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New particle formation events in semi-clean South African savannah

Article  in  Atmospheric Chemistry and Physics · December 2011

DOI: 10.5194/acp-11-3333-2011

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Markku Kulmala Moses Molefe

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 NEW PARTICLE FORMATION EVENTS IN SEMI-CLEAN SOUTH AFRICAN
SAVANNAH
Ville Vakkari* , Heikki Laakso , Markku Kulmala1, Ari Laaksonen2,3, Desmond Mabaso4,
1 1

5 5 6 1,2,6
Moses Molefe , Nnenesi Kgabi , Johan P. Beukes and Lauri Laakso
1
Department of Physics, University of Helsinki, P.O. BOX 64, 00014 University of Helsinki, Finland,
ville.vakkari@helsinki.fi
2
Finnish Meteorological Institute, P.O. BOX 503, 00101 Helsinki, Finland
3
Department of Applied Physics, University of Eastern Finland, Kuopio 70211, Finland
4
Rustenburg Local Municipality, Rustenburg, South Africa
5
Department of Physics, North-West University, Private Bag X 2046, Mmabatho, South Africa
6
School of Physical and Chemical Sciences, North-West University, Potchefstroom, South Africa

Abstract

This study is based on 18 months (20 July 2006 – 5 February 2008) of continuous measurements of
aerosol particle size distributions, air ion size distributions, trace gas concentrations and basic
meteorology in the Botsalano game reserve in the North-West Province, South Africa. New particle
formation and growth up to sizes where the particles can act as cloud condensation nuclei (CCN) was
observed on 69% of the days and bursts of non-growing ions/sub-10 nm particles on additional 14% of the
days. This new particle formation frequency is the highest reported from boundary layer so far. Also the
new particle formation and growth rates were among the highest reported in the literature for continental
-3 -1
boundary layer locations; median 10 nm formation rate was 2.2 cm s and median 10–30 nm growth rate
-1 -3 -1
8.9 nm h . The median 2 nm ion formation rate was 0.5 cm s and the median ion growth rates were 6.2,
8.0 and 8.1 nm h-1 for size ranges 1.5–3 nm, 3–7 nm and 7–20 nm, respectively. The growth rates had a
clear seasonal dependency with minimum during winter and maxima in spring and late summer. The
relative contribution of estimated sulphuric acid to the growth rate decreased with increasing particle size
and could explain more than 20% of the observed growth rate only for the 1.5–3 nm size range. Also the
air mass history analysis indicated the highest formation and growth rates to be associated with the area
of highest VOC (Volatile Organic Compounds) emissions following from biological activity rather than the
highest estimated sulphuric acid concentrations. The frequency of new particle formation, however,
increased nearly monotonously with the estimated sulphuric acid reaching 100% at H2SO4 concentration
of 6∙107 cm-3, which suggests the formation and growth to be independent of each other.
Keywords: new particle formation, savannah, air mass history, sulphuric acid.

Introduction during the period 20 July 2006 – 30 January

Combined long-term measurements of trace
gas concentrations, aerosol particle number
size distributions (especially in ultrafine size
range), air ion number size distributions and
meteorological variables are few in Southern
Africa (Piketh et al. 2005, Laakso et al. 2008).
The first long-term measurements of aerosol
size distributions in continental Africa have
revealed new particle formation to be a very
frequent phenomenon in the savannah
environment (Laakso et al. 2008, Vakkari et al.
2011) and therefore it is likely to have a regional
effect on cloud condensation nucleus budget
and on the properties of the clouds.
This study presents a detailed analysis on the
new particle formation observed in a relatively
clean savannah environment in Botsalano game
reserve, North-West Province, South Africa
2008. The seasonal variation of the formation
and growth rates is studied and, in order to
understand the processes behind the
observations, the measurements are combined
with air mass history analysis and estimated
sulphuric acid concentration.
Measurements and methods
The measurement station and the site are
described in detail in Laakso et al. (2008) and the
mobile measurement trailer and the
instrumentation in the trailer in Petäjä et al.
(2011). In this study we utilize aerosol particle
size distributions from the differential mobility
particle sizer (DMPS) (Hoppel 1978, Jokinen
and Mäkelä 1997), size range 10 – 840 nm, air
ion size distributions from the air ion
spectrometer (AIS) (Mirme et al. 2007), size
range 0.8 – 42 nm, sulphur dioxide

