Five-ring Polycyclic Aromatic Hydrocarbons Research Articles

Leaching of polycyclic aromatic hydrocarbons and heavy metals from stored reclaimed asphalt pavement

The construction, maintenance, and expansion of roads results in the generation of huge quantities of milled asphalt viz. reclaimed asphalt pavement (RAP). However, recycling of RAP is rarely followed in developing countries such as India. Due to rainfall, stockpiled RAP in open areas may generate leachate containing polycyclic aromatic hydrocarbons (PAHs) and heavy metals, raising concern about the stockpiling of RAP. This study addresses the environmental concerns associated with the possible leaching of PAHs and heavy metals from RAP by batch leaching procedures. The leachate predominantly contained three-, and five-ring PAHs. ΣBenzo(k)fluoranthene (ΣBkF) showed the highest concentration (397 µg/kg), followed by ΣPhenanthrene (ΣPHE) (290 µg/kg) among the all sixteen PAH compounds analysed. The results showed that the leaching potential of RAP was rather weak; hence RAP cannot be classified as hazardous waste. Further, none of the samples exceeded the soil risk-based threshold (RBT) values of PAH for residential or commercial settings indicating negligible risk.

Occurrence, Sources, and Health Risks of Polycyclic Aromatic Hydrocarbons in Road Environments from Harbin, a Megacity of China.

To obtain a comprehensive understanding about that occurrence, sources, and effects on human health of polycyclic aromatic hydrocarbons (PAHs) in road environmental samples from Harbin, concentrations of 32 PAHs in road dust, green belt soil, and parking lot dust samples were quantified. The total PAH concentrations ranged from 0.95 to 40.7 μg/g and 0.39 to 43.9 μg/g in road dust and green belt soil, respectively, and were dominated by high molecular weight PAHs (HMW-PAHs). Despite the content of PAHs in arterial roads being higher, the composition profile of PAHs was hardly influenced by road types. For parking lot dust, the range of total PAH concentrations was 0.81-190 μg/g, and three-ring to five-ring PAHs produced the maximum contribution. Compared with surface parking lots (mean: 6.12 μg/g), higher total PAH concentrations were detected in underground parking lots (mean: 33.1 μg/g). The diagnostic ratios of PAHs showed that petroleum, petroleum combustion, and biomass/coal combustion were major sources of PAHs in the samples. Furthermore, according to the Incremental Lifetime Cancer Risk model, the cancer risks of three kinds of samples for adults and children were above the threshold (10-6). Overall, this study demonstrated that PAHs in the road environment of Harbin have a certain health impact on local citizens.

Emission factors for a biofuel impacted fleet in South America's largest metropolitan area

The Metropolitan Area of São Paulo (MASP) is among the largest urban areas in the Southern Hemisphere. Vehicular emissions are of great concern in metropolitan areas and MASP is unique due to the use of biofuels on a large scale (sugarcane ethanol and biodiesel). In this work, tunnel measurements were employed to assess vehicle emissions and to calculate emission factors (EFs) for heavy-duty and light-duty vehicles (HDVs and LDVs). The EFs were determined for particulate matter (PM) and its chemical compounds. The EFs obtained for 2018 were compared with previous tunnel experiments performed in the same area. An overall trend of reduction of fine and coarse PM, organic carbon (OC), and elemental carbon (EC) EFs for both LDVs and HDVs was observed if compared to those observed in past years, suggesting the effectiveness of vehicular emissions control policies implemented in Brazil. A predominance of Fe, Cu, Al, and Ba emissions was observed for the LDV fleet in the fine fraction. Cu presented higher emissions than two decades ago, which was associated with the increased use of ethanol fuel in the region. For HDVs, Zn and Pb were mostly emitted in the fine mode and were linked with lubricating oil emissions from diesel vehicles. A predominance in the emission of three- and four-ring polycyclic aromatic hydrocarbons (PAHs) for HDVs and five-ring PAHs for LDVs agreed with what was observed in previous studies. The use of biofuels may explain the lower PAH emissions for LDVs (including carcinogenic benzo[a]pyrene) compared to those observed in other countries. The tendency observed was that LDVs emitted higher amounts of carcinogenic species. The use of these real EFs in air quality modeling resulted in more accurate simulations of PM concentrations, showing the importance of updating data with real-world measurements.

