Variations in the OM/OC ratio of urban organic aerosol next to a major roadway

Abstract

Understanding the organic matter/organic carbon (OM/OC) ratio in ambient particulate matter (PM) is critical to achieve mass closure in routine PM measurements, to assess the sources of and the degree of chemical processing organic aerosol particles have undergone, and to relate ambient pollutant concentrations to health effects. Of particular interest is how the OM/OC ratio varies in the urban environment, where strong spatial and temporal gradients in source emissions are common. We provide results of near-roadway high-time-resolution PM1 OM concentration and OM/OC ratio observations during January 2008 at Fyfe Elementary School in Las Vegas, NV, 18 m from the U.S. 95 freeway soundwall, measured with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The average OM/OC ratio was 1.54 (± 0.20 standard deviation), typical of environments with a low amount of secondary aerosol formation. The 2-min average OM/OC ratios varied between 1.17 and 2.67, and daily average OM/OC ratios varied between 1.44 and 1.73. The ratios were highest during periods of low OM concentrations and generally low during periods of high OM concentrations. OM/OC ratios were low (1.52 ± 0.14, on average) during the morning rush hour (average OM = 2.4 µg/m3), when vehicular emissions dominate this near-road measurement site. The ratios were slightly lower (1.46 ± 0.10) in the evening (average OM = 6.3 µg/m3), when a combination of vehicular and fresh residential biomass burning emissions was typically present during times with temperature inversions. The hourly averaged OM/OC ratio peaked at 1.66 at midday. OM concentrations were similar, regardless of whether the monitoring site was downwind or upwind of the adjacent freeway throughout the day, though they were higher during stagnant conditions (wind speed < 0.5 m/sec). The OM/OC ratio generally varied more with time of day than with wind direction and speed. Implications: Day-to-day variability in the fine particle OM/OC ratio is quite large, suggesting that using a fixed OM/OC value in PM mass closure calculations, even one that changes seasonally, may be insufficient to achieve accurate mass closure on individual days. Health studies that rely on OC measurements may under- or overestimate exposure to OM, and converting OC to OM with a fixed OM/OC ratio represents a significant source of uncertainty; thus, air quality managers may not have sufficient information about the importance of OM contributions to PM2.5 to make optimal regulatory decisions. Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association.