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TROP.

RADICAL CHEMISTRY

(ADAPTED FROM DISS. A. GEYER)

1 CHEMISTRY OF FREE RADICALS IN THE PLANETARY BOUNDARY LAYER . 2


1.1 Atmospheric Chemistry of HOx and ROx Radicals.............................................................................. 2
1.1.1 The Formation of OH Radicals in the Atmosphere......................................................................... 2
1.1.2 Reactions of OH with Volatile Organic Compounds ...................................................................... 3
1.1.3 Chemistry of Peroxy and Alkoxy Radicals ..................................................................................... 5

1.2 Chemistry of the Nitrate Radical........................................................................................................... 9


1.2.1 Production of NO3 ......................................................................................................................... 10
1.2.2 Photolysis of NO3 .......................................................................................................................... 11
1.2.3 Non-photochemical NO3 Loss Mechanism ................................................................................... 11

1.3 Correlation Studies as Indicator for the NO3 Removal Path ............................................................ 16
1.3.1 Correlation Studies with respect to NO2 ....................................................................................... 17
1.3.2 The Temperature Dependence of the NO3 Degradation Rate........................................................ 18
1 CHEMISTRY OF FREE RADICALS IN THE PLANETARY
BOUNDARY LAYER
The planetary boundary layer (PBL) is the region of the atmosphere in which we live and into which chemical
compounds, in particular oxides of nitrogen (NOx = NO + NO2) and volatile organic compounds (VOCs), are
generally emitted by human and natural activities. This immission into the atmosphere leads to a complex system
of chemical and physical transformations which results effects such as the formation of ozone and photosmog
[e.g. Levy 1971; Liu et al., 1987; McKenzie et al., 1991; Carsey et al., 1997], acid deposition [e.g. review by
Schwartz, 1989], and the production of secondary particulate matter, which contributes to the so called
greenhouse effect [refer to recent reviews by Pandis et al., 1992; and Kulmala and Wagner, 1996].
Sources of nitrogen compounds in the troposphere are emission from soils and natural fires and their formation
from lightning [National Research Council, 1991; World Meteorological Organization, 1995], and, on the other
hand, emission from combustion processes such as traffic emissions and fossil-fueled power plants [National
Research Council, 1991; Guenther et al., 2000; Norbeck, 2000; Placet et al., 2000; Sawyer et al., 2000]. The
estimated world-wide emissions of NOx are 10 million metric tons of N per year from natural sources and 40 Mt
yr-1 from anthropogenic sources, respectively [National Research Council, 1991; World Meteorological
Organization, 1995].
Organic compounds are emitted by the biosphere and by human activities including combustion processes and
the use of solvents. Large quantities of methane [Hein et al., 1997] and non-methane organic compounds
(NMOC, VOCs), including isoprene (2-methyl-1,3-butadiene), a series of monoterpenes (C10H16), sesquiterpenes
(C15H24), and oxygenated VOCs (e.g. methanol, 2-methyl-3-buten-2-ol, and linalool) are emitted by vegetation
[Arey et al., 1991; Winer et al., 1992; Guenther et al., 1995, 2000; Knig et al., 1995]. VOCs are also emitted
from several anthropogenic sources, including combustion (vehicle and fossil-fueled power plant emissions),
emissions from industrial operations, fuel storage, solvent usage, and hazardous waste facilities [Norbeck, 2000;
Sawyer et al., 2000; Placet et al., 2000]. Literature estimates of the world-wide emissions of VOCs are 60-140
Mt of carbon yr -1 from anthropogenic and 1150 Mt carbon yr-1 from biogenic sources [National Research
Council, 1991; Lamb et al., 1993; World Meteorological Organization, 1995; Guenther et al., 1995]. In urban
areas both VOC and nitrogen oxide emission from anthropogenic sources dominate over natural sources, and the
reverse is generally the case in rural and remote areas, with, for example, isoprene dominating over
anthropogenic NMOC in the southeastern U.S. [Geron et al., 1994, 1995].
In the PBL, NOx and VOCs are either removed by the physical processes of wet and dry deposition [Wesley and
Hicks, 2000; Jacob, 2000], or are transformed by the chemical processes of photolysis and the oxidation by free
radicals1 such as hydroxyl (OH) radicals, nitrate (NO3 ) radicals, and ozone (O3) [e.g. Atkinson, 1994, 1995;
Heintz et al., 1996; Geyer et al., 2000a].
Hydroxyl radicals are mainly produced by the photolysis of ozone and other species like HONO and
formaldehyde so that nighttime OH levels are generally low compared to daytime concentrations, which are
usually in the range of some 106 cm-3. In contrary nitrate radicals are rapidly destroyed by sun light so that NO3
can only accumulate during nighttime.

1.1 Atmospheric Chemistry of HOx and ROx Radicals


The hydroxyl radical is proposed to be the major scavenger of a large number of VOCs and nitrogen compounds
in the atmosphere. Within this oxidation chain, ozone is produced by the reaction of peroxy radicals (RO2 and
HO2) with NO. This ozone production contributes to the formation of photo smog conditions frequently
observed during summer time. Figure 1 provides an overview over the complex chemical reaction scheme of
OH, HO2, and RO2 radicals during daytime.

1.1.1 The Formation of OH Radicals in the Atmosphere


Hydroxyl radicals are generally produced by the photolysis of O3 at wavelengths < 335 nm forming the excited
oxygen, O(1D), atom [DeMore et al., 1997; Atkinson et al., 1997b]. The O(1D) atoms either get quenched to
ground-state oxygen O(3P) atoms, or react with water vapor to produce OH radicals.

1 Free radicals are very reactive molecules. They are capable of independent existence and act as intermediates
in chemical reactions. Although they have the ability to exist independently they usually have a fleeting
existence. Free radicals have one or more unpaired electrons.
O3 + h O2 + O(1D) ( < 335 nm) J(1DO) ( 1)

O(1D) + M O(3P) + M (M = N2 , O2 ) ( 2)

O(3P) + O2 + M O3 + M ( 3)

O(1D) + H2O 2 OH ( 4)
The photolytic lifetime of O3 for a solar zenith angle of 0 is of the order 10 hours. At 298 K, standard
atmospheric pressure and 50 % relative humidity, about 1 OH radical is produced per 5 O(1D) atoms formed.
Photolysis of O3 in the presence of water vapor is the major tropospheric source of OH radicals. Other sources of
OH radicals in the troposphere include the photolysis of nitrous acid (HONO) [e.g. Platt 1985], the photolysis of
formaldehyde and other carbonyls in the presence of NO [via HO2, e.g. Winer and Biermann, 1994], and, as
discussed later, the dark reactions of NO3 and O3 with alkenes [Platt et al., 1990; Mihelcic et al., 1993; Paulson
and Orlando, 1996; Paulson et al., 1999; Geyer et al., 2000d].
Using spectroscopic techniques [e.g. Brauers et al., 1996; Mount et al., 1997; Mather et al., 1997; Holland et al.,
1997], peak daytime hydroxyl radical concentrations in the range (2 - 10) x 106 cm-3 have been measured at
ground level at mid-latitude northern hemisphere sites during summer time-periods. A diurnally and annually
averaged global mean tropospheric OH concentration has been estimated by comparing the emissions of
methylchloroform with its atmospheric concentrations resulting in an averaged 24-hour OH radical concentration
of 1.0 x 106 cm-3 [Prinn et al., 1995; Hein et al., 1997].

1.1.2 Reactions of OH with Volatile Organic Compounds


Hydroxyl radicals are the key reactive species in the daytime troposphere, reacting with almost all organic
compounds [e.g. Atkinson, 1989, 1994, 1999; DeMore et al., 1997; Atkinson et al., 1997a].
Figure 1 Simplified tropospheric reaction scheme of HOx radicals and VOCs.