Spatiotemporal distribution, sources apportionment and ecological risks of PAHs: a study in the Wuhan section of the Yangtze River.

This study investigated the sources, contamination and ecological risks of polycyclic aromatic hydrocarbons (PAHs) based on their spatiotemporal distribution in aquatic environment in the Wuhan section of the Yangtze River (WYR). The fugacity ratio evaluation indicated that sediment was secondary release sources of two- and three-ring PAHs and sinks of four- and five-ring PAHs. The total concentrations of PAHs (Σ16PAHs) ranged from 2.51 to 102.5ng/L in water with the dominant contribution of 47.8% by two-ring PAHs. Σ16PAHs in sediments varied from 5.90 to 2926ng/g with the contribution of 35.4% by four-ring PAHs. The higher levels of PAHs occurred around developed industrial areas during the wet season, which was related to local industrial emissions and influenced by rainfall/runoff. Annual flux of Σ16PAHs was estimated of 28.77t. The PMF model analysis revealed that petroleum and industrial emissions were the dominant sources in water accounting for 58.5% of the total pollution, although traffic emission was the main source for sediment accounting for 44.6%. Risk assessments showed that PAHs in water were at low risks, whereas about 44% of the sediments were identified as medium risks. Therefore, energy structure adjustment and further implement of regulation and monitoring are necessary to reduce PAH emissions.

Immunofluorescence Visualization of Polycyclic Aromatic Hydrocarbon Mixtures in the Eastern Oyster Crassostrea virginica.

Bivalve mollusks including oysters have low metabolic potential and are therefore susceptible to accumulating high levels of lipophilic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs). Human exposure to PAHs via consumption of this important commercial shellfish can be a serious public health concern in areas where high PAH contamination exists. Previous PAH immunohistochemical studies have been limited to laboratory-based exposures focusing on one or a few individual PAH compounds. To date, such studies have yet to explore PAH accumulation in oysters, known to have some of the highest levels of PAHs across different food products. Using a monoclonal antibody selective for a range of three- to five-ring PAHs, we present a method to detect and localize complex mixtures of PAHs in oyster tissues via fluorescent immunohistochemistry. Observed immunofluorescence intensity followed a similar trend as measured levels of PAHs in oyster interstitial fluid from PAH-contaminated sites and oysters exposed to the water accommodated fraction of crude oil. This method will be valuable in understanding internal partitioning mechanisms of PAH-exposed oysters and will have important applications in studies on PAH distribution in the tissues of additional organisms for environmental, medical, or veterinary purposes. Environ Toxicol Chem 2023;42:475-480. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Comprehensive characterization of particulate intermediate-volatility and semi-volatile organic compounds (I/SVOCs) from heavy-duty diesel vehicles using two-dimensional gas chromatography time-of-flight mass spectrometry

Abstract. Tailpipe emissions from three heavy-duty diesel vehicles (HDDVs), complying with varying emission standards and installed with diverse aftertreatment technologies, are collected at a certified chassis dynamometer laboratory. The HDDV-emitted intermediate-volatility and semi-volatile organic compound (I/SVOC) emission and the gas–particle partitioning of the I/SVOCs are investigated. Over 4000 compounds are identified and grouped into 21 categories. The dominant compound groups of particulate I/SVOCs are alkanes and phenolic compounds. For HDDVs without aftertreatment devices, i.e., diesel oxidation catalysts (DOCs) and diesel particulate filters (DPFs), the emitted I/SVOCs partition dramatically into the gas phase (accounting for ∼ 93 % of the total I/SVOC mass), with a few exceptions: hopane, four-ring polycyclic aromatic hydrocarbons (PAH4rings), and five-ring polycyclic aromatic hydrocarbons (PAH5rings). For HDDVs with DPFs and DOCs, the particulate fractions are reduced to a negligible level (i.e., less than 2 %). Nevertheless, 50 % of the total two-ring PAH mass is detected in the particle phase, which is much higher than the high-molecular-weight PAHs, arising from the positive sampling artifact of quartz filter absorbing organic vapors. The positive sampling artifact of quartz filter absorbing organic vapors is clearly observed, and uncertainties are discussed and quantified. Particulate I/SVOCs at low-speed, middle-speed, and high-speed phases are collected and analyzed separately. The emission factor (EF) distribution of the speciated organic aerosol (OA) on a two-dimensional volatility basis set (2D-VBS) space reveals that the fractions of OA with oxygen to carbon (O : C) ratios > 0.3 (0.4, 0.5) are 18.2 % (11.5 %, 9.5 %), 23 % (15.4 %, 13.6 %), and 29.1 % (20.6 %, 19.1 %) at the low-speed, middle-speed, and high-speed stages. These results help to resolve complex organic mixtures and trace the evolution of OA.

