Impact of Polycyclic Aromatic Hydrocarbon Emissions from Medical Waste Incinerators on the Urban Atmosphere

Abstract

In this study, polycyclic aromatic hydrocarbon (PAH) emissions from two batch-type medical waste incinerators (MWIs), one with a mechanical grate and the other with a fixed grate, both operated by a medical center, were assessed. Both MWIs shared the same air-pollution control devices (APCDs), with an electrostatic precipitator and a wet scrubber installed in series. Results show that when APCDs were used, total PAHs and total benzo- [a]pyrene equivalent (total BaP_eq) emission concentrations of both MWIs were reduced from 2220 to 1870 µg/m³ and 50 to 12.4 µg/m³, respectively. We used the Industrial Source Complex Short Term model (ISCST) to estimate the ground-level concentrations of the residential area and the traffic intersection located at the down-wind side of the two MWIs. For the traffic intersection, we found both total PAHs and total BaP_eq transported from MWIs to both studied areas were not significant. For the residential area, similar results were found when APCDs were used in MWIs. When APCDs were not included, we found that total PAHs transported from MWIs accounted for <12%, but total BaP_eq accounted for >90%, of the on-site measured concentrations. These results suggest that the use of proper APCDs during incineration would significantly reduce the carcinogenic potencies associated with PAH emissions from MWIs to the residential area.     

Environmental Progress and Problems: A Chemical Industry Perspective

From 1995 to 2004, in Genoa, Italy, daily concentrations of twelve polycyclic aromatic hydrocarbons (PAHs) were measured in particulate phase (PM10), around a coke oven plant in operation from the 1950s and closed in 2002. The study permitted to identify the coke oven as the main PAH source in Genoa, causing constant exceeding of benzo(a)pyrene (BaP) air quality target (1.0 ng/m3) in the urban area till 1,900 meters distance downwind the plant. For this reason the plant was closed. Distance and daily hours downwind the coke plant were the main sources of variability of toxic BaP equivalent (BaPeq) concentrations and equations that best fitted these variables were experimentally obtained. During full plant activity, annual average BaPeq concentrations, measured in the three sampling sites aligned downwind to the summer prevalent winds, were: 85 ng/m3 at 40 m (site 2, industrial area), 13.2 ng/m3 at 300 m (site 3, residential area) and 5.6 ng/m3 at 575 m (site 4, residential area).

Soon after the coke oven's closure (February 2002) BaPeq concentrations (annual average) measured in residential area, decreased drastically: 0.2 ng/m3 at site 3, 0.4 ng/m3 at site 4. Comparing 1998 and 2003 data, BaPeq concentrations decreased 97.6% in site 3 and 92.8% in site 4.

Samples collected at site 3, during the longest downwind conditions, provided a reliable PAH profile of fugitive coke oven emissions. This profile was significantly different from the PAH profile, contemporary found at site 5, near the traffic flow.

This study demonstrates that risk assessment based only on distance of residences from a coke plant can be heavily inaccurate and confirmed that seasonal variability of BaPeq concentrations and high variability of fugitive emissions of PAHs during coke oven activities require at least one year of frequent and constant monitoring (10-15 samples each month).

Implications: Around a coking plant, polycyclic aromatic hydrocarbons (PAHs), concentrations depend mainly on downwind hours and distance. Equations that best fit these variables were experimentally calculated. Fugitive emissions of an old coke oven did not comply with the threshold BAP air concentration proposed by the World Health Organization (WHO), up to 1,900 m distance. The study identified the PAH profile of fugitive emissions of a coke oven, statistically different from the profile of traffic emissions. During its activity, in the Genoa residential area, 575 m away from the plant, 92.8% of found PAHs was due to coke oven emission only.     

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.     

Estimation of PAHs dry deposition and BaP toxic equivalency factors (TEFs) study at Urban, Industry Park and rural sampling sites in central Taiwan, Taichung

