Development of an improved optical transmission technique for black carbon (BC) analysis

A new optical transmission technique for black carbon (BC) analysis was developed to minimize interferences due to scattering effects in filter samples. A standard thermal analysis method (VDI, 1999) is used to link light attenuation by the filter samples to elemental carbon (EC) concentration. Scattering effects are minimized by immersion of the filters in oil of a similar refractive index, as is often done for microscopy purposes. Light attenuation was measured using both a white light source and a red LED of 650 nm. The usual increase in overestimation of BC concentrations with decreasing BC amount in filter samples was found considerably reduced. Some effects of BC properties (e.g. fractal dimension, microstructure and size distribution) on the specific attenuation coefficient B_ATN, however, are still present for the treated samples. B_ATN was found close to 1 m² g⁻¹ for dry-dispersed industrial BC and 7 m² g⁻¹ for nebulized BC. Good agreement was found between the oil immersion, integrating sphere and a polar photometer technique and Mie calculations. The average specific attenuation coefficient of ambient samples in oil varied between 7 and 11 m² g⁻¹ for white light and 6 and 9 m² g⁻¹ for red light (LED). B_ATN was found to have much less site variation for the treated than for the untreated samples. The oil immersion technique improved also the correlation with thermally analyzed EC. This new immersion technique therefore presents a considerable improvement over conventional optical transmission techniques and may therefore serve as a simple, fast and cost-effective alternative to thermal methods.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

Validating a nondestructive optical method for apportioning colored particulate matter into black carbon and additional components

Exposure of black carbon (BC) is associated with a variety of adverse health outcomes. A number of optical methods for estimating BC on Teflon filters have been adopted but most assume all light absorption is due to BC while other sources of colored particulate matter exist. Recently, a four-wavelength-optical reflectance measurement for distinguishing second hand cigarette smoke (SHS) from soot-BC was developed (Brook et al., 2010; Lawless et al., 2004). However, the method has not been validated for soot-BC nor SHS and little work has been done to look at the methodological issues of the optical reflectance measurements for samples that could have SHS, BC, and other colored particles. We refined this method using a lab-modified integrating sphere with absorption measured continuously from 350 nm to 1000 nm. Furthermore, we characterized the absorption spectrum of additional components of particulate matter (PM) on PM(2.5) filters including ammonium sulfate, hematite, goethite, and magnetite. Finally, we validate this method for BC by comparison to other standard methods. Use of synthesized data indicates that it is important to optimize the choice of wavelengths to minimize computational errors as additional components (more than 2) are added to the apportionment model of colored components. We found that substantial errors are introduced when using 4 wavelengths suggested by Lawless et al. to quantify four substances, while an optimized choice of wavelengths can reduce model-derived error from over 10% to less than 2%. For environmental samples, the method was sensitive for estimating airborne levels of BC and SHS, but not mass loadings of iron oxides and sulfate. Duplicate samples collected in NYC show high reproducibility (points consistent with a 1:1 line, R(2) = 0.95). BC data measured by this method were consistent with those measured by other optical methods, including Aethalometer and Smoke-stain Reflectometer (SSR); although the SSR looses sensitivity at filter loadings above 90 ng/mm(2). Furthermore, positive correlations (R(2) = 0.7) were observed between EC measured by NIOSH Method 5040 on quartz filters and BC measured in co-located Teflon filter samples collected from both heating and non-heating seasons. Overall, the validation data demonstrates the usefulness of this method to evaluate BC from archived Teflon filters while potentially providing additional component information.     

Evaluation of thermal optical analysis method of elemental carbon for marine fuel exhaust