Combined effects of engine characteristics and fuel aromatic content on polycyclic aromatic hydrocarbons and toxicity

ABSTRACT Polycyclic aromatic hydrocarbons (PAHs) are harmful compounds because of their toxicity, adverse effects on human health, and threats to engine components (i.e. wetstacking). With the increased use of renewable fuels, it is imperative that the formation of PAHs be examined, in detail, with respect to the combustion characteristics and aromatic content of biofuels used in diesel engines. Since biodiesel is free of aromatic content in its chemical structure, this study provides comparative assessments of the PAHs, toxicity and regulated emissions of biodiesel (B100) and diesel fuel (D100), based on the fuel aromaticity and engine characteristics when used in two diverse engines. Results indicate that the use of B100 in both engines reduced total PAH emissions by 48.02% − 49.36% and PAH toxicity by 83.49% − 84.8% as compared to diesel fuel, which is a clear indication of the importance of the aromatic content of the base fuel on PAH formation and toxicity (i.e. aromatic-free fuel produces less PAH than diesel with high aromaticity). The aromatic ring distribution associated with B100 exhaust consisted of 50% two, 34% three and 16% four aromatic rings for the Onan engine, and 53% two, 32% three and 15% four aromatic rings for the Kubota engine. Benzo[a]pyrene, a five-ring PAH with great carcinogenic threat, was eliminated in both engines as a result of using B100. To demonstrate the significance of combustion processes on PAH formation, performances of the engines were compared and it was determined that the Kubota engine performed better for both fuels in reducing PAH emissions, due to such features as its injection system and combustion chamber design as compared to the Onan engine. Therefore, it has been concluded that PAH emissions and toxicity strongly depend on both the aromatic content and the combustion processes, as aromatic-free biodiesel significantly decreased PAHs along with additional reduction in PAHs and toxicity depending on the structural specifications of the diesel engine. Based on this study, aromaticity has been determined to be more effective than the type of engine in use for PAH reduction.

Comprehensive characterization of polycyclic aromatic hydrocarbon emissions from heavy-duty diesel vehicles utilizing GC × GC-ToF-MS

Comprehensive characterization of diesel vehicle emitted polycyclic aromatic hydrocarbon (PAH) emissions is yet to achieve due to the limitation of analytical methods. Therefore, we herein developed a two-dimensional gas chromatography time-of-flight mass spectrometry (GC × GC-ToF-MS) method and quantified the total PAHs from diesel vehicles based on their characteristic fragments and mass spectral patterns. Overall, the emission factors (EFs) of total PAHs (gas + particle) are observed to range from 4.1 ± 2.5 mg km−1 to 51.4 ± 22.2 mg km−1 under cold-start and hot-start conditions for one China IV and two China VI heavy-duty diesel vehicles (HDDVs), of which the un-speciated PAHs account for more than 97%. Gaseous PAHs (g-PAHs) are dominated by three-ring PAHs, whereas particulate PAHs (p-PAHs) are dominated by two-ring PAHs. The total PAHs partition significantly into the gas phase for whole fleets and cycles, except that five-ring PAHs partition almost completely into the particle phase. The aftertreatment technologies (e.g., diesel particulate filter, DPF) significantly reduce the total PAH emissions by 49.8 ± 33.2%. The minimum toxic equivalency factors (TEFs) are deployed to estimate the toxicity of the total PAHs. Much higher toxicity is obtained than those in previous studies, indicating that the PAH toxicity of diesel vehicle emissions might be largely underestimated.

