Search

Air pollution has been associated with poor health outcomes and continues to be a risk factor for respiratory health in children. While higher particulate matter (PM) levels are associated with increased frequency of symptoms, lower lung function, and increase airway inflammation from asthma, the precise composition of the particles that are more highly associated with poor health outcomes or healthcare utilization are not fully elucidated. PM is measured quantifiably by current air pollution monitoring systems. To better determine sources of PM and speciation of such sources, a particulate matter (PM) source apportionment study, the Cleveland Multiple Air Pollutant Study (CMAPS), was conducted in Cleveland, Ohio, in 2009–2010, which allowed more refined assessment of associations with health outcomes. This article presents an evaluation of short-term (daily) and long-term associations between motor vehicle and industrial air pollution components and pediatric asthma emergency department (ED) visits by evaluating two sets of air quality data with healthcare utilization for pediatric asthma. Exposure estimates were developed using land use regression models for long-term exposures for nitrogen dioxide (NO2) and coarse (i.e., with aerodynamic diameters between 2.5 and 10 μm) particulate matter (PM) and the US EPA Positive Matrix Factorization receptor model for short-term exposures to fine (

A comprehensive filter-based particulate matter polycyclic aromatic hydrocarbon (PAH) source apportionment study was conducted at the Wood Buffalo Environmental Association Bertha Ganter-Fort McKay (BGFM) community monitoring station from 2014 to 2015 to quantify ambient concentrations and identify major sources. The BGFM station is located in close proximity to several surface oil sands production facilities and was previously found to be impacted by their air emissions. 24-hour integrated PM2.5 and PM10–2.5 samples were collected on a 1-in-3-day schedule yielding 108 complete organic/inorganic filter sets for source apportionment modeling. During the study period PM2.5 averaged 8.6 ± 11.8 μg m−3 (mean ± standard deviation), and PM10–2.5 averaged 8.5 ± 9.5 μg m−3. Wind regression analysis indicated that the oil sands production facilities were significant sources of PM2.5 mass and black carbon (BC), and that wildland fires were a significant source of the highest PM2.5 (>10 μg m−3) and BC events. A six-factor positive matrix factorization (PMF) model solution explained 95% of the measured PM2.5 and 78% of the measured ΣPAH. Five sources significantly contributed to PM2.5 including: Biomass Combustion (3.57 μg m−3; 40%); Fugitive Dust (1.86 μg m−3; 28%); Upgrader Stack Emissions (1.44 μg m−3; 21%); Petrogenic PAH (1.20 μg m−3; 18%); and Transported Aerosol (0.43 μg m−3 and 6%). However, the analysis indicated that only the pyrogenic PAH source factor significantly contributed (78%) to the measured ΣPAH. A five-factor PMF model dominated by fugitive dust sources explained 98% of PM10–2.5 mass and 86% of the ΣPAH. The predominant sources of PM10–2.5 mass were (i) Haul Road Dust (4.82 μg m−3; 53%), (ii) Mixed Fugitive Dust (2.89 μg m−3; 32%), (iii) Fugitive Oil Sand (0.88 μg m−3; 10%), Mobile Sources (0.23 μg m−3; 2%), and Organic Aerosol (0.06 μg m−3; 1%). Only the Organic Aerosol source significantly contributed (86%) to the measured ΣPAH.

Ambient air particulate matter (PM) was collected at the Wood Buffalo Environmental Association Bertha Ganter Fort McKay monitoring station in the Athabasca Oil Sand Region (AOSR) in Alberta, Canada from February 2010 to July 2011 as part of an air quality source assessment study. Daily 24-hour duration fine (PM2.5) and coarse (PM10–2.5) PM was collected using a sequential dichotomous sampler. 100 pairs of PM2.5 and PM10–2.5 were selected for lead (Pb) concentration and isotope analysis. Pb isotope and concentration results from 250 epiphytic lichen samples collected as far as 160 km from surface mining operations in 2008, 2011, and 2014 were analyzed to examine longer term spatial variations in Pb source contributions. A key finding was recognition of thorogenic 208Pb from eastern Asia in the springtime in the PM2.5 in 2010 and 2011. 206Pb/207Pb and 208Pb/207Pb isotope ratios were used in a three-component mixing model to quantify local, regional, and global Pb sources in the PM and lichen data sets. 47 ± 3% of the Pb in the PM2.5 at AMS-1 was attributed to sources from eastern Asia. Combined results from PM10–2.5 and PM2.5 indicate PM2.5 Pb contributions from eastern Asia (34%) exceed local AOSR sources of PM2.5 Pb (20%), western Canada sources of PM2.5 Pb (19%), and PM10–2.5 Pb from fugitive dust including oil sands (14%), tailings (10%), and haul roads (3%). The lichen analysis indicates regional sources contribute 46% of the Pb, local sources 32%, and global sources 22% over the 2008–2014 timeframe. Local sources dominate atmospheric Pb deposition to lichens at near field sites (0–30 km from mining operations) whereas regional Pb sources are prevalent at distal sites (30–160 km). The Pb isotope methodology successfully quantified trans-Pacific transport of Pb to the AOSR superimposed over the aerosol footprint of the world's largest concentration of bitumen mining and upgrading facilities.

