Profile analysis of ambient and source emitted particle-bound polycyclic aromatic hydrocarbons from three sites in northern Greece

Polycyclic aromatic hydrocarbons (PAHs) adsorbed to ambient PM(10) were determined at three sites in Thessaloniki, northern Greece, during the period June 1997-July 1998. Ambient PAH profiles exhibited significant seasonal and spatial variations. Source PAH profiles were obtained for a number of urban, industrial and geological sources including cement, fertilizer and asphalt production, quarry operations, metal electroplating, metal welding and tempering, steel manufacture, lead and bronze smelters, metal scrap incineration, oil burning, non-catalyst equipped passenger cars, diesel fueled taxies and buses, paved road dust and soil dust. Principal component analysis (PCA) and diagnostic ratios were employed to compare ambient and source PAH profiles in an attempt to recognize compositional patterns. Similarities between the ambient PAH profiles and the profiles of certain sources, such as vehicular emissions, oil burning and metal industries, were identified.     

Characterization of atmospheric polycyclic aromatic hydrocarbons in a mixed-use urban community in Paterson, NJ: concentrations and sources

Exposure to ambient polycyclic aromatic hydrocarbons (PAHs) is a potential health concern for communities because many PAHs are known to be mutagenic and carcinogenic. However, information on ambient concentrations of PAHs in communities is very limited. During the Urban Community Air Toxics Monitoring Project, Paterson City, NJ, PAH concentrations in ambient air PM10 (particulate matter < or = 10 microm in aerodynamic diameter) were measured from November 2005 through December 2006 in Paterson, a mixed-use urban community located in Passaic County, NJ. Three locations dominated by industrial, commercial, and mobile sources were chosen as monitoring sites. The comparison background site was located in Chester, NJ, which is approximately 58 km west/southwest of Paterson. The concentrations of all of the individual PAHs at all three Paterson sites were found to be significantly higher than those at the background site (P < 0.05). The PAH profiles obtained from the three sites with different land-use patterns showed that the contributions of heavier PAHs (molecular weight > 202) to the total PAHs were significantly higher at the industrial site than those at the commercial and mobile sites. Analysis of the diagnostic ratios between PAH isomers suggested that the diesel-powered vehicles were the major PAH sources in the Paterson area throughout the year. The operation of industrial facilities and other combustion sources also partially contributed to PAH air pollution in Paterson. The correlation of individual PAH, total PAH, and the correlation of total PAHs with other air co-pollutants (copper, iron, manganese, lead, zinc, elemental carbon, and organic carbon) within and between the sampling sites supported the conclusions obtained from the diagnostic ratio analysis.     

Emission inventory and sources of polycyclic aromatic hydrocarbons in the atmosphere at a suburban area in Taiwan

The application of a chemical mass balance air pollution model to ambient measurements of polycyclic aromatic hydrocarbons (PAHs) is presented. Sixteen air samples were collected at seven sites in a suburban area in Taiwan and analyzed for the concentration of 21 compounds between July 2001 and September 2001. Each ambient sample was evaluated for the PAH contribution from six sources (heavy oil combustion, natural gas combustion, coal combustion, diesel combustion, vehicles and municipal solid waste incinerator). Average predictions agree well with the emission inventory. By this method, the average contributions are 49%, 14%, 22%, 12%, and 2% from vehicles, heavy oil combustion, natural gas combustion, coal combustion and diesel combustion at these seven receptors. By far, vehicles are the major PAH emission sources and municipal solid waste incinerator is a minor contributor. The calculated result of particulate PAHs is compared with that of total (gaseous and particulate) PAHs. The estimate based on total PAHs is better than the estimate based on particulate PAHs only. Contributions of eight low reactive PAHs for the same emission sources and receptors were calculated. Atmospheric reactivity seems not a problem for source apportionment in this study.     

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.     

