Ezra C. Wood

Evolution of Organic Aerosols in the Atmosphere

Framework for Change Organic aerosols make up 20 to 90% of the particulate mass of the troposphere and are important factors in both climate and human heath. However, their sources and removal pathways are very uncertain, and their atmospheric evolution is poorly characterized. Jimenez et al. (p. 1525; see the Perspective by Andreae) present an integrated framework of organic aerosol compositional evolution in the atmosphere, based on model results and field and laboratory data that simulate the dynamic aging behavior of organic aerosols. Particles become more oxidized, more hygroscopic, and less volatile with age, as they become oxygenated organic aerosols. These results should lead to better predictions of climate and air quality. Organic aerosols are not compositionally static, but they evolve dramatically within hours to days of their formation. Organic aerosol (OA) particles affect climate forcing and human health, but their sources and evolution remain poorly characterized. We present a unifying model framework describing the atmospheric evolution of OA that is constrained by high–time-resolution measurements of its composition, volatility, and oxidation state. OA and OA precursor gases evolve by becoming increasingly oxidized, less volatile, and more hygroscopic, leading to the formation of oxygenated organic aerosol (OOA), with concentrations comparable to those of sulfate aerosol throughout the Northern Hemisphere. Our model framework captures the dynamic aging behavior observed in both the atmosphere and laboratory: It can serve as a basis for improving parameterizations in regional and global models.

Application of quantum cascade lasers to high-precision atmospheric trace gas measurements

We review our recent results in development of high-precision laser spectroscopic instrumentation using midinfrared quantum cascade lasers (QCLs). Some of these instruments have been directed at mea- surements of atmospheric trace gases where a fractional precision of 10 −3 or better of ambient concentration may be required. Such high precision is needed in measurements of fluxes of stable atmospheric gases and measurements of isotopic ratios. Instruments that are based on thermoelectrically cooled midinfrared QCLs and thermoelectrically cooled detectors have been demonstrated that meet the requirements of high-precision atmospheric measurements, without the need for cryo- gens. We also describe the design of and results from a new dual QCL instrument with a 200-m path-length absorption cell. This instrument has demonstrated 1-s noise of 32 ppt for formaldehyde (HCHO) and 9 ppt for carbonyl sulfide (OCS). C 2010 Society of Photo-Optical Instrumentation Engineers.

Correlation of secondary organic aerosol with odd oxygen in Mexico City

> 0.9. The dependence of the observed proportionality onthe gas-phase hydrocarbon profile is discussed. Theobservationally-based correlation between oxygenatedorganic aerosol mass and odd oxygen may provide insightinto poorly understood secondary organic aerosolproduction mechanisms by leveraging knowledge of gas-phase ozone production chemistry. These results suggestthat global and regional models may be able to use theobserved proportionality to estimate SOA as a co-product ofmodeled O

On-Road Measurement of Gas and Particle Phase Pollutant Emission Factors for Individual Heavy-Duty Diesel Trucks

Pollutant concentrations in the exhaust plumes of individual diesel trucks were measured at high time resolution in a highway tunnel in Oakland, CA, during July 2010. Emission factors for individual trucks were calculated using a carbon balance method, in which pollutants measured in each exhaust plume were normalized to measured concentrations of carbon dioxide. Pollutants considered here include nitric oxide, nitrogen dioxide (NO(2)), carbon monoxide, formaldehyde, ethene, and black carbon (BC), as well as optical properties of emitted particles. Fleet-average emission factors for oxides of nitrogen (NO(x)) and BC respectively decreased 30 ± 6 and 37 ± 10% relative to levels measured at the same location in 2006, whereas a 34 ± 18% increase in the average NO(2) emission factor was observed. Emissions distributions for all species were skewed with a small fraction of trucks contributing disproportionately to total emissions. For example, the dirtiest 10% of trucks emitted half of total NO(2) and BC emissions. Emission rates for NO(2) were found to be anticorrelated with all other species considered here, likely due to the use of catalyzed diesel particle filters to help control exhaust emissions. Absorption and scattering cross-section emission factors were used to calculate the aerosol single scattering albedo (SSA, at 532 nm) for individual truck exhaust plumes, which averaged 0.14 ± 0.03.

