Methylated Polycyclic Aromatic Hydrocarbons Research Articles

The impact of gaseous degradation on the gas–particle partitioning of methylated polycyclic aromatic hydrocarbons

Abstract. The partitioning of semi-volatile organic compounds (SVOCs) between gas and particle phases plays a crucial role in their long-range transport and health risk assessment. However, the accurate prediction of the gas–particle (G–P) partitioning quotient (KP′) remains a challenge, especially for the light-molecular-weight (LMW) SVOCs due to their upward deviation from equilibrium state. In this study, the phenomenon with the influence of gaseous degradation on G–P partitioning was observed. Based on the diurnal study of concentrations and KP′ values for methylated polycyclic aromatic hydrocarbons (Me-PAHs), it was found that the KP′ values of methylated naphthalenes (Me-Naps; one type of LMW SVOC) during the daytime were higher than during the nighttime, and the regression lines of log KP′ versus log KOA (octanol–air partitioning coefficient) for daytime and nighttime were non-overlapping, which were different from other Me-PAHs. Compared with other diurnal influencing factors, the higher gaseous degradation of Me-Naps in the daytime than in the nighttime should partially explain their special diurnal variation in KP′, which provided a new explanation for the non-equilibrium behavior of KP′ for LMW SVOCs. Moreover, the influence of gaseous degradation on the deviation of KP′ from equilibrium state was deeply studied based on the steady-state G–P partitioning model considering particulate proportion in emission (ϕ0). The increasing times of KP′ influenced by the gaseous degradation deviated from equilibrium state can be calculated by 1 + 13.2ϕ0 × kdeg (kdeg, gaseous degradation rate). The increase in KP′ along with the increase in kdeg proved that higher gaseous degradation in the daytime could increase the KP′ value. Furthermore, an amplification in KP′ ranging from 1.11 to 5.58 times (90 % confidence interval: 1.01 to 14.4) under different ϕ0 values (0 to 1) in the temperature range of −50 to 50 °C was estimated by the Monte Carlo analysis. In summary, it can be concluded that the influence of gaseous degradation should also be considered in the G–P partitioning models of SVOCs, especially for the LMW SVOCs, which provided new insights into the related fields.

Occurrence, removal, and risk assessment of polycyclic aromatic hydrocarbons and their derivatives in typical wastewater treatment plants

Wastewater treatment plants (WWTPs) have a certain removal capacity for polycyclic aromatic hydrocarbons (PAHs) and their derivatives, but some of them are discharged with effluent into the environment, which can affect the environment. Therefore, to understand the presence, sources, and potential risks of PAHs and their derivatives in WWTPs. Sixteen PAHs, three chlorinated polycyclic aromatic hydrocarbons (ClPAHs), three oxidized polycyclic aromatic hydrocarbons (OPAHs), and three methylated polycyclic aromatic hydrocarbons (MPAHs) were detected in the influent and effluent water of three WWTPs in China. The average concentrations of their influent ∑PAHs, ∑ClPAHs, ∑OPAHs, and ∑MPAHs ranged from 2682.50 to 2774.53 ng/L, 553.26–906.28 ng/L, 415.40–731.56 ng/L, and 534.04–969.83 ng/L, respectively, and the effluent concentrations ranged from 823.28 to 993.37 ng/L, 269.43–489.94 ng/L, 285.93–463.55 ng/L, and 376.25–512.34 ng/L, respectively. The growth of heat transport and industrial energy consumption in the region has a significant impact on the level of PAHs in WWTPs. According to the calculated removal efficiencies of PAHs and their derivatives in the three WWTPs (A, B, and C), the removal rates of PAHs and their derivatives were 69–72%, 62–71%, and 68–73%, respectively, and for the substituted polycyclic aromatic hydrocarbons (SPAHs), the removal rates were 41–49%, 31–40%, and 33–39%, respectively; moreover, the removal rates of PAHs were greater than those of SPAHs in the WWTPs. The results obtained via the ratio method indicated that the main sources of PAHs in the influent of WWTPs were the combustion of coal and biomass, and petroleum contamination was the secondary source. In risk evaluation, there were 5 compounds for which the risk quotient was considered high ecological risk. During chronic disease evaluation, there were 11 compounds with a risk quotient considered to indicate high risk. PAHs and SPAHs with high relative molecular masses in the effluent of WWTPs pose more serious environmental hazards than their PAHs counterparts.

