ARTICLE IN PRESS
AE International – North America
Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
Review
Gas-phase tropospheric chemistry of biogenic volatile organic
compounds: a review
Roger Atkinsona,b,c,1, Janet Areya,b,c,*
a
Air Pollution Research Center, 201 Fawcett Laboratory, University of California, Riverside, CA 92521, USA
b
Department of Environmental Sciences, University of California, Riverside, CA 92521, USA
c
Graduate Program in Environmental Toxicology, University of California, Riverside, CA 92521, USA
Received 31 October 2001; accepted 10 March 2003
Abstract
Large quantities of non-methane organic compounds are emitted into the atmosphere from biogenic sources, mainly
from vegetation. These organic compounds include isoprene, C10H16 monoterpenes, C15H24 sesquiterpenes, and a
number of oxygenated compounds including methanol, hexene derivatives, 2-methyl-3-buten-2-ol, and 6-methyl-5hepten-2-one. In the troposphere these organic compounds react with hydroxyl (OH) radicals, nitrate (NO3) radicals
and ozone (O3), and play an important role in the chemistry of the lower troposphere. In this article the kinetics,
products and mechanisms of the tropospheric reactions of biogenic organic compounds are presented and briefly
discussed.
r 2003 Elsevier Ltd. All rights reserved.
Keywords: Biogenic volatile organic compound; Atmospheric chemistry; Hydroxyl radical; Nitrate radical; Ozone; Reaction products
Contents
1.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
S198
2.
Tropospheric loss processes for BVOCS . . . . . . . . .
2.1. Presence of O3 in the troposphere . . . . . . . . .
2.2. Formation of hydroxyl radicals in the troposphere
2.3. Formation of nitrate radicals in the troposphere . .
.
.
.
.
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S200
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3.
Lifetimes of biogenic organic compounds in the troposphere . . . . . . . . . . . . . . . .
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4.
Reaction mechanisms and products . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Reactions of first-generation BVOC products . . . . . . . . . . . . . . . . . . . . .
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5.
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
S214
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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*Corresponding author. Tel.: +1-909-787-3502; fax: +1-909-787-5004.
E-mail addresses: [email protected] (R. Atkinson), [email protected] (J. Arey).
1
Also Department of Chemistry, University of California, Riverside, CA 92521, USA. Tel.: +1-909-787-4191; fax: +1-909-7875004.
1352-2310/03/$ - see front matter r 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/S1352-2310(03)00391-1
ARTICLE IN PRESS
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R. Atkinson, J. Arey / Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
1. Introduction
It is now well recognized that a wide variety of volatile
non-methane organic compounds (referred to hereafter
as biogenic volatile organic compounds (BVOCs)) are
emitted into the atmosphere from vegetation (Guenther
et al., 1995, 2000; Fall, 1999; Fuentes et al., 2000; Geron
et al., 2000). Table 1 lists a subset of the total number of
BVOCs observed as plant emissions, chosen to be
representative of the organic compound classes involved
and including the dominant emissions. Guenther et al.
(1995) have estimated that 1150 1012 g carbon (1150
Tg C) year1 of BVOCs are emitted worldwide. As
discussed in detail elsewhere (see, for example, Fall,
1999; Fuentes et al., 2000), the emission rates of BVOCs
are, in general, dependent on temperature and light
intensity. Although there are large uncertainties in the
magnitude of emission rates of individual (and total)
BVOCs, a recent estimate for North America (Guenther
et al., 2000) suggests that of an estimated 84 Tg C year1
of BVOC emissions, 30% are isoprene, 25% terpenoid
compounds (see Figs. 1 and 2 for structures of selected
C10 and C15 BVOCs), and 40% are non-terpenoid
compounds including methanol, hexene derivatives, and
2-methyl-3-buten-2-ol.
Emission inventories of BVOCs and of anthropogenic
non-methane organic compounds (NMOCs) indicate
that on regional and global scales the emissions of
BVOCs exceed those of anthropogenic compounds, by a
factor of B10 worldwide and a factor of B1.5 for the
USA (Lamb et al., 1987, 1993; World Meteorological
Organization, 1995). Because of the higher atmospheric
reactivity of most BVOCs compared to many anthropogenic NMOCs [calculated lifetimes of BVOCs are
typically a few hours or less (see Table 1) compared to a
few days for most anthropogenic NMOCs (Atkinson
and Arey, 1998; Atkinson, 2000)], BVOCs are calculated
to play a dominant role in the chemistry of the lower
troposphere and atmospheric boundary layer (Fuentes
et al., 2000).
In the presence of NO emitted from combustion
sources (mainly anthropogenic and exemplified by
vehicle exhaust in an urban area such as Los Angeles,
CA) and, to a lesser extent, from soils, atmospheric
reactions of BVOCs lead to the formation of O3 and
other manifestations of photochemical air pollution
(National Research Council, 1991). The only significant
formation route of O3 in the troposphere is the
photolysis of NO2:
NO2 þ hn-NO þ Oð3 PÞ
Oð3 PÞ þ O2 þ M-O3 þ M
ð1Þ
ðM ¼ airÞ
ð2Þ
Organic peroxy (RO2 ) radicals and HO2 radicals
formed during the photooxidations of biogenic and
Table 1
Calculated atmospheric lifetimes of biogenic volatile organic
compounds
Biogenic VOC
Lifetimea for reaction with
OHb
O3c
NO3d
Isoprene
1.4 h
1.3 day
1.6 h
Monoterpenes
Camphene
2-Carene
3-Carene
Limonene
Myrcene
cis-/trans-Ocimene
a-Phellandrene
b-Phellandrene
a-Pinene
b-Pinene
Sabinene
a-Terpinene
g-Terpinene
Terpinolene
2.6 h
1.7 h
1.6 h
49 min
39 min
33 min
27 min
50 min
2.6 h
1.8 h
1.2 h
23 min
47 min
37 min
18 day
1.7 h
11 h
2.0 h
50 min
44 min
8 min
8.4 h
4.6 h
1.1 day
4.8 h
1 min
2.8 h
13 min
1.7 h
4 min
7 min
5 min
6 min
3 min
0.9 min
8 min
11 min
27 min
7 min
0.5 min
2 min
0.7 min
Sesquiterpenes
b-Caryophyllene
a-Cedrene
a-Copaene
a-Humulene
Longifolene
42 min
2.1 h
1.5 h
28 min
2.9 h
2 min
14 h
2.5 h
2 min
>33 day
3 min
8 min
4 min
2 min
1.6 h
Oxygenates
Acetonee
Camphor
1,8-Cineole
cis-3-Hexen-1-ol
cis-3-Hexenyl acetate
Linalool
Methanol
2-Methyl-3-buten-2-ol
6-Methyl-5-hepten-2-one
61 dayf
2.5 dayh
1.0 dayi
1.3 hk
1.8 hk
52 mink
12 dayf
2.4 hl
53 mino
>4.5 yearg
>235 dayh
>110 dayj
6.2 hk
7.3 hk
55 mink
>4.5 yearg
1.7 daym
1.0 ho
>8 yearf
>300 dayh
1.5 yeari
4.1 hk
4.5 hk
6 mink
2.0 yearf
7.7 dayn
9 mino
a
From Calvert et al. (2000) unless noted otherwise.