The concentrations of polycyclic aromatic hydrocarbons (PAHs) in gas phase and particle bound were measured simultaneously at industrial (INDUSTRY), urban (URBAN), and rural areas (RURAL) in Taichung, Taiwan. And the PAH concentrations, size distributions, estimated PAHs dry deposition fluxes and health risk study of PAHs in the ambient air of central Taiwan were discussed in this study. Total PAH concentrations at INDUSTRY, URBAN, and RURAL sampling sites were found to be 1650 +/- 1240, 1220 +/- 520, and 831 +/- 427 ng/m3, respectively. The results indicated that PAH concentrations were higher at INDUSTRY and URBAN sampling sites than the RURAL sampling sites because of the more industrial processes, traffic exhausts and human activities. The estimation dry deposition and size distribution of PAHs were also studied. The results indicated that the estimated dry deposition fluxes of total PAHs were 58.5, 48.8, and 38.6 microg/m2/day at INDUSTRY, URBAN, and RURAL, respectively. The BaP equivalency results indicated that the health risk of gas phase PAHs were higher than the particle phase at three sampling sites of central Taiwan. However, compared with the BaP equivalency results to other studies conducted in factory, this study indicated the health risk of PAHs was acceptable in the ambient air of central Taiwan.     

Atmospheric polycyclic aromatic hydrocarbons (PAHs) in Asia: a review from 1999 to 2004

Polycyclic aromatic hydrocarbons (PAHs) are present in both gaseous and particulate phases. These compounds are considered to be atmospheric contaminants and are human carcinogens. Many studies have monitored atmospheric particulate and gaseous phases of PAH in Asia over the past 5 years. This work compares and discusses different sample collection, pretreatment and analytical methods. The main PAH sources are traffic exhausts (AcPy, FL, Flu, PA, Pyr, CHR, BeP) and industrial emissions (BaP, BaA, PER, BeP, COR, CYC). PAH concentrations are highest in areas of traffic, followed by the urban sites, and lowest in rural sites. Meteorological conditions, such as temperature, wind speed and humidity, strongly affect PAH concentrations at all sampling sites. This work elucidates the characteristics, sources and distribution, and the healthy impacts of atmospheric PAH species in Asia.     

Distribution and spatial trends of PAHs and PCBs in soils in the Seine River basin, France

Persistent organic pollutants (PAHs and PCBs) in soil samples from seven sites across the Seine basin were analysed. Samples were taken from industrialized, urban, suburban and remote sites. Results showed spatial differences, in terms of concentrations and congener profiles. PAH (Sigma14 PAHs) and PCB (Sigma 7 PCBs) concentrations ranged from 450 to 5650 microg kg(-1) and 0.09 to 150 microg kg(-1), respectively. A clear gradient from industrial to remote sites was highlighted, with a ratio of up to one order of magnitude for PAHs and two orders of magnitude for PCBs. Fluoranthene and pyrene were predominant, while the carcinogenic PAHs represented 15-46% of the total PAH content. Using hierarchical cluster analysis, soil samples profiles were compared and the influence of site location and potential sources were identified: automobile traffic, domestic heating, and industrial emissions were the prevalent PAHs sources in the Seine basin. PCB profiles suggested different transport patterns among congeners. For remote sites, the congener fingerprint showed a relatively higher proportion of the most volatile congeners, which were attributed to increased atmospheric residence times. Thus, PAH and PCB distributions in soils provided information on sources and evidence for short-range transport, and profiles of compounds reflected differences between regional and local emissions. This study demonstrates that soil sampling can be used to investigate spatial differences in atmospheric inputs of persistent organic pollutants based on differences in the mixtures of compounds, reflecting differences in regional and local atmospheric emissions.     

The effect of EURO-0 vehicle substitution on polycyclic aromatic hydrocarbon and carbon monoxide concentrations in an urban area

From 1994 to 2003, daily air concentrations of particle-bound polycyclic aromatic hydrocarbons (PAHs) and carbon monoxide (CO) were regularly monitored at two traffic-oriented sampling sites (A and B) in urban Genoa, Italy. The data were used to estimate effects on air quality in real situations due to progressive substitution of EURO-0 vehicles, started in 1993, with less-polluting vehicles (EURO-1, EURO-2), mainly gasoline vehicles with a catalyst. PAH profile classification and diagnostic PAH ratios were used to identify 345 samples of predominantly traffic origin. At both sites, CO and PAH daily concentrations decreased exponentially with time and the apparent half-life values calculated were 6.3 and 5.5 for CO and 3.7 and 3.5 years for PAHs at sites A and B, respectively. At site A, monitored for traffic intensity, multiple regression analyses confirmed that daily PAH and CO concentrations were positively correlated with the number of non-catalytic vehicles estimated to cross this site during sampling and negatively correlated with seasonal variables (air temperature, ozone concentration, relative air humidity). The reduction in air pollution estimated for complete substitution of non-catalytic gasoline vehicles was 89% for BaP, 85% for total PAHs and 69% for CO.     

