Quantification of Biogenic and Anthropogenic Hydrocarbons using a Commercial Gas Chromatograph - Ion Trap Mass Spectrometer at a Ground Site near Fort McKay, AB

Abstract:

The extraction of fossil fuels from the Alberta oil sands has been the focus of considerable attention due to its association with sizeable emissions of a variety of atmospheric pollutants, the magnitude and impacts of which are currently poorly constrained by observations. In order to more reliably estimate the magnitude and impact of these emissions, an intensive air quality measurement campaign, called "Fort McMurray Oil Sands Strategic Investigation of Local Sources" (FOSSILS), was conducted in the summer of 2013 as part of the Alberta-Canada joint oil sands monitoring program (JOSM) to identify and quantify emissions and their transformations from the Alberta oil sands. The challenge is that the region is surrounded by boreal forest, which provides a substantial background of biogenic hydrocarbons during summer.

In this presentation, measurements of volatile organic compounds (VOCs) at the AMS13 ground site near Fort McKay, Alberta, from Aug 17 to Sept 6, 2013 using a commercial Griffin 450 gas chromatograph equipped with ion trap mass spectrometric detection and Tenax preconcentration are described. The combination of retention information and electron impact mass spectral data allowed unambiguous identification and quantification of the major biogenic monoterpenes, e.g., α and β-pinene, limonene, camphene, and 3Δ-carene, and of many anthropogenically derived hydrocarbons. Mixing ratios of biogenic hydrocarbons varied with time of day, temperature, and solar radiation, with maxima typically occurring at night, rationalized by nocturnal mixing heights and low mixing ratios of the nocturnal oxidants ozone (O₃) and the nitrate radical (NO₃). In contrast, mixing ratios of anthropogenic VOCs, e.g., benzene, toluene, ethyl benzene, and o-, p-, and m-xylene (BTEX), strongly depended on meteorological conditions, i.e., local wind direction. During episodes with high BTEX abundance, many additional high molecular weight hydrocarbons were observed which were not resolved on the chromatographic column. Data are presented and discussed with minor details on calibration and software development included.