a message to partygoers on new year‘s eve smoke signals

GERSTEL Solutions Worldwide Application

A message to partygoers on New Year‘s eve

Fireworks weave beautiful patterns in the night skies and fl eetingly 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 fi recrackers. While these visual and acoustic impressions never cease to excite and please onlookers, our respiratory system begs to differ. The air quality plummets towards levels last seen in areas with heavy industry and coal heating in days of yore. Every rocket fi red on New Year’s Eve releases signifi cant amounts of fi ne particulate matter according to the German Federal Environmental Agency (UBA). Incidentally, just because particulate matter is labeled “fi ne” that doesn’t mean it is good or healthy. Rather, the “fi ne” 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 signifi cant amounts by fi reworks.

Smoke signals

Kaj Petersen, Marketing Manager GERSTEL

by Kaj Petersen


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 ex-cessive alcohol consumption. It could be re-lated 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 be-fore as more and more fi reworks were sent off into the skies. Even as eyes are burning and we start wheezing and coughing, tradi-tion is adhered to and we duly continue to send off the old year and welcome in the new

with loud and beautiful displays of joy. Han-dling fi reworks poses a challenge in terms of keeping fi ngers, hands, face and eyes out of harm’s way. Other, less visible, harm can be done when fi reworks 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 accompany-ing cocktail of toxic chemicals. The particu-late 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 na-ked eye. The German Federal Environmen-tal Agency (UBA) website provides the fol-

lowing information: “Fine particulate mat-ter has a proven negative impact on health. With decreasing particle size, the risk to our health increases”.

Ongoing and recent monitoring in Ger-many has shown that levels of toxic partic-ulate matter on New Year’s Eve are higher than on any other day of the year: In the fi rst 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 concentra-tion measured at inner city monitoring sta-tions in Germany throughout 2006 was only around 30 μg per cubic meter air.

Halogenated and aromatic compounds Isoparaffi nic compounds

1,1-Dichloroethylene Bromobenzene Isopentane

Methylene chloride 1,3,5-Trimethylbenzene 2,3-Dimethylbutane

trans-1,2-Dichloroethane 2-Chlorotoluene 2-Methylpentane

1,1-Dichloroethane 4-Chlorotoluene 3-Methylpentane

2,2-Dichloropropane tert-Butylbenzene 2,2-Dimethylpentane

cis-1,2-Dichloroethylene 1,2,4-Trimethylbenzene 2,4-Dimethylpentane

Chloroform sec-Butylbenzene 2,2,3-Trimethylbutane

Bromochloromethane 4-Isopropyltoluene 3,3-Dimethylpentane

1,1,1-Trichloroethane 1,3-Dichlorobenzene 2-Methylhexane

1,1-Dichloropropene 1,4-Dichlorobenzene 2,3-Dimethylpentane

Carbon tetrachloride n-Butylbenzene 3-Methylhexane

1,2-Dichloroethane 1,2-Dichlorobenzene 3-Ethylpentane

Benzene 1,2-Dibromo-3-chloropropane 2,2-Dimethylhexane

Trichloroethane 1,2,4-Trichlorobenzene 2,5-Dimethylhexane

1,2-Dichloropropane Hexachlorobutadiene 2,2,3-Trimethylpentane

Bromodichloromethane Naphthalene 2,4-Dimethylhexane

Dibromomethane 1,2,3-Trichlorobenzene 2,3-Dimethylhexane

cis-1,3-Dichloropropene 2-Methylheptane

Toluene 4-Methylheptane

trans-1,3-Dichloropropene 3-Methylheptane

1,1,2-Trichloroethane 3-Ethylhexane

1,3-Dichloropropane 2,5-Dimethylheptane

Tetrachloroethane 3,5-Dimethylheptane(D)

Dibromochloromethane 3,3-Dimethylheptane

1,2-Dibromoethane 3,5-Dimethylheptane(L)

Chlorobenzene 2,3-Dimethylheptane

1,1,1,2-Tetrachloroethane 3,4-Dimethylheptane(D)

Ethylbenzene 3,4-Dimethylheptane(L)