The influence of Sarcocornia fruticosa on retention of PAHs in salt marsh sediments (Sado estuary, Portugal)

Depth concentration profiles of PAHs, organic carbon and dissolved oxygen in non-colonised sediments and sediments colonised by Sarcocornia fruticosa from Mitrena salt marsh (Sado, Portugal) were determined in November 2004 and April 2005. Belowground biomass and PAH levels in below and aboveground material were also determined. In both periods, colonised sediments were oxygenated until 15-cm, rich in organic carbon (max 4.4%) and presented much higher PAH concentrations (max. 7.1 microg g(-1)) than non-colonised sediments (max. 0.55 microg g(-1)). Rooting sediments contained the highest PAH concentrations. The five- and six-ring compounds accounted to 50-75% of the total PAHs in colonised sediments, while only to 30% in non-colonised sediments. The elevated concentrations of PAHs in colonised sediments may be attributed to the transfer of dissolved PAH compounds towards the roots as plant uptake water and subsequent sequestration onto organically rich particles. A phase-partitioning mechanism probably explains the higher retention of the heavier PAHs. In addition oxygenated conditions of the rooting sediments favour the degradation of the lighter PAHs and explain the elevated proportion of the heavier compounds. Below and aboveground materials presented lower PAH concentrations (0.18-0.38 microg g(-1)) than colonised sediments. Only 3- and 4-PAHs were quantified in aboveground material, reflecting either preferential translocation of lighter compounds from roots or atmospheric deposition.     

Pollutants in Hong Kong soils: polycyclic aromatic hydrocarbons

An extensive soil survey was carried out to study the polycyclic aromatic hydrocarbon (PAH) contaminations in 138 soil samples collected throughout Hong Kong. Results demonstrated that there were low levels of PAH contaminations (median of summation operator 16US EPA PAHs=140 microg kg(-1)) for all land uses (urban park, greening area, country park, rural area, restored landfill, agricultural farmland, orchard farm, crematorium, industrial and near highway area). However, localized hotspots were identified with summation operator 16PAH concentrations as high as 19,500 microg kg(-1) in one urban park. These findings were also confirmed by multivariate analysis. Comparison of PAH profiles showed a widespread domination of its 4-ring member. The major contribution was vehicular emissions from petroleum, and however at the hotspots, the improper disposal of used motor oils. In general, the pollution levels for all the land uses were below the recommended values for residential and general purposes stated in soil quality guidelines such as Netherlands and Denmark except certain identified hotspots. The potential health hazards imposed by these hotspots were alarming, and their existence (3 out of 138 samples) suggested that sole monitoring of atmospheric PAHs may not adequately address the hidden risks to human in urban city.     

Polycyclic aromatic hydrocarbons (PAHs) concentrations and related carcinogenic potencies in soil at a semi-arid region of India

A study of polycyclic aromatic hydrocarbons in surface soil was conducted at selected locations in Agra (semi-arid region of India) for a span of one year in order to ascertain the contamination levels. The concentrations of PAH were measured at four locations in the city of Agra, which covers industrial, residential, roadside and agricultural areas. The samples were extracted with hexane by ultrasonic agitation. The extracts were then fractioned on a silica-gel column and the aromatic fraction was subjected to HPLC. The average concentration of total PAH in all samples was 12.1 microg g(-1) and the range was from 3.1 microg g(-1) to 28.5 microg g(-1). The maximum concentrations of PAHs were found to be in winter season. The concentration of PAH decreased in the order chrysene > benzo(b)fluoranthene > fluoranthene. Factor analysis suggests that the mixed signature of all the sources are intermediate between vehicular and combustion activities.     

