David A. Sodeman

Advances in integrated and continuous measurements for particle mass and chemical composition.

Abstract Recent improvements in integrated and continuous PM2.5 mass and chemical measurements from the Supersite program and related studies in the past decade are summarized. Analytical capabilities of the measurement methods, including accuracy, precision, interferences, minimum detectable levels, comparability, and data completeness are documented. Upstream denuders followed by filter packs in integrated samplers allow an estimation of sampling artifacts. Efforts are needed to: (1) address positive and negative artifacts for organic carbon (OC), and (2) develop carbon standards to better separate organic versus elemental carbon (EC) under different temperature settings and analysis atmospheres. Advances in thermal desorption followed by gas chromatography/mass spectrometry (GC/MS) provide organic speciation of approximately 130 nonpolar compounds (e.g., n-alkanes, alkenes, hopanes, steranes, and polycyclic aromatic hydrocarbons [PAHs]) using small portions of filters from existing integrated samples. Speciation of water-soluble OC (WSOC) using ion chromatography (IC)-based instruments can replace labor-intensive solvent extraction for many compounds used as source markers. Thermal gas-based continuous nitrate and sulfate measurements underestimate filter ions by 10–50% and require calibration against on-site filter-based measurements. IC-based instruments provide multiple ions and report comparable (±10%) results to filter-based measurements. Maintaining a greater than 80% data capture rate in continuous instruments is labor intensive and requires experienced operators. Several instruments quantify black carbon (BC) by optical or photoacoustic methods, or EC by thermal methods. A few instruments provide real-time OC, EC, and organic speciation. BC and EC concentrations from continuous instruments are highly correlated but the concentrations differ by a factor of two or more. Site- and season-specific mass absorption efficiencies are needed to convert light absorption to BC. Particle mass spectrometers, although semiquantitative, provide much information on particle size and composition related to formation, growth, and characteristics over short averaging times. Efforts are made to quantify mass by collocating with other particle sizing instruments. Common parameters should be identified and consistent approaches are needed to establish comparability among measurements.

Three-dimensional simulations of inorganic aerosol distributions in east Asia during spring 2001

In this paper, aerosol composition and size distributions in east Asia are simulated using a comprehensive chemical transport model. Three-dimensional aerosol simulations for the TRACE-P and ACE-Asia periods are performed and used to help interpret actual observations. The regional chemical transport model, STEM-2K3, which includes the on-line gas-aerosol thermodynamic module SCAPE II, and explicitly considers chemical aging of dust, is used in the analysis. The model is found to represent many of the important observed features. The Asian outflow during March and April of 2001 is heavily polluted with high aerosol loadings. Under conditions of low dust loading, SO_2 condensation and gas phase ammonia distribution determine the nitrate size and gas-aerosol distributions along air mass trajectories, a situation that is analyzed in detail for two TRACE-P flights. Dust is predicted to alter the partitioning of the semivolatile components between the gas and aerosol phases as well as the size distributions of the secondary aerosol constituents. Calcium in the dust affects the gas-aerosol equilibrium by shifting the equilibrium balance to an anion-limited status, which benefits the uptake of sulfate and nitrate, but reduces the amount of aerosol ammonium. Surface reactions on dust provide an additional mechanism to produce aerosol nitrate and sulfate. The size distribution of dust is shown to be a critical factor in determining the size distribution of secondary aerosols. As much of the dust mass is found in the supermicron mode (70–90%), appreciable amounts of sulfate and nitrate are found in the supermicron particles. For sulfate the observations and the analysis indicate that 10–30% of sulfate is in the supermicron fraction during dust events; in the case of nitrate, more than 80% is found in the supermicron fraction.

Particulate emission factors for mobile fossil fuel and biomass combustion sources

PM emission factors (EFs) for gasoline- and diesel-fueled vehicles and biomass combustion were measured in several recent studies. In the Gas/Diesel Split Study (GD-Split), PM(2.5) EFs for heavy-duty diesel vehicles (HDDV) ranged from 0.2 to ~2 g/mile and increased with vehicle age. EFs for HDDV estimated with the U.S. EPA MOBILE 6.2 and California Air Resources Board (ARB) EMFAC2007 models correlated well with measured values. PM(2.5) EFs measured for gasoline vehicles were ~two orders of magnitude lower than those for HDDV and did not correlate with model estimates. In the Kansas City Study, PM(2.5) EFs for gasoline-powered vehicles (e.g., passenger cars and light trucks) were generally <0.03 g/mile and were higher in winter than summer. EMFAC2007 reported higher PM(2.5) EFs than MOBILE 6.2 during winter, but not during summer, and neither model captured the variability of the measured EFs. Total PM EFs for heavy-duty diesel military vehicles ranged from 0.18±0.03 and 1.20±0.12 g/kg fuel, corresponding to 0.3 and 2 g/mile, respectively. These values are comparable to those of on-road HDDV. EFs for biomass burning measured during the Fire Laboratory at Missoula Experiment (FLAME) were compared with EFs from the ARB Emission Estimation System (EES) model. The highest PM(2.5) EFs (76.8±37.5 g/kg) were measured for wet (>50% moisture content) Ponderosa Pine needles. EFs were generally <20 g/kg when moisture content was <20%. The EES model agreed with measured EFs for fuels with low moisture content but underestimated measured EFs for fuel with moisture content >40%. Average EFs for dry chamise, rice straw, and dry grass were within a factor of three of values adopted by ARB in Californias San Joaquin Valley (SJV). Discrepancies between measured and modeled emission factors suggest that there may be important uncertainties in current PM(2.5) emission inventories.

In-Plume Emission Test Stand 2: Emission Factors for 10- to 100-kW U.S. Military Generators

Abstract Although emissions of air pollutants from some military tactical equipment are not subject to the emissions standards, local communities near military bases must conform to the National Ambient Air Quality Standards. Military diesel generators are widely used in training. A portable in-plume system was used to measure fuel-based emission factors (EFs) for particulate matter (PM), carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbons (HCs) for 30-, 60-, and 100-kW generators at five load levels and for cold starts. It was found that EFs depend on multiple parameters including engine size, engine load, unit age, and total running hours. The average CO EF of generators tested was 5% lower, and the average NOx EF was 63% lower than AP-42 estimates; average PM EF was 80% less than the AP-42 estimates. A 2002 model-year 60-kW engine produced 25% less PM than a 1995 engine of the same family with similar running hours. CO EFs decrease with increasing engine load, NOx EFs increase up to mid-loads and decrease slightly at high loads, PM EFs increase with loads for 30- and 60-kW engines. CO and PM have higher EFs and NOx has a lower EF during cold starts than during hot-stabilized operation. PM chemical source profiles were also examined.