Chemical Composition of Gas-Phase Organic Carbon Emissions from Motor Vehicles and Implications for Ozone Production

Motor vehicles are major sources of gas-phase organic carbon, which includes volatile organic compounds (VOCs) and other compounds with lower vapor pressures. These emissions react in the atmosphere, leading to the formation of ozone and secondary organic aerosol (SOA). With more chemical detail than previous studies, we report emission factors for over 230 compounds from gasoline and diesel vehicles via two methods. First we use speciated measurements of exhaust emissions from on-road vehicles in summer 2010. Second, we use a fuel composition-based approach to quantify uncombusted fuel components in exhaust using the emission factor for total uncombusted fuel in exhaust together with detailed chemical characterization of liquid fuel samples. There is good agreement between the two methods except for products of incomplete combustion, which are not present in uncombusted fuels and comprise 32 ± 2% of gasoline exhaust and 26 ± 1% of diesel exhaust by mass. We calculate and compare ozone production potentials of diesel exhaust, gasoline exhaust, and nontailpipe gasoline emissions. Per mass emitted, the gas-phase organic compounds in gasoline exhaust have the largest potential impact on ozone production with over half of the ozone formation due to products of incomplete combustion (e.g., alkenes and oxygenated VOCs). When combined with data on gasoline and diesel fuel sales in the U.S., these results indicate that gasoline sources are responsible for 69-96% of emissions and 79-97% of the ozone formation potential from gas-phase organic carbon emitted by motor vehicles.

Evolution of Vehicle Exhaust Particles in the Atmosphere

Abstract Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 μm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.

Adaptation of a proton transfer reaction mass spectrometer instrument to employ NO+ as reagent ion for the detection of 1,3-butadiene in the ambient atmosphere

A proton transfer reaction mass spectrometer (PTR-MS) instrument was adapted to employ NO+ as a chemical reagent ion without any hardware changes by switching the reagent ion source gas from water vapor to dry air. Ionization of dry air within the hollow cathode ion source generates a very intense source of NO+ with only a minor impurity of NO2+. The intensities of the primary NO+ reagent ion and the unwanted impurity NO2+ are controllable and dependent on the operational conditions of the hollow cathode ion source. Ion source tuning parameters are described, which maintain an intense source of NO+ while keeping the impurity NO2+ signal to less than 2% of the total reagent ion intensity. This method is applied to the detection of 1,3-butadiene. NO+ reacts efficiently with 1,3-butadiene via a charge exchange reaction to produce only the molecular ion, which is detected at m/z 54. Detection sensitivities of the order of 45 pptv for a 1-s measurement of 1,3-butadiene are demonstrated. We present the first real-time on-line sub parts per billion measurement of 1,3-butadiene in the ambient atmosphere. The only likely interference is from 1,2-butadiene. Concurrent measurements of benzene are provided and suggest that the vehicular emissions are the predominant source of 1,3-butadiene in a suburban Boston area monitoring location.

Gas Turbine Engine Emissions—Part I: Volatile Organic Compounds and Nitrogen Oxides

The potential human health and environmental impacts of aircraft gas turbine engine emissions during normal airport operation are issues of growing concern. During the JETS/Aircraft Particle Emissions eXperiment(APEX)-2 and APEX-3 field campaigns, we performed an extensive series of gas phase and particulate emissions measurements of on-wing gas turbine engines. In all, nine different CFM56 style engines (including both CFM56-3B1 and -7B22 models) and seven additional engines (two RB211-535E4-B engines, three AE3007 engines, one PW4158, and one CJ6108A) were studied to evaluate engine-to-engine variability. Specific gas-phase measurements include NO2, NO, and total NOx, HCHO, C2H4, CO, and a range of volatile organic compounds (e.g., benzene, styrene, toluene, naphthalene). A number of broad conclusions can be made based on the gas-phase data set: (1) field measurements of gas-phase emission indices (EIs) are generally consistent with ICAO certification values; (2) speciation of gas phase NOx between NO and NO2 is reproducible for different engine types and favors NO2 at low power (and low fuel flow rate) and NO at high power (high fuel flow rate); (3) emission indices of gas-phase organic compounds and CO decrease rapidly with increasing fuel flow rate; (4) plotting EI-CO or volatile organic compound EIs against fuel flow rate collapses much of the variability between the different engines, with one exception (AE3007); (5) HCHO, ethylene, acetaldehyde, and propene are the most abundant volatile organic compounds present in the exhaust gases that we can detect, independent of engine technology differences. Empirical correlations accurate to within 30% and based on the publicly available engine parameters are presented for estimating EI-NOx and EI-NO2. Engine-to-engine variability, unavailability of combustor input conditions, changing ambient temperatures, and complex reaction dynamics limit the accuracy of global correlations for CO or volatile organic compound EIs.

