Abstract
Issues concerning polycyclic aromatic hydrocarbons (PAH) carcinogenicity, and their important role in formation of dangerous pollutants, such as soot, have motivated their study under a wide range of laboratory conditions and for several kinds of thermochemical processes. Every experimental system, depending on the operating conditions, demands a specific protocol for PAH determination. This chapter aims to contribute to the knowledge of different procedures for PAH quantification both at the gas phase and when they are associated with soot particles. Different kinds of experimental set-ups for PAH formation together with the collection systems to capture them are explained here. Besides, some sample extraction techniques are reviewed, mainly focused on Soxhlet extraction because of its inexpensive equipment and overall simplicity to be applied by staff with limited analytical experience. Chromatographic techniques are also considered, paying special attention to gas chromatography coupled to mass spectrometry (GC–MS), popular in PAH analysis.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Abbreviations
- PAH:
-
Polycyclic aromatic hydrocarbons
- GC–MS:
-
Gas chromatography coupled to mass spectrometry
- HACA:
-
H-abstraction/C2H2 addition route
- EPA:
-
Environmental Protection Agency
- EPA–PAH:
-
Polycyclic aromatic hydrocarbons classified by EPA as priority pollutants
- PUF:
-
Polyurethane foam
- PTFE:
-
Polytetrafluoroethylene
- DCM:
-
Dichloromethane
- ASE:
-
Accelerated solvent extraction
- SFE:
-
Supercritical fluid extraction
- GPT:
-
Thermochemical Processes Group
- I3A:
-
Aragón Institute of Engineering Research
- HPLC–UV:
-
Reversed-phase high performance liquid chromatograph with ultraviolet detection
- FID:
-
Flame ionization detection
- SIM:
-
Selected ion monitoring
- SRM:
-
Standard reference material
References
ATSDR, Agency for Toxic Substances and Disease Registry (1996) Polycyclic aromatic hydrocarbons (PAHs), Atlanta. http://www.atsdr.cdc.gov/es/toxfaqs/es_tfacts69.html
Allouis C, Apicella B, Barbella R et al (2003) Monitoring of fuel consumption and aromatics formation in a kerosene spray flame as characterized by fluorescence spectroscopy. Chemosphere 51:1097–1102
Andrade-Eiroa A, Leroy V, Dagaut P et al (2010a) Determination of polycyclic aromatic hydrocarbons in kerosene and bio-kerosene soot. Chemosphere 78:1342–1349
Andrade-Eiroa A, Diévart P, Dagaut P (2010b) Improved optimization of polycyclic aromatic hydrocarbons (PAH) mixtures resolution in reversed-phase-high-performance liquid chromatography by using factorial design and response methodology. Talanta 81:265–274
Apicella B, Ciajolo A, Barbella R et al (2003) Size exclusion chromatography of particulate produced in fuel-rich combustion of different fuels. Energy Fuels 217:565–570
Appel J, Bockhorn H, Frenklach M (2000) Kinetic modeling of soot formation with detailed chemistry and physics: laminar premixed flames of C2 hydrocarbons. Combust Flame 121:122–136
Ardag H, Ozel MZ, Sen A (2011) Polycyclic aromatic hydrocarbons in water from the Menderes river. Turkey Bull Environ Contam Toxicol 86:221–225
Ballesteros R, Hernández JJ, Lyons LL (2009) Determination of PAHs in diesel gas matter using thermal extraction and solid phase micro-extraction. Atmos Environ 43:655–662
Ballesteros R, Hernández JJ, Lyons LL (2010) An experimental study of the influence of biofuel origin on particle-associated. Atmos Environ 44:930–938
Becnel JM, Dooley KM (1998) Supercritical fluid extraction of polycyclic aromatic hydrocarbon mixtures from contaminated soils. Ind Eng Chem Res 37:584–594
Borrás E, Tortajada-Genaro LA (2007) Characterization of polycyclic aromatic hydrocarbons in atmospheric aerosols by gas chromatography-mass spectrometry. Anal Chim Acta 583:266–276