Assumed OH radical concentration: 2.0 106 molecule cm3,
12-h daytime average.
c
Assumed O3 concentration: 7 1011 molecule cm3, 24-h
average.
d
Assumed NO3 radical concentration: 2.5 108 molecule cm3,
12-h nighttime average.
e
Photolysis will also occur with a calculated photolysis
lifetime of B60 day for the lower troposphere, July, 40 N
(Meyrahn et al., 1986).
f
Atkinson et al. (1999).
g
Estimated.
h
Reissell et al. (2001).
i
Corchnoy and Atkinson (1990).
j
Atkinson et al. (1990).
k
Atkinson et al. (1995).
l
Papagni et al. (2001).
m
Grosjean and Grosjean (1994).
n
Rudich et al. (1996).
o
Smith et al. (1996).
b
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R. Atkinson, J. Arey / Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
Camphene
2-Carene
3-Carene
cis -Ocimene
α -Phellandrene
β -Phellandrene
Sabinene
α -Terpinene
Limonene
Myrcene
α -Pinene
β -Pinene
γ -Terpinene
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Terpinolene
Fig. 1. Structures of selected monoterpenes.
anthropogenic NMOCs react with NO to form NO2:
RO2
þ NO-RO þ NO2
HO2 þ NO-OH þ NO2
ð3Þ
ð4Þ
whose photolysis then leads to net O3 formation through
reactions (1) and (2).
Even for such a highly urbanized area as Los Angeles,
CA, the estimated summer-day BVOC emissions are
125–140 ton/day (Benjamin et al., 1997), which is B15%
of the estimated 2000 summertime anthropogenic
NMOC emissions of 937 ton/day and B33% of the
413 ton/day of NMOC emissions calculated to be the
upper value allowable if the 120 ppbv Federal National
Ambient Air Quality Standard (NAAQS) for O3 (1-h
average) is to be achieved in the Los Angeles air basin
(South Coast Air Quality Management District, 2002).
BVOCs therefore make the attainment of the NAAQS
for O3 more difficult utilizing only control of anthropogenic NMOC emissions, and it may be necessary in
many parts of the USA, and indeed in many urban areas
worldwide, to also control anthropogenic NOx emissions from, for example, fossil-fueled power plants and
gasoline- and diesel-fueled vehicles. Region-specific
strategies utilizing VOC and/or NOx controls in the
USA must now, of course, be reexamined in the light of
the new Federal 80 ppbv, 8-h average ozone standard.
For example, while the 120 ppbv, 1-h standard was
violated in the Los Angeles air basin on 40 and 36 days
in 2000 and 2001, respectively, the corresponding
violations of the 80 ppbv, 8-h standard were 111 and
100 days (South Coast Air Quality Management
District, 2002).
2. Tropospheric loss processes for BVOCS
As with other volatile organic compounds (Atkinson,
2000), the potential removal and transformation processes for BVOCs are wet and dry deposition, photolysis, reaction with the hydroxyl (OH) radical, reaction
with the nitrate (NO3) radical, and reaction with ozone
(O3). Reaction with chlorine (Cl) atoms may also be
important in, for example, coastal areas (Oum et al.,
1998). For most BVOCs, dry and wet deposition is
probably of minor importance, though these physical
removal processes could be important for the chemically
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β -Caryophyllene
α -Copaene
α -Cedrene
α -Humulene
Longifolene
OH
O
O
Camphor
1,8-Cineole
Linalool
Fig. 2. Structures of selected sesquiterpenes and C10 oxygenated BVOCs.
long-lived methanol and for certain BVOC reaction
products. Because of absorption of short-wavelength
solar radiation by O2 and O3 in the stratosphere,
photolysis in the troposphere requires the BVOC to
absorb radiation of wavelengths X290 nm and is
expected to be potentially important for carbonyls and
organic nitrates (and hence for many of the BVOC
reaction products). The processes leading to the presence
of O3, OH radicals and NO3 radicals in the troposphere
are briefly discussed below.
2.1. Presence of O3 in the troposphere
Because of the presence of high mixing ratios of O3 in
the stratosphere, there is net transport of O3 by eddy
diffusion from the stratosphere into the troposphere
(Logan, 1985; Roelofs and Lelieveld, 1997). In addition,
O3 is formed photochemically in the troposphere from
the interactions of NMOCs and oxides of nitrogen
(NO+NO2; NOx) in the presence of sunlight (Logan,
1985; Atkinson, 2000) [see reactions (1)–(4)]. These
sources of tropospheric O3 are balanced by in situ
photochemical destruction and by dry deposition at the
Earth’s surface (Logan, 1985; Roelofs and Lelieveld,
1997). The result of these processes is the presence of
ozone throughout the troposphere with mixing ratios
at ‘‘clean’’ remote sites at ground level in the range of
10–40 ppbv (Logan, 1985; Oltmans and Levy, 1994), and
with O3 mixing ratios in polluted urban areas often
exceeding 100 ppbv.
2.2. Formation of hydroxyl radicals in the troposphere
The presence of relatively low levels of O3 in the
troposphere is extremely important because photolysis
of O3 at wavelengths X290 nm occurs to form the O(1D)
atom. O(1D) atoms are either deactivated to groundstate oxygen, O(3P), atoms or react with water vapor to
generate OH radicals:
O3 þ hn-O2 þ Oð1 DÞ
ðlp350 nmÞ
ð5Þ
Oð1 DÞ þ M-Oð3 PÞ þ M ðM ¼ N2 ; O2 Þ
ð6Þ
Oð1 DÞ þ H2 O-2OH
ð7Þ
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R. Atkinson, J. Arey / Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
Direct spectroscopic measurements of OH radical
concentrations at ground level at Claremont, CA in
the Los Angeles air basin in September 1993 showed
peak daytime OH radical concentrations in the range
(4–6) 106 molecule cm3 (George et al., 1999). A
diurnally, seasonally and annually averaged global
tropospheric OH radical concentration of 1.0 106
molecule cm3 (24-h average) has been estimated from
the emissions, atmospheric concentrations and atmospheric chemistry of methyl chloroform (Prinn et al.,
1995, 2001; Hein et al., 1997). While the photolysis of O3
results in the formation of OH radicals only during
daylight hours, it has been suggested that OH radical
formation from the reactions of O3 with alkenes
(including BVOCs containing CQC bonds such as
isoprene, monoterpenes and 2-methyl-3-buten-2-ol) during both daytime and nighttime could be significant
(Paulson and Orlando, 1996; see the discussion below of
the O3 reaction mechanism).
2.3. Formation of nitrate radicals in the troposphere
The presence of NO in the troposphere from natural
and anthropogenic sources is followed by the reactions
NO þ O3 -NO2 þ O2
ð8Þ
NO2 þ O3 -NO3 þ O2
ð9Þ
leading to the formation of the NO3 radical. Because the
NO3 radical photolyses rapidly, with a lifetime due to
photolysis of B5 s for overhead sun, and reacts rapidly
with NO, NO3 radical concentrations remain low during
daylight hours but can increase to measurable levels
during nighttime. Measurements made over the past
B20 years show nighttime NO3 radical concentrations
at or near ground level over continental areas ranging up
to 1 1010 molecule cm3 [a mixing ratio of 430 partsper-trillion (pptv)] (Atkinson et al., 1986; Mihelcic et al.,
1993; Platt and Heintz, 1994). A 12-h average nighttime
concentration of 5 108 molecule cm3 (20 pptv mixing
ratio) has been proposed as a reasonable value for
lifetime calculations (Atkinson, 1991).
