Comparison of two winter air quality episodes during the California Regional Particulate Air Quality Study

The duration, strength, spatial extent, and chemical makeup of particulate matter (PM) are compared for two winter air quality episodes captured during the California Regional Particulate Air Quality Study (CRPAQS). Each episode, from the beginning of the buildup through dissolution, lasted about 3 weeks. The first episode occurred from December 14, 1999, through January 1, 2000, with peak 24-hr average fine particulate matter (PM2.5) concentrations reaching 129 microg/m3. The second episode occurred a year later, from December 18, 2000, through January 8, 2001, with peak 24-hr average PM2.5 concentrations reaching 179 microg/m3. Although similar in duration, each episode exhibited unique characteristics. One significant difference was the episode buildup rate; rapid in 1999, but slow and steady in 2000. The rapid buildup of the first episode resulted in more days with PM2.5 concentrations above the 24-hr federal standard, whereas the slow and steady increase of the second episode produced higher peaks. Spatial extent and progress also differed between the two episodes. The Northern Valley was impacted more during the December 1999 episode, and the Southern Valley during the December 2000 episode. The differences carried over into chemical composition. Ammonium nitrate dominated the PM2.5 mass during the December 1999 episode. The second episode reflected a dichotomy typical to the San Joaquin Valley, with Fresno concentrations dominated by organic and elemental carbon and the rest of the Valley concentrations dominated by ammonium nitrate. Each episode showed a regional as well as a local component. Ammonium nitrate concentrations, which result from more regional-scale secondary formation and mixing of emissions, were fairly uniform among the urban and rural sites. Carbon concentrations were always higher at urban sites than at rural sites, corresponding to the higher emissions density of primary carbon sources in urban areas.     

Characterization of major chemical components of fine particulate matter in North Carolina

This paper presents measurements of daily sampling of fine particulate matter (PM2.5) and its major chemical components at three urban and one rural locations in North Carolina during 2002. At both urban and rural sites, the major insoluble component of PM2.5 is organic matter, and the major soluble components are sulfate (SO4(2-)), ammonium (NH4(+)), and nitrate (NO3(-)). NH4(+) is neutralized mainly by SO4(2-) rather than by NO3(-), except in winter when SO4(2-) concentration is relatively low, whereas NO3(-) concentration is high. The equivalent ratio of NH4(+) to the sum of SO4(2-) and NO3(-) is < 1, suggesting that SO4(2-) and NO3(-) are not completely neutralized by NH4(+). At both rural and urban sites, SO4(2-) concentration displays a maximum in summer and a minimum in winter, whereas NO3(-) displays an opposite seasonal trend. Mass ratio of NO3(-) to SO4(2-) is consistently < 1 at all sites, suggesting that stationary source emissions may play an important role in PM2.5 formation in those areas. Organic carbon and elemental carbon are well correlated at three urban sites although they are poorly correlated at the agriculture site. Other than the daily samples, hourly samples were measured at one urban site. PM2.5 mass concentrations display a peak in early morning, and a second peak in late afternoon. Back trajectory analysis shows that air masses with lower PM2.5 mass content mainly originate from the marine environment or from a continental environment but with a strong subsidence from the upper troposphere. Air masses with high PM2.5 mass concentrations are largely from continental sources. Our study of fine particulate matter and its chemical composition in North Carolina provides crucial information that may be used to determine the efficacy of the new National Ambient Air Quality Standard (NAAQS) for PM fine. Moreover, the gas-to-particle conversion processes provide improved prediction of long-range transport of pollutants and air quality.     

Seasonal and spatial variation of solvent extractable organic compounds in fine suspended particulate matter in Hong Kong

