Atmospheric Environment 212 (2019) 36–40

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

Short communication

Extreme levels and chemistry of PM from the consumer fireworks in the T

Netherlands
Harry ten Brink∗, René Otjes, Ernie Weijers1
Energy-research Centre of the Netherlands ECN, 1755, ZG Petten, the Netherlands

ARTICLE INFO ABSTRACT

Keywords: Mass concentrations of Particulate Matter (PM) in New-Year's nights can be high in the Netherlands because of
Consumer fireworks the unconstrained use of consumer fireworks. In the study presented here the chemical compounds of the PM
Sulphuric acid were determined. It is for the first time that this information was used to deduced the average composition of the
KClO4 explosive mixture/black powder. Measurements were made during the turn of the year 2007–2008 at an urban
Nitrate
background location, when hourly PM10 mass concentrations exceeded 2000 μg m−3 at street sites. These ex-
Topochemistry
treme levels were due to the stagnant weather conditions occurring that night. The on-line artefact-free
“MARGA” was deployed for assessment of the major compounds. These were found to be the (hygroscopic) salts
KCl, MgSO4 and K2SO4. The mass ratio of sulphur and potassium showed that a standard black powder mix is
used as explosive. The potassium was for 65% present as KCl. This is the reduction product of the oxidiser KClO4,
which is hence the main oxidiser. The rest of the potassium was present in the form of K2SO4. We proved that this
compound derives from the “standard” oxidiser KNO3 of black powder. The formation of the SO42--salts is
explained as follows. The sulphur in the black powder oxidises to H2SO4. This compound reacts with the re-
duction product of the KNO3 to K2SO4. MgSO4 forms in a reaction of the main colouring agent magnesium with
the H2SO4. The full composition of the PM, including carbonaceous material and trace metals, was obtained from
an analysis of 24-hr filter samples. This showed that the mentioned salts comprised about half of the mass, while
almost all of the remainder is “carbon” deriving from the incomplete combustion of the cardboard wrapping.
About 85% of the PM10 is in the more harmful PM2.5.

1. Introduction metallic elements could not be determined. Information on the com-

There are no restrictions in the private use of fireworks during New-
Year's night in The Netherlands. As a result fireworks are ignited in
virtually every street. During stagnant weather this leads to extreme
mass levels of PM10 [Manders et al., 2014]. Concentrations at street
sites can reach levels of over 2000 μg m−3 in the first hour of the New
Year [CLO, 2018]. 24-hr averaged concentrations of over 200 μg m−3,
signifying a very sever smog day, are quite frequent in such years. Si-
milar levels are observed in our neighbouring country Germany [UBA,
2018].
There is little information on the chemical composition of the PM/
aerosol. Drewnick et al., (2006) made measurements with a time-re-
solution of 5 min close to a central site in Mainz, Germany, where
consumer fireworks were lit. The authors indicate that their approach
had some limitations in that the upper diameter size-cut was 0.8 μm. In
addition, the refractory components such as Elemental Carbon and most
position of PM from the fireworks in other countries in Europe might be
less applicable because there high-rising professional fireworks are used
intended for display purposes, with their special effects caused by col-
ouring metallic agents [e.g., Vecchi et al., 2008; Crespo et al., 2012]. In
contrast, consumer fireworks contain a significant fraction of low-level
crackers and the explosives used and their products might be quite
different.
In view of the foregoing it was the objective of the present study to
assess the chemical composition of the products of the fireworks in the
Netherlands. A secondary aim was to assess the actual chemical com-
pounds and to deduce from these the average mix of ingredients of the
explosives/black powder. As guidance for the rest of this study we
should mention that these ingredients are sulphur, carbon and po-
tassium-containing oxidisers such as KNO3 or the more harmful KClO4.
The sulphur and oxidisers form PM products. There are in addition
colouring agents that end up in the PM, like magnesium.

∗
Corresponding author.