3. Lifetimes of biogenic organic compounds in the
troposphere
Rate constants for the gas-phase reactions of many of
the BVOCs emitted from vegetation with OH radicals,
NO3 radicals and O3 have been measured. These rate
constants can be combined with assumed ambient
tropospheric concentrations of OH radicals, NO3
radicals and O3 to calculate the BVOC lifetime (time
for decay of the BVOC to 1/e of its initial concentration)
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with respect to each of these loss processes (as shown in
Table 1 for selected BVOCs). The data in Table 1
indicate that many of the BVOCs emitted (including
isoprene, monoterpenes, sesquiterpenes, hexene derivatives, 2-methyl-3-buten-2-ol, linalool and 6-methyl-5hepten-2-one) are highly reactive in the troposphere,
with calculated lifetimes of a few hours or less. Of the
BVOCs studied, a-terpinene, b-caryophyllene and ahumulene react so rapidly with O3 (Table 1) that if these
particular BVOCs are emitted from vegetation they will
be rapidly removed by reaction, even at ‘‘clean’’ remote
sites. The highly reactive nature of many of the BVOCs
explains some of the difficulties encountered in reconciling BVOC emission inventories calculated from measured emission rates with observed ambient
concentrations of these compounds. Note that the
ambient atmospheric concentrations of OH radicals,
NO3 radicals and O3 are variable, and those of OH and
NO3 radicals have pronounced diurnal profiles. Hence
the instantaneous lifetimes of BVOCs depend on the
time of day, season, latitude, cloud cover, and
the chemical composition of the airmass containing the
BVOC. The lifetimes given in Table 1 are inversely
proportional to the OH radical, NO3 radical and O3
concentrations used in the calculations and should be
considered as only approximations, useful, for example,
in ranking the reactivity of the various BVOCs.
4. Reaction mechanisms and products
The initial reactions of OH radicals, NO3 radicals and
O3 with NMOCs (including BVOCs) have been elucidated over the past two decades (see, for example,
Atkinson, 1997a, 2000; Calvert et al., 2000) and the
reactions of BVOCs have been previously reviewed by
Atkinson and Arey (1998) and Calogirou et al. (1999a).
For the BVOCs listed in Table 1 there are two general
reaction mechanisms: (1) addition to CQC bonds by
OH radicals, NO3 radicals and O3 and (2) H-atom
abstraction from C–H bonds (and to a much lesser
extent, from O–H bonds) by OH radicals and NO3
radicals. Ozone reacts only by addition to CQC bonds,
and for BVOCs with CQC bonds, addition of OH and
NO3 will generally dominate over H-atom abstraction
by these radicals and will lead to hydroxy- or nitrooxysubstituted alkyl radicals, respectively. H-atom abstraction by OH radicals and NO3 radicals occurs from the
various C–H bonds in alkanes, ethers, alcohols, carbonyls and esters. This reaction pathway is of minor
importance for isoprene, monoterpenes and sesquiterpenes, and for alcohols, ethers, esters and ketones
containing CQC bonds, but is important for aldehydes
containing CQC bonds (for example, for methacrolein). These H-atom abstraction reactions lead to the
formation of alkyl or substituted alkyl radicals.
ARTICLE IN PRESS
R. Atkinson, J. Arey / Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
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membered transition state, and react with O2 (Atkinson,
1997b, 2000). Representative reaction schemes are
shown in Schemes 2 and 3 for the OH-radical-initiated
reactions of 2-methyl-3-buten-2-ol and isoprene, respectively, and in Scheme 4 for the reaction of NO3 radicals
with isoprene.
In Scheme 2 only one of the two hydroxyalkyl radicals
formed after initial OH radical addition is followed
through its detailed reactions; analogous reactions occur
for the other initially formed hydroxyalkyl radical
(CH3)2C(OH)CH(OH)CH2. Note that in Scheme 2
the intermediate hydroxyalkoxy radical (CH3)2C(OH)CH(O)CH2OH cannot isomerize and its decompositions dominate over reaction with O2. In Scheme 3 the
reactions are followed for only one of the six possible
hydroxyalkyl radicals (Atkinson, 1997a); note that for
OH radical addition at the 1-position the initially
formed allylic radical HOCH2C(CH3)CHQCH2 is in
resonance with HOCH2C(CH3)QCHCH2 (an analogous situation occurs for OH radical addition at the
4-position), and that isomerization of the 1,4-hydroxyalkoxy radical HOCH2C(CH3)QCHCH2O proceeds through a six-membered transition state (as
shown). The reactions shown in Schemes 2 and 3 are
for conditions such that organic peroxy (RO2 ) radicals
react dominantly with NO (and therefore alkoxy
radicals are the key radical intermediates). In the
presence of low enough NO concentrations that
The reactions of the alkyl or substituted alkyl radicals
(R) formed after H-atom abstraction from C–H bonds
or after OH or NO3 radical addition to C=C bonds
are shown schematically in Scheme 1, with the reactions
proceeding through the intermediary of organic peroxy
(RO2 ) and alkoxy (RO) radicals (Atkinson, 2000). In
the atmosphere, alkoxy radicals can decompose by C–C
bond scission, isomerize by a 1,5-H shift through a sixR
biogenic VOC
O2
HO2
ROOH
carbonyl
+
alcohol
NO2
RO 2
ROONO 2
NO
RO 2
RONO 2
RO
O2
decomposition
isomerization
products
Scheme 1.
OH
OH + H3C
C
OH
CH
CH2
H3C
CH3
C
OH OH
CH2OH and H3C
CH
CH3
C
CH
CH2
CH3
O2
OH OO
H3C
C
CH
CH2OH
CH3
OH ONO 2
H3C
C
CH
NO
CH2OH
CH3
OH O
H3C
C
CH
CH2OH + NO2
CH3
decomposition
decomposition
OH
H3C
C
OH
CH3 + HOCH2CHO
CH2OH +
O2
O2
HCHO + HO2
CH3C(O)CH 3 + HO2
Scheme 2.
H3C
C
CH3
CHO
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CH3
CH3
OH +
CH2
CH
C
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HOCH2
CH2
CH
C
CH2
CH3
HOCH2
C
CH
CH2
O2
CH3
HOCH2
CH
C
CH2OO
CH3
NO
HOCH2
CH3
H
CH2
C
HO
isomer.
CH
C
H
C
CH
CH2ONO 2
CH3
HOCH2
C
O
CH
CH2O + NO2
O2
CH3
HOCH2
CH3
HOCH
CH
C
C
CH
CHO + HO2
CH2OH
O2
CH3
OCH
C
CH
CH2OH + HO2
Scheme 3.
RO2 +HO2 and RO2 +RO2 reactions dominate over
RO2 +NO reactions, then additional products would
also be formed (including, from the OH+isoprene
reaction, hydroxyhydroperoxides, hydroxycarbonyls
and diols) [see, for example, Benkelberg et al., 2000;
Ruppert and Becker, 2000].
