GERSTEL Solutions Worldwide Application
A message to partygoers on New Year‘s eve
Smoke signals
by Kaj Petersen
Fireworks weave beautiful patterns in the night skies and fleetingly
place brightly colored stars in the canopy above us. Closer to the
ground we are awed by fountains of shooting stars, beautiful suns
and loud firecrackers. While these visual and acoustic impressions
never cease to excite and please onlookers, our respiratory system Kaj Petersen,
begs to differ. The air quality plummets towards levels last seen in Marketing Manager
GERSTEL
areas with heavy industry and coal heating in days of yore. Every
rocket fired on New Year’s Eve releases significant amounts of
fine particulate matter according to the German Federal Environmental Agency
(UBA). Incidentally, just because particulate matter is labeled “fine” that doesn’t
mean it is good or healthy. Rather, the “fine” particles are small enough to
penetrate to the inner reaches of our lungs, from where they can no longer be
exhaled. They then proceed onward through the blood vessels or the lymphatic
system to the entire body, potentially carrying a load of toxic chemicals with
them. Scientists from Korea have now shown that Hazardous Air Pollutants
(HAPs) are also released in significant amounts by fireworks.
GERSTEL Solutions Worldwide Application
Halogenated and aromatic compounds
1,1-Dichloroethylene
Bromobenzene
Methylene chloride
1,3,5-Trimethylbenzene
trans-1,2-Dichloroethane
2-Chlorotoluene
1,1-Dichloroethane
4-Chlorotoluene
2,2-Dichloropropane
tert-Butylbenzene
cis-1,2-Dichloroethylene
1,2,4-Trimethylbenzene
Chloroform
sec-Butylbenzene
Bromochloromethane
4-Isopropyltoluene
1,1,1-Trichloroethane
1,3-Dichlorobenzene
1,1-Dichloropropene
1,4-Dichlorobenzene
Carbon tetrachloride
n-Butylbenzene
1,2-Dichloroethane
1,2-Dichlorobenzene
Benzene
1,2-Dibromo-3-chloropropane
Trichloroethane
1,2,4-Trichlorobenzene
1,2-Dichloropropane
Hexachlorobutadiene
Bromodichloromethane
Naphthalene
Dibromomethane
1,2,3-Trichlorobenzene
cis-1,3-Dichloropropene
Toluene
trans-1,3-Dichloropropene
1,1,2-Trichloroethane
1,3-Dichloropropane
Tetrachloroethane
Dibromochloromethane
1,2-Dibromoethane
Chlorobenzene
1,1,1,2-Tetrachloroethane
Ethylbenzene
m-Xylene
p-Xylene
o-Xylene
Styrene
Isopropylbenzene
Bromoform
1,1,2,2-Tetrachloroethane
1,2,3-Trichloropropane]
n-Propylbenzene
I
f your first and foremost sensation on
New Year’s Day is a throbbing headache,
accompanied by a desire to spend the rest
of the year in bed, it need not be due to excessive alcohol consumption. It could be related to the noise levels experienced on New
Year’s Eve. Equally the culprits could be the
increasing levels of Hazardous Air Pollutants
(HAPs) accompanied by particulate matter
that you have been inhaling the night before as more and more fireworks were sent
off into the skies. Even as eyes are burning
and we start wheezing and coughing, tradition is adhered to and we duly continue to
send off the old year and welcome in the new
Isoparaffi nic compounds
Isopentane
2,3-Dimethylbutane
2-Methylpentane
3-Methylpentane
2,2-Dimethylpentane
2,4-Dimethylpentane
2,2,3-Trimethylbutane
3,3-Dimethylpentane
2-Methylhexane
2,3-Dimethylpentane
3-Methylhexane
3-Ethylpentane
2,2-Dimethylhexane
2,5-Dimethylhexane
2,2,3-Trimethylpentane
2,4-Dimethylhexane
2,3-Dimethylhexane
2-Methylheptane
4-Methylheptane
3-Methylheptane
3-Ethylhexane
2,5-Dimethylheptane
3,5-Dimethylheptane(D)
3,3-Dimethylheptane
3,5-Dimethylheptane(L)
2,3-Dimethylheptane
3,4-Dimethylheptane(D)
3,4-Dimethylheptane(L)
2-Methyloctane
3-Methyloctane
3,3-Diethylpentane
2,2-Dimethyloctane
3,3-Dimethyloctane
2,3-Dimethyloctane
2-Methylnonane
3-Ethyloctane
3-Methylnonane
Olefinic compounds
3-Methyl-1-Butene
1-Pentene
2-Methyl-1-Butene
2-Methyl-1,3-Butadiene
trans-2-Pentene
