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Cookstove emissions are a significant source of indoor air pollution in developing countries and rural communities world-wide. Considering that many research sites for evaluating cookstove emissions and interventions are remote and require potentially lengthy periods of particulate matter (PM) filter sample storage in sub-optimal conditions (e.g., lack of cold storage), an important question is whether samples collected in the field are stable over time. To investigate this, red oak was burned in a natural-draft stove, and fine PM (PM2.5) was collected on polytetrafluoroethylene filters. Filters were stored at either ambient temperature or more optimal conditions (-20 °C or -80 °C) for up to 3months and extracted. The effects of storage temperature and length on stability were evaluated for measurements of extractable organic matter (EOM), PM2.5, and polycyclic aromatic compound (PAC) levels in the filter extracts. A parallel, controlled laboratory condition was also evaluated to further explore sources of variability. In general, PM2.5 and EOM in both simulated field and laboratory samples were similar regardless of the storage condition or duration. The extracts were also analyzed by gas chromatography to quantify 22 PACs and determine similarities and/or differences between the conditions. PAC levels were a more sensitive stability measure in differentiating between storage conditions. The findings suggest that measurements are relatively consistent across storage duration/temperatures for filter samples with relatively low EOM levels. This study aims to inform protocols and filter storage procedures for exposure and intervention research conducted in low- and middle-income countries where studies may be budget- and infrastructure-limited. [ABSTRACT FROM AUTHOR]

Alkyl polycyclic aromatic hydrocarbons (APAHs) are more toxic and persistent than their parent compounds. In this study, the concentrations of polycyclic aromatic compounds (PACs) in dust, topsoil and coal gangue from Huaibei Coal mine, China were analyzed by gas chromatography-mass spectrometry, confirming APAHs were the dominant pollutants. The mean concentrations of APAHs were substantially higher than those of 16 PAHs in both dust and topsoil. The mean concentration of APAHs in dust was 9197 µg kg−1, accounting for 80% of the total mean concentration of PACs. The mean concentration of APAHs in topsoil was 2835 µg kg−1, accounting for 77% of the mean concentration of PACs. Alkyl naphthalenes and alkyl phenanthrenes were the primary pollutants in APAHs. Their mean concentrations in dust and topsoil were 7782 µg kg−1 and 2333 µg kg−1, respectively. This accounted for 85% and 82% of the concentration of APAHs, respectively. Additionally, low-molecular-weight APAHs dominated the PACs of the coal mine, exhibiting petrogenic characteristics; distribution of C1-C4 NAP and C1-C4 PHE exhibited "bell shape" pattern indicated as petrogenic source. Source identification indicated that the PACs were mainly derived from petrogenic sources and vehicle emissions, followed by biomass and coal burning. Fingerprinting information of dust and topsoil were consistent with coal gangue, indicating that PACs are most likely derived from coal gangue. Coalfields comparable to our study area are widely distributed in China. Therefore, investigating PAC pollution derived from coal gangue warrants further attention. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic compounds (PACs) are potential pollutants emitted from the petrochemical industry, whereas their occurrence and sources in petrochemical regions are still poorly known. The present study revealed the spatial variations, compositional profiles, sources and contributions, and health risks of PM-bound PACs in two large-scale petrochemical bases (GDPB and HNPB) in South China. The concentrations of parent polycyclic aromatic hydrocarbons (PAHs) were 7.14 ± 3.16 ng/m3 for ∑18PAHs and 0.608 ± 0.294 ng/m3 for the PAHs with molecular weight of 302 amu (MW302 PAHs) in the GDPB base and 2.55 ± 1.26 ng/m3 and 0.189 ± 0.088 ng/m3 in the HNPB base. Oxygenated PAHs (OPAHs) showed comparable concentrations to the parent PAHs in both the bases and nitrated PAHs (NPAHs) had the lowest mean levels (260 pg/m3 and 59.4 pg/m3 in the two regions). Coronene, 2,8-dinitrodibenzothiophene, and dibenzo[a,e]fluoranthene showed remarkably higher contributions to the PAC and can be PAC markers of the petrochemical industry source. Five sources of PACs were identified respectively in both petrochemical bases by the positive matrix factorization (PMF) model. The vehicle (and ship) traffic exhaust was the primary source of PACs (contributed 33% to the ∑PACs), and the sources related to the coking of coal and heavy petroleum and refinery exhaust were identified in both bases, with contributions of 10–20%. PACs in GDPB also contributed from secondary atmospheric reactions (17.3%) and the usage of sulfur-containing fuels (20.9%), while the aromatics industry made a significant contribution (20.1%) to the PACs in the HNPB region. The cumulative incremental lifetime cancer risks (ILCRs) induced by inhalation of PM-bound PACs in both petrochemical bases were low (10–8–10–6). For the sources related to the petrochemical industry, coking activities and the aromatic industry were the significant contributors to the ∑ILCRs in GDPB and HNPB, respectively. This research has implications for further source-targeted control and health risk reduction of PACs in petrochemical regions. [ABSTRACT FROM AUTHOR]