Wildland fire activity and associated emission of particulate matter air pollution is increasing in the United States over the last two decades due primarily to a combination of increased temperature, drought, and historically high forest fuel loading. The regulatory monitoring networks in the Unites States are mostly concentrated in larger population centers where anthropogenic air pollution sources are concentrated. Smaller population centers in areas more likely to be impacted by wildland fire smoke in many instances lack adequate observational air quality data. Several commercially available small form factor filter-based PM2.5 samplers (SFFFS) were evaluated under typical ambient and simulated near-to mid-field wildland fire smoke conditions to evaluate their accuracy for use in temporary deployments during prescribed and wildfire events. The performance of all the SFFFS tested versus the designated federal reference methods (FRM) was acceptable in determining PM2.5 concentration in both ambient (2.7–14.0 μg m−3) and chamber smoke environments (24.6–3044.6 μg m−3) with accuracies ranging from ∼92 to 98%. However, only the ARA Instruments model N-FRM Sampler was found to provide PM2.5 mass measurement accuracies that meet FRM guideline performance specifications under both typical ambient (97.3 ± 1.9%) and simulated wildland fire conditions (98.2 ± 1.4%).

The increasing emission of primary and gaseous precursors of secondarily formed atmospheric particulate matter due to continuing industrial development and urbanization are leading to an increased public awareness of environmental issues and human health risks in China. As part of a pilot study, 12-h integrated fine fraction particulate matter (PM2.5) filter samples were collected to chemically characterize and investigate the sources of ambient particulate matter in Guiyang City, Guizhou Province, southwestern China. Results showed that the 12-h integrated PM2.5 concentrations exhibited a daytime average of 51 ± 22 µg m−3 (mean ± standard deviation) with a range of 17–128 µg m−3 and a nighttime average of 55 ± 32 µg m−3 with a range of 4–186 µg m−3. The 24-h integrated PM2.5 concentrations varied from 15 to 157 µg m−3, with a mean value of 53 ± 25 µg m−3, which exceeded the 24-h PM2.5 standard of 35 µg m−3 set by USEPA, but was below the standard of 75 µg m−3, set by China Ministry of Environmental Protection. Energy-dispersive X-ray fluorescence spectrometry (XRF) was applied to determine PM2.5 chemical element concentrations. The order of concentrations of heavy metals in PM2.5 were iron (Fe) > zinc (Zn) > manganese (Mn) > lead (Pb) > arsenic (As) > chromium (Cr). The total concentration of 18 chemical elements was 13 ± 2 µg m−3, accounting for 25% in PM2.5, which is comparable to other major cities in China, but much higher than cities outside of China.

An unprecedented wildfire impacted the northern Alberta city of Fort McMurray in May 2016 causing a mandatory city wide evacuation and the loss of 2,400 homes and commercial structures. A two-hectare wildfire was discovered on May 1, grew to ~157,000 ha by May 5, and continued to burn an estimated ~590,000 ha by June 13. A comprehensive air monitoring network operated by the Wood Buffalo Environmental Association (WBEA) in and around Fort McMurray provided essential health-related real-time air quality data to firefighters during the emergency, and provided a rare opportunity to elucidate the impact of gaseous and particulate matter emissions on near-field communities and regional air pollution concentrations. The WBEA network recorded 188 fire-related exceedances of 1-hr and 24-hr Alberta Ambient Air Quality Objectives. Two air monitoring sites within Fort McMurray recorded mean/maximum 1-hr PM2.5 concentrations of 291/5229 μg m−3 (AMS-6) and 293/3259 μg m−3 (AMS-7) during fire impact periods. High correlations (r2 = 0.83–0.97) between biomass combustion related gases (carbon monoxide (CO), non-methane hydrocarbons (NMHC), total hydrocarbons (THC), total reduced sulfur (TRS), ammonia) and PM2.5 were observed at the sites. Filter-based 24-hr integrated PM2.5 samples collected every 6 days showed maximum concentrations of 267 μg m−3 (AMS-6) and 394 μg m−3 (AMS-7). Normalized excess emission ratios relative to CO were 149.87 ± 3.37 μg m−3 ppm−1 (PM2.5), 0.274 ± 0.002 ppm ppm−1 (THC), 0.169 ± 0.001 ppm ppm−1 (NMHC), 0.104 ± 0.001 ppm ppm−1 (CH4), 0.694 ± 0.007 ppb ppm−1 (TRS), 0.519 ± 0.040 ppb ppm−1 (SO2), 0.412 ± 0.045 ppb ppm−1 (NO), 1.968 ± 0.053 ppb ppm−1 (NO2), and 2.337 ± 0.077 ppb ppm−1 (NOX). A subset of PM2.5 filter samples was analyzed for trace elements, major ions, organic carbon, elemental carbon, and carbohydrates. Sample mass reconstruction and fire specific emission profiles are presented and discussed. Potential fire-related photometric ozone instrument positive interferences were observed and were positively correlated with NO and NMHC., GRAPHICAL ABSTRACT

