Air Quality, Atmosphere & Health

, Volume 10, Issue 7, pp 799–807 | Cite as

Hopanoid hydrocarbons in PM10 from road tunnels in São Paulo, Brazil

  • Célia A. Alves
  • Ana M. Vicente
  • Sónia Rocha
  • Pérola Vasconcellos


The fleet of flexible fuel vehicles in Brazil is the largest in the world. To diagnose the contribution of vehicle emissions to atmospheric particulate matter, organic molecular markers, such as hopanes, can be used. However, nothing is known about the particulate matter mass fractions of these tracers in environments exclusively impacted by road emissions. In this study, the hopanoid composition of PM10 inside two tunnels in the São Paulo metropolitan area with very distinct circulating fleets (Jânio Quadros (JQ) and Rodoanel (RA)) was obtained. Higher mean concentrations (82.4 ng m−3) and PM10 mass fractions (239 ng mg−1) were obtained in RA, in which the fleet is composed of both light and heavy duty vehicles. The most abundant species were 17α(H),21β(H)-30-norhopane (27.9 ng mg−1 in JQ, 47.9 ng mg−1 in RA) and 17α(H),21β(H)-hopane (32.6 ng mg−1 in JQ, 44.3 ng mg−1 in RA). Diverse concentration ratios were calculated and compared with those of other sources. Overlapping values may preclude the use of these parameters as source assignment tools. Some compounds, such as 18α(H)-22,29,30-trisnorneohopane, 17α(H)-22,29,30-trisnorhopane, 17α(H),21β(H)-30-norhopane, 18α(H)-30-norneohopane, 17α(H),21β(H)-hopane, 17α(H),21β(H)-22S-homohopane and 17α(H),21β(H)-22R-homohopane, were found to be very good predictors of the total concentrations of hopanoids.


PM10 Road tunnels Flexible fuel vehicles Brazil Hopanes 



The sampling programme was supported by the Research Foundation of the State of São Paulo (FAPESP, project 2008/58104-8) and by the National Council for Scientific and Technological Development (CNPq, project 402383/2009-5). Pérola Vasconcellos thanks INCT-Energy and Environment. The analytical work benefited from funds allocated by the Portuguese Foundation for Science and Technology (FCT) to the Centre for Environmental and Marine Studies (CESAM) through the strategic project UID/AMB/50017/2013. Ana Vicente acknowledges the postdoc grant SFRH/BPD/88988/2012 from FCT.


