Effects of Fire Conditions on the Formation of Polycyclic Aromatic

Effects of fire conditions on the formation of Centre for Fire and polycyclic aromatic hydrocarbons (PAHs): Hazards Science Sampling and analysis of fire effluents

Presented by:

Dr Abdulrhman M Dhabbah a,b aCentre for Fire and Hazards Science, University of Central Lancashire,Preston, UK bDepartment of Forensic Science, King Fahad Security College, Riyadh, Saudi Arabia Effects of fire conditions on the formation of Centre for Fire and polycyclic aromatic hydrocarbons (PAHs): Hazards Science Sampling and analysis of fire effluents Overview •Introduction •Factors affecting fire •Characterization of Polycyclic Aromatic Hydrocarbons (PAHs) •PAH’s generation and analysis •Different methods of sampling •Results •Conclusions Centre for Fire and Hazards Science

Introduction Since 1950s there have been increasing quantities of synthetic polymer materials derived from crude oil. These materials used for construction, transport, electrical and electronic equipment, furniture etc. These materials make life easier and more comfortable.

However, these materials are easier for ignition and flame spread, accompanied by significant release of toxic combustion products. Centre for Fire and What is in fire? Hazards Science

Majority of the toxic organic compounds such as volatile organic compounds (VOCs) or semi-volatile organic compounds (SOVCs) including polycyclic aromatic hydrocarbons (PAHs) are formed and released in fires, particularly as a result of incomplete combustion.

Exposure to some of these compounds may show both acute and chronic toxicity. The acute and chronic effects can occur immediately or over a couple of weeks. Painful sensory irritation occurs immediately in the upper respiratory tract, while lung inflammation and pulmonary oedema occur several days after exposure deeper in the lung

Subsequence to exposure of these compounds may result in different types of cancers as documented in fire fighters, who are subject to more frequent exposure. Factors affecting fire Centre for Fire and Hazards Science

Fire toxicity

Acute Chronic

Volatile and semi- Halogenated dibenzo-p-dioxins volatile organic Asphyxiants Irritants Isocyanates and dibenzo compounds furans (VOCs),(SVOCs)

Acrolein and 12378 12378 Methyl isocyanate Pentachlorodibenzo- Pentachlorodibenz (CO) Formaldehyde Polycyclic (MIC) p-dioxin(1,2,3,7,8- ofuran (1,2,3,7,8- (HCN) (NOx) aromatic PeCDD) PeCDF) hydrocarbons (HX)

(Benzo-a-pyrene) Benzene Styrene

Centre for Fire and Characterization of Polyaromatic Hydrocarbons (PAHs) Hazards Science

PAHs are a large group of organic compounds that are consisted of two or more joined aromatic rings. It can be formed small unstable precursor compounds for PAHs by two paths;

From saturated hydrocarbons in vitiated Thermal breakdown of heavier combustion atmospheres. In this case, hydrocarbons. Several hundred of PAHs low molecular weight hydrocarbons act have been found. The best known is as precursors in the pyro-synthesis of benzo[a]pyrene (BaP), metabolised to PAH compounds that take place at oxygenated forms acting as a carcinogen temperatures above 500°C. in the body.

Individual PAHs can also cause a range of non-cancer effects (mutagenicity, teratogenicity). PAHs generation and analysis Centre for Fire and Hazards Science

Different sampling methods were used and compared (SPME, syringe, midget impingers, etc) for PAHs quantification. A range of different fire conditions was generated using NF X 70-100. Fire conditions varied from non-flaming (oxidative pyrolysis) to well-ventilated and under-ventilated flaming by using different combinations of temperature and fuel/air ratios.

GC-MS was used to identify different components of mixtures in the effluent.