The results of a 12-month study of more than 100 solvent extractable organic compounds (SEOC) in particulate matter (PM) less than or equal to 2.5 microm (PM2.5) collected at three air monitoring stations located at roadside, urban, and rural sites in Hong Kong are reported. The total yield of SEOC that accounts for approximately 8-18% of organic carbon (OC) determined by a thermal optical transmittance method was 125-2060 ng/m3, which included 14.6-128 ng/m3 resolved aliphatic hydrocarbons, 39.4-1380 ng/m3 unresolved complex mixtures, 0.6-17.2 ng/m3 polycyclic aromatic hydrocarbons, 41.6-520 ng/m3 fatty acids, and < 0.1-12.1 ng/m3 alkanols. Distinct seasonal variations (summer/winter differences) were observed with higher concentrations of the total and each class of SEOC in the winter and lower concentrations in the summer. Spatial variations are also obvious, with the roadside samples having the highest concentrations of SEOC and the rural samples having the lowest concentrations in all seasons. Characteristic ratios of petroleum hydrocarbons, such as carbon preference index, unresolved to resolved components, and carbon number with maximum concentration, suggest that PM2.5 carbon in Hong Kong originates from both biogenic and anthropogenic sources. The proportion of SEOC in PM2.5 from anthropogenic sources is estimated.     

Air quality and organic compounds in aerosols from a coastal rural area in the Western Iberian Peninsula over a year long period: Characterisation,loads and seasonal trends

Ambient samples of fine organic aerosol collected from a rural area (Moitinhos) in the vicinity of the small coastal Portuguese city of Aveiro over a period of more than one year have been solvent-extracted and quantitatively characterised by gas chromatography–mass spectrometry. Particles were also analysed with a thermal-optical technique in order to determine their elemental and organic carbon content. In addition, meteorological sensors and real-time black carbon, ozone and carbon monoxide monitors were used. Particulate matter values were higher than background levels in continental Europe. A patent seasonal variation for organic and elemental carbon concentrations was observed, presumably related to stronger local primary emissions and to limited vertical dispersion. The higher levels were most likely a result of residential wood burning, since black carbon and carbon monoxide maximised during late evening hours in wintertime. Of the bulk of elutable organics, more than a half, on average, was present as acidic fraction. Alcohols, aliphatic and polyaromatic hydrocarbons represented together, more than 30% of the elutable mass, also showing a marked seasonal pattern with a minimum in summer and a maximum in winter. The winter increase was more evident for resinic acids, phytosterols, n-alkanoic acids and polycyclic aromatic hydrocarbons.     

Sources of atmospheric carbonaceous particulate matter in Pittsburgh,Pennsylvania

The organic carbon (OC)/elemental carbon (EC) tracer method is applied to the Pittsburgh, PA, area to estimate the contribution of secondary organic aerosol (SOA) to the monthly average concentration of organic particulate matter (PM) during 1995. An emissions inventory is constructed for the primary emissions of OC and EC in the area of interest. The ratio of primary emissions of OC to those of EC ranges between 2.4 in the winter months and 1.0 in the summer months. A mass balance model and ambient measurements were used to assess the accuracy of the emissions inventory. It is estimated to be accurate to within 50%. The results from this analysis show a strong monthly dependence of the SOA contribution to the total organic PM concentration, varying from near zero during winter months to as much as 50% of the total OC concentration in the summer.     

Sampling artefacts,concentration and chemical composition of fine water-soluble organic carbon and humic-like substances in a continental urban atmospheric environment

Water-soluble organic carbon (WSOC) and atmospheric humic-like substances (HULIS) were investigated for urban PM2.5-fraction aerosol samples, which were collected with the tandem filter method on quartz fibre filters over a non-heating spring season. Sampling artefacts were of importance for all organic chemical fractions, and the back-to-front-filter concentration ratios were on average 28% for WSOC and 17% for HULIS and organic carbon (OC). The difference in the ratios indicates that the water-soluble organics play a more important role in adsorptive artefacts than the organic matter (OM) in general. The results emphasize the need for an appropriate sampling and/or correction method for measuring particulate organic substances in urban environments. The corrected atmospheric concentration of HULIS, obtained by subtracting the back-filter from the front-filter data, was on average 2 μg m⁻³; which represented 6% of the mean PM2.5 particulate mass, and it made up 45% of the secondary OC. The HULIS carbon accounted for 20% of the OC and 62% of the WSOC, while WSOC made up 32% of OC. The major element composition of HULIS, expressed in molar ratios, was C:H:O:N=22:32:10:1. The molar H/C ratio of 1.49 implies the presence of unsaturated organic compounds, although these were depleted in comparison with rural aerosol or standard fulvic acids. The molar O/C ratio of 0.47 indicates the existence of oxygenated functional groups; comparison to rural aerosol suggests that the (fresh) urban-type aerosol is less oxidized (and, therefore, less water soluble as well) than the rural one. The OM/OC mass conversion factor for the isolated (water-soluble) HULIS was derived to be 1.81. It was inferred from comparisons with published data that there are substantial differences in abundance and chemical composition of HULIS for different environments.     

