Atmospheric Environment 43 (2009) 689–696

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Particulate matter at a rural location in southern England during 2006:

Model sensitivities to precursor emissions
Richard Derwent a, *, Claire Witham b, Alison Redington b, Michael Jenkin c, John Stedman d,
Rachel Yardley e, Garry Hayman e
a
rdscientific, Newbury, Berkshire, United Kingdom
b
Met Office, Exeter, Devon, United Kingdom
c
Centre for Environmental Policy, Imperial College London, Silwood Park, Ascot, United Kingdom
d
netcen, AEA Energy & Environment, Harwell International Business Centre, Oxfordshire, United Kingdom
e
National Physical Laboratory, Teddington, Middlesex, United Kingdom

a r t i c l e i n f o a b s t r a c t

Article history: A moving air parcel trajectory model has been used to estimate the mid-afternoon mass concentrations of
Received 19 February 2008 a number of suspended particulate matter (PM) components for each day of 2006 for a rural location,
Received in revised form 1 September 2008 Harwell, Oxfordshire, in the southern UK. A large number of equally probable and randomly selected 96-h
Accepted 23 September 2008
3-dimensional air mass trajectories were used to describe the variability of the atmospheric transport
paths during each day. A chemical kinetic description was given for the major PM formation processes.
Keywords:
The linearity of the chemical production pathways forming the secondary PM components was examined
PM2.5 mass concentrations
by sensitivity studies to 30% reductions in SO2, NOx, NH3, VOC and CO emissions. The chemical envi-
PM nitrate
PM sulphate ronment revealed by these sensitivity studies appeared to be ‘ammonia-limited’. Consequently, PM mass
PM ammonium concentrations appeared to be markedly non-linear with PM precursor emissions. Policy strategies for
Emission sensitivities PM2.5 therefore need to take into account emission reductions for a wide range of primary PM compo-
nents and secondary PM precursors and to focus primarily on the abatement of NH3. This complex
interlinking may help to explain why PM levels have remained constant despite falling primary PM
emissions.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction European Monitoring and Evaluation Programme (EMEP) model

There is much current interest from policy-makers concerning
air quality in Europe (European Commission, 2001). Observed
levels of ozone and particulate matter at most sites in north-west
Europe during most years (European Environment Agency, 2005),
exceed internationally accepted guidelines set to protect human
health (WHO, 2006). Monitoring networks are excellent at
revealing the extent to which air quality guidelines are exceeded
but, on their own, do not explain where the poor air quality has
originated from nor can they explain what can be done in the future
to improve it. Air quality modelling has been employed to answer
such questions and to give a lead to policy-makers in tackling poor
ozone and particulate matter (PM) air quality.
A number of air quality models are available addressing PM in
north-west Europe. By far the most important air quality model
from the policy-makers perspective is the Unified Eulerian
* Corresponding author. Tel.: þ44 1635 569377.
E-mail address: r.derwent@btopenworld.com (R. Derwent).
(Tarrason et al., 2003) because of its strategic role in the scientific
and policy analyses that underpin the Convention on Long-range
Transboundary Air Pollution (CLRTAP). There are a number of
additional Eulerian grid-based models that address ozone and PM
on the European scale and the performance of seven of them has
been recently evaluated against observations in some detail (Van
Loon et al., 2007). The EMEP model has been used extensively to
quantify the non-linear relationships between secondary inorganic
aerosol (SIA) and SO2, NOx and NH3 emissions (Tarrason et al.,
2003).
In this study, a Lagrangian trajectory model has been used to
describe the day-to-day variations in the mass concentrations of
a number of PM components during 2006 at a representative
rural location, Harwell in Oxfordshire in southern England. We
have extended the species coverage of the above models by
treating the formation of secondary organic PM. Furthermore, our
approach adopts a kinetic rather than a thermodynamic approach
to the formation of SIA. The aim has been to identify the major
sources of the precursor pollutants that are responsible for the
observed PM in rural southern England and to quantify the