Polycyclic aromatic hydrocarbons in the surface soils from outskirts of Beijing, China

Surface soils from the outskirts of Beijing were analyzed for 16 priority polycyclic aromatic hydrocarbons (PAHs) using gas chromatography and mass spectrometry (GC-MS). The distribution map of total PAHs content was obtained as a contour plot. The concentration range of 16 PAHs varied by over two orders of magnitude from 0.016 microg g-1 in rural to 3.884 microg g-1 in suburban soils with the relatively standard deviation of 70.5%, showing large differences in the extent of PAHs pollution at the various sampling sites. It was notable that the concentration of BaP was 0.005-0.270 microg g-1 with a mean of 0.055 microg g-1. In general, the distribution of PAHs centered on the high molecular weight PAHs known to be carcinogenic. The 4-6 ring PAHs represented about 66% in rural samples and 70% in suburban soils of the total PAHs found. There was relatively good relationship among most of the individual PAHs and the compounds of Pyr, BaA, Flu, BbF, BaP, Chr and Ph gave strong correlation (r>0.8) with the sum of PAHs. The selected marked compounds, a principal component analysis (PCA) and special PAHs compound ratios (Ph/An vs Flu/Pyr; summation operator COMB/ summation operator EPA-PAHs) suggest the pyrogenic origins, especially traffic exhausts, are the dominant sources of PAHs in Beijing outskirts soils.     

Reconstructing historical trends of polycyclic aromatic hydrocarbon deposition in a remote area of Spain using herbarium moss material

Herbarium mosses from 1879–1881, 1973–1975 and 2006–2007 were used to investigate the historical changes of atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) at a remote site in Northern Spain. Natural abundance of nitrogen and carbon isotopes was also measured in order to assess the evolution of emissions from anthropogenic sources. Nitrogen and PAH concentrations as well as δ¹³C and δ¹⁵N ratios were significantly higher in 19th century samples compared to present century samples. Moreover, PAH distribution varied over the centuries, with the trend towards enrichment in light PAHs. The carbon, nitrogen and PAH concentrations measured in the mosses tally with the historical evolution of anthropogenic emissions in the area, mainly influenced by changes in economic activities, domestic heating and road traffic density. Mosses provided by herbaria seem to offer the possibility of studying long-term temporal evolution of atmospheric PAH deposition.     

Assessment of the bioaccessibility of polycyclic aromatic hydrocarbons in soils from Beijing using an in vitro test

As an important human exposure pathway of contaminants, soil ingestion is of increasing concern for assessing health risk from polycyclic aromatic hydrocarbons (PAHs) in soils. A wide range of total PAH concentrations ranging from 0.112 microg g(-1) to 27.8 microg g(-1) in soils collected from different public sites, including gas stations, roadsides, bus stops, a kindergarten, primary and middle schools, a university and residential area, was detected. In general, total PAHs concentrations in soils from traffic areas were significantly higher than that from the other sites, indicating a dominant contribution from motor vehicles. Physiologically based in vitro tests were used to evaluate the oral bioaccessibility of PAHs in surface soil under different land uses in Beijing regarding both gastric and small intestinal conditions. It was found that the oral bioaccessibility of total PAHs in small intestinal condition, ranging from 9.2% to 60.5% of total PAHs in soil, was significantly higher than gastric condition, ranging from 3.9% to 54.9%. The bioaccessibility of individual PAHs in soils generally decreased with the increasing ring number of PAHs in both gastric and small intestinal conditions. However, the ratio of bioaccessibility of individual PAHs in gastric condition to that in small intestinal condition, generally increased with increasing ring number, indicating the relatively pronounced effect of bile extract on improving bioaccessibility of PAHs with relatively high ring numbers characterized by their high K(ow) values. The observation that bile extract at a level higher than critical micelle concentration could reduce the surface tension of digestive juice substantially, which may cause PAHs to be available for intestinal absorption, calls for more careful establishment of reliable soil criteria for PAHs, especially concerning the health of children who may ingest a considerable amount of PAH-contaminated soil via outdoor hand-mouth activities.     

Polycyclic aromatic hydrocarbon contamination in an urban area assessed by Quercus ilex leaves and soil

We investigated the PAH contamination of Naples urban area, densely populated and with high traffic flow, by analyses of environmental matrices: soil and Quercus ilex leaves. Being some PAHs demonstrated to have hazardous effects on human health, the accumulation of carcinogenic and toxic PAHs (expressed as B(a)Peq) was evaluated in the leaves and soil. The main sources of the PAHs were discriminated by the diagnostic ratios in the two matrices. The urban area appeared heavily contaminated by PAHs, showing in soil and leaves total PAH concentrations also fivefold higher than those from the remote area. The soil mainly accumulated heavy PAHs, whereas leaves the lightest ones. Median values of carcinogenic PAH concentrations were higher in soil (440 ng g^?1 d.w.) and leaves (340 ng g^?1 d.w.) from the urban than the remote area (60 and 70 ng g^?1 d.w., respectively, for soil and leaves). Also, median B(a)Peq concentrations were higher both in soil and leaves from the urban (137 and 63 ng g^?1 d.w., respectively) than those from the remote area (19 and 49 ng g^?1 d.w., respectively). Different from the soils, the diagnostic ratios found for the leaves discerned PAH sources in the remote and urban areas, highlighting a great contribution of vehicular traffic emission as main PAH source in the urban area.     

