Determination of the sources of indoor PM2.5 in Amsterdam and Helsinki

Daily PM2.5 samples were repeatedly collected (1-8 times) in the homes of elderly nonsmoking individuals with coronary heart disease in Amsterdam, The Netherlands (33 individuals) and Helsinki, Finland (44 individuals). Sources of indoor PM2.5 were evaluated using a two-way multilinear engine model. Because the indoor elemental data lacked a traffic marker, separation of traffic related PM was attempted by combining the indoor data with fixed site outdoor data that also contained NO. Six outdoor sources, including long-range transport (LRT), urban mixture, oil combustion, traffic, sea-salt, and soil were identified, and three indoor sources were resolved: resuspension, potassium-rich and copper-rich sources. The average contribution of the indoor factors was 6% (1.1 microg m(-3)) and 22% (2.4 microg m(-3)) in Amsterdam and Helsinki, respectively. The highest longitudinal correlations between source-specific outdoor and indoor PM2.5 concentrations were found for LRT and urban mixture; the median R was above 0.6 for most sources. The longitudinal correlations were lower in Helsinki than in Amsterdam. Indoor-generated PM2.5 was not related to ambient concentrations. We conclude that using outdoor and indoor data together improved the source apportionment of indoor PM2.5. The results support the use of fixed site outdoor measurements in epidemiological time-series studies on outdoor air pollution.     

Use of personal-indoor-outdoor sulfur concentrations to estimate the infiltration factor and outdoor exposure factor for individual homes and persons

A study of personal, indoor, and outdoor exposure to PM2.5 and associated elements has been carried out for 37 residents of the Research Triangle Park area in North Carolina. Participants were selected from persons expected to be at elevated risk from exposure to particles, and included 29 persons with hypertension and 8 cardiac patients with implanted defibrillators. Participants were monitored for 7 consecutive days in each of four seasons. One goal of the study was to estimate the contribution of outdoor PM2.5 to indoor concentrations. This depends on the infiltration factor Finf, the fraction of outdoor PM2.5 remaining airborne after penetrating indoors. After confirming with our measurements the findings of previous studies that sulfur has few indoor sources, we estimated an average Finf for each house based on indoor/outdoor sulfur ratios. These estimates ranged from 0.26 to 0.87, with a median value of 0.55. Since these estimates apply only to particles of size similar to that of sulfur particles (0.06-0.5 microm diameter), and since larger particles (0.5-2.5 microm) have lower penetration rates and higher deposition rates, these estimates are likely to be higher than the true infiltration factors for PM2.5 as a whole. In summer when air conditioners were in use, the sulfur-based infiltration factor was at its lowest (averaging 0.50) for most homes, whereas the average Finf for the other three seasons was 0.62-0.63. Using the daily estimated infiltration factor for each house, we calculated the contribution of outdoor PM2.5 to indoor air concentrations. The indoor-generated contributions to indoor PM2.5 had a wider range (0-33 microg/m3) than the outdoor contributions (5-22 microg/m3). However, outdoor contributions exceeded the indoor-generated contributions in 27 of 36 homes. A second goal of the study was to determine the contribution of outdoor particles to personal exposure. This is determined by the "outdoor exposure factor" Fpex, the fraction of outdoor PM2.5 contributing to personal exposure. As with Finf, we estimated Fpex by the personal/outdoor sulfur ratios. The estimates ranged from 0.33 to 0.77 with a median value of 0.53. Outdoor air particles were less important for personal exposures than for indoor concentrations, with the median outdoor contribution to personal exposure just 49%. We regressed the outdoor contributions to personal exposures on measured outdoor PM2.5 at the central site. The regressions had R2 values ranging from 0.19 to 0.88 (median = 0.73). These values provide an indication of the extent of misclassification error in epidemiological estimates of the effect of outdoor particles on health.     