NO(O 2)

R'O 2
CH3O 2
(RO 2) NO 3(O 2) R''CHO

OH
OH(O 2)
sources
P(OH)
CH4 CO(O 2) h(O2)
(VOC=RH OH(O 2)
) H2(O 2)

CH2O(O 2)

O3 O3
HONO h
carbonyls OH HO2
O3

H 2O OH

O3
NO 2 NO
h

HO x sinks
HNO3 H 2O 2
ROOH
Kinetic reaction coefficients for the reaction of OH radicals with alkanes, alkenes and aromatic hydrocarbons are
given in Table 1. Typical lifetimes of VOCs with respect to reactions with OH (including NO3 and O3) are
presented in Table 2. As for other saturated VOCs, reactions of OH with alkanes proceed via H-abstraction from
the C-H bonds. Reactions of OH with alkenes proceed mainly by initial addition of OH to the >C=C< bonds
forming -hydroxyalkyl radicals. The rapid reaction of these organic radicals with atmospheric oxygen leads to
the formation of peroxy radicals. For further details of the various aspects of OH - VOC reactions see Atkinson et
al. [1997a].
Table 1 Rate constants at 298 K for reactions of VOCs with NO3, OH and ozone [Atkinson,
1991; 1994; 1997; De More et al., 1997] (x = no data available).

VOC k(NO3) k(OH) k(O3) VOC k(NO3) k(OH) k(O3)


-17 -12 -18 -17 -12 -18
10 10 10 10 10 10
3 -1 3 -1 3 -1 3 -1 3 -1 3 -1
[cm s ] [cm s ] [cm s ] [cm s ] [cm s ] [cm s ]
alkanes alkenes
ethane 0.14 0.254 <10-5 ethene 20.5 8.52 1.59
propane 1.7 1.12 <10-5 propene 949 26.3 10.1
2-methylpropane 10.6 2.19 <10-5 i/1-butene 1350 31.4 9.64
n-butane 4.59 2.44 <10-5 cis-2-butene 35000 56.4 125
2-methylbutane 16.2 3.7 <10-5 2-methyl-1-butene 33000 61 16
2,2-dimethylbutane x 2.34 <10-5 2-methyl-2-butene 937000 86.9 403
2,3-dimethylbutane 40.6 5.78 <10-5 1-pentene 19000 31.4 10
n-pentane 8.7 4 <10-5 trans-2-pentene 37000 67 160
cyclopentane x 5.02 <10-5 1-hexene 1200 37 11
2-methylpentane 18 5.3 <10-5 cis-3-hexene 37000 60 150
3-methylpentane 22 5.4 <10-5 trans-2-hexene 37000 60 160
methylcyclopentane x x <10-5 1,3-butadiene 10000 66.6 6.3
2,4-dimethylpentane 15 5 <10-5 isoprene 67800 101 12.8
2,3-dimethylpentane x x <10-5 -pinene 616000 53.7 86.6
2,2,4-trimethylpentane 9 3.57 <10-5 -pinene 251000 78.9 15
2,3,4-trimethylpentane x 7.1 <10-5 d-limonene 1220000 171 200
n-hexane 11 5.45 <10-5 3-carene 910000 88 37
cyclohexane 14 7.21 <10-5 myrcene 1100000 215 470
2-methylhexane x 6.79 <10-5 camphene 66000 53 0.9
3-methylhexane x 7.16 <10-5 -terpinene 2900000 177 140
methylcyclohexane x 10 <10-5 sabinene 1000000 117 86
n-heptane 15 7.02 <10-5 -phellandrene 800000 168 47
2-methylheptane x x <10-5
3-methylheptane x x <10-5 aromatics
n-oktane 19 8.71 <10-5 benzene 3 1.23 < 10-2
n-nonane 23 10 <10-5 toluene 6.8 5.96 < 10-2
n-dekane 28 11.2 <10-5 ethylbenzene 70 7.1 < 10-2
m/p-xylene 40 18.8 < 10-2
alkynes o-xylene 37 13.7 < 10-2
ethine 5.1 0.82 0.0078 i-propylbenzene 70 6.5 < 10-2
n-propylbenzene 70 6.08 < 10-2
dimethylsulphide 100000 5 <1 m-ethyltoluene 70 19.2 < 10-2
p-ethyltoluene 70 12.1 < 10-2
1,2,4-trimethylbenzene 180 32.5 < 10-2
Table 2 Calculated lifetimes for selected volatile organic compounds with respect to the
reaction with OH, NO3, and ozone. For the rate constants see Table 1. Values are calculated
for a 12-hr daytime average OH radical concentration of 2 x 106 molecule cm-3, for a 12-hr
nighttime average NO3 radical concentration of 5 x 108 molecules cm-3, and for a 24-hr
average O3 concentration of 7 x 1011 molecules cm-3.

VOC lifetime due to VOC lifetime due to


NO3 OH O3 NO3 OH O3

alkanes alkenes
ethane 90 yr 45 d > 4500 yr ethene 225 d 1.4 d 10 d
propane 8 yr 10 d > 4500 yr propene 4.9 d 5.3 h 1.6 d
2-methylpropane 218 d 5.2 d > 4500 yr i/1-butene 3.4 d 4.4 h 1.7 d
n-butane 2.8 yr 4.7 d > 4500 yr cis-2-butene 95 min 2.5 h 3h
2-methylbutane 286 d 3.2 d > 4500 yr 2-methyl-1-butene 1.7 h 2.3 h 1d
2,2-dimethylbutane 4.9 d > 4500 yr 2-methyl-2-butene 4 min 96 min 59 min
2,3-dimethylbutane 114 d 2d > 4500 yr 1-pentene 2.9 h 4.4 h 1.7 d
n-pentane 1.5 yr 2.9 d > 4500 yr trans-2-pentene 90 min 2h 2.5 h
cyclopentane 2.3 d > 4500 yr 1-hexene 3.8 d 3.8 h 1.5 d
2-methylpentane 260 d 2.2 d > 4500 yr cis-3-hexene 90 min 2.3 h 3h
3-methylpentane 210 d 2.2 d > 4500 yr trans-2-hexene 90 min 2.3 h 2.5 h
methylcyclopentane > 4500 yr 1,3-butadiene 5.6 h 2h 2.6 d
2,4-dimethylpentane 310 d 2.3 d > 4500 yr isoprene 49 min 83 min 1.3 d
2,3-dimethylpentane > 4500 yr -pinene 5 min 2.6 h 5h
2,2,4-trimethylpentane 1.4 yr 3.3 d > 4500 yr -pinene 13 min 1.8 h 1.1 d
2,3,4-trimethylpentane 1.7 d > 4500 yr d-limonene 3 min 49 min 2h
n-hexane 1.2 yr 2.1 d > 4500 yr 3-carene 4 min 95 min 11 h
cyclohexane 330 d 1.6 d > 4500 yr myrcene 3 min 39 min 51 min
2-methylhexane 1.7 d > 4500 yr camphene 50 min 2.6 h 18 d
3-methylhexane 1.6 d > 4500 yr -terpinene 1 min 47 min 3h
methylcyclohexane 1.2 d > 4500 yr sabinene 3 min 71 min 5h
n-heptane 310 d 1.7 d > 4500 yr -phellandrene 4 min 50 min 8h
2-methylheptane > 4500 yr
3-methylheptane > 4500 yr aromatics
n-oktane 240 d 1.4 d > 4500 yr benzene > 4 yr 9.4 d > 4.5 yr
n-nonane 200 d 1.2 d > 4500 yr toluene 2.2 yr 1.9 d > 4.5 yr
n-dekane 166 d 1d > 4500 yr ethylbenzene 60 d 1.6 d > 4.5 yr
m/p-xylene 105 d 7.4 h > 4.5 yr
alkynes o-xylene 115 d 10.2 h > 4.5 yr
ethine 2.5 yr 14 d 5.8 yr i-propylbenzene 60 d 1.7 d > 4.5 yr
n-propylbenzene 60 d 1.8 d > 4.5 yr
dimethylsulphide 33 min 2.4 d > 20 d m-ethyltoluene 60 d 7.2 h > 4.5 yr
p-ethyltoluene 60 d 11.5 h > 4.5 yr
1,2,4-trimethylbenzene 23 d 4.3 h > 4.5 yr