Molecular evidence for benzo[a]pyrene and naphthalene genotoxicity in Trifolium repens L

Polycyclic aromatic hydrocarbons (PAHs) are among the most dangerous environmental contaminants due to their toxic, carcinogenic and mutagenic effects. Although there are many data in literature that detail the effects of PAHs on animals, little is known about their action on higher plants which are often used as bioindicators. The aim of the present study was to evaluate the genotoxicity of two different PAHs, benzo[a]pyrene (BaP) and naphthalene (Naph), on Trifolium repens L. Clover plants were exposed to soil which had been artificially contaminated with three concentrations of BaP (5, 10 and 20 microg g-1) or Naph (25, 50 and 100 microg g-1). After 15 days, changes in the DNA content and sequence of roots and shoots were evaluated by flow cytometry (FCM) and amplified fragment length polymorphism (AFLP). Root and shoot dry weight were also determined to assess plant growth. Results showed that BaP and Naph were both genotoxic for white clover, inducing significant changes in root and shoot DNA sequence. Damage was more severe in the root than in the shoot suggesting that the translocation of these compounds and their genotoxic metabolites was limited. Ploidy alterations were not detected and the extent of damage caused by all the tested PAH concentrations was not sufficient to affect plant development.     

Seasonal variations and trends in concentrations of filter-collected polycyclic aromatic hydrocarbons (PAH) and mutagenic activity in the San Francisco Bay area

Air monitoring in the San Francisco Bay Area was carried out to measure outdoor community air concentrations of polycyclic aromatic hydrocarbons (PAH) and mutagenic activity (mutagenicity) in particulate organic matter (POM). Monitoring began in 1979 and is currently conducted at six stations. PAH and mutagenicity tests were performed on organic extracts prepared from high volume (hi-vol) filters composited every four months, by meterological season. PAH were determined by high pressure liquid chromatography (HPLC) with fluorescence and ultraviolet detection. Mutagenicity was measured in the Ames Salmonella bioassay using strain TA98 with and without metabolic activation. The nine-year mean concentration of benzo(a)pyrene (BaP) was 0.4 ng/m3. The mutagenicity of this amount of BaP accounted for only about 0.2% of the observed mutagenicity in POM and other measured PAH accounted for even less. Concentrations of PAH and mutagenicity were three to nine times higher during the winter than during other seasons. Year-to-year wintertime trends in several PAH were also seen. Early in the 1980s, winter concentrations of BaP and benzo (g,h,i)perylene increased. However since the mid-1980's, their concentrations have fallen. The decrease in PAH concentrations may be the result of an increasing proportion of vehicles with relatively low organic emissions. In contrast to PAH, mutagenicity did not show significantly year-to-year time trends.     

Effects of meteorology on diurnal and nocturnal levels of priority polycyclic aromatic hydrocarbons and elemental and organic carbon in PM10 at a source and a receptor area in Mexico City

PM₁₀ levels of the 16 US-EPA Priority Pollutant polycyclic aromatic hydrocarbons (PAHs) were measured from March 17 to 31, 2003, in 8-h time bins (morning, afternoon and nighttime) at Merced, a source site dominated by vehicular traffic emissions near the center of Mexico City, and at Pedregal, a receptor area located downwind in a residential area of low traffic. Along with PAH, elemental (EC) and organic carbon (OC), mass, and prevailing meteorological parameters were measured. At the source location, measured concentrations of benzo[a]pyrene (BAP), an agent suspected of being carcinogenic to humans and of causing oxidative DNA damage, reached concentrations as high as 2.04 and 2.11 ng m^?3 during the morning of a weekday and the night period of a holiday. Compared with source dominated areas in Central Los Angeles, the BAP levels found in Central Mexico City are approximately 6 times higher. Benzo[ghi]perylene (BGP) levels were, in general, the highest among the target PAH, both at the source (7.2 ng m^?3) and the receptor site (2.8 ng m^?3), suggesting that, at both locations, exhaust emission by light-duty (LD) vehicles is an important contributor to the atmospheric PAH burden. Higher PAH concentrations were observed during the morning period (5:00–13:00 h) at the source and the receptor site. The concentrations of PAHs found predominantly in the particle-phase (MW > 202) correlated well (r = 0.57–0.71) with the occurrence of surface thermal inversions and with mixing heights (r = ?0.57 to ?0.72). Organic and elemental carbon ratios also indicated that Pedregal is impacted by secondary aerosols during the afternoon hours.     

