The mutagenic activity of thirty polycyclic aromatic hydrocarbons (PAH) and oxides in urban airborne particulates

Data are presented on the mutagenicity of an organic extract of a composite sample of urban air particulates and of thirty PAH compounds in such samples, including four quinone derivatives, isolated quantitatively by thin-layer chromatography and identified by fluorescence or other spectral techniques. Mutagenic activity was determined by the Ames assay, using histidine auxotrophs of Salmonella typhimurium strains TA98, TA100, TA1537 and TA1538. All compounds were dissolved in dimethyl sulfoxide (DMSO) which was the least toxic of eight organic solvents tested.The mutagenic activity of a benzene extract of suspended particulates from the air of Hamilton, Ontario was significantly greater with strain TA98 than with strain TA100, suggesting the presence of more frame-shift acting mutagens. The mutagenic response of this extract was similar with and without S-9 activation.Mutagenic tests on the 30 PAH compounds indicated that only the benzo(a)pyrene quinones were direct acting mutagens. All of the chemical compounds were tested with and without S-9 activation. The following PAH showed unequivocal mutagenic activity, with S-9 activation: benz(a)anthracene, benzo-(a)pyrene, benzo(ghi)perylene, benzo(rst)pentaphene, benzophenanthrene, chrysene, 1, 2, 3, 4-dibenzanthracene, 2, 3, 6, 7-dibenzanthracene, and 3-methyl cholanthrene. The quinones of 1, 6-; 3, 6-; and 6, 12-benzo(a)pyrenes showed weak mutagenic activity but 3, 6-benzo(a)pyrene elicited also a photodynamic response.     

Polynuclear aromatic hydrocarbons,phenols, and trace metals in selected soil profiles and plant bioindicators in the Holy Cross Mountains,south-central Poland

This report presents the results of PAH, phenol, and selected trace element (Cd, Cu, Hg, Pb, S, and Zn) determinations on detailed soil profiles and associated plant bioindicators (including lichen Hypogymnia physodes, moss Hylocomium splendens, pine Pinus sylvetris) from the three most representative habitats in the Holy Cross Mts, south-central Poland. This study is only part of a larger ongoing environmental study that includes complex sulfur isotope and element determinations in three national parks in N, central and S parts of Poland. The highest concentrations of PAHs (1887 ppb) and numerous trace elements are found in the organic horizon-O and humic horizon-A of each soil type. Different plant species and their individual tissues reveal considerable variability in the concentration of PAHs, phenols and elements examined. Most of the H. physodes thalli also reveal higher concentrations of individual hydrocarbons and some elements (including S and Zn) than their host bark. The highest concentration levels of phenols (1217 ppb) are noted in the 1-year pine needles. Most of the PAHs and elements examined seem to be of anthropogenic origin. The only exception is the distribution pattern of elements in southwestern part of the study area, which is linked to the local bedrock geochemical anomaly. The results of this study indicate that the content of PAHs, Cd, Cu, Hg, Pb, S and Zn in the soils and plant bioindicators examined has not changed considerably since 1998.     

Trace analysis for aromatic hydrocarbons in natural waters

A method for trace analysis of volatile aromatic hydrocarbons in natural water is described. The method is based on sparging water samples with nitrogen, adsorption of hydrocarbons on activated charcoal, followed by desorption into carbon disulfide and gas chromatographic analysis. The sensitivity of the method reaches into the 0.1 to 0.2 μg/L concentration range for individual aromatic hydrocarbons. The accuracy and reliability of the method was validated. The method was used in three field studies: dispersion of aromatic hydrocarbons discharged from the Trans-Alaska Pipeline southern terminal throughout Port Valdez; survey of the Atigun River Watershed after oil spill on June 10, 1979; and chemical characterization of treated effluents from offshore oil extraction platforms in the Gulf of Mexico.     