Primary and secondary carbonaceous species in PM2.5 samples in Milan (Italy)

Seasonal elemental carbon (EC) and organic carbon (OC) concentration levels in PM2.5 samples collected in Milan (Italy) are presented and discussed, enriching the world-wide database of carbonaceous species in fine particulate matter (PM). High-volume PM2.5 sampling campaigns were performed from August 2002 through December 2003 in downtown Milan at an urban background site. Compared to worldwide average concentrations, in Milan warm-season OC and both warm- and cold-season EC are relatively low; conversely, cold-season OC concentrations are rather high. Consequently, high values for the OC/EC ratio are observed, especially in the winter period. The relation between OC/EC ratio values and wind direction is investigated, pointing out that the highest ratios are associated to winds blowing from those nearby areas where wood consumption for domestic heating is larger. Information on the OC partitioning between its primary and secondary fraction are derived by means of the EC-tracer method and principal component analysis. In the warm-season, OC is mainly of secondary origin, secondary organic aerosol (SOA) accounting for about 84% of the particulate organic matter and 25–28% of the PM2.5 mass. For the cold season the full application of the EC-tracer method was not possible and the primary organic aerosol deriving from traffic could only be estimated. However, principal component analysis (PCA) suggest a prevailing primary origin for OC, thus raising the attention on space heating emissions, and on wood combustion in particular, for air quality control. The role of traffic emissions on PM2.5 concentration levels, as a primary source, are also assessed: EC and primary organic matter from traffic account for a warm-season 30% and a cold-season 7% of the total carbon in PM2.5, that is for about 10% and 6% of PM2.5 mass, respectively. This latter small primary contribution estimated for the cold-season points out that stationary sources, which were not thought to play a significant role on PM concentration levels, may conversely be as much responsible for ambient particulate pollution.     

Characteristics of organic matter in PM2.5 in Shanghai

Solvent extractable organic compounds (SEOC), organic carbon, elemental carbon and water soluble organic carbon (WSOC) in PM(2.5) samples collected in Shanghai, China in 2002 and 2003 were measured to determine the composition and sources of the organic matter in atmospheric aerosols. Distinct seasonal variations were detected with higher concentrations of organic matter in winter. The concentration of total carbon of about 20 microg m(-3) in winter was about three times the summer value. About 30% of the total carbon was water soluble. Unresolved complex mixture (UCM) and fatty acids were the most abundant components quantified in SEOC, similar to other Chinese cities previously studied. High ratio of UCM to n-alkanes (U:R) and the composition of triterpanes indicated that engine exhaust was a major source of the airborne organic matter. Emissions from coal burning had more impact in the rural areas, according to the U:R value and PAHs composition. Chemical mass balance (CMB) modeling shows that about half of the organic carbon was from engine exhaust and about 15% was from coal burning. No clear spatial variation in the concentration of the organic matter was found between urban and rural areas. Our results showed that due to the rapid urbanization and relocation of industrial plants from urban areas to rural areas in the past 20 years, air pollution in rural areas is becoming a serious problem in Shanghai and the Yangtze River delta.     

Measurement, analysis, and modeling of fine particulate matter in eastern North Carolina

An analysis of fine particulate data in eastern North Carolina was conducted to investigate the impact of the hog industry and its emissions of ammonia into the atmosphere. The fine particulate data are simulated using ISORROPIA, an equilibrium thermodynamic model that simulates the gas and aerosol equilibrium of inorganic atmospheric species. The observational data analyses show that the major constituents of fine particulate matter (PM2.5) are organic carbon, elemental carbon, sulfate, nitrate, and ammonium. The observed PM2.5 concentration is positively correlated with temperature but anticorrelated with wind speed. The correlation between PM2.5 and wind direction at some locations suggests an impact of ammonia emissions from hog facilities on PM2.5 formation. The modeled results are in good agreement with observations, with slightly better agreement at urban sites than at rural sites. The predicted total inorganic particulate matter (PM) concentrations are within 5% of the observed values under conditions with median initial total PM species concentrations, median relative humidity (RH), and median temperature. Ambient conditions with high PM precursor concentrations, low temperature, and high RH appear to favor the formation of secondary PM.     