Bouvier Y, Mihesan C, Ziskind M et al (2007) Molecular species adsorbed on soot particles issued from low sooting methane and acetylene laminar flames: A laser-based experiment. Proc Combust Inst 31:841–849
Chen BH, Wang CY, Chiu CP (1996) Evaluation of analysis of polycyclic aromatic hydrocarbons in meat products by liquid chromatography. J Agric Food Chem 44:2244–2251
Christensen A (2003) Polycyclic aromatic hydrocarbon in exhaust emission from mobile sources-sampling and determination. Ph.D. thesis, University of Stockholm, Stockholm
Christensen A, Ostman C, Westerholm R (2005) Ultrasound-assisted extraction and on-line LC–GC–MS for determination of polycyclic aromatic hydrocarbons (PAH) in urban dust and diesel particulate matter. Anal Bioanal Chem 381:1206–1216
Chuang JC, Hannan SW, Wilson NK (1987) Field comparison of polyurethane foam and XAD-2 resin for air sampling for polynuclear aromatic hydrocarbons. Environ Sci Technol 21:798–804
Ciajolo A, Ragucci R, Apicella B et al (2001) Fluorescence spectroscopy of aromatic species produced in rich premixed ethylene flames. Chemosphere 42:835–841
De Kok TMCM, Driece HAL, Hogervorst JGF, Briedé JJ (2006) Toxicological assessment of ambient and traffic-related particulate matter: A review of recent studies. Mutat Res 613:103–112
Durlak SK, Biswas P, Shi J et al (1998) Characterization of polycyclic aromatic hydrocarbon particulate and gaseous emissions from polystyrene combustion. Environ Sci Technol 32:2301–2307
EPA, Environmental Protection Agency (1996a) EPA-Method 3561: supercritical fluid extraction of polynuclear aromatic hydrocarbons, Ohio. http://www.caslab.com/EPA-Methods/PDF/EPA-Method-3561.pdf
EPA, Environmental Protection Agency (1996b) EPA-Method 3540C: Soxhlet extraction, Ohio. http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/3540c.pdf
EPA, Environmental Protection Agency (1998a) Locating and estimating air emissions from sources of polycyclic organic matter, Ohio. http://www.epa.gov/ttn/chief
EPA, Environmental Protection Agency (1998b) EPA-Method 8270D: determination of semivolatile organic compounds by gas chromatography/mass spectrometry (CG/MS), Ohio. http://www.epa.gov/osw/hazard/testmethods/sw846/pdfs/8270d.pdf
EPA, Environmental Protection Agency (1999) EPA-Method TO-13A: Compendium of methods for the determination of toxic organic compounds in ambient air, Ohio. http://www.epa.gov/ttnamti1/files/ambient/airtox/to-13arr.pdf
EPA, Environmetal Protection Agency (2000) EPA-Method 3550C: ultrasonic extraction, Ohio. http://www.caslab.com/EPA-Methods/PDF/EPA-Method-3550C.pdf
Esarte C, Millera A, Bilbao R et al (2009) Gas and soot products formed in the pyrolysis of acetylene–ethanol blends under flow reactor conditions. Fuel Process Technol 90:496–503
Faccinetto A, Desgroux P, Ziskind M et al (2011) High-sensivity detection of polycyclic aromatic hydrocarbons adsorbed onto soot particles using laser desorption/laser ionization/time-of-flight mass spectrometry: an approach to studying the soot inception process in low-pressure flames. Combust Flame 158:227–239
Ferreira V (2007) Cromatografía: fundamentos y práctica, 2nd edn. Publication Service of the University of Zaragoza, Zaragoza
Finlayson-Pitts BJ, Pitts JN (2000) Chemistry of the upper and lower atmosphere. Academic Press, California
Font R, Esperanza M, García AN (2003) Toxic by-products from the combustion of kraft lignin. Chemosphere 52:1047–1058
Frenklach M (2002) Reaction mechanism of soot formation in flames. Phys Chem Chem Phys 4:2028–2037
Furton KG, Pentzke G (1998) Polycyclic aromatic hydrocarbons. In: Shibamoto T (ed) Chromatographic analysis of environmental and food toxicants, 1st edn. Marcel Dekker, New York
Furuhata T, Kobayashi Y, Hayashida K et al (2012) Behavior of PAHs and PM in a diffusion flame of paraffin fuels. Fuel 91:16–25
