The Science of the Total Environment 189/190 (1996) 391-399

Sources of nitrogen dioxide in winter smog episodes

Roy M. Harrison*, Ji Ping Shi

Institute of Public and Environmental Health, School of Chemistry, The University of Birmingham, Edgbaston,
Birmingham B15 2TT, UK

Abstract

Highly elevatedconcentrationsof nitrogen dioxide have beenobservedin urban air in winter episodesin the UK,
and cannot readily be explainedby current knowledgeof emissions and atmosphericchemistry, sinceformation from
NO is thought to be limited by the availability of atmosphericozone. Measurementsof NOJNO, ratios in a road
tunnel, and in a wind tunnel into which exhaust gasesare introduced show ratios of lessthan loo/, and primary
emissionsand/or rapid oxidation of exhaust gas plumescannot wholly explain elevated concentrationsof NOz in
urban air. Studiesin a laboratory reactor reveal that the rate of the NO + O2reaction can be enhancedin the presence
of other vehicleexhaustconstituentsto an extent which may account for the episodicpeak concentrationsof nitrogen
dioxide.

Keywords: Atmospheric chemistry; Nitrogen dioxide; Smog

1. Introduction trogen dioxide have remained constant at most

Nitrogen dioxide is one of the most important
pollutants in urban air. At elevated concentra-
tions it is directly toxic to humans [l], and in the
UK ambient concentrations widely exceed the EC
guide value of 26 ppb (50 percentile), and at some
sites approach the limit value of 105 ppb ex-
pressed as a 98 percentile of hourly average con-
centrations over 1 year. It is of particular concern
that whilst annual average concentrations of ni-
* Corr$sponding author. Tel.: + 44 121 4143494;
121 4143709.
central urban sites, peak and 98 percentile concen-
trations have tended to increase.
There are few sourcesof primary nitrogen diox-
ide and the major part of NO, in urban air is
formed from oxidation of nitric oxide within the
atmosphere. In most urban areas motor traffic is
the predominant source of nitric oxide emissions.
During summer months, elevated concentrations
of NO, can arise due to atmospheric photochem-
istry producing peroxy radicals which accelerate
the conversion of NO to NO,. However, the
highest concentrations of NO, in UK urban areas
fax: + 44 typically occur in the winter. Most notably, in the
December 1991 air pollution episode in London,

0048-9697/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved

PII SOO48-9697(96)05236-9
392 R.M. Harrison, J.P. Shi / The Science of the Total Environment 189/190 (1996) 391-399

400

i
1000 1500 2000
NOx (wb)

Fig. 1. Hourly NO2 and NO, concentrations at a busy roadside (Cromwell Road) in London in January, February, November and
December 1991.