Fine particulate chemical composition and light extinction at Meadview, AZ

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was +/- 0.6 microg/m3 organic material, +/- 0.3 microg/m3 ammonium sulfate, and +/- 0.07 microg/m3 ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Transfer of nutrients and labile metals from the continent to the sea by a small Mediterranean river

The contribution of small watersheds to coastal pollution in Mediterranean areas is still poorly known, and presents great variations along an hydrological year. This work deals with the characterization and quantification of Al, Fe, Zn, Cu, Pb, Si, NO(3)(-) and organic carbon transported from the continent to the sea by a small coastal river in the French Mediterranean area. Transported species were characterized both during rainy and dry periods. During non-rainy periods (base-flow), waters showed a low content of contaminants, whereas during heavy rain events, following dry periods, some metals and organic carbon reached concentrations that could affect biological populations. These contaminants were mainly found in the particulate fraction, originating from the runoff of surface waters, which represents the main process of pollution in urban areas.     

Characteristics of PM2.5 carbonaceous aerosol in the Sihwa industrial area,Korea

In order to investigate the characteristics of carbonaceous fine aerosols, PM_2.5 particulate samples were collected in the Sihwa industrial complex area between February 1998 and 1999 and in Seoul between 31 May and 9 June 1999, respectively. The carbonaceous species were analyzed by the selective thermal manganese dioxide oxidation (TMO) method. In Sihwa, average OC and EC concentrations for the entire data set were measured to be 9.8 and 1.8 μg m⁻³, respectively. The OC concentrations were higher than those measured in other urban environments. The EC concentrations were lower than those of other urban environments. The OC/EC ratio measured at the Sihwa area was higher than those at other urban and rural environments. Backward trajectories of sampled air masses were performed to find out the sources of those higher OC/EC levels. Enrichment in the organic compounds during winter periods can be explained by the combination of primary local emissions from the industrial complex area and long-range transport of organic species from outside the Sihwa area. High OC values in June resulted from primary anthropogenic emissions and secondary organic aerosol formation rather than the atmospheric transport of organic compounds from the outside. In urban area of Seoul, the OC and EC concentrations in PM_2.5 during the summer were higher than those measured at other urban atmospheres. OC/EC ratios obtained in Seoul were lower than Sihwa. It can be concluded that carbonaceous species in Seoul were mainly emitted from primary anthropogenic sources.     

Carbonaceous aerosol over a Pinus taeda forest in Central North Carolina,USA

Organic aerosol is the least understood component of ambient fine particulate matter (PM_2.5). In this study, organic and elemental carbon (OC and EC) within ambient PM_2.5 over a three-year period at a forested site in the North Carolina Piedmont are presented. EC exhibited significant weekday/weekend effects and less significant seasonal effects, in contrast to OC, which showed strong seasonal differences and smaller weekend/weekday effects. Summer OC concentrations are about twice as high as winter concentrations, while EC was somewhat higher in the winter. OC was highly correlated with EC during cool periods when both were controlled by primary combustion sources. This correlation decreased with increasing temperature, reflecting higher contributions from secondary organic aerosol, likely of biogenic origin. PM_2.5 radiocarbon data from the site confirms that a large fraction of the carbon in PM_2.5 is indeed of biogenic origin, since modern (non-fossil fuel derived) carbon accounted for 80% of the PM_2.5 carbon over the course of a year. OC and EC exhibited distinct diurnal profiles, with summertime OC peaking in late evening and declining until midday. During winter, OC peaked during the early morning hours and again declined until midday. Summertime EC peaked during late morning hours except on weekends. Wintertime EC often peaked in late PM or early AM hours due to local residential wood combustion emissions. The highest short term peaks in OC and EC were associated with wildfire events. These data corroborate recent source apportionment studies conducted within 20 km of our site, where oxidation products of isoprene, α-pinene, and β-caryophyllene were identified as important precursors to organic aerosols. A large fraction of the carbon in rural southeastern ambient PM_2.5 appears to be of biogenic origin, which is probably difficult to reduce by anthropogenic controls.     