Compound-specific radiocarbon reveals sources and land–sea transport of polycyclic aromatic hydrocarbons in an urban estuary

As typical chemical indicators of the Anthropocene, polycyclic aromatic hydrocarbons (PAHs) and their environmental behavior in urban estuaries can reveal the influence of anthropogenic activities on coastal zones worldwide. In contrast to conventional approaches based on concentration datasets, we provide a compound-specific radiocarbon (14C) perspective to quantitatively evaluate the sources and land‒sea transport of PAHs in an estuarine‒coastal surficial sedimentary system impacted by anthropogenic activities and coastal currents. Compound-specific 14C of PAHs and their 14C end-member mixing models showed that 67−73% of fluoranthene and pyrene and 76−80% of five- and six-ring PAHs in the Jiulong River Estuary (JRE, China) originated from fossil fuels (e.g., coal, oil spill, and petroleum-related emissions). In the adjacent Western Taiwan Strait (WTS), the contributions of fossil fuel to these PAH groups were higher at 74−79% and 84−87%, respectively. Furthermore, as a significant biomarker for source allocation of terrigenous organic matter, perylene, a typical five-ring PAH, and its land‒sea transport from the basin through the JRE and finally to the WTS was quantitatively evaluated based on the 14C transport models. In the JRE, fluvial erosions and anthropogenic emissions affected the 14C signature of perylene (Δ14Cperylene, -535 ± 5‰) with contributions of > 38% and < 62%, respectively. From the JRE to the WTS, the decreased Δ14Cperylene (-735 ± 4‰) could be attributed to the long‒range transport of “ocean current-driven” perylene (-919 ± 53‰) with a contribution of 53 ± 8%. This compound-specific 14C approach and PAH transport model help provide a valuable reference for accurately quantifying land‒sea transport and burial of organic pollutants in estuarine‒coastal sedimentary systems.

Spatial distributions and sources of PAHs in soil in chemical industry parks in the Yangtze River Delta, China

The Yangtze River Delta (YRD) is one of the fastest developing areas in eastern China and contains many chemical industry parks. The profiles and sources of polycyclic aromatic hydrocarbons (PAHs) in soil in chemical industry parks and surrounding areas in the YRD were investigated by analyzing soil samples (n = 64) were collected in the YRD and Rudong chemical park (RD), a typical chemical park in the Yangtze River Delta. The total concentrations of 19 PAHs in the YRD soil samples were 16.3–4694 ng g−1 (mean 688 ng g−1), and the total concentrations of PAHs in RD were 21.6–246 ng g−1 (mean 75.4 ng g−1). The PAHs in soil in YRD were dominated by four-ring and five-ring PAHs, and the PAHs in RD were dominated by two-ring and three-ring PAHs. It suggested that PAHs may have been supplied to soil in YRD predominantly through coal combustion and vehicle emissions, PAHs in the soil of RD may be due to the volatilization and leakage of chemical raw material. According to the different distribution characteristics of PAHs, the ratio (1.5) of (2 + 3) rings/4 rings was proposed to identify the chemical source of PAHs. The PAH isomer ratios and principal component analysis/multiple linear regression (PCA/MLRA) results indicated that PAHs concentrations in soil in the YRD and RD are mainly supplied by industrial and traffic emissions. Incremental lifetime cancer risks (ILCRs) indicated that PAHs in soil pose negligible cancer risks to children and adults, but much stronger risks to children than adults.

Correlation between Polycyclic Aromatic Hydrocarbons in Wharf Roach (Ligia spp.) and Environmental Components of the Intertidal and Supralittoral Zone along the Japanese Coast.

