Evaluation of the thermal/optical reflectance method for quantification of elemental carbon in sediments

The IMPROVE thermal/optical reflectance (TOR) method, commonly used for EC quantification in atmospheric aerosols, is applied to soils and sediments and compared with a thermochemical method commonly applied to these non-atmospheric samples. TOR determines elemental carbon (EC) by an optical method, but it also yields thermally defined EC fractions in a 2% O2/98% He oxidizing atmosphere at 550 degrees C (EC1), 700 degrees C (EC2), and 800 degrees C (EC3). Replicate TOR TC, OC, and EC values exhibited precisions of approximately +/-10% as determined from multiple analyses of the same samples. EC abundances relative to total mass concentrations were within the ranges reported by other methods for diesel exhaust soot, n-hexane soot, wood and rice chars, and coals, as well as for environmental matrices. A direct comparison with the chemothermal (CTO) method of Gustafson et al. for ten soil and sediment samples demonstrated that almost all of the OC and EC1 are eliminated, as is part of the EC2. The CTO soot carbon is bounded by the EC3 and EC2+EC3 fractions of the IMPROVE TOR analysis. It might be possible to adjust these fractions to obtain better agreement between atmospheric aerosol and soil/sediment analysis methods. Given its linking the EC measurement in the atmosphere to sediments, the TOR method will not only provide useful information on the explanation and comparison between different environmental matrices, but also can be used to derive information on global cycling of EC.     

The IMPROVE_A temperature protocol for thermal/optical carbon analysis: maintaining consistency with a long-term database

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

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

Abstract

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

Spatial distribution and seasonal variation of char-EC and soot-EC in the atmosphere over China

A previous study on PM_2.5 carbonaceous aerosols measured with the thermal optical reflectance (TOR) method in fourteen Chinese cities is extended by subdividing total EC into char-EC and soot-EC. Average char-EC concentrations show great differences between the fourteen cities and between winter and summer periods, with concentrations of 8.67 and 2.41 μg m^?3 in winter and summer, respectively. Meanwhile spatial and seasonal soot-EC variations are small, with average concentrations of 1.26 and 1.21 μg m^?3 in winter and summer, respectively. Spatial and temporal distributions of char-EC, similar to EC, are mainly influenced by local fuel consumption, as well as the East Asian monsoon and some meteorological factors such as the mixing height and wet precipitation. The small spatial and seasonal variation of soot-EC is consistent with its regional-to-global dispersion, which may suggest that soot carbon is not local carbon, but regional carbon. Char-EC/soot-EC ratios show summer minimum and winter maximum in all cities, which is in good agreement with the difference in source contributions between the two periods. As OC/EC ratio is affected by the formation of the secondary organic aerosol (SOA), char-EC/soot-EC ratio is a more effective indicator for source identification of carbonaceous aerosol than previously used OC/EC ratio.     

Characterization of carbon fractions for atmospheric fine particles and nanoparticles in a highway tunnel

Fine particles (PM_2.5) and nanoparticles (PM_0.1) were sampled using Dichotomous sampler and MOUDI, respectively, in Xueshan Tunnel, Taiwan. Eight carbon fractions were analyzed using IMPROVE thermal-optical reflectance (TOR) method. The concentrations of different temperature carbon fractions (OC1–OC4, EC1–EC3) in both PM_2.5 and PM_0.1 were measured and the correlations between OC and EC were discussed. Results showed that the ratios of OC/EC were 1.26 and 0.67 for PM_2.5 and PM_0.1, respectively. The concentration of EC1 was found to be more abundant than other elemental carbon fractions in PM_2.5, while the most abundant EC fraction in PM_0.1 was found to be EC2. The variation of contributions for elemental carbon fractions was different among PM_2.5 and PM_0.1 samples, which was partly owing to the metal catalysts for soot oxidation. The correlations between char-EC and soot-EC showed that char-EC dominated EC in PM_2.5 while soot-EC dominated EC in PM_0.1. Using eight individual carbon fractions, the gasoline and diesel source profiles of PM_0.1 and PM_2.5 were extracted and analyzed with the positive matrix factorization (PMF) method.     