A 2014 case study investigated the relative accumulation efficiency of polycyclic aromatic hydrocarbons (PAHs), total sulfur (S), total nitrogen (N), major and minor elements and Pb isotopes in five common lichen species at three boreal forest sites in the Athabasca Oil Sands Region (AOSR) in northeastern Alberta, Canada to identify the optimum lichen species for future biomonitoring. Differences in concentrations of PAHs, multiple elements, and Pb isotopes in fruticose (Bryoria furcellata, Cladina mitis, Evernia mesomorpha) and foliose (Hypogymnia physodes and Tuckermannopsis americana) lichens were found along a 100 km distance gradient from the primary oil sands operations. Integration of insights from emission source samples and oil sands mineralogy in consort with aerosol collection indicates incorporation of more fine particulate matter (PM) into foliose than fruticose lichen biomass. Contrasting PAH with element concentrations allowed lichen species specific accumulation patterns to be identified. The ability of lichen species to incorporate different amounts of gas phase (S and N), petrogenic (V, Ni, Mo), clay (low Si/Al and more rare earth elements), and sand (higher Si/Al and Ti) components from the oil sand operations reflects aerosol particle size and lichen physiology differences that translate into differences in PM transport distances and lichen accumulation efficiencies. Based on these findings Hypogymnia physodes is recommended for future PAH biomonitoring and source attribution studies.

International audience; Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg (Hg0(g)). However, little is known about the fraction of Hg bound to particulate matter (HgP) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric HgP concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improvement when considering a fraction of HgP from BB. The set of sensitivity runs also showed how the quantity and geographical distribution of HgP emitted from BB has a limited impact on a global scale, although the inclusion of increasing fractions HgP does limit Hg0(g) availability to the global atmospheric pool. This reduces the fraction of Hg from BB which deposits to the world's oceans from 71 to 62 %. The impact locally is, however, significant on northern boreal and tropical forests, where fires are frequent, uncontrolled and lead to notable Hg inputs to local ecosystems. In the light of ongoing climatic changes this effect could be potentially be exacerbated in the future.

The characteristics of wildland fire smoke exposures which initiate or exacerbate cardiopulmonary conditions are unclear. We previously reported that, on a mass basis, lung toxicity associated with particulate matter (PM) from flaming smoke aspirated into mouse lungs is greater than smoldering PM. In this study, we developed a computer-controlled inhalation system which can precisely control complex biomass smoke emissions from different combustion conditions. This system was used to examine the toxicity of inhaled biomass smoke from peat, eucalyptus, and oak fuels generated under smoldering and flaming phases with emissions set to the same approximate concentration of carbon monoxide (CO) for each exposure (60–110 ppm), resulting in PM levels of ~ 4 mg/m3 for flaming and ~ 40 mg/m3 for smoldering conditions. Mice were exposed by inhalation 1 h/day for 2 days, and assessed for lung toxicity at 4 and 24 h after the final exposure. Peat (flaming and smoldering) and eucalyptus (smoldering) smoke elicited significant inflammation (neutrophil influx) in mouse lungs at 4 h with the peat (flaming) smoke causing even greater lung inflammation at 24-h post-exposure. A significant alteration in ventilatory timing was also observed in mice exposed to the peat (flaming) and eucalyptus (flaming and smoldering) smoke immediately after each day of exposure. No responses were seen for exposures to similar concentrations of flaming or smoldering oak smoke. The lung toxicity potencies (neutrophil influx per PM mass) agreed well between the inhalation and previously reported aspiration studies, demonstrating that although flaming smoke contains much less PM mass than smoldering smoke, it is more toxic on a mass basis than smoldering smoke exposure, and that fuel type is also a controlling factor.

Communities near major roadways are disproportionately affected by traffic-related air pollution which can contribute to adverse health outcomes. The specific role of particulate matter (PM) from traffic sources is not fully understood due to complex emissions processes and physical/chemical properties of PM in the near-road environment. To investigate the spatial profile and water solubility of elemental PM species near a major roadway, filter-based measurements of fine (PM 2.5 ) and coarse (PM 10-2.5 ) PM were simultaneously collected at multiple distances (10 m, 100 m, and 300 m) from Interstate I-96 in Detroit, Michigan during September–November 2010. Filters were extracted in water, followed by a hot acid extraction, and analyzed by magnetic sector field high resolution inductively coupled plasma mass spectrometry (HR-ICPMS) to quantify water-soluble and acid-soluble trace elements for each PM size fraction. PM 2.5 and PM 10-2.5 species measured in the near-road samples included elements associated with traffic activity, local industrial sources, and regional pollution. Metals indicative of brake wear (Ba, Cu) were dramatically enriched near the roadway during downwind conditions (factor of 5 concentration increase), with the largest increase within 100 m of the roadway. Moderate near-roadway increases were observed for crustal elements and other traffic-related PM (Fe, Ca), and the lowest increases observed for regional PM species (S). Water solubility varied by PM species and size, and for PM 2.5 included highly (S, K, Ca, Mg, Zn, Ba), moderately (Cu, Mn, Sb, Pb), and minimally (Fe, Ti) water-soluble species, with lower water solubility for most species in PM 10-2.5 . Results from this study indicate that water-soluble PM 2.5 and PM 10-2.5 metals, particularly from brake/tire wear, were enhanced in the near-roadway environment which may have human health implications.