Determination of PAH sources in dated sediments from Green Bay, Wisconsin, by a chemical mass balance model

Six sediment cores were collected from Green Bay, Wisconsin, in order to identify possible sources of polycyclic aromatic hydrocarbons (PAHs) by a chemical mass balance (CMB) model. The cores which were obtained in 1995 had total PAH concentrations between 8.04 and 0.460 ppm. 210Pb and 137Cs dating was used to determine historical trends of PAH inputs, and elemental carbon particle analysis was done to characterize particles from combustion of coal, wood and petroleum. The results show that coke burning, highway dust, and wood burning are likely sources of PAHs to Green Bay. The contribution of coke oven emissions (CB) for the Green Bay cores is in the range of 5 to 90%. The overall highway dust (HWY) contribution is between 5 and 70%. There is a maximum (approximately 67%) contribution of HWY around 1988 which is in agreement with the historical US petroleum consumption. The wood burning (WB) contribution is between 1 to 30%, except in core GB-A where a maximum (approximately 50%) is found around 1994. The average relative errors of measurement for x2 equal to the number of degrees of freedom, are 52.5, 56.2, 36.2, 52.3, and 42.8 (df = 3) for the Green Bay cores A, B, C, E, and F, respectively. The sums of the contribution factors are less than one, indicating gain of inert biological or other bulk material between source and receptor. The results of carbon particles for Green Bay core D show that coal, oil, and wood burning are consistent with the CMB modeling results.     

Polycyclic aromatic hydrocarbons in the ambient air of Greek towns in relation to other atmospheric pollutants

Polycyclic aromatic hydrocarbons (PAHs) were determined in the ambient air of six towns in N. Greece. This paper presents the variability of the particle-bound PAHs concentrations and the particle PAH content during the cold and the warm months. Correlations of total PAHs with other atmospheric pollutants were largely different among towns indicating that the relative contribution of emission sources is different in each location. In the warm months PAHs were significantly correlated with vehicular pollutants thus suggesting traffic as the major PAH emmitting source. The same was also deduced from the comparison of the ambient PAH profiles to the profiles of particular sources. The contribution of residential heating was significant in most towns during winter. Principal component analysis of the data did not result in a clear distinction between towns thus suggesting that all are influenced by similar source types. Finally, the risk associated with the inhallation of carcinogenic PAHs in each town was estimated and compared to the risk from more urbanized/industrialized sites in N. Greece.     

The mobile source effect on curbside 1,3-butadiene,benzene, and particle-bound polycyclic aromatic hydrocarbons assessed at a tollbooth

On-road mobile sources contribute substantially to ambient air concentrations of the carcinogens 1,3-butadiene, benzene, and polycyclic aromatic hydrocarbons (PAHs). The current study measured benzene and 1,3-butadiene at the Baltimore Harbor Tunnel tollbooth over 3-hr intervals on seven weekdays (n = 56). Particle-bound PAH was measured on a subset of three days. The 3-hr outdoor 1,3-butadiene levels varied according to time of day and traffic volume. The minimum occurred at night (12 a.m.-3 a.m.) with a mean of 2 microg/m3 (SD = 1.3, n = 7), while the maximum occurred during the morning rush hour (6 a.m.-9 a.m.) with a mean of 11.9 microg/m3 (SD = 4.6, n = 7). The corresponding traffic counts were 1413 (SD = 144) and 16,893 (SD = 692), respectively. During the same intervals, mean benzene concentration varied from 3 microg/m3 (SD = 3.1, n = 7) to 22.3 microg/m3 (SD = 7.6, n = 7). Median PAH concentrations ranged from 9 to 199 ng/m3. Using multivariate regression, a significant association (p < 0.001) between traffic and curbside concentration was observed. Much of the pollutant variability (1,3-butadiene 62%, benzene 77%, and PAH 85%) was explained by traffic volume, class, and meteorology. Results suggest > 2-axle vehicles emit 60, 32, and 9 times more PAH, 1,3-butadiene, and benzene, respectively, than do 2-axle vehicles. This study provides a model for estimating curbside pollution levels associated with traffic that may be relevant to exposures in the urban environment.     