Particle-bound PAH content in ambient air

Ambient air samples from a traffic intersection, an urban site and a petrochemical-industrial site (PCI) were collected by using several dry deposition plates, two Microorifice uniform deposited impactors (MOUDIs), one Noll Rotary Impactor (NRI) and several PS-1 (General Metal Work) samplers from March 1994 to June 1995 in southern Taiwan, to characterize the atmospheric particle-bound PAH content of these three areas. Twenty-one individual polycyclic aromatic hydrocarbons (PAHs) were analyzed primarily by using a gas chromatograph/mass spectrometer (GC/MS). In general, the sub-micron particles have a higher PAH content. This is due to the fact that soot from combustion sources consists primarily of fine particles and has a high PAH content. In addition, a smaller particle has a higher specific surface area and therefore may contain more organic carbon, which allows for more PAH adsorption. For a particle size range between 0.31 and 3.2 microm, both Urban/Traffic and PCI/Traffic ratios of particle-bound total-PAH content have the lowest values, ranging from 0.25 to 0.28 (mean = 0.26) and from 0.07 to 0.13 (mean = 0.10), respectively. This indicates that, during the accumulation process, the PAH mass shifted from a particle phase to a gas phase, or the particles aggregated with lower PAH-content particles, resulting in a reduction in particle-bound PAH content. By using the particle size distribution data, the dry deposition model in this study can provide a good prediction for the PAH content of dry deposition materials. In general, lower molecular weight PAHs had a larger fraction of dry deposition flux contributed by the gas phase; for 2-ring PAH (50.4, 46.3 and 28.4%), 3-ring PAHs (15.2, 15.4 and 11.7%) and 4-ring PAHs (13.0, 3.60 and 5.01%) for the traffic intersection, urban and PCI sites, respectively. For higher molecular weight PAHs-5-ring, 6-ring and 7-ring PAHs-their cumulation fraction (F%) of dry deposition flux contributed by the gas phase was lower than 3.26%. At the traffic intersection, urban and PCI sites, the mass median diameter of dry deposition materials (MMD(F)) of individual PAHs was between 25.3 and 49.6 microm, between 27.6 and 43.9 microm, and between 19.1 and 41.9 microm, respectively. This is due to the fact that PAH dry-deposition primarily resulted from gravitational settling of the coarse particulates (> 10 microm).     

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.     

The temporal variability of the profile of carcinogenic polycyclic aromatic hydrocarbons in urban air: a study in a medium traffic area in Rome, 1993–1998

The constancy, both temporal and spatial, of the profile of polycyclic aromatic hydrocarbons (PAHs) relative to benzo[a]pyrene (BaP) is a prerequisite to using the BaP-indicator approach in the carcinogenic risk assessment for PAHs. The principal aim of this study was to provide a contribution to validate this approach, by studying the variability of the profile at a typical urban site through a multi-year data set and by comparing the profiles available for different cities. Seven carcinogenic PAHs (benz[a]anthracene, benzo[b+j+k]fluoranthenes, BaP, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene) were determined in PM₁₀ 24-h samples collected every third day at a road site; moreover, benzo[e]pyrene was determined as a reference PAH due to its stability. The profile was found stable from year to year. Besides, it was similar to those recently found in other European cities (observed differences within a factor of four) and to those elaborated from earlier (1970s–1980s) investigations. The substantial similarity of profiles, both temporal (on an annual basis) and spatial, supports the validity of the BaP-indicator approach. Large PAH-to-PAH differences were, however, found in the seasonal pattern of profile: they were explained by the different atmospheric degradability of PAHs, whose effect is enhanced under the meteoclimatic conditions typical of the European Mediterranean countries. PAH annual means showed a slight declining trend since 1994. In the last sampling year, mean concentration of BaP was 1.2 ng m⁻³. Within-year differences among monthly averaged PAH concentrations were observed, as large as up to 44-fold for BaP, underlining the need for whole-year monitoring.