1352-2310/$ – see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2008.09.077
690 R. Derwent et al. / Atmospheric Environment 43 (2009) 689–696
relationships between PM mass concentrations and their
precursor emissions.
2. The photochemical trajectory model PTM
For a model to generate an acceptable account of the day-to-day
variations in PM at a given location, two major prerequisites have to
be satisfied. Firstly, the model must contain an accurate description
of the meteorological processes that transport PM, together with
their precursors, to that location. Secondly, the model must have an
accurate description of the chemical transformation processes that
convert the primary emitted precursors into PM. To achieve, we
have extended the Photochemical Trajectory Model (PTM) to meet
these requirements. Full details of the PTM are given elsewhere
(Derwent et al., 1996; Abdalmogith et al., 2006) but a brief
description of the extensions and improvements made is given
below.
2.1. Model description
The model describes the chemical development within an air
parcel that follows an air parcel trajectory for up to 10 days,
forwards in time, reaching the arrival point at Harwell, Oxfordshire
(51340 N, 1190 W). The rate of change of the concentration of
species, ci, in molecule cm3 s1 was described by a series of
differential equations of the form in equation (1) below:
dci =dt ¼ Pi  Li ci  Vi ci =h þ Ei =h
where Pi is the instantaneous production of species i from photo-
chemistry, Lici is the instantaneous loss rate from photochemistry,
Vi is the species dependent dry deposition velocity, h, the time-
dependent boundary layer depth and Ei the local areal emission
rate of the pollutant sources in molecule cm2 s1.
2.2. Treatment of meteorological processes
To capture the inherent variability in the meteorological
processes, a Lagrangian or moving air parcel approach has been
adopted. For each mid-afternoon of each day of the year 2006,
a set of 30 equally probable and randomly selected 96-h air
parcel trajectories have been generated using the Met Office
Nuclear Accident Model (NAME) model, a sophisticated
Lagrangian atmospheric dispersion model (Manning et al., 2003).
The NAME model was driven by meteorology from the Met Office
mesoscale numerical weather prediction NWP model (Cullen
et al., 1997; Davies et al., 2005) at 40 km horizontal resolution
with 33 vertical levels. Each trajectory arrived at Harwell,
Oxfordshire at 1500z and was randomly selected from the many
thousands of air parcel tracks simulated by NAME that described
the histories of air parcels that had passed over that location. In
this way, we have been able to describe the inherent variability
in the atmospheric transport processes and have not relied on
single back-track air mass trajectories as in our previous work
(Abdalmogith et al., 2006). Each air parcel trajectory was fully
3-dimensional with information on the latitude, longitude and
height of the air parcel and the temperature and atmospheric
boundary layer depth at the air parcel location, recorded at
hourly intervals backwards in time. If the air parcel height was
less than the current atmospheric boundary layer depth at the
current air parcel location, then the air parcel was assumed to be
in the boundary layer and all deposition and emission processes
were switched on. Otherwise, the deposition and emission
processes were switched off.
2.3. Treatment of emissions
The PTM used four coordinate systems to identify the location of
the air parcel at any point along each air mass trajectory:
a) Latitude and longitude were used to fix the solar zenith angle
and hence the photolysis rates. This coordinate system was also
used to describe the emissions of a-pinene from natural
biogenic sources, together with their variation with month of
the year, based on the inventories provided by Guenther et al.
(1995).
b) a 150 km  150 km grid defined for the entire EMEP region.
c) a 50 km  50 km coordinate system which was used to fix the
local instantaneous areal emission rates, Ei, of SO2, CO, NOx,
VOCs, methane from man-made sources (Tuovinen et al., 1994),
of ammonia and primary PM (EMEP, 2007) and of isoprene
from natural biogenic sources (Simpson et al., 1995) when the
air parcels were over the continent of Europe closest to the UK.
d) the UK Ordnance Survey 10 km  10 km grid system was uti-
lised to fix areal emission rates over the United Kingdom based
on the National Atmospheric Emission Inventory (Dore et al.,
2007).
All gridded emissions were scaled over each country and for
each pollutant, separately, to reproduce the national emissions
totals for 2000 from EMEP (2007) in the absence of detailed esti-
mates for 2006. Emissions were assumed to be constant
throughout the year at the annual rate, except for the emissions of
a-pinene from natural biogenic sources for which monthly gridded
(1)
emissions were available. For the entire European continent,
independent of location, the speciation of the total VOC emissions
was taken from Passant (2002). The 665 emitted VOC species were
converted into Carbon Bond 4 species: ETH, OLE, PAR, ALD2, TOL
and XYL as described by Gery et al. (1989). The primary carbona-
ceous PM emissions from all sources were split into 78% by mass as
C elemental carbon and 22% organic carbon based on data for diesel
exhaust emissions (US EPA, 2002).
2.4. Gas-phase chemical mechanism
The chemical mechanism employed in the PTM describes the
oxidation of methane, non-methane VOCs, carbon monoxide,
sulphur dioxide and NOx to form ozone and PM components. In
previous studies (Derwent et al., 1996; Abdalmogith et al., 2006)
the Master Chemical Mechanism has been employed for this
purpose. Here we have used the Carbon Bond Mechanism (CBM) to
represent the gas-phase, homogeneous photochemical reactions
with extensions to address the formation of secondary PM
precursors. We have compared the results from the PTM with the
two versions of the gas-phase chemistry for the standard worst-
case five-day trajectory (Derwent et al., 1996). Final ozone
concentrations differed by 0.4 ppb in 87.8 ppb and the time-aver-
aged difference between the two mechanisms was 4.2% over the
five days.
2.5. Formation of PM components
Extensions have been added to CBM to address PM formation.
The approach adopted is highly simplistic and utilises a chemical
kinetic approach following the study of kinetic limitations in the
NH4NO3 – HNO3 – NH3 system by Harrison and Mackenzie (1990). A
summary of the approach to inorganic PM formation is given in
Table 1.
The formation of secondary organic aerosol (SOA) was assumed
to have two components involving the oxidation of biogenic-
derived a-pinene by hydroxyl OH, nitrate NO3 and ozone and the
 R. Derwent et al. / Atmospheric Environment 43 (2009) 689–696 691

