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).     

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.     

Multi-year hourly PM2.5 carbon measurements in New York: Diurnal,day of week and seasonal patterns

Multi-year hourly measurements of PM_2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m^?3 with peak hourly values of several μg m^?3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO_x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m^?3 with maximum hourly concentrations of 7–11 μg m^?3 predominantly in summer or winter months. OC concentrations generally correlated with PM_2.5 total mass and aerosol sulfate and with NO_x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO_x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.     

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.     

Carbon content of atmospheric aerosols in a residential area during the wood combustion season in Sweden

Carbonaceous aerosol particles were observed in a residential area with wood combustion during wintertime in Northern Sweden. Filter samples were analyzed for elemental carbon (EC) and organic carbon (OC) content by using a thermo-optical transmittance method. The light-absorbing carbon (LAC) content was determined by employing a commercial Aethalometer and a custom-built particle soot absorption photometer. Filter samples were used to convert the optical signals to LAC mass concentrations. Additional total PM₁₀ mass concentrations and meteorological parameters were measured. The mean and standard deviation mass concentrations were 4.4±3.6 μg m⁻³ for OC, and 1.4±1.2 μg m⁻³ for EC. On average, EC accounted for 10.7% of the total PM₁₀ and the contribution of OC to the total PM₁₀ was 35.4%. Aethalometer and custom-built PSAP measurements were highly correlated (R²=0.92). The hourly mean value of LAC mass concentration was 1.76 μg m⁻³ (median 0.88 μg m⁻³) for the winter 2005–2006. This study shows that the custom-built PSAP is a reliable alternative for the commercial Aethalometer with the advantage of being a low-cost instrument.     

Chemical characteristics of principal PM2.5 species in Chongju,South Korea

Fine particles were collected over four seasons from October 1995 to August 1996 to evaluate the chemical characteristics of principal PM_2.5 components in Chongju, South Korea. The annual mean concentrations of PM_2.5 (d_p⩽2.5 μm), sulfate, nitrate, ammonium, elemental carbon (EC) and organic carbon (OC) were 44.2, 8.22, 3.63, 2.84, 4.44 and 4.99 μg m⁻³, respectively. The sum of the species measured from this study accounted for 50–62% of the PM_2.5 mass. Sulfate was the most abundant species and constituted 13–23% of the PM_2.5 mass. The EC and OC accounted for 17–28% of PM_2.5. The correlation between OC and EC was strong, and the annual mean ratio of OC/EC was 1.12, suggesting that OC measured in the Chongju area may be emitted directly in particulate form as a primary aerosol.     

Characteristics of vertical profiles and sources of PM2.5, PM10 and carbonaceous species in Beijing

In August 2003 during the anticipated month of the 2008 Beijing Summer Olympic Games, we simultaneously collected PM₁₀ and PM_2.5 samples at 8, 100, 200 and 325 m heights up a meteorological tower and in an urban and a suburban site in Beijing. The samples were analysed for organic carbon (OC) and elemental carbon (EC) contents. Particulate matter (PM) and carbonaceous species pollution in the Beijing region were serious and widespread with 86% of PM_2.5 samples exceeding the daily National Ambient Air Quality Standard of the USA (65 μg m⁻³) and the overall daily average PM₁₀ concentrations of the three surface sites exceeding the Class II National Air Quality Standard of China (150 μg m⁻³). The maximum daily PM_2.5 and PM₁₀ concentrations reached 178.7 and 368.1 μg m⁻³, respectively, while those of OC and EC reached 22.2 and 9.1 μg m⁻³ in PM_2.5 and 30.0 and 13.0 μg m⁻³ in PM₁₀, respectively. PM, especially PM_2.5, OC and EC showed complex vertical distributions and distinct layered structures up the meteorological tower with elevated levels extending to the 100, 200 and 300 m heights. Meteorological evidence suggested that there exist fine atmospheric layers over urban Beijing. These layers were featured by strong temperature inversions close to the surface (<50 m) and more stable conditions aloft. They enhanced the accumulation of pollutants and probably caused the complex vertical distributions of PM and carbonaceous species over urban Beijing. The built-up of PM was accompanied by transport of industrial emissions from the southwest direction of the city. Emissions from road traffic and construction activities as well as secondary organic carbon (SOC) are important sources of PM. High OC/EC ratios (range of 1.8–5.1 for PM_2.5 and 2.0–4.3 for PM₁₀) were found, especially in the higher levels of the meteorological tower suggesting there were substantial productions of SOC in summer Beijing. SOC is estimated to account for at least 33.8% and 28.1% of OC in PM_2.5 and PM₁₀, respectively, with higher percentages at the higher levels of the tower.     

