Apportioning black carbon to sources using highly time-resolved ambient measurements of organic molecular markers in Pittsburgh

We present highly time-resolved measurements of organic molecular markers in downtown Pittsburgh, which are used to investigate sources contributing to atmospheric aerosols in the area. Two-hour average concentrations of condensed-phase and semivolatile organic species were measured using a Thermal Desorption Aerosol GC/MS (TAG). Concentrations for mobile source markers like hopanes had regular diurnal and day-of-week patterns. Pairing high time-resolved measurements with meteorological data helped identify contributions from known point sources for markers correlated with wind direction. Black carbon (BC), volatile organic compounds (VOCs) and organic molecular markers were apportioned to sources using the Chemical Mass Balance (CMB) and Positive Matrix Factorization (PMF) receptor models. Diesel and gasoline mobile source factors were identified as the main sources of BC in the downtown Pittsburgh area, contributing 67% and 20% of the study-average BC. 13% of the BC was associated with a source factor tentatively identified as an industrial or regional source. The high time resolution of the TAG has the potential to provide important new insight into source apportionment efforts using organic molecular marker measurements.     

Atmospheric particle size distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) and their implications for wet and dry deposition

Concurrent measurements of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs) in different size fractions of atmospheric particulate matter are presented for a winter and a summer sampling period. The PCDD/Fs and PAHs were primarily associated with particles of <1.35 μm aerodynamic diameter. The particle size distributions were similar for the compounds within each substance group and, surprisingly, also between the PCDD/Fs and PAHs. Changes in the particle size distribution of particle mass were reflected in the particle size distributions of the PCDD/Fs and PAHs.The data were employed to identify those particle size fractions dominating the wet and dry particle bound deposition of PCDD/Fs and PAHs and, furthermore, to assess the relative contributions of wet and dry deposition to the total particle bound deposition fluxes. The calculations indicate that coarse particles contribute most to the dry deposition while, in contrast, the wet deposition of the PCDD/Fs and PAHs is dominated by fine particles. Furthermore, it is estimated that in Bayreuth wet deposition dominates the total particle bound deposition of PCDD/Fs and PAHs.     

Atmospheric deposition of polycyclic aromatic hydrocarbons to Izmit Bay, Turkey

Wet deposition and dry deposition samples were collected in an urban/industrialized area of Izmit Bay, North-eastern Marmara Sea, Turkey, from September 2002 to July 2003. The samples were analyzed for sixteen polycyclic aromatic hydrocarbon (PAH) compounds by using HPLC-UV technique. Wet and dry deposition concentrations and fluxes of PAHs were determined. The results showed that PAH concentrations were high because of industrial processes, heavy traffic and residential areas next to the sampling site. Total dry deposition flux of the fifteen 3-6 ring PAHs was 8.30 microg m(-2)day(-1), with a range of 0.034-1.77 microg m(-2)day(-1). The total wet deposition flux of the fifteen 3-6 ring PAHs was 1716 microg m(-2) 11 month(-1), with a range of 10-440 microg m(-2) 11 month(-1). Significant seasonal differences were observed in both types of deposition samples. The winter fluxes of total PAHs were 1.5 and 2.5 times greater than those of the warm period for wet and dry deposition samples, respectively. Factor analysis of dry deposition samples and back trajectory analysis of wet deposition samples were also used to characterize and identify the PAH emission sources in this study.     

Characterization and source presumption of wintertime submicron organic aerosols at Saitama,Japan, using the Aerodyne aerosol mass spectrometer

