PAH Composition Research Articles

Characterization of elemental and polycyclic aromatic hydrocarbon compositions of urban air in Brisbane

Characterization of the elemental and PAHs compositions of urban air was undertaken at three major sites in Brisbane, Australia. 17 elements and 16 US EPA priority PAHs were quantified at the sites. The most commonly detected elements in the TSP and PM2.5 fractions were Al, Cd, Co, Cr, Cu, Fe, Mn, Mo, Si, Sn, Sr and Zn. Compared to the two other sites, PM2.5 was found to contain higher concentrations of Zr, Mo, V, Al, Mn and Sr at the QUT site. In contrast, the Woolloongabba sampling site, which was highly influenced by the vehicular emission and local industrial activities, has higher concentrations of Co, Sn, Cu, Zn and Mg while ANZ site has significantly lower concentration levels of most elements than the other sites; possibly due to the shielding effect of the nearby bush and forest. NAP, PHE, ANT, FLT, PYR and CRY were the most widespread PAHs found in all sites. But only QUT and Woolloongabba bus platform sites had detectable levels of the most carcinogenic US EPA PAH, BAP. The multi-criteria decision making procedures, PROMETHEE and GAIA were used to rank the air samples and to identify the sources of the pollutants. Thus Woolloongabba bus platform was ranked as the most polluted site on the basis of the elemental and PAH compositions of its air samples while Woolloongabba bus platform and QUT sites were ranked as the worst polluted sites in terms of PAHs and PM2.5 elemental contents respectively.

Physicochemical Characteristics and Biological Activities of Seasonal Atmospheric Particulate Matter Sampling in Two Locations of Paris

Fine particulate matter present in urban areas seems to be incriminated in respiratory disorders. The aim of this study was to relate physicochemical characteristics of PM2.5 (particulate matter collected with a 50% efficiency for particles with an aerodynamic diameter of 2.5 microm) to their biological activities toward a bronchial epithelial cell line 16-HBE. Two seasonal sampling campaigns of particles were realized, respectively, in a kerbside and an urban background station in Paris. Sampled-PM2.5 mainly consist of particles with a size below 1 microm and are mainly composed of soot as assessed by analytical scanning electron microscopy. The different PM2.5 samples contrasted in their PAH content, which was the highest in the kerbside station in winter, as well as in their metal content. Kerbside station samples were characterized by the highest Fe and Cu content, which appears correlated to their hydroxyl radical generating properties measured by electron paramagnetic resonance. Particles were compared by their capacity to induce cytotoxicity, intracellular ROS production, and proinflammatory cytokine release (GM-CSF and TNF-alpha). At a concentration of 10 microg/cm2, all samples induced peroxide production and cytokine release to the similar extent in the absence of cytotoxicity. In conclusion, whereas the PM2.5 samples differ by their PAH and metal composition, they induce the same biological responses likely either due to components bioavailability and/ or interactions between PM components.

Emission Rates and Comparative Chemical Composition from Selected In-Use Diesel and Gasoline-Fueled Vehicles

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30°F), “black” and “white” smokers, and a new-technology vehicle (tested at 72 °F). Diesel vehicles included current-technology vehicles (tested at 72 and 30°F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.