the highest concentration of NO, ever recorded at
a UK site of 423 ppb was measured in central
London. The pathways for NO, formation from
NO, are complex, as exemplified by Fig. 1 which
shows the relationship of hourly mean NO, to
hourly NO, for the months January, February,
November and December 1991 at a busy roadside
site in central London. The Figure is divided into
three regimes; in the region marked A, concentra-
tions of both NO, and NO, are low and NO,
increases as a relatively constant proportion of
NO,. As NO, exceeds approximately 75 ppb, the
graph enters section B in which there is a plateau
of near constant NOz concentrations with little
change in NO2 as NO, continues to increase.
Both sections A and B may be explained by
oxidation of nitric oxide by ozone. In section A
this reaction is not consuming all ambient ozone,
whilst in section B the process is oxidant limited
and virtually all ozone is destroyed. Section C,
however, which occurs with NO, concentrations
above about 600 ppb shows rapidly increasing
NO, with further increases in NO,. It is this
section of the graph which is associated with
winter pollution episodes. Clearly, additional
chemical reactions are occurring as this stage and
the NO plus O2 reaction begins to play a role.
.However, the analysis of the London December
1991 episode by Bower et al. [2] showed that
inclusion of this reaction could not explain the
rapidity of rise of NO, during episodic conditions.
This paper presents results of an investigation
of NO, formation in the high NO, region (Region
C) of Fig. 1. The work has important implica-
tions, as at present the impact of reducing vehicu-
lar NO, emissions upon ambient NO,
concentrations is uncertain.
2. Measurement of the NO,/NO, ratio in road
traffic emissions
NO and NO, concentrations were measured in
a road tunnel (Queensway Tunnel) on 31st Octo-
ber 1992; 26th January and 1lth February 1993.
The Queensway tunnel is located in Birmingham
city centre and has dimensions of approximately 5
m in height and width for each of the two car-
 R.M. Harrison, J.P. Shi / The Science of the Total Environment 189/190 (1996) 391-399
180 i, - --- NO (Moving Average)
/ - NOPlNOX (Moving Average)
160
,oo .:
.$--...-,-o--ll 12
Fig. 2. Measurements of NO and NO, (recorded every 1.5 s, 30 min average) in Queensway Tunnel, Birmingham,
January 1993.
riageways {which are separated by a concrete
dividing wall) and 600 m in length. There are a
total of 18 ventilation sites in the tunnel which are
switched on when the levels of CO in the tunnel
exceed 50 ppm. The flow of traffic through the
tunnel is of the order of 20-45 vehicles/min in
each direction. Diesel vehicles accounted for ap-
proximately 5% of this total at the time of the
measurements. A chemiluminescence analyser
(Environnement AC 30 M) was employed to mea-
sure NO and NO, concentrations in the tunnel.
The precision of measurements was greater than
3% for NO and 5% for NOz. The sampling site
was in the emergency bay near the half-way point
of the tunnel. The inlet of the NO-NO, analyser
was located approximately 0.5 m from the kerb-
side and at about 1.8 m height.
Results of the measurements of NO and NO2
concentrations and NO,/NO, ratios on 26th Jan-
uary 1993 are presented in Fig. 2. The meteoro-
logical conditions were as follows: relative
humidity ranged from 5 1 to 81%, temperature
from 6.8 to 9.4”C and it was raining in the
afternoon. Nitric oxide varied from 1280 to 1780
393
.--.-8.5
n NO2 (Moving Average) “JbI
’ I +,
s/
Traffic Jam
,6
13 14 15 16 17 18
Time
UK on 26th
ppb, nitrogen dioxide from 104 to 175 ppb and
NO,/NO, ratio from 6.3 to 8.1% in the tunnel. It
should be noted that a traffic jam occurred from
17:46 to 18:Ol (shown in Fig. 2). During this
period nitrogen dioxide increased from 121 to 152
ppb and the ratio from 6.8 to 8.1%, while nitric
oxide increased only slightly.
The concentrations of total oxidants (NO, +
03) at a background site in the city kept steady at
a level of approximately 40 ppb during the three
sampling days. Because of high concentrations of
NO in the tunnel and low light intensity, it is
reasonable to assume that the ozone concentra-
tion was zero and about 40 ppb NOz was con-
tributed from background ozone. Compared with
the high NO concentration in the tunnel, back-
ground NO was negligible. Subtracting the NO,
formed from background ozone, the NO,/NO,
ratios would be 3-5.5%, 4-6% and 5-7.5%, re-
spectively on three sampling days. Clearly, these
ratios should be reflective of those in the actual
vehicle emissions.
It appears that idling vehicles give higher NO,/
NO, ratios, as shown in Fig. 2, which is consistent
 R.M. Harrison, J.P. Shi / The Science
ai Distribution ofNOx in the wind tunnel (tunntl velocity 1.O m/q
Distance from orifice (cm)
Fig. 3. Exhaust from a petrol generator in the wind tunnel at a velocity of 1 m/s. (a) NO,v concentrations, (b) NO,/NO,
with the results of Lenner and Lindqvist 131, but
even the maximum ratio during the traffic jam
was only 8.5%.
3. NO2 formation near the tailpipe
In vehicle exhaust gas, the NO, concentration is
a function of driving mode, and is typically lOOO-
4000 ppm during acceleration, lOOC-3000 ppm
during cruising, and 5-50 ppm during decelera-
tion 141. The NO, concentration in exhaust will
typically be below 1200 ppm when driving at a
speed of 50 km h - ’ or less (ref [5] and therein), as
is normal in urban areas. The homogeneous reac-
tion
2N0 + O2--, 2N0,
is normally of little significance in the atmosphere
because the NO concentration is insufficient. It
has been unclear, however, whether NO,? could
form significantly near the tailpipe from reaction
(1). Hov and Larssen [5] set up a simple numerical
model of the combined effect of chemistry and
dilution with eight different dilution functions
which indicated that the dilution rate during the
initial few seconds was extremely important for
NOz formation.
In order to evaluate the extent and significance
of NO, formation in the exhaust plume immedi-
of the Total Environment 189/190 (1996) 391-399
b) Disbibutlon ofNOmOx ratio 1” the wind tunnel (tunnel velocity I .O m/s)
ratios.
ately after emission, experiments have been car-
ried out in a wind tunnel with the dimensions of 3
m length x 0.3 m x 0.3 m section fitted with an
adjustable speed fan. The maximum velocity cre-
ated by the fan was 3.0 m/s which was measured
with a pitot tube and digital micromanometer
(MP Series 4 Autozero). The Reynolds Number
of the wind tunnel is 6.4 x 104, 4.3 x lo4 and
2.1 x lo4 at tunnel velocities of 3 m/s, 2 m/s and
1 m/s, respectively. Three types of nitrogen oxide
sources were used. NO and NO, were measured
simultaneously with a chemiluminescent NO,
analyser (Environnement AC 30 M, range 10
ppm) preceded with a dilution system.
3.1. Emissionfrom a petrol generator
(1)
A petrol generator, model Honda EM 2200X
was employed as an emission source of NO,. The
load was fixed at 400 W by using four 100 W
lights. A flexible metal tube connected to the
generator exhaust was located at the centre of one
end of the wind tunnel. The diameter of the tube
was 2.5 cm, and the emission velocity was 10.6
m/s. Air sampled at the distance of 30, 60, 90 and
120 cm from the emission orifice by using a 0.25
inch diameter steel tube probe which could move
freely across the wind tunnel. Typical results are
shown in Fig. 3.
 R.M. Harrison, J.P. Shi / The Science of the Total Environment 189/190 (1996) 391-399 395

