153 it was possible to account for the non-OH losses of LA as shown in Fig. S8.

154 The total uncertainty in the bimolecular rate coefficients listed in Table 1 is a sum of
155 precision of the kLA/kref data fits obtained from linear regression analysis (standard error) as well as
156 uncertainties of the kref values (±10%). 34, 36 The uncertainties of the analytes measurements was ±5%
157 as estimated from the reproducibility of the integrated MRM peak areas (2σ). Thus, the combined
158 uncertainty for k1 value calculated for basic pH conditions was ±10% and ± 20 % for reaction (1)
159 under acidic conditions.

160 3. Results and discussion

161 3.1. Determination of the reaction rate coefficients with OH and O3

162 Relative kinetic plots for reaction (1) are shown in Fig. 1.

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163
164 Figure 1 Relative kinetic data for reaction (1)

165 Linear regression analysis (straight lines in Fig. 1) was used to calculate k1/kref ratios listed in
166 Table 1.
167 Table 1 Measured k1 and k2

Reference R2 Slope, kref pH Average k1

k1/krefa (109 M−1 s−1)b (1010 M−1 s−1)
Caffeine 0.996 1.45 ± 0.04 6.9 ± 0.7 k1 for pH=2
2
Phenylalanine 0.994 3.00 ± 0.09 5.7 ± 0.5 1.3 ± 0.3
p-Toluic acid 0.993 0.72 ± 0.02 8.0 ± 0.8 k1 for pH=10
10
Phenylalanine 0.995 0.62 ± 0.02 9.0 ± 0.9 0.57 ± 0.06
a
168 ± standard uncertainty; b listed by Buxton et al. 34

169 As shown in Fig. 1, the kinetic plots were linear: R2 > 0.99. Calculated k1 values listed in Table
170 1 for pH=10 were very consistent for both reference compounds, and the average value of 5.70 ±
171 0.06 × 109 M−1 s−1 was obtained. Because there was a need to correct for a non-OH losses of LA under
172 acidic conditions (section 2.6), the uncertainty of k1 obtained for pH=2 was higher. For the
173 undissociated LA, an average k1 value of 1.3 ± 0.3 × 1010 M−1 s−1 was obtained.

174 For CPA, a saturated compound, considerably lower k1 values of 3.6 ± 0.3 and 3.3 ± 0.5 × 109
175 M−1 s−1 for pH=2 and 3.0 ± 0.3 × 109 M−1 s−1 for pH = 10 were recently reported. 29, 36
Thus, this
176 increased reactivity is most likely due to the OH addition to the double bond. Using aqueous-phase
17, 18
177 structure–activity relationship (SAR) it can be roughly estimated that ca. 70 % of LA molecules
178 will react with OH via addition mechanism (section S5).

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179 It is difficult to discuss the pH-dependence of k1, especially since the current literature
180 database for keto-acids oxidation by OH is rather limited. 34, 36 Similar results were presented in our
181 previous study for OH reaction with CPA, where the apparent lack of pH dependence on the kOH was
182 associated with the unexpectedly high acidity of the hydrogen atom in α position to the carbonyl
183 group. 36
184 For reaction (2), k2 = 4.2 ± 0.4 × 104 M−1 s−1 was obtained as shown in Fig. S12. As expected,
185 ozonolysis of the exocyclic double bond of LA was significantly slower than the ozonolysis of
186 endocyclic double bonds. 40, 41

187 The data acquired was used to calculate atmospheric lifetimes of LA - section 3.3.

188 3.2. Mechanisms of limononic acid oxidation by OH and O3

189 The products of reaction (1) and (2) detected using LC/MS as shown in Fig 2. 2

190

191 Figure 2 Chromatograms (total ion current): red - reaction mixtures at t=0 and, blue – 60 min
192 after reactions initiation

193 Fragmentation spectra of the products detected with LC/MS were used to propose the
194 mechanisms of reactions (1) and (2). Molar yields (section S7) were estimated using integrated peak
195 areas for the [M-H]- ions. Since the lack of standards the yields calculated using this method are most
196 likely underestimated. The ESI response increases together with the percentage of volatile organic
197 modifier (ACN), 42 hence it was lower in the beginning of the gradient run - see section S3. Thus, the

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198 highly oxygenated compounds that were eluted earlier than limononic acid (tr =27.5 min) were
199 ionized less efficiently.