Polycyclic aromatic hydrocarbons in suspended particulate matter and sediments from the Pearl River Estuary and adjacent coastal areas, China

The spatial distribution, composition, and sources of polycyclic aromatic hydrocarbons (PAHs) in sediments and suspended particulate matter (SPM) from the Pearl River Estuary and adjacent coastal areas were examined. Total PAH concentrations varied from 189 to 637 ng/g in sediments and 422 to 1,850 ng/g in SPM. PAHs were dominated by 5,6-ring compounds in sediments and by 2,3-ring compounds in SPM samples. Assessment of PAH sources suggested that biomass and coal combustion is the major PAH source to the outer part of the estuary sediments and that petroleum combustion is the major PAH source to the inner part of estuary sediments. As for SPM samples, PAH isomer pair ratios indicated multiple (petroleum, petroleum combustion, and biomass and coal combustion) PAH sources, and significant temporal variations could exist for the sources of water column PAHs in the study area. The distribution of perylene in SPM samples indicated that the river was the dominant source of perylene in SPM and that perylene could be taken as an index to assess the contribution of river inflow to the total PAHs in SPM samples. The high concentration of perylene in the sediment was indicative of an in situ biogenic origin.     

Gas-particle concentration and distribution of n-alkanes and polycyclic aromatic hydrocarbons in the atmosphere of Prato (Italy)

Air samples were collected in an urban and industrialised area of Prato (Italy) during 2002, as part of a study to identify and measure aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs). Total concentrations of aliphatic hydrocarbons ranged between 170 and 282ngm(-3) in the gas phase and from 48.9 to 276ngm(-3) in the particulate phase. The average total PAH concentrations (gas+particulate) were 59.4+/-26.5ngm(-3), and both gas and particulate phase PAH concentrations decreased with increasing temperature. Source identification using diagnostic ratios and principal component analysis identified automobile traffic, in particular, the strong influence of diesel fuel burning, as the major PAH source. Gas-particle partition coefficients (K(p)'s) of n-alkane and PAHs were well correlated with the sub-cooled liquid vapour pressure (P(L)(0)) and indicate stronger sorption of PAHs to aerosol particles compared with n-alkanes.     

Comparison and evaluation of chemically speciated mobile source PM2.5 particulate matter profiles

Mobile sources are significant contributors to ambient PM2.5, accounting for 50% or more of the total observed levels in some locations. One of the important methods for resolving the mobile source contribution is through chemical mass balance (CMB) receptor modeling. CMB requires chemically speciated source profiles with known uncertainty to ensure accurate source contribution estimates. Mobile source PM profiles are available from various sources and are generally in the form of weight fraction by chemical species. The weight fraction format is commonly used, since it is required for input into the CMB receptor model. This paper examines the similarities and differences in mobile source PM2.5 profiles that contain data for elements, ions, elemental carbon (EC) and organic carbon (OC), and in some cases speciated organics (e.g., polycyclic aromatic hydrocarbons [PAHs]), drawn from four different sources. Notable characteristics of the mass fraction data include variability (relative contributions of elements and ions) among supposedly similar sources and a wide range of average EC:OC ratios (0.60 +/- 0.53 to 1.42 +/- 2.99) for light-duty gasoline vehicles (LDGVs), indicating significant EC emissions from LDGVs in some cases. For diesel vehicles, average EC:OC ratios range from 1.09 +/- 2.66 to 3.54 +/- 3.07. That different populations of the same class of emitters can show considerable variability suggests caution should be exercised when selecting and using profiles in source apportionment studies.     

Polycyclic aromatic hydrocarbon emission from straw burning and the influence of combustion parameters

A simulated burning experiment was conducted in a tubular furnace system to examine the emission of polycyclic aromatic hydrocarbons (PAHs) from the burning of rice and bean straw, and the influence of combustion parameters was investigated. Total emission amounts of 16 PAHs (∑PAHs) from the burning of rice and bean straw ranged from 9.29 to 23.6 μg g^?1 and from 3.13 to 49.9 μg g^?1, respectively, which increased with the increase of temperatures from 200 to 700 °C. The contribution of combustion to individual PAH yields was about 80.6–100%, which was generally increased with the increase of burning temperature. Moisture content in straw had a negative effect on PAH formation, especially on PAHs with low molecular weight. ∑PAHs emission amounts decreased by 78.2% for bean straw with a moisture content of 30% in comparison with that for dried straw. In addition, PAH emission amounts increased with the increase of O₂ content in supplied air and then decreased, which showed a maximum emission at O₂ content of 40%. The source fingerprint of PAHs in emission from straw burning was established, which showed that naphthalene accounted for 35.0 ± 7.4% of ∑PAHs. Based on the experimental data, emission amounts of ∑PAHs from the burning of rice and bean straw were estimated to be 320–357 and 32.5–76.0 tons to ambient air per year in China, respectively.     