Genotoxicity of syrian hamster lung cells treated in vivo with diesel exhaust particulates

Polycyclic aromatic hydrocarbons extracted and concentrated from diesel exhaust particulates have been shown to be mutagenic and carcinogenic, but attempts to induce pulmonary tumors through chronic inhalation of diesel exhaust by experimental animals have failed. We have attempted to resolve this incongruity by measuring chromosomal damage in lung tissue of chronically exposed hamsters, using the highly sensitive test for genotoxic chemical agents, sister chromatid exchange (SCE) analysis. To determine the degree of responsiveness of the test system to both diesel exhaust particulates and benzo(a)pyrene (BaP), these agents were instilled intratracheally into anesthetized hamsters as suspensions in 0.25 ml volumes of Hank's balanced salt solution (HBSS). Lung tissues from these animals were subsequently cultured in vitro and chromosomes from the resulting cell divisions were scored for exchanges of chromatin between sister chromatids. Control animals, treated weekly with 0.25 ml of BSS for 10 weeks, showed an average value of 12 SCE's per cell, while animals treated weekly with 200 ng BaP over a 10-week period showed an average of 17 SCE's per cell. HBSS, given as a single treatment, also produced an average of 12 SCE's per cell in control animals, but animals treated with a single instillation of 12.5 μg BaP showed an average SCE value of 19. These data confirmed that the procarcinogen BaP can be metabolically activated by lung cells in vivo and also demonstrated the efficacy of using this technical approach to study the effect of chemical mutagens that enter the lungs. Diesel exhaust particulates, administered in a range from 0 to 20 mg per hamster over a 24 h exposure period, produced a linear SCE dose-response ranging from 12 to 26 SCE's per metaphase. This curve suggested that a concentration of 3 mg of diesel particulates per hamster would not produce a statistically significant increase in SCE's above control values. One group of 8 hamsters, chronically exposed to diesel exhaust particulates for 3 months showed an average of 12 SCE's per cell. This was equivalent to a set of 5 control animals which also showed an average of 12 SCE's per cell. Although the scope of this study was limited, the data demonstrated that diesel exhaust particulates can induce genotoxic damage but a 3-month exposure to 6 mg/m³ of diesel exhaust particulates was insufficient to produce measurable mutagenic changes in lung cells. This negative response is consistent with the results from other studies in which similar exposures failed to produce pulmonary tumors.     

A review of occurrences and treatment of polynuclear aromatic hydrocarbons in water

The scope of PAH contamination of raw, finished, and distributed waters is reviewed. The concentrations of PAHs in drinking water sources range from nanogram to microgram-per-liter quantities. Conventional treatment (flocculation, sedimentation, chlorination, and filtration) appears to substantially reduce total PAH concentrations present at higher concentrations in source waters. A major factor in this reduction is the removal of PAHs adsorbed onto particulate matter. The role of chlorination is not clear and reactions of PAHs with chlorine may in fact produce products which themselves are deleterious. Activated carbon can further assist in PAH removal. However, it may be inappropriate for treatment of PAHs present at low concentrations. Water entering the distribution system can become recontaminated via contact with reservoirs and pipes coated with coal-tar or asphalt based products.     

Polycyclic aromatic hydrocarbons and effects on marine organisms in the Istanbul Strait

Surficial sediments and mussels (Mytilus galloprovincialis) from the Istanbul Strait and Marmara Sea were analysed for sixteen parent polycyclic aromatic hydrocarbon (PAH) contents by gas chromatography-mass spectrometry (GC-MS) employing isotope dilution technique. Microalgae toxicity testing was applied to sediment elutriates and biological responses in terms of filtration rate and lysosomal stability were measured in mussels. Total PAH concentrations ranged from 2.1 to 3152 ng g^? 1 dry wt in sediments and from 43–601 ng g^? 1 wet weight in mussels. Molecular indices of phenanthrene/ anthracene, fluoranthene/pyrene and benzo(a)anthracene/chrysene were used to differentiate between pyrolytic and petroleum origin. Results showed that most of the contamination originates from high temperature pyrolytic inputs with some slight contribution of petrogenic PAH. PAH in sediments were frequently lower than the National Oceanic and Atmospheric Administration (NOAA)–ERM (Effects Range Medium) index. Results of sediment elutriate toxicity testing and biomarkers indicate that the cause of negative effects in sediments may result from different classes of pollutants and does not only relate with PAH contamination. Mussels from most of the stations showed both reduced lysosomal membrane stability and filtration rate indicating disturbed health although the two biomarker results did not always complement each other. The effect studies showed that the pollutants in the strait ecosystem have more pronounced effects in the middle parts than those at the Black Sea entrance.     

