Volatile Polycyclic Aromatic Hydrocarbons Research Articles

Influence of a large steel complex on the spatial distribution of volatile polycyclic aromatic hydrocarbons (PAHs) determined by passive air sampling using membrane-enclosed copolymer (MECOP)

Membrane-enclosed copolymer (MECOPs) samplers containing crystalline copolymers of ethylvinylbenzene-divinylbenzene in polyethylene membranes were used to assess the influence of a steel complex on the level and spatial distribution of polycyclic aromatic hydrocarbons (PAHs) in ambient air. MECOPs were deployed at six sites in Pohang, Korea for 37 days (August 9, 2005–September 14, 2005). Fluorene, phenanthrene, anthracene, and fluoranthene were dominant PAHs with the highest contribution of phenanthrene (59%) to the total amount of vapor-phase PAHs. The spatial distribution of total PAHs in the vapor phase ranging from 76 to 1077 ng MECOP −1 and air dispersion modeling suggested that the steel complex was the major PAH source in Pohang. It was revealed that the major wind directions rather than the distance from the steel complex were a significant factor affecting the levels of PAHs at the sampling sites. Finally, we tried to convert MECOP concentrations (ng MECOP −1) to air concentrations (ng m −3) with the modified sampling rates (m 3 day −1). This study demonstrates again that passive air samplers are useful tools for spatially resolved and time-integrated monitoring of semivolatile organic compounds (SOCs) in ambient air.

Hot gas cleaning in power stations by using electron beam technology. Influence on PAH emissions

The Electron Beam Technology (EBT), proven treatment for SO 2 and NO x removal, is applied to different power stations as a hot gas cleaning system. In this paper, an assessment of this technique installed in a Bulgarian power station on organic emissions is analyzed. The Polycyclic Aromatic Hydrocarbons (PAH) content, not only emitted in the gas phase but also trapped in the solid phase, has been carried out before and after the irradiation. The main aim has been to know whether the EBT affects organic emissions, like PAH, as it happens with inorganic pollutants, like SO 2 and NO x , studying EBT effects from an organic environmental point of view. The PAH quantification was performed by using a very sensitive analytical technique, gas chromatography with mass spectrometry mass spectrometry detection (GC–MS–MS). Results showed that PAH are influenced by the EBT showing a reduction of the most volatile PAH in the gas phase. With regard to the solid by-products obtained after the irradiation, fertilizers, similar PAH concentration to the fly ashes produced when no irradiation is applied were found. These fertilizers were considered like unpolluted soils being adequate for agriculture applications with PAH concentrations below the target value set up by the Dutch government.

Flue gas cleaning in power stations by using electron beam technology. Influence on PAH emissions

The electron beam technology (EBT), proven treatment for SO 2 and NO x removal, is applied to different power stations as hot gas cleaning system. In this paper, an assessment of this technique installed in a Bulgarian power station on organic emissions is analyzed. The Polycyclic Aromatic Hydrocarbons (PAH) content, not only emitted in the gas phase but also trapped in the solid phase, has been carried out before and after the irradiation. The main aim has been to know whether the EBT affects organic emissions, like PAH, as it happens with inorganic pollutants, like SO 2 and NO x , studying EBT effects from an organic environmental point of view. The PAH quantification was performed by using a very sensitive analytical technique, gas chromatography with mass spectrometry mass spectrometry detection (GC–MS–MS). Results showed that PAH are influenced by the EBT showing a reduction of the most volatile PAH in the gas phase. PAH concentrations in the fertilizers obtained after irradiation were found to be similar to those in the fly ashes produced when no irradiation is applied. These fertilizers were considered like unpolluted soils being adequate for agriculture applications with PAH concentrations below the target value set up by the Dutch government.