Table 1 monitoring site at Harwell, Oxfordshire for 2006, together with

Description of the kinetic processes used to describe the formation of inorganic PM daily gravimetric PM2.5 observations. A fixed offset of 7 mg m3 was
components in the PTM.
subtracted from the latter observations to allow for field blanks.
PM formation process Notes Daily measurements of the inorganic components of PM10
OH þ SO2 þ M ¼ HOSO2 þ M Atkinson et al. (2006) (sulphate, nitrate and chloride) were made at the Harwell site using
SO2 ¼ H2SO4 2.8  106 s1, representing cloud a Thermo Partisol 2025 sequential air sampler (Yardley et al., 2007).
phase oxidation (Eliassen and Saltbones, 1983)
The PM10 samples were collected on glass fibre (Emfab, PTFE-bound
N2O5 ¼ 2NO3 Atkinson et al. (2006)
HNO3 ¼ NO3 Atkinson et al. (2006) glass fibre) filters. The instrument provided uninterrupted
N2O5 ¼ 2HNO3 Temperature dependent, based on sampling of ambient air and automatic exchange of filters for up to
Dentener and Crutzen (1993) 16 days. The instrument used an airflow of 16.7 litres per minute
NO2 ¼ HONO Modelled as a deposition process based through a PM10 inlet and the filter temperature was maintained to
on Harrison and Kitto (1994)
NH3 þ H2SO4 ¼ NH4HSO4 2.5  1013 cm3 molecule1 s1, note a
within 5  C of ambient temperature. The exposed filters were
NH4HSO4 þ NH3 ¼ (NH4)2SO4 2.5  1013 cm3 molecule1 s1, note a stored in small polypropylene filter bags and kept in a cold room
NH3 þ HNO3 ¼ NH4NO3 2.5  1014 cm3 molecule1 s1, note a until analysis to minimise loss of volatile components. Extracts
NH4NO3 ¼ NH3 þ HNO3 2.8  104 exp(118.87(24084/T)  6.025  ln(T)) s1, from the filters were dissolved in an eluent of 3.5 mM sodium
note a, based on Mozurkewich (1993).
carbonate and 1 mM sodium hydrogen carbonate and analysed in
Note: a. these processes are described using a kinetic approach to represent the laboratory by ion chromatography, for sulphate, nitrate and
constraints on the establishment of thermodynamic equilibrium in the NH4NO3 – chloride content. Ambient concentrations were derived from the
HNO3 – NH3 system.
b. T is temperature in K.
mass measured on the filter and the airflow during the sampling
period.
Routine observations of gaseous NH3, HNO3 and PM ammonium
oxidation of man-made aromatic compounds by OH (Derwent and were not available for the Harwell site. Monthly mean measure-
Malcolm, 2000). In reality, SOA formation is far more complex ments were, however, available at rural sites in the UK National
involving many different classes of SOA precursors (Kroll and Ammonia and Nitric Acid Monitoring Networks within a 75 km
Seinfeld, 2008). Our approach necessarily represents a preliminary range (Aston Rowant, Drayton, Rothamsted, Savarnake and
first attempt only. Wytham Woods) for the 1996–2004 period from: http://www.cara.
ceh.ac.uk.
2.6. Photolysis reactions
3. Modelling the seasonal cycles in PM components and their
The rates of the photolysis reactions, J, of the photochemically precursors at Harwell, Oxfordshire
labile species were calculated from the instantaneous solar zenith
angle, Z, using expressions of the form in equation (2): 3.1. Nitrogen oxides NOx ¼ NO þ NO2

