Nehzat Motallebi

Black and Organic Carbon Emission Inventories: Review and Application to California

Abstract Particulate black or elemental carbon (EC) (black carbon [BC]) and organic carbon (OC) affect climate, visibility, and human health. Several “top-down” and “bottom-up” global emission inventories for these components have compiled country-wide emission factors, source profiles, and activity levels that do not necessarily reflect local conditions. Recent estimates of global BC and OC emissions range from 8 to 24 and 33 to 62 Tg (1012 g) per year, respectively. U.S. BC emissions account for 5.6% of the global total emissions. Uncertainties in global BC emission estimates are a factor of 2 or more. The U.S. National Emissions Inventory is well documented, but its major source categories are not easily related to EC- and OC-emitting source subcategories. California’s bottom-up emission inventory is easily accessible at many levels of detail and provides an example of how sources can be regrouped for speciated emission rates. PM2.5 (particulate matter with aerodynamic diameters < 2.5 µm) emissions from these categories are associated with EC and OC source profiles to generate California’s speciated emissions. A BC inventory for California of 38,731 t/yr was comparable to the 33,281 t/yr estimated from a bottom-up global BC inventory. However, further examination showed substantial differences among subcategories, with the global inventory BC from fossil fuel combustion at two-thirds that from the California inventory and the remainder attributed to biomass burning. Major discrepancies were found for directly emitted OC, with the global inventory estimating more than twice that of the California inventory. Most of the discrepancy was due to differences in open biomass burning (wildfires and agricultural waste) for which carbon emissions are highly variable. BC and OC emissions are sensitive to the availability and variability of existing source profiles, and profiles more specific to fuels and operating conditions are needed to increase emission accuracy.

Day-of-Week Patterns of Particulate Matter and Its Chemical Components at Selected Sites in California

Abstract This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NOx) are not only precursors of ozone (O3) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM ≤10 μm (PM10) and ≤2.5[H9262]m in aerodynamic diameter (PM2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO3 -) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988–1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997–2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.

Particulate matter in California: part 2--Spatial, temporal, and compositional patterns of PM2.5, PM10-2.5, and PM10.

Abstract Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM2.5 and PM10 concentrations range from 3 to 10 [H9262]g/m3 and from 5 to 18 µg/m3, respectively. In the urban areas of California, annual-averages for PM2.5 range from 7 to 30 [H9262]g/m3, with observed 24-hr peaks reaching levels as high as 160 [H9262]g/m3. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM2.5 concentrations that are more prolonged and regional in nature. PM2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO4 2−) and nitrate (NO3 −) components of PM2.5 and PM10 and correlate with reductions in ambient levels of oxides of sulfur (SOx) and oxides of nitrogen (NOx). Annual averages for PM10–2.5 and PM10 exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse 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.

A fabric denuder for sampling semi-volatile species

ABSTRACT A new style of diffusion denuder has been evaluated specifically for sampling HNO3. A coated fabric is used as the denuder substrate, which can be loaded directly into a standard filter holder. This approach allows direct denuder sampling with no additional capital costs over filter sampling and simplifies the coating and extraction process. Potential denuder materials and coatings were evaluated in the laboratory to test the removal efficiency. NaCl coatings were used to assess more than 20 materials for HNO3 collection efficiency. Particle retention, which would cause a denuder to have a positive bias for gas concentration measurements, was evaluated by ambient air sampling using particulate sulfate as the reference aerosol. Particle retention varied from 0 to 15%, depending on the denuder material tested. The best performing material showed an average particle retention of less than 3%. Denuder efficiency of four fabric materials was tested under ambient conditions to determine removal efficiency. The fabric denuder method was compared with a long path-length Fourier transform infrared (FTIR) spectrometer, a tunable diode laser absorption spectrometer (TDLAS), and a denuder difference sampler to independently measure HNO3. HNO3 collection efficiency was typically 90% for the denuders, whether coated with NaCl or not. For 10-L/min sampling rates with the fabric denuder, the square of the correlation coefficient with the FTIR spectrometer was 0.73, compared to 0.24 with the TDLAS.