Ambient Concentrations and Gas/Particle Partitioning of Polycyclic Aromatic Hydrocarbons in an Urban Site in Turkey

Atmospheric samples were collected between July 2004 and May 2005 in Bursa, Turkey, when there was no rain, and analyzed for gas and particle concentrations of polycyclic aromatic hydrocarbons (PAHs). This study targeted 15 PAH compounds. Vapor-phase PAH compositions were dominated by the more volatile PAHs, relative to the particle phase. On average, 76% of the total (gas + particulate) PAH concentration was in the vapor phase. Average total PAH concentration was 298 ± 418 ng/m3. The large seasonal concentration fluctuation was attributed to residential heating, vaporization, industrial activities, and meteorological conditions. The measured average seasonal concentrations were 55 ± 40, 187 ± 202, 645 ± 588 and 148 ± 132 ng/m3 for summer, fall, winter, and spring, respectively. The partitioning of PAHs between gas and particle phases was investigated employing the Junge-Pankow model. Plots of log gas/particle partition coefficient (K p ) versus log liquid vapor pressures (PL o) had reasonable correlations for individual samples. Experimentally determined K p values were compared with the result obtained using absorption (octanol–air partition coefficient [K OA ]) into aerosol organic matter and adsorption (K SA + K OA ) onto soot carbon models. Experimentally determined K p values were generally in the same range with the ones obtained from the models.

Quantification of volatile PAHs present at trace levels in air flow by aqueous trapping—SPE and HPLC analysis with fluorimetric detection

In the context of a European project, a new approach of sampling of volatile polycyclic aromatic hydrocarbons (PAHs) from air was developed. In fact, the aim of this project was to test the efficiency of an air cleansing prototype reactor, which was operating by non-thermal plasmolysis. With an eye to model the atmosphere ejected by the prototype, we needed to vaporise the volatile PAHs in an air stream at concentrations as low as those recommended by European Directives (96/62/CE) for PAHs in ambient air (i.e. 1 ng m −3). Our strategy was based on the analysis of PAHs trapped in an aqueous medium, in order to avoid important losses of volatile compounds observed during the delicate desorption–concentration step when classical solid supports are used. Then a study was carried out to determine: the design of the collecting part, the flow-rate of the air sampling, the nature and concentration of chemical additives used to enhance PAH solubility in water. The very highly diluted aqueous media obtained after the bubbling step were concentrated by solid-phase extraction (SPE) on hydrophobic cartridges and analysed on-line by reversed-phase HPLC with UV and fluorimetric detections. Lastly, the sampling technique was directly applied to the outlet of the air cleansing prototype and the analysis after 3–6 h of non-thermal plasmolysis showed that the target volatile PAHs were not present in an air stream initially polluted by volatile organic compounds.

Determination of octanol–air partition coefficients and supercooled liquid vapor pressures of PAHs as a function of temperature: Application to gas–particle partitioning in an urban atmosphere

Octanol–air partition coefficients ( K OA) for 14 polycyclic aromatic hydrocarbons (PAHs) were determined as a function of temperature using the gas chromatographic retention time method. log K OA values at 25° ranged over six orders of magnitude, between 6.34 (acenaphthylene) and 12.59 (dibenz[ a,h]anthracene). The determined K OA values were within factor of 0.7 (dibenz[ a,h]anthracene) to 15.1 (benz[ a]anthracene) of values calculated as the ratio of octanol–water partition coefficient to dimensionless Henry's law constant. Supercooled liquid vapor pressures ( P L) of 13 PAHs were also determined using the gas chromatographic retention time technique. Activity coefficients in octanol calculated using K OA and P L ranged between 3.2 and 6.2 indicating near-ideal solution behavior. Atmospheric concentrations measured in this study in Izmir, Turkey were used to investigate the partitioning of PAHs between particle and gas-phases. Experimental gas–particle partition coefficients ( K p) were compared to the predictions of K OA absorption and K SA (soot–air partition coefficient) models. Octanol-based absorptive partitioning model predicted lower partition coefficients especially for relatively volatile PAHs. Ratios of measured/modeled partition coefficients ranged between 1.1 and 15.5 (4.5±6.0, average±SD) for K OA model. K SA model predictions were relatively better and measured to modeled ratios ranged between 0.6 and 5.6 (2.3±2.7, average±SD).

An Assessment of Occupational Exposure to Polycyclic Aromatic Hydrocarbons in the UK