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta—Seasonal variations at urban,suburban, and rural ambient air monitoring sites

Twenty-eight polycyclic aromatic hydrocarbons (PAH) and methylated PAHs (Me-PAH) were measured in daily PM_2.5 samples collected at an urban site, a suburban site, and a rural site in and near Atlanta during 2004 (5 samples/month/site). The suburban site, located near a major highway, had higher PM_2.5-bound PAH concentrations than did the urban site, and the rural site had the lowest PAH levels. Monthly variations are described for concentrations of total PAHs (∑PAHs) and individual PAHs. PAH concentrations were much higher in cold months than in warm months, with average monthly ∑PAH concentrations at the urban and suburban-highway monitoring sites ranging from 2.12 to 6.85 ng m^?3 during January–February and November–December 2004, compared to 0.38–0.98 ng m^?3 during May–September 2004. ∑PAH concentrations were found to be well correlated with PM_2.5 and organic carbon (OC) within seasons, and the fractions of PAHs in PM_2.5 and OC were higher in winter than in summer. Methyl phenanthrenes were present at higher levels than their un-substituted homologue (phenanthrene), suggesting a petrogenic (unburned petroleum products) input. Retene, a proposed tracer for biomass burning, peaked in March, the month with the highest acreage and frequency of prescribed burning and unplanned fires, and in December, during the high residential wood-burning season, indicating that retene might be a good marker for burning of all biomass materials. In contrast, potassium peaked only in December, indicating that it might be a more specific tracer for wood-burning.     

Concentrations and bioaccessibility of polycyclic aromatic hydrocarbons in wastewater-irrigated soil using in vitro gastrointestinal test

BACKGROUND, AIM, AND SCOPE: Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of soil environment. Soil ingestion is of increasing concern for assessing health risk from PAH-contaminated soils because soil ingestion is one of the potentially important pathways of exposure to environmental pollutants, particularly relevant for children playing at contaminated sites due to their hand-to-mouth activities. In vitro gastro-intestinal tests imitate the human digestive tract, based on the physiology of humans, generally more simple, less time-consuming, and especially more reproducible than animal tests. This study was conducted to investigate the level of PAH contamination and oral bioaccessibility in surface soils, using physiologically based in vitro gastro-intestinal tests regarding both gastric and small intestinal conditions. MATERIALS AND METHODS: Wastewater-irrigated soils were sampled from the metropolitan areas of Beijing and Tianjin, China, which were highly contaminated with PAHs. Reference soil samples were also collected for comparisons. At each site, four soils were sampled in the upper horizon at the depth of 0-20 cm randomly and were bulked together to form one composite sample. PAH concentrations and origin were investigated and a physiologically based in vitro test was conducted using all analytical grade reagents. Linear regression model was used to assess the relationship between total PAH concentrations in soils and soil organic carbon (SOC). RESULTS: A wide range of total PAH concentrations ranging from 1,304 to 3,369 mug kg(-1) in soils collected from different wastewater-irrigated sites in Tianjin, while ranging from 2,687 to 4,916 mug kg(-1) in soils collected from different wastewater-irrigated sites in Beijing, was detected. In general, total PAH concentrations in soils from Beijing sites were significantly higher than those from Tianjin sites, indicating a dominant contribution from both pyrogenic and petrogenic sources. Results indicated that the oral bioaccessibility of PAHs in small intestinal was significantly higher (from P < 0.05 to P < 0.001) than gastric condition. Similarly, the oral bioaccessibility of PAHs in contaminated sites was significantly higher (from P < or = 0.05 to P < 0.001) than in reference sites. Individual PAH ratios (three to six rings), a more accurate and reliable estimation about the emission sources, were used to distinguish the natural and anthropogenic PAH inputs in the soils. Results indicated that PAHs were both pyrogenic and petrogenic in nature. DISCUSSION: The identification of PAH sources and importance of in vitro test for PAH bioaccessibility were emphasized in this study. The oral bioaccessibility of individual PAHs in soils generally decreased with increasing ring numbers of PAHs in both the gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric conditions to that in the small intestinal condition generally increased with increasing ring numbers, indicating the relatively pronounced effect of bile extract on improving the bioaccessibility of PAHs with relatively high ring numbers characterized by their high K ( ow ) values. Similarly, total PAH concentrations in soils were strongly correlated with SOC, indicating that SOC was the key factor determining the retention of PAHs in soils. CONCLUSIONS: Soils were contaminated with PAHs due to long-term wastewater irrigation. PAHs with two to six rings showed high concentrations with a significant increase over reference soils. Based on the molecular indices, it was suggested that PAHs in soils had both pyrogenic and petrogenic sources. It was also concluded that the oral bioaccessibility of total PAHs in the small intestinal condition was significantly higher than that in the gastric condition. Furthermore, the bioaccessibility of individual PAHs in soils generally decreased with the increasing ring numbers in both the gastric and small intestinal conditions. RECOMMENDATIONS AND PERSPECTIVES: It is suggested that more care should be given while establishing reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-to-mouth activities.     