  1. Alves AC, Oliveira C, Martins N, Mirante F, Caseiro A, Pio C, Matos M, Silva HF, Oliveira C, Camões F (2016) Road tunnel, roadside and urban background measurements of aliphatic compounds in size-segregated particulate matter. Atmos Res 168:139–148CrossRefGoogle Scholar
  2. Alves CA, Gomes J, Nunes T, Duarte M, Calvo A, Custódio D, Pio C, Karanasiou A, Querol X (2015) Size-segregated particulate matter and gaseous emissions from motor vehicles in a road tunnel. Atmos Res 153:134–144CrossRefGoogle Scholar
  3. Alves C, Nunes T, Vicente A, Gonçalves C, Evtyugina M, Marques T, Pio C, Bate-Epey F (2014) Speciation of organic compounds in aerosols from urban background sites in the winter season. Atmos Res 150:57–68CrossRefGoogle Scholar
  4. Bahry PS, Zakaria MP, Abdullah AMB, Abdullah DK, Sakari M, Chandru K, Shahbazi A (2009) Forensic characterization of polycyclic aromatic hydrocarbons and hopanes in aerosols from Peninsular Malaysia. Environ Forensic 10:240–252CrossRefGoogle Scholar
  5. Bi X, Simoneit BRT, Sheng G, Fu J (2008) Characterization of molecular markers in smoke from residential coal combustion in China. Fuel 87:112–119CrossRefGoogle Scholar
  6. Boonyatumanond R, Murakami M, Wattayakorn G, Togo A, Takada H (2007) Sources of polycyclic aromatic hydrocarbons (PAHs) in street dust in a tropical Asian mega-city, Bangkok, Thailand. Sci Total Environ 384:420–432CrossRefGoogle Scholar
  7. Bozlaker A, Spada NJ, Fraser MP, Chellam S (2014) Elemental characterization of PM2.5 and PM10 emitted from light duty vehicles in the Washburn Tunnel of Houston, Texas: release of rhodium, palladium, and platinum. Environ Sci Technol 48:54–62CrossRefGoogle Scholar
  8. Brito J, Rizzo LV, Herckes P, Vasconcellos PC, Caumo SES, Fornaro A, Ynoue RY, Artaxo P, Andrade MF (2013) Physical–chemical characterisation of the particulate matter inside two road tunnels in the São Paulo metropolitan area. Atmos Chem Phys 13:2199–12213CrossRefGoogle Scholar
  9. Cheung K, Ntziachristos L, Tzamkiozis T, Schauer J, Samaras Z, Moore K, Sioutas C (2010) Emissions of particulate trace elements, metals and organic species from gasoline, diesel, and biodiesel passenger vehicles and their relation to oxidative potential. Aerosol Sci Technol 44:500–513CrossRefGoogle Scholar
  10. Fabiańska MJ, Kozielska B, Konieczyński J, Kowalski A (2016b) Sources of organic pollution in particulate matter and soil of Silesian agglomeration (Poland): evidence from geochemical markers. Environ Geochem Health 38:821–842CrossRefGoogle Scholar
  11. Fabiańska M, Kozielska B, Bielaczyc P, Woodburn J, Konieczyński J (2016a) Geochemical markers and polycyclic aromatic hydrocarbons in solvent extracts from diesel engine particulate matter. Environ Sci Pollut Res 23:6999–7011CrossRefGoogle Scholar
  12. Han F, Cao J, Peng L, Bai H, Hu D, Mu L, Liu X (2015) Characteristics of hopanoid hydrocarbons in ambient PM10 and motor vehicle emissions and coal ash in Taiyuan, China. Environ Geochem Health 37:813–829CrossRefGoogle Scholar
  13. He LY, Hu M, Huang XF, Zhang YH, Yu BD, Liu DQ (2006) Chemical characterization of fine particles from on-road vehicles in the Wutong tunnel in Shenzhen, China. Chemosphere 62:1565–1573CrossRefGoogle Scholar
  14. He LY, Hu M, Zhang YH, Huang XF, Yao TT (2008) Fine particle emissions from on-road vehicles in Zhujiang Tunnel, China. Environ Sci Technol 42:4461–4466CrossRefGoogle Scholar
  15. Huang L, Bohac SV, Chernyak SM, Batterman SA (2015) Effects of fuels, engine load and exhaust after-treatment on diesel engine SVOC emissions and development of SVOC profiles for receptor modelling. Atmos Environ 102:228–238CrossRefGoogle Scholar
  16. Kleeman MJ, Riddle SG, Robert MA, Jakober CA (2007) Lubricating oil and fuel contributions to particulate matter emissions from light-duty gasoline and heavy-duty diesel vehicles. Environ Sci Technol 42:235–242CrossRefGoogle Scholar
  17. Kraus U, Breitner S, Schnelle-Kreis J, Cyrys J, Lanki T, Rückerl R, Schneider A, Brüske I, Gu J, Devlin R, Wichmann HE, Zimmermann R, Peters A (2011) Particle-associated organic compounds and symptoms in myocardial infarction survivors. Inhal Toxicol 23:431–447CrossRefGoogle Scholar
  18. Krudysz MA, Dutton SJ, Brinkman GL, Hannigan MP, Fine PM, Sioutas C, Froines JR (2009) Intra-community spatial variation of size-fractionated organic compounds in Long Beach, California. Air Qual Atmos Health 2:69–88CrossRefGoogle Scholar