Polycyclic aromatic hydrocarbon (PAH) concentrations in wharf roach (Ligia spp.), as an environmental indicator, and in environmental components of the intertidal and supralittoral zones were determined, and the PAH exposure pathways in wharf roach were estimated. Wharf roaches, mussels, and environmental media (water, soil and sand, and drifting seaweed) were collected from 12 sites in Japan along coastal areas of the Sea of Japan. PAH concentrations in wharf roaches were higher than those in mussels (median total of 15 PAHs: 48.5 and 39.9 ng/g-dry weight (dw), respectively) except for samples from Ishikawa (wharf roach: 47.9 ng/g-dw; mussel: 132 ng/g-dw). The highest total PAH concentration in wharf roach was from Akita (96.0 ng/g-dw), followed by a sample from Niigata (85.2 ng/g-dw). Diagnostic ratio analysis showed that nearly all PAHs in soil and sand were of petrogenic origin. Based on a correlation analysis of PAH concentrations between wharf roach and the environmental components, wharf roach exposure to three- and four-ring PAHs was likely from food (drifting seaweed) and from soil and sand, whereas exposure to four- and five-ring PAHs was from several environmental components. These findings suggest that the wharf roach can be used to monitor PAH pollution in the supralittoral zone and in the intertidal zone.

A comparison of PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt;-bound polycyclic aromatic hydrocarbons in summer Beijing (China) and Delhi (India)

Abstract. Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in air, soil, and water and are known to have harmful effects on human health and the environment. The diurnal and nocturnal variations of 17 PAHs in ambient particle-bound PAHs were measured in urban Beijing (China) and Delhi (India) during the summer season using gas-chromatography–quadrupole time-of-flight mass spectrometry (GC-Q-TOF-MS). The mean concentration of particles less than 2.5 µm (PM2.5) observed in Delhi was 3.6 times higher than in Beijing during the measurement period in both the daytime and night-time. In Beijing, the mean concentration of the sum of the 17 PAHs (∑17 PAHs) was 8.2 ± 5.1 ng m−3 in daytime, with the highest contribution from indeno[1,2,3-cd]pyrene (12 %), while at night-time the total PAHs was 7.2 ± 2.0 ng m−3, with the largest contribution from benzo[b]fluoranthene (14 %). In Delhi, the mean ∑17 PAHs was 13.6 ± 5.9 ng m−3 in daytime and 22.7 ± 9.4 ng m−3 at night-time, with the largest contribution from indeno[1,2,3-cd]pyrene in both the day (17 %) and night (20 %). Elevated mean concentrations of total PAHs in Delhi observed at night were attributed to emissions from vehicles and biomass burning and to meteorological conditions leading to their accumulation from a stable and low atmospheric boundary layer. Local emission sources were typically identified as the major contributors to total measured PAHs in both cities. Major emission sources were characterized based on the contribution from each class of PAHs, with the four-, five- and six-ring PAHs accounting ∼ 95 % of the total PM2.5-bound PAHs mass in both locations. The high contribution of five-ring PAHs to total PAH concentration in summer Beijing and Delhi suggests a high contribution from petroleum combustion. In Delhi, a high contribution from six-ring PAHs was observed at night, suggesting a potential emission source from the combustion of fuel and oil in power generators, widely used in Delhi. The lifetime excess lung cancer risk (LECR) was calculated for Beijing and Delhi, with the highest estimated risk attributed to Delhi (LECR = 155 per million people), which is 2.2 times higher than the Beijing risk assessment value (LECR = 70 per million people). Finally, we have assessed the emission control policies in each city and identified those major sectors that could be subject to mitigation measures.

Quantification of polycyclic aromatic hydrocarbons in kitchen depositions by SUPRAS-LC-FLR and human health risk assessment

Concentration, composition and sources of polycyclic aromatic hydrocarbons (PAHs) in kitchen depositions from different sampling categories such as restaurants, university mess and houses were investigated, and associated human exposure risk through dietary intake, inhalation and dermal contact was determined. The PAHs in the samples were extracted by supramolecular solvent based microextraction (SUPRAS) method and the concentrations were determined by high pressure liquid chromatography (HPLC) with fluorescence detection. The mean of Σ16PAHs concentration was found to be the highest (386.09 ± 413.17 mg kg−1) for restaurants followed by mess (80.91 ± 92.81 mg kg−1) and houses (24.65 ± 10.52 mg kg−1). Traffic sources were found to be predominant contributors of PAHs in restaurants while cooking activities were the sources for mess and houses. Three- and five-ring PAHs were prominent in restaurants and mess samples while two- and three-ring PAHs contributed the most in houses samples. Non-cancer risk (hazard index) from exposure to these PAHs was found to be within safe limits i.e. 2.70E-09 to 7.46E-08. Estimated lifetime cancer risk was found to range from 2.46E-06 to 7.81E-04 from exposure to these PAHs and indicates significant risk due to exceeding the guideline value of 10−6.