Methylated derivatives of polycyclic aromatic hydrocarbons in road dust, green belt soil and parking lot dust: occurrence, spatial distribution and emission sources.

Convenient transportation facilities not only bring the higher standard of living to big cities, but also bring some environmental pollution problems. In order to understand the presence and sources of methylated polycyclic aromatic hydrocarbons (Me-PAHs) in environmental samples and their association with total organic carbon (TOC), 49 Me-PAHs were analyzed in road dust, green belt soil and parking lot dust samples in Harbin. The results showed that the ranges of the total Me-PAHs (ΣMe-PAHs) content in road dust were 221-5826ng/g in autumn and 697-7302ng/g in spring, and those in green belt soil were 170-2509ng/g and 155-9215ng/g in autumn and spring, respectively. And ΣMe-PAHs content in parking lot dust ranged from 269 to 2515ng/g in surface parking lots and from 778 to 10,052ng/g in underground parking lots. In these samples, the composition profile of Me-PAHs was dominated by 4-ring Me-PAHs. The results of diagnostic ratios and principal component analysis (PCA) indicated that petrogenic and pyrogenic sources were the main sources of Me-PAHs in the samples. Spearman correlation analysis showed that there was no correlation for Me-PAHs in road dust and green belt soil on the same road. Furthermore, there was a significant positive relationship (0.12 ≤ R2 ≤ 0.67, P < 0.05) between Me-PAHs concentrations and the TOC content. This study demonstrated the presence of Me-PAHs with high concentrations in the road environment samples of Harbin.

Analysis and Assessment of Contamination Degree and Emission Sources of Polycyclic Aromatic Hydrocarbons (PAHs and Me-PAHs) in Surface Sediments from Central Coast of Vietnam

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives are a diverse group of organic pollutants, which are relatively persistent and toxic. Simultaneous determination of unsubstituted PAHs and methylated PAHs (Me-PAHs) is necessary to provide comprehensive insights into contamination levels and sources of these pollutants. In this study, we collected surface sediment samples in Vietnamese central coast to analyze 7 PAHs and 12 Me-PAHs. The sediment samples were extracted by using a focused ultrasonic processor with acetone/hexane (1:1) mixture and toluene. The extract was purified by column chromatography technique with activated silica gel and dichloromethane/hexane (1:3) as elution solvent. PAHs and Me-PAHs were determined by a gas chromatography/mass spectrometry (GC/MS) system operated in electron impact ionization (EI) and selected ion monitoring mode (SIM). Concentrations of total 7 PAHs and 12 Me-PAHs ranged from 30 to 246 (average 92) nanograms per gram sediment (ng/g). These levels were comparable to or lower than those measured in Vietnamese river sediments and marine sediments from some other countries in the world. The accumulation profiles of PAHs and Me-PAHs indicated that their emissions are likely associated with mixed pyrogenic and petrogenic sources. Our results have provided preliminary information about the pollution degree and accumulation characteristics of these substances in Vietnamese marine environments. Additional comprehensive studies should be performed to characterize contamination characterisrics, emission sources, and ecological risks of PAHs and their derivatives in this country.

Polycyclic aromatic hydrocarbons in the sediments of highly polluted coastal area in the Red Sea: levels, spatial distribution, and risk assessment.