Particulate Matter in California: Part 1—Intercomparison of Several PM2.5, PM10–2.5, and PM10 Monitoring Networks

Abstract It will be many years before the recently deployed network of fine particulate matter with an aerodynamic diameter less than 2.5 [H9262]m (PM2.5) Federal Reference Method (FRM) samplers produces information on nonattainment areas, trends, and source impacts. However, data on PM2.5 and its major constituents have been routinely collected in California for the past 20 years. The California Air Resources Board operated as many as 20 dichotomous (dichot) samplers for PM2.5 and coarse PM (PM10–2.5). The California Acid Deposition Monitoring Program (CADMP) collected 12-h-average PM2.5 and PM10 from 1988 to 1995 at ten urban and rural sites and 24-h-average PM2.5 at five urban sites since 1995. Beginning in 1994, the Children’s Health Study collected 2-week averages of PM2.5 in 12 communities in southern California using the Two-Week Sampler (TWS). Comparisons of collocated samples establish relationships between the dichot, CADMP, and TWS samplers and the 82-site network of PM2.5 FRM samplers deployed since 1999 in California. PM mass data from the different monitoring programs have modest to high correlation to FRM mass data, fairly small systematic biases and negative proportional biases ranging from 7 to 22%. If the biases are taken into account, all of the programs should be considered comparable with the FRM program. Thus, historical data can be used to develop long-term PM trends in California.

Characterization of Particulate Matter in California

The size, composition, and concentration of particulate matter (PM) vary with location and time. Several monitoring/sampling programs are operated in California to characterize PM less than 2.5 and 10 µm in aerodynamic diameter (PM2.5 and PM10). This paper presents a broad summary of the spatial and temporal variations observed in ambient PM2.5 and PM10 concentrations in California. Many areas that have high PM10 concentrations also have relatively high PM2.5 concentrations, and data indicate that a significant portion of the PM10 air quality problem is caused by PM2.5. To develop effective plans for attaining the ambient PM standards, improved understanding of these unique problems is needed. Since 1989, pollution control efforts-whether specifically targeted for particulate matter or indirectly via controls on gaseous emissions-have caused annual average PM2.5 and PM10 concentrations to decline at most sites in California.

Wintertime PM2.5 and PM10 Source Apportionment at Sacramento, California

The chemical mass balance (CMB) model was applied to winter (November through January) 1991-1996 PM2.5 and PM10 data from the Sacramento 13th and T Streets site in order to identify the contributions from major source categories to peak 24-hr ambient PM2.5 and PM10 levels. The average monthly PM10 monitoring data for the nine-year period in Sacramento County indicate that elevated concentrations are typical in the winter months. Concentrations on days of highest PM10 are dominated by the PM2.5 fraction. One factor contributing to increased PM2.5 concentrations in the winter is meteorology (cool temperatures, low wind speeds, low inversion layers, and more humid conditions) that favors the formation of secondary nitrate and sulfate aerosols. Residential wood burning also elevates fine particulate concentrations in the Sacramento area. The results of the CMB analysis highlight three key points. First, the source apportionment results indicate that primary motor vehicle exhaust and wood smoke are significant sources of both PM2.5 and PM10 in winter. Second, nitrates, secondarily formed as a result of motor-vehicle and other sources of nitrogen oxide (NOx), are another principal cause of the high PM2.5 and PM10 levels during the winter months. Third, fugitive dust, whether it is resuspended soil and dust or agricultural tillage, is not the major contributor to peak winter PM2.5 and PM10 levels in the Sacramento area.

Spatial and Temporal Characterization of PM2.5 Mass Concentrations in California, 1980–2007

ABSTRACT Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 μm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r 2 > 0.9; mean absolute error ∼2 μg m−3) from PM with an aerodynamic diameter ≤10 μm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980–2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 μg m−3 yr−1 (median -0.11 μg m−3 yr−1), whereas urban-site trends ranged from -0.13 to -1.29 μg m−3 yr−1 (median -0.59 μg m−3 yr−1). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 μg m−3 at IMPROVE sites and from 9.3 to 37.1 μg m−3 at urban sites. IMPLICATIONS Mean measured and reconstructed fine particulate matter mass concentrations declined by about a factor of 2 in California over the period 1980 to 2007 and varied by about a factor of 4 among air basins. The integrated data record is of interest for epidemiological studies and for assessments of emission control programs.