The awareness of black carbon (BC) as the second largest anthropogenic contributor in global warming and an ice melting enhancer has increased. Due to prospected increase in shipping especially in the Arctic reliability of BC emissions and their invented amounts from ships is gaining more attention. The International Maritime Organization (IMO) is actively working toward estimation of quantities and effects of BC especially in the Arctic. IMO has launched work toward constituting a definition for BC and agreeing appropriate methods for its determination from shipping emission sources. In our study we evaluated the suitability of elemental carbon (EC) analysis by a thermal-optical transmittance (TOT) method to marine exhausts and possible measures to overcome the analysis interferences related to the chemically complex emissions. The measures included drying with CaSO_4, evaporation at 40–180ºC, H₂O treatment, and variation of the sampling method (in-stack and diluted) and its parameters (e.g., dilution ratio, Dr). A reevaluation of the nominal organic carbon (OC)/EC split point was made. Measurement of residual carbon after solvent extraction (TC-C_SOF) was used as a reference, and later also filter smoke number (FSN) measurement, which is dealt with in a forthcoming paper by the authors. Exhaust sources used for collecting the particle sample were mainly four-stroke marine engines operated with variable loads and marine fuels ranging from light to heavy fuel oils (LFO and HFO) with a sulfur content range of <0.1–2.4% S. The results were found to be dependent on many factors, namely, sampling, preparation and analysis method, and fuel quality. It was found that the condensed H₂SO₄ + H₂O on the particulate matter (PM) filter had an effect on the measured EC content, and also promoted the formation of pyrolytic carbon (PyC) from OC, affecting the accuracy of EC determination. Thus, uncertainty remained regarding the EC results from HFO fuels.

Implications: The work supports one part of the decision making in black carbon (BC) determination methodology. If regulations regarding BC emissions from marine engines will be implemented in the future, a well-defined and at best unequivocal method of BC determination is required for coherent and comparable emission inventories and estimating BC effects. As the aerosol from marine emission sources may be very heterogeneous and low in BC, special attention to the effects of sampling conditions and sample pretreatments on the validity of the results was paid in developing the thermal-optical analysis methodology (TOT).     

Intercomparison of measurement methods for black carbon aerosols

In this study, two method intercomparisons were performed. One thermal and two optical methods for the measurement of black carbon (BC) were applied to laboratory generated aerosols containing only BC. For the optical measurements, an aethalometer (Hansen et al., 1984. Science of Total Environment 36, 191–196) and an integrating sphere technique (Hitzenberger et al., 1996b. Journal of Geophysical Research 101, D14, 19 601–19 606) were used. The thermal method was described by Cachier et al. (1989a. Tellus 41B, 379–390). In an additional comparison, the integrating sphere was compared to a thermal optical technique (Birch and Cary, 1996. Aerosol Science Technology 25, 221–241) on ambient aerosol samples. The absorption coefficients were obtained from transmission measurements on filter samples for both the aethalometer and the integrating sphere. The BC mass concentration for the aethalometer was derived from this absorption measurement. The BC mass concentration for the integrating sphere, however, was obtained using an independent calibration curve. The agreement between the absorption coefficient σ_a obtained for the BC test aerosol on parallel filters with the aethalometer and the integrating sphere was satisfactory. The slope of the regression lines depended on filter type. A comparison between BC mass concentrations, however, showed that the aethalometer values were only 23% of those obtained by the integrating sphere technique indicating that for pure BC aerosols, the standard aethalometer calibration should not be used. Compared to the thermal method, the integrating sphere gave an overestimation of the BC mass concentrations by 21%. For the ambient samples, the integrating sphere and the thermal optical methods for BC mass concentration determination showed agreement within 5% of the 1 : 1 line, although the data were not so well correlated.     

Quantification of elemental and total carbon in combustion particulate matter using thermal-oxidative analysis

The use of a two-step thermal-oxidative analysis (TOA) technique for quantification of the mass of total carbon (TC) and elemental carbon (EC) of turbine engine-borne particulate matter (PM) has been evaluated. This approach could be used in lieu of analysis methods which were developed to characterize diluted PM. This effort is of particular interest as turbine engine PM emissions typically have a higher EC content than ambient aerosols, and filter sample mass loadings can be significantly greater than recommended for existing analysis techniques. Analyses were performed under a pure oxygen environment using a two-step temperature profile; reference carbon and actual PM samples were used to identify appropriate analysis conditions. Thermal gravimetric analysis (TGA) methods were used to provide guidance on the nature of the carbon in several of the materials. This was necessary as a standard reference material does not exist for determination of the EC fraction in PM. The TGA also assisted in identifying an appropriate temperature range for the first-stage of the TOA method. Quantification of TC and EC for turbine engine PM samples using TOA was compared to results obtained using the NIOSH 5040 thermal-optical method. For first-stage TOA temperatures of 350°C and 400°C, excellent agreement between the techniques was observed in both the quantified TC and EC, supporting the viability for using TOA for analysis of turbine engine PM samples. A primary benefit of using TOA for these types of PM samples is that filters with relatively high PM mass loadings (sampled at the emission source) can be readily analyzed. In addition, an entire filter sample can be evaluated, as compared to the use of a filter punch sample for the NIOSH technique. While the feasibility of using a TOA method for engine PM samples has been demonstrated, future studies to estimate potential OC charring and oxidation of EC-type material may provide additional data to assess its impact on the OC/EC fractions for other carbon-type measurements.