Spatiotemporal distribution, source, and ecological risk of polycyclic aromatic hydrocarbons (PAHs) in the urbanized semi-enclosed Jiaozhou Bay, China

Coastal contamination by polycyclic aromatic hydrocarbons (PAHs) is a worldwide issue. Nevertheless, the spatiotemporal distribution of PAHs in the urbanized semi-enclosed bays in China remains relatively uncharacterized. Here we present measurements of 15 priority PAHs in the water and sediment of the Jiaozhou Bay, as well the assessment of their spatiotemporal distribution, sources and ecological risk. The total PAH (ΣPAH) concentrations ranged from 23.6 to 86.2 ng L −1 in the water and from 37.7 to 290.9 ng g−1 in the sediment. The average ΣPAH concentration in the water was significantly higher in the winter (52.8 ng L −1) than in the spring (30.4 ng L −1) (α = 0.05 level). Average concentration of phenanthrene in the water was 8.9 ng L−1 in the spring and 15.7 ng L−1 in the winter and the highest of PAHs, contributing about 29.4% to ΣPAHs. Compared with three-ring PAHs, four- and five-ring PAHs were more tended to accumulate in the sediment, and the partitioning into sediment was influenced by the water salinity. The spatial distribution of ΣPAH concentrations in the water were controlled by water exchange capability. Organic matter content and sediment texture played important roles in determining the spatial distribution of ΣPAHs in the sediment. Molecular diagnostic ratio analysis indicated that pyrogenic source was the main source for PAHs in the Bay. Specifically, the positive matrix factorization (PMF) model indicated that vehicle emission, biomass combustion, coal combustion, and petrogenic sources contributed for 41.6, 20.2, 20, and 18.2% of ΣPAHs, respectively. The risk assessment by sediment quality guidelines suggested that adverse biological effects are expected to occur rarely in the sediment.

Determination of polycyclic aromatic hydrocarbons (PAHs) and other organic pollutants in freshwaters on the western shore of Admiralty Bay (King George Island, Maritime Antarctica)

Organic contamination in freshwater samples has never been investigated at the western shore of Admiralty Bay. Therefore, the presence of polycyclic aromatic hydrocarbons (PAHs) in five different sites distributed along a shore running from the Arctowski Station to the Baranowski Glacier was studied. Moreover, organic compounds such as n-alkanes, toluene and ethylbenzene were also noted. Increased ΣPAHs in late Austral summer 2016 are the result of long-range atmospheric transport of air masses from South America, confirmed by 10-day backward air mass trajectories analysis. The presence of n-alkanes and other hydrocarbons, as well as the evaluation of PAH indices (e.g. ΣLMW/ΣHMW* > 1), shows the use of fuel and indicate local human activity. As a final conclusion, our analysis indicates a mixed origin of PAHs (global and local). The presence of PAHs and other hydrocarbons in the water environment may constitute a potentially negative effect on the Antarctic ecosystem and it should be investigated in detail during further research (//*ΣLMW—sum of low molecular weight PAHs (two- and three-ring PAHs); ΣHMW—sum of high molecular weight PAHs (four- and five-ring PAHs)//).Graphical abstract

Characterization of PM2.5-bound polycyclic aromatic hydrocarbons and their derivatives (nitro-and oxy-PAHs) emissions from two ship engines under different operating conditions