Comparison and Evaluation of Chemically Speciated Mobile Source PM2.5 Particulate Matter Profiles

ABSTRACT

Mobile sources are significant contributors to ambient PM_{2 5}, accounting for 50% or more of the total observed levels in some locations. One of the important methods for resolving the mobile source contribution is through chemical mass balance (CMB) receptor modeling. CMB requires chemically speciated source profiles with known uncertainty to ensure accurate source contribution estimates. Mobile source PM profiles are available from various sources and are generally in the form of weight fraction by chemical species. The weight fraction format is commonly used, since it is required for input into the CMB receptor model. This paper examines the similarities and differences in mobile source PM_2.5 profiles that contain data for elements, ions, elemental carbon (EC) and organic carbon (OC), and in some cases speciated organics (e.g., polycyclic aromatic hydrocarbons [PAHs]), drawn from four different sources.

Notable characteristics of the mass fraction data include variability (relative contributions of elements and ions) among supposedly similar sources and a wide range of average EC:OC ratios (0.60 ± 0.53 to 1.42 ± 2.99) for light-duty gasoline vehicles (LDGVs), indicating significant EC emissions from LDGVs in some cases. For diesel vehicles, average EC:OC ratios range from 1.09 ± 2.66 to 3.54 ± 3.07. That different populations of the same class of emitters can show considerable variability suggests caution should be exercised when selecting and using profiles in source apportionment studies.     

The impact of infield biomass burning on PM levels and its chemical composition

In the South of Italy, it is common for farmers to burn pruning waste from olive trees in spring. In order to evaluate the impact of the biomass burning source on the physical and chemical characteristics of the particulate matter (PM) emitted by these fires, a PM monitoring campaign was carried out in an olive grove. Daily PM10 samples were collected for 1 week, when there were no open fires, and when biomass was being burned, and at two different distances from the fires. Moreover, an optical particle counter and a polycyclic aromatic hydrocarbon (PAH) analyzer were used to measure the high time-resolved dimensional distribution of particles emitted and total PAHs concentrations, respectively. Chemical analysis of PM10 samples identified organic and inorganic components such as PAHs, ions, elements, and carbonaceous fractions (OC, EC). Analysis of the collected data showed the usefulness of organic and inorganic tracer species and of PAH diagnostic ratios for interpreting the impact of biomass fires on PM levels and on its chemical composition. Finally, high time-resolved monitoring of particle numbers and PAH concentrations was performed before, during, and after biomass burning, and these concentrations were seen to be very dependent on factors such as weather conditions, combustion efficiency, and temperature (smoldering versus flaming conditions), and moisture content of the wood burned.     