A cross-industry occupational hygiene survey was commissioned by the Health and Safety Executive (HSE) to determine the levels of polycyclic aromatic hydrocarbon (PAH) exposure in UK industry and to determine if one or more target analytes were suitable as markers for assessing total exposure to PAHs. There were no broadly applicable UK exposure standards for assessing total exposure to PAHs. Until 1993 a guidance value for assessing exposure in coke ovens only, where PAH exposure is known to be the highest, was based on gravimetric analysis of cyclohexane-soluble material. Biological monitoring based on urinary 1-hydroxypyrene (1-OHP) is widely reported to be an effective indicator of exposure by both dermal and inhalation routes but there was no UK guidance value. The survey involved an occupational hygiene study of 25 sites using both airborne monitoring of a total of 17 individual PAHs and biological monitoring. The results showed 8 h TWA levels of total PAH in air ranged from 0.4 to 1912.6 microg m(-3) with a GM of 15.8 microg m(-3). The profile of PAHs was dominated by naphthalene, the most volatile 2-ring PAH. Airborne benzo(a)pyrene (BaP) correlated well (r(2) = 0.971) with levels of carcinogenic 4-6 ring PAHs and was an effective marker of exposure for all industries where significant particle bound PAH levels were found and, in particular, for CTPV exposure. The 8 h TWA levels of BaP ranged from <0.01 to 6.21 microg m(-3) with a GM of 0.036 microg m(-3); 90% were <0.75 microg m(-3) and 95% were <2.0 microg m(-3). Two hundred and eighteen urine samples collected from different workers at the end of shift and 213 samples collected pre-shift next day were analysed for 1-OHP. Levels of 1-OHP in end-of-shift samples were generally higher than those in pre-shift-next-day samples and showed a good correlation (r(2) = 0.768) to airborne BaP levels if samples from workers using respiratory protection or with significant dermal exposure were excluded. Urinary 1-OHP in end-of-shift samples ranged from the limit of detection (0.5 micromol mol(-1) creatinine) to 60 micromol mol(-1) creatinine with a mean of 2.49 micromol mol(-1) and a 90th percentile value of 6.7 micromol mol(-1) creatinine. The highest 1-OHP levels were found in samples from workers impregnating timber with creosote where exposure was dominated by naphthalene. If the 11 samples from these workers were excluded from the dataset, the 90% value for end-of-shift urine samples was 4 micromol mol(-1) creatinine (n = 207) and this value has since been adopted by the HSE as a biological monitoring benchmark value.

Unregulated Emissions from Compressed Natural Gas (CNG) Transit Buses Configured with and without Oxidation Catalyst

The unregulated emissions from two in-use heavy-duty transit buses fueled by compressed natural gas (CNG) and equipped with oxidation catalyst (OxiCat) control were evaluated. We tested emissions from a transit bus powered by a 2001 Cummins Westport C Gas Plus 8.3-L engine (CWest), which meets the California Air Resources Board's (CARB) 2002 optional NOx standard (2.0 g/bhp-hr). In California, this engine is certified only with an OxiCat, so our study did not include emissions testing without it. We also tested a 2000 New Flyer 40-passenger low-floor bus powered by a Detroit Diesel series 50G engine (DDCs50G) that is currently certified in California without an OxiCat. The original equipment manufacturer (OEM) offers a "low-emission" package for this bus that includes an OxiCat for transit bus applications, thus, this configuration was also tested in this study. Previously, we reported that formaldehyde and other volatile organic emissions detected in the exhaust of the DDCs50G bus equipped with an OxiCat were significantly reduced relative to the same DDCs50G bus without OxiCat. In this paper, we examine othertoxic unregulated emissions of significance. The specific mutagenic activity of emission sample extracts was examined using the microsuspension assay. The total mutagenic activity of emissions (activity per mile) from the OxiCat-equipped DDC bus was generally lower than that from the DDC bus without the OxiCat. The CWest bus emission samples had mutagenic activity that was comparable to that of the OxiCat-equipped DDC bus. In general, polycyclic aromatic hydrocarbon (PAH) emissions were lower forthe OxiCat-equipped buses, with greater reductions observed for the volatile and semivolatile PAH emissions. Elemental carbon (EC) was detected in the exhaust from the all three bus configurations, and we found that the total carbon (TC) composition of particulate matter (PM) emissions was primarily organic carbon (OC). The amount of carbon emissions far exceeded the PM-associated inorganic element emissions, which were detected in all exhaust samples, at comparatively small emission rates. In summary, based on these results and those referenced from our group, the use of OxiCat for the new CWest engine and as a retrofit option for the DDCs50G engine generally results in the reduction of tailpipe toxic emissions. However, the conclusions of this study do not take into account OxiCat durability, deterioration, lubricant consumption, or vehicle maintenance, and these parameters merit further study.

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: Evaluation of sampling artefact

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO 2 ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[ a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.