E-mail address: htenbrink48@hotmail.com (H. ten Brink).
1
Presently at National Institute for Health and Environment RIVM, Bilthoven, the Netherlands.

https://doi.org/10.1016/j.atmosenv.2019.04.046
Received 31 January 2019; Received in revised form 15 April 2019; Accepted 21 April 2019
Available online 08 May 2019
1352-2310/ © 2019 Elsevier Ltd. All rights reserved.
H. ten Brink, et al.
The composition of the PM is normally assessed by collection and
chemical analysis of filter samples. In such an approach particles con-
taining different reactive compounds are deposited onto each other that
can react in an interaction known as topochemistry. The composition is
thereby not representative for the actual compounds. This prevents
assigning the products to the original ingredients. An example of a to-
pochemical is the presence of Na2SO4 in filter samples in coastal areas.
This compound is in actuality produced in the co-deposition of NaCl
(sea-salt) and H2SO4 particles [Yao et al., 2001]. As a result there is a
Cl−-deficit, because in the reaction HCl-gas is formed that evaporates
from the filter. An analogous reaction was expected here for KCl, the
reduction product of KClO4, and H2SO4 as oxidation product of the
sulphur. This would lead to the formation of K2SO4 and an under-
estimate of the amount of KCl and thus of the parent compound KClO4.
To avoid the indicated topochemical artefacts and to assess the
actual compounds as occurring in the airborne state the on-line
“MARGA” was used. In this instrument particles cannot interact during
collection, because sampling occurs in water in which the compounds
instantaneously dissolve and dilute and possible reactions are im-
mediately quenched. It should be mentioned in this respect that
“MARGA” stands for Monitor for Aerosol and Gases and that HCl that
may form from the oxidiser KClO4 is detectable with the instrument.
The MARGA also measures other gases that may be produced by the
fireworks like SO2 from the sulphur. For assessment of the contribution
of the products of the explosives to the total mass of the PM the full
elemental composition of the PM, including carbon, was measured in
24-hr filter samples.
To be complete we should mention that in China and India con-
sumer fireworks on national holidays lead to levels of PM exceeding
those in the Netherlands. Yang et al., (2014) made a study in which also
an instrument was used that analyses on-line the major inorganic ions.
That investigation is the most comprehensive made this far and there-
fore served as a main reference in the present study.
2. Experimental
2.1. Campaign
Measurements occurred during the turn of the year 2007–2008 and
were part of a longer study to assess the average annual composition of
PM10 and PM2.5 in the Netherlands [Weijers et al., 2011; ten Brink
et al., 2009]. The measurement site was an urban background location
in a business park in Schiedam, a town west of Rotterdam, to be precise
at the premises of Applikon-Metrohm. The site is 200 m north-east of
exit 11 of highway A20 and remote from residential areas and thus not
directly affected by specific local fireworks. The products measured are
thus representative of the generic chemical composition of the PM from
fireworks in the Netherlands.
We first provide background information on the PM10-levels in re-
lation to the meteorological conditions. Both New Year and New Year's
Eve classified as very severe smog days [RIVM, 2008a], viz., with 24-hr
concentrations of over 200 μg m−3, thereby representing the most
polluted period in the past decades [RIVM, 2008b]. The detailed PM10
values are tabulated in Table 1. These are from beta-gauge monitors of
Table 1
PM10-concentrations (in μg m−3) in the hours ending at the indicated time at the turn of the year 2007–2008 in the Rotterdam conurbation. Data, in μg m−3, are for
the street and urban background station described in the text. Wind velocity in m s−1, wind direction in degrees, and visible range in meters are from the
meteorological station at Rotterdam International Airport, 3.5 km NE of the measuring site.