Scheme 4 shows the reaction of NO3 radicals with
isoprene under conditions where RO2 +HO2 and
RO2 +RO2 reactions dominate over the RO2 +NO
reactions (note that when NO3 radicals are present at
appreciable concentrations then NO is not, because of
the rapid reactions of NO with NO3 radicals and with
O3). Scheme 4 again shows the reactions of only one of
the initially formed radicals (see Skov et al., 1992). The
reactions of organic peroxy (RO2 ) radicals with HO2
and RO2 radicals shown in Scheme 4 proceed by the
pathways, taking the ethyl peroxy radical as an example:
CH3 CH2 OO þ HO2 -CH3 CH2 OOH þ O2
ð10Þ
CH3 CH2 OO þ CH3 CH2 OO
-CH3 CHO þ CH3 CH2 OH þ O2
ð11aÞ
CH3 CH2 OO þ CH3 CH2 OO
-CH3 CH2 O þ CH3 CH2 O þ O2
ð11bÞ
As noted above, the reactions of O3 with BVOCs
containing CQC bonds proceed by initial O3 addition
to the CQC bond, to form a primary ozonide which
rapidly decomposes via two pathways to a carbonyl plus
a ‘‘Criegee intermediate’’ as shown in Scheme 5 for
isoprene [pathways (1) and (2)]. Note that for cyclic
alkenes with an internal double bond (such as a-pinene
and 2- and 3-carene), a carbonyl-substituted Criegee
intermediate is formed from each primary ozonide
decomposition pathway. Theoretical calculations (see,
for example, Gutbrod et al., 1996; Kroll et al., 2002)
indicate that the Criegee intermediate is a carbonyl oxide
which, for monoalkyl-substituted intermediates, can
exist in the syn- or anti-configuration. The initially
energy-rich Criegee intermediates react by a number of
routes (Atkinson, 1997a, 2000; Calvert et al., 2000;
Fenske et al., 2000; Kroll et al., 2001a–c, 2002; Zhang
et al., 2002) including (a) collisional stabilization to a
thermalized Criegee intermediate [pathway (4) in
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CH3
CH3
NO3 +
CH2
C
CH
O2NOCH2
CH2
CH
C
CH2
CH3
O2NOCH2
C
CH
CH2
O2
CH3
CH3
O2NOCH2
CH
C
HO2
CH2OOH
O2NOCH2
C
CH
CH2OO
RO 2
RO 2
CH3
CH3
O2NOCH2
CH
C
O2
CH2O
O2NOCH2
C
CH
CH
CHO
and
isomer.
CH3
O2NOCH2
C
CH3
CHO + HO2
O2NOCH2
C
CH
CH2OH
CH3
O2NOCH
CH
C
CH2OH
decomp.
CH3
OCH
C
CH
CH2OH + NO2
Scheme 4.
Scheme 5], (b) for dialkyl- and syn-monoalkyl-substituted Criegee intermediates, isomerization to a ‘‘hot’’
hydroperoxide followed by decomposition to an OH
radical plus a substituted alkyl radical [pathway (5) in
Scheme 5], and (c) rearrangement to a ‘‘hot’’ ester
followed by decomposition (for example, to
CO2+CH3CHQCH2 for the Criegee intermediate of
structure [CH2QC(CH3)CHOO]* formed after initial
O3 addition to the other (3,4-) double bond in isoprene).
Additionally, for isoprene and a-pinene the formation of
epoxides, presumably via a direct reaction [pathway (3)
in Scheme 5], has been observed in low, B2–5%, yield
(Paulson et al., 1992a; Atkinson et al., 1994; Alvarado
et al., 1998a).
The formation of OH radicals from the reactions of
O3 with alkenes at atmospheric pressure is well
established (Paulson et al., 1997; Pfeiffer et al., 1998;
Kroll et al., 2001a, b; Siese et al., 2001). Recently, Kroll
et al. (2001a–c) have reported that OH radicals are
formed via both ‘‘prompt’’ and ‘‘slow’’ processes at
atmospheric pressure, with the ‘‘slow’’ process involving
participation of the thermalized dialkyl- or syn-monoalkyl-substituted Criegee intermediates (Fenske et al.,
2000; Kroll et al., 2001b, c, 2002). Under typical
atmospheric conditions, thermalized Criegee intermediates also react with water vapor to form a-hydroxyhydroperoxides, which may be stable in the gas phase or
decompose to a carbonyl plus H2O2 or to a carboxylic
acid plus H2O (Becker et al., 1990, 1993; Alvarado et al.,
1998a; Sauer et al., 1999; Winterhalter et al., 2000; Baker
et al., 2002).
However, laboratory studies conducted at atmospheric pressure of air have shown that the OH radical
formation yields from the reactions of O3 with 2-methyl2-butene (Johnson et al., 2001) and a series of
monoterpenes (Atkinson et al., 1992; Aschmann et al.,
2002b) are not affected by the presence of water vapor,
up to 36–74% relative humidity at 295–296 K. Furthermore, Johnson et al. (2001) have shown that addition of
SO2, 2-butanone or acetic acid, which are known to
react with thermalized Criegee intermediates, have no
effect on the OH radical yield from the reaction of O3
with 2-methyl-2-butene. While more studies are required
for a complete understanding of the mechanisms of the
reaction of O3 with alkenes under atmospheric conditions, the information to date indicate that syn- and
ARTICLE IN PRESS
R. Atkinson, J. Arey / Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
O3 +
CH2
C
*
CH3
CH3
CH
CH2
CH2
C
O
O
S205
CH
CH2
O
(1)
(2)
(3)
*
OO
HCHO + CH3
C
CH
H2COO
CH2
*+
CH3
O
C
CH
CH2
CH3
CH2 C
O
*
OO
CH3
C
CH
CH3
C
(4)
*
OO
CH
CH2
CH2 + O2
OO
+ M
CH2
CH
CH3
C
CH
*
OOH
(5)
CH2
C
CH
CH2 + M
CH2
O
CH2
C
CH
CH2 + OH
Scheme 5.
anti-Criegee intermediates are formed (with dialkylsubstituted intermediates having one alkyl group in the
syn-configuration) and that the syn-intermediates lead to
OH radical formation while the anti-intermediates are
collisionally thermalized and react with water vapor (see
Johnson et al., 2001; Aschmann et al., 2002b; Zhang
et al., 2002; Kroll et al., 2002).
Unless OH radicals are scavenged in laboratory
product studies, the O3–alkene reaction systems involve
both OH radicals and O3, and the products observed
and quantified are not applicable solely to the O3
reaction. For most BVOCs containing tri- and tetraalkyl-substituted CQC bonds, the measured OH
radical formation yields are close to unity (Atkinson,
1997a; Aschmann et al., 2002b). The reactions of O3
with BVOCs and anthropogenic NMOCs containing
CQC bonds may then be an additional source of OH
radicals in the troposphere, including during nighttime
(Paulson and Orlando, 1996). Obviously, the importance
of a particular BVOC to OH radical production depends
on its ambient concentration, its OH radical formation
yield, the rate constant for its reaction with O3, and the
O3 concentration (Paulson and Orlando, 1996).