Emissions from ship exhaust have been recognized as an important source of air pollution in coastal areas. To investigate the impacts of engine type, fuel and operating conditions on polycyclic aromatic compounds (PACs) emissions, particle matter (PM2.5) samples emitted from an inland-river bulk freighter (BF) using marine diesel oil (MDO) and an ocean-going passenger vessel (PV) using heavy fuel oil (HFO) were collected under five operation conditions (preheating, leaving, cruising, entering and berthing). The concentrations of 17 polycyclic aromatic hydrocarbons (PAHs), 12 nitro-PAHs (NPAHs) and 4 oxygenated-PAHs species were determined. The concentrations of ΣPAHs, ΣNPAHs and ΣOPAHs measured on the BF and PV exhausts ranged from 1.95 to 417 μg/m3, 86.5 to 6.89 × 103 ng/m3 and 2.00–102 μg/m3, respectively. Both ships showed a high proportion of four-ring PAHs, while the BF had more three-ring PAHs (34.00–70.38%) and the PV had more five-ring PAHs (30.02–35.95%). The calculation of indicatory PACs are able to increase the precision of source appointment. The emission factors (EFs) of PACs under maneuvering (including preheating, leaving, entering and berthing) was much higher than those under cruising, which might be due to the engine load, fuel consumption, and secondary reactions. Compared with HFO, combustion with MDO decreased the power-based ΣPAH EFs by 82–99%, power-based ΣNPAH EFs by 86–98%, and power-based ΣOPAHs EFs by 50–82%. These data highlight the importance of quantifying and monitoring ship emissions in close proximity to port area, and are useful for enhancing the relevant databases and improving the accuracy of ship emission inventories.

Comparative toxicity of selected PAHs in rainbow trout hepatocytes: genotoxicity, oxidative stress and cytotoxicity

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous contaminants in aquatic ecosystems, which may have potentially toxic effects on organisms. In this study occurrence of DNA strand breaks, oxidative stress, and cytotoxicity were investigated in rainbow trout hepatocytes following in vitro exposure for 24 h to four PAHs (0.01–10 µM): naphthalene, fluoranthene, pyrene, and benzo[a]pyrene (B[a]P). The exposed hepatocytes were analyzed for DNA strand breaks using the comet assay and for antioxidant status by measuring intracellular glutathione (GSH) content using the fluorescent probe mBCl. The cytotoxicity of PAHs was assessed using the fluorescent probe CFDA-AM. The results showed that fluoranthene, pyrene, and B[a]P were genotoxic at all exposure concentrations, whereas naphthalene was genotoxic at concentrations ≥0.1 µM. All treatments reduced the intracellular concentrations of GSH for all four PAHs, except 10 µM of B[a]P, suggesting that some level of oxidative stress was present. The cytotoxic effect was observed for naphthalene at concentrations ≥0.1 µM and pyrene at all exposure concentrations, whereas fluoranthene and B[a]P were not cytotoxic at the tested concentrations. The study shows that low-molecular-weight PAHs may cause DNA strand breaks as high-molecular-weight PAHs do in fish tissue. In addition, two- to five-ring PAHs can induce oxidative stress and cytotoxicity.

Abstract 4021: The evaluation of carcinogenicity evidence of dibenzanthracenes

Abstract Dibenzanthracenes (DBAs) are identified as carcinogens and are on the California Proposition 65 list. DBAs are five-ring polycyclic aromatic hydrocarbons (PAHs). This chemical group consists of three isomers: DB[a,c]A, DB[a,h]A, and DB[a,j]A. DBAs are products of the incomplete combustion or pyrolysis of organic matter and can be formed during high temperature cooking. They are air pollutants present in engine exhaust, tobacco and marijuana smoke, and may also contaminate soil and water. DB[a,h]A is a well-studied International Agency for Research on Cancer (IARC) Group 2A carcinogen, whereas fewer studies relevant to carcinogenicity have been conducted with DB[a,c]A and DB[a,j]A. Carcinogenicity evidence from multiple data streams was integrated in the hazard identification of this chemical group. These data streams include animal cancer bioassays, mechanistic studies and other relevant data, including high-throughput studies (e.g., ToxCast), toxicogenomic studies, and information from quantitative structure-activity relationship (QSAR) models. Structure activity comparisons across the three DBAs and related carcinogenic PAHs served to bridge the data gaps for the two less studied isomers. The results of our analyses showed that each of the DBAs share similar biological activities in animals: all induce tumors in mice, are mouse skin tumor initiators, form DNA adducts, are genotoxic, and form metabolites that are also genotoxic and initiators of mouse skin tumors. All three DBAs activate the aryl hydrocarbon receptor (AhR) in reporter gene assays, and DB[a,h]A and DB[a,c]A have been shown to bind to the AhR. In addition to strong evidence of genotoxicity, other carcinogenic mechanisms are likely also operative, including receptor activation (e.g., AhR), immune suppression, altered cell proliferation, apoptosis, and cell cycle regulation. There are strong structure-activity similarities among the DBAs and several carcinogenic 4-, 5- and 6-ring PAHs, including benzo[a]pyrene and dibenzo[a,h]pyrene. In addition, DB[a,c]A and DB[a,j]A were predicted to be mutagenic and carcinogenic in several QSAR models, including VEGA, Lazar and OECD QSAR Toolbox. Integration of the evidence from these multiple data streams resulted in the identification of the DBAs as a chemical group as carcinogens. Citation Format: Feng Tsai, Jennifer C. Hsieh, Gwendolyn Osborne, Martha Sandy. The evaluation of carcinogenicity evidence of dibenzanthracenes [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2018; 2018 Apr 14-18; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2018;78(13 Suppl):Abstract nr 4021.