Time hr 19 20 21 22 23
PM10 Street 355 1225 474 163 972
PM10 Urban 166 108 100 219 137
Wind veloc 1 1 1 2 2 1
Wind dir 180 200 var 100 140
Visibility 800 600 500 500 300
Atmospheric Environment 212 (2019) 36–40
the regional air quality network of DCMR [RIVM, 2008a] for a street-
site in the city of Rotterdam, 5.2 km to the SE and a site 5.5 west at a
rather similar urban background setting as the measuring site. The in-
dicated hours span the period that fireworks could be legally lit on
December 31st, 2007 and January 1st, 2008. The data in Table 1 show
that the peak of the fireworks occurred in the hour after midnight, but
that also before midnight appreciable lighting occurred.
The high levels of PM10 can be understood with the detailed data
from the meteorological station of Rotterdam international airport
3.5 km to the NE from the measuring site [KNMI, 2008]. Those data are
provided in Table 1. It is seen that wind speeds during the night were on
average 2 m s−1. Relative humidities were at saturation values as re-
flected in a visual range of less than 1000 m characteristic of fog. The
presence of fog is evidence of the absence of vertical mixing of the air
and of a very low nocturnal surface air layer in which the air pollution
caused by the fireworks could accumulate to the levels as given in
Table 1.
2.2. Instrumentation
At the monitoring site a MARGA (Monitor for measuring the con-
centration of AeRosol and Gases; Metrohm-Applikon BV, Schiedam)
measured on-line the concentration of the major inorganic ions in PM10,
with a time-resolution of 1 h. It provides hourly values. The instrument
has been extensively discussed in literature [Rumsey et al., 2014 and
references therein]. We summarise its operating principle here. The
inorganic ions are collected and measured in the aqueous phase, be-
cause the particles are taken up in water droplets. This is accomplished
by condensation of water vapour that derives from steam added to the
sampling air. The droplets formed in this way are collected in a cyclone
and the ions dissolve in the water. The drain from the collector with the
dissolved ions is split in two with one line feeding into the cation de-
tection loop that is analysed after 1 h of sampling. Similarly the anions
are measured in the second analysis line.
The performance of the MARGA in measuring the concentration of
potassium and magnesium cations has not been presented in detail
before, but is a key factor in evaluating the data on the composition of
the PM from the fireworks that contain substantial quantities of these
ions. A first good performance check for the cations is that for the ratio
of the main cations of sea-salt (Na+ and Mg2+) in strong westerly
winds. The MARGA reproduced this ratio [Manders et al., 2009]. The
average concentration of potassium in the Netherlands is below the
detection limit.
Finally we like to mention that the MARGA also determined the
concentration of possible gaseous products of the fireworks like SO2,
HONO and HNO3, as well as HCl.
At a distance of 600 m to the SW of the site at which the MARGA
was operated 24-hr filters for PM10 and PM2.5 were sampled. Filter
collection occurred every fourth day. Because of the aim to arrive at an
average annual composition for the Netherlands there were no filter-
measurements on the January 1st. This day was intentionally omitted
because it is not representative for the average composition.
Fortunately filters were collected on 31 December. While the peak of
the PM10 occurs after midnight there was ample use of fireworks on
24 1 2 3 4 5 6
823 1548 1057 1313 758 453 137
311 456 586 290 166 292 346
2 1 2 3 2 3
200 var 80 130 110 90 110
100 < 100 < 100 < 100 100 400 < 100
37
H. ten Brink, et al.
December 31st as evidenced by the data in Table 1. This lead to filter
samples with a dominant contribution of the species deriving from the
fireworks, as further discussed in section 3.2.
The filter samples were weighed and analysed for the full range of
components. Two types of filter were used; samples on the quartz fibre
filters were analysed for the major anions and ammonium and for
carbon. Teflon filters were analysed for a large number of elements with
ICP-MS; details of the digestion and analysis procedure can be found in
the open access publication of Weijers et al., (2011).
Details on the sampling and analysis of the carbon are in a report
available via the internet (ten Brink et al., 2009). There was a variable
filter blank which means that the value of carbon for a specific filter
sample is uncertain by an estimated 2 μg m−3. The carbon was spe-
ciated, as usual, as EC and OC.