cis-2-Pentene
4-Methyl-1-Pentene
1-Hexene
trans-2-Hexene
2-Methyl-2-Pentene
cis-2-Hexene
1-Heptene
trans-3-Heptene
cis-3-Heptene
trans-2-Heptene
cis-2-Heptene
1-Octene
trans-2-Octene
cis-2-Octene
1-Nonene
trans-3-Nonene
cis-3-Nonene
trans-2-Nonene
cis-2-Nonene
1-Decene
Naphthtenic compounds
cyclopentene
Methylcyclopentane
Cyclohexane
1,1-Dimethylcyclopentane
cis-1,3-Dimethylcyclopentane
trans-1,3-Dimethylcyclopentane
trans-1,2-Dimethylcyclopentane
Methylcyclohexane
Ethylcyclopentane
ctc-1,2,4-Trimethylcyclopentane
ctc-1,2,3-Trimethylcyclopentane
cct-1,2,4-Trimethylcyclopentane
trans-1,4-Dimethylcyclohexane
1-Ethyl-1-Methylcyclopentane
trans-1,2-Dimethylcyclphexane
ccc-1,2,3-Trimethylcyclopentane
Isopropylcyclopentane
cis-1,2-Dimethylcyclopentane
n-propylcyclopentane
ccc-1,3,5-Trimethylcyclohexane
1,1,4-Trimethylcyclohexane
ctt-1,2,4-Trimethylcyclohexane
ctc-1,2,4-Trimethylcyclohexane
1,1,2-Trimethylcyclohexane
Isobutylcyclopentane
Isopropylcyclohexane
n-Butylcyclopentane
Isobutylcyclohexane
t-1-Methyl-2-Propylcyclohexane
t-1-Methyl-2(4MP)Propylcyclopentane
Table: List of determined Hazardous Air Pollutants (HAPs)
with loud and beautiful displays of joy. Handling fireworks poses a challenge in terms of
keeping fingers, hands, face and eyes out of
harm’s way. Other, less visible, harm can be
done when fireworks do what they do best
– burn at high temperatures. The “smoke”
we see is largely made up of aerosols and of
particulate matter (PM) and an accompanying cocktail of toxic chemicals. The particulate matter that is of most interest, in terms
of health effects, is PM10. These are particles
that are less than 10 μm in diameter (< 0.01
mm O.D.) and thus not visible to the naked eye. The German Federal Environmental Agency (UBA) website provides the fol-
lowing information: “Fine particulate matter has a proven negative impact on health.
With decreasing particle size, the risk to our
health increases”.
Ongoing and recent monitoring in Germany has shown that levels of toxic particulate matter on New Year’s Eve are higher
than on any other day of the year: In the first
hours of 2007, inner city PM10 levels of up to
4,000 μg/m3 were measured (4,000 μg/m3 =
4,000 micrograms PM10 per cubic meter air).
For comparison, the mean PM10 concentration measured at inner city monitoring stations in Germany throughout 2006 was only
around 30 μg per cubic meter air.
GERSTEL Solutions Worldwide – February 2008
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GERSTEL Solutions Worldwide Application
Prof. Gon Ok from the Department
of Earth Environmental Engineering
at the Pukyong National University.
GERSTEL
Gas Sampler GS 1
Schematic diagram of a reactor
system used for firecrackers.
Adsorbent Packing of Thermal desorption tube.
Technical and analysis detail
In addition to particulate matter, the fumes
released during and after the combustion
of fire-work materials contain significant amounts of Hazardous Air Pollutants
(HAPs). This is the conclusion reached by
scientists at the Pukyong National University in Busan, Korea. Since fireworks are
among the favorite pastimes of Koreans, the
scientists set out to determine the environmental impact of fireworks and the quality of the air breathed by those in the area
where the spectacle unfolds. In short, the
goal of the project was to get quantitative
data about HAP concentrations. Prof. Gon
Ok and his colleagues from the Department
of Earth Environmental Engineering at the
Pukyong National University proceeded as
follows to determine the increase in HAP
concentrations during fireworks: Air samples were taken at a beach in Haeundae in
the summer season, when tourists light up
an estimated 1,000 – 2,000 firecrackers per
night, or 50,000 – 100,000 per season pursuing their pyrotechnical hobby.