The Cleveland airshed comprises a complex mixture of industrial source emissions that contribute to periods of non-attainment for fine particulate matter (PM2.5) and are associated with increased adverse health outcomes in the exposed population. Specific PM sources responsible for health effects however are not fully understood. Size-fractionated PM (coarse, fine, and ultrafine) samples were collected using a ChemVol sampler at an urban site (G.T. Craig (GTC)) and rural site (Chippewa Lake (CLM)) from July 2009 to June 2010, and then chemically analyzed. The resulting speciated PM data were apportioned by EPA positive matrix factorization to identify emission sources for each size fraction and location. For comparisons with the ChemVol results, PM samples were also collected with sequential dichotomous and passive samplers, and evaluated for source contributions to each sampling site. The ChemVol results showed that annual average concentrations of PM, elemental carbon, and inorganic elements in the coarse fraction at GTC were ∼2, ∼7, and ∼3 times higher than those at CLM, respectively, while the smaller size fractions at both sites showed similar annual average concentrations. Seasonal variations of secondary aerosols (e.g., high NO3− level in winter and high SO42− level in summer) were observed at both sites. Source apportionment results demonstrated that the PM samples at GTC and CLM were enriched with local industrial sources (e.g., steel plant and coal-fired power plant) but their contributions were influenced by meteorological conditions and the emission source's operation conditions. Taken together the year-long PM collection and data analysis provides valuable insights into the characteristics and sources of PM impacting the Cleveland airshed in both the urban center and the rural upwind background locations. These data will be used to classify the PM samples for toxicology studies to determine which PM sources, species, and size fractions are of greatest health concern.

Trace gas, particulate matter and deposition data collected in the Athabasca Oil Sands Region (AOSR) from 2000 to 2017 were evaluated as part of a broad scientific programmatic review. Results showed significant spatial patterns and temporal trends across the region. Concentrations of reactive gases were highest near the center of surface oil sands production operations and decreased towards the edges of the monitoring domain by factors of 8, 20, 4 and 3 for SO2, NO2, HNO3 and NH3, respectively. 18 of 30 sites showed statistically significant (p 80% of SO42− was in the PM2.5 fraction, while > 60% of Ca2+, Mg2+, Na+ and Cl− were in the PM10-2.5 fraction. Ion balances of both PM10 and PM2.5 contained cation excesses at near-field oil sand sites, but PM2.5 samples at forest health sites >20 km from surface production locations contained anion excesses. Monthly average concentrations of PM10 ions showed peak Ca2+ during March-April to November, but peak SO42−, NH4+ and NO3− from November-March. Deposition estimates showed rapid declines as a function of distance to oil sand operations. Estimated total N and total S deposition to forest health monitoring sites ranged from 2.0 to 5.7 kg ha−1 a−1 and 2.1–14.0 kg ha−1 a−1, respectively. Potential acid input (PAI) ranged from −0.46 to 0.79 keq ha−1 a−1 and was mostly 0.1–0.2 keq ha−1 a−1 throughout the domain, except for two clusters of sites near oil sand operations.

Accurate characterization of the chemical composition of particulate matter (PM) is essential for improved understanding of source attribution and resultant health impacts. To explore this we conducted ambient monitoring of a suite of 15 combustion-related organic species in temporally resolved PM 2.5 samples during an ongoing animal exposure study in a near source environment in Detroit, MI. All of the 15 species detected were above the method detection limit in 8 hour samples. This study focused on two molecular classes: Polycyclic Aromatic Hydrocarbons (PAHs) and Hopanes measured in samples. Of the 12 PAHs studied, benzo[b]fluoranthene (169 pg m−3), benzo[g,h,i]perylene (124 pg m−3), and benzo[e]pyrene (118, pg m−3) exhibited the three highest mean concentrations while 17α(H),21β(H)-Hopane (189 pg m−3) and 17α(H),21β(H)-30-Norhopane (145 pg m−3) had the highest mean concentrations of the 3 Hopanes analyzed in samples. Ratios of individual compound concentrations to total compound concentrations (∑ 15 compounds) showed the greatest daily variation for 17α(H),21β(H)-Hopane (11–28%) and 17α(H),21β(H)-30-Norhopane (8–20%). Diagnostic PAH concentration ratios ([IP]/[IP + BP] (range 0.30 – 0.45), [BaP]/[BaP+BeP] (range 0.26 – 0.44), [BaP]/[BP] (range 0.41 – 0.82), [Bb]/[Bk] (range 2.07 – 2.66), in samples reflected impacts froma mixture of combustion sources consistent with greater prevalence of petroleum combustion source emissions (gasoline, diesel, kerosene, and crude oil) compared to coal or wood combustion emissions impacts at this urban site. Results from this study demonstrate that short duration sampling for organic speciation provides temporally relevant exposure information.