Seasonal and spatial trends in the sources of fine particle organic carbon in Israel,Jordan, and Palestine

A study of carbonaceous particulate matter (PM) was conducted in the Middle East at sites in Israel, Jordan, and Palestine. The sources and seasonal variation of organic carbon, as well as the contribution to fine aerosol (PM_2.5) mass, were determined. Of the 11 sites studied, Nablus had the highest contribution of organic carbon (OC), 29%, and elemental carbon (EC), 19%, to total PM_2.5 mass. The lowest concentrations of PM_2.5 mass, OC, and EC were measured at southern desert sites, located in Aqaba, Eilat, and Rachma. The OC contribution to PM_2.5 mass at these sites ranged between 9.4% and 16%, with mean annual PM_2.5 mass concentrations ranging from 21 to 25 ug m^?3. These sites were also observed to have the highest OC to EC ratios (4.1–5.0), indicative of smaller contributions from primary combustion sources and/or a higher contribution of secondary organic aerosol. Biomass burning and vehicular emissions were found to be important sources of carbonaceous PM in this region at the non-southern desert sites, which together accounted for 30%–55% of the fine particle organic carbon at these sites. The fraction of measured OC unapportioned to primary sources (1.4 μgC m^?3 to 4.9 μgC m^?3; 30%–74%), which has been shown to be largely from secondary organic aerosol, is relatively constant at the sites examined in this study. This suggests that secondary organic aerosol is important in the Middle East during all seasons of the year.     

Quantification and radiocarbon source apportionment of black carbon in atmospheric aerosols using the CTO-375 method

To make progress towards linking the atmosphere and biogeosphere parts of the black carbon (BC) cycle, a chemothermal oxidation method (CTO-375), commonly applied for isolating BC from complex geomatrices such as soils, sediments and aquatic particles, was applied to investigate the BC also in atmospheric particles. Concentrations and ¹⁴C-based source apportionment of CTO-375 based BC was established for a reference aerosol (NIST RM-8785) and for wintertime aerosols collected in Stockholm and in a Swedish background area. The results were compared with thermal–optical (OC/EC) measurements. For NIST RM-8785, a good agreement was found between the BC_CTO-375 concentration and the reported elemental carbon (EC) concentration measured by the “Speciation Trends Network—National Institute of Occupational Safety and Health” method (EC_NIOSH) with BC_CTO-375 of 0.054±0.002 g g⁻¹ and EC_NIOSH of 0.067±0.008 g g⁻¹. In contrast, there was an average factor of ca. 20 difference between BC_CTO-375 and EC_NIOSH for the ambient Scandinavian wintertime aerosols, presumably reflecting a combination of BC_CTO-375 isolating only the recalcitrant soot-BC portion of the BC continuum and the EC_NIOSH metric inadvertently including some intrinsically non-pyrogenic organic matter. Isolation of BC_CTO-375 with subsequent off-line radiocarbon analysis yielded fraction modern values (fM) for total organic carbon (TOC) of 0.93 (aerosols from a Swedish background area), and 0.58 (aerosols collected in Stockholm); whereas the fM for BC_CTO-375 isolates were 1.08 (aerosols from a Swedish background area), and 0.87 (aerosols collected in Stockholm). This radiocarbon-based source apportionment suggests that contribution from biomass combustion to cold-season atmospheric BC_CTO-375 in Stockholm was 70% and in the background area 88%.     

Contribution of carbonaceous material to cloud condensation nuclei concentrations in European background (Mt. Sonnblick) and urban (Vienna) aerosols