How does infiltration behavior modify the composition of ambient PM2.5 in indoor spaces? An analysis of RIOPA data

The indoor environment is an important venue for exposure to fine particulate matter (PM2.5) of ambient (outdoor) origin. In this work, paired indoor and outdoor PM2.5 species concentrations from three geographically distinct cities (Houston, TX, Los Angeles County, CA, and Elizabeth, NJ) were analyzed using positive matrix factorization (PMF) and demonstrate that the composition and source contributions of ambient PM2.5 are substantially modified by outdoor-to-indoor transport. Our results suggest that predictions of "indoor PM2.5 of ambient origin" are improved when ambient PM2.5 is treated as a combination of four distinct particle types with differing infiltration behavior (primary combustion, secondary sulfate and organics, secondary nitrate, and mechanically generated PM) rather than as a "single internally mixed entity". Study-wide average infiltration factors (i.e., fraction of ambient PM2.5 found indoors) for Relationship of Indoor, Outdoor, and Personal Air (RIOPA) study homes were 0.51, 0.78, and 0.04 (consistent with P = 0.6, 0.9, and 0.09; k = 0.2, 0.1, and 0.6 h(-1)) for PM2.5 associated with primary combustion, secondary formation (excluding nitrate), and mechanical generation, respectively. Modification of the composition, properties, and source contributions of ambient PM2.5 in indoor environments has important implications for exposure mitigation strategies, development of health hypotheses, and evaluation of exposure error in epidemiological studies that use ambient central-site PM2.5 as a surrogate for PM2.5 exposure.     

Using sulfur as a tracer of outdoor fine particulate matter

Six homes in the metropolitan Boston area were sampled between 6 and 12 consecutive days for indoor and outdoor particle volume and mass concentrations, particle elemental concentrations, and air exchange rates (AERs). Indoor/outdoor (I/O) ratios of nighttime (i.e., particle nonindoor source periods) sulfur, PM2.5 and the specific particle size intervals were used to provide estimates of the effective penetration efficiency. Mixed models and graphical displays were used to assess the ability of the I/O ratios for sulfur to estimate corresponding I/O ratios for PM2.5 and the various particle sizes. Results from this analysis showed that particulate sulfur compounds were primarily of outdoor origin and behaved in a manner that was representative of total PM2.5 in Boston, MA. These findings support the conclusion that sulfur can be used as a suitable tracer of outdoor PM2.5 for the homes sampled in this study. Sulfur was more representative of particles of similar size (0.06-0.5 microm), providing evidence that the size composition of total PM2.5 is an important characteristic affecting the robustness of sulfur-based estimation methods.     

Intake fraction for particulate matter: recommendations for life cycle impact assessment

Particulate matter (PM) is a significant contributor to death and disease globally. This paper summarizes the work of an international expert group on the integration of human exposure to PM into life cycle impact assessment (LCIA), within the UNEP/SETAC Life Cycle Initiative. We review literature-derived intake fraction values (the fraction of emissions that are inhaled), based on emission release height and "archetypal" environment (indoor versus outdoor; urban, rural, or remote locations). Recommended intake fraction values are provided for primary PM(10-2.5) (coarse particles), primary PM(2.5) (fine particles), and secondary PM(2.5) from SO(2), NO(x), and NH(3). Intake fraction values vary by orders of magnitude among conditions considered. For outdoor primary PM(2.5), representative intake fraction values (units: milligrams inhaled per kilogram emitted) for urban, rural, and remote areas, respectively, are 44, 3.8, and 0.1 for ground-level emissions, versus 26, 2.6, and 0.1 for an emission-weighted stack height. For outdoor secondary PM, source location and source characteristics typically have only a minor influence on the magnitude of the intake fraction (exception: intake fraction values can be an order of magnitude lower for remote-location emission than for other locations). Outdoor secondary PM(2.5) intake fractions averaged over respective locations and stack heights are 0.89 (from SO(2)), 0.18 (NO(x)), and 1.7 (NH(3)). Estimated average intake fractions are greater for primary PM(10-2.5) than for primary PM(2.5) (21 versus 15), owing in part to differences in average emission height (lower, and therefore closer to people, for PM(10-2.5) than PM(2.5)). For indoor emissions, typical intake fraction values are ～1000-7000. This paper aims to provide as complete and consistent an archetype framework as possible, given current understanding of each pollutant. Values presented here facilitate incorporating regional impacts into LCIA for human health damage from PM.     