For comparison, air samples were
drawn in the urban area around the university where firecracker fuses are rarely, if
ever, lit as a leisure activity.
“In order to provide quantitative results
and solid conclusions“, Prof. Gon Ok explains, “we developed a special reactor in
which we can explode fireworks under controlled laboratory conditions while sampling the emitted gases for analysis.
The resulting gases were sampled using
the GERSTEL Gas Sampler GS 1 directly attached to the fireworks reactor. Gas samples were drawn onto thermal desorption
tubes filled with carbon-based absorbents,
Carbosieve S-III, Carbopack B, and Carbopack C. Sampling and analysis was performed following US-EPA method TO-17:
“Determination of Volatile Organic Compounds in Ambient Air Using Active Sampling Onto Sorbent Tubes”. The tubes were
subsequently thermally desorbed using a
GERSTEL Thermal Desorption System
GERSTEL Solutions Worldwide – February 2008
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GERSTEL Solutions Worldwide Application
Total
Tot
a ion
al
on ch
chromatograms
hrom
mato
togra
grams
gra
ms of HAP
HAPss by
by GC/M
G
GC/MS
C/ S
C/M
(TDS) and the analytes were refocused in
the Cooled Injection System (CIS) mounted in an Agilent Technologies GC 6890.
TDS tubes packed with the same types of
adsorbent were used to sample air at the
beach of Haeundae. Compound identification and quantification were performed
using an Agilent MSD 5973.
Thermal desorption of analytes from the
TDS tube was performed using a temperature program: The starting temperature was
set to 30 °C, ramping at a rate of 60 °C/min
to an end temperature of 220 °C. Helium
carrier gas was used. Cryofocusing was performed at -50 °C in the CIS. The CIS was
subsequently heated at a rate of 8 °C per sec-
ond to 220 °C, transferring the analytes to
the GC column (Supelco VOCOL, 60 m x
320 μm x 1.8 μm). The GC oven temperature program started at 30 °C, with an initial hold time of 5 minutes. The oven was first
ramped at 3 °C/min to 60 °C, followed by a
second ramp at 5 °C/min to 150 °C and a third
ramp of 2 °C/min to the end temperature of
190 °C, which was held for 2 minutes.
Results and Discussion
In total, around 150 different HAPs were
detected in the gases emitted from the fireworks reactor. Among these were 60 different aromatic compounds, 35 isoparaffines, 20 olefines and 30 naphthenes (see ta-
ble). Armed with this knowledge, the scientists went about analyzing air samples from
the beach at Haeundae.
The results were a wake-up call. Inner
city air levels of HAPs near the Pukyong National University, were between 2.5 ppb and
42 ppb as an annual average. BTEX compounds made up 99.9 percent of the total concentration of aromatic compounds.
