Measurement of black carbon (BC) by an optical method and a thermal-optical method: Intercomparison for four sites

Comparison of black carbon (BC) measurements obtained by two methods was performed for aerosols samples collected on Whatman 41 (W-41) filters, using an optical method (Magee Scientific Optical Transmissometer Model OT-21) and a thermal-optical method (Sunset Laboratory Thermal-optical analyzer). Samples were collected from four sites: Albany (a small urban site, NY), Antalya (coastal site, Turkey), Whiteface Mountain (remote site, NY) and Mayville (rural site, NY). At Albany, comparison between the two methods showed excellent agreement; a least-squares regression line yielded a slope of 1.02, and r² = 0.88. Similar comparisons at Antalya (slope of 1.02, r² = 0.5) and Whiteface Mountain (slope of 0.92 and r² = 0.58) also gave very good relationship. At Mayville, the relationship between the two methods yielded somewhat lower regression: a slope of 0.75, and r² = 0.44. The data from the four locations, when plotted together, yielded an excellent agreement: a slope of 0.91, and r² of 0.84. Based on our measurements, it appears that optical measurement using the OT-21 can be successfully applied to determination of BC in W-41 filters. However, because of the variability in the chemical composition of BC aerosol at different locations, it is suggested that the calibration of OT-21 when using W-41 filters should be performed with a statistically significant numbers of samples for specific sites.     

Size distribution of black (BC) and total carbon (TC) in Vienna and Ljubljana

During two campaigns in winter 2004, size segregated impactor samples (0.1-10 microm) and filter samples were taken in two Central European cities (Vienna, Austria and Ljubljana, Slovenia). The impactor samples were analyzed for major inorganic ions and short-chain organic acids, total carbon (TC) and black carbon (BC). Maximum concentrations of total mass were 71.6 microg m(-3) in Vienna and 73.1 microg m(-3) in Ljubljana. Minimum concentrations in Vienna were only half those in Ljubljana. The BC content of the aerosol was similar (ca. 8%), but the BC/TC ratio was higher in Vienna than in Ljubljana (0.39 vs. 0.29), reflecting the different contribution of diesel traffic emissions. The mass median diameters of the submicron size distributions of all major fractions (total mass, TC, BC and SO(4)(2-)) were smaller in Vienna (0.43 microm, 0.41 microm, 0.38 microm and 0.48 microm, respectively) than in Ljubljana (0.55 microm, 0.44 microm, 0.42 microm and 0.60 microm, respectively). Impactor/filter ratios for total mass were 0.79 in Vienna and 0.82 in Ljubljana, while the ratios for BC were 0.56 in Vienna and 0.49 in Ljubljana. An estimation of the mixing state of accumulation mode BC indicated that 33% and 37% of BC, respectively, are mixed externally to the aerosol in the accumulation size range in Vienna and Ljubljana.     

Elemental carbon (EC) and black carbon (BC) measurements with a thermal method and an aethalometer at the high-alpine research station Jungfraujoch

A thermal method for the determination of ambient organic carbon (OC) and elemental carbon (EC) concentrations in carbonaceous samples was further developed. Possible artifacts were investigated and were shown to be low. Good agreement of EC data with the German VDI reference method was found and detection limits were 1.3 μg for EC and 1.8 μg for OC. The method was applied to samples obtained with an aethalometer from an ongoing campaign at the high-alpine research station Jungfraujoch from July 1995 to June 1997. Measurements of EC concentration were used to derive a new site-specific calibration factor (instrumental absorption efficiency α_API) for the determination of the black carbon (BC) concentration. Despite a distinct seasonal cycle in BC, of around one order in magnitude with a maximum in summer and minimum in winter, α_API exhibited no significant seasonality. The derived calibration factor for the Jungfraujoch, α_API=9.3±0.4 m² g^-1, is lower than the manufacturer calibration by a factor ∼2. The results confirm the observation that the aethalometer determined BC concentration, underestimates the true value at remote sites, when the manufacturer calibration is used.     

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).     