Evaluation of OC/EC speciation by thermal manganese dioxide oxidation and the IMPROVE method

Ambient particulate samples are routinely analyzed for organic and elemental carbon (OC/EC) using either thermal manganese dioxide oxidation (TMO) or thermal volatilization-pyrolysis correction methods, such as the Interagency Monitoring of PROtected Visual Environments (IMPROVE) method with correction by reflectance, or a variation of the National Institute of Occupational Safety and Health (NIOSH) Method 5040 using thermal optical transmittance (TOT). With TMO, EC is modeled after the oxidation properties of submicron graphite and needle coke by MnO2, and is the fraction of total carbon (TC) that is not oxidized at >525 degrees C. In thermal volatilization methods, EC is the fraction of TC that accounts for the light extinction properties of the sample at the start of analysis. Chow et al. (2001) compared IMPROVE and NIOSH methods implemented on the same instrument using 60 samples of various types and found that NIOSH EC was lower than IMPROVE. This study compares total, organic, and elemental carbon measurements from the TMO and IMPROVE thermal optical reflectance (TOR) methods using a sample set consisting of 60 IMPROVE nonurban, 16 Korean urban, 10 Hong Kong urban, and 14 synthetic carbon black samples.     

Identification of haze-creating sources from fine particulate matter in Dhaka aerosol using carbon fractions

Fine particulate matter (PM_2.5) samples were simultaneously collected on Teflon and quartz filters between February 2010 and February 2011 at an urban monitoring site (CAMS2) in Dhaka, Bangladesh. The samples were collected using AirMetrics MiniVol samplers. The samples on Teflon filters were analyzed for their elemental composition by PIXE and PESA. Particulate carbon on quartz filters was analyzed using the IMPROVE thermal optical reflectance (TOR) method that divides carbon into four organic carbons (OC), pyrolized organic carbon (OP), and three elemental carbon (EC) fractions. The data were analyzed by positive matrix factorization using the PMF2 program. Initially, only total OC and total EC were included in the analysis and five sources, including road dust, sea salt and Zn, soil dust, motor vehicles, and brick kilns, were obtained. In the second analysis, the eight carbon fractions (OC1, OC2, OC3, OC4, OP, EC1, EC2, EC3) were included in order to ascertain whether additional source information could be extracted from the data. In this case, it is possible to identify more sources than with only total OC and EC. The motor vehicle source was separated into gasoline and diesel emissions and a fugitive Pb source was identified. Brick kilns contribute 7.9 μg/m³ and 6.0 μg/m³ of OC and EC, respectively, to the fine particulate matter based on the two results. From the estimated mass extinction coefficients and the apportioned source contributions, soil dust, brick kiln, diesel, gasoline, and the Pb sources were found to contribute most strongly to visibility degradation, particularly in the winter.

Implications: Fine particle concentrations in Dhaka, Bangladesh, are very high and cause significant degradation of urban visibility. This work shows that using carbon fraction data from the IMPROVE OC/EC protocol provides improved source apportionment. Soil dust, brick kiln, diesel, gasoline, and the Pb sources contribute strongly to haze, particularly in the winter.     

Evaluation of OC/EC Speciation by Thermal Manganese Dioxide Oxidation and the IMPROVE Method

Abstract

Ambient particulate samples are routinely analyzed for organic and elemental carbon (OC/EC) using either thermal manganese dioxide oxidation (TMO) or thermal volatil-ization-pyrolysis correction methods, such as the Inter-agency Monitoring of PROtected Visual Environments (IMPROVE) method with correction by reflectance, or a variation of the National Institute of Occupational Safety and Health (NIOSH) Method 5040 using thermal optical transmittance (TOT). With TMO, EC is modeled after the oxidation properties of submicron graphite and needle coke by MnO₂, and is the fraction of total carbon (TC) that is not oxidized at >525 °C. In thermal volatilization methods, EC is the fraction of TC that accounts for the light extinction properties of the sample at the start of analysis. Chow et al. (2001) compared IMPROVE and NIOSH methods implemented on the same instrument using 60 samples of various types and found that NIOSH EC was lower than IMPROVE. This study compares total, organic, and elemental carbon measurements from the TMO and IMPROVE thermal optical reflectance (TOR) methods using a sample set consisting of 60 IMPROVE nonurban, 16 Korean urban, 10 Hong Kong urban, and 14 synthetic carbon black samples.     