Assessment of source apportionment by Positive Matrix Factorization analysis on fine and coarse urban aerosol size fractions

This study was conducted in order to investigate the differences observed in source profiles in the urban environment, when chemical composition parameters from different aerosol size fractions are subjected to factor analysis. Source apportionment was performed in an urban area where representative types of emission sources are present. PM₁₀ and PM₂ samples were collected within the Athens Metropolitan area and analysed for trace elements, inorganic ions and black carbon. Analysis by two-way and three-way Positive Matrix Factorization was performed, in order to resolve sources from data obtained for the fine and coarse aerosol fractions. A difference was observed: seven factors describe the best solution in PMF3 while six factors in PMF2. Six factors derived from PMF3 analysis correspond to those described by the PMF2 solution for the fine and coarse particles separately. These sources were attributed to road dust, marine aerosol, soil, motor vehicles, biomass burning, and oil combustion. The additional source resolved by PMF3 was attributed to a different type of road dust. Combustion sources (oil combustion and biomass burning) were correctly attributed by PMF3 solely to the fine fraction and the soil source to the coarse fraction. However, a motor vehicle's contribution to the coarse fraction was found only by three-way PMF. When PMF2 was employed in PM₁₀ concentrations the optimum solution included six factors. Four source profiles corresponded to the previously identified as vehicles, road dust, biomass burning and marine aerosol, while two could not be clearly identified. Source apportionment by PMF2 analysis based solely on PM₁₀ aerosol composition data, yielded unclear results, compared to results from PMF2 and PMF3 analyses on fine and coarse aerosol composition data.     

Distinguishing the relative contribution of fossil fuel and biomass combustion aerosols deposited at Summit,Greenland through isotopic and molecular characterization of insoluble carbon

Quantifying combustion aerosols transported to Summit, Greenland has typically involved the measurement of water-soluble inorganic and organic ions in air, snow, and ice. However, the ubiquitous nature of atmospheric soluble ions makes it difficult to separate the combustion component from the natural component. More specific combustion indicators are therefore needed to accurately quantify inputs from biomass and fossil-fuel burning. This work reports on radiocarbon (¹⁴C) analysis of elemental carbon (EC) and quantification of polycyclic aromatic hydrocarbons (PAHs) of water-insoluble particles from a snowpit excavated at Summit, Greenland in 1996. The ¹⁴C measurements allowed us to quantify the relative contribution of EC from biomass burning and fossil-fuel combustion transported to and deposited at Summit during periods of 1994 and 1995. Specific PAHs associated with conifer combustion helped to identify snowpit layers impacted by forest fires. Our results show that fossil EC was the major component during spring and fall 1994, while biomass EC and fossil EC were present in roughly equal amounts during summer 1994. PAH ratios in spring layers of the snowpit indicate substantial inputs from anthropogenic sources and the ΣPAH depth profile displays springtime maxima that coincided with non-sea-salt sulfate ion maximum concentrations. In other layers, ammonium ion concentrations were independent of the isotopic and molecular carbon measurements. This work demonstrates the utility of radiocarbon techniques to quantify the two different sources of combustion-generated particles at Summit; however, portions of the ¹⁴C results were indeterminate due to large uncertainties that were the result of chemical impurities introduced in the EC isolation technique. Additionally, PAH measurements were successfully performed on as little as 100 ml of snowmelt water, demonstrating the potential for future finer sample resolution.     

Polynuclear aromatic hydrocarbons in the United Kingdom environment: a preliminary source inventory and budget

