Load-Dependent Emission Factors and Chemical Characteristics of IVOCs from a Medium-Duty Diesel Engine.

A detailed understanding of the climate and air quality impacts of mobile-source emissions requires the characterization of intermediate-volatility organic compounds (IVOCs), relatively-low-vapor-pressure gas-phase species that may generate secondary organic aerosol with high yields. Due to challenges associated with IVOC detection and quantification, IVOC emissions remain poorly understood at present. Here, we describe measurements of the magnitude and composition of IVOC emissions from a medium-duty diesel engine. Measurements are made on an engine dynamometer and utilize a new mass-spectrometric instrument to characterize the load dependence of the emissions in near-real-time. Results from steady-state engine operation indicate that IVOC emissions are highly dependent on engine power, with highest emissions at engine idle and low-load operation (≤25% maximum rated power) with a chemical composition dominated by saturated hydrocarbon species. Results suggest that unburned fuel components are the dominant IVOCs emitted at low loads. As engine load increases, IVOC emissions decline rapidly and become increasingly characterized by unsaturated hydrocarbons and oxygenated organics, newly formed from incomplete combustion processes at elevated engine temperatures and pressures. Engine transients, including a cold-start ignition and engine acceleration, show IVOC emission profiles that are different in amount or composition compared to steady-state combustion, underscoring the utility of characterizing IVOC emissions with high time resolution across realistic engine operating conditions. We find possible evidence for IVOC losses on unheated dilution and sampling surfaces, which need to be carefully accounted for in IVOC emission studies.

[1]  Real-Time Measurements of Engine-Out Trace Elements: Application of a Novel Soot Particle Aerosol Mass Spectrometer for Emissions , 2012 .

[2]  B. Brunekreef,et al.  Air pollution and health , 2002, The Lancet.

[3]  A. Lewis,et al.  Diesel-related hydrocarbons can dominate gas phase reactive carbon in megacities , 2015 .

[4]  David E. Foster,et al.  Effect of Engine Operating Conditions on Particle-Phase Organic Compounds in Engine Exhaust of a Heavy-Duty Direct-Injection (D.I.) Diesel Engine , 2003 .

[5]  Andrew A. May,et al.  Intermediate Volatility Organic Compound Emissions from On-Road Diesel Vehicles: Chemical Composition, Emission Factors, and Estimated Secondary Organic Aerosol Production. , 2015, Environmental science & technology.

[6]  Glen R. Cass,et al.  Sources of fine organic aerosol. 2. Noncatalyst and catalyst-equipped automobiles and heavy-duty diesel trucks , 1993 .

[7]  Andrew A. May,et al.  Intermediate-volatility organic compounds: a large source of secondary organic aerosol. , 2014, Environmental science & technology.

[8]  Alexander Sappok,et al.  Lubricant-Derived Ash Properties and Their Effects on Diesel Particulate Filter Pressure-Drop Performance , 2009 .

[9]  Glen R. Cass,et al.  Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation , 1993 .

[10]  J. Chow Health Effects of Fine Particulate Air Pollution: Lines that Connect , 2006, Journal of the Air & Waste Management Association.

[11]  Richard Baldauf,et al.  Cold temperature and biodiesel fuel effects on speciated emissions of volatile organic compounds from diesel trucks. , 2014, Environmental science & technology.

[12]  J. Seinfeld,et al.  Emission factor ratios, SOA mass yields, and the impact of vehicular emissions on SOA formation , 2013 .

[13]  A. Middlebrook,et al.  Gasoline emissions dominate over diesel in formation of secondary organic aerosol mass , 2012 .

[14]  Christine Maddox,et al.  Gas- and particle-phase primary emissions from in-use, on-road gasoline and diesel vehicles , 2014 .

[15]  A. Robinson,et al.  Updating the conceptual model for fine particle mass emissions from combustion systems. , 2010, Journal of the Air & Waste Management Association.

[16]  Zuohua Huang,et al.  Diesel engine gaseous and particle emissions fueled with diesel-oxygenate blends , 2012 .