Tables 2–11 list the products observed (see Fig. 3
for structures of products I–X), and their formation
yields, from the reactions of BVOCs with OH and NO3
radicals and O3 at atmospheric pressure of air [note that,
for example, the products formed from the reactions of
NO3 radicals with alkenes at total pressures less than
atmospheric or in the absence of O2 differ from the
products formed at atmospheric pressure of air (see, for
.
example, Berndt et al., 1996; Berndt and Boge,
1997a, b)]. The products observed from the reactions
of OH radicals, NO3 radicals and O3 with BVOCs
are generally consistent with Schemes 1–5, and the
individual studies should be consulted for details of
the experimental methods and results obtained. The
identification and, especially, quantification of many
of the products observed or anticipated to be
formed from these reactions (in particular, hydroxycarbonyls, dihydroxycarbonyls, hydroxynitrates, and carbonylnitrates) has been and continues to be a
challenging problem, as evident by the lack of a product
mass balance for most of the BVOC reactions studied
to date. As seen from Tables 3 and 4, even for the
measurement of formation yields of pinonaldehyde
from a-pinene and of nopinone from b-pinene,
there remain significant discrepancies, and these
may be due in part to uncertainties in calibrations and
for the infrared measurements from overlapping absorption bands of other carbonyl-containing products.
During the past few years significant advances in
analytical methods have enabled many multifunctional
products to be identified, if not yet quantified (see, for
example, Skov et al., 1992; Calogirou et al., 1995, 1997,
1999b; Yu et al., 1995, 1998; Kwok et al., 1995, 1996;
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Table 2
Products formed, and their yields, from the reactions of isoprene, at atmospheric pressure of air, with OH radicals (in the presence of
NO), O3 (in the presence of an OH radical scavenger), and NO3 radicals
Product
Yield OH radical Yield O3 reaction Yield NO3
References
reaction
radical reaction
Formaldehyde
0.6370.10a
0.5770.06
0.90
0.11
o0.05
Methyl vinyl ketone
0.3270.07a
0.35570.03
0.3270.05
0.17
0.15970.013
0.03570.014
Methacrolein
0.2270.05a
0.2570.03
0.2270.02
0.44
0.38770.030
0.03570.014
Organic nitrates
0.08–0.14a
0.04470.008
3-Methylfuran
0.04870.006a
0.0470.02
Observedb
HOCH2C(CH3)QCHCHO and/or
HOCH2CHQC(CH3)CHO
1,2-Epoxy-2-methyl-3-butene
1,2-Epoxy-3-methyl-3-butene
1,2-Epoxymethyl-3-butenes
Methylglyoxal
Pyruvic acid
Acetaldehyde
Hydroxyl radical
B0.80
0.02870.007
0.01170.004
p0.01
0.03
0.02
0.03
0:27þ0:14
0:09
0.19
0.2570.06
0:26þ0:03
0:06
0.4470.11
0.5370.16
Majorb
Minorb
Minorb
O2NOCH2C(CH3)QCHCHO
O2NOCH2CHQC(CH3)CHO
O2NOCH2C(O)C(CH3)CHO
a
b
Tuazon and Atkinson (1990a)
Miyoshi et al. (1994)
Grosjean et al. (1993a)
Barnes et al. (1990)
Skov et al. (1992)
Tuazon and Atkinson (1990a)
Paulson et al. (1992b)
Miyoshi et al. (1994)
Grosjean et al. (1993a)
Aschmann and Atkinson (1994)
Kwok et al. (1996)
Tuazon and Atkinson (1990a)
Paulson et al. (1992b)
Miyoshi et al. (1994)
Grosjean et al. (1993a)
Aschmann and Atkinson (1994)
Kwok et al. (1996)
Tuazon and Atkinson (1990a)
Chen et al. (1998)
Barnes et al. (1990)
Atkinson et al. (1989)
Paulson et al. (1992b)
Kwok et al. (1995)
Atkinson et al. (1994)
Atkinson et al. (1994)
Skov et al. (1994)
Grosjean et al. (1993a)
Grosjean et al. (1993a)
Grosjean et al. (1993a)
Atkinson et al. (1992)
Gutbrod et al. (1997)
Paulson et al. (1998)
Neeb and Moortgat (1999)
Rickard et al. (1999)
Lewin et al. (2001)
Skov et al. (1992)
Skov et al. (1992)
Skov et al. (1992)
Corrected (Atkinson, 1997a) to take into account O(3P) atom reactions.
Products observed, but not quantified.
Aschmann et al., 1998, 2002a; Reisell et al., 2001; Baker
et al., 2002).
4.1. Reactions of first-generation BVOC products
Concurrently with studies of the atmospheric chemistry of BVOCs, kinetic and product studies have been
carried out for a number of the BVOC atmospheric
reaction products, and Table 12 lists the calculated
lifetimes of selected BVOC reaction products with
respect to gas-phase reactions with OH and NO3
radicals and O3. Product studies carried out to date
for BVOC reaction products include those for methyl
vinyl ketone (Tuazon and Atkinson, 1989; Grosjean
ARTICLE IN PRESS
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S207
Table 3
Products formed, and their yields, from the reactions of a-pinene with OH radicals (in the presence of NO), O3 (in the presence of an
OH radical scavenger), and NO3 radicals
Product
Pinonaldehyde (I)
Yield OH
radical
reactiona
0.29
0.5670.04
0.2870.05
0.8770.20
0.3470.09
0.2870.05
Yield O3
reaction
Yield NO3
radical reaction
0.1970.04
0.5170.06b
0.14370.024
0.48–0.19c
0.06–0.19
0.16470.029
0.6270.04
0.69
Acetone
0.1570.10
0.11070.027
0.0970.06
0.0570.02
0.1170.02
0.0370.01
0.0870.02
0.0770.02
Formaldehyde
0.2370.09
0.1970.05
0.2270.01b
0.1570.04
Formic acid
0.0770.02
Organic nitrates
0.1870.09
0.03–0.20
0.1470.007
0.19
a-Pinene oxide
0.02170.007
Hydroxyl radical
0:85þ0:43
0:29
0.7670.11
0.7070.17
0.8370.21
0.9170.23
0.03–0.06
0.019–0.112
0:08þ0:08
0:04
0.022–0.079
0.043–0.126
0.012–0.026
0.003–0.016
0.0370.005
Pinic acid
Hydroxypinonaldehydes
Pinonic acid
Norpinonic acid/isomers
Norpinonaldehyde
2,2-Dimethyl-cyclobutyl-1,3dicarboxaldehyde
Hydroxypinonic acid
Norpinic acid
Carbonyls
2-Hydroxypinan-3-nitrate
3-Oxopinan-2-nitrate
a
0.015–0.037
B0.001
0.71
0.0570.004
0.0370.002
References
Arey et al. (1990)
Hatakeyama et al. (1991)
Hakola et al. (1994)
Nozi"ere et al. (1999a)
Wisthaler et al. (2001)
Aschmann et al. (2002a)
Hatakeyama et al. (1989)
Alvarado et al. (1998a)
Ruppert et al. (1999)
Yu et al. (1999)
Baker et al. (2002)
W.angberg et al. (1997)
Hallquist et al. (1999)
Gu et al. (1984)
Aschmann et al. (1998)
Nozi"ere et al. (1999a)
Orlando et al. (2000)
Wisthaler et al. (2001)
Reissell et al. (1999)
Ruppert et al. (1999)
Nozi"ere et al. (1999a)
Orlando et al. (2000)
Hatakeyama et al. (1989)
Ruppert et al. (1999)
Orlando et al. (2000)
Ruppert et al. (1999)
Nozi"ere et al. (1999a)
W.angberg et al. (1997)
Hallquist et al. (1999)
Alvarado et al. (1998a)
W.angberg et al. (1997)
Atkinson et al. (1992)
Chew and Atkinson (1996)
Paulson et al. (1998)
Rickard et al. (1999)
Siese et al. (2001)
Yu et al. (1999)
Yu et al. (1999)
Baker et al. (2002)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Hallquist et al. (1999)
W.angberg et al. (1997)
W.angberg et al. (1997)
See also Van den Bergh et al. (2000) for the identification of campholenealdehyde as a product, from a study carried out at up to
100 Torr total pressure, and Aschmann et al. (1998, 2002a) for other products observed but with no isomer-specific identification or, in
some cases, quantification.