This paper presents the first attempt to quantify the production, cycling, storage and loss of PAHs in the UK environment. Over 53 000 tonnes of sigmaPAHs (sum of 12 individual compounds) are estimated to reside in the contemporary UK environment, with soil being the major repository. If soils at contaminated sites are included, this estimate increases dramatically. Emission of PAHs to the UK atmosphere from primary combustion sources are estimated to be greater than 1000 tonnes sigmaPAHs per annum, with over 95% coming from domestic coal combustion, unregulated fires and vehicle emissions. It is estimated that approximately 210 tonnes of sigmaPAH are delivered to terrestrial surfaces each year via atmospheric deposition. Therefore, inputs of PAHs to the UK atmosphere outweigh the outputs by a factor of over 4. This may be explained by enhanced particulate deposition near point sources, PAH degradation in the atmosphere and transport away from the UK with prevailing winds. Disposal of waste residues is estimated to contribute a further 1000 tonnes of sigmaPAH per year to the terrestrial environment. It is illustrated that the use of creosote has the potential to release considerable quantities of PAHs to the UK environment. Temporal trends in PAH cycling are then considered. There is good evidence to suggest that air concentrations and fluxes to the UK surface are now lower than at any time throughout this century. Nonetheless, the UK sigmaPAH burden is still increasing at the present time, principally through retention by soils. However, there are marked differences in the behaviour of individual compounds: there is evidence, for example, that phenanthrene concentrations in soils have declined since the 1960s, although soil concentrations of benzo[a]pyrene and other heavier PAHs have continued to increase through this century. Volatilisation of low molecular weight PAHs accumulated in soils over previous decades may be making an important contribution to the current atmospheric burden. The major uncertainties identified by data on this budget are: (1) the lack of PAH concentrations in some environmental matrices; (2) the possible importance of contaminated soils as a major repository and source of PAHs; (3) the lack of emission data (especially vapour phase releases) for some PAH sources; (4) the importance of biodegradation and volatilisation as loss mechanisms for low molecular weight PAHs in soils; and (5) the importance of creosote use in the PAH cycle.     

PAHs in the bulk atmospheric deposition of the Seine river basin: source identification and apportionment by ratios, multivariate statistical techniques and scanning electron microscopy

The origin of polycyclic aromatic hydrocarbons (PAH) contamination in bulk atmospheric deposition at two sites of the Seine estuary, one urban and one industrial, has been investigated. The PAH profiles indicate that PAHs mainly have a pyrolytic origin, both in urban and industrial areas. PAH sources vary during the year with an increase of high molecular weight PAH proportions (especially for carcinogenic PAHs) in winter, that means an increase of combustion processes such as domestic heating. Ratios of indicator PAHs (FTH/FTH+PYR and IcdP/IcdP+BghiP) confirm the pyrolytic origin of PAHs. In summer, ratios show the presence of industrial sources. In addition to these two methods, a factor analysis/multiple linear regression model was applied and gave an approximation of PAH source apportionment. PAH were found to be associated predominantly with emissions from road traffic (gasoline and diesel), that accounts for 17-34%. Domestic heating is a very important PAH source in urban areas and accounts for up to 85% of PAHs in winter. Industrial emissions (refineries...) account for 25% in the industrial area in summer. Each is an identified source category for the region and these results are consistent with fly-ashes identified by scanning electron microscopy. This study demonstrates that a combination of source identification methods is a far more efficient than one method alone.     

Introduction to the Air & Waste Management Association's 29th Annual Critical Review

Abstract

On-road mobile sources contribute substantially to ambient air concentrations of the carcinogens 1,3-butadiene, benzene, and polycyclic aromatic hydrocarbons (PAHs). The current study measured benzene and 1,3-butadiene at the Baltimore Harbor Tunnel tollbooth over 3-hr intervals on seven weekdays (n = 56). Particle-bound PAH was measured on a subset of three days. The 3-hr outdoor 1,3-butadiene levels varied according to time of day and traffic volume. The minimum occurred at night (12 a.m.–3 a.m.) with a mean of 2 µg/m³ (SD = 1.3, n = 7), while the maximum occurred during the morning rush hour (6 a.m.–9 a.m.) with a mean of 11.9 µg/m³ (SD = 4.6, n = 7). The corresponding traffic counts were 1413 (SD = 144) and 16,893 (SD = 692), respectively. During the same intervals, mean benzene concentration varied from 3 µg/m³ (SD = 3.1, n = 7) to 22.3 µg/m³ (SD = 7.6, n = 7). Median PAH concentrations ranged from 9 to 199 ng/m³. Using multivariate regression, a significant association (p < 0.001) between traffic and curbside concentration was observed. Much of the pollutant variability (1,3-butadiene 62%, benzene 77%, and PAH 85%) was explained by traffic volume, class, and meteorology. Results suggest >2-axle vehicles emit 60, 32, and 9 times more PAH, 1,3-butadiene, and benzene, respectively, than do 2-axle vehicles. This study provides a model for estimating curbside pollution levels associated with traffic that may be relevant to exposures in the urban environment.