1.1.3 Chemistry of Peroxy and Alkoxy Radicals


In general the degradation of VOCs is represented by Figure 2 (taking NO3-VOC reactions as an example), with
the important intermediate radicals being alkyl radicals (R, H or in the case of OH addition RH-OH), which
rapidly react with atmospheric oxygen forming alkyl peroxy radicals (RO2, HO2, or RH-OH-O2). Peroxy radicals
react with NO, NO3 or other peroxy radicals forming alkoxy radicals (RO, OH, or RH-OH-O). To a major
amount alkoxy radicals react back to peroxy radicals, however with a reduced alkyl group. This cycle will
continue until HOx radicals are formed at last. The rate constant for the following reactions are summarized in
Table 3. For a more detailed discussion of the peroxy radicals chemistry, please refer to [Lightfoot et al., 1992;
Wallington et al., 1992].
Figure 2 Reaction scheme of the degradation of volatile organic compounds (RH) including
the peroxy radical reaction chain. The gray colored species represent long living molecules.

RH

+OH
+N O 3

ROOH + O 2
+O 2
+H O 2 R'R ''C O + ROH+O 2
+R O 2
N O2 1.1.3.1 Peroxy
RO 2 ROONO 2
Radicals
+N O
The most simple peroxy
N O3 N O2 + O 2
RONO 2 radical in the atmosphere is
R O2 R O + O2
HO2, however a large number
NO N O2
of different RO2 species with
higher alkyl groups R can be
measured in the troposphere.
The alkyl radical can be a non
RO
substituted group (such as R =
CH3, CH3CH2, and so on), a
substituted group (e.g. R =
isomerization thermal decay
CH3CO, HOCH2CH2,
+O 2
CH3CHCH2ONO2) or it can be
even aromatic (e.g. R =
C6H5CH2). Peroxy radicals can
ROH R' + R''C O either be produced by the
HO 2 + R 'R ''C O reaction of free radicals such
as OH, NO3 and ozone with
VOCs and subsequent
+ NO combination with oxygen
molecules (cf. Figure 2 for the
degradation scheme following
NO3-VOC reactions) or during
OH day by the photolysis of
carbonyls like formaldehyde:

HCHO + h H + HCO J(HCHO) ( 5)

H + O2 +M HO2 + M ( 6)

HCO + O2 CO + HO2 ( 7)
Table 3 Kinetic data of selected non-organic reactions involved in tropospheric HOx
chemistry. The rate constant tabulation for bimolecular reactions is given in Arrhenius form:
k(T) = A exp(B/T). Reference: DeMore et al., 1997; *Moortgat 1994.

Nr. Reaction A [cm3s-1] B [K-1] k@ 288 K [cm3s-1]


4 O(1D) + H2O 2 OH 2.2 x 10-10 0 100 2.2 x 10-10
HO2 + NO OH + NO2 250 50
-12
8 3.5 x 10 8.1 x 10-12
9 CH3O2 + NO CH3O + NO2 3 x 10-12 280 60 8 x 10-12
C2H5O2 + NO C2H5O + NO2 2.6 x 10-12 365 150 9.2 x 10-12
11 NO + O3 NO2 + O2 2 x 10-12 -1400 200 1.55 x 10-14
15 OH + O3 HO2 + O2 1.6 x 10-12 -940 300 6.1 x 10-14
16 HO2 + O3 OH + 2 O2 1.1 x 10-14 -500 (+100-500) 1.9 x 10-15
18 NO3 + HO2 NO2 + OH + O2 4.1 x 10-12 - 4.1 x 10-12 *
20 NO3 + CH3O2 CH3O + NO2 + O2 1.2 x 10-12 - 1.2 x 10-12 *
24 HO2 + HO2 H2O2 + O2 2.3 x 10-13 600 200 1.8 x 10-12 *

The lifetime of HCHO at overhead sun is of the order of hours. During daytime these HO2 and RO2 radicals
convert NO to NO2 producing alkoxy radicals or in the case of HO2 hydroxyl radicals,

HO2 + NO OH + NO2 ( 8)

RO2 + NO RO + NO2 ( 9)
Another route of reaction 8 or 9 is the combination of NO and the peroxy radical yielding nitrates (RONO2),
which are a stable product of the peroxy radical degradation mechanism (see Figure 2). Kinetic studies of
reaction 8 and 9 showed that the rate coefficients are similar for different peroxy radicals with values in the
range of (4 20) x 10-12 cm3s-1 at room temperature (cf. Table 3). The ratio of combination to RONO2, however,
strongly depends on the alkyl group and increases with higher peroxy radicals (< 0.5 % for R = CH3 to 35 % for
R = C8H17).
The NO2 produced by reaction 8 and 9 photolyzes during daytime yielding NO and ozone. The photolytic
lifetime of NO2 in the troposphere is of the order of 100 seconds.

NO2 + h NO + O3 J(NO2) ( 10)


Additionally to the formation of NO2 by reactions 8 and 9 it is also produced by the rapid reaction of NO with
ozone:

NO + O3 NO2 + O2 ( 11)
However, as ozone also gets destroyed by reaction 11, no net production of ozone is constituted by the following
photolysis of NO2.
Reactions 10 and 11 can be combined yielding the photo stationary state (PSS) for ozone for VOC free
conditions, the so called Leighton ratio L (equations 12, 13). At sufficiently high NO and VOC concentrations
the PSS must be corrected according to 8 and 9:
J(NO2) [NO2] k11[NO][O3] = 0 ( 12)

[ NO2 ] k 11 [O 3] ( 13)
L= =
[ NO ] J ( NO 2 )
J(NO2) [NO2] k11[NO][O3] = k9[NO][RO2] + k8[NO][HO2] ( 14)
At low NO concentrations, reactions of O3 with OH and HO2 radicals,

OH + O3 HO2 + O2 ( 15)
HO2 + O3 OH + 2 O2 ( 16)
are additional loss processes for tropospheric ozone and peroxy radicals. Net photochemical formation of O3 in
the troposphere therefore depends on the NO concentration.
During night, when NO levels are generally low due to reaction 10, peroxy radicals are depleted by reactions
with the nitrogen oxides NO2 and NO3 and by self reaction. Reactions with NO2 usually establish a steady state
with peroxy nitrates (Figure 2):

RO2 + NO2 + M RO2NO2 + M ( 17)


Rate constants k+17 are of the order of (4 12) x 10-12 cm3s-1 at room temperature [Lightfoot et al., 1992]. The
value of k-17 greatly depends on temperature and the alkyl group and ranges from some (seconds)-1 to several
(hours)-1 [Lightfoot et al., 1992]. Another important path is the reaction of peroxy radicals with NO3 (Figure 2).
Recent studies of the reaction of HO2 and CH3O2 with NO3 were performed by Moortgat [1994] yielding two
channels for the HO2 reaction with the first one dominating under tropospheric conditions:

NO3 + HO2 NO2 + OH + O2 (80 %) ( 18)

HNO3 + O2 (20 %) ( 19)

NO3 + CH3O2 CH3O + NO2 + O2 ( 20)


Reactions of organic peroxy radicals with HO2 are known to be sinks of RO2 and HO2 and constitute the only
known source for hydro peroxides ROOH in the atmosphere:

RO2 + HO2 ROOH + O2 ( 21)


These reactions break the peroxy radical degradation chain because hydro peroxide are stable products in the
atmosphere at least during night, when photolysis can be neglected. In the case of CH3O2 and C2H5O2 rate
constants for reaction 21 of 5.8 x 10-12 cm3s-1 were found. Studies of other peroxy radicals yielded rate constants
which are about a factor of three higher than for CH3O2. The self reactions (of different peroxy radicals or of
RO2 having the same alkyl group) were studied for a large number of peroxy radicals. Thereby usually two
reaction paths were found, the forming of alkoxy radicals RO and a chain breaking path (Figure 2):

RO2 + RO2 2 RO + O2 (a) ( 22)

ROH + RRCO + O2 (b) ( 23)


Branching ratios between 10 % and 90 % for pathway (a) were found depending on the alkyl group of the peroxy
radical [e.g. Lightfoot et al., 1992; Tyndall et al., 1998]. The reaction coefficient depends on the type of the
peroxy radical. A variation over six decades was found in different kinetic studies ranging from 1.7 x 10-11 cm3s-1
(CH3COO2) to 3 x 10-17 cm3s-1 in the case of t-C4H9O2 [DeMore et al., 1997]. The rate constant decreases when
the degree of substitution increases. In the case of the HO2 self reaction, H2O2 molecules were identified as
products.

HO2 + HO2 H2O2 + O2 ( 24)


This reaction has been shown to have a bimolecular component and a pressure-dependent termolecular
component.
Finally peroxy radicals can react heterogeneously on aerosol surfaces. Uptake coefficients (see also 1.2.3.3) of
0.025 and 0.2 were found for HO2 for water ice and aerosols containing sulfuric acid and pure water [DeMore et
al., 1997], respectively. No data was found on the uptake coefficients of organic peroxy radicals.

1.1.3.2 Alkoxy Radicals


Three depletion mechanism are known for alkoxy radicals RO, the reaction with molecular oxygen, thermal
decay, and isomerization. The reaction with O2 leads to the formation of HO2 (H abstraction). In the case of the
thermal decay, which depends on the type of the peroxy radical, generally two smaller organic radicals were
formed. Both rapidly react with atmospheric oxygen to form further peroxy radicals [Atkinson et al., 1995;
Atkinson et al., 1997a]. However, taking nitrate oxy radicals as an example, which are produced by reactions of
NO3 with monoterpenes, it is also possible that separation of NO2 leads to the formation of stable products
breaking the radical chain reaction. Isomerization proceeds via H - shift producing an alkyl group with an OH
group. The time scale for all three sinks is very short under tropospheric conditions with lifetimes of less than
one second. The reaction with O2 dominates for small alkoxy radicals with increasing importance of the other
two pathways for higher alkyl groups [Atkinson et al., 1995].

1.2 Chemistry of the Nitrate Radical


During nighttime the oxidation of VOCs is dominated by reactions with nitrate radicals and ozonolysis [Paulson
and Orlando, 1996; Paulson et al., 1999] forming peroxy radicals as explained above for the OH reactions.
Daytime NO3 levels are low (some 0.1 ppt, [Geyer et al., 2000a]). However, NO3 is proposed to play a major
role in the oxidation of several hydrocarbons like phenolic aromatic compounds even during daytime.

NO, NO2 , NO3 RO2


HO2

O3
O3
NO NO3 VOCs:
NO2
esp.
h
h terpenes
isoprene
alkene
DMS

N2O5

H2O
emission vp./liq.

aerosols
NO3-

HNO3

Figure 3 Overview of the tropospheric reaction scheme of the nitrate radical.


The chemistry of the nitrate radical in the atmosphere has been explained in detail by different authors [e.g. Platt
et al., 1981; Wayne et al., 1991; Heintz et al., 1996]. In the following the discussion is restricted to processes,
which are expected to play a role in the nighttime boundary layer. Figure 3 presents the todays view of the NO3
reaction scheme of the troposphere. Rate constants of the following reactions are summarized in Table 4. With
respect to the correlation study in section 1.3.2 (f(NO3) vs. T) the temperature dependency of the various parts of
NO3 chemistry is discussed in this section.
Table 4 Kinetic data of the non-organic reactions involved in tropospheric NO3 chemistry.
The rate constant tabulation for bimolecular reactions is given in Arrhenius form: k(T) = A
exp(B/T). References:
a: DeMore et al., 1997; b: Mentel et al., 1996; c: Dimitroulopoulou and Marsh, 1997.

Nr. Reaction A in 10-13 B k(288 K) Ref.


[cm3s-1] [K-1] [cm3s-1]
25 NO2 + O3 NO3 + O2 1.2 -2450 150 2.4 x 10-17 a

29 NO3 + NO2 NO + NO2 + O2 0.45 -1260 5.7 x 10-16 a

30 NO3 + NO3 NO2 + NO2 + O2 8.5 -2450 500 1.7 x 10-16 a

31 NO3 + M NO + O2 + M 1.4 x 10-4 cm3 b

(293 K)

32 NO3 + NO 2 NO2 150 170 100 2.7 x 10-11 a

43 NO3 + NO2 + M N2O5 + M 1.3 x 10-12 a

N2O5 + M NO3 + NO2 + M 1.3 x 10-2 cm3 a

46 N2O5 + H2O 2 HNO3 1.2 - 3.6 -14570 1.3 - 3.8 x 10-22 b, c

x 1013

1.2.1 Production of NO3


The by far dominating source of nitrate radicals in the planetary boundary layer is the reaction
of NO2 with ozone,

NO2 + O3 NO3 + O2 ( 25)


Thus, the production rate of NO3 can easily be determined from known concentrations of
ozone and NO2:

P(NO3) = [NO2] [O3] k25(T) ( 26)


Assuming a local steady state for the nitrate radical, which is, as typical NO3 lifetimes are of the order of 100 s
[e.g. Heintz et al., 1996; Geyer et al., 2000a], usually established in few minutes, the steady state degradation
frequency f(NO3) can be calculated from the measured concentration of NO3 and its production rate P(NO3):

d
[ NO 3 ] = P ( NO 3 ) [ NO 3 ] f ( NO 3 ) = 0 ( 27)
dt

[ NO 2 ] [O 3 ] k 24 1
f ( NO 3 ) = = ( 28)
[ NO 3 ] ( NO 3 )

The inverse of the degradation frequency can be associated with the 1/e-lifetime of the nitrate radical.
1.2.2 Photolysis of NO3
During the day the lifetime of NO3 is limited due to the rapid photolysis back to NO2 or NO at wavelengths <
640 nm with NO2 + O being the favorite path (~ 90 %) [Orlando et al., 1993; Magnotta and Johnston, 1980].
The photolysis frequency J(NO3) for solar zenith angles below 70 is of the order of 0.2 s-1.

1.2.3 Non-photochemical NO3 Loss Mechanism


On the one hand, NO3 can react directly with NO and several VOCs or get lost on aerosol surfaces or by dry
deposition. Another route is its indirect depletion via sinks of N2O5, which is formed by the NO3 - NO2
combination. The loss of NO3 due to reactions with NO2 (29), its self reaction (30), and its thermal decay (31)
are negligible (cf. Table 4 for these reactions).

1.2.3.1 Reaction of NO3 with NO


The gas phase reaction of NO3 with NO represents a rapid loss mechanism near NO sources resulting in
degradation frequencies for NO3 of 0.1 1 s-1 (corresponding lifetimes of 10 - 1 s) at NO levels of 0.13 1.3 ppb
(cf. Figure 4).