The chemical composition and size distribution of submicron aerosols were analyzed at a suburban site at Saitama, Japan, in the winter of 2004/2005, using an Aerodyne aerosol mass spectrometer. Although organics and nitrate were the dominant species during the sampling period, a large fraction of sulfate was observed at the accumulation mode when mass loading was low and wind speed was high. The size distributions of m/z 44 (mostly CO₂⁺) and sulfate aerosols during periods of high wind speed showed remarkable similarities in the accumulation mode, indicating that oxygenated organics were aged aerosols and internally mixed with sulfate. Ozone concentrations were also increased during these high wind speed periods although nighttime (e.g., 12/17 2004), indicating that the oxygenated compounds were strongly influenced by transported and aged air masses. The diurnal profiles of ultrafine-mode organics and hydrocarbon-like organic aerosols (HOA) were similar to NO_X derived from traffic and other combustion sources. The temporal variation of oxygenated organic aerosols (OOA) agreed well with that of nitrate as a secondary aerosol tracer, and the diurnal profile of the OOA fraction of organics increased during the day associated with higher UV light intensity. The result of time and size-resolved chemical composition of submicron particles indicated that the OOA is associated with both photochemical activity and transboundary pollution, and ultrafine-mode organic and HOA aerosols are mainly associated with combustion sources.     

Identification,abundance and seasonal variation of anthropogenic organic aerosols from a mega-city in China

PM_2.5 aerosols were collected in Nanjing, a typical mega-city in China, during summer and winter 2004 and were characterized for aromatic and cyclic compounds using a GC/MS technique to understand the air pollution problem. They include polycyclic aromatic hydrocarbons (PAHs), hopanes, phthalates and hydroxy-PAHs (OH-PAHs). PAHs, hopanes and OH-PAHs presented higher concentrations in winter (26–178, 3.0–18, and 0.013–0.421 ng m⁻³, respectively) than in summer (12–96, 1.6–11, and 0.029–0.171 ng m⁻³, respectively) due to an enhanced coal burning for house heating and atmospheric inversion layers developed in the cold season. In contrast, phthalates are more abundant in summer (109–368 ng m⁻³, average 230 ng m⁻³) than in winter (33–390 ng m⁻³, average 170 ng m⁻³) due to an enhanced evaporation from plastics during the hot season and the subsequent deposition on the pre-existing particles. Generally, all the identified compounds showed higher concentrations in nighttime than in daytime due to inversion layers and increased emissions from heavy-duty trucks at night. PAHs, hopanes and phthalates in Nanjing aerosols are 5–100 times more abundant than those in Los Angeles, USA, indicating a serious air pollution problem in the city. Concentrations of OH-PAHs are 1–3 orders of magnitude less than their parent PAHs and comparable to those reported from other international cities. Source identification using diagnostic ratios of the organic tracers suggests that PAHs in Nanjing urban area are mainly derived from coal burning, whereas hopanes are more attributable to traffic emissions.     

Concentrations of aliphatic and polycyclic aromatic hydrocarbons in ambient PM2.5 and PM10 particulates in Doha,Qatar

Organic carbon (OC), elemental carbon (EC), and 90 organic compounds (36 polycyclic aromatic hydrocarbons [PAHs], 25 n-alkane homologues, 17 hopanes, and 12 steranes) were concurrently quantified in atmospheric particulate matter of PM_2.5 and PM₁₀. The 24-hr PM samples were collected using Harvard Impactors at a suburban site in Doha, Qatar, from May to December 2015. The mass concentrations (mean ± standard deviation) of PM_2.5 and PM₁₀ were 40 ± 15 and 145 ± 70 µg m^?3, respectively, exceeding the World Health Organization (WHO) air quality guidelines. Coarse particles comprised 70% of PM₁₀. Total carbonaceous contents accounted for 14% of PM_2.5 and 10% of PM₁₀ particulate mass. The major fraction (90%) of EC was associated with the PM_2.5. In contrast, 70% of OC content was found in the PM_2.5–10 fraction. The secondary OC accounted for 60–68% of the total OC in both PM fractions, indicating photochemical conversions of organics are much active in the area due to higher air temperatures and solar radiations. Among the studied compounds, n-alkanes were the most abundant group, followed by PAHs, hopanes, and steranes. n-Alkanes from C₂₅ to C₃₅ prevailed with a predominance of odd carbon numbered congeners (C₂₇–C₃₁). High-molecular-weight PAHs (5–6 rings) also prevailed, within their class, with benzo[b + j]fluoranthene (Bb + jF) being the dominant member. PAHs were mainly (80%) associated with the PM_2.5 fraction. Local vehicular and fugitive emissions were predominant during low-speed southeasterly winds from urban areas, while remote petrogenic/biogenic emissions were particularly significant under prevailing northwesterly wind conditions.