NF X 70-100 GC-MS Sampling methods Centre for Fire and Hazards Science

Typical extractive methods and examples of species analysed in each case include:

midget impingers SPME Tedlar bag

sorption tube Syringe Gas sampling bulb Centre for Fire and Analytical methods Hazards Science

• EPA TO-15 and TO-17 • EPA 8270 • EPA 8275 • Supleco bulletin 922 Different methods of sampling Centre for Fire and Hazards Science

Sample Condition Methods

Polymer Air flow/ Bubbler Bubbler by SPME SPME (glass SPME (tedlar Syringe Syringe Syringe Sorption tube by solvent solvent (direct) 250 ml) bag) (direct) (glass 250 (tedlar bag) (EPA TO-15 temperature (Supleco (Supleco (Supleco (Supleco ml) (Supleco (Supleco and TO-17) (EPA 8270) (EPA 8275) bulletin 922) bulletin 922) bulletin 922) bulletin 922) bulletin 922) bulletin 922)

LDPE 2L/ 800C° duplicate duplicate duplicate duplicate Data analysis duplicate duplicate Data analysis Data analysis

tests tests test tests on-going tests tests on-going on-going

(NFX)

Toluene Toluene

Acetonitrile Acetonitrile

Deionised water Deionised water Deionised LDPE 2L/ 600C° x x duplicate duplicate x duplicate duplicate x Data analysis

tests tests tests tests on-going

(NFX)

water

Toluene Toluene

Acetonitrile Acetonitrile

Deionised water Deionised Deionised Sampling methods at 800C° 1-midget impingers at 800 C

Solvent Time sampling Solvent Time sampling Solvent Time sampling

Ignition time : 35 Sec Ignition time : 36 Sec Ignition time : 38 Sec Extinction time : 2.45 min Extinction time : 2.48 min Extinction time : 2.50 min Deionised Toluene Experiment time : 0.00-4.30 Acetonitrile Experiment time : 0.00-4.30 Experiment time : 0.00-4.30 water min min min Sampling time: from 0.35 to Sampling time: from 0.35 to Sampling time: from 0.35 to 3.30 min 3.30 min 3.30 min Flow rate (l/min):1 Flow rate (l/min):1 Flow rate (l/min):1 2-Solid Phase Micro Extraction (SPME) at 800 C

Method Time sampling Method Time sampling Method Time sampling Ignition time : 37 Sec Ignition time : 38 Sec Ignition time : 38 Sec Extinction time : 2.43 min Extinction time : 2.45 min Extinction time : 2.45 min SPME (SPME) SPME Experiment time : 0.00-4.30 Experiment time : 0.00-4.30 Experiment time : 0.00-4.30 direct min Tedler bag min Glass 250 ml min Sampling time: (1:20 -1:30) = Sampling time: after Sampling time: after 10 Sec experiment for 10 Sec experiment for 5 min Flow rate (l/min):1 Flow rate (l/min):1 Flow rate (l/min): 1 3-Syringe at 800 C

Method Time sampling Method Time sampling method Time sampling Ignition time : 34 Sec Ignition time : 38 Sec Ignition time : 36 Sec Extinction time : 2.42 min Extinction time : 2.45 min Extinction time : 2.48 min Syringe Syringe Syringe Experiment time : 0.00-4.30 Experiment time : 0.00-4.30 Experiment time : 0.00-4.30 direct min tedler bag min glass 250 ml min Sampling time: (1:20 -1:24) = Sampling time: after Sampling time: after 4 Sec experiment experiment Volume: 200µl Volume: 200µl Volume: 200µl Flow rate (l/min):1 Flow rate (l/min):1 Flow rate (l/min): 1 Results of experiments at 800C°

Method Sampling Chromatogram Method midget Toluene impingers EPA 8270

midget Toluene impingers EPA 82705

midget Acetonitrile RT: 0.00 - 29.12 2.27 NL: 100 9.41E7 impingers TIC MS 8270 90 LDPE4- ACETONIT 80 RILE-NFX

50 1.50

40 Relative Abundance Relative 30

20 4.00

10 7.12 12.71 2.34 6.42 10.31 14.64 0 0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 Time (min)

