Characterization of Particulate Matter Emissions from a Current Technology Natural Gas Engine

Experiments were conducted to characterize the particulate matter (PM)-size distribution, number concentration, and chemical composition emitted from transit buses powered by a USEPA 2010 compliant, stoichiometric heavy-duty natural gas engine equipped with a three-way catalyst (TWC). Results of the particle-size distribution showed a predominant nucleation mode centered close to 10 nm. PM mass in the size range of 6.04 to 25.5 nm correlated strongly with mass of lubrication-oil-derived elemental species detected in the gravimetric PM sample. Results from oil analysis indicated an elemental composition that was similar to that detected in the PM samples. The source of elemental species in the oil sample can be attributed to additives and engine wear. Chemical speciation of particulate matter (PM) showed that lubrication-oil-based additives and wear metals were a major fraction of the PM mass emitted from the buses. The results of the study indicate the possible existence of nanoparticles below 25 nm formed as a result of lubrication oil passage through the combustion chamber. Furthermore, the results of oxidative stress (OS) analysis on the PM samples indicated strong correlations with both the PM mass calculated in the nanoparticle-size bin and the mass of elemental species that can be linked to lubrication oil as the source

Chemical Speciation of Vanadium in Particulate Matter Emitted from Diesel Vehicles and Urban Atmospheric Aerosols

We report on the development and application of an integrated set of analytical tools that enable accurate measurement of total, extractable, and, importantly, the oxidation state of vanadium in sub-milligram masses of environmental aerosols and solids. Through rigorous control of blanks, application of magnetic-sector-ICPMS, and miniaturization of the extraction/separation methods we have substantially improved upon published quantification limits. The study focused on the application of these methods to particulate matter (PM) emissions from diesel vehicles, both in baseline configuration without after-treatment and also equipped with advanced PM and NO_<i>x</i> emission controls. Particle size-resolved vanadium speciation data were obtained from dynamometer samples containing total vanadium pools of only 0.2–2 ng and provide some of the first measurements of the oxidation state of vanadium in diesel vehicle PM emissions. The emission rates and the measured fraction of V(V) in PM from diesel engines running without exhaust after-treatment were both low (2–3 ng/mile and 13–16%, respectively). The V(IV) species was measured as the dominant vanadium species in diesel PM emissions. A significantly greater fraction of V(V) (76%) was measured in PM from the engine fitted with a prototype vanadium-based selective catalytic reductors (V-SCR) retrofit. The emission rate of V(V) determined for the V-SCR equipped vehicle (103 ng/mile) was 40-fold greater than that from the baseline vehicle. A clear contrast between the PM size-distributions of V(V) and V(IV) emissions was apparent, with the V(V) distribution characterized by a major single mode in the ultrafine (<0.25 μm) size range and the V(IV) size distribution either flat or with a small maxima in the accumulation mode (0.5–2 μm). The V(V) content of the V-SCR PM (6.6 μg/g) was 400-fold greater than that in PM from baseline (0.016 μg/g) vehicles, and among the highest of all environmental samples examined. Synchrotron based V 1s XANES spectroscopy of vanadium-containing fine-particle PM from the V-SCR identified V₂O₅ as the dominant vanadium species

Using a new inversion matrix for a fast-sizing spectrometer and a photo-acoustic instrument to determine suspended particulate mass over a transient cycle for light-duty vehicles

<p>Integrated particle size distribution (IPSD) is a promising alternative method for estimating particulate matter (PM) emissions at low levels. However, a recent light-duty vehicle (LDV) emissions study showed that particle mass estimated using IPSD (<i>M</i>_IPSD) with the TSI Engine Exhaust Particle Sizer (EEPS) Default Matrix was 56–75% lower than mass derived using the reference gravimetric method (<i>M</i>_Grav) over the Federal Test Procedure (FTP). In this study, <i>M</i>_IPSD calculated with a new inversion matrix, the Soot Matrix, is compared with <i>M</i>_Grav and also photoacoustic soot mass (<i>M</i>_Soot), to evaluate potential improvement of the IPSD method for estimating PM mass emissions from LDVs. In addition, an aerodynamic particle sizer (APS) was used to estimate mass emission rates attributed to larger particles (0.54–2.5 µm in aerodynamic diameter) that are not measured by the EEPS. Based on testing of 10 light-duty vehicles over the FTP cycle, the Soot Matrix significantly improved agreement between <i>M</i>_IPSD and <i>M</i>_Grav by increasing slopes of <i>M</i>_IPSD/<i>M</i>_Grav from 0.45–0.57 to 0.76–1.01 for gasoline direct injected (GDI) vehicles; however, for port-fuel injection (PFI) gasoline vehicles, a significant discrepancy still existed between <i>M</i>_IPSD and <i>M</i>_Grav, with <i>M</i>_IPSD accounting for 34 ± 37% of <i>M</i>_Grav. For all vehicles, strong correlations between <i>M</i>_IPSD and <i>M</i>_Soot were obtained, indicating the IPSD method is capable of capturing mass of soot particles. The discrepancy between the <i>M</i>_IPSD and <i>M</i>_Grav for PFI vehicles, which have relatively low PM emissions (0.22 to 1.83 mg/mile), could be partially due to limited size range of the EEPS by not capturing larger particles (0.54–2.5 µm) that accounts for ∼0.08 mg/mile of PM emission, uncertainties of particle effective density, and/or gas-phase adsorption onto filters that is not detected by <i>in situ</i> aerosol instrumentation.</p> <p>Copyright © 2016 American Association for Aerosol Research</p

Measuring Particulate Emissions of Light Duty Passenger Vehicles Using Integrated Particle Size Distribution (IPSD)

The California Air Resources Board (ARB) adopted the low emission vehicle (LEV) III particulate matter (PM) standards in January 2012, which require, among other limits, vehicles to meet 1 mg/mi over the federal test procedure (FTP). One possible alternative measurement approach evaluated to support the implementation of the LEV III standards is integrated particle size distribution (IPSD), which reports real-time PM mass using size distribution and effective density. The IPSD method was evaluated using TSI’s engine exhaust particle sizer (EEPS, 5.6–560 nm) and gravimetric filter data from more than 250 tests and 34 vehicles at ARB’s Haagen-Smit Laboratory (HSL). IPSD mass was persistently lower than gravimetric mass by 56–75% over the FTP tests and by 81–84% over the supplemental FTP (US06) tests. Strong covariance between the methods suggests test-to-test variability originates from actual vehicle emission differences rather than measurement accuracy, where IPSD offered no statistical improvement over gravimetric measurement variability