J ¼ lðcos ZÞm expðn sec ZÞ
where the coefficients, l, m, n are available from the Master
Chemical Mechanism website (http://mcm.leeds.ac.uk/MCM).
2.7. Deposition
Dry deposition was represented using a species-dependent dry
deposition velocity approach. Deposition velocities for the gas
phase chemical components were unchanged from previous work
(Derwent et al., 1996). Aerosol dry deposition velocities were set to
0.5 mm s1 based on Nicholson and Davies (1987) and Wesely and
Hicks (2000) and the references therein. No allowance was made
for the wet removal of PM components.
2.8. Numerical methods
The system of 51 simultaneous stiff differential equations was
integrated with a variable order Gear’s method program FACSIMILE
(Curtis and Sweetenham, 1987). The initial concentrations for most
model species were set to zero. For ozone, methane and CO initial
concentrations were taken from the monthly mean baseline
observations for each month of 2006 for the atmospheric research
station at Mace Head, Ireland (Derwent et al., 2007). For NO2, SO2,
HNO3 þ NO þ
3 , NH3 þ NH4 initial concentrations were established
based on the annual mean observations reported for the Valentia
Observatory, Ireland (Fjaeraa, 2006).
2.9. Observations
Hourly observations of NOx and PM were taken from an Air
Quality Archive http://www.airquality.co.uk/archive/data_and_
statistics.php for the Automatic Urban and Rural Network AURN
(2) The PTM output comprised the histories of the chemical
development of the 51 model species along the 30 randomly
selected 96-h trajectories arriving at Harwell, Oxfordshire at 1500z
on each day of 2006. Examination of the 30 sets of results for each
day and each model species revealed the presence of a significant
amount of scatter about the average result for the arrival point.
There is evidence that this scatter increased dramatically on the
more polluted days compared with the cleaner days. There was
apparently much more variability in the model description of air
mass origins on polluted days compared with clean days. This
probably reflects the increasing stagnation and decreasing wind
speeds associated with pollution episodes. The arithmetic mean of
the 30 sets of results was taken as the best estimate of the model
result for that day and these estimates have been evaluated against
observations also for 1500z. Here, model performance require-
ments have focused on achieving mean fractional biases in the
range 0.2 and 50% of the model results within a factor of 2 of the
observations.
Comparison of the arithmetic means of the 30 model results for
NOx for each day with the available 1500z observed NOx concen-
trations taken from the AURN network site for Harwell, Oxfordshire
showed a general model underestimation. A scatter plot of the
model vs observations for each day of 2006 showed that the model
was able to capture the day-to-day variability in the observations
(R2 ¼ 0.4; 356 points) but with an apparent slope of about 0.76,
significantly below the 1:1 correspondence line. The observed
mean monthly NOx concentration was 5.3 ppb, compared with the
model value of 3.3 ppb. Monthly mean fractional biases were 0.82
and 107 of the 356 daily 1500z values were within a factor of two of
the observations. Root mean square errors RMSE were found to
average 4.6 ppb over 2006. In view of the difficulties of repre-
senting surface observations of a primary pollutant, NOx, with
a boundary layer-averaged model, some measure of model
692 R. Derwent et al. / Atmospheric Environment 43 (2009) 689–696
underestimation is to be expected. On this basis, the overall level of
PTM performance for NOx was considered acceptable.
3.2. Ammonia NH3
Monthly mean concentrations generally underestimated the
1996–2004 observations by a considerable margin. The annual
mean model NH3 concentration was 0.4 ppb compared with
2.4 ppb from the above observations. The available observations
showed a clear summertime maximum which was not evident in
the model results. The model underestimation was greatest during
March and April when it approached a factor of 11 and was least
during November and January when it was about a factor of 3. In
view of the difficulties found in representing surface (2 m) obser-
vations of a primary pollutant emitted from large, local agricultural
sources with poor dispersion, some measure of underestimation by
the boundary layer-averaged model is to be expected. It has thus
been difficult to evaluate the model performance for NH3.
3.3. Gaseous nitric acid HNO3
The annual mean model concentration was 0.89 ppb compared
with 0.82 ppb from the observations. Both observations and models
showed no evidence of a significant seasonal cycle. Fractional bia-
ses varied from 0.04 to 0.7 and averaged 0.07 over the year. Model
monthly mean concentrations in 11 out of the 12 months fell within
a factor of two of the observations. Root mean square errors
(RMSEs) averaged 0.08 ppb over the year. On this basis, model
performance was considered acceptable.
3.4. PM ammonium
The annual mean model concentration of 1.3 mg NH4 m3, taking
into account the contributions from NH4HSO4, (NH4)2SO4 and
NH4NO3, was close to the observed ammonium concentration of