HAP concentrations at the beach frequented by the noise-loving pyrotechnic enthusiasts were normally around a factor of ten
higher for m- and p-xylene and a factor of
400 higher for benzene. The BTEX contribution was 69 percent and at 1,260 ppb
the concentration was significantly higher
GERSTEL Solutions Worldwide – February 2008
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GERSTEL Solutions Worldwide Application
Concentrations of HAPs in the squib reactor
Halogenated and
aromatic compounds
Dichloromethane
trans-1,2-Dichloroethylene
1,1-Dichloroethane
Chloroform
Benzene
Trichloroethylene
Toluene
Chlorobenzene
Ethylbenzene
m,p-Xylene
o-Xylene
Styrene
Isopropylbenzene
n-Propylbenzene
1,3,5-Trimethylbenzene
2-chlorotoluene
tert-Butylbenzene
1,2,4-Trimethylbenzene
sec-Butylbenzene
p-Isopropyltoluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Butylbenzene
1,2-Dichlotobenzene
1,2,4-Trichlorobenzene
Naphthalene
1,2,3-Trichlorobenzene
Sum
GERSTEL
Gas Sampler GS 1
ppb
2877
2005
1106
6.085
91360
26.21
6954
284.0
818.4
484.8
699.2
2133
22.13
57.26
28.45
1.135
0.000
99.76
1.403
41.34
10.82
1.047
24.31
0.696
2.100
422.8
2.260
109500
Concentrations of HAPs in Haeundae beach air during firework
Isoparaffinic compounds
3-Methylpentane
2,4-Dimethylhexane
Sum
ppb
26.59
0.065
26.66
Olefinic compounds
3-Methyl-1-butene
1-Pentene
2-Methyl-1-butene
cis-2-Pentene
2-Methyl-1,3-butadiene
1-Hexene
trans-2-Hexene
2-Methylpentene-2
cis-2-Hexene
1-Heptene
trans-3-Heptene
trans-2-Heptene
1-Octene
1-Nonene
cis-2-Nonene
1-Decene
Sum
ppb
14.71
43.29
19.08
19.44
11.34
18.42
2.762
0.326
0.108
2.304
0.205
0.128
2.449
2.604
0.283
4.804
142.3
Naphthenic compounds
Methylcyclopentane
trans-1,3-Dimethylcyclopentane
cct-1,2,4-Trimethylcyclopentane
Sum
ppb
0.792
2.245
3.392
6.429
Halogenated and
aromatic compounds
Dichloromethane
Benzene
Toluene
Ethylbenzene
m,p-xylene
O-xylene
Styrene
Isopropylbenzene
n-Propylbenzene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
1,4-Dichlorobenzene
Naphthalene
1,2,3-Trichlorobenzene
Sum
Isoparaffinic compounds
2-Methylheptane
3-Methylheptane
2-Methyloctan
3-Methyloctan
Sum
Olefinic compounds
1-Pentene
1-Heptene
1-Decene
Sum
Naphthenic compounds
Methylcyclopentane
Methylcyclohexane
t-1-Methyl-2-(4MP)cyclopentane
Sum
ppb
N.D.
N.D.
N.D.
N.D.
ppb
41.1
12.2
8.56
61.9
ppb
9.90
0.68
0.05
10.6
Seasonal variations in concentration for various aromatic compounds
Aromatic compounds
Benzene
Toluene
Ethylbenzene
m,p-Xylene
Styrene
o-Xylene
Bromobenzene
n-Propylbenzene
1,2,4-Trimetylbenzene
tert-Butylbenzene
sec-Butylbenzene
n-Butylbenzene
Sum
BTEX
than the levels measured at the reference
site. „Setting off firecrackers has a tremendous influence on air quality”, the scientists conclude.
Professor Gon Ok and his colleagues
have come to a clear and unequivocal conclusion: They are proposing changes in legislation that would restrict the use of fireworks in order to protect the health of people living in affected areas.
GERSTEL
Gas Sampler GS 1
ppb
476
690
557
6.05
4.66
3.58
9.84
0.33
0.93
1.04
3.27
1.51
1.49
N.D.
1760
Spring (ppb)
2.50
5.99
9.80
8.88
1.94
6.27
N.D.*
0.90
4.80
N.D.
N.D.
N.D.
41.1
33.4
Summer (ppb)
1.70
2.43
0.39
0.45
0.11
0.28
N.D.*
0.03
0.16
N.D.
N.D.
N.D.
5.55
5.25
Autumn (ppb)
N.D.*
1.57
0.25
0.34
N.D.*
0.20
N.D.*
N.D.
0.09
N.D.
N.D.
N.D.
2.45
2.36
Winter (ppb)
0.84
7.25
1.19
1.82
1.18
1.45
N.D.*
0.62
2.82
N.D.
N.D.
0.28
17.5
12.6
In Germany, scientists involved are not
ready to go quite that far. The approach taken is more cautious in spite of clear evidence as to the pollution caused by fireworks. The UBA on its homepage appeals
to common sense: “Traditions and customs
are part of our lives and should remain so.
We are, however, asking you for help in limiting the amount of fine particulate matter
released into our atmosphere on New Year’s
Eve. Please reduce or completely eliminate
your personal fireworks. In this way you will
not only help improve the environment directly, you will help eliminate garbage from
packaging material and spent fireworks
while also reducing the amount of energy
needed for fireworks production.”
GERSTEL Solutions Worldwide – February 2008
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