The southern part of the Jeddah coast faces a range of pollution challenges that can impact the water quality and ecosystem in the area. Pollution sources are represented mainly by treated wastewater (TWW), harbor activities, and atmospheric deposition from vehicle exhaustemissions. Polycyclic aromatic hydrocarbons (PAHs) are among the persistent organic pollutants that interfere with all environmental matrices and could cause humane mutagenic and carcinogenic effects. In the present study, 16 priority parent and 21 methylated PAHs (∑37PAHs) were assessed in the sediments of three hot spot coastal sites (Islamic Jeddah port, Al-Arbaeen, and Al-Shabab lagoons) to evaluate the factors affecting their spatial distribution, examine their probable sources and potential adverse effects. The total detected concentrations of ∑37PAHs ranged from 785.9 to 8359.8ng/g dw (average: 2296.3 ± 2017.3ng/g dw). The highest levels of ∑37PAHs were detected near TWW stations. The highest individual PAH congeners observed were phenanthrene, anthracene, and pyrene. PAH molecular diagnostic ratios pointed out different pyrogenic sources. In some specific stations, there was an overlap of petrogenic origin. The sediment samples contained high concentrations of methylated PAHs, with concentrations ranging from 558.42 to 6321.21ng/g dw and an average concentration of 1679.1 ± 1430.7ng/g dw. The sediment quality guidelines indicated that adverse biological effects are likely to occur at least at the two TWW disposal stations and the sediments in these stations are at risk. The values of the mutagenic equivalence quotient (MEQ) and toxic equivalence quotient (TEQ) of carcinogenic PAHs were recorded at 39.88 and 33.17ng/g, respectively.

Application of Positive Matrix Factorization for Source Apportionment of Polycyclic Aromatic Hydrocarbons (PAH) in the Adriatic Sea, and the Evaluation of PAH-Related Carcinogenic Risks

Concentrations of polycyclic aromatic hydrocarbons (PAH) were studied in 36 sediment samples collected from 29 sites in the central Adriatic Sea. The total concentration of PAH showed high variability, ranging from 42.85 µg kg−1 in open sea sediments to 28,662 µg kg−1 in the sediments of Šibenik Bay. Unsubstituted, parent PAH were dominant PAH compounds in the entire area of Šibenik Bay and most of the stations in the coastal area. In Kaštela Bay, methyl PAH concentrations were higher than the concentrations of unsubstituted PAH, whereas in the sediments along the mid-Adriatic transect, similar concentrations of both PAH fractions were determined. PAH sources were investigated by applying the Positive Matrix Factorization software developed by the U.S. Environmental Protection Agency (USEPA). The results indicate the presence of four sources, two of which can be considered petrogenic and two pyrogenic. The contribution of the sources to the total concentration PAH at each station indicates the dominance of pyrogenic sources in Šibenik Bay and at most stations in the coastal area. In the sediments along the mid-Adriatic transversal, as well as in Kaštela Bay, PAHs originate mainly from petrogenic sources. The obtained results show that PMF can be a suitable tool for control of PAH pollution and thus, for the management of various activities in the Adriatic region. Seasonal differences between the contributions of sources in the Kaštela and Šibenik bays indicate that the contribution of traffic to the total concentration of PAH was higher during the tourist season. The carcinogenic risk of PAH determined by toxicity equivalent (TEQ) calculations showed an increased carcinogenic risk in the whole area of Šibenik Bay, regardless of the number of PAH compounds considered for the calculations. A low PAH-related carcinogenic risk was found for the rest of the study area.

Methylated polycyclic aromatic hydrocarbons from household coal use across the life course and risk of lung cancer in a large cohort of 42,420 subjects in Xuanwei, China

BackgroundWe previously showed that exposure to 5-methylchrysene (5MC) and other methylated polycyclic aromatic hydrocarbons (PAHs) best explains lung cancer risks in a case-control study among non-smoking women using smoky coal in China. Time-related factors (e.g., age at exposure) and non-linear relations were not explored. ObjectiveWe investigated the relation between coal-derived air pollutants and lung cancer mortality using data from a large retrospective cohort. MethodsParticipants were smoky (bituminous) or smokeless (anthracite) coal users from a cohort of 42,420 subjects from four communes in XuanWei. Follow-up was from 1976 to 2011, during which 4,827 deaths from lung-cancer occurred. Exposures were predicted for 43 different pollutants. Exposure clusters were identified using hierarchical clustering. Cox regression was used to estimate exposure–response relations for 5MC, while effect modification by age at exposure was investigated for cluster prototypes. A Bayesian penalized multi-pollutant model was fitted on a nested case-control sample, with more restricted models fitted to investigate non-linear exposure–response relations. ResultsWe confirmed the strong exposure–response relation for 5MC (Hazard Ratio [95% Confidence Interval] = 2.5 [2.4, 2.6] per standard-deviation (SD)). We identified four pollutant clusters, with all but two PAHs in a single cluster. Exposure to PAHs in the large cluster was associated with a higher lung cancer mortality rate (HR [95%CI] = 2.4 [2.2, 2.6] per SD), while exposure accrued before 18 years of age appeared more important than adulthood exposures. Results from the multi-pollutant model identified anthanthrene (ANT) and benzo(a)chrysene (BaC) as risk factors. 5MC remained strongly associated with lung cancer in models that included ANT and BaC and also benzo(a)pyrene (BaP). ConclusionWe confirmed the link between PAH exposures and lung cancer in smoky coal users and found exposures before age 18 to be especially important. We found some evidence for the carcinogen 5MC and non-carcinogens ANT and BaC.