20 Clean Air Journal, Vol 20, No.2 December 2011

concentration from the Thermo 42S analyser
(Thermo Environmental Instruments Inc. 1992)
and the basic meteorological quantities
including solar radiation from the
photosynthetically active radiation (PAR) sensor
(LiCor LI-190SB).
New particle formation events were determined
along the guidelines set in Dal Maso et al. (2005)
and in Yli-Juuti et al. (2009). During “event days”
there appears a new growing particle mode in
the sub-25nm range and correspondingly during
“non-event days” no new particles were formed.
The “undefined days” are such that it was not
possible to determine with complete certainty
whether there was new particle formation or not.
The new particle formation and growth rates
were calculated according to Dal Maso et al.
(2005) for the DMPS measurements and for the
ion spectra the growth rates for 1.5-3nm, 3-7nm
and 7-20nm ions were calculated using the
method described in Hirsikko et al. (2005). The 2
nm ion formation rate was calculated as in
Kulmala et al. (2007).
The sulphuric acid concentration was estimated
with a proxy calculated according to Eq. 4 in
Petäjä et al. (2009) and the contribution of
sulphuric acid to the aerosol particle growth was
estimated using Eq. 8 in Nieminen et al. (2010).
This gives the following relations for sulphuric
acid concentration and growth rate: for particles
7
between 1.5 and 3 nm 1.15∙10 molecules of
-3 -1
H2SO4 cm corresponds to 1 nm h growth rate,
for particles between 3 and 7 nm 1.5∙107
molecules of H2SO4 cm-3 corresponds to 1 nm h-1
growth rate, for particles between 7 and 20 nm
7 -3
1.7∙10 molecules of H2SO4 cm corresponds to
-1
1 nm h growth rate, and for particles between
7
10 and 30 nm 1.8∙10 molecules of H2SO4
corresponds to 1 nm h-1 growth rate.
detail in Vakkari et al. (2011).
Results
New particle formation and growth up to CCN
sizes was observed on 69% of the days during
the measurement period, which is the highest
frequency reported from the continental
boundary layer so far (Vakkari et al. 2011). The
new particle formation frequency did not have
seasonal variation.
The formation and growth rates did, however,
have a clear seasonal variation as is seen in
Figures 1 and 2. The formation and growth rates
clearly peak in spring and late summer, from
September to November and February, and
have a minimum in winter, from May to August.
This is in accordance with earlier observations
from northern hemisphere (e.g. Kulmala et al.
2004, Dal Maso et al. 2005) where the seasonal
variation of particle growth rates is explained by
changes in biogenic VOC-emissions (e.g.
Mäkelä et al. 1997, Dal Maso et al. 2005). In
case of southern Africa, the similar annual
biogenic emission cycle can be explained by
precipitation pattern and respective changes in
vegetation (Güenther et al. 1996, Otter et al.
2002, 2003).
The median 10nm formation rate was 2.2 cm-3s-1
and the median 10–30 nm growth rate 8.9 nm h-1,
which are among the highest reported in the
literature for continental boundary layer (Vakkari
et al. 2011).

The air mass history was investigated using

back-trajectories calculated using the HYbrid
Single-Particle Lagrangian Integrated Trajectory
(HYSPLIT) version 4.8 model developed by the
National Oceanic and Atmospheric
Administration (NOAA) Air Resources
Laboratory (ARL) (Draxler & Hess 2004). The
model was run with the GDAS meteorological
archive produced by the US National Weather Figure 1. Seasonal variation of 10 nm formation rate.
Service's National Centre for Environmental
Prediction (NCEP) and archived by ARL (Air
Resources Laboratory 2009). The HYSPLIT
model was run for 96-hour back-trajectories at
every hour throughout the complete
measurement period. The methods for the air
mass history analysis are described in more

Clean Air Journal, Vol 20, No.2 December 2011 21

 growth rate explained by the estimated sulphuric
acid is decreasing with increasing particle size so
that it can explain only 10% of the 10–30 nm
growth rate.