Implications: An unprecedented study in Qatar established concentration profiles of EC, OC, and 90 organic compounds in PM_2.5 and PM₁₀. Multiple tracer organic compounds for each source can be used for convincing source apportionment. Particle concentrations exceeded WHO air quality guidelines for 82–96% of the time, revealing a severe problem of atmospheric PM in Doha. Dominance of EC and PAHs in fine particles signifies contributions from combustion sources. Dependence of pollutants concentrations on wind speed and direction suggests their significant temporal and spatial variability, indicating opportunities for improving the air quality by identifying sources of airborne contaminants.     

Polycyclic aromatic hydrocarbon (PAH) deposition to and exchange at the air-water interface of Luhu, an urban lake in Guangzhou, China

Urban lakes are vulnerable to the accumulation of semivolatile organic compounds, such as PAHs from wet and dry atmospheric deposition. Little was reported on the seasonal patterns of atmospheric deposition of PAHs under Asian monsoon climate. Bulk (dry + wet) particle deposition, air-water diffusion exchange, and vapour wet deposition of PAHs in a small urban lake in Guangzhou were estimated based on a year-round monitoring. The total PAH particle deposition fluxes observed were 0.44-3.46 μg m⁻² day⁻¹. The mean air-water diffusive exchange flux was 20.7 μg m⁻² day⁻¹. The vapour deposition fluxes of PAHs ranged 0.15-8.26 μg m⁻² day⁻¹. Remarkable seasonal variations of particulate PAH deposition, air-water exchange fluxes and vapour wet deposition were influenced by seasonal changes in meteorological parameters. The deposition fluxes were predominantly controlled by the precipitation intensity in wet season whereas by atmospheric concentration in dry season.     

Sources of polycyclic hydrocarbons and pesticides in soluble fraction of deposition samples in Kocaeli,Turkey

A wet–dry deposition sampler was located at The Scientific and Technological Research Council of Turkey-National Metrology Institute (TUBITAK-UME) station, and a bulk deposition sampler was placed at the Kad?ll? village to determine the atmospheric deposition flux of polycyclic aromatic hydrocarbons (PAHs) and pesticides (organochlorine and organophosphorus) in soluble fraction of samples in Kocaeli, Turkey. The 28 samples for each wet, dry, and total deposition were collected weekly from March 2006 to March 2007. Gas chromatography-tandem mass spectrometry was used to analyze the samples which were prepared by using solid-phase extraction (SPE) method. The sum of volume weighted mean of deposition fluxes was obtained as 7.43 μg m^?2 day^?1 for wet deposition, 0.28 μg m^?2 day^?1 for dry deposition and 0.54 μg m^?2 day^?1 for bulk deposition samples for PAHs and 9.88 μg m^?2 day^?1 for wet deposition, 4.49 μg m^?2 day^?1 for dry deposition, and 3.29 μg m^?2 day^?1 for bulk deposition samples for pesticides. While benzo(a)anthracene had the highest fluxes among PAH compounds for all types of depositions, guthion and phosphamidon had the highest deposition flux compared with the other pesticides. Benzo(ghi)perylene, dibenz(a,h)anthracene, indeno(1,2,3-c,d)pyrene, benzo(a)pyrene, and acenaphthene were not detected in any of the samples. Beta-HCH, gamma-HCH, and endrin aldehyde were the only compounds among 18 organochlorine pesticides to be detected in all deposition samples. The main sources of pesticides were the high number of greenhouses around the sampling stations. However, all of the organophosphorus pesticides were detected in all deposition samples. The pollution sources were identified as coal and natural gas combustion, petrogenic sources, and traffic for TUBITAK-UME station whereas coal and natural gas combustion and traffic were the main sources for Kad?ll? station by considering the results of factor analysis, ratios, and wind sector analysis.     