The role of receptor-mediated activities of 4- and 5-ring unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs) in developmental toxicity.

The present study evaluated the aryl hydrocarbon receptor (AhR), estrogen receptor-α (ER-α), and retinoic acid receptor (RAR) mediated activities of nine 4- and 5-ring unsubstituted and monomethylated polycyclic aromatic hydrocarbons (PAHs) using a series of Chemical-Activated LUciferase gene eXpression (CALUX) assays. The potential role of these aforementioned receptors in relation to the developmental toxicity of these PAHs was further assessed in the zebrafish embryotoxicity test (ZET). The results show that all nine tested PAHs were AhR agonists, benz[a]anthracene (BaA) and 8-methyl-benz[a]anthracene (8-MeBaA) were ER-α agonists, and none of the tested PAHs induced ER-α antagonistic or RAR (ant)agonistic activities. In the AhR CALUX assay, all the methylated PAHs showed higher potency (lower EC50) in activating the AhR than their respective unsubstituted PAHs, implying that the addition of a methyl substituent on the aromatic ring of PAHs could enhance their AhR-mediated activities. Co-exposure of zebrafish embryos with each individual PAH and an AhR antagonist (CH223191) counteracted the observed developmental retardations and embryo lethality to a certain extent, except for 8-methyl-benzo[a]pyrene (8-MeBaP). Co-exposure of zebrafish embryos with either of the two estrogenic PAHs (i.e., BaA and 8-MeBaA) and an ER-α antagonist (fulvestrant) neutralized embryo lethality induced by 50 μM BaA and the developmental retardations induced by 15 μM 8-MeBaA. Altogether, our findings suggest that the observed developmental retardations in zebrafish embryos by the PAH tested may partially be AhR- and/or ER-α-mediated, whereas the RAR seems not to be relevant for the PAH-induced developmental toxicity in the ZET.

Characterization of size-resolved emissions of alkylated and nitrated polycyclic aromatic hydrocarbons (PAHs) from various combustion scenarios

In this study, we examined the size-resolved emissions of alkylated and nitrated polycyclic aromatic hydrocarbons (alkyl- and nitro-PAHs) from various combustion sources including residential solid fuels, cigarette smoking, domestic waste burning, and vehicular exhausts, which have been scarcely addressed. The estimated emission factors (eEFs) of these PAH derivatives were generally highest from the biomass burning sources. Very few nitro-PAHs were detected in cigarette smoking, cooking, and vehicle emission sources. Significant linear or non-linear relationships were observed between methylated PAHs and their parent compounds; whereas the relationships were weak for most nitro-PAHs, revealing the difference and similarity in their emission or accumulation formation mechanisms. The size distributions of individual methylated phenanthrenes (PHEs) and PHE were very similar in each source, but different between the sources. Generally, in sources with higher eEFs, these compounds were more tendentious to associate with the fine fractions. The intra-source size distributions of the methylated naphthalenes (NAPs) and NAP were different in some sources. The cooking and vehicle sources showed the lowest distributions of these PAHs derivatives in fine particles. The size fractionations of nitro-PAHs among the sources were very variable due to the low emissions, except for a few high molecular weight compounds showing more robust enrichment in the fine fractions. In addition to the size-resolved characterization, this work also highlights the need for understanding their formation and fractionation mechanisms.

