M.-C. Oliver Chang

The IMPROVE_A Temperature Protocol for Thermal/Optical Carbon Analysis: Maintaining Consistency with a Long-Term Database

Abstract Thermally derived carbon fractions including organic carbon (OC) and elemental carbon (EC) have been reported for the U.S. Interagency Monitoring of PROtected Visual Environments (IMPROVE) network since 1987 and have been found useful in source apportionment studies and to evaluate quartz-fiber filter adsorption of organic vapors. The IMPROVE_A temperature protocol defines temperature plateaus for thermally derived carbon fractions of 140 °C for OC1, 280 °C for OC2, 480 °C for OC3, and 580 °C for OC4 in a helium (He) carrier gas and 580 °C for EC1, 740 °C for EC2, and 840 °C for EC3 in a 98% He/2% oxygen (O2) carrier gas. These temperatures differ from those used previously because new hardware used for the IMPROVE thermal/optical reflectance (IMPROVE_TOR) protocol better represents the sample temperature than did the old hardware. A newly developed temperature calibration method demonstrates that these temperatures better represent sample temperatures in the older units used to quantify IMPROVE carbon fractions from 1987 through 2004. Only the thermal fractions are affected by changes in temperature. The OC and EC by TOR are insensitive to the change in temperature protocol, and therefore the long-term consistency of the IMPROVE database is conserved. A method to detect small quantities of O2 in the pure He carrier gas shows that O2 levels above 100 ppmv also affect the comparability of thermal carbon fractions but have little effect on the IMPROVE_TOR split between OC and EC.

Effect of advanced aftertreatment for PM and NOx reduction on heavy-duty diesel engine ultrafine particle emissions.

Four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreament configurations using a chassis dynamometer to characterize the occurrence of nucleation (the conversion of exhaust gases to particles upon dilution). The aftertreatment included four different diesel particulate filters and two selective catalytic reduction (SCR) devices. All DPFs reduced the emissions of solid particles by several orders of magnitude, but in certain cases the occurrence of a volatile nucleation mode could increase total particle number emissions. The occurrence of a nucleation mode could be predicted based on the level of catalyst in the aftertreatment, the prevailing temperature in the aftertreatment, and the age of the aftertreatment. The particles measured during nucleation had a high fraction of sulfate, up to 62% of reconstructed mass. Additionally the catalyst reduced the toxicity measured in chemical and cellular assays suggesting a pathway for an inverse correlation between particle number and toxicity. The results have implications for exposure to and toxicity of diesel PM.

Measurement of ultrafine particle size distributions from coal-, oil-, and gas-fired stationary combustion sources

Abstract Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h−1 and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.

Dilution Based Emissions Sampling from Stationary Sources : Part 1 Compact Sampler Methodology and Performance

This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.Abstract This paper presents the design and performance of a compact dilution sampler (CDS) for characterizing fine particle emissions from stationary sources. The sampler is described, along with the methodology adopted for its use. Dilution sampling has a number of advantages, including source emissions that are measured under conditions simulating stack gas entry and mixing in the ambient atmosphere. This is particularly important for characterizing the semivolatile species in effluents as a part of particulate emissions. The CDS characteristics and performance are given, along with sampling methodology. The CDS was compared with a reference dilution sampler. The results indicate that the two designs are comparable for tests on gas-fired units and a diesel electrical generator. The performance data indicate that lower detection limits can be achieved relative to current regulatory methods for particulate emissions. Test data for the fine particulate matter (PM2.5) emissions are provided for comparison with U.S. Environment Protection Agency (EPA) Conditional Test Method 040 for filterable particulate matter (FPM) and the EPA Method 202 for condensable particulate matter. This comparison showed important differences between methods, depending on whether a comparison is done between in situ FPM determinations or the sum of such values with condensable PM from liquid filled impingers chilled in an ice bath. These differences are interpretable in the light of semivolatile material present in the stack effluent and, in some cases, differences in detection and quantification limits. Determination of emissions from combustors using liquid fuels can be readily achieved using 1-hr sampling with the CDS. Emissions from gasfired combustors are very low, requiring careful attention to sample volumes. Sampling volumes corresponding with 6-hr operation were used for the combined mass and broad chemical speciation. Particular attention to dilution sampler operation with clean dilution air also is essential for gas-fired sources.