Polycyclic aromatic hydrocarbons in San Francisco Estuary sediments

The objectives of this study were to examine surface sediments in the San Francisco Estuary for PAH composition over a range of spatial and temporal scales to determine distributions, trends, and possible sources. Surface sediments (top 5 cm) were collected at 26 sites from 1993 to 2001. The mean total PAH (∑PAH) concentration in sediments was spatially distributed as Central Bay (230 mg/kg TOC), South Bay (217 mg/kg TOC), North Estuary (96 mg/kg TOC), Extreme South Bay (87 mg/kg TOC), and Delta (31 mg/kg TOC). Overall, the mean ∑PAH concentrations were significantly higher in the Central Bay and South Bay segments compared to the North Estuary, Extreme South Bay and Delta segments, and the Delta was significantly lower than all other segments (Kruskal–Wallis, H=156.94, df=4, p=0.000). In addition, no significant difference in ∑PAH concentration was found between the Central Bay and South Bay. This distribution reflects the large amount of urbanized and industrialized areas that surround the Central Bay and South Bay compared to the less urbanized and rural areas surrounding the Delta. Temporal trend analysis showed a statistically significant temporal trend in ∑PAH concentration at only 1 of the 26 sampling sites located throughout the estuary (San Pablo Bay, significant decrease, p=0.024, r 2=0.314, n=16), which suggests that ∑PAH concentrations in the estuary generally remained constant from 1993 to 2001. Source analysis using PAH isomer pair ratios as indicators showed that PAH are derived primarily from combustion of fossil fuels/petroleum (gasoline, crude oil, and coal) and biomass (wood and grasses), with minor amounts of PAH derived from direct petroleum input.

Hydrothermal petroleum in the sediments of the Andaman Backarc Basin, Indian Ocean

Recent sediments of the Andaman Backarc Basin, Indian Ocean, between the Andaman Nicobar islands and the Malay Peninsula have been analyzed for biomarker lipids. Three cores were selected: one each from the fault zone in a deep basin (a graben between two fault systems), another from a location adjacent to the fault, and the third from the topographic high in the rift valley. The molecular composition of the lipid classes ( n-alkanes, isoprenoids, alkylbenzenes, alkylcyclohexanes, hopanoids, polycyclic aromatic hydrocarbons, steranes, alcohols, sterols and fatty acids) was examined by gas chromatography (GC) and GC/mass spectrometry to understand the nature and source of the hydrocarbons present and the processes of maturation of organic matter. The data show that the hydrocarbons are of hydrothermal origin, derived from thermal alteration of sedimentary organic matter, consisting of a mixture predominantly of marine-derived components with some terrestrial inputs. Normal alcohols and fatty acids also corroborate the distribution of n-alkanes. The distribution profiles and various parameters computed from the concentration of the target compounds suggest that oxidative reactions and microbial degradation in this environment are insignificant. Triterpane and PAH compositions indicate that the thermal maturity of the bitumen in the samples is comparable to or lower than that found at other hydrothermal regions such as the Northern Juan de Fuca Ridge, Guaymas Basin and Escanaba Trough.

Absence of stable carbon isotope fractionation of saturated and polycyclic aromatic hydrocarbons during aerobic bacterial biodegradation

Compound-specific stable carbon isotopic composition measurement is a promising discriminative tool for source identification of hydrocarbons in modern environments. Nevertheless, to be considered as a source tracer, the 13C/12C ratio either has to be unmodified or at least modified in a predictable fashion by the different processes affecting hydrocarbons in the environment (photo-oxidation, evaporation, biodegradation, etc.). Possible isotopic fractionations introduced by microbial biodegradation have been investigated in this study. Stable carbon isotopic compositions of saturated hydrocarbons and phenanthrene compounds were stable during the course of a crude oil biodegradation experiment with a marine bacterial community. The 13C/12C ratio of some standard 2-methylphenanthrene also remained constant during the course of a biodegradation experiment with a pure bacterial strain. These results indicate the absence of isotopic fractionation of hydrocarbons during aerobic bacterial biodegradation. Therefore, molecular stable carbon isotopic composition of n-alkanes and PAHs can be used for source identification of these compounds in environmental studies.