Characterization of carbonaceous species in PM2.5 in Xi'an during spring

The characterization of carbonaceous species in PM_2.5 during a spring period in a suburb of Xi'an, China was investigated. PM_2.5 samples were collected on quartz filters and analyzed for organic carbon (OC) and elemental carbon (EC). The thermal optical reflectance method was used. The minimum OC/EC ratio method was used to estimate the concentration of secondary organic carbon (SOC). The distribution of eight carbon fractions was investigated as well. The average mass concentrations of OC and EC were 15.90 and 8.38 μg/m³, respectively. The average OC/EC ratio ranged from 1.16 to 3.16 with an average value of 2.25. This implies the existence of SOC in PM_2.5. The mean SOC concentration was 7.20 μg/m³, accounting for 45.28% of total OC. This result suggests that SOC is a significant component of OC in the suburb of Xi'an. Results from the distribution of eight carbon fractions revealed that emissions from motor vehicle, coal combustion, and road dust were the main source of carbonaceous particles in the sampling period.     

Comparison of PM2.5 carbon measurement methods in Hong Kong, China

Samples from Hong Kong, China, were analyzed for organic carbon (OC), elemental carbon (EC), and total carbon (TC) by three thermal protocols (low-temperature IMPROVE and high-temperature STN and NIOSH) and two optical monitoring methods: reflectance and transmittance. Good agreement (+/-10%) for TC among the three protocols was observed for sample loadings of 1-55 microg m(-3). The two protocols using a reflectance pyrolysis correction showed best agreement for EC, with <20% differences found for approximately 80% of the samples. Hong Kong has a large diesel fleet, and for some heavily loaded samples the light transmittance was too low for quantitative detection, resulting in large uncertainties in the OC/EC split based on transmittance. Hong Kong experienced OC levels similar to those at US sites, but has much higher EC concentrations. OC/EC ratios range from 2 to 5 at two US sites and from 0.2 to 1.2 at three Hong Kong sites.     

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.     

Elemental carbon in urban soils and road dusts in Xi'an,China and its implication for air pollution

Increasing evidence confirms that elemental carbon (EC) is not only a light-absorbing constituent that warms the atmosphere but also a significant environmental pollutant. Investigations were conducted to identify carbonaceous pollution signatures in road dusts and urban soils and to evaluate potential sources in Xi'an. Average concentrations of EC, char-EC, and soot-EC in soils were 0.90, 0.51, and 0.39 mg g^?1, respectively, a little higher than or comparable to prior studies on the Loess Plateau. Vertical profiles in soils revealed soot-EC concentrations from pre-industrialized samples close to ～0.20 mg g^?1, while EC and char-EC varied widely, with no distinct pattern. Enrichment factor analysis indicated that EC, char-EC, and soot-EC in road dusts were all elevated by an order of magnitude. The spatial distribution of total EC, char-EC, and soot-EC in road dusts revealed close correspondence with human activities such as coal combustion and vehicle emissions. The average char-EC/soot-EC ratio was 1.66 for road dusts, suggesting that the main sources of carbonaceous particles are local coal combustion and vehicle emissions. The study demonstrated that EC, char-EC, and soot-EC levels in road dusts are effective indicators of anthropogenic pollution.     

Carbonaceous aerosol characteristics in outdoor and indoor environments of Nanchang, China, during summer 2009

A study of carbonaceous aerosol was initiated in Nanchang, a city in eastern China, for the first time. Daily and diurnal (daytime and nighttime) PM2.5 (particulate matter with aerodynamic diameter < or =2.5 microm) samples were collected at an outdoor site and in three different indoor environments (common office, special printing and copying office, and student dormitory) in a campus of Nanchang University during summer 2009 (5-20 June). Daily PM10 (particulate matter with aerodynamic diameter < or =10 microm) samples were collected only at the outdoor site, whereas PM2.5 samples were collected at both indoor and outdoor sites. Loaded PM2.5 and PM10 samples were analyzed for organic and elemental carbon (OC, EC) by thermal/optical reflectance following the Interagency Monitoring of Protected Visual Environments-Advanced (IMPROVE-A) protocol. Ambient mass concentrations of PM10 and PM2.5 in Nanchang were compared with the air quality standards in China and the United States, and revealed high air pollution levels in Nanchang. PM2.5 accounted for about 70% of PM10, but the ratio of OC and EC in PM2.5 to that in PM10 was higher than 80%, which indicated that OC and EC were mainly distributed in the fine particles. The variations of carbonaceous aerosol between daytime and nighttime indicated that OC was released and formed more rapidly in daytime than in nighttime. OC/EC ratios were used to quantify secondary organic carbon (SOC). The differences in SOC and SOC/OC between daytime and nighttime were useful in interpreting the secondary formation mechanism. The results of (1) OC and EC contributions to PM2.5 at indoor sites and the outdoor site; (2) indoor-outdoor correlation of OC and EC; (3) OC-EC correlation; and (4) relative contributions of indoor and outdoor sources to indoor carbonaceous aerosol indicated that OC indoor sources existed in indoor sites, with the highest OC emissions in I2 (the special printing and copying office), and that indoor EC originated from outdoor sources. The distributions of eight carbon fractions in emissions from the printer and copier showed obviously high OC1 (>20%) and OC2 (approximately 30%), and obviously low EC1-OP (a pyrolyzed carbon fraction) (<10%), when compared with other sources.     