RT: 0.00 - 34.12 midget Acetonitrile 2.27 NL: 100 5.82E7 TIC MS impingers 90 LDPE4- 8275 ACETONIT 80 RILE- NFX8275 70 1.40

40 Relative Abundance Relative 30 4.00

10 7.11 12.72 10.31 33.80 6.62 14.64 16.56 30.18 32.25 0 0 5 10 15 20 25 30 Time (min) midget Deionised No species found impingers water 8270 midget Deionised No species found impingers water 8275 Results of experiments at 800C°

Method Sampling Chromatogram Method

SPME RT: 0.00 - 25.31 direct 3.72 NL: 100 5.50E7 TIC MS 90 2.30 LDPE- SPME- 80 direct5

60 5.94 50

40 Relative Abundance Relative 30

20 5.39 8.69 10.97 2.10 2.39 10 4.10 5.97 7.70 10.41 1.47 12.40 13.78 14.75 16.27 18.52 19.55 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min)

RT: 0.00 - 25.30 SPME 11.02 NL: glass 100 1.58E8 TIC MS 90 LDPE1- SPME- 80 GLASS

70 8.70 60

10.41 14.76 Relative Abundance Relative 30 5.94 13.78 12.62 18.69 15.07 20 18.52 19.56 9.40 20.57 7.81 21.72 10 23.17 5.39 5.98 3.72 24.92 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min)

RT: 0.00 - 25.29 Syringe direct 2.36 NL: 100 1.26E8 TIC MS 90 LDPE- syringe- 80 direct5

50 3.76

40 1.29 Relative Abundance Relative 30

20 2.45 10 5.95 10.98 5.41 5.99 8.70 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min)

RT: 0.00 - 25.28 Syringe glass 10.95 NL: 100 5.81E7 TIC MS 90 LDPE-4- SYRINGE- 80 GLASS

40 Relative Abundance Relative 30 8.66

2.29 20 14.72 10.38 12.58 18.67 10 3.70 5.91 15.03 1.22 8.33 16.38 2.37 5.37 7.74 9.36 18.78 22.50 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min) Summary of experiment results at 800C° Method MW Structure Method Method Method EPA Method Method Method SPME SPME Syringe Syringe Volatile EPA 8270 EPA 8275 8270 EPA8275 EPA 8270 EPA 8275 direct glass direct glass (toluene) (toluene) (acetonitrile) (acetonitrile) (deionised (deionise water) d water) Name 1,4- 80 cyclohexadiene √ √ √ √ x x √ x √ x Benzene 78 √ √ √ √ x x √ x √ x Toluene 92 x x √ √ x x √ √ √ √

Ethyl benzene 106 √ √ √ √ x x √ √ √ √

Styrene 104 √ √ √ √ √ x √ √ √ √

Indane 118 x x √ √ x x x √ √ √

Benzene, propyl 120 x x x x x x √ √ x √

Indene 116 x x √ √ x x √ √ √ √

Naphthalene 128 √ √ √ √ x x √ √ √ √

Naphthalene, 130 1,2dihydro x x x x x x √ √ √ √

Naphthalene, 1- 142 methyl- √ √ √ √ x x √ √ √ √ Biphenylene 152 √ √ √ √ x x √ √ √ √

Biphenyl 154 x x x x x x x √ x √

Anthracene 178 √ √ √ √ x x √ √ √ √

pyrene 202 √ √ x x x x √ √ √ √ Sampling methods at 600C° Centre for Fire and Hazards Science

5-SPME at 600 C°

method Time sampling method Time sampling Ignition time : 38 Sec Ignition time : 88 Sec Extinction time : 2.45 min Extinction time : 3.45 min SPME SPME Experiment time : 0.00-4.30 min Experiment time : 0.00-5.00 min glass 250 Sampling time: after experiment for 5 min direct Sampling time: (2:50 -3:00) = 10 Sec Flow rate (l/min): 1 Flow rate (l/min): 1 ml