NO3 + NO NO2 + NO2 ( 32)


The temperature dependency of this reaction is small. The rate constant k32 decreases with temperature and is 5
% lower at 297 K compared to 273 K (Figure 8). At night, due to missing photolysis of NO2 and the rapid
reaction of NO with ozone (reaction 11) with typical lifetimes of NO of the order of 1 minute (288 K, 40 ppb
ozone), this loss mechanism can be neglected away from NO sources. Nighttime emission of NO usually is
restricted to urban environments. In the following anthropogenic NO emission is assumed to be not correlated
with ambient temperature. In some places NO can also be emitted from the ground [e.g. Sanhueza et al., 1990;
Slemr and Seiler, 1991; Wildt et al., 1997]. Soil organisms, in particular bacteria, algae, fungi and anthropods,
are known to produce NO in the upper few centimeters of soils [e.g. Remde et al., 1993; Hutchinson et al.,
1995]. Both nitrification and de-nitrification activities of microbes in the soil can result in NO production and
release to the atmosphere. The temperature dependence of biogenic NO emission is discussed contrarily in
literature. While several authors like Remde et al. [1993] and Slemr and Seiler [1991] did not find a temperature
dependency of NO emission from soils, a significant diurnal variation correlated with soil temperature was
reported in other publications [e.g. Slemr and Seiler, 1984; Williams et al., 1992]. Nevertheless the observed
dependencies on ambient air temperature are weak compared to that of other NO3 sinks like the reaction with
monoterpene.
Figure 4 Lifetime of NO3 in dependency of the NO concentration at 288 K. In addition the
lifetime of NO3 for photolysis is included in this plot.

NO3 + NO
100
J(NO3) clear sky
NO [s]
3

10

1
0.01 0.1 1

NO [ppb]
1.2.3.2 Reactions of NO3 with VOCs

Reactions with continental VOCs


In the continental boundary layer NO3 can rapidly react with several organic compounds, in particular with
monoterpenes and isoprene [e.g. Atkinson, 1997]. In Europe large quantities of both species are emitted by
vegetation. Estimates of the European emissions of isoprene and monoterpenes range from 3.7 up to 6.1 million
tons (Mt) per year compared to approximately 20 Mt yr-1 of total VOC emissions from anthropogenic sources
[Guenther et al., 1995; Simpson et al., 1995]. The reactions of NO3 with terpenes or isoprene constitute a major
sink of NO3 in rural environments with monoterpenes are usually the most important reaction partner near
forests [Glz et al., 2000; Geyer et al., 2000a]. The initial step of these reactions is the addition of NO3 to a
double bond forming a radical adduct intermediate.

>C=C< + NO3 >C(ONO2)C< ( 33)


The resulting nitratoalkyl radical rapidly reacts with oxygen forming a nitratoalkylperoxy radical, which then can
react with NO forming a nitratoalkoxy radical or dinitrate. In the absence of NO molecules (mainly during night
time) the peroxy radical can react with other peroxy radicals to form nitratoperoxides, nitratocarbonyls and
nitratoalcohols. Thus a large number of products can be formed from reactions of NO3 with monoterpenes or
isoprene.
Taking -pinene as an example, which is probably one of the most abundant terpenes in the atmosphere as it
dominates emissions of a number of trees such as Norway spruce and Scots pine [e.g. Janson, 1993], pinon
aldehyde has been identified as major product (Figure 5). Molar yields have been reported to be close to 0.6
[Hakola et al., 1994; Wngberg et al., 1997a].

NO3 + -pinene ... pinon aldehyde, other products ( 34)


For a more detailed discussion of the atmospheric oxidizing scheme of monoterpenes please refer to a recent
review by Calogirou et al. [1999].
The temperature dependence of reaction 34 is weak with a decrease of 13 % from 273 K to 297 K (Figure 8).
The temperature dependence of the reaction with isoprene was found to be similar to that of the NO3--pinene
reaction (Table 4).
Controlling factors of boundary layer terpene concentrations are mainly (1) the emission rate of terpenes from
vegetation, (2) the height of the planetary boundary layer as well as the strength of exchange between the PBL
and the free troposphere, and (3) the oxidation rate of terpenes, which is generally correlated to the concentration
of nitrate radicals during nighttime (Table 2).
The emission flux of monoterpenes and isoprene (1) can be described following Guenther et al. [1996]:

Flux (g m -2 yr -1 ) = D dt ( 35)

where is the average emission potential for a particular species, D is the foliar biomass density, and is a
unitless correction factor representing the effect of temperature and solar radiation on emission. For isoprene this
correction factor can be described by the product of a light dependent factor CL and a temperature factor CT
[Guenther et al., 1991; 1993]. The light factor CL is given by:

c L1 L
C LIiso = ( 36)
1 + 2 L2
where and cL1 are empirical constants and L is the PAR flux (photosynthetically active radiation). Following
equation 36 no isoprene should be emitted during night, thus equation 35 can not be used to calculate nighttime
emission and concentrations of isoprene. In contrast to isoprene the emission flux of monoterpenes does not
depend on light but only on ambient temperature. The environmental correction factors from most plants are
parameterized using the following equation [Guenther et al., 1993]:

monoterpenes = e (T T
S )
( 37)
where = 0.09 K-1 is an empirical factor based on the analysis of a large number of measurements published.
The maximum of monoterpene emission was observed at temperatures arrived 40 C. Because of this strong
temperature dependency the flux of monoterpenes increases by a factor of 8.6 when the temperature rises from
273 K to 297 K.
Figure 5 Chemical scheme of the reaction of a-pinene and nitrate radicals (adapted from
O
2 O
ONO2 ONO2 O O
1 3
+ NO3 + NO2 + NO 2
(2) (3) (8a)
Pinane epoxide Pinonaldehyde

O2
(4)

O 2NO2 O
O2
ONO2 NO 2 ONO2 ONO2
+ CH 3
(8b)
(5/-5)

O2 O O O2 ONO2 OH ONO2
ONO2 ONO2 ONO2 ONO2 O2 ONO2 O
self reaction + + O2 + + + O2
(6) (9)
2-hydroxy-Pinan- 3-oxo-Pinan-
3-nitrate 2-nitrate

O2 O O2 OH
ONO2 ONO2 ONO2 ONO2
NO 3
+ NO 2 + O2 + CH 3O2 + HCHO + O2
(7) (10)
2-hydroxy-Pinan-
3-nitrate

Wngberg et al. [1997a].


No correlation to temperature is assumed for the PBL height and NO3 concentration (compare to long term
observation of NO3 in the PBL by Geyer et al. [2000b]). Thus terpene concentrations are mainly depending on
their flux from vegetation.

Reactions with marine VOCs


Dimethylsulphide (DMS) is known to be probably the most important VOC in marine air masses. It is produced
in large quantities by biological processes from phytoplankton in surface water [Charlson et al., 1987; Andreae
et al., 1994; Cainey et al., 1996] and it is estimated that it accounts for ~ 60 % of the total natural sulphur
emission to atmosphere [Andreae and Raemdonck, 1983; Bates et al., 1992; Berresheim et al., 1995]. In the
atmosphere DMS is oxidized by NO3, OH, and possibly halogen oxide radicals [Toumi, 1994; Langer et al.,
1996; Platt and Le Bras, 1997]. The reaction of DMS and NO3,