Gfrerer M, Gawlik BM, Lankmayr E (2004) Validation of a fluidized-bed extraction method for solid materials for the determination of PAHs and PCBs using certified reference materials. Anal Chim Acta 527:53–60
Howard JB, Longwell JP, Marr JA et al (1995) Effects of PAH isomerizations on mutagenicity of combustion products. Combust Flame 101:262–270
Indarto A, Giordana A, Ghigo G et al (2010) Polycyclic aromatic hydrocarbon formation mechanism in the particle phase. Phys Chem Chem Phys 12:9429–9440
Kado NY, Okamoto RA, Karim J et al (2000) Airborne particle emissions from 2-and 4-stroke outboard marine engines: polycyclic aromatic hydrocarbon and bioassay analyses. Environ Sci Technol 34:2714–2720
Kim JY, Lee JY, Choi S-D et al (2012) Gaseous and particulate polycyclic aromatic hydrocarbons at the Gosan background site in East Asia. Atmos Environ 49:311–319
Ledesma EB, Marsh ND, Sandrowitz AK et al (2002) Global kinetic rate parameters for the formation of polycyclic aromatic hydrocarbons from the pyrolyis of catechol, a model compound representative of solid fuel moieties. Energy Fuels 16:1331–1336
Lee HK (1995) Recent applications of gas and high-performance liquid chromatographic techniques to the analysis of polycyclic aromatic hydrocarbons in airborne particulates. J Chromatogr A 710:79–92
Lee HK (2001) Modern techniques for the analysis of polycyclic aromatic hydrocarbons. In: Kleiböhmer W (ed) Handbook of analytical separations, 1st edn. Elsevier, Amsterdam
Lee JJ, Huang K-L, Yu YY et al (2004) Laboratory retention of vapor-phase PAHs using XAD adsorbents. Atmos Environ 38:6185–6193
Lemaire R, Therssen E, Desgroux P (2010) Effect of ethanol addition in gasoline and gasoline–surrogate on soot formation in turbulent spray flames. Fuel 89:3952–3959
Levendis YA, Atal A, Carlson JB et al (2001) PAH and soot emissions from burning components of medical waste: examination/surgical gloves and cotton pads. Chemosphere 42:775–783
Li Y, Tian Z, Zhang L et al (2009) An experimental study of the rich premixed ethylbenzene flame at low pressure. Proc Combust Inst 32:647–655
Li-bin L, Yan L, Jin-ming L et al (2007) Development of analytical methods for polycyclic aromatic hydrocarbons (PAHs) in airborne particulates: a review. J Environ Sci 19:1–11
Librando V, Hutzinger O, Tringali G et al (2004) Supercritical fluid extraction of polycyclic aromatic hydrocarbons from marine sediments and soil samples. Chemosphere 54:1189–1197
Liu K, Han W, Pan W-P et al (2001) Polycyclic aromatic hydrocarbon (PAH) emissions from a coal-fired pilot FBC system. J Hazard Mater B84:175–188
Luch A (2005) Polycyclic aromatic hydrocarbon-induced carcinogenesis-an introduction. In: Lunch A (ed) The carcinogenic effects of polycyclic aromatic hydrocarbons, 1st edn. Imperial College Press, London
Luque de Castro MD, Luque de García JL (2002) Acceleration and automation of solid sample treatment. Elsevier Science, Amsterdam
Luque de Castro MD, Priego-Capote F (2010) Soxhlet extraction: past and present panacea. J Chromatogr A 1217:2383–2389
Macadam S, Beér JM, Safofim AF (1996) Soot surface growth by polycyclic aromatic hydrocarbon and acetylene addition. Proc Combust Inst 26:2295–2302
Manzello SL, Lenhert DB, Yozgatligil A et al (2007) Soot particle size distributions in a well-stirred reactor/plug flow reactor. Proc Combust Inst 31:675–683
Mastral AM, Callén M, Murillo R (1996) Assessment of PAH emissions as a function of coal combustion variables. Fuel 75:1533–1536
Mastral AM, Callén MS, García T et al (2001) Benzo(a)pyrene, benzo(a)anthracene, and dibenzo(a, h)anthracene emissions from coal and waste tire energy generation at atmospheric fluidized bed combustion (AFBC). Environ Sci Technol 35:2645–2649