Implications: This work presents results and procedures of an analytical method for the determination of total and elemental carbon, i.e., TC and EC present in combustion source particulate matter samples. In general, it is shown that the LECO TOA methodology is as reliable and comprehensive as NIOSH 5040 for determining TC and EC carbon types in particulate matter present in turbine emission sources, and should be considered as an alternative. Principles of the methodology, differences, and corresponding agreement with the standard NIOSH 5040 method and TGA analysis are discussed.     

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.     

State of mixture of atmospheric submicrometer black carbon particles and its effect on particulate light absorption

The state of mixture of light-absorbing carbonaceous particles was investigated in relation to light absorption properties using electron microscopic examinations, black carbon (BC) analyses of quartz filter by thermal/optical reflectance (TOR) method, measurements with two continuous light-absorbing photometers at a suburban site of Tsukuba, about 60 km northeast of Tokyo. The volume fraction of water-soluble material (?) in individual particles is important for assessing particulate light-absorbing and/or scattering of atmospheric aerosols. The values of ? in BC particles were evaluated by electron micrographs before and after dialysis (extraction) of water-soluble material. The mass absorption coefficient (MAC in units of m² g^?1) tended to increase with increasing the average ? in BC particles with the radius range of 0.05–0.5 μm. Thus, our results indicate that coatings of water-soluble material around BC particles can enhance the absorption of solar radiation. Moreover, the single scattering albedo (SSA) will increase because a large amount of coating material will scatter more light.     

Evaluation of solid particle number and black carbon for very low particulate matter emissions standards in light-duty vehicles

To reliably measure at the low particulate matter (PM) levels needed to meet California’s Low Emission Vehicle (LEV III) 3- and 1-mg/mile particulate matter (PM) standards, various approaches other than gravimetric measurement have been suggested for testing purposes. In this work, a feasibility study of solid particle number (SPN, d50 = 23 nm) and black carbon (BC) as alternatives to gravimetric PM mass was conducted, based on the relationship of these two metrics to gravimetric PM mass, as well as the variability of each of these metrics. More than 150 Federal Test Procedure (FTP-75) or Supplemental Federal Test Procedure (US06) tests were conducted on 46 light-duty vehicles, including port-fuel-injected and direct-injected gasoline vehicles, as well as several light-duty diesel vehicles equipped with diesel particle filters (LDD/DPF). For FTP tests, emission variability of gravimetric PM mass was found to be slightly less than that of either SPN or BC, whereas the opposite was observed for US06 tests. Emission variability of PM mass for LDD/DPF was higher than that of both SPN and BC, primarily because of higher PM mass measurement uncertainties (background and precision) near or below 0.1 mg/mile. While strong correlations were observed from both SPN and BC to PM mass, the slopes are dependent on engine technologies and driving cycles, and the proportionality between the metrics can vary over the course of the test. Replacement of the LEV III PM mass emission standard with one other measurement metric may imperil the effectiveness of emission reduction, as a correlation-based relationship may evolve over future technologies for meeting stringent greenhouse standards.

Implications: Solid particle number and black carbon were suggested in place of PM mass for the California LEV III 1-mg/mile FTP standard. Their equivalence, proportionality, and emission variability in comparison to PM mass, based on a large light-duty vehicle fleet examined, are dependent on engine technologies and driving cycles. Such empirical derived correlations exhibit the limitation of using these metrics for enforcement and certification standards as vehicle combustion and after-treatment technologies advance.     