Photodissociation dynamics of xylene isomers C6H4(CH3)2 at 157 nm using an ultracompact velocity map imaging spectrometer – The C7H7 channel

We investigated the photodissociation dynamics of three xylene isomers C6H4(CH3)2 at 157 nm. The center-of-mass translational energy distributions of C7H7 radicals were found to peak at 26 kJ mol−1. Although the ionization energy of the C7H7 tolyl fragment exceeds the energy of a 157 nm photon, C7H7+ was observed as a result of the photoionization of vibrationally ‘hot’ tolyl (C7H7) radicals and/or two-photon ionization. The formation of rovibrationally excited tolyl fragments was discussed. Our experiments suggest the presence of tolyl radicals in the interstellar medium as a precursor to methylated polycyclic aromatic hydrocarbons upon reaction with vinylacetylene (C4H4).

Detection of Nitrated, Oxygenated and Hydrogenated Polycyclic Aromatic Compounds in Smoked Fish and Meat Products.

Polycyclic aromatic hydrocarbons (PAHs) are present in smoked food products. More toxic nitrated (NPAH) and oxygenated (OPAH) PAHs derivatives are found concomitantly to PAHs and are therefore believed to be found in smoked food products. However, only a few PAH analyses on food include these derivatives. We adjusted and successfully validated a GC-QTOFMS method including 13 NPAHs and 2 OPAHs as well as the 4 regulated PAHs for analysis of 14 smoked (13 fish and one bacon) and one pan fried fish samples.OPAHs were detected in the highest concentrations in 13 of 15 samples. Non-target screening revealed the presence of an additional four OPAHs and two methylated PAHs. Future food analysis should, based on these results, focus on PAH and oxygenated derivatives.

Infrared spectroscopy of the benzylium-like (and tropylium-like) isomers formed in the –H dissociative ionization of methylated PAHs

Cationic benzylium and tropylium are known to be two competitive isomers for the –H fragment of the methylbenzene (toluene) cation. Methylated polycyclic aromatic hydrocarbon (PAH) cations are expected to be abundant in space and their dehydrogenation could lead to the formation of both the benzylium- and tropylium-like cations, which are expected to be the two lowest-energy isomers. Here, we considered 1-methylpyrene and two less compact acene-substituted species, namely 2-methylnaphthalene and 2-methylanthracene, as precursors. The cationic –H fragments, C17H11+, C11H9+, and C15H11+, were produced by dissociative ionization, and their neon tagged complexes were formed in the 22-pole cryogenic ion trap instrument FELion that is coupled to the FELIX free electron laser. Infrared (IR) predissociation spectroscopy was performed showing that the strongest depletion band is located at about 1620cm−1, which reveals the predominance of the benzylium-like, XCH2+, isomers, where X = Pyr, Nap, or Ant. Saturation depletion measurements showed that only this isomer is present in the case of C17H11+, whereas for the acene-derived species at least two are present with a large abundance. Synthetic spectra were generated from the theoretical anharmonic IR spectra of the two lowest-energy isomers, namely XCH2+ and the tropylium-like isomers, XC7+. Spectral comparison led us to conclude that there is no evidence for PyrC7+ but clear evidence for NapC7+. No specific spectral features could be identified for AntC7+ due to a high spectral congestion. These results support the important role of PAH compactness in preventing the formation of XC7+ species. They also reveal the potential of XCH2+ species to account for the aromatic infrared band observed in emission at 6.2μm in astrophysical environments.

Characterization of unsubstituted and methylated polycyclic aromatic hydrocarbons in settled dust: Combination of instrumental analysis and in vitro reporter gene assays and implications for cancer risk assessment