Status of persistent organic pollutants in the sediment from several estuaries in China

Sediment samples from three estuaries on the east coast of China were analyzed for persistent organic pollutants. Total PCB, PAH, and DDT concentrations in the sediments from Minjiang, Jiulongjiang, and Zhujiang estuaries ranged from 2 to 14 ng/g, 400 to 1500 ng/g, and 6 to 73 ng/g, respectively, in the sediments from these estuaries. The sources of PAH contamination were inferred from PAH compositions, with pyrogenic PAHs being the dominant source for Minjiang Estuary and petroleum related PAHs being the primary contributors to Jiulongjiang and Zhujiang estuaries. The high concentrations of DDT in the sediments from these estuaries were likely the result of widespread use of DDT in China in the 1960s and 1970s. Butyltin compounds were detected in the sediment from Jiulongjiang Estuary and Victoria Harbor, Hong Kong. Presence of butyltin compounds probably result from the shipping activities in these estuaries. Butyltin compounds were not detected in the sediments from Minjiang and Zhujiang estuaries. Contaminant concentrations were generally below levels expected to affect benthic organisms with the exception of DDTs.

Distribution of polycyclic aromatic hydrocarbons among different compartments of a river ecosystem

Distribution of PAHs in a river ecosystem was studied by sampling of four abiotic compartments (surface water, suspended matter, pore water and sediments) under two different hydro‐logical conditions. PAHs were detected at significant concentrations in both the solid and aqueous phase of the river ecosystem. Water concentrations were relatively low despite greater contamination of sediments. Lower MW PAHs were prevailing in the dissolved phase, higher MW PAHs in particulate materials. Concentrations of PAHs in surface waters were greater in summer than in fall. PAHs composition in the sediments was found to be relatively uniform across sites reflecting combustion generated PAH profile. Correlation and multivariate statistical analysis have shown differences between PAH patterns in solid and water samples. In aquatic samples and suspended matter, principal component analysis distinguished two separated groups of PAHs with different distribution depending on their molecular weight. In‐situ partition coefficients between the solid and aqueous phase did not differ very much between seasons. The role of organic carbon for PAHs partitioning to sediments in situ was examined. PAHs concentrations correlated to OC content only in summer. In‐situ Kocs were up to two orders of magnitude greater than tabulated Kocs based on the equilibrium partitioning model. The main reasons are the lower availibility of PAHs bound to particles from combustion sources to partition into the aqueous phase and dynamic conditions in the river ecosystem which do not enable the full equilibrium to appear.

Analysis by GC-MS of Polycyclic Aromatic Hydrocarbons in a Cream Containing Coal Tar

Qualitative and quantitative PAHs composition of a cream containing coal tar (5%), used in cutaneous diseases treatment, was studied. Eleven PAHs were analysed in pure coal tar and in the cream by GC-MS, after ultrasonic extraction by pyridine. Ten PAHs were found in pure coal tar: naphthalene, biphenyl, acenaphthylene, fluorene, phenanthrene, anthracene, carbazole, fluoranthene, pyrene and benzo[a]pyrene. No traces of 2,3-benzofluorene were detected. Seven PAHs were identified in the cream: naphthalene, biphenyl, acenaphthylene, fluorene, phenanthrene, fluoranthene and pyrene. 2,3-benzofluorene was also absent in the cream. Anthracene, carbazole and benzo[a]pyrene (one of the most toxic) were present in coal tar and not detected in the cream. The seven PAHs found in the cream and in coal tar were quantified. Hydrocarbons concentrations were between 0.107 ± 0.0038 mg.g−1 (for biphenyl) and 0.734 ± 0.0438 mg.g−1 (for phenanthrene) in the cream and between 4.31 ± 0.23 mg.g−1 (for biphenyl) and 21.9 ± 0.57 mg.g−1 (for fluorene) in coal tar.