[17]  Michael J. Kleeman,et al.  MEASUREMENT OF EMISSIONS FROM AIR POLLUTION SOURCES. 2. C1 THROUGH C30 ORGANIC COMPOUNDS FROM MEDIUM DUTY DIESEL TRUCKS , 1999 .

[18]  Y. Kissin Acyclic components in dewaxed heavy distillates , 1990 .

[19]  Robert Henry Hammerle,et al.  Organic emissions profile for a light-duty diesel vehicle , 1999 .

[20]  R C Flagan,et al.  Measurements of secondary organic aerosol from oxidation of cycloalkenes, terpenes, and m-xylene using an Aerodyne aerosol mass spectrometer. , 2005, Environmental science & technology.

[21]  R. Hites,et al.  Aromatic diesel emissions as a function of engine conditions , 1983 .

[22]  A. Robinson,et al.  Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle , 2013 .

[23]  Scott C Herndon,et al.  Hydrocarbon emissions from in-use commercial aircraft during airport operations. , 2006, Environmental science & technology.

[24]  Qi Zhang,et al.  O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry. , 2008, Environmental science & technology.

[25]  M. Andreae,et al.  Mass spectrometric analysis and aerodynamic properties of various types of combustion-related aerosol particles , 2006 .

[26]  Jared D. Smith,et al.  Characterisation of lightly oxidised organic aerosol formed from the photochemical aging of diesel exhaust particles , 2012 .

[27]  Timothy R. Dallmann,et al.  Elucidating secondary organic aerosol from diesel and gasoline vehicles through detailed characterization of organic carbon emissions , 2012, Proceedings of the National Academy of Sciences.

[28]  Shishan Hu,et al.  Neighborhood-scale air quality impacts of emissions from motor vehicles and aircraft , 2013 .

[29]  Joseph Acar,et al.  Emissions and In-Cylinder Combustion Characteristics of Fischer-Tropsch and Conventional Diesel Fuels in a Modern CI Engine , 2005 .

[30]  D. Dockery,et al.  Health Effects of Fine Particulate Air Pollution: Lines that Connect , 2006, Journal of the Air & Waste Management Association.

[31]  Edward Charles Fortner,et al.  Real-Time Measurements of Engine-Out Trace Elements: Application of a Novel Soot Particle Aerosol Mass Spectrometer for Emissions Characterization , 2011 .

[32]  G. Cass,et al.  Quantitative Characterization of Urban Sources of Organic Aerosol by High-Resolution Gas Chromatography , 1991 .

[33]  Charles E. Kolb,et al.  Chase Studies of Particulate Emissions from in-use New York City Vehicles , 2004 .

[34]  R. Selin The Outlook for Energy: A View to 2040 , 2013 .

[35]  Experimental investigation of regulated and unregulated emissions from a diesel engine fueled with ultralow-sulfur diesel fuel blended with ethanol and dodecanol. , 2008 .

[36]  P. DeCarlo,et al.  Elemental analysis of organic species with electron ionization high-resolution mass spectrometry. , 2007, Analytical chemistry.

[37]  A. Robinson,et al.  Secondary organic aerosol formation from photo-oxidation of unburned fuel: experimental results and implications for aerosol formation from combustion emissions. , 2013, Environmental science & technology.

[38]  B. Simoneit,et al.  Characterization of Organic Constituents in Aerosols in Relation to Their rigin and Transport: A Review , 1986 .

[39]  V. Wong,et al.  Detailed Chemical and Physical Characterization of Ash Species in Diesel Exhaust Entering Aftertreatment Systems , 2007 .

[40]  S. Herndon,et al.  Online measurements of the emissions of intermediate-volatility and semi-volatile organic compounds from aircraft , 2013 .

[41]  Zoran Ristovski,et al.  Ambient nano and ultrafine particles from motor vehicle emissions: Characteristics, ambient processing and implications on human exposure , 2008 .

[42]  Allen L Robinson,et al.  Rethinking Organic Aerosols: Semivolatile Emissions and Photochemical Aging , 2007, Science.