:- NOx (ppm) --- N02/NOx (% )

-a

Fig. 4. NO, concentrations and NO,/NO, ratios at wind tunnel exhaust arising from the petrol generator emissions.

The NO, concentration in the original ex- 3.2. Emissionfrom vehicle exhaust
haust plume was approximately 30 ppm,
which quickly diluted after emission. Because of Exhaust from an idling car, a university-owned
the high emission velocity, it is reasonable to van (Ford Escort; 1.3 1 petrol) registered in 1985,
treat the emission as a free jet [6]. Using free was passed into the wind tunnel as a NO, emis-
jet theory, it may be calculated that oxygen will sion source. The emission velocity was 10.5 m/s;
reach the plume centre at a distance of approx- the diameter of the emission tube was the same as
imately 11 cm. The distribution fluctuated near before. The emission of NO, and initial NO,/NO,
the edge of the tunnel as a result of the large was recorded in the plume at a distance of 30, 60,
90 and 120 cm from the emission point.
ratio of the diameter of the emission tube (2.5
cm) to the cross-section of the tunnel (30 x 30
3.3. Emissionfrom a pure NO cylinder
cm).
The highest ratio of NO,/NO, in each run,
An artificial exhaust jet was made by mixing
up to 9%, was in the centre of the plume at a pure NO and nitrogen gas. The NO concentration
distance of 30 cm. NO, formation from the re- in the original emission was 1000 ppm. The di-
action 2N0 + 0, +2NO, with an initial NO ameter of the steel emission tube was 6.35 mm,
concentration of 30 ppm and short residence giving an emission velocity of 14.7 and 29.4 m/s.
time could not account for this phenomenon. The corresponding Reynolds number was 6350
Overall, the NO,/NO, ratio of the plume was and 12 700 in the steel tube, and the wind tunnel
low (see Fig. 4). velocity was up to 3 m/s. The results are shown in
The wind speed in the tunnel was varied Figs. 5 and 6. Clearly, the NOJNO, ratio was
from O-3 m/s. The tunnel speed changed the low and insensitive to the emission velocity and
rate of NO, dilution, but did not affect the tunnel speed.
NO,/NO, ratio appreciably. Fig. 4 shows the The vehicle exhaust plume behaves as a free jet
measurements taken at the exhaust of the wind because of its much greater emission speed than
tunnel at different tunnel speeds. the surrounding fluid [6]. The turbulent jet dilutes
396 R.M. Harrison, J.P. Shi / The Science of the Total Environment 189/190 (1996) 391-399