Molecular markers, essential oils and diagnostic parameters as indicators for assessing the origin and constitution of organic matter in atmospheric aerosols

Atmospheric particulate matter was collected at two sites: an Abies boressi forest in central Greece and in Giesta, a coastal-rural site in the centre of Portugal. The extractable organic material consisted primarily of aliphatic hydrocarbons, acids, alcohols, and ketones, with a predominance of molecular weights >C20, derived from vascular plant waxes. Biomarkers for vegetation sources such as phytosterols, triterpenic compounds and essential oils were also detected. Microbial components (>C20), pyrogenic aromatic hydrocarbons and petroleum residues, including hopanes, steranes and cyclic and branched hydrocarbons, were present in the various aerosol extracts. In the apportionment of the various organic fractions to sources, vegetation waxes dominated, contributing to 50–60% of the solvent-extractable material in the aerosols. Petroleum residues and microbial components comprise 25–30% and 15–25% of the organic matter, respectively.     

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Characterization of saccharides and other organic compounds in fine particles and the use of saccharides to track primary biologically derived carbon sources

A total of 134 aerosol samples (d_p < 2.5 μm) were collected at one rural site and one urban site in Texas from November 2005 to July 2006 to investigate the different sources that contribute to the ambient levels of different compounds. In particular, saccharide compounds were studied as potential tracers to track aerosols of biologically derived origin. The ambient concentration, seasonal variation, and urban/rural comparison of major saccharides and other organic compounds including normal alkanes, hopanes, and carboxylic acids were determined and analyzed relative to characterizing sources of PM2.5. Saccharides, together with other known molecular markers, were analyzed by a positive matrix factorization model and eight source factors were isolated that provide meaningful interpretation of aerosol sources. Three isolated factors were characterized by the dominance of different saccharide compounds and were attributed to wood smoke, sucrose rich bio-aerosols, and fungal spore derived bio-aerosols. It was estimated that wood smoke and primary biologically derived carbon sources contributed 22% and 14% to the measured ambient PM2.5 mass at San Augustine and 16% and 5% to the measured ambient PM2.5 mass at Dallas. The relative PM contribution from other resolved sources were also calculated.     

Influence of meteorological factors and polluting environment on rain chemistry and wet deposition in a rural area near Chimay,Belgium

This paper focuses on a detailed analysis of the effects of meteorological factors explaining the variability of rain composition.Inorganic composition of 113 individual rain events was measured from May 2002 to October 2005 at a rural site near Chimay, in the western part of the Belgian Ardennes. Original models were fitted for each studied ion (H⁺, Mg²⁺, Ca²⁺, K⁺, NH₄⁺, Na⁺, Cl⁻, NO₃⁻ and SO₄²⁻) to relate rain event concentration or wet deposition to the rainfall volume (R), the length of the antecedent dry period (ADP), the volume of the previous event (R_prev) as well as to the mean wind speed and the prevailing wind direction during both the dry and the rainy periods. These variables explained from 32% (H⁺) to 69% (NO₃⁻) of rain concentration variability. Concentrations decreased logarithmically with increasing R values except in case of H⁺ for which a positive effect of rain volume on rain concentration was observed. ADP affected positively rain concentrations of all ions excluding K⁺ and H⁺ for which, respectively, a nonsignificant and a negative effect of this variable was observed. Increasing R_prev strengthened the effect of the variable R on H⁺, Mg²⁺, Ca²⁺, Na⁺, NH₄⁺ and SO₄²⁻ concentrations while it softened the effect of ADP on NO₃⁻ concentrations. Wind speed and direction during dry and rainy periods explained together from 8% (K⁺) to 38% (Na⁺) of rain concentration total variability. R² coefficients of the wet deposition models ranged from 0.51 (K⁺) to 0.79 (SO₄²⁻). For all ions, wet deposition increased significantly with increasing R values while the effects of the other variables were similar to those on concentrations. Wind conditions during dry and rainy periods explained from 4% (H⁺) to 24% (Na⁺) of wet deposition total variability. On an annual scale, the total dry period duration, the total rainfall volume as well as the shape of the distributions of the length of the antecedent dry periods and of the rain event volume are important parameters that influence annual wet deposition.     