During four intensive measurement campaigns (two on Mt. Sonnblick, European background aerosol, and two in Vienna, urban aerosol), cloud condensation nuclei (CCN) were measured at supersaturations of 0.5%. Impactor measurements of the mass size distribution in the size range 0.1–10 μm were performed and later analyzed for Cl^-, NO^-₃, SO^2-₄, Na⁺, NH⁺₄, K⁺, Ca²⁺ and Mg²⁺ by ion chromatography, for total carbon (TC) using a combustion method, and for black carbon (BC) by an optical method (integrating sphere). Organic carbon (OC) was defined as the difference between TC (minus carbonate carbon) and BC. At all sites, the mass fraction of BC in the submicron aerosol was comparable (4–5%). CCN concentrations on Mt. Sonnblick were found to be 10–30% of those measured in Vienna, although high Mt. Sonnblick concentrations were comparable to low Vienna concentrations (around 800 cm^-3). The contribution of organic material was estimated from the mass concentrations of the chemical species sampled on the impactor stage with the lowest cut point (0.1–0.215 μm aerodynamic equivalent diameter). On Mt. Sonnblick, TC material contributed 11% to the total mass in fall 1995, and 67% in summer 1996, while the OC fraction was 6 and 61%. The combined electrolytes and mineral material contributed 18 and 16% in fall and summer. During the Vienna spring campaign, the contributions of OC and electrolytes to the total mass concentration in this size range were 48 and 36%, respectively.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

Sources and characteristics of carbonaceous aerosol in two largest cities in Pearl River Delta Region,China

PM_2.5 samples were collected at five sites in Guangzhou and Hong Kong, Pearl River Delta Region (PRDR), China in both summer and winter during 2004–2005. Elemental carbon (EC) and organic carbon (OC) in these samples were measured. The OC and EC concentrations ranked in the order of urban Guangzhou > urban Hong Kong > background Hong Kong. Total carbonaceous aerosol (TCA) contributed less to PM_2.5 in urban Guangzhou (32–35%) than that in urban Hong Kong (43–57%). The reason may be that, as an major industrial city in South China, Guangzhou would receive large amount of inorganic aerosol from all kinds of industries, however, as a trade center and seaport, urban Hong Kong would mainly receive organic aerosol and EC from container vessels and heavy-duty diesel trucks. At Hong Kong background site Hok Tsui, relatively lower contribution of TCA to PM_2.5 may result from contributions of marine inorganic aerosol and inland China pollutant. Strong correlation (R²=0.76–0.83) between OC and EC indicates minor fluctuation of emission and the secondary organic aerosol (SOA) formation in urban Guangzhou. Weak correlation between OC and EC in Hong Kong can be related to the impact of the long-range transported aerosol from inland China. Averagely, secondary OC (SOC) concentrations were 3.8–5.9 and 10.2–12.8 μg m⁻³, respectively, accounting for 21–32% and 36–42% of OC in summer and winter in Guangzhou. The average values of 4.2–6.8% for SOA/ PM_2.5 indicate that SOA was minor component in PM_2.5 in Guangzhou.     

Comparative analysis of organic and elemental carbon concentrations in carbonaceous aerosols in three European cities

Sampling and analysis of carbonaceous compounds in particulate matter presents a number of difficulties related to artefacts during sampling and to the distinction between organic (OC) and elemental carbon (EC) during analysis. Our study reports on a comparative analysis of OC, EC and WSOC (water-soluble organic carbon) concentrations, as well as sampling artefacts, for PM2.5 aerosol in three European cities (Amsterdam, Barcelona and Ghent) representing Southern and Western European urban environments. Comparability of results was ensured by using a single system for sample analysis from the different sites. OC and EC concentrations were higher in the vicinity of roads, thus having higher levels in Amsterdam (3.9–6.7 and 1.7–1.9 μg m⁻³, respectively) and Barcelona (3.6–6.9 and 1.5–2.6 μg m⁻³) than in Ghent (2.7–5.4 and 0.8–1.2 μg m⁻³). A relatively larger influence of secondary organic aerosols (SOA), as deduced from a larger OC/EC ratio, was observed in Ghent. In absolute sense, WSOC concentrations were similar at the three sites (1.0–2.3 μg m⁻³). Positive artefacts were higher in Southern (11–16% of the OC concentration in Barcelona) than in Western Europe (5–12% in Amsterdam, 5–7% in Ghent). During special episodes, the contribution of carbonaceous aerosols from non-local sources accounted for 67–69% of the OC concentration in Western Europe, and for 44% in Southern Europe.     