Polycyclic Aromatic Hydrocarbons in the Atmosphere of the Eastern Mediterranean

Atmospheric processes governing the fate of the polycyclic aromatic hydrocarbons (PAHs) in the atmosphere of the Eastern Mediterranean were studied for a two-year period (2000-2001). Atmospheric samples were collected off-shore over the Eastern Mediterranean Sea as well as at a background station in Northeastern Crete, Greece. PAH total concentration varied from 4.1 to 57.2 ng m(-3), with >90% in the gas phase. Gas-to-particle distribution of PAHs was correlated (R2 0.75-0.98, p < 0.001) with their subcooled vapor pressure. Seasonal changes in the total concentration of PAHs were not observed, while the origin of air mass was the dominant factor determining their atmospheric concentration levels. Air masses, originating from central and eastern Europe, were associated with the highest PAH concentrations. Gas-to-particle distribution of sigmaPAHs correlated well (R2 0.75-0.98, p < 0.001) with their subcooled vapor pressure. Tropospheric ozone concentration correlated with the vapor-phase PAH concentration (p < 0.001) but less (p < 0.01) with the particulate PAH concentration. Distribution of volatile PAHs over the Eastern Mediterranean basin was uniform. Conversely, particulate PAH concentrations were higher at sampling sites located close to urban centers. Calculated relative removal rates of PAHs associated with particles were significantly higher than those of volatile members.

Evaluating emission levels of polycyclic aromatic hydrocarbons from organic materials by analytical pyrolysis

A procedure in off-line analytical pyrolysis was investigated for the rapid determination of polycyclic aromatic hydrocarbons (PAHs) evolved from thermal degradation of organic materials. Samples spiked with perdeuterated PAHs were pyrolysed at 1000 °C for 60 s by means of a resistively heated filament pyrolyser inserted into a glass chamber connected to a cartridge with a sorbent (XAD-2 resin). PAHs trapped onto the resin were extracted with dichloromethane and analysed by gas chromatography–mass spectrometry (GC–MS). The analytical performance of the overall procedure (precision, recovery, effect of experimental parameters) was evaluated by pyrolysing a bituminous coal certified reference material (CRM). Emission levels of naphthalene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphtylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene were determined for bituminous and anthracite coals, tyre, and cellulose. Despite some limitations, the method was adequate to the purpose of quantitatively measuring the tendency of various materials to release volatile PAHs upon heating.

Estrogenic Activity in Sediments from European Mountain Lakes

Superficial and bottom sediment samples from 83 European mountain lakes, ranging from Norway to the Pyrenees and East Europe, were tested for estrogenic compounds by the recombinant yeast assay. The results showed widespread potential estrogenic activity arriving at remote lakes. Tatra Mountains (Slovakia) and Scotland Highlands were the regions with the highest prevalence of lakes with high estrogenic values. Comparison of the estrogenic activity in the superficial layer of sediments with pre-industrial age sections showed that estrogenic compounds were predominantly deposited in recent times. Chemical analysis showed that highly estrogenic sediments were significantly enriched in both polycyclic aromatic hydrocarbons (PAH) and organochlorine compounds. For PAH, enrichment ratios in highly estrogenic samples versus nonestrogenic ones were inversely correlated with the vapor pressure value for each compound, indicating a significant relationship between estrogenicity and accumulation of less volatile PAH. Two PAH of predominantly diagenetic origin, retene and perylene, did not show specific enrichment in estrogenic samples. Principal component analysis revealed a strong correlation between estrogenic activity and the presence of contaminants of anthropogenic origin. These data reveal significant amounts of estrogenic compounds in remote lakes, relate them to the overall human activity, and suggest that they may affect organisms inhabiting these ecosystems.

Pinus nigra and Pinus pinaster needles as passive samplers of polycyclic aromatic hydrocarbons

Nine polycyclic aromatic hydrocarbons (PAHs) were analysed in pine needles of different ages (from 6 to 30 months) collected from two species, Pinus nigra and Pinus pinaster, in seven sites located along a transect from a suburban to a rural area of Genoa (Italy). In all sites and for both species, concentrations of more volatile PAHs (phenanthrene, anthracene, fluoranthene, pyrene) were higher than those for other less volatile PAHs, which are preferentially sorbed to airborne particulates (benzo[ a]anthracene, chrysene, benzofluoranthenes, benzo[ a]pyrene). Concentrations of total PAHs found in P. nigra in the rural sites were, on the average, 2.3 times higher than those in P. pinaster growing nearby. In both pine species, concentrations of volatile PAHs increased according to needle age. Annual trends of other PAHs were more variable, with a general decrease in older needles. P. pinaster needles are shown to be more reliable passive samplers, since they are more resistant to plant diseases, and considerable variation in PAH concentration was observed in P. nigra needles with moulds and fungi.