3. Results and discussion
3.1. Hourly data
3.1.1. Individual ions
The results of the on-line analysis of the ionic composition of the
PM, as monitored during and around the period with the fireworks of
the year 2008, are depicted in Fig. 1 and Fig. 2. These comprise the
hourly averaged concentration values, with collection ending at the
time indicated. It is seen that in the first hour after midnight the mass
concentrations of potassium (K+ ion), sulphate, chloride and ammo-
nium peaked, while that of nitrate did not change. There is a secondary
peak in the 3 d and 4th hour of the New Year. This extended peak is of a
non-local origin because fireworks are finished before 1:00 am. This PM
must derive from the nearby city of Rotterdam advected in the light
easterly winds (Table 1).
The relative concentrations of the ions as seen in Fig. 1 seem
characteristic for the products of the fireworks in Netherlands, because
the composition of the PM advected at 3:00 am was very similar to that
of the more local PM at 1:00 am. PM from the fireworks of the next year
was assessed at a more remote site and its composition was similar to
that obtained here (ten Brink et al., 2018).
The K+ derives from the oxidiser in the black powder which is ei-
ther KClO4 or KNO3. Cl− is the reduction product of the ClO4− and
SO42− is the final oxidation product of the sulphur in the black powder.
The mass ratio of the sulphur in the SO42− and potassium was in ac-
cordance to that in black powder of standard explosive mixtures [e.g.,
Dutcher et al., 1999]. We continue with a more detailed discussion on
the individual ions.
Fig. 1. Concentrations of the major ions in the PM from the fireworks in the
town of Schiedam in the hour starting at the indicated time around New Year
2008. The data are 1-h averaged values, in μg m−3. For clarity the much lower
concentration profile for Mg2+ is not shown.
38
Atmospheric Environment 212 (2019) 36–40
Fig. 2. Concentrations of the major background ions in the PM; same conditions
as in Fig. 1. Note the different scales in the two figures and the peaks for NH4+
after midnight.
Cations. The concentration of K+ was three orders of magnitude
higher than the average value at any other time outside of the period
around New Year. It is thus the best tracer for the PM produced by the
fireworks. The mass concentration of Mg2+ followed that of K+ at an
average ratio of 0.13. The species is a typical colouring agent.
Peaks are also visible for NH4+ above a rather large background, see
Fig. 2. NH4+ is of special interest. Its mass concentration followed the
concentration of nitrate quite closely outside of the period of the fire-
works, see Fig. 2. During the fireworks there were peaks that can be ex-
plained as follows. The initial oxidation product of the sulphur of the
black powder is H2SO4 and this free acid rapidly reacts with NH3, which
was present that day at a concentration of several μg m−3 [RIVM, 2008b].
Anions. SO42− and Cl− had peak concentrations of a similar mag-
nitude as K+. The NO3− concentration did not increase during the time
of the fireworks, as can be deduced from a comparison of its time
variation in Fig. 2 with that of K+ in Fig. 1. Little SO2 formed, as the
measurements with the MARGA showed: there is an increase by
5 μg m−3 in the first hour after midnight compared to that earlier in the
evening. This is a small amount compared to an SO42− concentration of
over 100 μg m−3. SO42− is thus by far the most important oxidation
product of the sulphur in the black powder.
Ion balance. This parameter is the ratio between the sum of the ion-
equivalent values of the cations divided by the sum of that of the an-
ions. This includes the values for the background ions. The ion balance
was close to unity, within the aggregated uncertainties in the mea-
surement of the concentrations of the various components. While the
concentration of Mg2+ is relatively small, it is of major importance as
an ionic species, because it is divalent and has a low atomic weight. It
therefore contributed substantially to the ion balance. The good ion
balance shows that that there is a negligible percentage of H+ from the
initially formed sulphuric acid; see below for a further discussion.