A new source-type identification method, Reduction and Species Clustering Using Episodes (ReSCUE), was developed to exploit the temporal synchronicity typically observed between ambient species in high time resolution fine particulate matter (PM2.5) data to form clusters that vary together. High time-resolution (30 min) PM2.5 sampling was conducted for a month during the summer of 2006 in Steubenville, OH, an EPA designated nonattainment area for the U.S. National Ambient Air Quality Standards (NAAQS). When the data were evaluated, the species clusters from ReSCUE matched extremely well with the source types identified by EPA Unmix demonstrating that ReSCUE is a valuable tool in identifying source types. Results from EPA Unmix show that contributions to PM2.5 are mostly from iron/steel manufacturing (36% ± 9%), crustal matter (33% ± 11%), and coal combustion (11% ± 19%). More importantly, ReSCUE was useful in (i) providing objective data driven guidance for the number of source factors and key fitting species for EPA Unmix, and (ii) detecting tenuous associations between some species and source types in the results derived by EPA Unmix.

Prescribed pasture burning plays a critical role in ecosystem maintenance in tallgrass prairie ecosystems and may contribute to agricultural productivity but can also have negative impacts on air quality. Volatile organic compound (VOC) concentrations were measured immediately downwind of prescribed tallgrass prairie fires in the Flint Hills region of Kansas, United States. The VOC mixture is dominated by alkenes and oxygenated VOCs, which are highly reactive and can drive photochemical production of ozone downwind of the fires. The computed emission factors are comparable to those previous measured from pasture maintenance fires in Brazil. In addition to the emission of large amounts of particulate matter, hazardous air pollutants such as benzene and acrolein are emitted in significant amounts and could contribute to adverse health effects in exposed populations.

An ambient air particulate matter sampling study was conducted at the Wood Buffalo Environmental Association (WBEA) AMS-1 Fort McKay monitoring station in the Athabasca Oil Sand Region (AOSR) in Alberta, Canada from February 2010 to July 2011. Daily 24h integrated fine (PM2.5) and coarse (PM10-2.5) particulate matter was collected using a sequential dichotomous sampler. Over the duration of the study, 392 valid daily dichotomous PM2.5 and PM10-2.5 sample pairs were collected with concentrations of 6.8±12.9μgm-3 (mean±standard deviation) and 6.9±5.9μgm-3, respectively. A subset of 100 filter pairs was selected for element analysis by energy dispersive X-ray fluorescence and dynamic reaction cell inductively coupled plasma mass spectrometry. Application of the U.S. EPA positive matrix factorization (PMF) receptor model to the study data matrix resolved five PM2.5 sources explaining 96% of the mass including oil sands upgrading (32%), fugitive dust (26%), biomass combustion (25%), long-range Asian transport lead source (9%), and winter road salt (4%). An analysis of historical PM2.5 data at this site shows that the impact of smoke from wildland fires was particularly high during the summer of 2011. PMF resolved six PM10-2.5 sources explaining 99% of the mass including fugitive haul road dust (40%), fugitive oil sand (27%), a mixed source fugitive dust (16%), biomass combustion (12%), mobile source (3%), and a local copper factor (1%). Results support the conclusion of a previous epiphytic lichen biomonitor study that near-field atmospheric deposition in the AOSR is dominated by coarse fraction fugitive dust from bitumen mining and upgrading operations, and suggest that fugitive dust abatement strategies targeting the three major sources of PM10-2.5 (e.g., oil sand mining, haul roads, bulk material stockpiles) would significantly reduce near-field atmospheric deposition gradients in the AOSR and reduce ambient PM concentrations in the Fort McKay community.

Intensive ambient air sampling was conducted in Tampa, FL, during October and November of 2002. Fine particulate matter (PM(2.5)) was collected at 30 min resolution using the Semicontinuous Elements in Aerosol Sampler II (SEAS-II) and analyzed off-line for up to 45 trace elements by high-resolution ICPMS (HR-ICPMS). Divalent reactive gaseous mercury and particulate bound mercury were also measured semicontinuously (2 h). Application of the United States Environmental Protection Agency's (EPA) Unmix receptor model on the 30 min resolution trace metals data set identified eight possible sources: residual oil combustion, lead recycling, coal combustion, a Cd-rich source, biomass burning, marine aerosol, general industrial, and coarse dust contamination. The source contribution estimates from EPA Unmix were then run in a nonparametric wind regression (NWR) model, which convincingly identified plausible source origins. When the 30 min ambient concentrations of trace elements were time integrated (2 h) and combined with speciated mercury concentrations, the model identified only four sources, some of which appeared to be merged source profiles that were identified as separate sources by using the 30 min resolution data. This work demonstrates that source signatures that can be captured at 30 min resolution may be lost when sampling for longer durations.