Optimizing detection limits for the analysis of petroleum hydrocarbons in complex environmental samples.

To evaluate the sources, transport, bioremediation, fate, and effects of spilled petroleum and petroleum products, environmental studies often measure parent and alkylated polycyclic aromatic hydrocarbons (PAH), alkanes, and chemical biomarkers (e.g., triterpanes). Accurate data for low analyte concentrations are required when environmental samples contain hydrocarbons from multiple sources that need to be resolved and quantified. The accuracy and usefulness of the analyses can be improved by lowering the method detection limits (MDLs) for these compounds. Misidentification of hydrocarbon source can result when the MDLs are too high. Modifications to standard analytical methods (i.e., U.S. Environmental Protection Agency Method 8270) can lower MDLs by factors ranging from 10 to 1000. This reduction has important implications for ecological-risk assessments. Modifications having the greatest impact on the MDL include GCMS analysis in the selected-ion-monitoring mode (SIM), increased sample size, column cleanup of the extract, and decreased preinjection volume (volume of final extract prior to injection into instrument). In one study in which a benthic sediment sample was spiked with low levels of topped (heated to remove more volatile PAH that are naturally enriched in crude oil) Alaska North Slope crude, MDLs for individual PAH analytes and biomarkers were determined to be less than 0.5 ng/g (ppb) dry weight and less than 5 ppb dry weightfor individual alkanes. Similar results were obtained when the sediment was spiked with the 16 EPA priority pollutants. In addition, a method has been developed to estimate MDLs for source-specific alkylated PAH analytes and chemical biomarker compounds for which standards are not commercially available or are prohibitively expensive. These improved analytical techniques have been used to identify and quantify low levels of hydrocarbons, derived from both natural and anthropogenic sources, found in the benthic sediments of Prince William Sound, AK.

Phase and size distribution of polycyclic aromatic hydrocarbons in diesel and gasoline vehicle emissions.

Emission measurements were obtained for a variety of military vehicles at Hill Air Force Base (Ogden, UT) in November 2000 as part of a Strategic Environmental Research and Development Program. Aircraft ground support equipment vehicles using gasoline, diesel, and JP8 fuels were tested using chassis dynamometers under predetermined load. The exhaust from the tested vehicle was passed to a dilution tunnel where it was diluted 30-40 times and collected using Micro-Orifice Uniform Deposit Impactor (MOUDI) fitted with aluminum substrates, an XAD-coated annular denuder, and a filter followed by a solid adsorbent. All MOUDI substrates were analyzed for mass and for organic and elemental (EC) carbon by the thermal/optical reflectance method and for polycyclic aromatic hydrocarbons (PAHs) by GC/MS. Black carbon was measured with a photoacoustic instrument. The denuder and filter/solid adsorbent samples were analyzed for semivolatile PAH. Overall, there is more mass and higher EC contribution when the vehicle is run under higher load in comparison with the low load. However, older vehicles generally show more mass and EC emissions than newer vehicles, and there is a shift toward smaller particle sizes for the low load, which is most pronounced for newer vehicles. The particle-associated semivolatile PAHs and nonvolatile four-through six-ring PAHs are present predominantly on the submicron particles collected on MOUDI stages 0.1-0.18, 0.18-0.32, and 0.32-0.56 microm. For the low-load runs, the distribution of PAHs seems to be shifted toward smaller size particles. The gas-particle phase distribution of semivolatile PAHs depends also on the engine loading. For idle, not only are the more volatile two- and three-ring PAHs, from naphthalene to dimethylphenanthrenes, retained on the denuder portion, but also less volatile four-ring PAHs, such as fluoranthene and pyrene, are retained by the denuder at the 80-90% range, which implies that they are present predominantly in the gas phase. In contrast, for engines under high loads, a much larger portion of three- and four-ring PAHs are partitioned to the particle phase.