Partitioning coefficients of polycyclic aromatic hydrocarbons in stack gas from a municipal incinerator

In this study, solid-gas partitioning coefficients of PAHs on fly ash in stack gas from a municipal incinerator were determined according to elution analysis with gas-solid chromatography. The fly ash from the electrostatic precipitator was sieved and packed into a 1/4 inch (6.3 mm) pyrex column. Elution analysis with gas-solid chromatography was conducted for three PAHs, Napthalene, Anthracene, and Pyrene. The temperature for elution analysis was in the range of 100°C to 300°C. V_g, specific retention volume obtained from elution analysis, and S, specific surface area of fly ash measured by a surface area measurement instrument, were used to estimate the solid-gas partitioning coefficient, K_R. In addition, the relationships between K_R and temperature and K_R and PAH concentrations were investigated.     

Monitoring exposure to polycyclic aromatic hydrocarbons in an Australian population using pooled urine samples

Integrated exposure to polycyclic aromatic hydrocarbons (PAHs) can be assessed through monitoring of urinary mono-hydroxylated PAHs (OH-PAHs). The aim of this study was to provide the first assessment of exposure to PAHs in a large sample of the population in Queensland, Australia including exposure to infant (0–4 years). De-identified urine specimens, obtained from a pathology laboratory, were stratified by age and sex, and pooled (n = 24 pools of 100) and OH-PAHs were measured by gas chromatography–isotope dilution–tandem mass spectrometry. Geometric mean (GM) concentrations ranged from 30 ng/L (4-hydroxyphenanthrene) to 9221 ng/L (1-naphthol). GM of 1-hydroxypyrene, the most commonly used PAH exposure biomarker, was 142 ng/L. The concentrations of OH-PAHs found in this study are consistent with those in developed countries and lower than those in developing countries. We observed no association between sex and OH-PAH concentrations. However, we observed lower urinary concentrations of all OH-PAHs in samples from infants (0–4 years), children (5–14 years) and the elderly (> 60 year old) compared with samples from other age groups (15–29, 30–44 and 45–59 years) which may be attributed to age-dependent behaviour-specific exposure sources.     

Exposure to multiple sources of polycyclic aromatic hydrocarbons and breast cancer incidence

BackgroundDespite studies having consistently linked exposure to single-source polycyclic aromatic hydrocarbons (PAHs) to breast cancer, it is unclear whether single sources or specific groups of PAH sources should be targeted for breast cancer risk reduction.ObjectivesThis study considers the impact on breast cancer incidence from multiple PAH exposure sources in a single model, which better reflects exposure to these complex mixtures.MethodsIn a population-based case-control study conducted on Long Island, New York (N = 1508 breast cancer cases/1556 controls), a Bayesian hierarchical regression approach was used to estimate adjusted posterior means and credible intervals (CrI) for the adjusted odds ratios (ORs) for PAH exposure sources, considered singly and as groups: active smoking; residential environmental tobacco smoke (ETS); indoor and outdoor air pollution; and grilled/smoked meat intake.ResultsMost women were exposed to PAHs from multiple sources, and the most common included active/passive smoking and grilled/smoked food intake. In multiple-PAH source models, breast cancer incidence was associated with residential ETS from a spouse (OR = 1.20, 95%CrI = 1.03, 1.40) and synthetic firelog burning (OR = 1.29, 95%CrI = 1.06, 1.57); these estimates are similar, but slightly attenuated, to those from single-source models. Additionally when we considered PAH exposure groups, the most pronounced significant associations included total indoor sources (active smoking, ETS from spouse, grilled/smoked meat intake, stove/fireplace use, OR = 1.45, 95%CrI = 1.02, 2.04).ConclusionsGroups of PAH sources, particularly indoor sources, were associated with a 30–50% increase in breast cancer incidence. PAH exposure is ubiquitous and a potentially modifiable breast cancer risk factor.     