NO3 + CH3SCH3 HNO3 + CH3SCH2 ( 38)


appears to proceed exclusively by hydrogen abstraction producing nitrous acid. In the laboratory SO2, methane
sulphonic acid (MSA), and HNO3 have been identified as final products following reaction 38 [Le Bras et al.,
1993]. The rate constants of DMS reactions are given in Table 1. The lifetime of DMS mainly depends on the
concentration of NO3 and can be large (of the order of many hours) for low NO3 levels. The temperature
dependency of the rate constant k38 is similar to that of k34, decreasing by 13 % from 273 K to 297 K (Figure 8).
Dimethylsulphide is produced in the sea surface water and emitted into the atmosphere by sea-air exchange. The
emission flux of DMS is controlled by its concentration in the seawater cw and the transfer velocity Kw [Tarrason
et al., 1995; Gabric et al., 1996]. Measurements of DMS in sea surface water indicate a strong seasonal variation
with maximum concentrations during spring/summer [Bates et al., 1987; Turner et al., 1988; Leck et al., 1990;
Nagao et al., 1999]. Differences between the spring and winter season seem to increase at higher latitudes and
can span over to two orders of magnitude. This seasonal variation can be explained by a phytoplankton growth
rate affected by light, temperature and nutrient availability. On a long term basis this variation constitutes an
exponential dependency between DMS flux and air temperature. However the slope of this correlation largely
depends on local conditions and therefore can not be calculated on a larger geographical scale. Nighttime DMS
concentration also depends on the height of the marine boundary layer and the concentration of NO3, both
assumed not to depend on ambient temperature (cf. long term observation of NO3 in the marine boundary layer
by Heintz et al. [1996]).
Of importance for NO3 depletion is also the emission of isoprene by marine biota. Laboratory studies have
shown the production of isoprene by phytoplankton cultures [Moore et al., 1994; Milne et al., 1995]. Recent
measurements of isoprene in the Indian Ocean yielded mixing ratios exceeding 100 ppt [Yokouchi et al., 1999]
which lead to NO3 degradation frequencies of the order of some 10-3 s-1. Isoprene emission rates from
phytoplankton are proposed to be correlated with that of DMS, however observations cover only limited areas.

1.2.3.3 Reactions of NO3 with Aerosols or on the Ground


The loss of nitrate radicals on aerosol surfaces is proposed to be of minor importance [Thomas et al., 1998].
Hydrolysis of NO3 is believed to be slow, however in solutions it might react with anions like Cl-. The
degradation frequency of this heterogeneous loss mechanism is determined by the uptake coefficient , which
largely depends on the chemical composition of the aerosols and on temperature (Table 5). The value of (NO3)
seems to be very low (few times 10-3 [e.g. Thomas et al., 1998, DeMore et al. 1997 and references therein]). For
small values of (< ~ 10 %) and particles below ~ 1 m (most of the aerosol surface is contributed by sub-m
particles except for foggy conditions) the degradation frequency due to reactions with aerosols can be estimated
using a simplified form of the expression given by Fuchs and Sutugin [1971]:

fN2O5-Aero. = 0.25 v S ( 39)


with the total aerosol surface density S, the temperature dependent (proportional to the square root of the
temperature) mean molecular velocity v and the uptake coefficient .
Depending on meteorology NO3 can also be removed by dry deposition on the ground. The associated
degradation frequencies depend on the height of the mixing layer and can be estimated from the wind speed
[Haugen, 1973]:
1
f dep . = ( 40)
h [RT + R L + RC ]

with the height h of the mixing layer, and the turbulent and laminar transport resistance RT and RL, respectively.
The chemical resistance RC describes the rate of reactions on the surface, which depends on the physical and
chemical properties of the surface. Up to now, no experimental observations of the surface resistance of NO3
have been published in literature. Assuming RC = 0, only upper limits of the dry deposition are calculated in the
following. The turbulent transport resistance can be estimated by assuming neutral stratification in the mixing
layer:

h
ln
z1
RT = ( 41)
u

with = 0.4, the von-Karman constant, z1 the height of the laminar boundary layer, and the friction velocity u*,
which can be calculated [Haugen, 1973] from the wind speed v(z) and the surface roughness z0 estimated from
the size of the macroscopic structures like vegetation around the station. The transport resistance in the laminar
boundary layer can be estimated by expression 42 with the molecular diffusion constant Dg-1 = 0.11 cms-1 for air.

ln( u z o D g1 )
RL = ( 42)
u

For stable or unstable stratification u* must be corrected accordingly. Assuming typical values of u* = 15 cm s-1,
z1 = 0.1 cm, z0 = 10 cm, and h = 100 m, values of RT = 1.9 s cm-1 and RL = 1.1 s cm-1 (total deposition velocity vd
= 0.33 cm s-1) are obtained resulting in a deposition frequency of 3 x 10-5 s-1 (about 10 hours lifetime).

1.2.3.4 Indirect Sinks of Nitrate Radicals


Another major scavenging process besides direct NO3 sinks is based on the combination of NO3 and NO2 to
yield N2O5 (Figure 3):
NO3 + NO2 + M N2O5 + M +( 43)
Due to the thermal decay of N2O5 (reaction -43) a temperature dependent equilibrium between the three species
is established favoring N2O5 at typical boundary layer temperatures and moderate NO2-levels of more than ~1
ppb:
[N2O5] = Keq(43) (T) [NO2] [NO3]. ( 44)
The strongly temperature dependent equilibrium constant is Keq(43) (T) = 5.5 x 10-27 x exp((10724 75) K / T)
cm3, Keq(43) (288 K) = 8.2 x 10-11 cm3 [Wngberg et al., 1997b]. Due to 44 loss processes for N2O5 act indirectly
as sinks of NO3. The corresponding degradation frequencies for NO3, findir., can be calculated using equation 45:
findir = Keq(43) (T) [NO2] fN2O5 ( 45)
The value of Keq(43) exponentially decreases with temperature (Figure 8) and is a factor of 24 higher at a
temperature of 273 K compared to 297 K. Therefore indirect sinks are most effective during the winter months.

Homogeneous Hydrolysis of N2O5


A possible sink of N2O5 is its homogeneous reaction with water vapor producing HNO3

N2O5 + H2O HNO3 + HNO3 ( 46)


A recent study by Mentel et al. [1996] observed components of first order (k = 2.6 0.1 x 10-22 cm3s-1) and
second order (k = 1.9 0.05 x 10-39 cm6s-1) in H2O at 293 K yielding an effective first order (in H2O) range of
the combined rate coefficients of (3 to 9) x 10-22 cm3s-1 depending on humidity (0.08 % < H2O / air < 1.3 %).
Wahner et al. [1998a] showed that the second order process in H2O can most likely be attributed to gas phase
reactions of N2O5, either termolecular or with water dimers. The temperature dependence of reaction 46 was
derived from field data by Dimitroulopoulou and Marsh [1997] showing a strong increase of k46 with
temperature (factor 74 between 273 K and 297 K). In the following analysis this dependency was used to
calculate the value of Mentel et al. [1996] for different temperatures (k46 from Table 4).

Reactions of N2O5 on Aerosol Surfaces


Hydrolysis of N2O5 is well known to be catalyzed by surfaces. Thus reaction 46 occurs rapidly on the aqueous
layer found on many surfaces like tropospheric aerosols. There have been several studies of the reaction
probability on sulfuric acid or sulfate aerosols yielding uptake coefficients (N2O5) in the range of 0.02 - 0.14
over H2SO4 concentrations from 1 - 84 % (molar ratio) and boundary layer temperatures [DeMore et al., 1997
and references therein]. Hu and Abbatt [1997] observed an decrease from 0.05 to 0.02 as the relative humidity
(RH) falls for both sulfuric acid and ammonium sulfate aerosols. However, Wahner et al. [1998b] have reported
smaller values on NaNO3 particles of 0.0032 at 62 % RH, which they attributed to an increasing importance of
the reverse reaction of NO2+ (from the hydrolysis of N2O5) with NO3- regenerating N2O5. Uptake coefficients on
pure liquid water seem to be in the same range as for sulfuric acid - water mixtures (0.01 - 0.06 over a
temperature range from 262 to 293 K [e.g. Van Doren et al., 1990; Kirchner et al., 1990; George et al., 1994].
Similar reactions of N2O5 also occur on dry soot [Kamm et al., 2000] with cationic or anionic water clusters
[Wincel et al., 1994; 1995]. Besides relative humidity and chemical composition uptake coefficients also depend
on ambient temperature generally showing a slow decrease of with temperature for typical ground level
conditions. Table 5 summarizes recent studies of the uptake coefficient of N2O5 on different surfaces.
Table 5 Recent studies of the uptake coefficient of N2O5 and NO3 on aerosol surfaces under
tropospheric conditions.