Atmospheric deposition of polycyclic aromatic hydrocarbons to Atlantic Canada: geographic and temporal distributions and trends 1980-2001.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants. The semivolatile organic compounds may disperse into the atmosphere by direct input from several sources such as the burning of fossil fuels, from motor vehicle emissions, and forest fires. Once in the atmosphere, they may travel great distances before being deposited to the earth's surface by the scavenging action of rain and snow. Up to 14 PAHs were determined in wet precipitation samples collected monthly from five sites in the four Canadian Atlantic Provinces during 1980-2001. The relatively more volatile PAHs (phenanthrene, fluoranthene, naphthalene, and pyrene) were predominant in the samples. Significant (P < 0.05) spatial variations in the deposition of some PAHs were observed among sites, but there were no consistent geographic patterns. Seasonal patterns were discernible with peak deposition for sigma6&14 PAHs occurring during the colder months of the year (December to March) and coinciding with higher energy consumption for heating and transport. The monthly volume weighed mean concentration for sigma6 PAHs has declined steadily since the mid-1980s at Kejimkujik National Park in southwest Nova Scotia, with a calculated half-life of 6.4 +/- 0.3 years. The maximum annual deposition flux of 20 microg m(-2) yr(-1) reached in 1985 for sigma6 PAHs decreased approximately 1 order of magnitude by the year 2000. The decrease in sigma6&14 PAHs for the region was found to be correlated (P < 0.05) with decreasing sulfate ion concentrations in the precipitation. The implementation of air pollution abatement programs in Canada, the United States, and elsewhere, switching to cleaner sources of energy and improved technology during the pastfew decades is most likely responsible for the observed decline.

POLYCYCLIC AROMATIC HYDROCARBONS OF DIESEL AND GASOLINE EXHAUST AND DNA ADDUCT DETECTION IN CALF THYMUS DNA AND LYMPHOCYTE DNA OF WORKERS EXPOSED TO DIESEL EXHAUST

Particles present in urban air pollution are mainly derived from diesel- and gasoline-fueled vehicles. Exhaust emission is able to cause several health effects in humans including mutagenicity and carcinogenicity. Polycyclic aromatic hydrocarbons (PAHs) were measured in diesel and gasoline particulate extracts and DNA binding to CT DNA (±S9 and ±XO) was investigated. A large difference in content of 14 PAHs in diesel and gasoline extracts was observed, showing higher concentration of 14 PAHs, 6 carcinogenic PAHs, benzo[a]pyrene (B[a]P) in diesel than in gasoline extracts. Selected PAH standards of B[a]P, benzo[c]fluoranthene (B[c]F), and 3-nitrobenzanthrone (NBA) were used in 32P-postlabeling/polyacrylamide gel electrophoresis (PAGE) technique to identify CT DNA adducts formed by diesel particulate extracts. CT DNA adduct formation was higher for diesel extracts in comparison with gasoline extracts; however, no clear origin of DNA adducts derived from B[c]F-, 3-NBA-, B[a]P was detected. 32P-postlabeling/PAGE was a useful assay for analyzing and identifying PAH-DNA adducts. Occupational exposure to particulate and volatile PAH concentrations were evaluated using personal air samples and lymphocyte DNA adducts as markers of exposure. Overall air PAH concentrations were low in all eight workplaces, consisting of 97% of vapor phase compounds. DNA adducts analyzed by 32P-postlabeling assay were compared between the butanol and nuclease P1 enrichment procedures. Only in winter samples of exposed workers, butanol extraction revealed significantly higher adduct levels in comparison with those of control persons. No differences in adduct levels between exposed and control persons in summer were detected by using either butanol extraction or nuclease P1 treatment. Total concentrations of particulate and volatile PAHs measured in eight workplaces in winter showed a significant correlation with total DNA adducts analyzed in workers' lymphocytes (r = 0.852N = 8, p = .007).

Gas/particle partitioning of seven volatile polycyclic aromatic hydrocarbons in a heavy traffic urban area