50 r--- 10
/ Runl: l(m/s) Run3: 3(m/s) Run4: 3(m/s)
I 7
i --c NOX - NOx - NOx
z N02/NOx N02/NOx ~8 N02/NOx I
+8

10 +

0 I
-4 -2 0 2 4 8 8
Distance from Central line (cm)

Fig. 5. NO, concentrations and NO,/NO, ratios distribution across the tunnel 60 cm from emission orifice. Emission jet speed 14.7
m/s in run 1 and run 3, 29.4 m/s in run 4. The original wind tunnel velocity as shown.

quickly and NO, formation by reaction (1) in the
plume of idling exhaust is of little significance
because of the modest NO concentration and fast
dilution. The ratio of NO,/NO,, formed by reac-
tion (1) in an emission jet with 1000 ppm of NO,
is insensitive to the jet speed and wind speed in
the wind tunnel, and ranges from 0 to 6%. This is
consistent with the results obtained from the mea-
surements in the road tunnel where the NO,/NO,
ratio from the motor traffic was less than lo%,
even within a 15 min traffic jam.
4. An investigation of NO2 formation
vehicle exhaust
Two semi-collapsible FEP-teflon (thickness 0.13
mm) chambers were employed as reactors, each
was about 550 1 in volume. Chamber walls were
washed by a high speed clean air jet before each
run. A petrol-fuelled generator (EM 2200X,
Honda), two passenger cars (Nissan Sunny 1.3 1
1983 and Austin Metro 1 1 1982), and an engine
dynamometer were employed during this study to
provide a source of exhaust gas. The load of the
generator was 90 W; passenger cars were in a
driving mode of warm start idling.
The chambers were standardised by conducting
purified air experiments with injection of pure NO
(purity 99.9% from BOC) by syringe. Exhaust
gases were passed to the chambers either directly
through a flexible metal tube or using a pump
(Hawker Siddeley) with a 0.5 pm PTFE teflon
filter in the line. NO and NO, were measured by
a chemiluminescent nitrogen oxides analyser (En-
vironnement AC 30 M range 10 ppm and Dasibi
2108 range 100 ppm); NOa was obtained by sub-
in diluted tracting NO from NO,.
The initial conditions and results of some ex-
periments are listed in Table 1. It is clear that
vastly accelerated conversion of NO to NO2 is
occurring in some runs, but the mechanism is
unclear. In order to make the measured conver-
sion rates of NO to NO* comparable, rate con-
stants of diluted exhaust runs in Table 1 are
derived in terms of the equation,
 R.M. Harrison, J.P. Shi 1 The Science of the Total Environment 189/190 (1996) 391-399 397

10(-J - .._--.___ - I--. ~~-~~~~ - _.-. -_ ---. ~~~~~

Run!? 3(m/s) Run6: 1(&s) Run7: O(m/s)

i * NOX - NOx -~ NOx
1 N02/NOx N02/NOx ‘2 N02/NOx

I
z 60 j

$ 40i/
/

0 +--..A.-- ,--j-------t-- -... - -.... , .]- ~-0

-6 -4 -2 0 2 4
Distance from Central line (cm)