Separation of brown carbon from black carbon for IMPROVE and Chemical Speciation Network PM2.5 samples

The replacement of the Desert Research Institute (DRI) model 2001 with model 2015 thermal/optical analyzers (TOAs) results in continuity of the long-term organic carbon (OC) and elemental carbon (EC) database, and it adds optical information with no additional carbon analysis effort. The value of multiwavelength light attenuation is that light absorption due to black carbon (BC) can be separated from that of brown carbon (BrC), with subsequent attribution to known sources such as biomass burning and secondary organic aerosols. There is evidence of filter loading effects for the 25% of all samples with the highest EC concentrations based on the ratio of light attenuation to EC. Loading corrections similar to those used for the seven-wavelength aethalometer need to be investigated. On average, nonurban Interagency Monitoring of PROtected Visual Environments (IMPROVE) samples show higher BrC fractions of short-wavelength absorption than urban Chemical Speciation Network (CSN) samples, owing to greater influence from biomass burning and aged aerosols, as well as to higher primary BC contributions from engine exhaust at urban sites. Sequential samples taken during an Everglades National Park wildfire demonstrate the evolution from flaming to smoldering combustion, with the BrC fraction increasing as smoldering begins to dominate the fire event.

Implications: The inclusion of seven wavelengths in thermal/optical carbon analysis of speciated PM_2.5 (particulate matter with an aerodynamic diameter ≤2.5 μm) samples allows contributions from biomass burning and secondary organic aerosols to be estimated. This separation is useful for evaluating control strategy effectiveness, identifying exceptional events, and determining natural visibility conditions.     

Field validation of a semi-continuous method for aerosol black carbon (aethalometer) and temporal patterns of summertime hourly black carbon measurements in southwestern PA

Two methods for measuring aerosol elemental carbon (EC) are compared. Three-hour integrated carbon samples were collected on quartz filters during the summer of 1990 in Uniontown, PA, primarily during episodes of elevated particulate pollution levels. These samples were analyzed for EC and organic carbon (OC) using a thermo/optical reflectance (TOR) method. Aerosol black carbon (BC) was measured using an Aethalometer, a semi-continuous optical absorption method. The optical attenuation factor for ambient BC was supplied by the instrument manufacturer. Three-hour average concentrations were calculated from the semi-continuous BC measurements to temporally match the EC/OC integrated quartz filter samples. BC and EC concentrations are highly correlated over the study period (R²=0.925). The regression equation is BC (μg m^-3)=0.95 (±0.04) EC−0.2 (±0.4). The means of 3 h average measurements for EC and BC are 2.3 and 2.0 μg m^-3, respectively, average concentrations of EC and BC ranged from 0.6 to 9.4 and 0.5 to 9.0 μg m^-3 respectively. TOR OC and EC concentrations were not highly correlated (R²=0.22). The mean OC/EC ratio was 1.85.The 10-week Aethalometer hourly dataset was analyzed for daily and weekly temporal patterns. A strong diurnal BC pattern was observed, with peaks occurring between 7 a.m. and 9 a.m. local time. This is consistent with the increase in emissions from ground level combustion sources in the morning, coupled with poor dispersion before daytime vertical mixing is established. There was also some indication of a day-of-week effect on BC concentrations, attributed to activity of local ground level anthropogenic sources. Comparison of BC concentrations with co-located measurements of coefficient of haze in a separate field study in Philadelphia, PA, during the summer of 1992 showed good correlation between the two measurements (R²=0.82).     

Characterisation of fresh particulate vehicular exhausts near a Paris high flow road

Simultaneous continuous measurements of PM_2.5, PM₁₀, black carbon mass (BCae), Black smoke (BS) and particle number density (N) were conducted in the close vicinity of a high traffic road around Paris during a three-month period beginning in August 1997. In parallel some aerosol collection was performed on filters in order to assess the black carbon (BC), organic carbon (OC) and water soluble organic fractions (WSOC) of the freshly emitted traffic aerosols. The high hourly concentrations of PM_2.5 (39±20 μg m⁻³), BCae (14±7 μg m⁻³), and N (220,000±115,000 cm⁻³), were found to be well correlated with each other. On average PM_2.5 represented 66±13% of PM₁₀ and appears to be composed primarily of BC (43±20%). On the contrary no correlation was found between PM_2.5 and the coarse (PM₁₀–PM_2.5) mass fractions which was attributed to resuspension processes by vehicles. Black carbon mass concentrations obtained from both filter analyses (BC) and Aethalometre data (BCae) show a good agreement suggesting that the Aethalometre calibration based on a black carbon specific attenuation coefficient (σ) of 19 m² g⁻¹ is well adapted to nearby roadside measurements. Daily BC (used as a surrogate for fine particles) concentrations and wind speed were found to be anti-correlated. Average daily variations of BC could be related to traffic intensity and regime as well as to the boundary layer height. As expected for freshly emitted traffic aerosols, filter analyses indicated a high BC/TC ratio (29±5%) and a low mean WSOC/OC ratio (12.5±5%) for the bulk aerosol. For these two ratios no day/night differences were observed, the sampling station being probably too close to traffic to evidence photochemical modification of the aerosol phase. Finally, a linear relationship was found between BC and BS hourly concentrations (BC=0.10×BS+1.18; r²=0.93) which offers interesting perspectives to retrieve BC concentrations from existing BS archives.     