There is an issue to be discussed before proceeding to the next step
of allotting the ions to compounds. SO42− is partly of a non-firework
origin. This is inferred from the much lower ratio of K+ to SO42− in the
periods outside of the peaks of the fireworks, see Fig. 1. We used the
concentration of the background component NO3− during New Year
and New Year's Eve as the reference for the concentration of the
background SO42− to estimate the concentration of SO42− in the
background PM at the time of the fireworks. We arrive at a value of
5 μg m−3 for the background concentration of SO42− during the fire-
works. This leaves a peak concentration for SO42− deriving from the
fireworks of 106 μg m−3, making it the ionic product with the highest
mass concentration.
3.1.2. Chemical compounds and origin
The first product of which the origin is easily identified is KCl. It
must be the reduction product of the oxidiser KClO4 in the black
H. ten Brink, et al.
powder. K+ and Cl− are not present at the same ion-equivalent con-
centrations. There is 30–35% less Cl−. Yet this small difference implies
that the dominant oxidiser in the fireworks is KClO4. The remainder of
the K+ is associated with the other major anion, SO42−. This K2SO4
derives from KNO3 as discussed below. It implies that the average mass
ratio of the oxidisers KClO4 and KNO3 is around two.
The initial product of the oxidation of the sulphur in the black
powder is H2SO4, as discussed above. At combustion temperatures it is
present as a vapour that later on condenses onto existing aerosol par-
ticles. Here it interacts with the prime colouring agent magnesium to
MgSO4. About half of the SO42− is present in this form.
The formation of (NH4)2SO4 was described above. The other salt-
combination of SO42− is K2SO4. This compound can be formed in a
reaction of H2SO4 with KCl. In the interaction Cl− reacts with the H+ of
the sulphuric acid to form HCl that volatilises. However this gaseous
product was not observed by the MARGA. The K2SO4 can thus only be
formed in a reaction of H2SO4 and another potassium salt. The most
likely candidate is K2CO3; this is the final product of a reaction of the
oxidiser KNO3 with the carbon of the black powder.
We like to emphasise that the data are for the bulk chemical com-
position of the inorganic species of the PM. In practice the compounds
are present at different ratios in individual aerosol particles.
We now like to compare our findings with those of Yang et al.,
(2014) who measured the ions with a similar on-line instrument during
consumer fireworks in China. There the major components were K+,
SO42− and Cl− in that order. The concentration of Mg2+ was 5% of that
of K+. We deduce an ion balance of 1.2 from the tabulated data; given
the stated uncertainty of 10% in the data of the individual ions this is
not statistically different from unity, as found by us. Values of the
mentioned ions on days outside of the fireworks period were higher
than in our case. For SO42− the average background concentration was
25% of that on the day of the fireworks. The ratio of K+ (also back-
ground corrected) and SO42− from the fireworks is 1.9. This is higher
than our ratio and also twice that based on the ratio of potassium and
sulphur in standard black powder. The ratio of K+ and Cl− (corrected
for an 8% background contribution) is 1.75. This is the same as our
value of 1.7, given the mentioned measuring uncertainties. Like in our
case, the NO3− concentration was not enhanced during the fireworks.
3.2. 24-Hr filter data
The complete composition of the PM10 deriving from the fireworks
was derived from the analysis of filter samples collected at a site 600 m
SW of the location where the MARGA data were collected. This con-
cerns the concentration of the metals used as colouring agents and of
carbon, discussed in the respective subsections below. It might be in-
dicated beforehand that the contribution of the metals to the mass of
PM is very minor compared to that of the salts presented above and that
of carbon.
3.2.1. Inorganic species
The concentrations as derived from the 24-hr filter samples on 31
December are given in Table 2. The concentrations for the metals are
based on elemental analysis. Because of the day-long sampling the
samples contain relatively small amounts of the components from the
fireworks because that is mostly present in the period after 18:00, as
seen in Fig. 1.