Fig. 6. NO., concentrations and NO,/NO, ratio distribution across the wind tunnel 30 cm from emission orifice. Emission jet speed
14.7 m/s and the original wind tunnel velocity as shown.

for reactions second order in NO and the equa- NOz was found in the diluted exhaust of the
tion, petrol-fuelled generator, engine dynamometer and
cars in the idling mode. High concentrations of
WOlld~ = bi&llW hydrocarbon species exist in idling exhausts and it
for first order in NO. Where [OJ = 0.21 x lo6 is believed that organic species may play a role in
ppm. A much faster conversion rate of NO to the conversion of NO to NO,.

Table 1
Results of selected experiments with diluted exhaust gas in a dark reactor

Run No. Temperature f”C) k& (10-9/ppm* min) kg, (IO-‘/ppm mm) Dilution ratio Note

1A 22.0 1.52 Pure NO injection

54B 23.5 1.55 Pure NO injection
37A 14.4 1.57 7.03 Diluted petrol car exhaust
under idling driving mode
37B 16.5 10.96 9.62 Diluted petrol car exhaust
under idling driving mode
74A 26.8 18.46 11.16 8 Generator exhaust
74B 26.8 20.16 11.43 8 Generator exhaust
73A 25.9 75.7 22.77 16 Engine dynamometer exhaust
890 rpm 75 W
70A 26.7 1.5 500 Engine dynamometer exhaust
1500 rpm 2.2 kW

a See text for meaning of k,,, and k,,

398 R.M. Harrison, J.P. Shi / The Science of the Total Environment 189/190 (1996) 391-399

800 1400
-- CRD NO2 --0. BRI NO2 --- WL NO2
- CRD NO l BRI NO A WLNO
700
I I I 1200
. I
600 I I
. n I
. I
I

I
1000
500 I
.
I

. -
z *
*
. : l z-
.
k . . l .

;400 - .
*
l .
. z * 800 E
. * .

P . I
.
. . z
: x
.

300 . .
I
- i
l . l

. - 600
+-eL .b‘-_

‘&‘-Q
200 -h:

400
100

0 / 1 / / 1 I I / I I I / I / / I 200
0 1 2 3 4 !i 6 7 8 9 10111213141516171819202i2223
Hours

Fig. 7. Hourly NO and NO, concentrations at two urban background sites (BRI and WL) and one busy roadside site (CRD) in
London during a pollution episode on 14th December 1991.

5. Further analysis of ambient air quality data measurements and wind tunnel experiments
showed that the original ratio of NO,/NO, in
Fig. 7 shows data from three sites in London bulk vehicle emissions was low, less than lo%,
during the December 1991 episode. One site even in a 15 min traffic jam; NO2 formation near
(CRD) is at roadside, whilst two (BRI and WL) the emission orifice did not contribute to the
are central urban background. Roadside hourly NO,/NO, ratio signficantly. Much faster conver-
NO concentrations were much higher than at sion of NO to NO2 was found in diluted ex-
background sites, but roadside NO, was at the hausts of petrol-fuelled cars, which probably
same level as background NO,. This suggests represents an important NO, source in winter
that vehicle emissions were not elevated abnor- smog episodes. Further work is investigating the
mally in NO* and that enhanced NO to NO* mechanisms of the chemical reactions responsi-
oxidation took place widely in the atmosphere. ble.
Thus, the chemical processes alluded to above
are likely to be very important.
Acknowledgements

6. Summary This work was conducted as part of the UK

Department of Environment Air Quality Re-
The sources of NO1 in winter smog episodes in search Programme under contract No. PECD 7/
the UK have been investigated. The road tunnel 12/120.
 R.M. Harrison, J.P. Shi / The Science of the Total Environment 189/190 (1996) 391-399 399

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[3] M. Lenner and 0. Lindqvist, The NO,/NO, Ratio in
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[4] J.H. Seinfeld, Atmospheric Chemistry and Physics of Air
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