Road tunnel, roadside, and urban background measurements of aliphatic compounds in size-segregated particulate matter

• Size-segregated PM was collected at 3 sites differently impacted by traffic in Lisbon.
• Concentrations were up to 143 times higher in the tunnel than outdoors.
• Compounds were heavily concentrated in the smallest particle sizes.
• Norhopane-to-OC ratio of the tunnel was used to estimate OC from traffic in the city.
• Factors influencing the Σhopane-to-EC ratios between seasons were discussed.

Particulate matter samples were collected in a road tunnel in Lisbon (PM0.5, PM0.5–1, PM1–2.5, and PM2.5–10) and at two urban locations representing roadside and background stations (PM2.5 and PM2.5–10). Samples were analysed for organic and elemental carbon (OC and EC), n-alkanes, n-alkenes, hopanes, some isoprenoid compounds, and steranes. Particulate matter concentrations in the tunnel were 17–31 times higher than at roadside in the vicinity, evidencing an aerosol origin almost exclusively in fresh vehicle emissions. PM0.5 in the tunnel comprised more than 60% and 80% of the total OC and EC mass in PM10, respectively. Concentrations of the different aliphatic groups of compounds in the tunnel were up to 89 times higher than at roadside and 143 times higher than at urban background. Based on the application of hopane-to-OC or hopanes-to-EC ratios obtained in the tunnel, it was found that vehicle emissions are the dominant contributor to carbonaceous particles in the city but do not represent the only source of these triterpenic compounds. Contrary to what has been observed in other studies, the Σhopane-to-EC ratios were higher in summer than in winter, suggesting that other factors (e.g. biomass burning, dust resuspension, and different fuels/engine technologies) prevail in relation to the photochemical decay of triterpenoid hydrocarbons from vehicle exhaust.