Concentrations of 34 unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs and Me-PAHs) and AhR-mediated activities in settled dust samples were determined by a combination of gas chromatography–mass spectrometry and an in vitro reporter gene assay (PAH-CALUX). The levels of Σ34PAHs and bioassay-derived benzo[a]pyrene equivalents (CALUX BaP-EQs) were significantly higher in workplace dust from informal end-of-life vehicle dismantling workshops than in common house dust and road dust. In all the samples, the theoretical BaP-EQs of PAHs (calculated using PAH-CALUX relative potencies) accounted for 28 ± 19% of the CALUX BaP-EQs, suggesting significant contribution of aryl hydrocarbon receptor (AhR) agonists and/or mixture effects. Interestingly, the bioassay-derived BaP-EQs in these samples were significantly correlated with not only unsubstituted PAHs with known carcinogenic potencies but also many Me-PAHs, which should be included in future monitoring and toxicity tests. The bioassay responses of many sample extracts were substantially reduced but not suppressed with sulfuric acid treatment, indicating contribution of persistent AhR agonists. Cancer risk assessment based on the CALUX BaP-EQs has revealed unacceptable level of risk in many cases. The application of bioassay-derived BaP-EQs may reduce underestimation in environmental management and risk evaluation regarding PAHs and their derivatives (notably Me-PAHs), suggesting a consideration of using in vitro toxic activity instead of conventional chemical-specific approach in such assessment practices.

Polycyclic aromatic hydrocarbons in airborne particulate matter samples from Hanoi, Vietnam: Particle size distribution, aryl hydrocarbon ligand receptor activity, and implication for cancer risk assessment

Concentrations and profiles of unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs and Me-PAHs) were analyzed in airborne particulate matter (PM) samples collected from high-traffic roads in Hanoi urban area. Levels of PAHs and Me-PAHs ranged from 210 to 660 (average 420) ng/m3 in total PM, and these pollutants were mainly associated with fine particles (PM2.5) rather than coarser ones (PM > 10 and PM10). Proportions of high-molecular-weight compounds (i.e., 5- and 6-ring) increased with decreasing particle size. Benzo[b+k]fluoranthene, indeno[1,2,3-cd]pyrene, and benzo[ghi]perylene were the most predominant compounds in the PM2.5 samples. In all the samples, Me-PAHs were less abundant than unsubstituted PAHs. The PAH-CALUX assays were applied to evaluate aryl hydrocarbon receptor (AhR) ligand activities in crude extracts and different fractions from the PM samples. Benzo[a]pyrene equivalents (BaP-EQs) derived by the PAH-CALUX assays for low polar fractions (mainly PAHs and Me-PAHs) ranged from 300 to 840 ng/m3, which were more consistent with theoretical values derived by using PAH-CALUX relative potencies (270–710 ng/m3) rather than conventional toxic equivalency factor-based values (22–69 ng/m3). Concentrations of PAHs and Me-PAHs highly correlated with bioassay-derived BaP-EQs. AhR-mediated activities of more polar compounds and interaction effects between PAH-related compounds were observed. By using PAH-CALUX BaP-EQs, the ILCR values ranged from 1.0 × 10−4 to 2.8 × 10−4 for adults and from 6.4 × 10−5 to 1.8 × 10−4 for children. Underestimation of cancer risk can be eliminated by using effect-directed method (e.g., PAH-CALUX) rather than chemical-specific approach.

Occurrence, Removal, and Mass Balance of Polycyclic Aromatic Hydrocarbons and Their Derivatives in Wastewater Treatment Plants in Northeast China

Polycyclic aromatic hydrocarbons (PAHs), 33 methylated PAHs (Me-PAHs), and 14 nitrated PAHs (NPAHs) were measured in wastewater treatment plants (WWTPs) to study the removal efficiency of these compounds through the WWTPs, as well as their source appointment and potential risk in the effluent. The concentrations of ∑PAHs, ∑Me-PAHs, and ∑NPAHs were 2.01–8.91, 23.0–102, and 6.21–171 µg/L in the influent, and 0.17–1.37, 0.06–0.41 and 0.01–2.41 µg/L in the effluent, respectively. Simple Treat 4.0 and meta-regression methods were applied to calculate the removal efficiencies (REs) for the 63 PAHs and their derivatives in 10 WWTPs and the results were compared with the monitoring data. Overall, the ranges of REs were 55.3–95.4% predicated by the Simple Treat and 47.5–97.7% by the meta-regression. The results by diagnostic ratios and principal component analysis PCA showed that “mixed source” biomass, coal composition, and petroleum could be recognized to either petrogenic or pyrogenic sources. The risk assessment of the effluent was also evaluated, indicating that seven carcinogenic PAHs, Benzo[a]pyrene, Dibenz[a,h]anthracene, and Benzo(a)anthracene were major contributors to the toxics equivalency concentrations (TEQs) in the effluent of WWTPs, to which attention should be paid.