Mastral AM, López JM, Callén MS et al (2003) Spatial and temporal PAH concentrations in Zaragoza. Spain Sci Total Environ 307:111–124
Mathieu O, Franche G, Djebaili-Chaumeix N et al (2007) Characterization of adsorbed species on soot formed behind reflected shock waves. Proc Combust Inst 31:511–519
Mendiara T, Domene MP, Millera A et al (2005) An experimental study of the soot formed in the pyrolysis of acetylene. J Anal Appl Pyrolysis 74:486–493
Moltó J, Conesa JA, Font R et al (2005) Organic compounds produced during the thermal decomposition of cotton fabrics. Environ Sci Technol 39:5141–5147
Moltó J, Egea S, Conesa JA et al (2011) Thermal decomposition of electronic wastes: mobile phone case and other parts. Waste Manage 31:2546–2552
NIST, National Institute of Standards and Technology (2006) Certified of analysis for standard reference material 1650b, diesel particulate matter, Gaithersburg. https://www-s.nist.gov/srmors/certificates/view_certGIF.cfm?certificate=1650B
Norinaga K, Janardhanan VM, Deutschamann O (2007) Detailed chemical kinetic modeling of pyrolysis of ethylene, acetylene, and propylene at 1073–1373 K with a plug-flow reactor model. Int J Chem Kinet 40:199–208
Norinaga K, Deutschmann O, Saegusa N et al (2009) Analysis of pyrolysis products from light hydrocarbons and kinetic modeling for growth of polycyclic aromatic hydrocarbons with detailed chemistry. J Anal Appl Pyrolysis 86:148–160
Ortiz R, Vega S, Gutiérrez R et al (2012) Presence of polycyclic aromatic hydrocarbons (PAHs) in top soils from rural terrains in Mexico City. Bull Environ Contam Toxicol 88:428–432
Pandey SK, Kim K-H, Brown RJC (2011) A review of techniques for the determination of polycyclic aromatic hydrocarbons in air. Trends Anal Chem 30:1716–1739
Portet-Koltalo F, Oukebdane K, Dionnet F et al (2008) Optimisation of the extraction of polycyclic aromatic hydrocarbons and their nitrated derivatives from diesel particulate matter using microwave-assisted extraction. Anal Bioanal Chem 390:389–398
Poster DL, Schantz MM, Sander LC et al (2006) Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods. Anal Bioanal Chem 386:859–881
Ruiz MP, Guzmán R, Millera A et al (2007a) Influence of different operation conditions on soot formation from C2H2 pyrolysis. Ind Eng Chem Res 46:7550–7560
Ruiz MP, Callejas A, Millera A et al (2007b) Soot formation from C2H2 and C2H4 pyrolysis at different temperatures. J Anal Appl Pyrolysis 79:244–251
Sánchez NE, Callejas A, Millera A et al (2010) Determination of polycyclic aromatic hydrocarbons (PAH) adsorbed on soot formed in pyrolysis of acetylene at different temperatures. Chem Eng Trans 22:131–136
Sánchez NE, Callejas A, Millera A et al (2012a) Formation of PAH and soot during acetylene pyrolysis at different gas residence times and reaction temperatures. Energy 43:30–36
Sánchez NE, Callejas A, Millera A et al (2012b) Polycyclic aromatic hydrocarbons (PAH) and soot formation in the pyrolysis of acetylene and ethylene: Effect of the Reaction Temperature. Energy Fuels 26:4823–4829
Sánchez NE, Salafranca J, Callejas A et al (2013) Quantification of polycyclic aromatic hydrocarbons (PAH) found in gas and particle phases from pyrolytic processes using gas chromatography-mass spectrometry (GC-MS). Fuel 107:246–253
Sander LC, Wise SA (1997) Polycyclic aromatic hydrocarbon structure index. NIST special publication 922. http://www.nist.gov/mml/analytical/organic/upload/SP-922-Polycyclic-Aromatic-Hydrocarbon-Structure-Index-2.pdf
Schneider K, Roller M, Kalberlah F et al (2002) Cancer risk assessment for oral exposure to PAH mixtures. J Appl Toxicol 22:73–83
Shen G, Wang W, Yang Y et al (2011) Emissions of PAHs from indoor crop residue burning in a typical rural stove: emission factors, size distributions, and gas-particle partitioning. Environ Sci Technol 45:1206–1212