An analysis of continuous black carbon concentrations in proximity to an airport and major roadways

Black carbon (BC), a constituent of particulate matter, is emitted from multiple combustion sources, complicating determination of contributions from individual sources or source categories from monitoring data. In close proximity to an airport, this may include aircraft emissions, other emissions on the airport grounds, and nearby major roadways, and it would be valuable to determine the factors most strongly related to measured BC concentrations. In this study, continuous BC concentrations were measured at five monitoring sites in proximity to a small regional airport in Warwick, Rhode Island from July 2005 to August 2006. Regression was used to model the relative contributions of aircraft and related sources, using real-time flight activity (departures and arrivals) and meteorological data, including mixing height, wind speed and direction. The latter two were included as a nonparametric smooth spatial term using thin-plate splines applied to wind velocity vectors and fit in a linear mixed model framework. Standard errors were computed using a moving-block bootstrap to account for temporal autocorrelation. Results suggest significant positive associations between hourly departures and arrivals at the airport and BC concentrations within the community, with departures having a more substantial impact. Generalized Additive Models for wind speed and direction were consistent with significant contributions from the airport, major highway, and multiple local roads. Additionally, inverse mixing height, temperature, precipitation, and at one location relative humidity, were associated with BC concentrations. Median contribution estimates indicate that aircraft departures and arrivals (and other sources coincident in space and time) contribute to approximately 24–28% of the BC concentrations at the monitoring sites in the community. Our analysis demonstrated that a regression-based approach with detailed meteorological and source characterization can provide insights about source contributions, which could be used to devise control strategies or to provide monitor-based comparisons with source-specific atmospheric dispersion models.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

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.     

Intercomparison of two different thermal-optical elemental carbons and optical black carbon during ABC-EAREX2005

A formal intercomparison of fine particle elemental (black) carbon is conducted involving three real-time semi-continuous measurement systems. Two-hourly interval time-resolved measurements of organic carbon (OC) and elemental carbon (EC) were performed at the Gosan site, Korea during Atmospheric Brown Clouds–East Asian Regional Experiment 2005 (ABC-EAREX2005) campaign. They were operated by the same semi-continuous field carbon instruments of Sunset Laboratory (thermal optical transmittance) in PM_2.5 particulate. However, their thermal protocols (four and two steps for OC and five and two steps for EC) were different. The co-located 1 min black carbon (BC) concentrations were compared by an Aethalometer for an intercomparison study.As a result, the poor R² of OC between two different temperature protocols suggested that OC can be significantly more biased by the slight differences of maximum temperature (870 and 840 °C) and a number of temperature steps (four steps and two steps) with their hold times. However, EC that is a smaller fraction of total carbon (TC) shows the good agreement between two different protocols, which are under a mixture of 2% O₂ and 98% He in six temperature steps and two temperature steps as max as 900 and 880 °C with the slope of 1.05±0.15 (R² of 0.98). The different slopes between EC and BC, which show the range of 1.23–1.61, demonstrate the variability of the attenuation coefficient of the BC particulate.     

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.     

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).     

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.     

Black carbon (BC) in urban and surrounding rural soils of Beijing, China: spatial distribution and relationship with polycyclic aromatic hydrocarbons (PAHs)

The concentrations of black carbon (BC), total organic carbon (TOC) and polycyclic aromatic hydrocarbons (PAHs) have been determined in soils from urban and rural areas of Beijing. The rural area can be divided into plain and mountainous areas which are close to and relatively far from the urban area, respectively. Concentration of BC (5.83 ± 3.05 mg g⁻¹) and BC/TOC concentration ratio (0.37 ± 0.15) in Beijing’s urban soil are high compared with that in world background soils and rural soils of Beijing, suggesting the urban environment to be an essential source and sink of BC. Concentration of BC in the urban area decreases from the inner city to exterior areas, which correlates with the urbanization history of Beijing and infers accumulation of BC in old urban soils. Black carbon in Beijing soils mainly comes from fossil fuel combustion, especially traffic emission. Median PAH concentration in the urban area (502 ng g⁻¹) is one order of magnitude higher than that in the rural plain (148 ng g⁻¹) and mountainous area (146 ng g⁻¹) where PAHs are supposed to mainly come from atmospheric deposition from the urban area. Concentrations of BC correlate significantly with those of PAHs (p < 0.01, except naphthalene) in the urban area and with those of heavier 4-, 5- and 6- ring PAHs (p < 0.01) in the adjacent rural plain area, while there is no significant correlation with any PAH in the farther rural mountainous area.     