Prediction of personal exposure to PM2.5 and carcinogenic polycyclic aromatic hydrocarbons by their concentrations in residential microenvironments

We measured exposure to fine particles (PM2.5) and polycyclic aromatic hydrocarbons (PAHs), including carcinogenic PAHs, in multiple locations for a diverse population of participants who resided in Shizuoka, Japan. In summer and winter 2002 we surveyed personal concentrations, those of four primary indoor microenvironments-living room, bedroom, kitchen (summer only), and workplace--and those outside the subjects' houses. Concentrations of PM2.5 and PAHs tended to be higher during winter. Median PM2.5 concentration was highest in living room samples during winter but in personal samples during summer. The median PAH concentrations normalized to the cancer potency equivalence factor of benzo[a]pyrene (BaP-TEQ) was highest in the bedroom during winter but outdoors in summer. Personal exposure level profiles differed markedly between smokers and nonsmokers. Personal exposures to BaP ([BaP]p) and BaP-TEQ ([BaP-TEQ]P) in nonsmokers were strongly correlated. Personal exposures of nonsmokers, as calculated from the corresponding time-weighted indoor and outdoor concentrations, were consistent with measured levels of BaP but not PM2.5. Personal exposure of nonsmokers to BaP, as calculated from the time-weighted living room, bedroom, and either workplace or outdoor concentrations, accounted for 92-107% of the measured levels of BaP-TEQ.     

Chemical characterization and source apportionment of fine and coarse particulate matter inside the refectory of Santa Maria Delle Grazie Church, home of Leonardo Da Vinci's "Last Supper"

The association between exposure to indoor particulate matter (PM) and damage to cultural assets has been of primary relevance to museum conservators. PM-induced damage to the "Last Supper" painting, one of Leonardo da Vinci's most famous artworks, has been a major concern, given the location of this masterpiece inside a refectory in the city center of Milan, one of Europe's most polluted cities. To assess this risk, a one-year sampling campaign was conducted at indoor and outdoor sites of the painting's location, where time-integrated fine and coarse PM (PM(2.5) and PM(2.5-10)) samples were simultaneously collected. Findings showed that PM(2.5) and PM(2.5-10) concentrations were reduced indoors by 88 and 94% on a yearly average basis, respectively. This large reduction is mainly attributed to the efficacy of the deployed ventilation system in removing particles. Furthermore, PM(2.5) dominated indoor particle levels, with organic matter as the most abundant species. Next, the chemical mass balance model was applied to apportion primary and secondary sources to monthly indoor fine organic carbon (OC) and PM mass. Results revealed that gasoline vehicles, urban soil, and wood-smoke only contributed to an annual average of 11.2 ± 3.7% of OC mass. Tracers for these major sources had minimal infiltration factors. On the other hand, fatty acids and squalane had high indoor-to-outdoor concentration ratios with fatty acids showing a good correlation with indoor OC, implying a common indoor source.     

Development and evaluation of a personal particulate organic and mass sampler

Accurate measurement of personal exposure to particulate matter and its constituents requires samplers that are accurate, compact, lightweight, inexpensive, and convenient to use. The personal particulate organic and mass sampler (PPOMS) has been developed to meet these criteria. The PPOMS uses activated carbon-impregnated foam as a combined 2.5-microm size-selective inlet and denuder for assessment of fine particle mass and organic carbon. Proof of the PPOMS concept has been established by comparing mass and organic carbon in particles collected with collocated samplers in Seattle, at a central outdoor site, and in residences. Daily particulate mass concentrations averaged 10.0 +/- 5.2, 12.0 +/- 5.3, and 11.2 +/- 5.1 microg m(-3) for the Federal Reference Method, the Harvard Personal Exposure Monitor, and the PPOMS, respectively, for 10 24-h sampling periods. During a series of PM2.5 indoor organic carbon (OC) measurements from single quartz filters, the apparent indoor OC averaged 7.7 +/- 0.8 microg of C m(-3), which was close to the indoor PM2.5 mass from collocated Teflon filters (7.3 +/- 2.3 microg of C m(-3)), indicating the presence of a large positive OC artifact. In collocated measurements, the PPOMS eliminated this artifact just as well as the integrated gas and particle sampler that incorporated a macroreticular polystyrene-divinylbenzene (XAD-4) resin-coated denuder, yielding OC concentrations of 2.5 +/- 0.4 and 2.4 +/- 1.0 microg of C m(-3), respectively. Thermal analysis for OC indicated that the indoor positive artifact was due to adsorption of gas-phase semivolatile organic compounds (SVOC). This study shows that the PPOMS design provides a 2.5-microm size-selective inlet that also prevents the adsorption of gas-phase SVOC onto quartz filters, thus eliminating the filter positive artifact The PPOMS meets a significant current challenge for indoor and personal sampling of particulate organic carbon. The PPOMS design can also simplify accurate ambient sampling for PM2.5.     