Atmospheric nitrogen deposition in south-east Scotland: Quantification of the organic nitrogen fraction in wet,dry and bulk deposition

Water soluble organic nitrogen (WSON) compounds are ubiquitous in precipitation and in the planetary boundary layer, and therefore are a potential source of bioavailable reactive nitrogen. This paper examines weekly rain data over a period of 22 months from June 2005 to March 2007 collected in 2 types of rain collector (bulk deposition and “dry + wet” deposition) located in a semi-rural area 15 km southwest of Edinburgh, UK (N55°51′44″, W3°12′19″). Bulk deposition collectors are denoted in this paper as “standard rain gauges”, and they are the design used in the UK national network for monitoring precipitation composition. “Dry + wet” deposition collectors are flushing rain gauges and they are equipped with a rain detector (conductivity array), a spray nozzle, a 2-way valve and two independent bottles to collect funnel washings (dry deposition) and true wet deposition. On average, for the 27 weekly samples with 3 valid replicates for the 2 types of collectors, dissolved organic nitrogen (DON) represented 23% of the total dissolved nitrogen (TDN) in bulk deposition. Dry deposition of particles and gas on the funnel surface, rather than rain, contributed over half of all N-containing species (inorganic and organic). Some discrepancies were found between bulk rain gauges and flushing rain gauges, for deposition of both TDN and DON, suggesting biological conversion and loss of inorganic N in the flushing samplers.     

Molecular signatures of organic particulates as tracers of emission sources

Chemical signature of airborne particulates and deposition dusts is subject of study since decades. Usually, three complementary composition markers are investigated, namely, (i) specific organic compounds; (ii) concentration ratios between congeners, and (iii) percent distributions of homologs. Due to its intrinsic limits (e.g., variability depending on decomposition and gas/particle equilibrium), the identification of pollution sources based on molecular signatures results overall restricted to qualitative purposes. Nevertheless, chemical fingerprints allow drawing preliminary information, suitable for successfully approaching multivariate analysis and valuing the relative importance of sources. Here, the state-of-the-art is presented about the molecular fingerprints of non-polar aliphatic, polyaromatic (PAHs, nitro-PAHs), and polar (fatty acids, organic halides, polysaccharides) compounds in emissions. Special concern was addressed to alkenes and alkanes with carbon numbers ranging from 12 to 23 and?≥?24, which displayed distinct relative abundances in petrol-derived spills and exhausts, emissions from microorganisms, high vegetation, and sediments. Long-chain alkanes associated with tobacco smoke were characterized by a peculiar iso/anteiso/normal homolog fingerprint and by n-hentriacontane percentages higher than elsewhere. Several concentration ratios of PAHs were identified as diagnostic of the type of emission, and the sources of uncertainty were elucidated. Despite extensive investigations conducted so far, the origin of uncommon molecular fingerprints, e.g., alkane/alkene relationships in deposition dusts and airborne particles, remains quite unclear. Polar organics resulted scarcely investigated for pollution apportioning purposes, though they looked as indicative of the nature of sources. Finally, the role of humans and living organisms as actual emitters of chemicals seems to need concern in the future.

     

Organic composition of PM2.5 and size-segregated aerosols and their sources during the 2002 Bay Regional Atmospheric Chemistry Experiment (BRACE), Florida,USA