m-Xylene 2-Methyloctane

p-Xylene 3-Methyloctane

o-Xylene 3,3-Diethylpentane

Styrene 2,2-Dimethyloctane

Isopropylbenzene 3,3-Dimethyloctane

Bromoform 2,3-Dimethyloctane

1,1,2,2-Tetrachloroethane 2-Methylnonane

1,2,3-Trichloropropane] 3-Ethyloctane

n-Propylbenzene 3-Methylnonane

Olefi nic compounds Naphthtenic compounds

3-Methyl-1-Butene cyclopentene

1-Pentene Methylcyclopentane

2-Methyl-1-Butene Cyclohexane

2-Methyl-1,3-Butadiene 1,1-Dimethylcyclopentane

trans-2-Pentene cis-1,3-Dimethylcyclopentane

cis-2-Pentene trans-1,3-Dimethylcyclopentane

4-Methyl-1-Pentene trans-1,2-Dimethylcyclopentane

1-Hexene Methylcyclohexane

trans-2-Hexene Ethylcyclopentane

2-Methyl-2-Pentene ctc-1,2,4-Trimethylcyclopentane

cis-2-Hexene ctc-1,2,3-Trimethylcyclopentane

1-Heptene cct-1,2,4-Trimethylcyclopentane

trans-3-Heptene trans-1,4-Dimethylcyclohexane

cis-3-Heptene 1-Ethyl-1-Methylcyclopentane

trans-2-Heptene trans-1,2-Dimethylcyclphexane

cis-2-Heptene ccc-1,2,3-Trimethylcyclopentane

1-Octene Isopropylcyclopentane

trans-2-Octene cis-1,2-Dimethylcyclopentane

cis-2-Octene n-propylcyclopentane

1-Nonene ccc-1,3,5-Trimethylcyclohexane

trans-3-Nonene 1,1,4-Trimethylcyclohexane

cis-3-Nonene ctt-1,2,4-Trimethylcyclohexane

trans-2-Nonene ctc-1,2,4-Trimethylcyclohexane

cis-2-Nonene 1,1,2-Trimethylcyclohexane

1-Decene Isobutylcyclopentane

Isopropylcyclohexane

n-Butylcyclopentane

Isobutylcyclohexane

t-1-Methyl-2-Propylcyclohexane

t-1-Methyl-2(4MP)Propylcyclopentane

Table: List of determined Hazardous Air Pollutants (HAPs)

21GERSTEL Solutions Worldwide – February 2008


Technical and analysis detail In addition to particulate matter, the fumes released during and after the combustion of fire-work materials contain signifi-cant amounts of Hazardous Air Pollutants (HAPs). This is the conclusion reached by scientists at the Pukyong National Univer-sity in Busan, Korea. Since fireworks are among the favorite pastimes of Koreans, the scientists set out to determine the environ-mental impact of fi reworks and the qual-ity 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 fi reworks: Air sam-ples were taken at a beach in Haeundae in the summer season, when tourists light up an estimated 1,000 – 2,000 fi recrackers per night, or 50,000 – 100,000 per season pur-suing their pyrotechnical hobby.

For comparison, air samples were drawn in the urban area around the uni-versity where fi recracker fuses are rarely, if ever, lit as a leisure activity.

“In order to provide quantitative results and solid conclusions“, Prof. Gon Ok ex-plains, “we developed a special reactor in

which we can explode fi reworks under con-trolled laboratory conditions while sam-pling the emitted gases for analysis.

The resulting gases were sampled using the GERSTEL Gas Sampler GS 1 directly at-tached to the fi reworks reactor. Gas sam-ples were drawn onto thermal desorption tubes fi lled with carbon-based absorbents, Carbosieve S-III, Carbopack B, and Car-bopack C. Sampling and analysis was per-formed following US-EPA method TO-17: “Determination of Volatile Organic Com-pounds in Ambient Air Using Active Sam-pling Onto Sorbent Tubes”. The tubes were subsequently thermally desorbed using a GERSTEL Thermal Desorption System

Adsorbent Packing of Thermal desorption tube.

Schematic diagram of a reactor system used for fi recrackers.

Prof. Gon Ok from the Department of Earth Environmental Engineering at the Pukyong National University.

GERSTELGas Sampler GS 1



(TDS) and the analytes were refocused in the Cooled Injection System (CIS) mount-ed 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 identifi -cation and quantifi cation were performed using an Agilent MSD 5973.

Thermal desorption of analytes from the TDS tube was performed using a tempera-ture 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 per-formed 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 tempera-ture program started at 30 °C, with an ini-tial hold time of 5 minutes. The oven was fi rst 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 DiscussionIn total, around 150 different HAPs were detected in the gases emitted from the fi re-works reactor. Among these were 60 dif-ferent aromatic compounds, 35 isoparaf-fi nes, 20 olefi nes and 30 naphthenes (see ta-

ble). Armed with this knowledge, the scien-tists 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 Na-tional University, were between 2.5 ppb and 42 ppb as an annual average. BTEX com-pounds made up 99.9 percent of the to-tal concentration of aromatic compounds. HAP concentrations at the beach frequent-ed by the noise-loving pyrotechnic enthu-siasts were normally around a factor of ten higher for m- and p-xylene and a factor of 400 higher for benzene. The BTEX con-tribution was 69 percent and at 1,260 ppb the concentration was signifi cantly higher

Total ion chromatograms of HAPs by GC/MSTotTotTotalalaa ionionon ch chchhromromrommatoatotogragragramsmsms ofofofof HAPHAPHAPHAPs bs bs bs bs by Gy Gy Gy Gy Gy GC/MC/MC/MC/MC/MC/MC/ SSSS



than the levels measured at the reference site. „Setting off fi recrackers has a tremen-dous infl uence on air quality”, the scien-tists conclude.