200 3.2.1. Aqueous phase oxidation of limononic acid by OH

201 Extracted ion chromatograms (EICs) and fragmentation spectra of the reaction (1) products
202 are shown in Fig. 3.

203
204

205 Figure 3 EICs and fragmentation spectra of reaction (1) products

206 As it is shown in Fig. 3, the major product of reaction (1) was keto-LA – see section S7. Keto-
207 LA was also identified using the data reported in our previous study of limonene SOA composition. 17
208 The small quantities of compounds with MW 234 Da were most likely produced due to the non-
209 radical addition of H2O2 to LA as it could be inferred from the retention time of these peaks – see
210 section S8.
211 To further investigate the non-radical addition of H2O2 to LA, a series of experiments was carried
212 out, using linear carboxylic acids, carboxylic acids containing hydroxyl and carbonyl groups as well as
213 dicarboxylic acids – see section S8. These carboxylic acids were dissolved in the H2O/H2O2 mixture,
214 evaporated to dryness and re-dissolved in pure water. H2O2 only reacted with the keto-acids (Table
215 S3), including LA. As shown in Fig. 3, LA + H2O2 reaction generated products detected as negatively

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216 charged ions with m/z 233. Retention times of some of these ions overlapped with the products of
217 reaction (1), as shown in Fig.3. Interestingly, H2O2 did not cause any measurable decay of LA during
218 control experiments but small peaks as m/z 233 ions were detected in these experiments. Perhaps a
219 substantial amount of H2O2 was produced during the photooxidation experiments, thereby increasing
220 the yields of these non-radical products.
221 The other chromatographic peaks for the m/z 185 ion are most likely a result of the in-
222 source fragmentation as m/z 233 ions (the same retention times of the chromatographic peaks). As
223 shown in Fig. 3, compounds detected as m/z 233 ions readily produced m/z 185 fragmentation ion
224 following collision induced dissociation (CID). A number of minor products of reaction (1) were also
225 detected as shown in Fig. 4.

226

227 Figure 4 EICs and fragmentation spectra of the additional products of reaction (1)

228 As shown in Fig. 4, minor products of reaction (1) were detected as m/z 215 (two isomers),
229 201 (three isomers) and 197 (two isomers). Compounds detected as m/z 215 and 197 ions are most
230 likely carboxylic acids as indicated by the neutral loss of 44 Da (CO2). Neutral losses of 18 Da (H2O)
231 and 62 Da (CO2 + H2O) from m/z 215, 201 as well as from 197 ions indicate that these compounds
232 could be hydroxy carboxylic acids. These compounds were most likely produced by the abstraction
233 mechanism that is shown Fig. 5

234 The proposed mechanism for reaction (1) is shown in Fig. 5.

235

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236

237 Figure 5 Proposed mechanism of LA oxidation by OH, products detected with LC/MS are
238 shown in blue

239 As shown in Fig.5 addition mechanism is expected to dominate over H atom abstraction as
17, 18
240 already discussed in section 3.1 and section S5. This assumption is consistent with the
241 experimental data, since keto-LA (major product detected) is formed by conversion of the terminal
242 double bond to a carbonyl.

243 As shown in Fig. 5, the two peroxy radicals (RO2) are produced due to OH addition to the
244 double bond and reaction of the hydroxylalkyl radicals with O2. The formation of peroxy radical (1)
43
245 should be favored because it is produced from a tertiary alkyl radical. The two RO2 radicals react
44
246 with each other to form the unstable tetroxides (the water-cage effect). Both tetroxides can
247 decompose to primary or tertiary alkoxy radicals. Keto-LA can be produced following •CH2OH
248 elimination from the tertiary alkoxy radical – this pathway is most likely favored. 43, 44 Alternatively,
249 after elimination of formaldehyde from the primary alkoxy radical a C9 α-hydroxyalkyl radical is
250 formed. The C9 α-hydroxyalkyl radical can react with O2 thereby yielding keto-LA by eliminating HO2

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45 44
251 or to produce α-hydroxyalkyl alkoxy radical. Keto-LA is then produced from the α-hydroxyalkyl
44
252 alkoxy radical by OH elimination.