Air samples (vapor- and particle-phase) were taken for 19 sampling events during the period from December 1997 to July 1998 in an urban site in the center of Athens. The urban site is densely populated and characterized by heavy traffic circulation and elevated concentrations of VOCs, NO x , CO and smoke. Seven volatile polycyclic aromatic hydrocarbons (PAHs) were determined in samples. The temperature dependence of gas-phase atmospheric concentration of PAHs, C g, was investigated using diagrams of natural logarithm of partial pressures (ln P) vs. reciprocal mid-point temperatures. For the six of seven volatile PAHs, the temperature dependence of ln P was statistically significant (at least at the 90% confidence level) and the temperature accounted for 21–67% of the variability in gas-phase concentrations. The gas-phase concentration C g of the very volatile PAHs was affected more significantly by changes in temperature, but the variation of the less-volatile PAHs fluoranthene and pyrene C g, was better explained by changes in temperature. The temperature dependence of gas/particle partitioning constant K P was also examined. Regressions of log( K P) −1 vs. T −1 for fluorene, fluoranthene and pyrene were classified into two different temperature ranges. The gas/particle partitioning of PAHs was studied by correlating the partition constant to the sub-cooled liquid saturation vapor pressure ( P L o). The Junge adsorption model underestimated the particle fraction of volatile PAHs probably due to the presence of non-exchangeable fraction. Slopes ( m r) of the regressions log K P vs. log P L o were different from the value −1 as Pankow's theory predicts. The short distance between the sampling point and the emission sources is also estimated to be a factor that causes deviations from the theoretical value. Evidence that atmospheric conditions favorable for secondary aerosol formation coincide with higher value of m r, was provided by limited sampling events. An interrelation was found to exist between the m r values, allowing the prediction of the gas/particle partitioning of a series of seven PAHs by the measurement of a single PAH partitioning.

Use of ionic liquids for liquid-phase microextraction of polycyclic aromatic hydrocarbons.

This paper demonstrates, for the first time, that ionic liquids (IL) such as 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)MIM][PF(6)]) are excellent extraction solvents in liquid-phase microextraction (LPME). The unique properties of nonvolatility and adequate viscosity allow IL to be conveniently adopted as extraction solvents in both direct-immersion and headspace LPME. Model compounds, polycyclic aromatic hydrocarbons (PAHs), are conveniently and rapidly enriched in a 3-microL drop of [C(8)MIM][PF(6)] suspended on the tip of a microsyringe followed by liquid chromatographic determination. Compared to 1-octanol, a larger volume drop of [C(8)MIM][PF(6)] can be formed and survive for a longer extraction time; therefore, a much higher enrichment factor for PAHs can be reached. For low-volatility PAHs, direct-immersion LPME provides higher enrichment factors than that of headspace LPME. However, the enrichment factor obtained by headspace LPME was almost 3-fold of that by direct-immersion LPME in a 30-min extraction of the most volatile PAH, naphthalene. For 30-min direction-immersion LPME of EPA priority PAHs, the enrichment factor, correlation coefficient (R(2)), and reproducibility (RSD, n = 5) were in the range of 42-166, 0.9169-0.9976, and 2.8-12%, respectively. Considering that IL can be easily prepared from relatively inexpensive materials and tuned by combination of different anions and cations for task-specific extraction of analytes from various solvent media, this proposed method should have great potentiality in sample preparation. Furthermore, the nonvolatility of IL makes it potentially useful for headspace LPME of volatile analytes.

Sea breeze modulated volatilization of polycyclic aromatic hydrocarbons from the Masnou Harbor (NW Mediterranean Sea).

Harbors, marinas, and coastal environments are impacted by important pollutant loadings, particularly of polycyclic aromatic hydrocarbons (PAHs). Air-water exchange is an important process driving the environmental fate of organic pollutants in aquatic environments. However, its relevance as a factor affecting the environmental fate of pollutants from harbor sediments and waters has not been properly assessed, so far, except for few coastal environments. The objective of this study is to quantify the importance of volatilization losses of PAHs from harbor sediments and waters and to study the potential role of sea breeze as a modulator of air-water exchange in coastal environments. The results show that volatilization fluxes from a medium size marina located in the NW Mediterranean sea are relatively high in comparison to those observed in other aquatic systems, particularly for the low molecular weight (MW) compounds. This is consistent with PAHs profiles observed in harbor sediments, which are depleted by the lower MW hydrocarbons. Therefore, volatilization is an important loss of low MW PAHs such as phenanthrene, methyl phenanthrene, dibenzothiophene, etc. Indeed, these PAHs have a residence time of few days in the harbor waters and sediments. Finally, the diurnal trends in volatilization fluxes mimics that of the sea breeze influenced wind speed. These results show the important role that the diurnal sea breeze exerts on the environmental fate of pollutants such as PAHs in coastal environments as a modulator of air-water exchange and as a potential driver of transport of pollutants between adjacent coastal and terrestrial environments.