PM_2.5 and size-segregated aerosols were collected in May 2002 as part of the Bay Regional Atmospheric Chemistry Experiment (BRACE), Florida, USA. Aerosol organic composition was used to estimate sources of a series of alkanes and polycyclic aromatic hydrocarbons (PAHs) using chemical indices, hierarchical cluster analysis (HCA) and a chemical mass balance receptor model (CMB). Aerosols were collected on quartz fiber filters (QFF) using a PM_2.5 high volume sampler and on aluminum foil discs using a Micro-Orifice Uniform Deposit Impactor (MOUDI, 50% aerodynamic cut diameters were 18, 10, 5.6, 3.2, 1.8, 1.0, 0.56, 0.315 and 0.171 μm). Target compounds included alkanes and PAHs and were solvent extracted using a mixture of dichloromethane, acetone and hexane, concentrated and then analyzed using a gas chromatograph/mass spectrometer (GC/MS). The target compounds in PM_2.5 were dominated by six sources during the study period: mobile sources (39±5%), coal burning (33±5%), biogenic primary emission (20±2%), oil combustion (5±2%), biomass burning (1.0±0.3%) and an unidentified source (3±2%). Results obtained from the chemical indices, HCA and CMB were in very good agreement with each other. PAH size distributions are presented for days dominated by a same source. Seventy-five percent and 50% of the PAH were found below 1.8 and 0.56 μm, respectively (monthly PAH geometric diameters averaged 0.43 μm). Coarse size PAHs were observed on 1 day (15 May) and were correlated with nitrate and sodium size distribution. It is hypothesized that the PAHs, sodium and nitrate were internally mixed and that the PAHs deposited onto a pre-existing marine aerosol. This transfer process has significant implications for PAH deposition and lifetime and warrants further study.     

Roadside measurements of size-segregated particulate organic compounds near gasoline and diesel-dominated freeways in Los Angeles,CA

Individual organic compounds such as hopanes and steranes (originating in lube oil) and selected polycyclic aromatic compounds (PAHs) (generated via combustion) found in particulate emissions from vehicles have proven useful in source apportionment of ambient particulate matter (PM). Detailed information on the size-segregated (ultrafine and accumulation mode) chemical characteristics of organic PM during the winter season originating from a pure gasoline traffic freeway (CA-110), and a mixed-fleet freeway with the highest fraction of heavy-duty diesel vehicles in the state of California (I-710) is reported in this study. Hopanes and steranes as well as high molecular weight PAHs such as benzo(ghi)perylene (BgP) and coronene levels are found comparable near these freeways, while elemental carbon (EC) and lighter molecular weight PAHs are found much elevated near I-710 compared to CA-110. The roadway organic speciation data presented here are compared with the emission factors (EFs) measured in the Caldecott tunnel, Berkeley, CA [Phuleria, H.C., Geller, M.D., Fine, P.M., Sioutas, C., 2006. Size-resolved emissions of organic tracers from light- and heavy-duty vehicles measured in a California roadway tunnel. Environmental Science and Technology 40, 4109–4118] for light-duty vehicles (LDVs) and heavy-duty vehicles. Very good agreement is observed between CA-110 measurements and LDV EFs as well as I-710 measurements and corresponding reconstructed EFs from Caldecott tunnel for hopanes and steranes as well as heavier PAHs such as BgP and coronene. Our results, therefore, suggest that the EFs for hopanes and steranes obtained in tunnel environments, where emissions are averaged over a large vehicle-fleet, enable reliable source apportionment of ambient PM, given the overall agreement between the roadway vs tunnel concentrations of these species.     

Temperature dependence of gas-phase polycyclic aromatic hydrocarbon and organochlorine pesticide concentrations in Chicago air

The temperature dependence of gas-phase atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides measured in Chicago, IL between June and October 1995 were investigated using plots of the natural logarithm of partial pressures (ln P) vs. reciprocal mean temperatures (1/T). For the eight lowest molecular weight PAHs, temperature dependence was statistically significant (at the 95% confidence level) and temperature accounted for 23–49% of the variability in gas-phase concentrations. The relatively higher slopes for most of the PAHs suggested that volatilization from local sources and short-range transport influenced their concentrations. For pesticides, temperature dependence was statistically significant for DDD and for trans-nonachlor (at the 95% and 90% confidence levels), and was not statistically significant for the other five compounds (2–18% of the variability in their gas-phase concentrations). The relatively lower slopes for individual pesticides suggested that they have mostly non-urban and distant sources.Results of back trajectory analyses suggested that the region, southwest of Chicago, might be an important local or regional source sector for PAHs and organochlorine pesticides. No statistically significant relationship was observed between wind speed and PAH or pesticide concentrations. None of the variables (temperature, wind speed, wind direction, local and regional sources) could fully explain the variation in their concentrations measured in Chicago, therefore, this variation can be attributed to the combined effect of those factors.     