Unsubstituted and Methylated PAHs in Surface Sediment of Urban Rivers in the Red River Delta (Hanoi, Vietnam): Concentrations, Profiles, Sources, and Ecological Risk Assessment.

Unsubstituted and methylated polycyclic aromatic hydrocarbons (22 PAHs and 17 Me-PAHs) were examined in surface sediments collected from the Red River and four inner-city rivers of Hanoi City, Vietnam. Concentrations of total PAHs and Me-PAHs ranged from 52 to 920 (median 710) and from 70 to 2600 (median 1000) ng/g dry weight in samples of dry and wet seasons, respectively. Significant correlation was observed between total PAHs and organic carbon contents (Spearman's ρ = 0.782; p < 0.05). PAHs were more abundant than Me-PAHs in all samples and dominated by 4-6 ring compounds. The most predominant PAHs were benzo[ghi]perylene, benzo[b/j]fluoranthene, chrysene, pyrene, fluoranthene, and phenanthrene. Methylated derivatives of naphthalene, phenanthrene, anthracene, and benz[a]anthracene were frequently detected. The patterns of PAHs indicated principal pyrogenic sources (notably gasoline exhaust) in this highly urbanized area. The occurrence of several PAHs were occasionally associated with adverse effects on benthic organisms of the inner-city rivers.

Analysis of recycled rubber: Development of an analytical method and determination of polycyclic aromatic hydrocarbons and heterocyclic aromatic compounds in rubber matrices

Recycled crumb rubber (CR) is rich in compounds with unrecognized toxic potency; this study aims at the development of an analytical method that would allow identification and quantification of a very wide range of organic compounds extractable from the complex rubber matrix.The analytical set-up includes target analysis of polycyclic aromatic hydrocarbons (PAHs) and methyl-PAHs and suspect screening of raw extracts to tentatively identify primary organic compounds present, but not included in the standard target analysis of recycled rubber, followed by analytical method development and target analysis of identified compounds. Analyzed samples included weathered and new CR originating from football turf granulates, rubber mats, and end-of-life car tires (ELTs).The developed analytical method involves sonication extraction, followed by solid phase extraction (SPE) fractionation that enables simple and efficient separation of analytes with broad polarity scale. The application of SPE fractionation resolves coelution problems and simplifies the chromatograms. This analytical approach allowed to identify and quantify 46 sample specific compounds, including several heterocyclic PAHs like 2-methylthiobenzothiazole, benzonapthothiophenes, benzonaphthofuranes and aromatic amines like diphenylamine and N-phenyl-2-naphthylamine, which to our knowledge were not determined before. The PAHs concentrations determined in CR tiles purchased in Dutch and Spanish shops exceed the EU limits for articles marketed for use by the public. Furthermore, sets of methylated PAHs, dibenzothiazoles and aromatic amines were identified and quantified, and several other compounds were tentatively identified. The obtained results stress the need for expanding the list of target compounds analyzed in CR and the need for longitudinal studies on weathering processes taking place in CR.

Parent and methyl polycyclic aromatic hydrocarbons and n-alkanes emitted by construction machinery in China

Construction machinery emits considerable quantities of organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and n-alkanes, which significantly affect air quality, human health, and climate change. However, actions to reduce the pollution caused by these pollutants are insufficient due to a lack of comprehensive studies. Therefore, 16 United States Environmental Protection Agency (EPA) priority control PAHs (pPAHs), nine methyl PAHs (mPAHs), and 27 n-alkanes (C12-C38) in particulate matter (PM2.5) emitted by 20 construction machines of different types and emission standards, operated under three modes, were measured in this study. The results showed that (1) the total fuel-based emission factors of pPAHs, mPAHs, and n-alkanes for construction machinery were in the ranges 0.033–1.43, 0.027–1.37, and 1.32–87 mg/kg fuel, respectively. (2) The average emission factors of pPAHs, mPAHs, and n-alkanes in excavator and bulldozer emissions were higher than those in loader and forklift emissions, which can be attributed to machine type, operation mode, emission standards, and engine power. (3) Pry, Phe, C18-C22, 1-mNaP, and mFluo emissions were significantly dominant. Some diagnostic ratios of PAHs (e.g., Ant/(Ant + Phe), Flu/(Flu + Pry), BaA/(BaA + Chry), and IP/(IP + BghiP)) were consistent with those emitted by liquid fossil fuel combustion, whereas the ratios of low molecular weight n-alkanes (C ≤ 24) to high molecular weight (C > 24) n-alkanes from construction machines were higher than those for on-road gasoline vehicles, diesel vehicles, and vessels. (4) The benzo(a)pyrene equivalents (BaPeq) and lifetime cancer risk (LCR) values of PAHs from bulldozer and forklift emissions were higher than those from excavator and loader emissions, especially under working modes. Furthermore, the BaPeq and LCR values of PAHs from construction machineries were higher than that specified by GB3095-2012 and 10^−4, respectively, thereby indicating that PAHs emitted from construction machines pose high health risks.