Composition of PCBs and PAHs in the Montreal urban community wastewater and in the surface water of the St. Lawrence River (Canada)

Samples of treated wastewater drawn from the effluent of the Montreal Urban Community (MUC), Canada, and surface water samples from the St. Lawrence River were collected in 1993 and 1994 and analysed for PCBs and PAHs. The average concentrations of Σ13 PCBs and Σ14 PAHs in the effluent were 1.34 ± 0.71 ng L-1 and 326 ± 229 ng L-1, respectively. PCB concentrations in the effluent did not show any clear seasonal pattern in the effluent but PAH concentrations increased during the winter period. In the effluent plume, both PCB and PAH concentrations increased significantly between the upstream control site and the effluent outfall, and subsequently decreased. The profiles of PCB congeners were similar within the effluent plume and also among water masses of the St. Lawrence River. PAH profiles were also similar within the effluent plume, but were different across the two water masses of the St. Lawrence River. Based on the composition of PCB congeners, atmospheric inputs appear to represent the major source of PCBs in the St. Lawrence River. The sources of PAHs in the MUC effluent and in the St. Lawrence River water would appear to be, respectively, petroleum products and combustion-derived products.

Dry deposition of atmospheric pollutants in Taiwan

Dry deposition pollutants were studied in Taiwan and compared with those reported in other areas of the world. The mean dry deposition fluxes in Taiwan were 2.40, 4.98 and 2.47 nm/m2/sec for Taichung, Tainan and Pingtung, respectively. The correlation coefficients (R2) of mean dry deposition mass flux vs. wind speed were 0.47, 0.90 and 0.69 for Taichung, Tainan and Pingtung, respectively. Dry deposition mass fluxes in Taiwan were the same as in Chicago and about 3 times higher than in the North Sea. Suspended particle concentrations of metal elements (Ca, Fe, Zn, Cu and Cd) in Taiwan were much higher than in Chicago, Olympic and Ventura. The results suggest that there is a greater heavy metal elements problem in Taiwan. The average dry deposition fluxes of total‐PAHs in Taiwan were 622, 529 and 575 μm/m2/sec at these three sampling sites. These were higher than reported in the Great Lakes, Siskiwit Lake and Chesapeake Bay, but were about the same as in Chicago. The total PAH compositions at the traffic sampling sites were 7275, 839 and 2450 ug/g for Taichung, Tainan and Pingtung, respectively. The Taichung traffic sampling site had a larger total‐PAH composition than the other two sampling sites. The total‐PAH compositions in the rural sampling sites were 523, 645 and 531 μg/g for Taichung, Tainan and PingTung, respectively. There was no significant difference for PAHs at the rural site of Taiwan. The cumulative fraction curve showed that atmospheric pollutants such as PAHs, sulfate, nitrate and heavy metals in Taiwan were mostly associated with fine particles (< 2.5 μm). However, more than 95% of PCBs tended to be associated with particle size greater than 2.5 μm.

Impact of PAH outlets from an oil refinery on the receiving water area—Sediment trap fluxes and multivariate statistical analysis

PAH concentrations (15 compounds) in settling particulate matter (SPM) collected in the waters outside a petroleum refinery on the Swedish Baltic coast, and in samples of particulate and dissolved fractions in the wastewater from the refinery were determined. SPM concentrations varied between 550 and 4250 ng × g dw −1 and the corresponding calculated fluxes varied between 0.1 and 3.7 ng × cm −2 × day −1. Both concentrations and fluxes did not differ significantly from background coastal or offshore locations in the Baltic. PAH profiles of the SPM samples were compared with the wastewater samples and SPM samples from background areas in the Baltic, using pattern recognition techniques. This analysis showed that the SPM samples from the petroleum refinery displayed a PAH composition similar to that found in background reference sites in the Baltic, and that the SPM samples could not be connected to the wastewater samples from the refinery. This indicates that Nynas AB is not a significant source of PAHs to the waters in its immediate surroundings, i.e. the waters in the Nynäshamn area, and/or that the hydraulic residence time of the water outside the refinery is low. A budget calculation showed that the wastewater outlet from Nynas AB is only a minor contributor of the PAH load to the waters outside the refinery.