Chemical characterization and source identification of polycyclic aromatic hydrocarbons in aerosols originating from different sources

To obtain the characteristic factors or signatures of particulate polycyclic aromatic hydrocarbons (PAHs) to help identify the sources of particulate PAHs in the atmosphere, different carbonaceous aerosols were generated by burning different fossil fuels and biomass under different conditions in the laboratory, and the chemical characteristics of 14 PAHs were studied in detail. The results showed that (1) carbonaceous aerosols derived from domestic burning of coal, diesel fuel, and gasoline have much higher concentrations of PAHs than those derived from domestic burning of biomass; (2) carbonaceous aerosols derived from domestic burning of diesel fuel/gasoline have similar PAH components as those derived from high-temperature combustion of diesel fuel/gasoline, although the former have much higher concentrations of PAHs than the latter, suggesting that the burning temperature obviously affects the emitting amount of particulate PAHs, but only slightly influences the PAHs components; and (3) the ratios of benzo[b]fluoranthene/acenaphthylene, benzo[b]fluoranthene/fluorene, dibenzo[a,h]anthracene/acenaphthylene, dibenzo[a,h]anthracene/fluorine, and benzo[b]fluoranthene/benzo[k]fluoranthene in carbonaceous aerosols are sensitively dependent on their sources, indicating that these ratios are suitable for use as characteristic factors or signatures of particulate PAHs in the atmosphere.     

A method of assessing air toxics concentrations in urban areas using mobile platform measurements

The objective of this paper is to demonstrate an approach to characterize the spatial variability in ambient air concentrations using mobile platform measurements. This approach may be useful for air toxics assessments in Environmental Justice applications, epidemiological studies, and environmental health risk assessments. In this study, we developed and applied a method to characterize air toxics concentrations in urban areas using results of the recently conducted field study in Wilmington, DE. Mobile measurements were collected over a 4- x 4-km area of downtown Wilmington for three components: formaldehyde (representative of volatile organic compounds and also photochemically reactive pollutants), aerosol size distribution (representing fine particulate matter), and water-soluble hexavalent chromium (representative of toxic metals). These measurements were,used to construct spatial and temporal distributions of air toxics in the area that show a very strong temporal variability, both diurnally and seasonally. An analysis of spatial variability indicates that all pollutants varied significantly by location, which suggests potential impact of local sources. From the comparison with measurements at the central monitoring site, we conclude that formaldehyde and fine particulates show a positive correlation with temperature, which could also be the reason that photochemically generated formaldehyde and fine particulates over the study area correlate well with the fine particulate matter measured at the central site.     

Characterization and sources assignation of PM2.5 organic aerosol in a rural area of Spain

The results from a year-long study of the organic composition of PM2.5 aerosol collected in a rural area influenced by a highway of Spain are reported. The lack of prior information related to the organic composition of PM2.5 aerosol in Spain, concretely in rural areas, led definition of the goals of this study. As a result, this work has been able to characterize the main organic components of atmospheric aerosols, including several compounds of SOA, and has conducted a multivariate analysis in order to assign sources of particulate matter. A total of 89 samples were taken between April 2004 and April 2005 using a high-volume sampler. Features and abundance of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), alcohols and acids were separately determined using gas chromatography/mass spectrometry and high performance liquid chromatography analysis. The Σn-alkane and ΣPAHs ranged from 3 to 81 ng m^?3 and 0.1 to 6 ng m^?3 respectively, with higher concentrations during colder months. Ambient concentrations of Σalcohols and Σacids ranged from 21 to 184 ng m^?3 and 39 to 733 ng m^?3, respectively. Also, several components of secondary organic aerosol have been quantified, confirming the biogenic contribution to ambient aerosol. In addition, factor analysis was used to reveal origin of organic compounds associated to particulate matter. Eight factors were extracted accounting more than 83% of the variability in the original data. These factors were assigned to a typical high pollution episode by anthropogenic particles, crustal material, plant waxes, fossil fuel combustion, temperature, microbiological emissions, SOA and dispersion of pollutants by wind action. Finally, a cluster analysis was used to compare the organic composition between the four seasons.