Fine Particulate Chemical Composition and Light Extinction at Meadview,AZ

Abstract

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was ±0.6 μg/m³ organic material, ±0.3 μg/m³ ammonium sulfate, and ±0.07 μg/m³ ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Composition of extractable organic matter of air particles from rural and urban Portuguese areas

Atmospheric particulate matter (PM₁₀) was collected simultaneously at three sites in the West Coast of Portugal, during an intensive campaign in August 1996. The sites were located in line with the breezes blowing from the sea. The collected aerosol was analysed in relation to black and organic carbon content. The particulate organic matter was extracted with solvents and characterised by gas chromatography and mass spectrometry (GC–MS). Most of the organic mass identified consists of alkanes, polycyclic aromatic hydrocarbons (PAH), ketones, aldehydes, alcohols and fatty acids with both biogenic and anthropogenic origin. Many photochemical products from volatile organic compounds emitted by vegetation were also detected. Biomarkers such as 6,10,14-trimethylpentadecanone, abieta-8,11,13-trien-7-one and Patchouli alcohol were observed at higher concentrations in the rural sites. Samples from the urban site present lower values of “carbon preference index” and higher concentrations of petrogenic/pyrogenic species, such as PAH. The PM₁₀ concentrations and the total organic extract measured for the more interior site were generally lower, indicating that dispersion and dry deposition into the forest canopy were more important during the transport of the air masses than aerosol production by condensation and photochemical reactions. On the contrary, the ratio between organic and black carbon was, in general, lower at sites near the coast, especially for compounds that evaporate at lower temperatures. The organic aerosol composition also seems to be strongly dependent on the meteorology.     

Fine particulate matter source apportionment for the Chemical speciation Trends Network site at Birmingham, Alabama, using Positive Matrix Factorization

The Positive Matrix Factorization (PMF) receptor model version 1.1 was used with data from the fine particulate matter (PM2.5) Chemical Speciation Trends Network (STN) to estimate source contributions to ambient PM2.5 in a highly industrialized urban setting in the southeastern United States. Model results consistently resolved 10 factors that are interpreted as two secondary, five industrial, one motor vehicle, one road dust, and one biomass burning sources. The STN dataset is generally not corrected for field blank levels, which are significant in the case of organic carbon (OC). Estimation of primary OC using the elemental carbon (EC) tracer method applied on a seasonal basis significantly improved the model's performance. Uniform increase of input data uncertainty and exclusion of a few outlier samples (associated with high potassium) further improved the model results. However, it was found that most PMF factors did not cleanly represent single source types and instead are "contaminated" by other sources, a situation that might be improved by controlling rotational ambiguity within the model. Secondary particulate matter formed by atmospheric processes, such as sulfate and secondary OC, contribute the majority of ambient PM2.5 and exhibit strong seasonality (37 +/- 10% winter vs. 55 +/- 16% summer average). Motor vehicle emissions constitute the biggest primary PM2.5 mass contribution with almost 25 +/- 2% long-term average and winter maximum of 29 +/- 11%. PM2.5 contributions from the five identified industrial sources vary little with season and average 14 +/- 1.3%. In summary, this study demonstrates the utility of the EC tracer method to effectively blank-correct the OC concentrations in the STN dataset. In addition, examination of the effect of input uncertainty estimates on model results indicates that the estimated uncertainties currently being provided with the STN data may be somewhat lower than the levels needed for optimum modeling results.     

Investigation of the time evolved spatial distribution of urban PM2.5 concentrations and aerosol composition during episodic high PM events in Yuma,AZ