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).     

Characterization of the Sunset Semi-Continuous Carbon Aerosol Analyzer

Abstract

The field-deployable Sunset Semi-Continuous Organic Carbon/Elemental Carbon (Sunset OCEC) aerosol analyzer utilizes the modified National Institute for Occupational Safety and Health thermal-optical method to determine total carbon (TC), organic carbon (OC), and elemental carbon (EC) at near real-time. Two sets of OC and EC are available: thermal OC and EC, and optical OC and EC. The former is obtained by the thermal-optical approach, and the latter is obtained by directly determining EC optically and deriving optical OC from TC. However, the performance of the Sunset OCEC is not yet fully characterized. Two collocated Sunset OCEC analyzers, Unit A and Unit B, were used to determine the pooled relative standard deviation (RSD) and limit of detection (LOD) between September 18 and November 6, 2007 in Richland, WA. The LOD of Unit A was approximately 0.2 μgC/m³ (0.1 μgC/cm²) for TC, optical OC, and thermal OC, and 0.01 μgC/m³ (0.01 μgC/cm²) for optical EC. Similarly, Unit B had an LOD of approximately 0.3 μgC/m³ (0.2 μgC/cm²) for TC, optical OC, and thermal OC, and 0.02 μgC/m³ (0.01 μgC/cm²) for optical EC. The LOD for thermal EC is estimated to be 0.2 μgC/m³ (0.1 μgC/cm²) for both units. The pooled RSDs were 4.9% for TC (carbon mass loadings 0.6–6.0 μgC/cm²), 5.6% for optical OC (carbon mass loadings 0.6–5.4 μgC/cm²), 5.3% for thermal OC (carbon mass loadings 0.6–5.3 μgC/cm²), and 9.6% for optical EC (carbon mass loadings 0–1.4 μgC/cm²), which indicates good precision between the instruments. The RSD for thermal EC is higher at 24.3% (carbon mass loadings 0–1.2 μgC/cm²). Low EC mass loadings in Richland contributed to the poor RSD of EC. The authors found that excessive noise from the nondispersive infrared (NDIR) laser in the Sunset OCEC analyzer could result in a worsened determination of OC and EC. It is recommended that a “quieter” NDIR laser and detector be used in the Sunset OCEC analyzer to improve quantification. Future work should re-evaluate the precision of the EC parameters in an environment favorable for EC collection. Investigation among quantification differences using various thermal-optical protocols to determine OC and EC is also in need.     

Hourly measurements of fine particulate sulfate and carbon aerosols at the Harvard-U.S. Environmental Protection Agency Supersite in Boston

Hourly concentrations of ambient fine particle sulfate and carbonaceous aerosols (elemental carbon [EC], organic carbon [OC], and black carbon [BC]) were measured at the Harvard-U.S. Environmental Protection Agency Supersite in Boston, MA, between January 2007 and October 2008. These hourly concentrations were compared with those made using integrated filter-based measurements over 6-day or 24-hr periods. For sulfate, the two measurement methods showed good agreement. Semicontinuous measurements of EC and OC also agreed (but not as well as for sulfate) with those obtained using 24-hr integrated filter-based and optical BC reference methods. During the study period, 24-hr PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter) concentrations ranged from 1.4 to 37.6 microg/m3, with an average of 9.3 microg/m3. Sulfate as the equivalent of ammonium sulfate accounted for 39.1% of the PM2.5 mass, whereas EC and OC accounted for 4.2 and 35.2%, respectively. Hourly sulfate concentrations showed no distinct diurnal pattern, whereas hourly EC and BC concentrations peaked during the morning rush hour between 7:00 and 9:00 a.m. OC concentrations also exhibited nonpronounced, small peaks during the day, most likely related to traffic, secondary organic aerosol, and local sources, respectively.     