1.2 mg NH4 m3. The observations exhibited a spring maximum
whereas the model a winter maximum. Fractional biases varied from
0.6 during March to 1.1 during December and averaged 0.14 over
the year. In 11 of the 12 months, the model monthly mean was within
a factor of 2 of the observations. RMSEs averaged 0.3 mg NH4 m3.
With reservations because of the spatial separation between the
model and observations and the 6 years separation in time, model
performance for ammonium was considered acceptable.
3.5. PM sulphate
A total of 318 days during 2006 had valid daily mean observa-
tions for which the annual average was 2.9 mg SO4 m3. The average
of the arithmetic means of the 15.00z concentrations from the 30
model experiments for each of the 318 days was 3.1 mg SO4 m3,
taking together the contributions from H2SO4, NH4HSO4 and
(NH4)2SO4. The model provided a good simulation of the observed
month-by-month variations and reproduced well the observed
winter and summer maxima. Monthly mean fractional biases
spanned the range from 0.13 to 0.64 and averaged 0.14 over the
year. For a total of 245 days out of 318, the model results were
within a factor of 2 of the observed daily values. Only the months of
October and December had less than one half of the days within
a factor of two of the observations. RMSEs averaged 1.9 mg SO4 m3
over the year. On this basis, PTM model performance was found to
be satisfactory for sulphate.
3.6. PM nitrate
The annual mean of the observed PM10 nitrate concentrations
was 3.2 mg NO3 m3 and model calculated sum of fine and coarse
nitrate was 3.0 mg NO3 m3. The model was able to provide a good
simulation of the observed seasonal cycle in nitrate, with its
marked winter maximum and summer minimum. Fractional biases
ranged from 0.4 to 0.6 and averaged 0.05 over the year. A total of
217 days reported model results within a factor of two of the
observations. Only two months, October and December, failed to
have more than one half of the days with daily values within
a factor of two of the observed values. RMSEs averaged
2.2 mg NO3 m3. Model performance was considered satisfactory for
fine and coarse nitrate.
3.7. Elemental carbon PM
No high time-resolution particulate elemental carbon (EC)
observations have been published for the Harwell location for
2006. Wintertime and summertime average EC observations of
0.63 and 0.38 mg C m3, respectively, have been reported for Bush
Estate, Penicuik, Midlothian from July 2002 to July 2003 for the
EMEP EC-OC campaign by Yttri et al. (2007). The model elemental
carbon concentrations show similar winter vs summer differences
but differ by a factor of 2 from the observations, producing winter
and summer mean concentrations of 0.29 and 0.19 mg C m3. It is
likely that a boundary layer-averaged model would underestimate
surface (2 m) observations of a primary pollutant such as EC
emitted largely by motor traffic. The extent of this underestimation
is consistent with that reported above for NOx. However, the lack of
adequate observations precludes a satisfactory evaluation of model
performance for EC.
3.8. Organic carbonaceous PM
The organic carbonaceous (OC) observations from the EMEP EC-
OC Campaign (Yttri et al., 2007) have been employed to examine
PTM model performance. The observations were converted from an
(OC) to an organic matter (OM) basis using a factor of 1.5 appro-
priate for UK conditions (Jones and Harrison, 2005), giving
a wintertime OM concentration of 2.5 mg m3 and a summertime
average of 2.1 mg m3. In comparison, the model indicated winter-
time and summertime mean concentrations of 2.0 and 3.2 mg m3,
respectively. The absence of a seasonal variation in the observations
contrasts markedly with the model results which show a clear
summertime maximum. Nevertheless, the model results appear to
be of a similar order of magnitude to the observations, particularly
during wintertime. However, the lack of adequate observations
precludes a satisfactory evaluation of model performance for OM.
3.9. PM2.5
Model PM2.5 mass concentrations were estimated from the
sulphate, fine nitrate, ammonium, EC and OM concentrations. The
contribution to model PM2.5 mass concentrations from strongly
bound water was estimated empirically from the mass concentra-
tions of ammonium sulphate and nitrate by scaling with a factor of
1.29 following Harrison et al. (2004). Model boundary layer mean
concentrations of EC were scaled by a factor of 2 to convert them to
surface concentrations. The resulting annual mean model PM2.5
concentration of 10.6 mg m3 compared closely with the observed
value, 10.5 mg m3. A comparison of the observed and model daily
PM2.5 concentrations is given in Fig. 1. Mean monthly fractional
biases were in the range 0.55–2.01 with 5 months in the
acceptable range of 0.2. 10 out of 12 months had monthly means
within a factor of 2 of the observations. Model performance
appeared least satisfactory for the summer months, see Fig. 1.
During these months, biomass burning fires in the Russian Feder-
ation contributed significantly to observed PM2.5 levels throughout
north west Europe (Bozier et al., 2007; Saarikoski et al., 2007;
 R. Derwent et al. / Atmospheric Environment 43 (2009) 689–696 693