Influence of accidental fire on black carbon aerosol concentrations over an urban environment

Carbonaceous aerosols are emitted by combustion sources and may influence the climate by altering the radiation balance of the atmosphere. Carbonaceous particles exist mainly in the accumulation mode and thus may be transported over long distances. The present study deals with the impact of anthropogenic activity associated with accidental fires on the black carbon aerosol concentrations over an urban environment, namely Hyderabad, India. Black carbon aerosol loading in association with meteorological parameters on a normal day, an accident day and a post-accident day have been analysed. Diurnal variations of black carbon aerosols on a normal day suggest that black carbon aerosol concentrations increased by a factor of about 2 during morning and evening hours compared with afternoon hours. A drastic increase in black carbon aerosol loading was found during an accident day compared with a normal day. An immediate return to normal black carbon concentration was found during the post-accident day. Black carbon aerosol loading in relation to rainfall is also discussed in the paper.     

Evaluation of an intensive sampling and analysis method for carbon monoxide

This paper describes a portable, low-cost whole air sampler capable of collecting 12 1-L samples in tedlar bags and using a single "D" cell for power. The results are presented from two tests of an intensive sampling and analysis method for measuring ambient carbon monoxide (CO) concentrations in urban areas using this sampler. The method is evaluated in comparison with an approved continuous CO analyzer, in intercomparisons of the results of re-analysis of the samples, and by examination of the results from co-located samplers. The precision of the analytical method was found to be +/-0.30 ppmv. The precision of the sampling method was found to be +/-0.73 ppmv and therefore is the limiting factor in the method's overall precision. These values are sufficient to verify attainment of National Ambient Air Quality Standards (NAAQS) levels in urban areas. Improvements in the sampler and analytical procedure are discussed.     

Development of ELISA technique for the analysis of atrazine residues in water

A highly sensitive enzyme immunoassay is described for the detection of atrazine residues in water. Atrazine derivative was conjugated to Bovine Serum Albumin (BSA) to obtain an immunizing antigen and to Horseradish Peroxidase enzyme (POD) to obtain a marker for immunoassay. The formation of these conjugations was confirmed by UV spectroscopy as well as by gel-electrophoresis. Polyclonal antibodies were raised in rabbits by immunization with an atrazine-BSA conjugate containing 29 atrazine residues per BSA molecule. An ELISA on microtitration plates was optimized with peroxidase-atrazine conjugate. The middle of the test (50% B/Bo) was found to be at 90 ng/l, which is well below the maximum concentration permitted by the EC guidelines for drinking water. Detection limits for atrazine of about 1 ng/l could be reached. The assay did not require concentration or cleanup steps for drinking or ground water samples. Validation experiments showed good accuracy and precision. No cross-reactivities were shown by other s-triazines like terbutryn, ametryn, terbuthylazine, des-isopropylatrazine, and de-ethylatrazine except hydroxyatrazine. The latter was present at very low levels that can be calibrated/standardized before analysis or it may be considered as leftover residues of atrazine. Based on these results, it is suggested that this test can be applied to obtain fairly accurate results for atrazine concentration in water samples from different sources.     