253 Minor products of reaction (1) are most likely produced by addition pathway and subsequent
254 oxidation of the terminal double-bonds of the first generation products. Hydroperoxy (MW = 216
255 Da), hydroxyl (MW = 200 Da) and carbonyl (MW = 198 Da) – substituted LA derivatives are produced
256 due to reaction of the peroxy radicals with HO2 or RO2. 36 Formation mechanism of hydroperoxy-LA
257 was most likely similar to the formation of hydroperoxy-CPA that was previously described. 36, 46, 47

258 Estimated LA conversion yield to keto-LA is rather low (ca. 10%). Clearly other products of
259 reaction (1) are formed, and these additional compounds were most likely not detected with LC/MS
260 (e.g. carbonyl compounds and lower-MW carboxylic acids). This might be a result of the
261 fragmentation of the alkoxy radicals. In case of carboxylic acids, it has been recently demonstrated
262 that fragmentation of alkoxy radicals is enhanced for the carboxylate ions. 48 Clearly, there is a need
263 to quantify the lower-MW products of reaction (1) for LA and similar compounds to further
264 investigate the impact of the carboxylic acid/carboxylate equilibrium on the alkoxy radicals
265 fragmentation.

266 3.2.2. Aqueous phase ozonolysis of limononic acid

267 EICs and fragmentation spectra of the reaction (2) products are shown in Fig. 6.

268

269 Figure 6 EIC chromatograms and fragmentation spectra of the reaction (2) products

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270 As shown in Fig. 6, the major product of reaction (2) is keto-LA; only a single chromatographic
271 peak was detected for m/z 185 ion. Fragmentation spectra and retention time of keto-LA were
17
272 consistent with data reported in our previous study. As shown in Fig.6 neutral losses of 18 (H2O)
273 and 34 Da (H2O2) from the m/z 201 ion indicated that the second product most likely contains
274 hydroperoxide moiety. This characteristic fragmentation mechanism confirms that at least the
275 compounds with MW 202 Da might be acyloxyhydroperoxy aldehydes. Fragmentation of the second
276 m/z 201 ion was very difficult (low intensity of the fragmentation ions), which might be consistent
277 with the formation of secondary ozonide (data not shown).

278 A proposed mechanism for reaction (2) is shown in Fig. 7.

279

280 Figure 7 Proposed mechanism of LA ozonolysis, products detected with LC/MS are shown in
281 blue

282 As it is shown in Fig. 7, when O3 adds to the terminal double bond, the unstable primary
40, 41, 49
283 ozonide (POZ) is formed. POZ can decompose to C9 Criegee intermediate (CI) and
284 formaldehyde (strongly favored) 49 or C1 CI and keto-LA (minor, not shown). 40 In the aqueous-phase,
285 the C9 CI is efficiently stabilized and a stabilized CI (SCI) is formed. 47, 57 In the laboratory reactor, the
286 C9 SCI can react with water to produce the α-hydroxyhydroperoxide (MW 220 Da). The α-
287 hydroxyhydroperoxides are unstable as confirmed by the very low intensity of the chromatographic
288 peak for the m/z 219 ion (data not shown) and decompose to keto-LA and H2O2. 40 The experimental
289 results also indicated that small fraction of the C9 SCIs can self-react, thus two products with MW 202
290 Da are observed as shown in Fig 7.

291 3.3. Atmospheric implications

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292 The following data was used to calculate the gas-phase lifetimes of LA that are shown in Fig. 8:
293 kOH = 7 × 10-11 cm3 × molecule-1 s-1, (calculated with SAR) 32, 33 and kozone = 5 × 10-19 cm3 × molecule-1 s-1
294 (ozonolysis reaction rate coefficient for the limonene exocyclic double bond), 11, 12, 16 [OH] = 2 × 106
295 molecule × cm-3 and [O3] = 2 × 1012 molecule × cm-3. 32
In the aqueous-phase, it was assumed that
-14 -9 25
296 [OH]= 2 × 10 M, [O3] =2 × 10 M, and pKa of LA ≈ 4.76. 50

