Philip J. Silva

Chase Studies of Particulate Emissions from in-use New York City Vehicles

Emissions from motor vehicles are a significant source of fine particulate matter (PM) and gaseous pollutants in urban environments. Few studies have characterized both gaseous and PM emissions from individual in-use vehicles under real-world driving conditions. Here we describe chase vehicle studies in which on-road emissions from individual vehicles were measured in real time within seconds of their emission. This work uses an Aerodyne aerosol mass spectrometer (AMS) to provide size-resolved and chemically resolved characterization of the nonrefractory portion of the emitted PM; refractory materials such as elemental carbon (EC) were not measured in this study. The AMS, together with other gas-phase and particle instrumentation, was deployed on the Aerodyne Research Inc. (ARI) mobile laboratory, which was used to “chase” the target vehicles. Tailpipe emission indices of the targeted vehicles were obtained by referencing the measured nonrefractory particulate mass loading to the instantaneous CO2 measured simultaneously in the plume. During these studies, nonrefractory PM1.0 (NRPM1) emission indices for a representative fraction of the New York City Metropolitan Transit Authority (MTA) bus fleet were determined. Diesel bus emissions ranged from 0.10 g NRPM1/kg fuel to 0.23 g NRPM1/kg, depending on the type of engine used by the bus. The average NRPM1 emission index of diesel-powered buses using Continuously Regenerating Technology (CRT™) trap systems was 0.052 g NRPM1/kg fuel. Buses fueled by compressed natural gas (CNG) had an average emission index of 0.034 g NRPM1/kg Fuel. The mass spectra of the nonrefractory diesel aerosol components measured by the AMS were dominated by lubricating oil spectral signatures. Mass-weighted size distributions of the particles in fresh diesel exhaust plumes peak at vacuum aerodynamic diameters around 90 nm with a typical full width at half maximum of 60 nm.

Direct evidence for chlorine-enhanced urban ozone formation in Houston, Texas

Urban air pollution is characterized by high ozone levels, formed when volatile organic compounds (VOCs) are oxidized in the presence of nitrogen oxides (NOx). VOC and NOx emissions controls have traditionally been implemented to reduce urban ozone formation, however, a separate chemical species implicated in ozone formation in Houston, TX and possibly other urban areas is the chlorine radical (Cl ). Cl enhances tropospheric VOC oxidation, but is not included in models used to develop air quality attainment plans. We present results of a three-fold approach to elucidate the importance of Cl in urban ozone formation: (1) the first direct evidence of chlorine chemistry in the urban troposphere, (2) enhanced ozone formation (>75 parts per 10 9 (ppb/h) observed when small amounts of chlorine (Cl2) are injected into captive ambient air, and (3) enhanced ozone formation (B16 ppb) predicted by regional photochemical models employing Cl chemistry. These results suggest that reducing chlorine emissions should be considered in urban ozone management strategies. r 2003 Elsevier Science Ltd. All rights reserved.

Single Particle Characterization of Automobile and Diesel Truck Emissions in the Caldecott Tunnel

Individual aerosol particles emitted from light-duty vehicles (LDV) and heavy-duty vehicles (HDV) were sampled in the Caldecott Tunnel (Berkeley, CA) using an aerosol time-of-flight mass spectrometer (ATOFMS). This instru ment determines both size and composition information of individual particles in real time. From the composition of individual particles, in conjunction with knowledge of the traffic patterns in the Caldecott Tunnel, information about the source of the particles can be determined. Based upon chemical composition, three main types of particles were detected: particles with significant mass spectral signal due to polycyclic aromatic hydrocarbons (PAH), elemental carbon (soot) particles, and inorganic particles containing substantial signal due to ions includ ing Al+, Ca+, Fe+, Ba+ and BaO+. Preliminary analysis of these classes shows that they encompass 61.4%, 10.3%, and 11.0%, respectively, of the total number of particles sampled with the ATOFMS instrument in 3 h, heavy traffic sampling periods, in an LDV-only bore of the tunnel. They represent 57.4%, 11.8%, and 18.0%, respectively, of the total number of particles sampled with the ATOFMS instrument in a 3 h sampling period in a mixed traffic (HDV and LDV) bore of the tunnel.

SpectraSort: A data analysis program for real-time aerosol analysis by aerosol time-of-flight mass spectrometry

Abstract A computer program, SpectraSort, has been written to facilitate the analysis of ambient aerosol data acquired in our laboratory using aerosol time-of-flight mass spectrometry (ATOFMS). ATOFMS is a unique aerosol analysis technique developed to obtain the size and chemical composition of individual aerosol particles. Conventional aerosol analysis methods can only provide the average chemical composition of many particles for a given size range, or the size of individual particles, but not their chemical composition. Knowledge of both the size and composition of individual aerosol particles ultimately will help evaluate particle toxicity and reactivity, as well as assist in the identification of particle emission sources. These three pieces of information are vital in any rigorous attempt to regulate particulate pollution in the atmosphere. At present, in ATOFMS data analysis, each individual particle mass spectrum must be calibrated manually, and any compositional information tabulated for subsequent correlation with the size of the corresponding particle. SpectraSort greatly facilitates the processing of particle size and composition information by maximizing the efficiency of manual classification; but, a fully automated solution is necessary if ATOFMS is to evolve into a routine real-time aerosol analysis tool.

Laboratory evaluation of species-dependent relative ionization efficiencies in the Aerodyne Aerosol Mass Spectrometer

ABSTRACT Mass concentrations calculated from Aerodynes aerosol mass spectrometers depend on particle collection efficiency (CE) and relative ionization efficiency (RIE, relative to the primary calibrant ammonium nitrate). We present new laboratory RIE measurements for a wide range of organic aerosol species (RIEOA). An improved laboratory RIE calibration protocol with size and mass selection of calibrant particles and a light scattering-based detection of CE is used. Simpler calibrations of alcohol RIEs using binary mixtures with NH4NO3 are demonstrated. Models that account for only thermal velocity and electron ionization of vaporized molecules do not reproduce RIEOA measurements, confirming that other processes are significant. The relationship between RIEOA and average carbon oxidation state (), a metric used to describe atmospheric OA, is investigated. An average RIEOA of 1.6 ± 0.5 (2σ) is found for −1.0 < < 0.5, a range consistent with most ambient OA except hydrocarbon-like organic aerosol (HOA) and cooking organic aerosol (COA). RIEOA from 2 to 7 are found for below and above this range. The RIEOA typically used for ambient OA (1.4 ± 0.3) is within the laboratory RIEOA measurement uncertainty of oxidized organic species, but is a factor of 2 to 5 lower than that of reduced species. Such biases in OA mass concentrations have not been observed in published field analyses. Chemically reduced ambient OA may have composition, phase states, or compensating CE effects that are not mimicked well in the laboratory. This work highlights the need for further ambient OA studies to better constrain the composition dependence of ambient RIEOA, and the need to always calibrate with the OA under study for laboratory experiments. Copyright