b
In the absence of an OH radical scavenger.
c
Measured yield decreased with extent of reaction.
ARTICLE IN PRESS
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R. Atkinson, J. Arey / Atmospheric Environment 37 Supplement No. 2 (2003) S197–S219
Table 4
Products formed, and their yields, from the reactions of b-pinene with OH radicals (in the presence of NO), O3 (in the presence of an
OH radical scavenger), and NO3 radicals
Product
Yield OH
radical
reactiona
Nopinone (II)
0.30070.045
0.7970.08
0.2770.04
0.2570.03
Yield O3
reaction
Yield NO3
radical reaction
0.2370.05
0.4070.02b
0.22
B0.40
0.158–0.170
0.1670.04c
B0.01–0.02
Formaldehyde
0.5470.05
0.4570.08
0.7670.02b
0.42
0.70
0.6570.04
Acetone
0.08570.018
0.0270.02
0.1370.02
0.00970.009
0.0770.05
0.04
Formic acid
Hydroxyl radical
Pinic acid
Norpinic acid
Pinonic acid
Norpinonic acid/isomers
Hydroxypine-ketones
3-Oxo-pina-ketones
2,2-Dimethyl-cyclobutane-1,3dicarboxaldehyde
Hydroxynorpinonic acid
Hydroxypinonic acid
Organic nitrates
Carbonyls
0.0270.01
0.02–0.05
0:35þ0:18
0:12
0.026–0.037
0.0270.01
0.0027–0.0035
0.0052–0.0074
0.059–0.165
0.073–0.090
0.1570.05
0.018–0.077
0.0029–0.0035
0.0068–0.012
0.0031–0.0043
0.61
0.14
References
Arey et al. (1990)
Hatakeyama et al. (1991)
Hakola et al. (1994)
Wisthaler et al. (2001)
Hatakeyama et al. (1989)
Grosjean et al. (1993b)
Ruppert et al. (1999)
Yu et al. (1999)
Winterhalter et al. (2000)
Hallquist et al. (1999)
Hatakeyama et al. (1991)
Orlando et al. (2000)
Hatakeyama et al. (1989)
Grosjean et al. (1993b)
Ruppert et al. (1999)
Winterhalter et al. (2000)
Aschmann et al. (1998)
Orlando et al. (2000)
Wisthaler et al. (2001)
Reissell et al. (1999)
Ruppert et al. (1999)
Orlando et al. (2000)
Ruppert et al. (1999)
Atkinson et al. (1992)
Yu et al. (1999)
Winterhalter et al. (2000)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Winterhalter et al. (2000)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Hallquist et al. (1999)
Hallquist et al. (1999)
a
See also Aschmann et al. (1998) for other products observed but with no isomer-specific identification or quantification.
In the absence of an OH radical scavenger.
c
Increases with increasing water vapor concentration to B0.51.
b
et al., 1993a; Aschmann et al., 1996; Paulson et al.,
1998), methacrolein (Tuazon and Atkinson, 1990b;
Grosjean et al., 1993a; Aschmann et al., 1996; Orlando
et al., 1999), pinonaldehyde (Nozi"ere and Barnes, 1998;
Nozie" re et al., 1999a), nopinone (Calogirou et al.,
1999b), endolim (Calogirou et al., 1999b), and 2ethenyl-2-methyl-5-hydroxytetrahydrofuran [5-methyl5-vinyltetrahydrofuran-2-ol] (Calogirou et al., 1999b),
and these references should be consulted for details.
5. Conclusions
Emissions of non-methane organic compounds
from vegetation are to a large extent composed of
compounds containing reactive CQC bonds. All
BVOCs react with OH radicals and many also react
rapidly with NO3 radicals and O3 and have calculated
lifetimes in the troposphere of a few hours or less. While
the kinetics of the gas-phase reactions of biogenic
ARTICLE IN PRESS
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S209
Table 5
Products formed, and their yields, from the reactions of myrcene and ocimene with OH radicals (in the presence of NO) and O3 (in the
presence of an OH radical scavenger)
BVOC studied
Product
Yield OH
radical
reaction
Myrcene
Acetone
0.36a
0.4570.06
0.3670.05
Formaldehyde
0.3070.06
Formic Acid
0.0570.02
CH2QCHC(QCH2)CH2CH2CHO
Hydroxyacetone
Hydroxyl radical
0.1970.04
Acetone
0.18a
0.2070.15
Yield O3
reaction
o0.01
0.7070.13
0.19
þ0:58
1:150:39
0.6370.09
Reissell et al. (1999)
Reissell et al. (1999)
Orlando et al. (2000)
Ruppert et al. (1999)
Reissell et al. (2002)
Orlando et al. (2000)
Ruppert et al. (1999)
Orlando et al. (2000)
Ruppert et al. (1999)
Reissell et al. (2002)
Ruppert et al. (1999)
Atkinson et al. (1992)
Aschmann et al. (2002b)
0.2170.04
0.2470.04
0.3370.06
þ0:32
0:630:21
0.5570.09
Reissell et al. (1999)
Reissell et al. (1999)
Reissell et al. (2002)
Reissell et al. (2002)
Atkinson et al. (1992)
Aschmann et al. (2002b)
0.2670.04b
0.2570.06
0.29
0.2170.03
0.26
cis-/trans-Ocimene
CH2QCHC(CH3)QCHCH2CHO
Hydroxyl radical
a
b
o0.02
References
From single point determination to minimize concurrent reaction of myrcene or ocimene with NO2 (see Reissell et al., 1999).
Corrected values (Reissell et al., 2002).
Table 6
Products formed, and their yields, from the reactions of 3-carene with OH radicals (in the presence of NO), O3 (in the presence of an
OH radical scavenger), and NO3 radicals
Product
Yield OH
radical reaction
Caronaldehyde (III)
0.31
0.3470.08
Yield O3
reaction
Yield NO3
radical reaction
p0.08
0.44–0.15a,b
0.085
0.02–0.03
Acetone
0.1570.03
0.1570.03
Formaldehyde
0.2170.04
0.2270.05
0.1070.015
0.09a
0.16a
Formic acid
Hydroxyl radical
0.0870.02
3-Caronic acid
Hydroxycaronaldehydes
3-Caric acid
Pinic acid
Nor-3-caronic acid/isomers
Hydroxy-3-caronic acid
Nor-3-caric acid
Organic nitrates
Carbonyls
a
b
In the absence of an OH radical scavenger.