A first finding was that the concentration of K in the PM10 filter
sample was comparable to that averaged from the hourly concentration
of K+ obtained with the MARGA on that day (Fig. 1). This means that K
is fully present in the form of its ion. This also applies for Mg. The filter
samples further provided data on the concentrations of a series of minor
elements. The concentrations of the most abundant of these are given in
Table 2.
The residues of the colouring agents were present at levels highly
elevated compared to those on any other day of the year. However their
39
Atmospheric Environment 212 (2019) 36–40
Table 2
Mass concentrations of the major components of the PM in 24-hr filter samples
at an urban background location in the town of Schiedam on 31 December
2007, in units of μg m−3. The concentration of the elements, including K and
Mg were obtained with ICP-MS.
Al Ba K Mg EC OC NH4+ NO3− SO42- Cl−a PM
PM10 0,7 0,6 5,6 0,9 2,7 12,9 2,1 6,4 10,7 3,9 70,3
PM2.5 0,4 0,5 4,8 0,7 NA NA NA NA NA NA 59,2
a
Cl− corrected for a small sea-salt contribution based on the concentration
of Na.
mass concentrations were low compared to those of the main compo-
nents, as seen from the values of the two most abundant species, Al and
Ba in Table 2. Strontium, also detected by the MARGA, but not quan-
tified, was present at a mass level of 1% of that of K. There is extra
copper at an even lower level. Other elements are present at insignif-
icant concentrations with respect to mass. Aluminium was not present
in ionic form because it was not observed with the MARGA.
The concentration as derived from the filter sample was translated
to that at the peak of the fireworks. This was done via the ratio of K+ as
determined with the MARGA versus that in the 24-hr filter sample. The
total inorganic material then amounts to 280 μg m−3, with an estimated
aggregated uncertainty of 15–20%.
The concentration of the inorganic components is available for two
size-fractions, viz., PM10 and PM2.5. Table 2 indicates that potassium,
the best tracer for the PM from the fireworks, resided for about 85% in
PM2.5. Aluminium was somewhat enriched in the coarse fraction of
PM10; this is most likely due to street-dust suspended by surface-level
explosions, as discussed by Crespo et al., (2012).
Topochemistry. As a corollary the study shows that topochemical
reactions in the filter collection are absent, in the following sense. The
filter samples have an atom-equivalent ratio of Cl− and K of less than
one. This could have been interpreted as a (topo)chemical reaction on
the filter of co-deposited aerosol particles consisting of KCl and H2SO4.
However, the measurements with the MARGA proved that this ratio is
already present in the airborne PM and thus not occurring during col-
lection. This shows that on-line instrumentation is required to assess
such an absence of topochemistry.
3.2.2. Carbon
The concentration of carbon is given in Table 2 as Elemental Carbon
and Organic Carbon (EC and OC respectively). Due to a variable OC
blank the uncertainty in that number can be up to 2 μg m−3, as dis-
cussed in section 2.1. Not all carbon derives from the fireworks. We
made an estimate of the contribution of that carbon using the con-
centration of nitrate on days with stagnant weather as a reference. The
reason is that on such stagnant days the ratio of the two constituents is
quite constant. We then arrive at a mass concentration of EC of
1.5 μg m−3 and 4.5 μg m−3 of OC from sources other than the fire-
works. Thus an estimated 1.2 and 8.4 μg m−3 of EC and OC respectively
derive from the fireworks.
To translate the mass of OC to that of Organic Matter we use a factor
of two as applying for wood combustion [El-Zanan et al., 2012]. The
reason is that the OC derives from the incomplete combustion of the
cardboard wrapping which is made of wood. We thus arrive at a con-
centration of 17 μg m−3 for OM. Together with the EC concentration
this amounts to 18 μg m−3 of carbonaceous material. Using K+ as re-
ference, this translates into a peak mass concentration of OM of
290 μg m−3. This suggests quite a precise figure, but with all mentioned
uncertainties it is not better than an estimate, indicating that the in-
organic and carbonaceous compounds stemming from the fireworks are
present in similar mass proportion in the PM.