Figure 2. Seasonal variation of 10–30 nm growth rate.

-3
The median 2 nm ion formation rate was 0.5 cm
-1
s and the median ion growth rates were 6.2, 8.0
-1
and 8.1 nm h for size ranges 1.5–3 nm, 3–7 nm
and 7–20 nm, respectively. The ion growth rates
show the same shape of annual behaviour as
DMPS in all size ranges, that is, a maximum Figure 3. The source areas of the observed 10–30 nm
growth rate. The black dots represent (from left to
during the spring and in the summer and a
right) Botsalano, Rustenburg and Johannesburg.
minimum in the winter. The seasonal variation of
the growth rate of 1.5–3 nm ions is the smallest in
the three size ranges. The 2 nm ion formation
rate does not have seasonal variation.

The air mass history analysis indicates the

highest formation and growth rates to originate in
the North-Eastern direction from Botsalano,
Figure 3, and not due East, which is the direction
of the highest anthropogenic emissions. The
Limpopo valley in the North-Eastern South Africa
is also the area of highest monoterpene
emissions in the SAFARI 2000 VOC emission
inventory (Otter 2004).

The effect of sulphuric acid on new particle

formation frequency is illustrated in Figure 4,
which clearly indicates how increasing sulphuric
acid concentration increases the frequency of
new particle formation and growth and
correspondingly decreases the frequency of
non-event days. Here the estimated sulphuric
acid concentration is divided into logarithmically
evenly spaced bins and the frequency of new
particle formation and growth is then calculated
7
in each bin. At concentrations higher than 3∙10
-3
molecules cm we do not observe any more non-
event days and above 6∙107 molecules cm-3 there
are only clear new particle formation and growth
days.
The contribution of the sulphuric acid to the
growth of the particles is, however, small except
for the smallest size range of 1.5–3 nm where the
estimated sulphuric acid can explain on average
25% of the observed growth. The fraction of
Figure 4. Frequency of new particle formation and
growth as a function of estimated sulphuric acid
concentration.
Conclusions
We have presented here the first detailed
analysis on new particle formation in a semi-
clean savannah environment based on one and
half years of continuous measurements of air
ions, aerosol particle size distribution, trace
gases and basic meteorological variables. New
particle formation and growth was observed on
69% of the days, which is the highest frequency
reported from boundary layer so far. The
observed formation and growth rates are among
the highest reported from continental locations.

22 Clean Air Journal, Vol 20, No.2 December 2011

The three different approaches used to study the
origin of the observed high growth rates –
seasonal variation, sulphuric acid estimates and
source areas – all indicate that sulphuric acid
alone is not enough to explain the growth. The
seasonal variation in the growth rate suggests
biological activity to contribute significantly to the
growth; furthermore, the air mass history
analysis connects highest growth rates to the
areas of highest biogenic VOC emissions
emphasizing the importance of biogenic VOC's
in the growth. On the other hand, the occurrence
of new particle formation and growth was
strongly dependent on sulphuric acid and the
contribution of sulphuric acid to the growth
immediately after nucleation was significant,
which implies that the formation and growth
processes are to a large degree independent of
each other.
Acknowledgments
The authors acknowledge the financial support
by the Academy of Finland under the projects Air
pollution in Southern Africa (APSA) (project
number 117505) and Atmospheric monitoring
capacity building in Southern Africa (project
number 132640) and by the European
Commission 6th Framework program project
EUCAARI, contract no 036833-2 (EUCAARI).
The authors thank Head of Botsalano game
reserve, M. Khukhela and the game reserve
employees for their kind and invaluable help
during our measurements. In addition, the
authors are grateful to M. Jokinen and E. Sjöberg
for their help to organizing the project.
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