Water-soluble iron emitted from vehicle exhaust is linked to primary speciated organic compounds

Abstract

Iron is the most abundant transition element in airborne particulate matter (PM), primarily existing as Fe(II) or Fe(III). Generally, the fraction of water-soluble iron is greater in urban areas compared to areas dominated by crustal emissions. To better understand the origin of water-soluble iron in urban areas, tailpipe emission samples were collected from 32 vehicles with emission certifications of Tier 0 low emission vehicles (LEV I), Tier 2 low emission vehicles (LEV II), ultralow emission vehicles (ULEVs), super-ultralow emission vehicles (SULEVs), and partial-zero emission vehicles (PZEVs). The components quantified included gases, inorganic ions, elemental carbon (EC), organic carbon (OC), total metals, and water-soluble metals. Naphthalene and intermediate-volatility organic compounds (IVOCs) were quantified for a subset of vehicles. The IVOCs quantified contained 12 to 18 carbons and were divided into three subgroups: aliphatic, single-ring aromatic (SRA), and polar (material not classified as either aliphatic or SRA). Iron solubility in the tested vehicles ranged from 0 % to 82 % (average 30 %). X-ray absorption near-edge structure (XANES) spectroscopy showed that Fe(III) was the primary oxidation state in 14 of the 16 tested vehicles, confirming that the presence of Fe(II) was not the main driver of water-soluble Fe. The correlation of water-soluble iron with sulfate was insignificant, as was correlation with every chemical component except naphthalene and some C12–C18 IVOCs with R2 values as high as 0.56. A controlled benchtop study confirmed that naphthalene alone increases iron solubility from soils by a factor of 5.5 and that oxidized naphthalene species are created in the extract solution. These results suggest that the large driver in water-soluble iron from primary vehicle tailpipe emissions is related to the organic composition of the PM. We hypothesize that, during the extraction process, specific components of the organic fraction of the PM are oxidized and chelate the iron into water.