Treatment of Polycyclic Aromatic Hydrocarbons in Oil Sands Process-Affected Water with a Surface Flow Treatment Wetland

This study applied a passive sampling approach using low-density polyethylene passive samplers to determine the treatment efficiency of the Kearl surface flow treatment wetland for polycyclic aromatic hydrocarbons (PAHs) in Oil Sands Process-affected Waters (OSPW). Treatment efficiency was measured as concentration-reduction and mass-removal from the OSPW. The results show that the wetland’s ability to remove individual PAHs from the influent varied substantially among the PAHs investigated. Treatment efficiencies of individual PAHs ranged between essentially 0% for certain methylated PAHs (e.g., 2,6-dimethylnaphthalene) to 95% for fluoranthene. Treatment in the Kearl wetland reduced the combined total mass of all detected PAHs by 54 to 83%. This corresponded to a reduction in the concentration of total PAHs in OSPW of 56 to 82% with inflow concentrations of total PAHs ranging from 7.5 to 19.4 ng/L. The concentration of pyrene in water fell below water quality targets in the Muskeg River Interim Management Framework as a result of wetland treatment. The application of the passive samplers for toxicity assessment showed that in this study PAHs in both the influent and effluent were not expected to cause acute toxicity. Passive sampling appeared to be a useful and cost-effective method for monitoring contaminants and for determining the treatment efficiency of contaminants in the treatment wetland.

Soil and sediment contamination by unsubstituted and methylated polycyclic aromatic hydrocarbons in an informal e-waste recycling area, northern Vietnam: Occurrence, source apportionment, and risk assessment

Improper processing activities of e-waste are potential sources of polycylic aromatic hydrocarbons (PAHs) and their derivatives, however, information about the environmental occurrence and adverse impacts of these toxic substances is still limited for informal e-waste recycling areas in Vietnam and Southeast Asia. In this study, unsubstituted and methylated PAHs were determined in surface soil and river sediment samples collected from a rural village with informal e-waste recycling activities in northern Vietnam. Total levels of PAHs and MePAHs decreased in the order: workshop soil (median 2900; range 870–42,000 ng g−1) > open burning soil (2400; 840–4200 ng g−1) > paddy field soil (1200; range 530–6700 ng g−1) > river sediment samples (750; 370–2500 ng g−1). About 60% of the soil samples examined in this study were heavily contaminated with PAHs. Fingerprint profiles of PAHs and MePAHs in the soil and sediment samples indicated that these pollutants were mainly released from pyrogenic sources rather than petrogenic sources. The emissions of PAHs and MePAHs in this area were probably attributed to uncontrolled burning of e-waste and agricultural by-products, domestic coal and biomass combustion, and traffic activities. Carcinogenicity and mutagenicity of PAHs in the e-waste workshop soils were significantly higher than those of the field soils; however, the incremental lifetime cancer risk of PAH-contaminated soils in this study ranged from 5.5 × 10−9 to 4.6 × 10−6, implying acceptable levels of human health risk. Meanwhile, concentrations of some compounds such as phenanthrene, anthracene, fluoranthene, benz[a]anthracene, and benzo[a]pyrene in several soil samples exceeded the maximum permissible concentrations, indicating the risk of ecotoxicological effects.