Measurement of real time black carbon for investigating spot loading effects of Aethalometer data

Measurements of real-time continuous PM_2.5 black carbon (BC) concentrations were made using a single-wavelength Aethalometer (@880 nm) in three different environments, i.e., an indoor office, a residential indoor living room and an urban site, to evaluate the difference in temporal behaviors of BC particles and investigate the optical shadowing effect in the Aethalometer BC data. An empirical method was used for correcting the optical saturation effect on the original BC data obtained from the measurements at the three sites. Also, the elemental carbon (EC) concentrations from 24-h filter-based measurements of PM_2.5 particles were determined using a thermal optical transmittance (TOT) method at the same urban site for comparison with the Aethalometer BC results. Transient events of BC were often observed for period of a few hours at all sites, reaching a maximum level of 27.3 μg m^?3 at the urban site. The diurnal cycles of the BC concentrations observed at the two indoor environments were found to be considerably affected by the air exchange rate, occupants' behavior patterns and nearby traffic emissions. The time-series plots of the Aethalometer data showed obvious discontinuities at the filter spot change, and a rise in the apparent BC concentrations after filter tape advances. Also, the relationship between the attenuation and BC concentration was found to be non-linear at all sites. The empirical approach presented here demonstrated a definite improvement in the continuity of the BC data across the time gaps of each tape advance. The compensated BC concentration was 1.10–1.23 times greater than the raw BC data, depending on the observation sites, with the highest difference observed between the raw and compensated BC data at an indoor office near a small traffic road. The 24-h integrated EC concentration was approximately 12% higher than the original 24-h average BC concentration and 6% lower than the loading compensated BC concentration, showing that the loading compensation process accounted for the saturation effect of the filter tape.     

Filter light attenuation as a surrogate for elemental carbon

Light attenuation (b(att)) measured from filter light transmission is compared with elemental carbon (EC) measurements for more than 180,000 collocated PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter) and PM10 (PM < or = 10 microm in aerodynamic diameter) samples from nearly 200 U.S. locations during the past 2 decades. Although there are theoretical reasons for expecting highly variable relationships between b(att) and EC (such as the effects of "brown carbon" and iron oxides in PM2.5), reasonable correlations are found. These correlations are not a strong function of season or location (e.g., rural vs. urban). Median EC concentrations can be predicted from filter transmittance measurements to within +/- 15-30%. Although EC predicted from b(att) shows larger uncertainties (30-60%), especially at concentrations less than 0.3 microg/m3, the consistent mass absorption efficiency (sigm(att)) derived from the regression analysis demonstrates the feasibility of using b(att) as a surrogate for EC. This study demonstrates that a constant factor of 0.1 g/m2 (equivalent to the 10 m2/g sigma(att) used in the Interagency Monitoring of Protected Visual Environments chemical extinction formula) can be used to estimate EC concentrations from b(att) through a Teflon-membrane filter sample. Greater accuracy is achieved with site-specific sigma(att) derived from a period with collocated EC measurements.     

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.     