During the fall of 1998, the US Environmental Protection Agency and the Florida Department of Environmental Protection sponsored a 7-day study at the Ft. McHenry tunnel in Baltimore, MD with the objective of obtaining PM 2.5 vehicle source profiles for use in atmospheric mercury source apportionment studies. PM 2.5 emission profiles from gasoline and diesel powered vehicles were developed from analysis of trace elements, polycyclic aromatic hydrocarbons (PAH), and condensed aliphatic hydrocarbons. PM 2.5 samples were collected using commercially available sampling systems and were extracted and analyzed using conventional well-established methods. Both inorganic and organic profiles were sufficiently unique to mathematically discriminate the contributions from each source type using a chemical mass balance source apportionment approach. However, only the organic source profiles provided unique PAH tracers (e.g., fluoranthene, pyrene, and chrysene) for diesel combustion that could be used to identify source contributions generated using multivariate statistical receptor modeling approaches. In addition, the study found significant emission of gaseous elemental mercury (Hg 0 ), divalent reactive gaseous mercury (RGM), and particulate mercury (Hg(p)) from gasoline but not from diesel powered motor vehicles. Fuel analysis supported the tunnel measurement results showing that total mercury content in all grades of gasoline (284±108 ng L −1 ) was substantially higher than total mercury content in diesel fuel (62±37 ng L −1 ) collected contemporaneously at local Baltimore retailers.

The Florida Everglades Dry-Deposition Study (FEDDS) was designed to test the viability of using new and existing measurement techniques in the estimation of the dry-depositional loading of speciated mercury (elemental gaseous, reactive gaseous and particulate) to a mixed sawgrass (Cladium jamaicense) and cattail (Typha domingensis) stand within the Florida Everglades. Measurement intensives were performed during 24 February–04 March 1999 and 05–21 June 2000, which corresponded to the climatological dry and wet seasons in South Florida, respectively. During these intensives, direct measurements of mercury dry-deposition were made using a newly developed surrogate water surface technique. These direct measurements were compared with modeled estimates of mercury dry-deposition to the site that were obtained through the use of an inferential or “bigleaf” model that was modified for use with speciated mercury. On-site measurements of ambient speciated mercury concentrations and numerous micrometeorological variables were used as input to the model. The average mercury dry-deposition measured during the 1999 FEDDS measurement intensive was 13.3±4.0 ng m−2 day−1, while the modeled deposition for this period was 3.4±2.3 ng m−2 day−1. The average mercury dry-deposition measured during the 2000 FEDDS measurement intensive was lower, 5.9±2.8 ng m−2 day−1, while the average modeled deposition for this period was 1.8±0.6 ng m−2 day−1. A least-squares linear regression suggests that the model was able to explain 74% and 73% of the variability in the datasets for the 1999 and 2000 FEDDS intensives, respectively. While reported reductions in total mercury emissions across South Florida between study periods could explain the reductions in both the measured and predicted mercury dry-deposition estimates, the increased presence of cumulus convection during the summer-intensive could have also resulted in a removal of reactive and particulate mercury species within the atmosphere of South Florida.

Near-road exposure to air pollutants has been associated with decreased lung function and other adverse health effects in susceptible populations. This study was designed to investigate whether different types of near-road particulate matter (PM) contribute to exacerbation of allergic asthma. Samples of upwind and downwind coarse, fine, and ultrafine PM were collected using a wind direction-actuated ChemVol sampler at a single site 100 m from Interstate-96 in Detroit, MI during winter 2010/2011. Upwind PM was enriched in crustal and wood combustion sources while downwind PM was dominated by traffic sources. Control and ovalbumin (OVA)-sensitized BALB/cJ mice were exposed via oropharyngeal (OP) aspiration to 20 or 100 μg of each PM sample 2 h prior to OP challenge with OVA. In OVA-allergic mice, 100 μg of downwind coarse PM caused greater increases than downwind fine/ultrafine PM in bronchoalveolar lavage neutrophils, eosinophils, and lactate dehydrogenase. Upwind fine PM (100 μg) produced greater increases in neutrophils and eosinophils compared to other upwind size fractions. Cytokine (IL-5) levels in BAL fluid also increased markedly following 100 μg downwind coarse and downwind ultrafine PM exposures. These findings indicate coarse PM downwind and fine PM upwind of an interstate highway promote inflammation in allergic mice.

Intensive field measurements of atmospheric mercury and related species were carried out in Ny Alesund, Spitsbergen, during the spring of 2003 at two altitudes. Measurements were made at the Italian research station Dirigibile Italia (12 m a.s.l.) and on the top of Zeppelin Mountain at the Norwegian Research Station (474 m a.s.l.). Ambient concentrations of gaseous elemental mercury, divalent reactive gaseous mercury and particulate phase mercury were semi-continuously measured at both sites using an integrated Tekran system. Atmospheric elemental gaseous mercury depletion events (AMDEs) were observed at both locations, the lowest observed Hg0 concentration was 0.3 ng m−3. At sea level, mercury species concentrations following AMDEs were found to be higher and to exhibit larger variability in comparison to those observed at Zeppelin station.