Use of real-time light scattering data to estimate the contribution of infiltrated and indoor-generated particles to indoor air

The contribution of outdoor particulate matter (PM) to residential indoor concentrations is currently not well understood. Most importantly, separating indoor PM into indoor- and outdoor-generated components will greatly enhance our knowledge of the outdoor contribution to total indoor and personal PM exposures. This paper examines continuous light scattering data at 44 residences in Seattle, WA. A newly adapted recursive model was used to model outdoor-originated PM entering indoor environments. After censoring the indoor time-series to remove the influence of indoor sources, nonlinear regression was used to estimate particle penetration (P, 0.94 +/- 0.10), air exchange rate (a, 0.54 +/- 0.60 h(-1)), particle decay rate (k, 0.20 +/- 0.16 h(-1)), and particle infiltration (F(inf), 0.65 +/- 0.21) for each of the 44 residences. All of these parameters showed seasonal differences. The F(inf) estimates agree well with those estimated from the sulfur-tracer method (R2 = 0.78). The F(inf) estimates also showed robust and expected behavior when compared against known influencing factors. Among our study residences, outdoor-generated particles accounted for an average of 79 +/- 17% of the indoor PM concentration, with a range of 40-100% at individual residences. Although estimates of P, a, and k were dependent on the modeling technique and constraints, we showed that a recursive mass balance model combined with our censoring algorithms can be used to attribute indoor PM into its outdoor and indoor components and to estimate an average P, a, k, and F(inf), for each residence.     

Indoor particulate matter of outdoor origin: importance of size-dependent removal mechanisms

Adverse human health effects have been observed to correlate with levels of outdoor particulate matter (PM), even though most human exposure to PM of outdoor origin occurs indoors. In this study, we apply a model and empirical data to explore the indoor PM levels of outdoor origin for two major building types: offices and residences. Typical ventilation rates for each building type are obtained from the literature. Published data are combined with theoretical analyses to develop representative particle penetration coefficients, deposition loss rates, and ventilation-system filter efficiencies for a broad particle size range (i.e., 0.001-10 microm). We apply archetypal outdoor number, surface area, and mass PM size distributions for both urban and rural airsheds. We also use data on mass-weighted size distributions for specific chemical constituents of PM: sulfate and elemental carbon. Predictions of the size-resolved indoor proportion of outdoor particles (IPOP) for various conditions and ambient particle distributions are then computed. The IPOP depends strongly on the ambient particle size distribution, building type and operational parameters, and PM metric. We conclude that an accurate determination of exposure to particles of ambient origin requires explicit consideration of how removal processes in buildings vary with particle size.     

Use of time- and chemically resolved particulate data to characterize the infiltration of outdoor PM2.5 into a residence in the San Joaquin Valley

Recent studies associate particulate air pollution with adverse health effects. The indoor exposure to particles of outdoor origin is not well-characterized, particularly for individual chemical species. In response to this, a field study in an unoccupied, single-story residence in Clovis, CA, was conducted. Real-time particle monitors were used both outdoors and indoors to quantity PM2.5 nitrate, sulfate, and carbon. The aggregate of the highly time-resolved sulfate data, as well as averages of these data, was fit using a time-averaged form of the infiltration equation, resulting in reasonable values for the penetration coefficient and deposition loss rate. In contrast, individual values of the indoor/outdoor ratio can vary significantly from that predicted by the model for time scales ranging from a few minutes to several hours. Measured indoor ammonium nitrate levels were typically significantly lower than expected solely on the basis of penetration and deposition losses. The additional reduction is due to the transformation of ammonium nitrate into ammonia and nitric acid gases indoors, which are subsequently lost by deposition and sorption to indoor surfaces. This result illustrates that exposure assessments based on total outdoor particle mass can obscure the actual causal relationships for indoor exposures to particles of outdoor origin.     