Determination of the organic aerosol mass to organic carbon ratio in IMPROVE samples

The ratio of organic mass (OM) to organic carbon (OC) in PM(2.5) aerosols at US national parks in the IMPROVE network was estimated experimentally from solvent extraction of sample filters and from the difference between PM(2.5) mass and chemical constituents other than OC (mass balance) in IMPROVE samples from 1988 to 2003. Archived IMPROVE filters from five IMPROVE sites were extracted with dichloromethane (DCM), acetone and water. The extract residues were weighed to determine OM and analyzed for OC by thermal optical reflectance (TOR). On average, successive extracts of DCM, acetone, and water contained 64%, 21%, and 15%, respectively, of the extractable OC, respectively. On average, the non-blank-corrected recovery of the OC initially measured in these samples by TOR was 115+/-42%. OM/OC ratios from the combined DCM and acetone extracts averaged 1.92 and ranged from 1.58 at Indian Gardens, AZ in the Grand Canyon to 2.58 at Mount Rainier, WA. The average OM/OC ratio determined by mass balance was 2.07 across the IMPROVE network. The sensitivity of this ratio to assumptions concerning sulfate neutralization, water uptake by hygroscopic species, soil mass, and nitrate volatilization were evaluated. These results suggest that the value of 1.4 for the OM/OC ratio commonly used for mass and light extinction reconstruction in IMPROVE is too low.     

Determination of elemental carbon in lake sediments using a thermal–optical transmittance (TOT) method

An improved chemical oxidation pretreatment method has been developed for the determination of elemental carbon (EC) [also known as black carbon (BC) or soot] in lake sediments, using a thermal–optical transmittance (TOT) carbon analyzer. The method employs six steps: (1) removal of carbonates by treatment with HCl; (2) removal of silicates by treatment with HF + HCl; (3) removal of any remaining carbonates by treatment with HCl; (4) removal of humic acids by treatment with NaOH; and (5) oxidation of kerogens by K₂Cr₂O₇ + H₂SO₄. A critical step of zinc chloride treatment was added; this apparently changes EC's morphology and enhances retention on quartz fiber filter, resulting in several-fold increased chemical yield. EC was determined using the TOT method with modified combustion timings. Carbon black (acetylene) and four NIST standard reference materials (SRMs) were used for quality control, and to assess the precision of the analysis. The EC recoveries from 18 carbon black samples varied from 90 to 111%, with a mean value of 99 ± 6%. The high EC recoveries confirmed the validity of the method. Char reference materials (i.e. chestnut wood and grass char) were used to determine potential contribution to EC in our measurements. The char references containing about 700 mg total organic carbon (OC) contributed ～1.5% EC. The measured EC values from four NIST standards were 17.0 ± 0.6, 24.2 ± 3.2, 5.6, and 1.9 ± 0.1 mg g_dw^?1 for SRM-1648, SRM-1649a, SRM-1941b and SRM-8704, respectively. These values in SRMs were in agreement (<±4%) with the previously reported values. The method was applied to determine the EC in sediment cores from an urban lake and a remote mountain lake in the Northeastern United States. The EC concentrations in two lakes mimic the model EC emissions from the industrial revolution in United States.     

Chemical composition of fine particles from incense burning in a large environmental chamber

 This study is aimed to characterize the major chemical compositions of PM_2.5 from incense burning in a large environmental chamber. Chemical analyses, including X-ray fluorescence for elemental species, ion chromatography for water soluble inorganic species (chloride, nitrate, sulfate, sodium, potassium, ammonium) and thermal/optical reflectance analysis for carbon species were carried out for combustion of three incense categories (traditional, aromatic and church incense). The average concentrations from incense burning ranged from 139.8 to 4414.7 μg m⁻³ for organic carbon (OC), and from 22.8 to 74.0 μg m⁻³ for elemental carbon (EC), respectively. The average OC and EC concentrations in PM_2.5 of three incense categories were in the order of church incense>traditional incense>aromatic incense. OC/EC ratios ranged from 7.0 to 39.1 for the traditional incense, with an average of 21.7; from 3.2 to 11.9 for the aromatic incense, with an average of 7.7. The concentrations of Cl⁻, SO₄²⁻, Na⁺ and K⁺ were highly variable. On average, the inorganic ion concentration sequence was traditional incense>church incense>aromatic incense. The profiles for elements were dominated by Na, Cl and K. In general, the major components in PM_2.5 fraction from incense burning are OC (especially OC2, OC3 and OC4), EC and K.