Traffic contribution of polycyclic aromatic hydrocarbons in the center of a large city

The presence of particulate PAH and other air pollutants (soot, CO, NO, gas NO y , SO 2, particulate metals, sulfate) in the air in a street (60,000 vehicles each day) in Central Copenhagen and in a park area adjacent to the street was investigated. The diurnal variation of PAH was determined. The PAH composition was also determined in the air in a street carrying only diesel buses. The concentrations of benzo(a)pyrene and benzo(e)pyrene (BeP) were 4.4 ± 1.2 and 4.4 ± 0.7 ng m −3 respectively, in the street air and 1.4 ± 0.6 and 1.3 ± 0.3 ng m −3, respectively, in the air in the park area. The investigation covered the winter months, January-March. The winter was mild, with a mean temperature of 2.8°C. The major PAH source in the street was the traffic. In the city park area also traffic was an important source, but not the major one. Applying BeP as PAH indicator, the traffic contribution was estimated to be 80% in the street. The weekdays distribution was as follows: Working days: 90%. Weekends: 60%. In the city park area the traffic contribution was estimated to be 40%. A city traffic PAH emission profile was determined. The street air PAH profile was very close to the city traffic emission profile. The diurnal variation of PAH showed peaks in the morning and afternoon rush hours and lowest concentrations in the night hours and was very close to the diurnal variation of the traffic gases, CO, NO and gas NO y . A method for differentiating between PAH contribution from petrol vehicles and those from diesel vehicles was developed and applied. It was concluded that the PAH contribution from diesel vehicles was about 2 3 of the total PAH traffic contribution. The shift to the application of a lighter diesel fuel in buses appears to have caused a minor decrease in the street air levels of PAH.

Time-trend analysis of PAH and PCB sediment fluxes in the northern Baltic proper using different dating methods

A recent laminated sediment was collected in the northern Baltic Proper with a Kajak-type gravity corer. The sediment core was analysed for content of polycyclic aromatic hydrocarbons, (PAHs) and mono-, di- and non-ortho polychlorinated biphenyls (PCBs). To evaluate different dating methods and to make dating as accurate as possible, four sediment-dating methods were used: activity measurements of the radio nuclides 210Pb, 239/240Pu and 137Cs, and counts of the number of laminae in the core. According to the 210Pb dating there was a peak in the annual flux of PAHs and ortho PCBs around 1950 after which the flux declined, but the peaks occurred during the 1970s according to the laminae counts. For non-ortho PCBs the trend was less clear, but a flux increasing with time was evident. Multivariate analysis showed a significant change in PAH composition over time, whereas the PCB composition was relatively constant.

Time trend analysis of PAHs and PCBs in the northern Baltic proper

Laminated sediments were collected with a combined box and piston coring technique at a location in the northern Baltic proper. Twenty-two horizontal sediment layers (laminae), each with a height of approx. 1.8 mm, were analysed for carbon, nitrogen and dry weight, and ten of these layers were analysed for the amount of extractable lipids, PAHs, PCBs and the activity of 210Pb for the dating of the sediment. The results indicated a homogeneous composition of the investigated laminated sediment with respect to the parameters describing the basic sediment characteristics, i.e. density, carbon-, nitrogen- and lipid contents. The results of the chemical analyses of PAHs and PCBs in combination with the dating results of the sediment laminae showed that the PAH and PCB peaks corresponded roughly to 15 to 30 years back in time not considering the time lag between pollutant input to the Baltic aquatic environment and the deposition on this deep off shore bottom. It was also found that the relative composition of both PCBs and PAHs (chemical profiles) was fairly constant with increasing sediment depth, indicating that mineralization processes are very slow and the sediment redistribution of these compounds are of minor significance in this sediment.

Environmental modification of PAH composition in coal tar containing samples

The PAH composition of coal tar containing samples collected at a number of coal gasworks sites has been studied. Samples were removed from areas where the coal tar components would have undergone varying degrees of environmental modification since deposition. The degree of environmental modification for individual PAHs exhibits a strong correlation with various molecular descriptors including octanol/water partition coefficient (K OW). Regression lines for environmental modification ratio-descriptor relationships show an increasing slope with increasing environmental attenuation of the coal tar sample. Aqueous partitioning and volatilization are probably the main processes which control environmental modification of coal tar at gasworks sites. The application of molecular descriptors shows promise for modelling the environmental behaviour of PAHs in these situations.