Observations Table 2
80 Annual mean model calculated PM component concentrations for Harwell,
Model
Oxfordshire with and without initial and boundary concentrations and for various
Bias emission reduction scenario cases.
60
Scenario case PM SO4, Fine PM PM NH4, PM2.5, Coarse PM
mg m3 NO3, mg m3 mg m3 mg m3 NO3, mg m3
PM2.5, ug/m3

40
With initial and boundary 3.11 1.32 1.29 10.0 1.54
concentrations
20
Base casea 1.55 1.31 0.72 7.4 0.80

Across-the-board cases
0
30% SO2 case 1.09 1.43 0.68 6.9 0.78
30% NOx case 1.62 1.06 0.66 7.1 0.63
-20 30% NH3 case 1.55 0.91 0.57 6.8 0.85
30% VOC case 1.53 1.30 0.72 7.4 0.75
30% CO case 1.55 1.31 0.72 7.4 0.80
-40
01/01/2006

01/02/2006

01/03/2006

01/04/2006

01/05/2006

01/06/2006

01/07/2006

01/08/2006

01/09/2006

01/10/2006

01/11/2006

01/12/2006
UK-only cases
30% SO2 case 1.32 1.35 0.71 7.2 0.79
30% NOx case 1.60 1.21 0.70 7.3 0.74
30% NH3 case 1.55 1.14 0.65 7.1 0.81
30% VOC case 1.54 1.30 0.72 7.4 0.77
Fig. 1. Comparison of the model and observed PM2.5 concentrations for Harwell, 30% CO case 1.55 1.31 0.72 7.4 0.80
Oxfordshire for each day of 2006, showing the daily bias (model – observation).
Rest of Europe-only cases
30% SO2 case 1.32 1.39 0.69 7.2 0.79
30% NOx case 1.57 1.16 0.68 7.2 0.69
Witham and Manning, 2007) but these non-inventoried PM sour-
30% NH3 case 1.55 1.08 0.64 7.1 0.84
ces were not included in this modelling study. Overall, model 30% VOC case 1.54 1.30 0.72 7.4 0.78
performance for PM2.5 was considered satisfactory. 30% CO case 1.55 1.31 0.72 7.4 0.80
a
Without initial and boundary concentrations of PM components and their
4. Estimation of emission sensitivity coefficients for PM precursors.
components

The sulphate has a sensitivity coefficient with respect to SO2

4.1. Background contributions
emissions that is unity, see Table 3, hence, sulphate mass concen-
trations respond linearly with SO2 emissions. Sulphate also shows
The PTM was run for mid-afternoon (1500z) conditions for each
a moderate negative sensitivity to NOx emissions of 0.15. That is to
day of 2006. The initial and boundary concentrations of the PM
say, sulphate increases as NOx emissions decrease. This arises
precursors and PM components were set to zero and the model was
because OH radical number densities rise as NOx levels are reduced,
rerun. The differences between these two runs represent the
increasing the homogeneous oxidation rate of SO2 to sulphate.
background contributions to each PM component. The annual
There appears to be a small, 0.05, positive sensitivity to VOC
mean PM component mass concentrations, together with their
emissions. That is to say, sulphate decreases as VOC emissions
background contributions are presented in Table 2. Background
decrease. This arises because decreasing VOC emissions inhibit the
contributions appear to be significant for fine sulphate and
formation of photochemical oxidants, thereby inhibiting the
ammonium, and coarse nitrate but not for fine nitrate.
photochemical conversion of SO2 to sulphate. The sensitivities of
sulphate to the emissions of CO and NH3 are vanishingly small as
4.2. Sensitivity coefficients for across-the-board emission changes were those of OM to all man-made emissions.
The fine nitrate formed within Europe appears to be less than
A series of sensitivity experiments were then run with PM linearly related to NOx emissions, showing a moderate sensitivity
precursor emissions: namely VOC, NOx, NH3, CO and SO2, reduced coefficient of 0.63 in Table 3. This less than linear relationship
by 30% across-the-board, relative to the base case emissions. The between fine nitrate and NOx emissions arises because as NOx
annual mean PM component concentrations are shown in Table 2 emissions decrease, OH radical number densities increase some-
for these sensitivity cases which were performed with initial and what, increasing the conversion rate of NOx to gaseous nitric acid
boundary concentrations set to zero. and partially counteracting for the decrease in NOx concentrations.
Sensitivity coefficients, Eij, were then calculated for PM In contrast, the fine nitrate is linear in NH3 emissions. This means
component, i, for changes in the emissions of precursor pollutant, j, that the formation of ammonium nitrate is linearly dependent on
as follows:

Change in PM component; i; concentration=Base case PM component; i; concentration

Eij ¼
Change in emission of pollutant; j=Base case emission of pollutant; j

They represent the sensitivity of the mass concentrations of the PM the availability of gaseous ammonia. There appears to be a negative
component to across-the-board emission changes, that is, to sensitivity, 0.32, to SO2 emissions. That is to say, as SO2 emissions
emission changes both in the United Kingdom and in the rest of decrease, fine nitrate increases, reflecting the shift from ammo-
Europe. nium sulphate to ammonium nitrate. There is a small sensitivity to
694 R. Derwent et al. / Atmospheric Environment 43 (2009) 689–696

Table 3
Emission sensitivity coefficients for the different PM components calculated with the PTM model for 30% across-the-board emission reductions.

Scenario case PM SO4, mg m3 Fine PM NO3, mg m3 PM NH4, mg m3 PM2.5, mg m3 Coarse PM NO3, mg m3
Across-the-board cases
30% SO2 case 1.0 0.32 0.20 0.21 0.07
30% NOx case 0.15 0.63 0.28 0.13 0.72
30% NH3 case 0 1.0 0.71 0.30 0.21
30% VOC case 0.05 0.02 0.02 0.02 0.22
30% CO case 0.005 0.003 0 0 0.01

UK-only cases
30% SO2 case 0.51 0.12 0.05 0.11 0.02
30% NOx case 0.11 0.24 0.10 0.03 0.26
30% NH3 case 0 0.44 0.33 0.13 0.05
30% VOC case 0.03 0.005 0.007 0.01 0.13
30% CO case 0.002 0 0 0 0.004

Rest of Europe-only cases

30% SO2 case 0.49 0.20 0.15 0.10 0.05
30% NOx case 0.05 0.38 0.18 0.09 0.46
30% NH3 case 0 0.57 0.37 0.16 0.16
30% VOC case 0.02 0.12 0.01 0.01 0.09
30% CO case 0.003 0.002 0 0 0.006