Measured yield decreased with extent of reaction.
1:06þ0:53
0:36
0.8670.11
0.042
0.032
0.019
0.012
0.023
0.012
0.0007
0.66
0.29
References
Arey et al. (1990)
Hakola et al. (1994)
Ruppert et al. (1999)
Yu et al. (1999)
Hallquist et al. (1999)
Reissell et al. (1999)
Orlando et al. (2000)
Ruppert et al. (1999)
Orlando et al. (2000)
Ruppert et al. (1999)
Orlando et al. (2000)
Atkinson et al. (1992)
Aschmann et al. (2002b)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Hallquist et al. (1999)
Hallquist et al. (1999)
ARTICLE IN PRESS
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Table 7
Products formed, and their yields, from the reactions of limonene with OH radicals (in the presence of NO), O3 (in the presence of an
OH radical scavenger), and NO3 radicals
Product
Yield OH
radical reaction
4-Acetyl-1-methyl-cyclohexene
(IV)
0.17470.028
0.2070.03
Endolim (V)
Yield O3
reaction
Yield NO3
radical reaction
Arey et al. (1990)
p0.04
0.02
B0.01
0.28
0.2970.06
B0.01
0.69
o0.03
Acetone
Formaldehyde
Formic acid
Hydroxyl radical
References
o0.02
B0.02
0.10
0.19
0.03–0.10
0:86þ0:43
0:29
0.6770.10
Organic nitrates
0.48
Hakola et al. (1994)
Grosjean et al. (1993b)
Ruppert et al. (1999)
Arey et al. (1990)
Hakola et al. (1994)
Ruppert et al. (1999)
Hallquist et al. (1999)
Reissell et al. (1999)
Ruppert et al. (1999)
Grosjean et al. (1993b)
Ruppert et al. (1999)
Ruppert et al. (1999)
Atkinson et al. (1992)
Aschmann et al. (2002b)
Hallquist et al. (1999)
Table 8
Products formed, and their yields, from the reactions of BVOCs with OH radicals (in the presence of NO) and O3 (in the presence of an
OH radical scavenger)
BVOC studied
Product
Yield OH
radical reaction
Yield O3
reaction
References
Camphene
Camphenilone (VI)
C9O2H14 (VII)
Acetone
Hydroxyl radical
Acetone
4-Isopropyl-2-cylcohexen-1-one
Hydroxyl radical
Sabinaketone (VIII)
o0.02
o0.02
0.3970.05
0.3670.06
B0.2
0.0870.04
0.2970.07
p0.18
o0.02
0.2970.06
B0.14
Hakola et al. (1994)
Hakola et al. (1994)
Reissell et al. (1999)
Atkinson et al. (1992)
Reissell et al. (1999)
Hakola et al. (1993)
Atkinson et al. (1992)
Arey et al. (1990)
Hakola et al. (1994)
Yu et al. (1999)
Reissell et al. (1999)
Atkinson et al. (1992)
Chew and Atkinson (1996)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Yu et al. (1999)
Reissell et al. (1999)
Aschmann et al. (2002b)
Reissell et al. (1999)
Aschmann et al. (2002b)
Arey et al. (1990)
a-Phellandrene
b-Phellandrene
Sabinene
Acetone
Hydroxyl radical
a-Terpinene
g-Terpinene
Terpinolene
Hydroxysabinaketones
Norsabinonic acid/isomers
Pinic acid
Sabinic acid
3-Oxo-sabinaketone
Norsabinic acid
Acetone
Hydroxyl radical
Acetone
Hydroxyl radical
4-Methyl-3-cyclohexen-1-one
(IX)
C10O2H16 (X)
0.17
0.1770.03
0.1970.03
B0.10
0.1070.03
0.5070.09
0.466
0.0370.02
0:26þ0:13
0:09
0.3370.06
0.070
0.047
0.014
0.012
0.0051
0.0025
0.0370.01
0.3870.05
0.1170.02
0.8170.11
0.24
0.2670.06
0.2670.05
0.10
0.4070.06
0.4070.08
Hakola et al. (1994)
Reissell et al. (1999)
Arey et al. (1990)
ARTICLE IN PRESS
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S211
Table 8 (continued)
BVOC studied
Product
Acetone
Formaldehyde
Formic acid
Hydroxyl radical
Caryophyllene
Yield OH
radical reaction
Yield O3
reaction
References
0.0870.02
0.32a
0.3970.05
0.2970.06
0.0870.02
p0.02
0.5070.05
0.5070.06
1:03þ0:52
0:35
0.7470.10
B0.14b
0.08
B0.08b
Hakola et al. (1994)
Reissell et al. (1999)
Orlando et al. (2000)
Orlando et al. (2000)
Orlando et al. (2000)
Atkinson et al. (1992)
Aschmann et al. (2002b)
Calogirou et al. (1997)
Grosjean et al. (1993b)
Calogirou et al. (1997)
B0.08b
Calogirou et al. (1997)
0:06þ0:03
0:02
Shu and Atkinson (1994)
Formaldehyde
3,3-Dimethyl-g-methylene-2-(3oxobutyl)-cyclobutanebutanal
3,3-Dimethyl-g-oxo-2-(3oxobutyl)-cyclobutanebutanal
Hydroxyl radical
a
b
Measured yield increased with extent of reaction; value cited is initial yield.
In the absence of an OH radical scavenger.
Table 9
Products formed, and their yields, from the reactions of 2-methyl-3-buten-2-ol with OH radicals (in the presence of NO), O3 (in the
presence of an OH radical scavenger), and NO3 radicals
Product
Yield OH
radical reaction
Yield O3
reaction
Formaldehyde
0.09370.033a
0.3570.04
0.2970.03
0.53
2-Hydroxy-2-methylpropanal
Acetone
Glycolaldehyde
Organic nitrates
Hydroxyl radical
0.1970.07
0.14170.002a
0.5270.05
0.5870.04
0.2970.03
0.3670.09
0.47b
0.3070.02
0.15
Yield NO3
radical reaction
0.68770.071
0.12–0.48c
0.2370.06
0.28070.028a
0.5070.05
0.6170.09
0.0570.02
0:19þ0:10
0:07
B0.13
References
Fantechi et al. (1998)
Ferronato et al. (1998)
Alvarado et al. (1999)
Grosjean and Grosjean (1995)
Alvarado et al. (1999)
Grosjean and Grosjean (1995)
Fantechi et al. (1998)
Ferronato et al. (1998)
Alvarado et al. (1999)
Grosjean and Grosjean (1995)
Fantechi et al. (1998)
Ferronato et al. (1998)
Alvarado et al. (1999)
Alvarado et al. (1999)
Fantechi et al. (1998)
Alvarado et al. (1999)
At low NOx concentrations; RO2 +RO2 and/or RO2 +HO2 may have dominated over RO2 +NO reactions.