Decamethylcyclopentasiloxane (D5) spiked sediment: Bioaccumulation and toxicity to the benthic invertebrate Hyalella azteca

Chronic toxicity and bioaccumulation of decamethylcyclopentasiloxane (D5) to Hyalella azteca was examined in a series of spiked sediment exposures. Juvenile H. azteca were exposed for 28 d (chronic) to a concentration series of D5 in two natural sediments of differing organic carbon content (O.C.) and particle size composition. The chronic, LC50s were 191 and 857 μg D5 g⁻¹ dry weight for Lakes Erie (0.5% O.C.) and Restoule (11% O.C.) respectively. Inhibition of growth only occurred with the L. Restoule spiked sediment with a resultant EC25 of 821 μg g⁻¹ dw. Lethality was a more sensitive endpoint than growth inhibition. Biota sediment accumulation factors (BSAFs, 28 d) were <1 indicating that D5 did not bioconcentrate based on lipid normalized tissue concentrations and organic carbon normalized sediment concentrations. Organic carbon (OC) in the sediment appeared to be protective, however normalization to OC did not normalize the toxicity. Normalization of D5 concentrations in the sediments to sand content did normalize the toxicity and LC50 values of 3180 and 3570 μg D5 g⁻¹ sand dw were determined to be statistically the same.     

Polychlorinated biphenyls and particulate organic/elemental carbon in the atmosphere of Chesapeake Bay,USA

Polychlorinated biphenyls (PCBs) and particulate organic/elemental carbon (OC/EC) differ as to sources, but are both elevated in major urban areas leading to loadings of proximate terrestrial and aquatic systems. Because of the dramatic difference in speciation, sources, and sinks of these compunds, gas+particulate phase PCBs and particulate OC/EC were measured in urban Baltimore, MD and over Chesapeake Bay at 4 and 12 h frequencies in July 1997. Gas phase ∑PCBs averaged 1180 pg m⁻³ for Baltimore and 550 pg m⁻³ for northern Chesapeake Bay. PCB homolog distributions in the gas phase differed between the land and over-water sites whereby the trichlorobiphenyls were higher in Baltimore compared to Chesapeake Bay. Autocorrelation analysis yielded a diurnal cycle for gas phase PCBs at Baltimore with the lowest concentrations observed during the day. Particulate organic and elemental carbon constituted 12.4% (17.4% organic matter) and 2.8% of total suspended particles (TSP) in Baltimore, and 15.0% (21.0% organic matter) and 5.3% over the Chesapeake Bay, respectively. Variability in PCB concentrations was not related to the variability in OC/EC concentrations. OC/EC ratios suggest that particulate organic carbon was mostly primary aerosol. Emissions of both classes of compounds into the Baltimore atmosphere and vicinity are major sources to the Bay.     

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.     

Carbonaceous and inorganic composition in long-range transported aerosols over northern Japan: Implication for aging of water-soluble organic fraction

To better understand the influence of sources and atmospheric processing on aerosol chemical composition, we collected atmospheric particles in Sapporo, northern Japan during spring and early summer 2005 under the air mass transport conditions from Siberia, China and surrounding seas. The aerosols were analyzed for inorganic ions, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC), and the major water-soluble organic compound classes (i.e., dicarboxylic acids and sugars). SO₄^2? is the most abundant inorganic constituent (average 44% of the identified inorganic ion mass) followed by NH₄⁺ (21%) and NO₃^? (13%). Concentrations of OC, EC, and WSOC ranged from 2.0–16, 0.24–2.9, and 0.80–7.9 μg m^?3 with a mean of 7.4, 1.0, and 3.1 μg m^?3, respectively. High OC/EC ratios (range: 3.6–19, mean: 8.7) were obtained, however WSOC/OC ratios (0.23–0.69, 0.44) do not show any significant diurnal changes. These results suggest that the Sapporo aerosols were already aged, but were not seriously affected by local photochemical processes. Identified water-soluble organic compounds (diacids + sugars) account for <10% of WSOC. Based on some marker species and air mass back trajectory analyses, and using stable carbon isotopic compositions of shorter-chain diacids (i.e., C₂–C₄) as photochemical aging factor of organic aerosols, the present study suggests that a fraction of WSOC in OC is most likely influenced by aerosol aging, although the OC loading in aerosols may be more influenced by their sources and source regions.     

Emission factors of PAHs,methoxyphenols, levoglucosan,elemental carbon and organic carbon from simulated wheat and Kentucky bluegrass stubble burns