Combustion Products of Petroleum Jet Fuel, a Fischer–Tropsch Synthetic Fuel, and a Biomass Fatty Acid Methyl Ester Fuel for a Gas Turbine Engine

We report combustion emissions data for several alternatives to petroleum based Jet A jet fuel, including a natural gas–derived Fischer–Tropsch (FT) synthetic fuel; a 50/50 blend of the FT synthetic fuel with Jet A-1; a 20/80 blend of a fatty acid methyl ester (FAME) with jet fuel; and a 40/60 blend of FAME with jet fuel. The chief distinguishing features of the alternative fuels are reduced (for blends) or negligible (for pure fuels) aromatic content and increased oxygen content (for FAME blends). A CFM International CFM56-7 gas turbine engine was the test engine, and we measured NOX, CO, speciated volatile organic compounds (including oxygenates, olefins, and aromatic compounds), and nonvolatile particle size distribution, number, and mass emissions. We developed several new methods that account for fuel energy content and used the new methods to evaluate potential fuel effects on emissions performance. Our results are categorized as follows: (1) regulated pollutant emissions, CO, and NOX; (2) volatile organic compound emissions speciation; and (3) particle emissions. Replacing all or part of the petroleum jet fuel with either FAME or FT fuel reduces NOX emissions and may reduce CO emissions. Combustion of FT fuel and fuel blends increases selectivities and in some cases yields of oxygenates and some hydrocarbon volatile organic compound emissions relative to petroleum jet fuel. Combustion of FAME fuel increases propene and butene emissions, but despite its oxygen content does not strongly affect oxygenate emissions. Replacing petroleum jet fuel with zero aromatic alternatives decreases the emissions of aromatic hydrocarbons. The fuel effects become more pronounced as the size of the aromatic molecule increases (e.g., toluene is reduced more strongly than benzene). Particle emissions are decreased in particle size, number density, and total mass when petroleum jet fuel is replaced with the zero aromatic fuels. The effects of fuel composition on particle emissions are most pronounced at lower power conditions, i.e., when combustion temperature and pressure are lower, and less efficient mixing may lead to locally higher fuel/air ratios than are present at higher power.

Infrared QC laser applications to field measurements of atmospheric trace gas sources and sinks in environmental research: enhanced capabilities using continuous wave QCLs

The advent of continuous wave quantum cascade lasers operating at near room temperature has greatly expanded the capability of spectroscopic detection of atmospheric trace gases using infrared absorption at wavelengths from 4 to 12 μm. The high optical power, narrow line width, and high degree of single mode purity result in minimal fractional absorptions of 5x10-6 Hz-1/2 detectable in direct absorption with path lengths up to 210 meters. The Allan plot minima correspond to a fractional absorbance of 1x10-6 or a minimum absorption per unit path length 5x10-11 cm-1 in 50s. This allows trace gas mixing ratio detection limits in the low part-per-trillion (1 ppt = 10-12) range for many trace gases of atmospheric interest. We present ambient measurements of NO2 with detection precision of 10 ppt Hz-1/2. The detection precision for the methane isotopologue 13CH4 is 25 ppt Hz-1/2 which allows direct measurements of ambient ratios of 13CH4/12CH4 with a precision of 0.5‰ in 100 s without pre-concentration. Projections are given for detection limits for other gases including COS, HONO and HCHO as CWRT lasers become available at appropriate wavelengths.