Fourier transform infrared measurement assuming that 2-hydroxy-2-methylpropanal and HCHO are co-products from the OH
radical reaction.
c
Measured yield increased with extent of reaction.
a
b
NMOCs with OH radicals, NO3 radicals and O3
appear to be reasonably well understood, the products
formed from these reactions and the detailed reaction
mechanisms are less well known. In large part,
this is because of the lack of analytical methods and
standards for the identification and quantification of
labile multi-functional products formed from these
reactions.
Ambient measurements of isoprene and of its first and
second-generation products have been made (see, for
example, Montzka et al., 1993, 1995; Yokouchi, 1994;
Williams et al., 1997; Nouaime et al., 1998; Starn et al.,
1998a, b; Reissell and Arey, 2001; Wiedinmyer et al.,
2001), and these ambient measurements are generally
consistent with laboratory kinetic and product data.
BVOCs play an important role in the chemistry of the
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Table 10
Products formed, and their yields, from the reactions of linalool with OH radicals (in the presence of NO), O3 (in the presence of an
OH radical scavenger), and NO3 radicals
Product
Yield OH
radical reaction
Yield O3
reactiton
Yield NO3
radical reaction
References
Acetone
0.50570.047
Observed
0.21170.024
0.22570.052
6-Methyl-5-hepten-2-one
4-Hydroxy-4-methyl-5-hexen-1-al
0.06870.006
0.4670.11
Observed
0.3670.06
0.01470.012
0.1170.01
0.12670.025
Shu et al. (1997)
Calogirou et al. (1995)
Grosjean and Grosjean (1997)
Shu et al. (1997)
Shu et al. (1997)
Calogirou et al. (1995)
Shu et al. (1997)
Grosjean and Grosjean (1997)
Grosjean and Grosjean (1997)
Shu et al. (1997)
0:72þ0:36
0:24
0.6670.10
Atkinson et al. (1995)
Aschmann et al. (2002b)
0.2870.01
Formaldehyde
Methylglyoxal
5-Ethenyldihydro-5-methyl2(3H)-furanone
Hydroxyl radical
0.8570.14
0.19170.051
Table 11
Products formed, and their yields, from the reactions of oxygenated BVOCs with OH radicals (in the presence of NO) and O3 (in the
presence of an OH radical scavenger)
BVOC studied
Product
Yield OH radical reaction
a
cis-3-Hexen-1-ol
Propanal
0.74670.067
0:48þ0:48
0:24
Observed
6-Methyl-5-hepten-2-one
3-Hydroxypropanal
Hydroxynitrates
Methylglyoxal
Formaldehyde
Acetaldehyde
Hydroxyl radical
Acetone
Camphorb
cis-3-Hexenyl acetate
4-Oxopentanal
Methylglyoxal
Formaldehyde
Hydroxyl radical
Acetone
Propanal
2-Oxoethyl acetate
Acetaldehyde
Methylglyoxal
Hydroxyl radical
0.70670.054
0.5970.13
Yield O3 reaction
References
0.49370.075
0.58770.120
0:33þ0:33
0:16
Aschmann et al. (1997)
Grosjean et al. (1993c)
Aschmann et al. (1997)
Aschmann et al. (1997)
Grosjean et al. (1993c)
Grosjean et al. (1993c)
Grosjean et al. (1993c)
Atkinson et al. (1995)
Smith et al. (1996)
Grosjean et al. (1996)
Smith et al. (1996)
Grosjean et al. (1996)
Grosjean et al. (1996)
Smith et al. (1996)
Reissell et al. (2001)
Grosjean and Grosjean
Grosjean and Grosjean
Grosjean and Grosjean
Grosjean and Grosjean
Atkinson et al. (1995)
0.17670.050
0.03570.010
0.13170.025
0:26þ0:13
0:09
0.30270.048
0.28270.023
0.8270.21
0.31970.037
0.03870.032
0:75þ0:38
0:25
0.2970.04
0.76070.043
0.06070.021
0.05270.007
0.04870.005
0:16þ0:08
0:06
(1999)
(1999)
(1999)
(1999)
a
Also observed by Grosjean et al. (1993c, d).
See Reissell et al. (2001) for additional products tentatively identified by atmospheric pressure ionization tandem mass
spectrometry.
b
planetary boundary layer and contribute to the formation of ozone in urban and rural areas. Furthermore,
acetone formation from BVOC reactions appears to be a
significant contributor to the global acetone budget
(Reissell et al., 1999; Orlando et al., 2000). Additionally,
recent studies indicate that several biogenic NMOCs
(monoterpenes and sesquiterpenes) contribute to secondary organic aerosol formation through gas/particle
partitioning of their tropospheric reaction products
(Pandis et al., 1991; Palen et al., 1992; Zhang et al.,
1992; Hoffmann et al., 1997, 1998; Christoffersen et al.,
1998; Griffin et al., 1999a, b; Jang and Kamens, 1999;
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S213
O
O
CHO
O
CHO
Pinonaldehyde (I)
Caronaldehyde (III)
Nopinone (II)
O
CHO
O
4-Acetyl-1-methylcyclohexene (IV)
Endolim (V)
O
O
O
Camphenilone (VI)
Camphene product (VII)
O
O
CHO
O
Sabinaketone (VIII)
4-Methyl-3-cyclohexene-1-one (IX)
Terpinolene product (X)
Fig. 3. Structures of BVOC reaction products I–X (see Tables 3, 4 and 6–8).
Table 12
Calculated atmospheric lifetimes of products from BVOCs
BVOC product
Lifetimea for reaction with
OH
Methyl vinyl ketone
Methacrolein
3-Methylfuran
Camphenilone
Caronaldehyde
Endolim
4-Acetyl-1-methylcyclohexene
2-Ethenyl-2-methyl-5-hydroxy-tetrahydrofuran
Nopinone
O3
b
6.9 h
4.8 hb
1.5 hf
2.3 dayg
2.9 hh
1.3 hi
1.1 hg
1.9 hi
9.0 hj
NO3
c
3.4 day
15 dayc
19 hf
>2.1 yeard
28 daye
3 minf
>2.2 yearh
2.0 dayi
2.6 hg
4.4 dayi
>9.1 yeari
3.7 dayh
4.3 hi
6 ming
4.6 dayi
>46 dayi
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Table 12 (continued)
BVOC product
Pinonaldehyde
Sabinaketone
Lifetimea for reaction with
OH
O3
NO3
3.2 hk
2.3 dayh
>2.2 yearh
>330 dayh
4.6 dayh
250 dayh
a
Assumed radical and O3 concentrations as listed in Table 1. Note that photolysis of carbonyls may also be important.
Atkinson et al. (1983), Gierczak et al. (1997).
c
Atkinson (1994).
d
Rudich et al. (1996).
e
Chew et al. (1998).
f
Calvert et al. (2002).
g
Atkinson and Aschmann (1993).
h
Alvarado et al. (1998b).
i
Calogirou et al. (1999b).
j
Atkinson and Aschmann (1993), Calogirou et al. (1999b).
k
Alvarado et al. (1998b), Nozi"ere et al. (1999b).
b
Kamens et al., 1999; Yu et al., 1999; Koch et al.,
2000; Larsen et al., 2001), although often the firstgeneration products are volatile and it is the second (or
later)-generation products that undergo gas/particle
partitioning.
Acknowledgements
The authors gratefully thank the National Science
Foundation (Grant No. ATM-9909852) and the University of California Agricultural Experiment Station for
support.
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