VOC emissions, reflecting their influence on photochemical oxidant
production. The sensitivity to CO emissions is vanishingly small.
The fine ammonium appears to be less than linearly related to
ammonia emissions, showing a moderate positive sensitivity
coefficient, 0.71. Since the sensitivity coefficient of fine nitrate to
NH3 emission changes is unity, the less than linear sensitivity found
for ammonium to NH3 emissions implies a change in the extent of
neutralisation of the strong acid, sulphuric acid, as NH3 levels fall.
This is plausible if there is another important fate for gaseous
ammonia, namely dry deposition, and if conditions are ‘ammonia-
limited’. Fine ammonium mass shows small, positive sensitivities to
NOx and SO2 emissions, consistent with ammonium formation
being ‘ammonia-limited’.
The coarse nitrate shows a moderate, positive sensitivity, 0.72,
to NOx emissions that is considerably less than linear because of the
coupling between NOx emissions and strong acid formation
through OH radical densities. A negative sensitivity, 0.21, is
observed to ammonia emissions, reflecting the competition
between the reactions of gaseous nitric acid with ammonia and
sea-salts to form fine and coarse nitrate, respectively. Small sensi-
tivities were observed to VOC and SO2 emissions, consistent with
the sensitivities reported for fine nitrate.
4.3. Sensitivity coefficients for national and foreign emission
reductions cases
A second and third series of sensitivity experiments were then
run with PM precursor emissions reduced by 30% relative to base
case emissions on a national, UK-only, and foreign, UK-excepted,
basis. The annual mean PM component concentrations are shown
in Table 3 for these additional sensitivity cases.
Considering first sulphate, Table 3 shows that the sensitivity
coefficients for SO2 emission reductions applied within the UK
(national reductions) or across the rest-of-Europe (Foreign reduc-
tions) are closely similar and are roughly one half of the value for
the across-the-board case. Broadly speaking, this implies that of the
total sulphate, one half comes from within the UK and the other half
from elsewhere across Europe.
There is an increase in sulphate in response to a decrease of 30%
in NOx emissions. The sensitivity coefficient for national NOx
reductions is about double that found for foreign reductions. This
non-linear term is therefore highly spatially variable. Sulphate
decreases in response to a 30% decrease in VOC emissions. The
sensitivity coefficient is considerably higher for VOC reductions in
the UK compared with those carried out in the rest of Europe.
Again, this non-linear term is highly spatially variable.
Fine nitrate shows a sensitivity coefficient of 0.24 for national
NOx emission reductions but 0.38 for foreign NOx emission reduc-
tions. So, of the total response to the 30% across-the-board reduc-
tion in NOx emissions found for fine nitrate, two-fifths comes from
the national response and three-fifths from the foreign response.
This pattern of responses for fine nitrate is characteristically
different to that seen for fine sulphate and is due to the larger
spatial scale of nitrogen compared with sulphur. This larger spatial
scale arises because NOx is not as efficiently dry deposited as SO2.
Fine nitrate shows a sensitivity coefficient of 0.44 for decreases
in national NH3 emissions but 0.57 for foreign emission reductions.
So, of the total response to the 30% across-the-board reduction in
NH3 emissions found for fine nitrate, two-fifths comes form the
national response and three-fifths from the foreign response,
following the pattern revealed for the NOx emission responses. Fine
nitrate increases in response to decreasing SO2 emissions. These
non-linear responses are greatest for foreign emission changes
compared with national changes. The opposite pattern of behav-
iour is also found for the small positive non-linearities found in
response to VOC emission reductions.
Ammonium shows almost identical sensitivity coefficients in
response to 30% NH3 emission reductions carried out in the UK or in
the rest of Europe. This follows as a consequence of the ammonia
limitation found for the across-the-board NH3 emission reductions.
The small positive sensitivities found for ammonium to across-the-
board NOx and SO2 emission reductions appear to have resulted
predominantly from responses to foreign reductions rather than
national ones.
Sensitivity coefficients for coarse nitrate to NOx emission
reductions are significantly larger for foreign reduction scenarios
compared with national ones. That is to say, there is a one-third to
two-thirds split in favour of the foreign reduction. This is because of
the large spatial scale associated with the night-time NO2 þ O3
reaction that acts as a major source of the N2O5 precursor to coarse
nitrate. The non-linear response of coarse nitrate to NH3 emissions
decreases produces an increase in coarse nitrate, of which one
quarter arises from the national emission reduction and three
quarters from the foreign. Ammonia competes for HNO3 in
competition with sea-salts to form fine and coarse nitrate,
respectively. As ammonia emissions are reduced, more nitric acid
becomes available to form coarse nitrate. Because these are rela-
tively slow and minor processes, they operate over a relatively large
spatial scale, hence the greater foreign responses are large
 R. Derwent et al. / Atmospheric Environment 43 (2009) 689–696
compared with national responses. Small decreases in coarse
nitrate were also observed in response to 30% reductions in SO2 and