4-Syringe at 600 C°

Method Time sampling Method Time sampling Ignition time : 85 Sec Ignition time : 88 Sec Extinction time : 3.42 min Extinction time : 3.47 min Syringe Syringe Experiment time : 0.00-5.00 min Experiment time : 0.00-5.00 min direct Sampling time: (2:40 -2:44) = 4 Sec glass 250 Sampling time: after experiment Volume: 200µl ml Volume: 200µl Flow rate (l/min):1 Flow rate (l/min):1 Results of experiments at 600C°

Method Sampling Chromatogram Method

SPME RT: 0.00 - 25.32 direct 10.95 NL: 100 5.90 9.84E6 TIC MS 90 LDPE-2- DIRECT- 80 SPME-600 7.67 70

60 3.69 8.65

50 2.27 9.35 40

Relative Abundance Relative 13.74 30 4.07 15.03 19.53 12.37 16.24 20.53 7.53 20 21.68 23.11 5.94 23.26 2.57 10 2.07 1.44 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min)

SPME glass RT: 0.00 - 25.30 10.94 NL: 100 7.33E7 TIC MS 90 LDPE-1- SPME- 80 GLASS-600

70 7.71

60 9.38 5.90 50 13.76 19.54 12.39 15.04 18.50 40 20.54

8.66 Relative Abundance Relative 30 21.69 23.13 20 7.54 24.99 23.28 10 5.73 3.68 6.04 2.25 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min)

RT: 0.00 - 25.31 Syringe direct 2.29 NL: 100 8.52E6 TIC MS 90 LDPE-1- DIRECT- 80 SYRINGE- 600 70 1.23 60

3.71 Relative Abundance Relative 30

2.37 19.53 20.53 20 7.67 10.95 18.48 4.08 5.91 9.36 13.74 15.03 16.24 21.68 23.21 10 8.67 24.97 5.37 7.53 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min)

RT: 0.00 - 25.33 Syringe glass 10.94 NL: 100 6.07E7 TIC MS 90 LDPE-1- SYRINGE- 80 GLASS-600

70 13.76 15.05 19.54 60 18.51 20.55 7.69 9.38 12.39 50 21.70 40 5.89

Relative Abundance Relative 23.14 30 8.66 24.99 20 2.28 3.69 7.54 23.21 10 1.22 4.07 2.57 6.03 0 0 2 4 6 8 10 12 14 16 18 20 22 24 Time (min) Summary of experiment results at 600C° Method MW Structure SPME direct SPME glass Syringe direct Syringe glass Volatile

Name 1,4-cyclohexadiene 80 √ x √ x Benzene 78 √ x √ x Toluene 92 √ √ √ √

Ethyl benzene 106 √ √ √ √

Styrene 104 √ √ √ √

Indane 118 x √ √ √

Benzene, propyl 120 √ √ x √

Indene 116 √ √ √ √

Naphthalene 128 √ √ √ √

Naphthalene, 1,2dihydro 130 √ √ √ √

Naphthalene, 1-methyl- 142 √ √ √ √

Biphenylene 152 √ √ √ √

Biphenyl 154 x √ x √

Anthracene 178 √ √ √ √

pyrene 202 √ √ √ √ Conclusions Centre for Fire and Hazards Science

Different methods for PAHs sampling were used for different fire conditions.

1-Midget impinger was used with acetonitrile, toluene and deionised water as solvents. The best results were obtained from acetonitrile.

2- SPME was used either by a direct injection or from the gas sampling vessel which was proven to have the best results.

3-Syringe was also used either by a direct injection or by gas sampling vessel. It was found that sampling by a gas sampling vessel has given better results compared to the direct sampling.

4-Many experiments were performed using Tedlar bag and sorption tubes, but results were much poorer compared to the other sampling techniques.

5- Benzene, a known carcinogen, was repeatedly identified as a volatile released from LDPE. Styrene and Naphthalene, two possibly carcinogenic compounds, were also identified amongst the PAHs products. Centre for Fire and Acknowledgements Hazards Science

Finally, I would like to acknowledge King Fahd Security College to give me a scholarship for doing this research in Centre for Fire and Hazards Science University of Central Lancashire.