Real-time indoor and outdoor measurements of black carbon in an occupied house: an examination of sources

Black carbon (BC) was measured every 5 min for two years (May 1998-May 2000) inside and immediately outside a northern Virginia house (suburban Washington, DC) occupied by two nonsmokers. Two aethalometers, which measure BC by optical transmission through a quartz fiber tape, were employed indoors and outdoors. Meteorological parameters were obtained on an hourly basis from nearby Dulles airport. Indoor activities were recorded to identify indoor sources such as combustion activities, which occurred 9% of the time during the first year and 4% of the time during the second year. At times without indoor sources, indoor/outdoor BC ratios averaged 0.53 in the first year and 0.35 in the second year. The main outdoor source of BC was the general regional background, contributing 83-84% of the total during each of the two years. Morning rush hour traffic contributed 8-9% of the total BC. An evening peak in the fall and winter, thought to include contributions from wood burning, was responsible for approximately 8% of the annual average BC concentration. The main indoor sources of BC were cooking and candle burning, contributing 16 and 31%, respectively, of the annual average indoor concentrations in the two years. Relative humidity (RH) affected the outdoor aethalometer in both years. An artifact associated with the tape advance was noted for the aethalometer, but a correction factor was developed that reduced the associated error by a factor of 2.     

The longitudinal dependence of black carbon concentration on traffic volume in an urban environment

The purpose of this study was to evaluate the effect of traffic volume on ambient black carbon (BC) concentration in an inner-city neighborhood "hot spot" while accounting for modifying effects of weather and time. Continuous monitoring was conducted for 12 months at the Baltimore Traffic Study site surrounded by major urban streets that together carry over 150,000 vehicles per day. Outdoor BC concentration was measured with an Aethalometer; vehicles were counted pneumatically on two nearby streets. Meteorological data were also obtained. Missing data were imputed and all data were normalized to a 5-min observational interval (n = 105,120). Time-series modeling accounted for autoregressively (AR) correlated errors. This study found that outdoor BC was positively correlated at a statistically significant level with neighborhood-level vehicle counts, which contributed at a rate of 66 +/- 10 (SE) ng/m3 per 100 vehicles every 5 min. Winds from the SW-S-SE quarter were associated with the greatest increases in BC (376-612 ng/m3). These winds would have entrained BC from Baltimore's densely trafficked central business district, as well as a nearby interstate highway. The strong influence of wind direction implicates atmospheric transport processes in determining BC exposure. Dew point, mixing height, wind speed, season, and workday were also statistically significant predictors. Background exposure to BC was estimated to be 905 ng/m3. The optimal, statistically significant representation of BC's autocorrelation was AR([1:6]) x 288 x 2016, where the short-term AR factor (lags 1-6) indicated that BC concentrations are correlated for up to 30 min, and the AR factors for lags 288 and 2016 indicate longer-term autocorrelations at diurnal and weekly cycles, respectively. It was concluded that local exposure to BC from mobile sources is substantially modified by meteorological and temporal conditions, including atmospheric transport processes. BC concentration also demonstrates statistically significant autocorrelation at several time scales.     

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.     

Surface functional characteristics (C, O, S) of waste tire-derived carbon black before and after steam activation

The effects of steam activation on the surface functional characteristics of waste tire-derived carbon black were investigated. Two carbon-based materials, powdered carbon black (PCB) and PCB-derived powdered activated carbon (PCB-PAC), were selected for this study. A stainless steel tubular oven was used to activate the PCB at an activation temperature of 900 degrees C and 1 atm using steam as an activating reagent. X-ray photoelectron spectroscopy (XPS) was adopted to measure the surface composition and chemical structure of carbon surface. Various elemental spectra (C, O, and S) of each carbon sample were further deconvoluted by peak synthesis. Results showed that the surfaces of PCB and PCB-PAC consisted mainly of C-C and C-O. The PCB-PAC surface had a higher percentage of oxygenated functional groups (C=O and O-C=O) than PCB. The O1s spectra show that the oxygen detected on the PCB surface was mainly bonded to carbon (C-O), whereas the oxygen on the PCB-PAC surface could be bonded to hydrogen (O-H) and carbon (C-O). Sulfur on the surface of PCB consisted of 58.9 wt% zinc sulfide (ZnS) and 41.1 wt% S=C=S, whereas that on the surfaces of PCB-PAC consisted mainly of S=C=S. Furthermore, the increase of oxygen content from 9.6% (PCB) to 11.9% (PCB-PAC) resulted in the increase of the pH values of PCB-PAC after steam activation.