  19. Ma CM, Hong GB, Chang CT (2011) Influence of traffic flow patterns on air quality inside the longest tunnel in Asia. Aerosol Air Qual Res 11:44–50Google Scholar
  20. Magara-Gomez KT, Olson MR, Okuda T, Walz KA, Schauer JJ (2012) Sensitivity of diesel particulate material emissions and composition to blends of petroleum diesel and biodiesel fuel. Aerosol Sci Technol 46:1109–1118CrossRefGoogle Scholar
  21. Malmquist L (2006) Chemometric analyses of in vitro weathering of a heavy fuel oil. Master Thesis. Roskilde University and National Environmental Research InstituteGoogle Scholar
  22. Mancilla Y, Mendoza A, Fraser MP, Herckes P (2016) Organic composition and source apportionment of fine aerosol at Monterrey, Mexico, based on organic markers. Atmos Chem Phys 16:953–970CrossRefGoogle Scholar
  23. McDonald JD, Eide I, Seagrave JC, Zielinska B, Whitney K, Lawson DR, Mauderly JL (2004) Relationship between composition and toxicity of motor vehicle emission samples. Environ Health Perspect 112:1527–1538CrossRefGoogle Scholar
  24. Omar N, Abas M, Rahman NA, Tahir N, Rushdi A, Simoneit BRT (2006) Levels and distributions of organic source tracers in air and roadside dust particles of Kuala Lumpur. Environ Geol 52:1485–1500CrossRefGoogle Scholar
  25. Oros DR, Simoneit BRT (2000) Identification and emission rates of molecular tracers in coal smoke particulate matter. Fuel 79:515–536CrossRefGoogle Scholar
  26. Pakbin P, Ning Z, Schauer JJ, Sioutas C (2009) Characterization of particle bound organic carbon from diesel vehicles equipped with advanced emission control technologies. Environ Sci Technol 43:4679–4686CrossRefGoogle Scholar
  27. Peters KE, Walters C, Moldowan J (2007) The biomarker guide. Biomarkers and isotopes in the environment and human history, vol 1, 2nd edn. Cambridge University Press, CambridgeGoogle Scholar
  28. Qadir RM, Schnelle-Kreis J, Abbaszade G, Arteaga-Salas JM, Diemer J, Zimmermann R (2014) Spatial and temporal variability of source contributions to ambient PM10 during winter in Augsburg, Germany using organic and inorganic tracers. Chemosphere 103:263–273CrossRefGoogle Scholar
  29. Rogge WF, Hildemann LM, Mazurek MA, Cass GR, Simoneit BRT (1993) Sources of fine organic aerosol: 2. Non-catalyst and catalyst-equipped automobiles and heavy duty diesel trucks. Environ Sci Technol 27:636–651CrossRefGoogle Scholar
  30. Sarnat SE, Winquist A, Schauer JJ, Turner JR, Sarnat JA (2015) Fine particulate matter components and emergency department visits for cardiovascular and respiratory diseases in the St. Louis, Missouri-Illinois, metropolitan area. Environ Health Perspect 123:437–444Google Scholar
  31. Seifert WK, Moldowan JM (1978) Applications of steranes, terpanes, monoaromatics to the maturation, migration, and source of crude oils. Geochim Cosmochim Acta 42:77–95CrossRefGoogle Scholar
  32. Subramanian R, Donahue NM, Bernardo-Bricker A, Rogge WF, Robinson AL (2006) Contribution of motor vehicle emissions to organic carbon and fine particle mass in Pittsburgh, Pennsylvania: effects of varying source profiles and seasonal trends in ambient marker concentrations. Atmos Environ 40:8002–8019CrossRefGoogle Scholar
  33. Wang G, Kawamura K, Lee S, Ho KF, Cao JJ (2006a) Molecular, seasonal, and spatial distributions of organic aerosols from fourteen Chinese cities. Environ Sci Technol 40:4619–4625CrossRefGoogle Scholar
  34. Wang H, Kawamura K, Shooter D (2006b) Wintertime organic aerosols in Christchurch and Auckland, New Zealand: contributions of residential wood and coal burning and petroleum utilization. Environ Sci Technol 40:5257–5262CrossRefGoogle Scholar
  35. Zakaria MP, Okuda T, Takada H (2001) Polycyclic aromatic hydrocarbons (PAHs) and hopanes in stranded tar-balls on the coast of Peninsular Malaysia: applications of biomarkers for identifying sources of oil pollution. Mar Pollut Bull 42:1357–1366CrossRefGoogle Scholar
  36. Zakaria MP, Takada H, Tsutsumi S, Ohno K, Yamada J, Kuono E, Kumata H (2002) Distribution of polycyclic aromatic hydrocarbons (PAHs) in rivers and estuaries in Malaysia: a widespread input of petrogenic PAHs. Environ Sci Technol 36:1907–1918CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2017

Authors and Affiliations

  • Célia A. Alves
    • 1
  • Ana M. Vicente
    • 1
  • Sónia Rocha
    • 1
  • Pérola Vasconcellos
    • 2
  1. 1.Centre for Environmental and Marine Studies, Department of EnvironmentUniversity of AveiroAveiroPortugal
  2. 2.Chemistry InstituteUniversity of São Paulo, Cidade UniversitáriaSão PauloBrazil

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