Surface T [K] in 10-2 Reference


N2O5
H2O 277 1.3 0.8 [George et al., 1994]
271 6.1 0.4 [Van Doren et al., 1990]
282 4 0.5
NH4HSO4 aerosol 274 8.5 1.9 [Mozurkewich and
293 4.9 0.7 Calvert, 1988]

297 (rH = 93.5 %) 1.7 0.2 [Hu and Abbatt, 1997]


297 (rH = 83 %) 2.3 0.4
297 (rH = 68.5 %) 5.3 0.6
H2SO4 aerosol 1 10% 274 13.9 0.9 [Mozurkewich and
293 10 1 Calvert, 1988]
H2SO4 64.0 81.4% 273 10.3 0.6 [Fried et al., 1994]
78.7 83.6% 293 62
H2SO4 73% 283 5.8 0.6 [Van Doren et al., 1991]
H2SO4 aerosols 297 (rH = 90 %) 2.3 0.4 [Hu and Abbatt, 1997]
297 (rH = 58.5 %) 3.8 1.2
NaCl 292 3 [Zetsch and Behnke,
1992]
NaNO3 293 (rH = 62 %) 0.32 [Wahner et al., 1998b]
soot aerosol 296 ~ 3 x 10-3 [Kamm et al., 2000]
NO3
H2O 273 0.044 [Rudich et al., 1995]
NaCl 0.02 0.5 M 273 0.011- 0.047 [Rudich et al., 1995]
NaCl 0.1 M 293 0.2 [Thomas et al., 1998]
NaNO2 0.0005 0.0038 M 273 0.017 0.046 [Rudich et al., 1995]

Dry Deposition of N2O5


Finally N2O5 can be removed by dry deposition to the ground. The corresponding degradation frequencies can be
calculated as described above for NO3.

1.3 Correlation Studies as Indicator for the NO3 Removal Path


With respect to the importance of NO3 a number of studies were carried out in the last few years focusing on
different patterns of its chemistry. Following its first detection in the troposphere by Platt et al. [1980] and
Noxon et al. [1980] measurements of the NO3 concentration were performed under both continental and marine
conditions as well as in urban environments. The observations suggest that in the clean nighttime planetary
boundary layer NO3 usually is only removed by two mechanism, (1) its reaction with organic species and (2)
indirectly via sinks of N2O5, which constitute an equilibrium with NO3. The splitting of these two processes
defines the contribution of NO3 to the oxidation capacity (1) and to the removal of NOx (2). In knowledge of this
sink splitting it is possible to calculate both contributions easily from the time series of NO3 and its precursors.
Measurements in forested areas found indirect evidence by modeling studies that NO3 is largely depleted by
reactions with monoterpenes, in particular -pinene, emitted in large quantities from the trees [Mihelcic et al.,
1993; Glz et al., 2000]. On the other hand long term measurements on the islands Rgen and Helgoland gave
strong evidence for dominant indirect removal [Heintz et al., 1996; Martinez-Harder, 1998]. Recent model
studies of the nitrate radical based on observation at the Weyborne Atmospheric Observatory located on the
western coast of England found that during winter, continental air masses prevailed and the major loss of NO3
occurred indirectly through reaction of N2O5. In the cleaner air masses of marine origin during summer, DMS
(dimethylsulphide) provided the major loss for NO3 [Allan et al., 1999]. In polluted urban air masses the
dominant scavenging process of NO3 was found to be its reaction with NO [Platt and Janssen, 1995] yielded
indirectly by an anti-correlation between the observed NO3 and NO concentrations.
In all cases analysis was rather expendable and quantitative information on the NO3 sink splitting was difficult to
obtain. These results were either obtained by direct measurements of a large number of important trace gases
(VOCs, NO3 and its precursors, low level NO and the aerosol surface and chemical properties of the particles are
needed for direct calculation methods) or by analyzing the correlation between NO3 and its production rate, and
the NO3 life time and NO2, respectively. This correlation study is explained in the following section. However,
this method is only evident under the presumption that the degradation of NO3 is not linked to its production rate
and quantitative results can not be obtained. Therefore a new correlation study which bases on the temperature
dependency of the NO3 degradation rate, was established in this work. The study showed that sink distribution
varies greatly with ambient temperature. This fact was not considered in former correlation studies.

1.3.1 Correlation Studies with respect to NO2


In order to estimate whether NO3 was depleted rather directly (e.g. by reaction with VOCs) or indirectly via
N2O5, the correlation between the lifetime of NO3 and its precursor NO2 can be studied. Considering a simple
reaction scheme (Figure 6) with the NO3 production reaction 25, the thermal equilibrium between NO3 and N2O5
(43), and two different sink mechanism of NO3, (a) direct and (b) indirect loss with corresponding NO3-
degradation rates fdir. and findir. (defined as the inverse of the NO3-lifetimes from direct reactions and loss of N2O5
following equation 44), the NO3 and N2O5 concentrations are given by the following equations:
k25 [NO2] [O3] + k-43 [N2O5] = fdir. [NO3] + k+43[NO2] [NO3] ( 47)

k+43 [NO2] [NO3] = findir. [N2O5] + k-43[N2O5] ( 48)

+O3 k+43
NO2 NO3 NO2 N2O5
k
k-43
fdir. findir.

loss of NO3

Figure 6 This simple reaction scheme of NO3 can be used to study the correlation between
NO3 and NO2 under the consumption of dominant direct and indirect sinks, respectively.
Equation 48 indicates that the effective steady state constant,
KSS = k+43 / (k-43 + findir.) < Keq(43) ( 49)
slightly decreases in the presence of N2O5 sinks. However, findir. is usually negligible compared to k-43 (taking
Geyer et al. [2000a] as an example, findir. was found to average at 1 x 10-3 s-1 compared to k-43 = 1.6 x 10-2 s-1 at
288 K). Both equations 47, 48 can easily be combined yielding
f indir .
[ NO 3 ] = [ NO 2 ][O 3 ]k 24 ( f dir . + [ NO 2 ]k + 42 ) 1
k 42 + f indir .

P(NO3) (fdir. + [NO2] Keq(43) findir.)-1 ( 50)


For conditions, where the nitrate radical's loss proceeds only via direct sinks (findir. = 0), equation 50 reduces to:
[NO3] = P(NO3) fdir.-1 ( 51)
From expression 51 a direct correlation between NO3 and its production rate is predicted with the slope being the
mean lifetime of NO3 at this location. Since the NO3 lifetime varies from some seconds to values of the order of
hours, it is apparent that the scattering of the points (NO3 vs. P(NO3)) is large.
In the case of negligible direct sinks of the nitrate radical (fdir. = 0), an indirect dependency of the concentrations
of NO3 and NO2 is obtained from equation 50 yielding an inverse correlation of NO2 and the lifetime of NO3:
[NO3] = P(NO3) / ([NO2] Keq(43) findir.) ( 52)

(NO3)-1 = [NO2] Keq(43) findir. ( 53)


However, as in the case of direct sinks, the scattering of the correlated points is large, because both Keq(43) and
the degradation rate from indirect sinks greatly vary with time and atmospheric conditions. Therefore these
correlation studies can only be used for large data sets such as long term measurements averaging over different
meteorological and chemical conditions of the atmosphere.