Contamination of polycyclic aromatic hydrocarbons (PAHs) in urban soils in Beijing, China

Soil contamination with polycyclic aromatic hydrocarbons (PAHs) is an increasing problem in many countries, including China. An extensive and systematic survey has been undertaken to evaluate the contamination with PAHs of urban soils in Beijing, China. Soil samples were collected from campuses of universities, schools and kindergartens, public squares, fallow land and roadsides, and were analyzed for 16 PAHs by GC-MS. There was a high variability in the total PAHs (SigmaPAHs) concentrations, ranging from less than 366 to 27,825 ng g(-1). The highest SigmaPAHs concentrations were found at roadsides and industrial sites. Soil organic carbon (SOC) is one of the important factors that can influence the concentrations of PAHs in soils. It was found that concentrations of SigmaPAHs were significantly correlated with that of soil organic carbon. To trace the sources of PAHs, the ratios of phenanthrene to anthracene and fluoranthene to pyrene were used to identify pyrogenic and petrogenic sources, respectively. In most cases, PAHs in soils in urban areas of Beijing were pyrogenic. These sources included motor vehicle exhausts, industrial activities and coal burning. These data can be further used to assess the health risk associated with soils polluted with PAHs.     

Performance and emission characteristic studies on CRDI diesel engine fuelled with plastic pyrolysis oil blended with ethanol and diesel

ABSTRACT

This paper mainly focuses on the utilisation of plastic pyrolysis oil (PPO) and its’ blends with diesel and ethanol in different proportions in a modified diesel engine fitted with common rail direct injection (CRDI) facility. PPO was subsequently blended with diesel and ethanol and characterisation has been done. Experiments were conducted to investigate the impact of injection timing (IT) and injection pressure (IP) on the performance of modified CRDI engine fuelled with PPO and its blends with diesel and ethanol. From the experimental investigations, IT of 10°bTDC and IP of 900 bar were found as best operating parameters to obtain maximum brake thermal efficiency (BTE) with lowered emissions for the fuel combinations utilised in the investigations. PPO as substitute to diesel fuel could be viable if its major concern is to finding permanent resources.     

Detection and average content levels of carcinogenic and mutagenic compounds from the particulates on diesel and gasoline engine mufflers

Carcinogenic and mutagenic compounds, which were extracted from the particulates that adhered to inner surfaces of diesel and gasoline engine mufflers, were quantified by the series method of Soxhlet extraction, liquid-liquid partition, thin-layer chromatography, and spectrofluorometry. Mutagenic activity of their neutral and acidic fractions was tested in the improved Ames assay by the preincubation method with Salmonella typhimurium TA98 in the presence and absence of metabolic activation system (S-9 mix). The average content levels (μg/g tar) of polycyclic aromatic hydrocarbons from gasoline engine cars were greater than those from diesel engine vehicles. However, the levels of nitro derivatives of PAHs and polycyclic quinones from the diesel engines were greater than from the gasoline engines. Mutagenic activity of the diesel acidic fraction was the highest among the diesel and gasoline fractions, and was significantly higher in the absence of the S-9 mix. Furthermore, the relative value (R_{c = 0}) of infrared absorption of carbonyl stretching vibration to that of methylene asymmetric stretching vibration of the diesel acidic fraction was the highest among the diesel and gasoline fractions. These results strongly suggest that highly direct-acting mutagens in the acidic fraction are at higher levels in diesel emission particulates than those from gasoline, and that these mutagens are carboxylic acid, aldehyde, and alcohol derivatives of PAHs and NPAHs.     

