Detailed gas and diesel vehicle emissions: PTR-MS measurements of real-time VOC profiles and comprehensive characterization of primary emissions for IVOC, SVOC, and LVOC by gas chromatography with vacuum ultra-violet ionization mass spectrometry

Abstract:

Over the past fifteen years US vehicle emissions standards have dramatically improved, with the goal of reducing urban air pollution. Recent studies demonstrate secondary organic aerosol (SOA) to be the dominant contributor to urban organic aerosol, but controversy remains regarding the contributions of different vehicle types to SOA. Increased potency for SOA formation from non methane hydrocarbons (NMHC) from newer vehicles that meet tighter emission standards has also been observed. Both speciation and temporal resolution of vehicular emissions are critical for predicting SOA formation. The relative importance of diesel and gasoline emissions to SOA formation depends critically on speciation. Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to better understand SOA formation for low, ultra-low, super ultra-low and partial zero emission vehicles (LEV, ULEV, SULEV, PZEV). Exhaust was sampled on filters and adsorbent tubes to measure intermediate-, semi-, and low-volatility NMHC (IVOC, SVOC, LVOC). A proton-transfer-reaction mass spectrometer (PTR-MS) measured volatile organics (VOC) emissions with high time-resolution. Analysis of filters and adsorbent tubes using gas chromatography with vacuum-ultra-violet ionization mass spectrometry provided unprecedented characterization of emissions according to degree of branching, number of cyclic rings, aromaticity, and molecular weight. ULEV vehicles show the composition distributions of primary particulate emissions peak for compounds in the SVOC range. PZEV vehicle emissions peak in the IVOC range. Diesel vehicles have up to ten times higher emissions than gasoline vehicles; their distributions have significant IVOC levels and peak in the SVOC/LVOC range. Our measurements are used to predict potential SOA formation by vehicle standard class and the relative SOA formation for diesel and gasoline vehicles. PTR-MS measurement show VOC emissions after cold start occur almost entirely in the first 30-60 seconds, and both their magnitude and duration consistently decrease with stricter standards.