Somers ML, McClaine JW, Wornat MJ (2007) The formation of polycyclic aromatic hydrocarbons from the supercritical pyrolysis of 1-methylnaphthalene. Proc Combust Inst 31:501–509
Song YF, Jing X, Fleischmann S et al (2002) Comparative study of extraction methods for determination of PAHs from contaminated soils and sediments. Chemosphere 48:993–1001
Tang L, Tang X-Y, Zhu Y-G, Zheng M-H, Miao Q-L (2005) Contamination of polycyclic aromatic hydrocarbons (PAHs) in urban soils in Beijing, China. Environ Int 31:822–828
Thomas S, Wornat MJ (2008) Effect of acetylene addition on yields of C1–C10 hydrocarbon products of catechol pyrolysis. Energy Fuels 22:976–986
Thomas S, Wornat MJ (2009) Polycyclic aromatic hydrocarbons from the co-pyrolysis of catechol and 1,3-butadiene. Proc Combust Inst 32:615–622
Thomas S, Ledesma EB, Wornat MJ (2007) The effects of oxygen on the yields of the thermal decomposition products of catechol under pyrolysis and fuel-rich oxidation conditions. Fuel 86:2581–2595
Viegas O, Novo P, Pinho O et al (2012) A comparison of the extraction procedures and quantification methods for the chromatographic determination of polycyclic aromatic hydrocarbons in charcoal grilled meat and fish. Talanta 88:677–683
Wang J, Richter H, Howard JB et al (2002) Polynuclear aromatic hydrocarbon and particulate emissions from two-stage combustion of polystyrene: The effects of the secondary furnace (afterburner) temperature and soot filtration. Environ Sci Technol 36:797–808
Wang R, Cadman P (1998) Soot and PAH production from spray combustion of different hydrocarbons behind reflected shock waves. Combust Flame 112:359–370
Wang Z, Wang J, Richter H et al (2003) Comparative study on polycyclic aromatic hydrocarbons, light hydrocarbons, carbon monoxide, and particulate emissions from the combustion of polyethylene, polystyrene, and poly(vinyl chloride). Energy Fuels 17:999–1013
Wartel M, Pauwels J-F, Desgroux P et al (2010) Quantitative measurement of naphthalene in low-pressure flames by jet-cooled laser-induced fluorescence. Appl Phys B 100:933–943
WHO, World Health organization, regional office for Europe (2000) Polycyclic aromatic hydrocarbons (PAHs). In: Air quality guidelines, 2nd edn. (CD-ROM version), Denmark. http://www.euro.who.int/__data/assets/pdf_file/0015/123063/AQG2ndEd_5_9PAH.pdf
Wu J, Song KH, Litzinger T et al (2006) Reduction of PAH and soot in premixed ethylene–air flames by addition of ethanol. Combust Flame 144:675–687
Xue J, Liu G, Niu Z et al (2007) Factors that influence the extraction of polycyclic aromatic hydrocarbons from coal. Energy Fuels 21:881–890
Acknowledgments
This work has been performed at the Aragón Institute of Engineering Research (I3A) of the University of Zaragoza in the frame of the Thermochemical Processes Group (GPT). The authors express their gratitude to the MICINN, FEDER (Project CTQ2009-12205), Aragón Government and European Social Fund (ESF), for financial support. Ms N.E. Sánchez acknowledges the Banco Santander Central Hispano, University of Zaragoza and the Colombian Institute for the Development of Science and Technology (COLCIENCIAS) for the predoctoral grant awarded.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2013 Springer-Verlag London
About this chapter
Cite this chapter
Sánchez, N.E., Callejas, A., Salafranca, J., Millera, Á., Bilbao, R., Alzueta, M.U. (2013). Formation and Characterization of Polyaromatic Hydrocarbons. In: Battin-Leclerc, F., Simmie, J., Blurock, E. (eds) Cleaner Combustion. Green Energy and Technology. Springer, London. https://doi.org/10.1007/978-1-4471-5307-8_11
Download citation
DOI: https://doi.org/10.1007/978-1-4471-5307-8_11
Published:
Publisher Name: Springer, London
Print ISBN: 978-1-4471-5306-1
Online ISBN: 978-1-4471-5307-8
eBook Packages: EnergyEnergy (R0)