Professor Gon Ok and his colleagues have come to a clear and unequivocal con-clusion: They are proposing changes in leg-islation that would restrict the use of fi re-works in order to protect the health of peo-ple living in affected areas.

In Germany, scientists involved are not ready to go quite that far. The approach tak-en is more cautious in spite of clear evi-dence as to the pollution caused by fi re-works. 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 lim-iting the amount of fi ne particulate matter released into our atmosphere on New Year’s Eve. Please reduce or completely eliminate your personal fi reworks. In this way you will not only help improve the environment di-rectly, you will help eliminate garbage from packaging material and spent fireworks while also reducing the amount of energy needed for fi reworks production.”

Concentrations of HAPs in the squib reactor

Aromatic compounds Spring (ppb) Summer (ppb) Autumn (ppb) Winter (ppb)

Benzene 2.50 1.70 N.D.* 0.84

Toluene 5.99 2.43 1.57 7.25

Ethylbenzene 9.80 0.39 0.25 1.19

m,p-Xylene 8.88 0.45 0.34 1.82

Styrene 1.94 0.11 N.D.* 1.18

o-Xylene 6.27 0.28 0.20 1.45

Bromobenzene N.D.* N.D.* N.D.* N.D.*

n-Propylbenzene 0.90 0.03 N.D. 0.62

1,2,4-Trimetylbenzene 4.80 0.16 0.09 2.82

tert-Butylbenzene N.D. N.D. N.D. N.D.

sec-Butylbenzene N.D. N.D. N.D. N.D.

n-Butylbenzene N.D. N.D. N.D. 0.28

Sum 41.1 5.55 2.45 17.5

BTEX 33.4 5.25 2.36 12.6

Concentrations of HAPs in Haeundae beach air during fi rework

Seasonal variations in concentration for various aromatic compounds



Halogenated and

aromatic compounds ppb Isoparaffi nic compounds ppb

Dichloromethane 2877 3-Methylpentane 26.59

trans-1,2-Dichloroethylene 2005 2,4-Dimethylhexane 0.065

1,1-Dichloroethane 1106 Sum 26.66

Chloroform 6.085

Benzene 91360 Olefi nic compounds ppb

Trichloroethylene 26.21 3-Methyl-1-butene 14.71

Toluene 6954 1-Pentene 43.29

Chlorobenzene 284.0 2-Methyl-1-butene 19.08

Ethylbenzene 818.4 cis-2-Pentene 19.44

m,p-Xylene 484.8 2-Methyl-1,3-butadiene 11.34

o-Xylene 699.2 1-Hexene 18.42

Styrene 2133 trans-2-Hexene 2.762

Isopropylbenzene 22.13 2-Methylpentene-2 0.326

n-Propylbenzene 57.26 cis-2-Hexene 0.108

1,3,5-Trimethylbenzene 28.45 1-Heptene 2.304

2-chlorotoluene 1.135 trans-3-Heptene 0.205

tert-Butylbenzene 0.000 trans-2-Heptene 0.128

1,2,4-Trimethylbenzene 99.76 1-Octene 2.449

sec-Butylbenzene 1.403 1-Nonene 2.604

p-Isopropyltoluene 41.34 cis-2-Nonene 0.283

1,3-Dichlorobenzene 10.82 1-Decene 4.804

1,4-Dichlorobenzene 1.047 Sum 142.3

n-Butylbenzene 24.31

1,2-Dichlotobenzene 0.696 Naphthenic compounds ppb

1,2,4-Trichlorobenzene 2.100 Methylcyclopentane 0.792

Naphthalene 422.8 trans-1,3-Dimethylcyclopentane 2.245

1,2,3-Trichlorobenzene 2.260 cct-1,2,4-Trimethylcyclopentane 3.392

Sum 109500 Sum 6.429

Halogenated and

aromatic compounds ppb Isoparaffi nic compounds ppb

Dichloromethane 476 2-Methylheptane N.D.

Benzene 690 3-Methylheptane N.D.

Toluene 557 2-Methyloctan N.D.

Ethylbenzene 6.05 3-Methyloctan N.D.

m,p-xylene 4.66 Sum -

O-xylene 3.58 Olefi nic compounds ppb

Styrene 9.84 1-Pentene 41.1

Isopropylbenzene 0.33 1-Heptene 12.2

n-Propylbenzene 0.93 1-Decene 8.56

1,3,5-Trimethylbenzene 1.04 Sum 61.9

1,2,4-Trimethylbenzene 3.27 Naphthenic compounds ppb

1,4-Dichlorobenzene 1.51 Methylcyclopentane 9.90

Naphthalene 1.49 Methylcyclohexane 0.68

1,2,3-Trichlorobenzene N.D. t-1-Methyl-2-(4MP)cyclopentane 0.05

Sum 1760 Sum 10.6


a message to partygoers on new year‘s eve smoke signals

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