Fingerprinting Techniques Investigation to Detect Petroleum Hydrocarbon Origin in Coastal Sediments of Persian Gulf

ABSTRACTPersian Gulf coasts are subjected to different sources of petroleum pollution. This paper enhanced fingerprinting method of applying biomarkers polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in identifying the distribution of oil spills and petroleum products. A total of 18 samples were collected from the northern coasts of Persian Gulf. PAH concentrations in the coastal sediments ranged from 184.49 to 2771.88 ng g−1. Distribution of three-ring PAHs was much higher than the others. PAHs concentration can be categorized as low to moderate comparing the global scale. Applying principal component analysis and data clustering revealed two major groups. The first group, including alkylated phenanthrenes, belongs to the low molecular weight PAHs with two and three rings, which are abundant in petrogenic sources mostly caused by petroleum spills. The second group consists of four- and five-ring PAHs. This group is frequently detected in pyrogenic source, such as combustion of coal, wood, vehicle fuel, and waste tire.

Source Apportionment and Risk Assessment of Atmospheric Polycyclic Aromatic Hydrocarbons in Lhasa, Tibet, China

Much attention has been given to the distributions, sources, and health risks of atmospheric polycyclic aromatic hydrocarbons (PAHs) in cities. In this study, a total of 62 suspended particle samples were collected from April 2013 till March 2014 in the city of Lhasa. Positive matrix factorization (PMF) was applied to investigate the source apportionment of 15 priority PAHs, the lifetime carcinogenic risk (LCR) levels of which were assessed. The average annual particle phase PAH concentration was 43.9 ± 60.4 ng m–3. Evident seasonal variations of PAHs were observed, with the highest concentration observed in winter, followed by autumn, spring, and summer. Four- and five-ring PAHs accounted for the predominant proportion (63.3%–84.4%) throughout the year. Correspondingly, gas phase PAHs showed the opposite variations, with the highest and lowest concentrations observed in summer and winter, respectively; also, three-ring PAHs, especially Ace, Acel, and Flu, were the largest contributors. Compositions of particle phase PAHs varied seasonally, with four-ring PAHs contributing more in winter than in summer and five-ring PAHs exhibiting the opposite trend, thereby reflecting the variety of emission sources. PMF analysis showed that biomass combustion (48.4%) and vehicle emissions (27.9%) were the two main sources, followed by coal combustion and the air–surface exchange. These results were consistent with the diagnostic molecular ratios. The benzo(a)pyrene equivalent (BaPeq) concentration of particle phase PAHs ranged from 1.48 to 24.5 ng m–3, which exceeds were higher than the new limit in China (1 ng m–3). The average BaPeq of gas phase PAHs was 6.43 ± 4.15 ng m–3, which was similar to that of particle phase PAHs. The LCR of the total PAHs (9.08 × 10–6) was one time higher than that of the particle phase; however, it was slightly lower than the acceptable level, thereby indicating that atmospheric PAHs in Lhasa pose little or no carcinogenic risk to the local population.