1.3.2 The Temperature Dependence of the NO3 Degradation Rate


As already explained above several temperature dependent quantities are involved in the degradation of NO3.
From correlation studies of the NO3 degradation rate calculated from equation 26 with ambient temperature, it is
possible to estimate the sink distribution of the nitrate radical. Note that the distribution of the sinks varies with
temperature and it is possible to extrapolate this change from the correlation study. This correlation study was
developed and applied in the frame of this work.
In the following the sink distribution is given for a temperature of 288 K and temperature dependent functions
are normalized to this temperature. However, a number of data points at different temperatures is needed (e.g. a
long term observation) to get a high statistical quality.
Three degradation pathways can be assumed for the nitrate radical during night, (1) its reaction with NO, (2) the
oxidation of VOCs, and (3) the indirect loss by homogeneous or heterogeneous hydrolysis of N2O5 (Figure 7).
The temperature dependencies of important quantities involved in the NO3 removal are shown in Figure 8.
The reaction of NO3 with NO should only be of importance in urban environments in the neighborhood of NO
emissions and can generally be neglected in rural areas (see section 1.2.3.1). As explained above a dominant
removal of NO3 by reaction 32 results in a degradation rate which does not depend on temperature (Figure 8):
fNO3NO(T) = constant ( 54)
For case (2) it is necessary to distinguish between the continental and marine boundary layer. Under continental
conditions monoterpenes are the most important organic species reacting with nitrate radicals. As explained
above the temperature dependency of their reaction with NO3 is dominated by the temperature dependent
emission rate of monoterpenes from trees (Figure 8):
fNO3MT(T) ~ exp(0.09 T/K-1) ( 55)
(2)
m onoterpenes,
Under marine conditions NO3 is generally reduced by the reaction with DMS. It is not possible to publish a
general temperature dependency of DMS (1 ) NO
(see isoprene
section 1.2.3.2). It remains necessary to determine this
DMS
dependency for the observation location of NO3 from long term observations of DMS or modeling studies.
However, on a long term basis,NO
DMS 2 concentration NO
generally
3 increases with RO2
temperature.
O3 HO2

N2O5

(3) H2O
vapor/aerosols

HNO3
Figure 7 Simplified reaction scheme of NO3 in the planetary boundary layer. Heterogeneous
reactions of NO3 as well as dry deposition were neglected as they are of minor importance in
the polluted boundary layer.
One can conclude that a removal of NO3 by reactions with VOCs in both the continental and marine boundary
layer results in an increase of the degradation rate with temperature.
The indirect loss of NO3 is proposed to be determined by the temperature dependency of the equilibrium
constant Keq(43), which decreases when temperature increases. Therefore a dominant removal of NO3 by indirect
loss results in a decrease of the NO3 degradation rate when temperature increases (Figure 8):
fNO3indir(T) ~ exp(10724 K / T) ( 56)
The temperature dependency of the homogenous reaction of N2O5 with water vapor (Figure 8) is not well
known. As this depletion pathway does not constitute a major sink for NO3 it can usually be neglected in
analysis. It is also possible to calculate the degradation rate from this reaction from standard meteorological data
and to subtract the result from the observed total degradation rate.
With respect to the clean continental boundary layer only the removal pathways (2) with monoterpenes and (3)
are considered in the following analysis. The total NO3 degradation rate calculated from equation 26 can then be
written as linear addition of the temperature functions of both multiplied by a factor representing (a) the
temperature independent part of each degradation rate and (b) the ratio of contribution of the respective sink.
Factor A was chosen for the removal of NO3 by the reaction with monoterpenes, and factor B represents the
indirect removal by N2O5 loss on aerosol surfaces.
Figure 8 Relative 10

temperature dependency of
rate constants and
emission flux of NO3
reaction partners as known
relative in-/decrease (set point = 288 K)

from literature. All


functions were calibrated
to their value at 288 K.

Keq
kNO + NO
3

kNO + -pinene
fNO3(T) = A exp(0.09 T) + 0.1 3

t erpene emission
B exp(10724 / T) kN O + H O
2 5 2

( 57) kNO + DMS


3

This temperature dependence of


270 275 280 285 290 295 300
the degradation rate was
simulated for different sink Temperature
distributions, each of them being
calculated for 288 K. Since the absolute value of fNO3 is of no importance in this correlation study, it was set to 1
at T = 288 K.
fNO3(288 K) = A exp(0.09 288) + B exp(10724 / 288) := 1 ( 58)
Taking a contribution of 50 % of each pathway as an example, factors A and B were calculated according to:
A exp(0.09 288) = B exp(10724 / 288) = 0.5 ( 59)
Following equation 57 fNO3 was then calculated for different temperatures typical for boundary layer
temperatures. Figure 9 shows the simulated functions of fNO3 (T) for different contributions of the VOCs sink (@
288 K) in logarithmic presentation yielding the effective factor in the exponential function (to be multiplied by ln

8
Contribution of
terpene at 288 K
10 % 20 %
30 % 40 %
50 % 60 %
(value at 288 K set to 1)

70 % 80 %
90 %
f(NO3) [s ]
-1

0.3
270 275 280 285 290 295 300
Temperature [K]
10). The corresponding contribution at 288 K of the indirect path is 100 % minus the contribution of the VOC
pathway.
Figure 9 Temperature dependency of the NO3 degradation frequency f(NO3) as simulated for
the rural continental boundary layer for different contributions (at 288 K) of reactions with
terpene and N2O5 aerosol reactions, respectively. All frequencies were normalized to a value
of one at 288 K.
As already explained, sink distribution varies with temperature. The influence of monoterpenes increases at
higher temperature, whereas the contribution of indirect sinks decreases (Figure 10).
As apparent from Figure 9 fNO3(T) can be appointed by a linear function close to 288 K. A linear regression was
performed for each simulated degradation function yielding slopes C from 0.05 to 0.039 K-1 (Figure 11 ) The
last one yielded for a 100 % contribution of VOC reactions represents the factor 0.09 K-1 (0.039 x ln 10 = 0.09)
from the monoterpene emission. The exponential factors C is linearly correlation with the contribution of
terpenes and N2O5 aerosol reactions, respectively. Using this dependency it is possible to calculate the sink
distribution of NO3 from any observed variation of fNO3(T) at a temperature of 288 K:
C 0.055
Contribution of monoterpenes = ( 60)
9.3 x10 4
The sink distribution at temperatures different from 288 K can be calculated from Figure 10.
Note that factor C is zero for a contribution of monoterpene reactions of about 59 %. In that
case it is not possible to exclude a dominant removal by NO, which would also result in a
factor C = 0.
1.0

Contribution at 288 K
10 %
Contribution of terpene reactions 20 %
0.8 30 %
40 %
50 %
to the total NO3 removal
60 %
70 %
0.6 80 %
90 %

0.4

0.2

0.0
270 275 280 285 290 295 300
Temperature [K]

Figure 10 Variation of the contribution of NO3 terpene reactions to the total NO3 removal
with temperature calculated for the simulated sink distributions of Figure 9.
For marine conditions analysis of the temperature dependency of fNO3 is similar, however a quantitative result of
the contribution can not be achieved until data on the temperature dependency of ambient DMS concentration on
temperature is determined for that location.
Figure 11 Close to a temperature of 288 K the simulated temperature dependency of the
Factor C in the exponential function of fNO (T) [K ]
-1

0.04

0.03
3

0.02

0.01

0.00

-0.01

-0.02

-0.03
Linear regression Y = A + B * X

-0.04 A= -0.055 +/- 2E-4


B= 9.3E-4 +/- 2E-6
2
-0.05 R = 0.99

0.0 0.2 0.4 0.6 0.8 1.0


Contribution of terpene reactions to the total NO3 removal
degradation frequencies of NO3 can be approximated by an exponential function fNO3(T) ~
exp(C x T).