Effects of Fire Conditions on the Formation of Polycyclic Aromatic
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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 70 60 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 60 50 40 Relative Abundance Relative 30 4.00 20 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 70 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 50 40 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 70 60 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 70 60 50 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