Exposure of churchgoers to airborne particles

Particle mass and number measurements in a church indicate significant increases of indoor particle concentrations during the burning of incense. Generally, varying concentration regimes can be attributed to different "modes of indoor activity" and emission sources. While periods of candle burning are negligible concerning particle concentrations, increases by a factor of 6.9 and 9.1 during incense burning were observed for PM10 and PM1, respectively. At maximum, indoor PM10 shows an 8.1-fold increase in comparison to outdoor measurements. The increase of particles < 2 microm is significantly enhanced in comparison to larger particles. Due to a particle decay rate of 0.9 h(-1) post-service concentrations are elevated for a time span of approximately 24 h above indoor background concentrations.     

Using time- and size-resolved particulate data to quantify indoor penetration and deposition behavior

Because people spend approximately 85-90% of their time indoors, it is widely recognized that a significant portion of total personal exposures to ambient particles occurs in indoor environments. Although penetration efficiencies and deposition rates regulate indoor exposures to ambient particles, few data exist on the levels or variability of these infiltration parameters, in particular for time- and size-resolved data. To investigate ambient particle infiltration, a comprehensive particle characterization study was conducted in nine nonsmoking homes in the metropolitan Boston area. Continuous indoor and outdoor PM2.5 and size distribution measurements were made in each of the study homes over weeklong periods. Data for nighttime, nonsource periods were used to quantify infiltration factors for PM2.5 as well as for 17 discrete particle size intervals between 0.02 and 10 microns. Infiltration factors for PM2.5 exhibited large intra- and interhome variability, which was attributed to seasonal effects and home dynamics. As expected, minimum infiltration factors were observed for ultrafine and coarse particles. A physical-statistical model was used to estimate size-specific penetration efficiencies and deposition rates for these study homes. Our data show that the penetration efficiency depends on particle size as well as home characteristics. These results provide new insight on the protective role of the building shell in reducing indoor exposures to ambient particles, especially for tighter (e.g., winterized) homes and for particles with diameters greater than 1 micron.     

PM2.5 of ambient origin: estimates and exposure errors relevant to PM epidemiology

Epidemiological studies routinely use central-site particulate matter (PM) as a surrogate for exposure to PM of ambient (outdoor) origin. Below we quantify exposure errors that arise from variations in particle infiltration to aid evaluation of the use of this surrogate, rather than actual exposure, in PM epidemiology. Measurements from 114 homes in three cities from the Relationship of Indoor, Outdoor and Personal Air (RIOPA) study were used. Indoor PM2.5 of outdoor origin was calculated as follows: (1) assuming a constant infiltration factor, as would be the case if central-site PM were a "perfect surrogate" for exposure to outdoor particles; (2) including variations in measured air exchange rates across homes; (3) also incorporating home-to-home variations in particle composition, and (4) calculating sample-specific infiltration factors. The final estimates of PM2.5 of outdoor origin take into account variations in building construction, ventilation practices, and particle properties that result in home-to-home and day-to-day variations in particle infiltration. As assumptions became more realistic (from the first, most constrained model to the fourth, least constrained model), the mean concentration of PM2.5 of outdoor origin increased. Perhaps more importantly, the bandwidth of the distribution increased. These results quantify several ways in which the use of central site PM results in underestimates of the ambient PM2.5 exposure distribution bandwidth. The result is larger uncertainties in relative risk factors for PM2.5 than would occur if epidemiological studies used more accurate exposure measures. In certain situations this can lead to bias.     