H. ten Brink, et al.
3.2.3. Aerosol-water
The large proportion of the mentioned salts in the PM means that a
substantial amount of water is attracted by the particles at the high
relative humidities occurring during stagnant weather, to the extent
that water becomes the major component of the aerosol [ten Brink
et al., 2018]. We showed in the mentioned publication that this uptake
of water leads to a major increase in the scattering of visible light and
that the ionic species thereby govern this low visibility. Another issue is
that the salts take up water in the humid airways and that a substantial
change in size occurs there compared to the size as measured with
aerosol sizing instruments in which the air and aerosol is dried. The
large increase in size should be an issue in assessing the deposition
characteristics in the airways.
3.2.4. Comparison with chemical composition elsewhere in Europe
Comparison with the results in Mainz [Drewnick et al., 2006] is of
most relevance because the PM there also derived from consumer
fireworks and it was also analysed with on-line instrumentation.
However those date can only be qualitative compared with ours be-
cause the composition is for “PM0.8” and furthermore Mg was not de-
termined. The ratio of K to S was similar to our ratio. This can be seen as
supporting the use of that ratio Drewnick et al. as calibration for their
K-concentration. The ratio of the mass concentrations of Cl and K was
only 10%, compared to 60% in our study. This is highly indicative that
the black powder predominantly contains KNO3.
A comparison with the fireworks at the other sites in Europe is not
straightforward because filter sampling was applied there and compo-
nents might be underestimated because of topochemical reactions. In
Milan (Vecchi et al., 2008) no enhanced level of SO42− was seen during
the fireworks; there was a marginal increase in Cl and a substantial
enhancement in the NO3−-level. The authors do not dwell upon these
unusual findings and we also do not know how to interpret these re-
sults. Mg was present at a higher atom-equivalent concentration than K;
this is indicative that the fireworks were for display with the light-ef-
fects induced by the magnesium. In Eastern Spain [Crespo et al., 2012]
the Cl-deficit was 40%. This means that at least 60% of the oxidisers
was present as KClO3.
4. Conclusions
The extreme levels of PM occurring in the night of December 31st,
2007/January 1st, 2008 were caused by lighting of fireworks in a
period of stagnant weather.
It was only with the use of on-line instrumentation that the actual
composition of the PM products could be assessed. This enabled
quantification of the explosive mix of the fireworks, in the sense that it
could be concluded that the explosive mixture consists of standard
black powder. However, the main oxidiser is KClO4 instead of KNO3.
This latter also appears to apply for the fireworks studied by Yang et al.
in China [2014].
Other inferences are the following. The PM from the consumer
fireworks during New-Year in the Netherlands derive for about half
from the explosives. These products are present in the form of highly
hygroscopic salts of which KCl, MgSO4 and K2SO4 are the main com-
ponents. Carbonaceous compounds, deriving from incomplete com-
bustion of the cardboard wrapping, comprise the other half of the PM-
mass. 85% of the PM10 was in the more harmful PM2.5.
Finally the following was concluded with respect to the fate of the
sulphur of the explosive mixture. H2SO4 is the major combustion pro-
duct, with only a few percent of SO2 formed. The H2SO4 reacts with the
main alkaline components, viz. magnesium and K2CO3 (the final pro-
duct of the oxidiser KNO3), to form the mentioned SO42--salts.
Conflicts of interest
None.
40
Atmospheric Environment 212 (2019) 36–40
Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The study was performed in the Netherlands Research Program on
Particulate Matter (BOP), a national program on PM10 and PM2.5, and
partly in the Dutch Climate Change and Spatial Planning program BSIK
Klimaat voor Ruimte. Both programmes were supported by the former
ministry of Housing, Spatial Planning and the Environment (VROM).
Data from the MARGA were kindly made available by Metrohm-
Applikon BV, Schiedam. We are indebted to two anonymous reviewers
for improvement of the original manuscript.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.atmosenv.2019.04.046.
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