An evaluation of mass absorption cross-section for optical carbon analysis on Teflon filter media

Black carbon (BC) or elemental carbon (EC) is a by-product of incomplete fuel combustion, and contributes adversely to human health, visibility, and climate impacts. Previous studies have examined nondestructive techniques for particle light attenuation measurements on Teflon® filters to estimate BC. The incorporation of an inline Magee Scientific OT21 transmissometer into the MTL AH-225 robotic weighing system provides the opportunity to perform optical transmission measurements on Teflon filters at the same time as the gravimetric mass measurement. In this study, we characterize the performance of the inline OT21, and apply it to determine the mass absorption cross-section (MAC) of PM_2.5 BC across the United States. We analyzed 5393 archived Teflon® filters from the Chemical Speciation Network (CSN) collected during 2010–2011 and determined MAC by comparing light attenuation on Teflon® filters to corresponding thermal EC on quartz-fiber filters. Results demonstrated the importance of the initial transmission (I₀) value used in light attenuation calculations. While light transmission varied greatly within filter lots, the average I₀ of filter blanks during the sampling period provided an estimate for archived filters. For newly collected samples, it is recommended that filter-specific I₀ measurements be made (i.e., same filter before sample collection). The estimated MAC ranged from 6.9 to 9.4 m²/g and varied by region and season across the United States, indicating that using a default value may lead to under- or overestimated BC concentrations. An analysis of the chemical composition of these samples indicated good correlation with EC for samples with higher EC content as a fraction of total PM_2.5 mass, while the presence of light-scattering species such as crustal elements impacted the correlation affecting the MAC estimate. Overall, the method is demonstrated to be a quick, cost-effective approach to estimate BC from archived and newly sampled Teflon® filters by combining both gravimetric and BC measurements.

Implications: Robotic optical analysis is a valid, cost-effective means to obtain a vast amount of BC data from archived and current routine filters. A tailored mass absorption cross-section by region and season is necessary for a more representative estimate of BC. Initial light transmission measurements play an important role due to the variability in blank filter transmission. Combining gravimetric mass and BC analysis on a single Teflon® filter reduces costs for monitoring agencies and maximizes data collection.     

A retrospective comparison of model-based forecasted PM2.5 concentrations with measurements

This study presents an assessment of the performance of the Community Multiscale Air Quality (CMAQ) photochemical model in forecasting daily PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) mass concentrations over most of the eastern United States for a 2-yr period from June 14, 2006 to June 13, 2008. Model predictions were compared with filter-based and continuous measurements of PM2.5 mass and species on a seasonal and regional basis. Results indicate an underprediction of PM2.5 mass in spring and summer, resulting from under-predictions in sulfate and total carbon concentrations. During winter, the model overpredicted mass concentrations, mostly at the urban sites in the northeastern United States because of overpredictions in unspeciated PM2.5 (suggesting possible overestimation of primary emissions) and sulfate. A comparison of observed and predicted diurnal profiles of PM2.5 mass at five sites in the domain showed significant discrepancies. Sulfate diurnal profiles agreed in shape across three sites in the southern portion of the domain but differed at two sites in the northern portion of the domain. Predicted organic carbon (OC) profiles were similar in shape to mass, suggesting that discrepancies in mass profiles probably resulted from the underprediction in OC. The diurnal profiles at a highly urbanized site in New York City suggested that the overpredictions at that site might be resulting from overpredictions during the morning and evening hours, displayed as sharp peaks in predicted profiles. An examination of the predicted planetary boundary layer (PBL) heights also showed possible issues in the modeling of PBL.     

Source apportionment of fine particles in Tennessee using a source-oriented model

Source apportionment of fine particles (PM2.5, particulate matter < 2 microm in aerodynamic diameter) is important to identify the source categories that are responsible for the concentrations observed at a particular receptor. Although receptor models have been used to do source apportionment, they do not fully take into account the chemical reactions (including photochemical reactions) involved in the formation of secondary fine particles. Secondary fine particles are formed from photochemical and other reactions involving precursor gases, such as sulfur dioxide, oxides of nitrogen, ammonia, and volatile organic compounds. This paper presents the results of modeling work aimed at developing a source apportionment of primary and secondary PM2.5. On-road mobile source and point source inventories for the state of Tennessee were estimated and compiled. The national emissions inventory for the year 1999 was used for the other states. U.S. Environmental Protection Agency Models3/Community Multi-Scale Air Quality modeling system was used for the photochemical/secondary particulate matter modeling. The modeling domain consisted of a nested 36-12-4-km domain. The 4-km domain covered the entire state of Tennessee. The episode chosen for the modeling runs was August 29 to September 9, 1999. This paper presents the approach used and the results from the modeling and attempts to quantify the contribution of major source categories, such as the on-road mobile sources (including the fugitive dust component) and coal-fired power plants, to observed PM2.5 concentrations in Tennessee. The results of this work will be helpful in policy issues targeted at designing control strategies to meet the PM2.5 National Ambient Air Quality Standards in Tennessee.     