Spatial and temporal trends of polycyclic aromatic hydrocarbons and other traffic-related airborne pollutants in New York City

Traffic-related air pollutants have been associated with adverse health effects. We hypothesized that exposure to polycyclic aromatic hydrocarbons (PAHs), elemental carbon (EC, diesel indicator), particulate matter (PM2.5), and a suite of metals declined from 1998 to 2006 in NYC due to policy interventions. PAH levels from personal monitoring of pregnant mothers participating in the Columbia's Center for Children's Environmental Health birth cohort study, and EC, PM2.5, and metal data from five New York State Department of Environmental Conservation stationary monitors were compared across sites and over time (1998-2006). Univariate analysis showed a decrease in personal PAHs exposures from 1998 to 2006 (p < 0.0001). After controlling for environmental tobacco smoke, indoor heat, and cooking, year of personal monitoring remained a predictor of decline in sigmaPAHs (beta = -0.269, p < 0.001). Linear trend analysis also suggested that PM2.5 declined (p = 0.09). Concentrations of EC and most metals measured by stationary site monitors, as measured by ANOVA, did not decline. Across stationary sites, levels of airborne EC and metals varied considerably. By contrast PM2.5 levels were highly intercorrelated (values ranged from 0.725 to 0.922, p < 0.01). Further policy initiatives targeting traffic-related air pollutants may be needed for a greater impact on public health.     

Development and application of an electron spin resonance spectrometry method for the determination of oxygen free radical formation by particulate matter

Exposure to increased levels of ambient particulate matter (PM) are associated with several health effects, including cardiopulmonary diseases. The formation of reactive oxygen species (ROS) is thought to play an important role in the induction of these health effects. To quantify the ROS generating capacityof PM,we developed an improved electron spin resonance (ESR) spectrometry-based method. ROS formation was measured directly on PM-containing filters, thereby avoiding the selective extraction of components and loss of material or reactivity, which is likely to occur during filter extraction. Also, ascorbic acid was added to stimulate ROS formation. This method was applied to PM10 samples originating from different sources. The radical generating capacity of PM10 from both gasoline and diesel engine exhaust was significantly higher as compared to that of PM10 from ambient or indoor air. Furthermore, in urban PM10 and PM2.5, ROS-generating capacity significantly correlated with concentrations of polycyclic aromatic hydrocarbon content and particular transition metals. This indicates thatthis improved ESR method may be a valuable tool for evaluating the relationship between ROS formation by PM and the adverse health effects associated with this type of air pollution.     

Chemical characterization of ambient particulate matter near the World Trade Center: elemental carbon, organic carbon, and mass reconstruction

Concentrations of elemental carbon (EC), organic carbon matter (OM), particulate matter less than 2.5 microm (PM2.5), reconstructed soil, trace element oxides, and sulfate are reported from four locations near the World Trade Center (WTC) complex for airborne particulate matter (PM) samples collected from September 2001 through January 2002. Across the four sampling sites, daily mean concentrations ranged from 1.5 to 6.8 microg/m3 for EC, from 10.2 to 31.4 microg/m3 for OM, and from 22.6 to 66.2 microg/m3 for PM2.5. Highest concentrations of PM species were generally measured north and west of the WTC complex. Total carbon matter and sulfate constituted the largest fraction of reconstructed PM2.5 concentrations. Concentrations of PM species across all sites decreased from the period when fires were present at the WTC complex (before December 19, 2001) to the period after the fires. Averaged over all sites, concentrations decreased by 25.6 microg/m3 for PM2.5, 2.7 microg/m3 for EC, and 9.2 microg/m3 for OM from the fire period to after fire period.     

Characterization of residential wood combustion particles using the two-wavelength aethalometer