Degradation of polycyclic aromatic hydrocarbons by a bacterial consortium enriched from mangrove sediments

The biodegradability of a polycyclic aromatic hydrocarbons (PAHs) mixture consisted of fluorene (Fl), phenanthrene (Phe) and pyrene (Pyr) by a bacterial consortium enriched from mangrove sediments under sediment-free and sediment slurry conditions was investigated. The enriched consortium made up of three bacterial strains, namely Rhodococcus sp., Acinetobacter sp. and Pseudomonas sp., had a good PAH degradation capability with 100% degradation of Fl and Phe in sediment-free liquid medium after 4 weeks of growth. The Fl and Phe degradation percentages in sediment slurry were higher than that in liquid medium. Autochthonous microorganisms in sediments also possessed satisfactory PAH degradation capability and all three PAHs were almost completely degraded after 4 weeks of growth. Bioaugumentation (inoculation of the enriched consortium to sediments) showed a positive effect on PAH biodegradation after 1 week of growth. Complete biodegradation of pyrene took longer time than that for Fl and Phe, indicating the enriched bacterial consortium had preference to utilize low-molecular weight PAHs.     

Polycyclic aromatic hydrocarbons in ambient air particles in the city of Las Palmas de Gran Canaria

Concentration levels, seasonal variation and winter/summer ratios of 11 polycyclic aromatic hydrocarbons (PAHs) in the TSP of Las Palmas de Gran Canaria city were determined. The study area is under the influence of heavy traffic (80000 vehicles/day). Pyr/BaA, Pyr/Flt, B(ghi)P/I(cd)P and B(b+k)F/B(ghi)P ratios were calculated; the values of these two last suggest a strong influence of diesel fuel burning. Levels of TSP and TSP-bound PAHs were also established. The hazard potential of PAHs in terms of carcinogenicity of BaP is acceptable. Potential risk on the basis of TEFs is also studied.     

Mutagenic activity of diesel emission particulate extracts and isolation of the mutagenic fractions

Mutagenic activity in diesel emission particulate extracts was detected by the Salmonella typhimurium/microsome assay. Direct-acting mutagens as well as promutagens requiring metabolic activation were detected. The extracts were fractionated into acidic, basic, and neutral fractions, and the neutral fraction was chromatographed into seven subfractions. Differences in the mutagenic potency of these fractions and subfractions were determined by the Salmonella assay. Fractions containing as yet unidentified compounds, but not polynuclear aromatic hydrocarbons, were found to make a major contribution to mutagenic activity of the extracts.     

Sidestream tobacco smoke constituents in indoor air modelled in an experimental chamber— Polycyclic aromatic hydrocarbons

Exposure to sidestream tobacco smoke is concerned with constituents in suspension in the indoor atmosphere. The natural dissipation of sidestream tobacco smoke has been investigated in a static atmosphere in a 10 m³ experimental chamber, and the rate of dissipation is expressed as T_0.5, the half-life of residence in the air. Respective T_0.5 of smoke components are calculated from the various sample data points, assuming a kinetic equation of the first-order process. Sidestream smoke has been generated by a smoking machine according to the Coresta standard protocol and then left to age over an 8-hour period, with subsequent sampling at defined time intervals. The experiments have been repeated over five days, and eight data point samples are obtained for each experiment. Besides nicotine, CO, and smoke particulate matter, interest has been focused on polycyclic aromatic hydrocarbons (PAH). The initial concentrations, C₀ for smoke particulate matter and nicotine (gas and particulate phases) are found to be 13.8 mg and 92 μg per cigarette per cubic meter, with T_0.5 being 2.6 and 2.1 hours, respectively. Low molecular-weight PAH have T_0.5 up to 20 hours, explainable only by their high concentrations in the gas phase, while the 3- to 7-ring PAH have T_0.5 of about 2 hours. The contribution of CO to ambient concentration is 91 mg per cigarette per cubic meter. The data can be useful in mathematical modellization studies regarding ventilation or exposure to sidestream smoke.     