PM2.5 carbon measurements in two urban areas: Seoul and Kwangju,Korea

24-h PM_2.5 carbonaceous samples were collected between 27 November and 9 December 1999 in Seoul, and between 7 and 20 June 2000 in Kwangju to investigate characteristics of carbonaceous species, and the relationship between elemental carbon (EC) and Aethalometer-based black carbon (BC) measurements. 5-min PM_2.5 BC and criteria air pollutant data were also measured using the Aethalometer and ambient air monitoring system. The PM_2.5 samples were analyzed for EC and OC using a selective thermal manganese dioxide oxidation (TMO) method. The daily average EC and OC concentrations in Seoul were higher in the winter than in the summer (Atmos. Environ. 35 (2001a) 657). It was found that difference between ambient BC levels in the two cities was not directly proportional to the population ratio (∼8) or diesel traffic ratio (∼5.9) since particulate matter or BC concentration is strongly influenced by a result of varying traffic and meteorological conditions at the site. Using the primary OC/EC ratio approach, the results suggest that most of the measured OC in Kwangju is of primary origin during the summer. In Seoul, the observed OC includes additional secondary organic aerosol during the wintertime conditions. The relationship between the 24-h TMO-EC and Aethalometer BC measurements in PM_2.5 reflected very good agreement for the two urban sites, with correlation coefficients of R²=0.99 and 0.92, and BC/EC slopes of 0.93 and 1.07, respectively. It was found that comparing TMO-EC to BC at a different location in Korea, a different scaling factor was needed.     

A Comparison of Filter Types in the Collection and Gravimetric Determination of Airborne Particulate Matter Less than 2.5 Microns (PM25)

ABSTRACT

Five identical, collocated, low-volume samplers were operated to collect airborne particulate matter less than 2.5 microns (PM₂₅). Five commercially available filter types were installed in the samplers to compare the gravimetric determination of PM_2.5 concentrations in the atmosphere. The filters were rotated through the five samplers for two study periods—one in summer and one in winter. The study was performed in Sheridan, WY, in close proximity to a gravimetric laboratory to minimize the introduction of errors associated with sample handling. Rigorous quality assurance procedures were employed throughout the study.Four of the five filter types provided comparable gravimetric determinations of airborne PM_2.5.     

Quantitative analysis of environmental factors in differential weighing of blank Teflon filters

Mass differences less than 100 microg must be correctly measured in gravimetric analysis of particles collected on filters. Even small variations in mass measurement may contribute significant errors to calculated concentrations. In addition to the collected particles, a number of other factors affect the observed mass difference between the measurements before and after sampling. The most often controlled of these factors are static charge, temperature, and humidity. Using 951 laboratory blank filter weights, we have statistically analyzed these and other factors that affect the observed filter weight. Some of these are controllable or correctable; others are not and enter into the final results as errors. The standard deviation of differential blank filter weighing after applying all corrections was 2.7 microg. The most important correctable factors are air buoyancy variation and filter storage time. When weighing blank Teflon filters at relative humidity < 50%, these are an order of magnitude more important than weighing-room humidity. Using field blank filters in each weighing batch could control these three factors but also doubles the errors caused by balance random variation and filter handling contamination, because four weighing measurements and the handling of two filters are needed to obtain one corrected differential mass result.     

Comparison of measurement methods for the characterization of the black carbon emissions from a T63 turboshaft engine burning conventional and Fischer-Tropsch fuels

Emission measurements of black carbon (BC) mass were conducted on a T63 turboshaft engine, operated at idle and cruise power with conventional and alternative fuels, using an Artium LII-300 laser-induced incandescence analyzer (LII) and AVL model 483 micro soot sensor (MSS) photoacoustic instrument using the manufacturer’s calibration for both instruments. These measurements were compared with elemental carbon (EC) determined by manual and semicontinuous thermal-optical transmission analyses according to National Institute for Occupational Safety and Health (NIOSH) method 5040 as the reference method. The results indicate that both the LII and MSS instruments show good linear correlation with EC for the two fuels and two engine power conditions evaluated. The LII measurements were observed to be biased high (27–49%) and the MSS measurements were biased low (24–35%) relative to EC. The agreement between the instruments and the reference method was substantially improved by applying a calibration of the instruments against a common BC aerosol source. Test data also suggest that the two instruments show some sensitivity to particle size (or properties related to size), specifically for particles with a geometric mean diameter (GMD) <30 nm. This sensitivity is problematic, since new engines or certain combustion conditions in current engines will produce smaller particles compared with the T63 model tested in this study. Further assessments of instrument performance for particles within this size range are therefore warranted.

Implications: Accurate black carbon emission measurements are needed to certify new and in-production commercial aircraft engines. Both the Artium LII-300 and AVL 483 micro soot sensor are currently approved by the International Civil Aviation Organization for this purpose. This study compares the two instruments against elemental carbon (EC) using NIOSH method 5040 as the reference using a T63 turboshaft engine. The results indicate that both instruments correlate reasonably well with EC, and the correlation substantially improved when applying a calibration against a common aerosol source. Sensitivity to particle size may be an issue for both instruments.