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RADICAL CHEMISTRY
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 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].
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).
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
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:
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.
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.
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):
O3
O3
NO NO3 VOCs:
NO2
esp.
h
h terpenes
isoprene
alkene
DMS
N2O5
H2O
emission vp./liq.
aerosols
NO3-
HNO3
(293 K)
x 1013
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.
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
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
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).
+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 .
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)
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
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