An interdisciplinary field study designed to investigate the spatial and temporal variability of atmospheric aerosols during high particulate matter (PM) events along the US–Mexico border near Yuma, AZ was run during the week of March 18, 2007. The experiments were designed to quantify chemical composition and physical phenomena governing the transport of aerosols generated from episodic high PM events. The field study included two micrometeorological monitoring sites; one rural and one urban, equipped with sonic anemometers, continuous particulate concentration monitors and ambient aerosol collection equipment. In addition to the two main monitoring sites, five additional locations were equipped with optical particle counters to allow for the investigation of the spatial and temporal distribution of PM_2.5 in the urban environment. In this paper, the meteorological and turbulence parameters governing the distribution and concentration of PM_2.5 in the urban environment for two high-wind erosion events and one burning event are compared. The interaction between local atmospheric conditions and the particulate distribution is investigated. Results indicate that a single point measurement in the urban area of Yuma may not be sufficient for determining the ambient PM concentrations that the local population experiences; all three high PM events indicated PM_2.5 varied considerably with maximum urban concentrations 5–10 times greater than the measured minima. A comparison of inorganic and carbonaceous content of the aerosols for the three high PM events is presented. The comparison shows an increase in silicon during crustal dust events and an increase in elemental and organic carbon during the burn event. Additional surface chemistry analysis, using time-of-flight secondary ion mass spectrometry (ToF-SIMS), for aerosols collected at the urban and rural sites during the burn event are discussed. The surface chemistry analysis provides positive ion mass spectra of organic and inorganic species in the ambient aerosol, and can be used to determine the type of combustion process that contributed to an increase in PM concentration during the burn event.     

Source apportionment of fine particles in Washington, DC, utilizing temperature-resolved carbon fractions

Integrated ambient particulate matter < or =2.5 microm in aerodynamic diameter (PM2.5) samples were collected at a centrally located urban monitoring site in Washington, DC, on Wednesdays and Saturdays using Interagency Monitoring of Protected Visual Environments samplers. Particulate carbon was analyzed using the thermal optical reflectance method that divides carbon into four organic carbon fractions, pyrolyzed organic carbon, and three elemental carbon fractions. A total of 35 variables measured in 718 samples collected between August 1988 and December 1997 were analyzed. The data were analyzed using Positive Matrix Factorization and 10 sources were identified: sulfate (SO4(2-))-rich secondary aerosol I (43%), gasoline vehicle (21%), SO4(2-)-rich secondary aerosol II (11%), nitrate-rich secondary aerosol (9%), SO4(2-)-rich secondary aerosol III (6%), incinerator (4%), aged sea salt (2%), airborne soil (2%), diesel emissions (2%), and oil combustion (2%). In contrast to a previous study that included only total organic carbon and elemental carbon fractions, motor vehicles were separated into fractions identified as gasoline vehicle and diesel emissions containing carbon fractions whose abundances were different between the two sources. This study indicates that the temperature-resolved carbon fraction data can be utilized to enhance source apportionment, especially with respect to the separation of diesel emissions from gasoline vehicle sources. Conditional probability functions using surface wind data and deduced source contributions aid in the identifications of local sources.     

Analysis and apportionment of organic carbon and fine particulate matter sources at multiple sites in the midwestern United States

Speciated fine particulate matter (PM2.5) data collected as part of the Speciation Trends Network at four sites in the Midwest (Detroit, MI; Cincinnati, OH; Indianapolis, IN; and Northbrook, IL) and as part of the Interagency Monitoring of Protected Visual Environments program at the rural Bondville, IL, site were analyzed to understand sources contributing to organic carbon (OC) and PM2.5 mass. Positive matrix factorization (PMF) was applied to available data collected from January 2002 through March 2005, and seven to nine factors were identified at each site. Common factors at all of the sites included mobile (gasoline)/secondary organic aerosols with high OC, diesel with a high elemental carbon/OC ratio (only at the urban sites), secondary sulfate, secondary nitrate, soil, and biomass burning. Identified industrial factors included copper smelting (Northbrook, Indianapolis, and Bondville), steel/manufacturing with iron (Northbrook), industrial zinc (Northbrook, Cincinnati, Indianapolis, and Detroit), metal plating with chromium and nickel (Detroit, Indianapolis, and Bondville), mixed industrial with copper and iron (Cincinnati), and limestone with calcium and iron (Bondville). PMF results, on average, accounted for 96% of the measured PM2.5 mass at each site; residuals were consistently within tolerance (+/-3), and goodness-of-fit (Q) was acceptable. Potential source contribution function analysis helped identify regional and local impacts of the identified source types. Secondary sulfate and soil factors showed regional characteristics at each site, whereas industrial sources typically appeared to be locally influenced. These regional factors contributed approximately one third of the total PM2.5 mass, on average, whereas local mobile and industrial sources contributed to the remaining mass. Mobile sources were a major contributor (55-76% at the urban sites) to OC mass, generally with at least twice as much mass from nondiesel sources as from diesel. Regional OC associated with secondary sulfate and soil was generally low.     

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.