In the United States, residential wood combustion (RWC) is responsible for 7.0% of the national primary PM(2.5) emissions. Exposure to RWC smoke represents a potential human health hazard. Organic components of wood smoke particles absorb light at 370 nm more effectively than 880 nm in two-wavelength aethalometer measurements. This enhanced absorption (Delta-C = BC(370 nm) - BC(880 nm)) can serve as an indicator of RWC particles. In this study, aethalometer Delta-C data along with measurements of molecular markers and potassium in PM(2.5) were used to identify the presence of airborne RWC particles in Rochester, NY. The aethalometer data were corrected for the loading effect. Delta-C was found to strongly correlate with wood smoke markers (levoglucosan and potassium) during the heating season. No statistically significant correlation was found between Delta-C and vehicle exhaust markers. The Delta-C values were substantially higher during winter compared to summer. The winter diurnal pattern showed an evening peak around 21:00 that was particularly enhanced on weekends. A relationship between Delta-C and PM(2.5) was found that permits the estimation of the contribution of RWC particles to the PM mass. RWC contributed 17.3% to the PM(2.5) concentration during the winter. Exponential decay was a good estimator for predicting Delta-C concentrations at different winter precipitation rates and different wind speeds. Delta-C was also sensitive to remote forest fire smoke.     

Source apportionment of PM2.5 in the Southeastern United States using solvent-extractable organic compounds as tracers

A chemical mass balance (CMB) receptor model using particle-phase organic compounds as tracers is applied to apportion the primary source contributions to fine particulate matter and fine particulate organic carbon concentrations in the southeastern United States to determine the seasonal variability of these concentrations. Source contributions to particles with aerodynamic diameter < or =2.5 microm (PM2.5) collected from four urban and four rural/suburban sites in AL, FL, GA, and MS during April, July, and October 1999 and January 2000 are calculated and presented. Organic compounds in monthly composite samples at each site are identified and quantified by gas chromatography/mass spectrometry and are used as molecular markers in the CMB model. The major contributors to identified PM2.5 organic carbon concentrations at these sites in the southeastern United States include wood combustion (25-66%), diesel exhaust (14-30%), meat cooking (5-12%), and gasoline-powered motor vehicle exhaust (0-10%), as well as smaller but statistically significant contributions from natural gas combustion, paved road dust, and vegetative detritus. The primary sources determined in the present study when added to secondary aerosol formation account for on average 89% of PM2.5 mass concentrations, with the major contributors to PM2.5 mass as secondary sulfate (30+/-6%), wood combustion (15+/-12%), diesel exhaust (16+/-7%), secondary ammonium (8+/-2%), secondary nitrate (4+/-3%), meat cooking (3+/-2%), gasoline-powered motor vehicle exhaust (2+/-2%), and road dust (2+/-2%). Distinct seasonality is observed in source contributions, including higher contributions from wood combustion during the colder months of October and January. In addition, higher percentages of unexplained fine organic carbon concentrations are observed in July, which are likely due to an increase in secondary organic aerosol formation during the summer season.     

Spatial distribution of polybrominated diphenyl ethers in southern Ontario as measured in indoor and outdoor window organic films

Organic films were collected from indoor and outdoor window surfaces, along an urban-rural transect extending northward from Toronto, Ontario, Canada, and analyzed for 41 polybrominated diphenyl ether congeners (PBDE). For exterior films, urban sigmaPBDE concentrations were approximately 10x greater than rural concentrations, indicating an urban-rural gradient and greater PBDE sources in urban areas. Urban films ranged from 2.5 to 14.5 ng/m2 (mean = 9.0 ng/ m2), excluding the regional "hotspot" Electronics Recycling Facility, compared to 1.1 and 0.56 ng/m2 at the Suburban and Rural sites. Interior urban films (mean = 34.4 ng/m2) were 3 times greater than rural films (10.3 ng/m2) and were representative of variations in building characteristics. Indoor films were 1.5-20 times greater than outdoor films, consistent with indoor sources of PBDEs and enhanced degradation in outdoor films. Congener profiles were dominated by BDE-209 (51.1%), consistent with deca-BDE as the main source mixture, followed by congeners from the penta-BDE mixture (BDE-99:13.6% and -47:9.4%) and some octa-BDE (BDE-183:1.5%). Congener patterns suggest a degradative loss of lower brominated compounds in outdoor films versus indoor films. Gas-phase air concentrations were back-calculated from film concentrations using the film-air partition coefficient (K(FA)). Mean calculated air concentrations were 4.8 pg/m3 for outdoor and 42.1 pg/m3 for indoor urban sites, indicating that urban indoor air is a source of PBDEs to urban outdoor air and the outdoor regional environment.