Habitat function of agricultural soils as affected by heavy metals and polycyclic aromatic hydrocarbons contamination

Ecotoxic activity of soils polluted with polycyclic aromatic hydrocarbon (PAH) and heavy metals (HM) was evaluated in pot and laboratory experiments. Plants and soil microorganisms were chosen as test organisms and six different soil materials were used in the study. The applied levels of HM and PAH were aimed to reflect environmental conditions in the "worst case" situation. Zn(2+), Pb(2+) and Cd(2+) were introduced to the soils as an aqueous solution of the mixture of salts at the concentrations corresponding to 1000, 500 and 3 mg kg(-1), respectively. Mixture of four PAH compounds (flourene, anthracene, pyrene and chrysene) as a CH(2)Cl(2) solution was applied at levels of 10-100 mg summation operator 4PAH kg(-1). Population and activity of soil microflora was evaluated as measured of total bacteria counts, intensity of respiration and enzyme activity (dehydrogenases and phosphatases). Effect on plants was evaluated on the base of the growth (plant at an early stage of their development) and yield (mature plant) measurements. The results indicate that combined effect of PAH and heavy metals on soil microorganisms activity and on some plants at an early stage of their development can be stronger than in soils amended with HM or PAH separately. Reaction of tested organisms was related to soil properties, PAH concentration, time and plant species. Mature plants (maize) were insensitive to the applied levels of both group of contaminants.     

A review of airborne polycyclic aromatic hydrocarbons (PAHs) and their human health effects

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds comprised of two or more fused benzene rings arranged in various configurations. PAHs are widespread environmental contaminants formed as a result of incomplete combustion of organic materials such as fossil fuels. The occurrence of PAHs in ambient air is an increasing concern because of their carcinogenicity and mutagenicity. Although emissions and allowable concentrations of PAHs in air are now regulated, the health risk posed by PAH exposure suggests a continuing need for their control through air quality management. In light of the environmental significance of PAH exposure, this review offers an overview of PAH properties, fates, transformations, human exposure, and health effects (acute and chronic) associated with their emission to the atmosphere. Biomarkers of PAH exposure and their significance are also discussed.     

Human dietary exposure to polycyclic aromatic hydrocarbons: Results of the second French Total Diet Study

In the frame of the second French Total Diet Study (TDS), the 15 + 1 EU priority polycyclic aromatics hydrocarbons (PAHs) were analyzed in 725 foodstuffs habitually consumed by the French population, using gas chromatography coupled to tandem mass spectrometry, after pressurized liquid extraction and purification on PS-DVB stationary phase. The highest PAH concentrations recovered in foodstuffs corresponded to the following contributors: chrysene (25.7%), benzo[b]fluoranthene (15.0%) and benz[a]anthracene (9.0%) whereas the lowest concentrations were those of dibenz[a,h]anthracene, 5 methylchrysene and dibenzo[a,h]pyrene (below 2.0%). By food groups, the current highest levels of total PAH were detected in mollusks and crustaceans, followed by the different oil based products. To estimate French population's exposure, contamination data were combined with national individual food consumption data. Mean daily exposure to the sum of benzo[a]pyrene, benz[a]anthracene, chrysene and benzo[b]fluoranthene (PAH4) was estimated to be 1.48 ng/kg bw/day in adults and 2.26 ng/kg bw/day in children. The main contributors to PAH exposure for adults are fats, bread and dried bread products followed by crustaceans and mollusks. The margin of exposure (MOE) approach indicates that exposure to PAHs through food is not a major health problem for French consumers.     

Exchange of polycyclic aromatic hydrocarbons across the air-water interface at the creek adjoining Mumbai harbour, India

Concentration levels of polycyclic aromatic hydrocarbons (PAHs) have been determined in air and water in order to estimate the magnitude and direction of gas flux across the air-water interface at the creek adjoining the Mumbai harbour, India. The range of total PAHs was found to be 4.1-30.4 ng/m3 in air and 84.3-377.5 ng/l in seawater, respectively. The lower molecular weight PAHs revealed positive values of the fluxes indicating the tendency for transfer of these contaminants from water to air. In contrast, fluxes of less volatile compounds like benzo(k)fluoranthene and benzo(a)pyrene were always from the atmosphere into the surface water of the creek at all locations and sampling periods. While the fugacity ratio ranged from 0.12 to 6.97, it was found greater than 1 for the lower molecular weight PAHs and less than 1 for higher molecular weight PAHs. The present study suggests the active transfer of lower molecular weight dissolved PAHs into the atmosphere due to volatilization and deposition of higher molecular weight gas-phase PAHs into the surface water.