A combined model–observation approach to estimate historic gridded fields of PM2.5 mass and species concentrations

This paper introduces a methodology for estimating gridded fields of total and speciated fine particulate matter (PM_2.5) concentrations for time periods and regions not covered by observational data. The methodology is based on performing long-term regional scale meteorological and air quality simulations and then integrating these simulations with available observational data. To illustrate this methodology, we present an application in which year-round simulations with a meteorological model (the National Center for Atmospheric Research/Penn State Mesoscale Model, hereafter referred to as MM5) and a photochemical air quality model (the Community Multiscale Air Quality Model, hereafter referred to as CMAQ) have been performed over the northeastern United States for 1988–2005. Model evaluation results for total PM_2.5 mass and individual species for the time period from 2000 to 2005 show that model performance varies by species, season, and location. Therefore, an approach is developed to adjust CMAQ output with factors based on these three variables. The adjusted model values for total PM_2.5 mass for 2000–2005 are compared against independent measurements not utilized for the adjustment approach. This comparison reveals that the adjusted model values have a lower root mean square error (RMSE) and higher correlation coefficients than the original model values. Furthermore, the PM_2.5 estimates from these adjusted model values are compared against an alternate method for estimating historic PM_2.5 values that is based on PM_2.5/PM₁₀ ratios calculated at co-located monitors. Results reveal that both methods yield estimates of historic PM_2.5 mass that are broadly consistent; however, the adjusted CMAQ values provide greater spatial coverage and information for PM_2.5 species in addition to total PM_2.5 mass. Finally, strengths and limitations of the proposed approach are discussed in the context of potential uses of this method.     

Continuous and filter-based measurements of PM2.5 nitrate and sulfate at the Fresno Supersite

PM(2.5) nitrate [Formula: see text] and sulfate ([Formula: see text]) were measured continuously with R&P8400N and R&P8400S instruments, respectively, and compared with filter-based measurements at the Fresno Supersite from October, 2000 through December, 2005. [Formula: see text] concentrations were higher in winter than summer with a long-term decreasing trend. Correlations between 24-h average continuous and filter-based [Formula: see text] were greater than 0.96 in 4 out of 5 years. Continuous [Formula: see text] was generally lower than filter-based [Formula: see text] although the difference decreased over time, from -52% in 2001 to +13% in 2005. These differences were similar in winter (-23%) and summer (-19%) while the corresponding differences between ambient and instrument temperature were -12 and 0.7 degrees C, respectively. Neither seasonal nor long-term trends in [Formula: see text] can be explained by variations in ambient temperature, the difference between ambient and instrument temperature, or changes in aerosol chemical composition. There were no seasonal or long-term trends in [Formula: see text] concentrations, partially due to low concentrations observed in Fresno. Long-term variability in the performance of R&P8400 [Formula: see text] and [Formula: see text] instruments suggest that collocation with filter measurements is needed for long-term measurements.     

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

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.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

Comparison of continuous and filter-based carbon measurements at the Fresno supersite

Results from six continuous and semicontinuous black carbon (BC) and elemental carbon (EC) measurement methods are compared for ambient samples collected from December 2003 through November 2004 at the Fresno Supersite in California. Instruments included a multi-angle absorption photometer (MAAP; lambda = 670 nm); a dual-wavelength (lambda = 370 and 880 nm) aethalometer; seven-color (lambda = 370, 470, 520, 590, 660, 880, and 950 nm) aethalometers; the Sunset Laboratory carbon aerosol analysis field instrument; a photoacoustic light absorption analyzer (lambda = 1047 nm); and the R&P 5400 ambient carbon particulate monitor. All of these acquired BC or EC measurements over periods of 1 min to 1 hr. Twenty-four-hour integrated filter samples were also acquired and analyzed by the Interagency Monitoring of Protected Visual Environments (IMPROVE) thermal/optical reflectance carbon analysis protocol. Site-specific mass absorption efficiencies estimated by comparing light absorption with IMPROVE EC concentrations were 5.5 m2/g for the MAAP, 10 m2/g for the aethalometer at a wavelength of 880 nm, and 2.3 m2/g for the photoacoustic analyzer; these differed from the default efficiencies of 6.5, 16.6, and 5 m2/g, respectively. Scaling absorption by inverse wavelength did not provide equivalent light absorption coefficients among the instruments for the Fresno aerosol measurements. Ratios of light absorption at 370 nm to those at 880 nm from the aethalometer were nearly twice as high in winter as in summer. This is consistent with wintertime contributions from vehicle exhaust and from residential wood combustion, which is believed to absorb more shorter-wavelength light. To reconcile BC and EC measurements obtained by different methods, a better understanding is needed of the wavelength dependence of light-absorption and mass-absorption efficiencies and how they vary with different aerosol composition.     

Source apportionment: findings from the U.S. Supersites Program

Receptor models are used to identify and quantify source contributions to particulate matter and volatile organic compounds based on measurements of many chemical components at receptor sites. These components are selected based on their consistent appearance in some source types and their absence in others. UNMIX, positive matrix factorization (PMF), and effective variance are different solutions to the chemical mass balance (CMB) receptor model equations and are implemented on available software. In their more general form, the CMB equations allow spatial, temporal, transport, and particle size profiles to be combined with chemical source profiles for improved source resolution. Although UNMIX and PMF do not use source profiles explicitly as input data, they still require measured profiles to justify their derived source factors. The U.S. Supersites Program provided advanced datasets to apply these CMB solutions in different urban areas. Still lacking are better characterization of source emissions, new methods to estimate profile changes between source and receptor, and systematic sensitivity tests of deviations from receptor model assumptions.