I would also like to thank both of Prof. Richard Hull and Dr. Anna Stec who assisted me with this research.

And, the last but not the least, I would like to thank all colleagues in Centre for Fire and Hazards Science for their support: Ashleigh Lyons, Antonis Christou, Kathryn Dickens, Cezary Dmochowski, Stephen Harris, Diana Rbehat and Fiona Hewitt. Centre for Fire and Hazards Science

Thank you for your attention

ANY QUESTIONS? GC-MS and Py-GCMS Data analysis

Method EPA 8270 EPA 8275 Sample LDPE LDPE Centre for Fire and Analytical GC-MS GC-MS Hazards Science instrument Solvents deionised water, toluene deionised water, toluene Method SPME and syringe (Supleco bulletin 922) Method Sorption tube (EPA TO-15 and TO-17)) and acetonitrile and acetonitrile Samples LDPE,PS Instrument control method Samples LDPE Instrument type: Thermo Scientific Trace Thermo Scientific Trace Analytical GC-MS Analytical Py-GCMS 1300 1300 instrument instrument Instrument control method Channel Parameters Instrument control method Run time: 29.00 34.00 Instrument type: Thermo Scientific Trace 1300 Instrument type: PE Autosystem GC with built-in Autosampler method Autosampler Channel Parameters Injection 1mL 1 mL Channel Parameters Run time: 25.30min volume(µl) Delay time: 0.00 min Column Thermo TG-SQC Thermo TG-SQC Manual sampling Run time: 30.00 min 30 meter, 0.25mmID, 30 meter, 0.25mmID, Sampling 10sec , headspace Channel offset: 5.0 mV 0.25umdf 0.25umdf Manual sampling SPME Fiber 100μm polydimethylsiloxane Mass range 35-650 amu 35-650 amu Sampling 5 min Column Thermo TG-SQC Scan time 0.94 sec/scan 0.95 sec/scan Type of sorption Tanex AG 30 meter, 0.25mmID, 0.25umdf Carriers Parameters tube Mass range 41-650 Carrier control: PFLow-He PFLow-He Column Thermo TG-SQC Scan time 0.59 Sec

Carriers length: 30.0 m 30.0 m Carriers Parameters 30 meter, 0.25mmID, 0.25umdf Carrier control: PFLow-He Mass range 41-650 Scan time 0.59 Sec Diameter: 250 mm 250 mm Carriers length: 30.0 m Split Flow: 50mL/min 50mL/min Carriers Parameters Diameter: 250 mm Flow rate: 1.00mL/min 1.00mL/min Carrier control: PFLow-He Split Flow: 50mL/min Detector MS MS Carriers length: 30.0 m HeatedZones Flow rate 1.00mL/min Diameter: 250 mL Split Flow: 20mL/min Injector: Split/ splitless Split/ splitless Detector MS Flow rate 1.00mL/min Initial Setpoint: 250 ºC 250 ºC HeatedZones Detector pyGC-MS Injector: Splitless (closed 1 min.) HeatedZones Oven Program Initial Setpoint: 250ºC Injector: PSSI Initial Temp.: 40oC 40oC Oven Program Initial Setpoint: 280oC o Initial Temp.: 38 C Oven Program Initial Hold: 4 min 4 min Initial Hold: 2 min Initial Temp.: 50oC Ramp 1: 10.0/min to 220oC Initial Hold: 2 mins Ramp 1: 10.0oC /min to 270oC 10.0oC /min to 320oC Final Temp.: hold until 5 min to 30oC/min at 300oC Ramp 1: 10.0/min to 230oC Final Temp.: 270 ºC, hold until 2 min 320 ºC, hold until 2 min Final Temp.: 30.00 min after benzo[g,h,i]perylene after benzo[g,h,i]perylene Total Run Time: 25.30min Total Run Time: 30.00 min elutes elutes Total Run Time: 29.00min 34.00min