VOC emissions. The former response arises from the greater avail-
ability of ammonia following the decreased strong acid production
from SO2 oxidation, leading to increased competition for nitric acid
and hence decreased coarse nitrate formation. The response of
national VOC emission reductions was greater than foreign reduc-
tions, reflecting the more NOx-limited nature of photochemical
ozone formation over the rest of Europe compared with the more
VOC-limited situation over the UK.
5. Discussion and conclusions
In this study, the PTM has been used to build up a picture of the
emission, transformation and transport processes that give rise to
PM components during each day of 2006 at a rural location in the
southern United Kingdom. The assessment of PM component mass
concentrations through the use of multiple trajectories is a consid-
erable enhancement over our previous single trajectory approach,
as it allows a much more comprehensive representation of the
meteorological situation. The agreement with observations and the
representativeness of the emission sensitivities have been signifi-
cantly improved with this approach. The aim has been to provide
a description of PM2.5 mass concentrations from the mass
concentrations of the major PM components: sulphate, nitrate,
ammonium, EC and OM. As a consequence of the number and
strength of the chemical processes linking the different PM
components and their precursors, non-linearities have been found
between PM component mass concentrations and their precursor
emissions. We are now in a position to evaluate the importance of
these non-linearities for PM2.5.
The response of PM2.5 to 30% reductions in SO2 emissions is
necessarily the resultant of a number of factors and interactions
involving each of the PM2.5 components. Sulphate levels decrease
but the increased availability of NH3 leads to an increase in
ammonium nitrate and an increase in the extent of neutralisation of
H2SO4. As a consequence ammonium decreases by much less than
30%, fine nitrate increases and coarse nitrate decreases. Hence,
PM2.5 responds less than linearly to reductions in SO2 emissions,
with a sensitivity coefficient of 0.21.
The corresponding response of PM2.5 to 30% reductions in NOx
emissions is much less than linear. Fine nitrate levels decrease in
response to NOx emission reductions but the attendant increase in
OH levels reduces the fine and coarse nitrate responses and also
leads to an increase in sulphate. Ammonium levels fall somewhat,
being the resultant of decreasing levels of ammonium nitrate and
increasing levels of ammonium sulphates. The sensitivity coeffi-
cient of PM2.5 to NOx emissions was accordingly 0.13.
Because the chemical environment of the southern UK was
found to be ‘ammonia-limited’, the response of PM2.5 to 30%
reductions in NH3 emissions was not straightforward. Fine nitrate
declined exactly linearly in line with NH3 emissions because
gaseous nitric acid formation was independent of ammonia and
hence there was a linear decline in ammonium nitrate formation.
This decline in ammonium nitrate formation drives an increase in
coarse nitrate formation. Sulphate levels were left unchanged by
reductions in ammonia emissions but significant changes were
observed in the extent of neutralisation of H2SO4. Overall, the
sensitivity of PM2.5 to NH3 emissions was found to be 0.30 and was
the largest of the SO2, NOx and NH3 PM precursors.
It has long been recognised that non-linearities exist between PM
components and SO2, NOx and NH3 emissions in PM policy models.
In Europe, these non-linearities are quantified by EMEP using
source-receptor relationships where PM precursor emissions are
reduced by 15% and the changes in SIA are presented as maps and
tables (Tarrason et al., 2003). The sensitivity coefficient determined
695
here for SIA to UK-only emissions was found to be 0.38 in good
agreement with 0.27 reported for the southern UK by EMEP (Klein
et al., 2007), reflecting a similar level of non-linearity. Using the PTM
we have thus been able to illuminate how these non-linearities can
be apportioned between the different PM precursor emissions and
have been able to formulate a representation of ‘ammonia-limited’
chemistry using a kinetic rather than a thermodynamic approach.
From these considerations, it is apparent that PM2.5 mass
concentrations in rural southern United Kingdom are likely to be
influenced strongly by reductions in SO2, NOx and NH3 emissions in
a complex and interlinked manner. In addition, there are weaker
influences from VOC and CO emission changes and from primary PM
emission changes, with sensitivity coefficients of 0.07 and 0.12 for EC
and OM, respectively. Policy strategies for PM2.5 therefore need to
take into account emission reductions from a range of primary PM
components as well as PM precursors. Policy-makers should
consider focusing on the abatement of NH3 to get the largest PM2.5
reduction. The non-linearities identified here may help to explain
why PM2.5 levels in north west Europe have failed to decline despite
falling primary PM emissions as identified by Harrison et al. (2008).
Acknowledgements
This work was supported by Air and Environmental Quality
Division, Defra through contract CSA 7267 AQ03508 and the work
at the National Physical Laboratory through the Defra Monitoring
Airborne Particulate Concentrations and Number in the UK (Phase
2) contract CPEA 28. The assistance of the Atmospheric Dispersion
Group of the Met Office and of Duncan Whyatt, University of Lan-
caster is gratefully appreciated.
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