297

298 Figure 8 Calculated LA atmospheric lifetimes in the gas and aqueous phase

299 As shown in Fig. 8, in the gas-phase LA primarily reacts with OH due to very slow ozonolysis
300 of the terminal double bond. 11, 12, 16 The data acquired also indicate that LA lifetime in the aqueous-
301 phase is similar to the estimated lifetime of this compound in the gas-phase. Moreover, since both k1
302 (Fig. S16) and k2 are pH-dependent, reaction (2) may dominate over reaction (1) for LA and related
303 compounds when pH ≥ 4.5 due to dissociation of the terpene-derived carboxylic acids under mildly
50, 51
304 acidic and basic conditions. Given a reasonable assumption that k2 is factor of 2-4 higher for
25
305 carboxylate ion of LA, reaction (2) can compete with reaction (1) in e.g. clouds, fogs and some
25
306 marine aerosols but not in the acidic aerosol particles (Fig. 8). Therefore, further studies of the
307 ozonolysis of monoterepene-derived, unsaturated carboxylic acids are needed.

308 When LWC ≥ 0.05 g × m-3 LA will reside entirely in the aqueous-phase (Fig. S17), therefore
309 reactions (1) and (2) can be relevant under realistic atmospheric conditions. However, in clouds the

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310 mechanisms of these reactions and products distribution will be different than in the laboratory
311 reactor.

312 The RO2 radicals that are formed due to reaction (1) will most likely react with the other RO2
313 radicals that are more abundant in clouds rather than self react. Consequently, the distribution of
314 products will depend on the branching ratios of the “mixed” tetroxides. Moreover, inside the water-
315 containing particles, atmospherically abundant carboxylic acids (formic, acetic etc.) 52, 53 will rapidly 54
316 scavenge the C9 SCIs that are produced folloging reaction (2) to yield the relatively stable,55 non-
5, 56, 57
317 volatile α-acyloxyhydroperoxy aldehydes. These α-acyloxyhydroperoxy aldehydes will most
318 likely remain in the particle phase after water evaporation thereby contributing to SOA. 56 Previously,
319 it was demonstrated that even when a low amounts of a non-volatile products are formed (such as
320 methyl-1,2,3-butanetricarboxylic acid, MBTCA from the CPA + OH reaction) the aqSOA relative yield
29
321 can be as high as 50%. Thus, reactions (1) and (2) can most likely contribute to aqSOA in the
322 atmosphere. Both reactions (1) and (2) also produce keto-LA, a well-known limonene SOA tracer that
323 was identified in the ambient particles. 58-60

324 Acknowledgments

325 This work was founded by the Polish National Science Centre: grant number
326 2014/13/B/ST4/04500. Sara Jurdana was supported by the EU Foundation for the Development of
327 the Education System Erasmus+ program 2014-2020. We thank the Structural Research Laboratory
328 (SRL) at the Department of Chemistry of University of Warsaw for making LC/MS measurements
329 possible. SRL has been established with financial support from European Regional Development
330 Found in the Sectoral Operational Programme “Improvement of the Competitiveness of Enterprises,
331 years 2004–2005” project no: WPK_1/ 1.4.3./1/2004/72/72/165/2005/U. The study was carried out
332 at the Biological and Chemical Research Centre, University of Warsaw, established within the project
333 co-financed by European Union from the European Regional Development Fund under the
334 Operational Programme Innovative Economy, 2007 – 2013. We thank dr Dagmara Tymecka for LA
1
335 purification with a semi-preparative HPLC. We thank dr Marcin Wilczek for the H NMR
336 measurements. We thank the anonymous reviewers for very helpful, constructive and insightful
337 comments.
338 Supporting Information available, this information is available free of charge via the Internet at
339 http://pubs.acs.org.
340
341 Literature

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392 18. Nørgaard, A. W.; Vibenholt, A.; Benassi, M.; Clausen, P. A.; Wolkoff, P., Study of Ozone-
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494 54. Tobias, H. J.; Ziemann, P. J., Kinetics of the Gas-Phase Reactions of Alcohols, Aldehydes,
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