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.

An assessment of trace metal quantification capabilities for indoor (123±53 μg; mean±standard deviation of particle mass) and personal exposure (PE) (32±12 μg) PM2.5 samples from Baltimore, MD was undertaken as part of an EPA study investigating health effects associated with particulate matter. This study included determination of total PM2.5 metal concentrations by energy dispersive X-ray fluorescence and instrumental neutron activation analysis, as well as method development to quantify amounts of water and acid-extractable metals from PM2.5 using inductively coupled plasma-mass spectrometry (ICP-MS). Analytical uncertainties, filter blank contributions, and sample preparation were all found to significantly impact quantification limits. The ICP-MS leaching procedure resulted in partial extraction of metals from the PM2.5. Most of the extractable components of the metals were in a water-soluble form suggesting a high potential for bioavailability of elements from respiratory exposure to PM2.5. A comparison of PM2.5 trace metal concentrations from indoor air samples collected from a central indoor site versus concurrently collected PE samples indicates that resident activities result in exposure to higher concentrations of soluble trace metals.

The United States Environmental Protection Agency (US EPA) recently conducted the 1998 Baltimore Particulate Matter (PM) Epidemiology-Exposure Study of the Elderly. The primary goal of that study was to establish the relationship between outdoor PM concentrations and actual human PM exposures within a susceptible (elderly) sub-population. Personal, indoor, and outdoor sampling of particulate matter was conducted at a retirement center in the Towson area of northern Baltimore County. Concurrent sampling was conducted at a central community site. The main objective of this work was to use computer-controlled scanning electron microscopy (CCSEM) with individual-particle X-ray analysis to measure the chemical and physical characteristics of geological and trace element particles collected at the various sampling locations in and around the retirement facility. The CCSEM results show that the relative abundances of some geological and trace element particle classes identified at the outdoor and community locations differ from each other and from the indoor location. Particle images acquired during the computer-controlled analyses played a key role in the identification of certain particle types. Review of these images was particularly useful in distinguishing spherical particles (usually indicative of combustion) from non-spherical particles of similar chemical composition. Pollens and spores were also identified through a manual review of the particle images.

Twelve hours integrated PM2.5 samples collected with a Weekly Air Particulate Sampler (URG Model 2000-01J) from September 2008 to November 2008 in Guiyang, China, were analyzed on the Kevex energy dispersive x-ray spectrometer (XRF) for elements. Monitoring results found elevated concentrations of heavy metals (Ti, Mn, Fe, Zn, and Pb) in PM2.5 in Guiyang. The average concentrations were 30±22 ng m -3 for Ti, 250±400 ng m -3 for Mn, 340±280 ng m -3 for Fe, 290±330 ng m -3 for Zn, and 130±130 ng m -3 for Pb, respectively. Temporal variation patterns in the resulting data were also obtained. It is hypothesized that local anthropogenic sources and the seasonal variability result in the temporal variability.

High time-resolution aerosol sampling was conducted for one month during July-August 2007 in Dearborn, MI, a non-attainment area for fine particulate matter (PM2.5) National Ambient Air Quality Standards (NAAQS). Measurements of more than 30 PM2.5 species were made using a suite of semi-continuous sampling and monitoring instruments. Dynamic variations in the sub-hourly concentrations of source 'marker' elements were observed when discrete plumes from local sources impacted the sampling site. Hourly averaged PM2.5 composition data for 639 samples were used to identify and apportion PM2.5 emission sources using the multivariate receptor modeling techniques EPA Positive Matrix Factorization (PMF) v4.2 and EPA Unmix v6.0. Source contribution estimates from PMF and Unmix were then evaluated using the Sustained Wind Instance Method (SWIM), which identified plausible source origins. Ten sources were identified by both PMF and Unmix: (1) secondary sulfate, (2) secondary nitrate characterized by a significant diurnal trend, (3) iron and steel production, (4) a potassium-rich factor attributable to iron/steel slag waste processing, (5) a cadmium-rich factor attributable to incineration, (6) an oil refinery characterized by La/Ce>1 specific to south wind, (7) oil combustion, (8) coal combustion, (9) motor vehicles, and (10) road dust enriched with organic carbon. While both models apportioned secondary sulfate, oil refinery, and oil combustion PM2.5 masses closely, the mobile and industrial source apportionments differed. Analyses were also carried out to help infer time-of-day variations in the contributions of local sources.