Dilution-Based Emissions Sampling from Stationary Sources: Part 2—Gas-Fired Combustors Compared with Other Fuel- Fired Systems

Abstract With the recent focus on fine particle matter (PM2.5),new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference.The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2, nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of ∼10-4 lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with ∼5 × 10-3 lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of ∼0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or woodfueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing “true” particulate carbon emission results.

Emissions of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs from heavy-duty diesel vehicles with DPF and SCR

In total, 24 polycyclic aromatic hydrocarbons (PAHs) in both gas and particle phases and 35 nitro-PAHs in particle phase were analyzed in the exhaust from heavy-duty diesel vehicles equipped with after-treatment for particulate matter (PM) and NOX control. The test vehicles were carried out using a chassis dynamometer under highway cruise, transient Urban Dynamometer Driving Schedule (UDDS), and idle operation. The after-treatment efficiently abated more than 90% of the total PAHs. Indeed, the particle-bound PAHs were reduced by >99%, and the gaseous PAHs were removed at various extents depending on the type of after-treatment and the test cycles. The PAHs in gas phase dominated the total PAH (gas + particle phases) emissions for all the test vehicles and for all cycles; that is, 99% of the two-ring and 98% of the three-ring and 97% of the four-ring and 95% of the carcinogenic PAHs were in the gas-phase after a diesel particle filter (DPF) and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must include this volatile fraction and cannot be based on the particle fraction only. The selective catalytic reduction (SCR) did not appear to promote nitration of the PAHs in general, although there might be some selective nitration of phenanthrene. Importantly the after-treatmtent reduced the equivalent B[a]P (B[a]Peq) emissions by >95%, suggesting a substantial health benefit. Implications: This study demonstrated that after-treatments, including diesel particulate filters (DPF), diesel oxidation catalysts (DOC), and selective catalytic reduction (SCR), significantly reduce the emissions of PAHs from heavy-duty diesel engines. The gas-phase PAHs dominate the total PAH (gas + particle phases) emissions from heavy-duty diesel vehicles retrofitted with various DPFs and not bound to the very small amount of particulate matter left after a DPF. Consequently, an evaluation of the toxicity of DPF exhaust must also include this volatile fraction and cannot be based on the particle fraction only. Supplemental Materials: Supplemental materials are available for this paper. Go to the publishers online edition of the Journal of the Air & Waste Management Association.

Black carbon emissions in gasoline vehicle exhaust: A measurement and instrument comparison

A pilot study was conducted to evaluate the performance and agreement of several commercially available black carbon (BC) measurement instruments, when applied to the quantification of BC in light-duty vehicle (LDV) exhaust. Samples from six vehicles, three fuels, and three driving cycles were used. The pilot study included determinations of the method detection limit (MDL) and repeatability. With respect to the MDL, the real-time instruments outperformed the time-integrated instruments, with MDL = 0.12 mg/mi for the AE51 Aethalometer, and 0.15 mg/mi for the Micro Soot Sensor (MSS), versus 0.38 mg/mi for the IMPROVE_A thermal/optical method, and 0.35 mg/mi for the OT21_T Optical Transmissometer. The real-time instruments had repeatability values ranging from 30% to 35%, which are somewhat better than those of the time-integrated instruments (40–41%). These results suggest that, despite being less resource intensive, real-time methods can be equivalent or superior to time-integrated methods in terms of sensitivity and repeatability. BC mass data, from the photoacoustic and light attenuation instruments, were compared against same-test EC data, determined using the IMPROVE_A method. The MSS BC data was well correlated with EC, with R 2 = 0.85 for the composite results and R2 = 0.86 for the phase-by-phase (PBP) results. The correlation of BC, by the AE51, AE22, and OT21_T, with EC was moderate to weak. The weaker correlation was driven by the inclusion of US06 test data in the linear regression analysis. We hypothesize that test-cycle-dependent BC:EC ratios are due to the different physicochemical properties of particulate matter (PM) in US06 and Federal Test Procedure (FTP) tests. Correlation amongst the real-time MSS, PASS-1, AE51, and AE22 instruments was excellent (R2 = 0.83–0.95), below 1 mg/mi levels. In the process of investigating these BC instruments, we learned that BC emissions at sub-1 mg/mi levels can be measured and are achievable by current-generation gasoline engines. Implications: Most comparison studies of black carbon (BC) measurement methods were carried out in the ambient air. This study assesses the agreement among various BC measurement instrument in emissions from light-duty gasoline vehicles (LDGVs) on standard test cycles, and evaluates applicability of these methods under various fuel types, driving cycles, and engine combustion technologies. This research helps to fill in the knowledge gap of BC method standardization as stated in the U.S. Environmental Protection Agency (EPA) 2011 Report to Congress on Black Carbon, and these results demonstrate the feasibility of quantification of BC at the 1 mg/mi PM standard in California Low Emission Vehicle III regulations.