Emission factors (EFs) of pollutants from post-harvest agricultural burning are required for predicting downwind impacts of smoke and inventorying emissions. EFs of polycyclic aromatic hydrocarbons (PAH), methoxyphenols (MP), levoglucosan (LG), elemental carbon (EC) and organic carbon (OC) from wheat and Kentucky bluegrass (KBG) stubble burning were quantified in a US EPA test burn facility. The PAH and MP EFs for combined solid+gas phases are 17±8.2 mg kg⁻¹ and 79±36 mg kg⁻¹, respectively, for wheat and 21±15 mg kg⁻¹ and 35±24 mg kg⁻¹, respectively, for KBG. LG, particulate EC and artifact-corrected OC EFs are 150±130 mg kg⁻¹, 0.35±0.16 g kg⁻¹ and 1.9±1.1 g kg⁻¹, respectively, for wheat and 350±510 mg kg⁻¹, 0.63±0.056 g kg⁻¹ and 6.9±0.85 g kg⁻¹, respectively, for KBG. Positive artifacts associated with OC sampling were evaluated and remedied with a two-filter system. EC and OC accounted for almost two-thirds of PM_2.5 mass, while LG accounted for just under 3% of the PM_2.5 mass. Since EFs of these pollutants generally decreased with increasing combustion efficiency (CE), identifying and implementing methods of increasing the CEs of burns would help reduce their emissions from agricultural field burning. PAH, OC and EC EFs are comparable to other similar studies reported in literature. MP EFs appear dependent on the stubble type and are lower than the EFs for hard and softwoods reported in literature, possibly due to the lower lignin content in wheat and KBG.     

Source apportionment of primary and secondary organic aerosols using positive matrix factorization (PMF) of molecular markers

Monthly average ambient concentrations of more than eighty particle-phase organic compounds, as well as total organic carbon (OC) and elemental carbon (EC), were measured from March 2004 through February 2005 in five cities in the Midwestern United States. A multi-variant source apportionment receptor model, positive matrix factorization (PMF), was applied to explore the average source contributions to the five sampling sites using molecular markers for primary and secondary organic aerosols (POA, SOA). Using the molecular makers in the model, POA and SOA were estimated for each month at each site. Three POA factors were derived, which were dominated by primary molecular markers such as EC, hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs), and which represented the following POA sources: urban primary sources, mobile sources, and other combustion sources. The three POA sources accounted for 57% of total average ambient OC. Three factors, characterized by the presence of reaction products of isoprene, α-pinene and β-caryophyllene, and displaying distinct seasonal trends, were consistent with the characteristics of SOA. The SOA factors made up 43% of the total average measured OC. The PMF-derived results are in good agreement with estimated SOA concentrations obtained from SOA to tracer yield estimates obtained from smog chamber experiments. A linear regression comparing the smog chamber yield estimates and the PMF SOA contributions had a regression slope of 1.01 ± 0.07 and an intercept of 0.19 ± 0.10 μg OC m^?3 (adjusted R² of 0.763, n = 58).     

On the variability of Black Smoke and carbonaceous aerosols in the Netherlands

The study addresses the characteristics of elemental carbon (EC) and organic carbon (OC) distributions in the Netherlands by using Black Smoke (BS) data in combination with dedicated measurements and modelling. The BS levels indicate a large-scale background concentration over the Netherlands with low spatial variability and a gradient with highest levels (∼9 μg m⁻³) in the south gradually decreasing to the north-west (∼5.5 μg m⁻³). The BS concentrations at rural sites in the Netherlands are highly correlated due to common (diffuse) sources and large-scale meteorology. Superimposed on the regional background are the contributions of local/urban sources. Urban and rural BS levels show a distinct variation over the week with minimum levels on Sundays.BS levels do not reflect a real concentration as they are obtained via an optical measurement in combination with an outdated calibration curve to arrive at total suspended particles (TSP). We have found that the relation between BS and EC in the Netherlands is linear and highly correlated but dependent on station type. Application of these relations to the BS time series yields a gradient in the rural background EC concentration from 0.5 μg m⁻³ in the north to 0.7 μg m⁻³ in the south of the Netherlands. The relationship between OC and BS appears to be location specific and is determined by the BS–EC relation in combination with a characteristic OC/EC ratio. OC/EC ratios are ∼5 at regional background sites and ∼2 at traffic locations. Minimum OC/EC ratios at the traffic sites reflect the primary OC/EC ratio of traffic. We argue that estimation of secondary organic aerosol by assuming the minimum OC/EC ratio to be a proxy for the primary OC/EC is not allowed since this approach does not account for sources with high OC/EC ratios. Based on European scale modelling and the measured data, we estimate that national sources contribute ∼40–60% to Dutch EC levels.The rather costly and laborious EC measurements provide a better indicator of the carbonaceous fraction in ambient particulate matter (PM) but the cheap BS method may provide valuable information on spatial distribution of EC when used in combination with validation sites to characterise the EC–BS relationship.