Intra-storm variability and soluble fractionation was explored for summer-time rain events in Steubenville, Ohio to evaluate the physical processes controlling mercury (Hg) in wet deposition in this industrialized region. Comprehensive precipitation sample collection was conducted from July through September 2006 using three different methods to evaluate both soluble and insoluble fractions as well as scavenging and washout properties of Hg and a suite of trace elements. Real-time filtration of event total precipitation revealed that 61 ± 17% (mean ± standard deviation) of Hg in wet deposition was in a soluble form. Comparison of total and dissolved element concentrations (solubility fractionation) showed the following order of decreasing solubility: S > Na > Se > Ca > Mg > Hg > As > Mn > V > Cr > Fe > La ≈ Ce ranging from 95% (S) to 4% (Ce). To examine removal mechanisms occurring during the course of a precipitation event, discrete, sequential sub-event precipitation samples were collected. Results indicated that Hg had lower “scavenging coefficients” (the rate of Hg concentration decrease throughout the events) than the majority of elements analyzed, indicating that either (i) Hg is incorporated into rain via gas phase inclusion or particulate nucleation within cloud, or (ii) Hg is available in the boundary layer for scavenging, even in the latter stages of precipitation. The Hg scavenging coefficient (− 0.39) was low compared to S (− 0.73), a co-pollutant of Hg. When compared to an upwind, regionally representative site, the scavenging coefficient of Hg for the locally influenced precipitation was 25% lower. This observation suggests that a continuous feed of soluble Hg was the reason for the low scavenging coefficient. Overall, this investigation of Hg wet deposition in Steubenville indicates that the physical and chemical properties of Hg emissions are driving the elevated deposition rates observed near point sources.

The contribution of inorganic air pollutant emissions to atmospheric deposition in the Athabasca Oil Sands Region (AOSR) of Alberta, Canada, was investigated in the surrounding boreal forests, using a common epiphytic lichen bioindicator species ( Hypogymnia physodes ) and applying multiple receptor models. Source materials from anthropogenic and natural emitters of air pollution in the AOSR were obtained and chemically characterized to aid in the assessment. The lichens selected for analysis were collected in 2008 using a stratified, nested grid approach radiating away from the central area of oil sands production at 121 sampling sites extending as far as 150 km. Source and lichen samples were extracted and analyzed for 43 elements using dynamic reaction cell quadrupole inductively coupled plasma mass spectroscopy (DRC-ICPMS). Source apportionment of the lichen tissue analytical results was conducted using principal component analysis (PCA), chemical mass balance (CMB), positive matrix factorization (PMF), and Unmix models. Initial Varimax-rotated PCA screening analysis indicated that there were five principal components that could explain 89% of the variance contained in the lichen data set, with the majority of the variance lumped into a fugitive dust factor. This fugitive dust source could be separated into tailing sand, haul road, and overburden components using CMB on lichen samples collected near the mining and oil processing facilities. However, the CMB model performance was limited by the similarity of sources and the lack of total nitrogen measurements in the emission source profiles. The PMF and Unmix models were found to perform best with this unique AOSR lichen data set, providing very similar results at near-source as well as remote lichen collection sites. The PMF results showed that sources significantly contributing to concentrations of elements in the lichen tissue include combustion processes (∼ 23%), tailing sand (∼ 19%), haul roads and limestone (∼ 15%), oil sand and processed materials (∼ 15%), and a general anthropogenic urban source (∼ 15%). The spatial patterns of CMB, PMF, and Unmix receptor models estimated that source impacts on the H. physodes tissue elemental concentrations from the oil sand processing and fugitive dust sources had a significant association with the distance from the primary oil sands surface mining operations and related production facilities. The spatial extent of the fugitive dust impact was limited to a radius of approximately 20 km around the major mining and oil production facilities, which is indicative of ground-level coarse particulate fugitive emissions from these sources. The impact of the general urban source was found to be enhanced in the southern portion of the sampling domain in the vicinity of the Fort McMurray urban area. The receptor model results showed lower Mn concentrations in lichen tissues near oil sands production operations suggesting a biogeochemical response. Overall, the largest impact on elemental concentrations of H. physodes tissue in the AOSR was related to fugitive dust, suggesting that implementation of a fugitive dust abatement strategy could minimize the near-field atmospheric deposition of any future mining-related production activities.

[1] Atmospheric mercury (Hg) species were investigated on the east coast of Florida during June 2000. The site was impacted by air mass transport from the Atlantic Ocean and south Florida. Periods with atmospheric transport from the Atlantic were characterized by low concentrations of elemental gaseous Hg and inorganic divalent reactive gaseous mercury (RGM), demonstrating that the marine boundary layer was not a significant source of RGM to this coastal site as previous researchers have hypothesized. When anthropogenic impacts were observed at the site, indicated by elevated concentrations of gases including HNO3 and SO2, RGM concentrations had higher daytime maximums. Particulate phase Hg concentrations were higher than can be explained by sea spray alone, as determined by chemical analysis of the seawater, suggesting that gaseous Hg is diffusing into the sea-salt aerosol. Although atmospheric Hg concentrations were not elevated, the observed scavenging of Hg gases by sea-salt aerosols indicates that Hg may be rapidly cycled at the atmosphere-ocean interface between gaseous, aerosol, and oceanic forms. Deposition of aerosol enriched in Hg via this process may constitute a significant global mercury flux to the oceans.