An in situ study on the distribution, biotransformation and flux of polycyclic aromatic hydrocarbons (pahs) in an aquatic food chain (seston‐Mytilus edulis L.‐Somateria mollissima L.) from the baltic: An ecotoxicological perspective

AbstractThis in situ study is focusing on the distribution, biotransformation and flux of 19 polycyclic aromatic hydrocarbons (PAH19) in the food chain seston‐blue mussel (Mytilus edulis L.)‐common eider duck (Somateria mollissiima L.) as well as the distribution in the gallbladder, liver, adipose tissue and egg of the duck. All samples were collected within the open northern Baltic proper coastal areas. Analyses were carried out by gas chromatography/mass spectrometry with electron impact (GC‐MSEI) and negative ion chemical ionization (GC‐MSNICI). With a multivariate statistical method (SIMCA) a significant change in the PAH composition through the food chain was found. This change probably depends on an increasing metabolic activity with increasing trophic level, due to a selective biotransformation capacity for different PAHs. Decreasing PAH concentrations with increasing trophic level were found. The PAH concentrations in the different eider duck organs were: gallbladder &gt; adipose tissue ≥ liver. The theoretical inhalation of air‐dispersed PAHs was of no significance compared to the exposure from food. The relatively high theoretical PAH flux through the food chain did not result in increasing concentrations with increasing trophic level, which indicates that PAHs are biotransformed quite fast. However, many intermediate metabolites of PAHs have a mutagenic and carcinogenic potential, which makes it important to observe these compounds when assessing ecotoxicological risks.

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Present-day and more than 30 years old road and footpath pavements from Auckland, New Zealand were analysed for PAHs to test the hypothesis that coal tar based pavement binders contribute to unusually high PAH concentrations in adjacent stream and estuarine sediments. Total PAH (∑28PAH) concentrations in the dichloromethane-soluble fraction (“binder”), comprising 5–10% of pavement mass, were as high as 200 000 mg kg−1 (10 000 mg kg−1 in binder + aggregate). Older and deeper pavement layers were strongly pyrogenic, whereas pavement layers from recently sealed roads had a more petrogenic composition and more than 1000 times lower ∑28PAH concentrations. Source identification analysis using three PAH isomer ratio pairs (benz(a)anthracene/(benz(a)anthracene + chrysene); benzo(a)pyrene/(benzo(a)pyrene + benzo(e)pyrene); and indeno(1,2,3-cd)pyrene/(indeno(1,2,3-cd)pyrene + benzo(g,h,i)perylene) revealed low PAH (bitumen) pavements to have consistently lower isomer ratios than high PAH (coal tar) samples. Moreover, pavement data for one isomer ratio (e.g. benzo(a)pyrene/(benzo(a)pyrene + benzo(e)pyrene) were highly correlated with those of another isomer ratio (e.g. benz(a)anthracene/(benz(a)anthracene + chrysene) and were bounded at their lower and higher extremes by the characteristics of pure bitumen and coal tar, respectively, suggesting that PAH composition of a given pavement sample could be accounted for by conservative mixing between coal tar and bitumen as source materials. A concentration-weighted mixing model, with coal tar and bitumen as source materials, explained more than 80% of the variance in isomer ratios and enveloped the entire PAH compositional and concentration range encountered. PAH composition and concentrations in adjacent stream sediments (> 15 mg kg−1 dry weight) were consistent with diluted coal tar material as a principal PAH source. Due to the very high PAH concentrations of coal tar, a coal tar content of as little as 0.01% of total sediment mass can account for more than 90% of PAH concentrations in adjacent stream sediments.