Characterization of Fine Particulate Emissions from Casting Processes

Fine particle (PM2.5) emission rates and compositions from gray iron metal casting foundry were characterized for No-Bake molds poured at the Research Foundry located at Technikon, LLC (McClellan, CA). For each mold, PM2.5 was collected for chemical analysis, and particle size distributions were measured by an Electrical Low Pressure Impactor (ELPI) to understand PM emissions during different part of the casting process. Molds prepared with phenolic urethane binders were poured with Class 30 gray cast iron at 1,427–1,480°C. PM2.5 was collected from the pouring, cooling, and shakeout processes for each mold. Most of the PM2.5 mass emitted from these processes was composed of carbonaceous compounds, including 37–67% organic carbon (OC) and 17–30% elemental carbon (EC). Oxides of aluminum (Al), silicon (Si), calcium (Ca), and iron (Fe) constituted 8–20% of PM2.5 mass, and trace elements (e.g., K, Ti, Mn, Cu, Zn, and Pb) contributed 3–6%. Chemical abundances in PM were different between pouring and shakeout for each discrete mold. PM2.5 mass emissions from pouring were 15–25% of the total from each discrete mold. Ultrafine particles (< 0.1 μm) contributed less than 1% of PM2.5 mass, but nearly all of the particle numbers. Different mechanisms for pouring and shakeout result in variations in chemical abundances and particle size distributions. The highest PM2.5 mass and number concentrations were observed when shakeout started. PM2.5 size distributions in mass concentration during shakeout contained particles in the tail of coarse particles (1.6–2.5 μm) and a vapor condensation mode (0.65–1.6 μm). Flame conditions, vaporization, thermal decomposition of organic materials, and the variability of mold breakup during shakeout affect PM emission rates. A detailed chemical speciation for size-segregated PM samples at different process points needs to be conducted at full-scale foundries to obtain emission factors and source profiles applicable to emission inventories, source receptor modeling, and implementation of emission standards.

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.

The In-Plume Emission Test Stand: An Instrument Platform for the Real-Time Characterization of Fuel-Based Combustion Emissions

Abstract The In-Plume Emission Test Stand (IPETS) characterizes gaseous and particulate matter (PM) emissions from combustion sources in real time. Carbon dioxide (CO2), carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO2), and other gases are quantified with a closed-path Fourier transform infrared spectrometer (FTIR). Particle concentrations, chemical composition, and other particle properties are characterized with an electrical low-pressure impactor (ELPI), a light-scattering particle detector, an optical particle counter, and filter samples amenable to different laboratory analysis. IPETS measurements of fuel-based emission factors for a diesel generator are compared with those from a Mobile Emissions Laboratory (MEL). IPETS emission factors ranged from 0.3 to 11.8, 0.2 to 3.7, and 22.2 to 32.8 g/kg fuel for CO, NO2, and NO, respectively. IPETS PM emission factors ranged from 0.4 to 1.4, 0.3 to 1.8, 0.3 to 2.2, and 1 to 3.4 g/kg fuel for filter, photoacoustic, nephelometer, and impactor measurements, respectively. Observed linear regression statistics for IPETS versus MEL concentrations were as follows: CO slope = 1.1, r2 = 0.99; NO slope = 1.1, r2 = 0.92; and NO2 slope = 0.8, r2 = 0.96. IPETS versus MEL PM regression statistics were: filter slope = 1.3, r2 = 0.80; ELPI slope = 1.7, r2 = 0.87; light-scattering slope = 2.7, r2 = 0.92; and photoacoustic slope = 2.1, r2 = 0.91. Lower temperatures in the dilution air (~25 °C for IPETS vs. ~50 °C for MEL) may result in greater condensation of semi-volatile compounds on existing particles, thereby explaining the 30% difference for filters. The other PM measurement devices are highly correlated with the filter, but their factory-default PM calibration factors do not represent the size and optical properties of diesel exhaust. They must be normalized to a simultaneous filter measurement.