Chemical Characterization of Airport-related Ultrafine Particles using Liquid Chromatography – High-Resolution Mass Spectrometry (UHPLC/HRMS)

Abstract:

We present the results from a chemical characterization study of ultrafine particles (UFP), collected nearby a large international airport where particle size distribution measurements showed high number concentrations for particles with a diameter <50 nm. Aluminium filter samples were collected at an air quality monitoring station in a distance of 4 km to Frankfurt airport, using the 13-stage cascade impactor Nano-MOUDI (MSP Model-115). The chemical characterization of the ultrafine particles in the size range of 0.010-0.018 μm, 0.018-0.032 μm and 0.032-0.056 μm was accomplished by the development of an optimized filter extraction method. An UHPLC method for chromatographic separation of homologue series of hydrophobic and high molecular weight organic compounds, followed by heated electrospray ionization (ESI) and mass analysis using an Orbitrap high-resolution mass spectrometer was developed. Using a non-target screening, ~200 compounds were detected in the positive ionization mode after filtering, in order to ensure high quality of the obtained data. We determined the molecular formula of positively charged adducts ([M+H]⁺; [M+Na]⁺), and for each impaction stage we present molecular fingerprints (Molecular weight vs Retention time, Kroll-diagram, Van-Krevelen-diagram, Kendrick mass defect plot) in order to visualize the complex chemical composition. The negative ionization mode led only to the detection of a few compounds (<20) for which reason the particle characterization focuses on the positive ionization mode. We found that the majority of detected compounds belong to homologue series of organic esters, which are base stocks of aircraft lubrication oils. In reference to five different jet engine lubrication oils of various manufacturers, we identified the corresponding lubricant base stocks and their additives in the ultrafine particles by the use of matching retention time, exact mass and MS/MS fragmentation pattern of single organic molecules. The hereby-introduced method allows the qualitative assignment of the aircraft emission impact towards the chemical composition of airport related ultrafine particles, whereas the quantitative determination is still lacking of the uncertainty regarding sampling artefacts in cascade impactors.