Coal gangue is a by-product of coal, the output of which is as high as 30% of raw coal, whereas only 30% of it is recycled. The leftover remains in the environment from gangue backfilling areas and overlap with residential, agricultural, and industrial areas. Coal gangue accumulated in the environment is easily weathered and oxidized and becomes a source of various pollutants. In this paper, 30 coal gangue samples (fresh and weathered coal gangues) were collected from three mine areas in Huaibei, Anhui province, China. Gas chromatography-triple quadrupole mass spectrometry (GC–MS/MS) was used to qualitatively and quantitatively analyze thirty polycyclic aromatic compounds (PACs), including 16 polycyclic aromatic hydrocarbons (16PAHs), preferentially controlled by the United States Environmental Protection Agency (US EPA), and the corresponding alkylated polycyclic aromatic hydrocarbons (a-PAHs). The results showed that PACs existed objectively in coal gangue, and the content of a-PAHs was higher than that of 16PAHs (average values for 16PAHs ranged from 77.8 to 581 ng/g; average values for a-PAHs ranged from 97.4 to 3179 ng/g). Moreover, coal types not only affected the content and type of PACs but also affected the distribution pattern of a-PAHs at different substitution sites. With the increase of gangue weathering degree, the composition of a-PAHs kept changing; the low ring a-PAHs were more easily diffused to the environment, and the high ring a-PAHs remained enriched in the weathered coal gangue. The correlation analysis showed that the correlation between fluoranthene (FLU) and alkylated fluoranthene (a-FLU) was as high as 94%, and the calculated ratios were not more than 1.5. The basic conclusion is that not only 16PAHs and a-PAHs objectively existed in the coal gangue, but also the characteristic compound belonging to the pollution source of coal gangue oxidation have been discovered. The results of the study provide a new perspective for the analysis of existing pollution sources. [ABSTRACT FROM AUTHOR]

Understanding the fate of polycyclic aromatic hydrocarbons (PAHs) in the deep ocean is crucial for elucidating the biogeochemical cycle of organic carbon under anthropogenic influences. In this study, surface sediments were collected from the deep sea of the Eastern Indian Ocean (water depth: 2161-4545 m) and analyzed for 29 semivolatile organic compounds (SVOCs), including parent PAHs and their alkylated derivatives, as well as source biomarkers. The target SVOCs (∑ 29 SVOCs: 23.0-183 ng/g, ∑ 16 PAHs: 11.3-93.3 ng/g) were mainly from pyrogenic sources, namely coal combustion, traffic emissions, and wood burning. The contributions from wood burning and coal combustion exhibited distinct trends with increasing total organic carbon contents, suggesting different dominant biogeochemical behaviors. Major fractions of PAHs from wood burning can be biodegraded or photodegraded, leading to a depletion-dominated fate in the water column. Conversely, PAHs from coal combustion showed an accumulation-dominated fate via their sedimentation due to their persistence and hydrophobicity. This study highlights the distinct biogeochemical fates of PAHs from biomass or fossil fuel combustion in deep oceans and has implications for the marine cycle of refractory organic carbon under anthropogenic impacts.

Abstract Canada has experienced a significant increase in the transport of diluted bitumen (dilbit), a predominant oil sands product that combines bitumen with diluents derived from oil-gas condensates and other proprietary compounds. The toxicity of dilbit to fish embryos, which are immobile and thus at a high risk of exposure to oil in the event of a spill, remains largely unknown for most species. This study assessed the toxicity of water accommodated fractions (WAF) and chemically enhanced water accommodated fractions (CEWAF) of two winter dilbit blends, Access Western Blend (AWB) and Cold Lake Blend (CLB), to fathead minnow (Pimephales promelas) embryos. The TPH-F EC50s for malformations were 834 and 1058 μg/L for AWB WAF and CEWAF, respectively, and 500 and 715 μg/L for CLB WAF and CEWAF, respectively. Levels of cyp1a mRNA increased up to 46- and 69-fold, respectively, reflecting increasing exposure to polycyclic aromatic compounds (PACs) in AWB and CLB. Similarly, levels of gst mRNA were elevated up to 3.8-fold and 2.7-fold with increasing total concentrations of PACs in AWB and CLB, respectively. However, there were no significant changes in mRNA levels of p53 , sod, cat , and gsr. These results suggest that the expression of cyp1a and gst may serve as biomarkers for dilbit exposure in fathead minnow, furthering our understanding of dilbit-responsive indicators of toxicity in fish species native to North America. This study is important as it utilizes the same exposure methodology to examine the toxicity of two commonly used Canadian dilbits, facilitating comparison of dilbit toxicity. [ABSTRACT FROM AUTHOR]

Atmospheric deposition is the most dominant source of polycyclic aromatic hydrocarbons (PAHs) in remote and pristine areas. Despite low bioaccumulation potential, PAHs and their persistent transformation products (PAH-derivatives) are chemicals of concern as they can harm human and animal health through chronic low dose exposure. In this study, atmospheric deposition fluxes of polycyclic aromatic compounds (PACs) were measured on a seasonal basis (3-month periods) from 2012 to 2016 in a remote subarctic forest catchment in northern Europe. The target PACs included 19 PAHs and 15 PAH-derivatives (oxygenated, nitrogenated, and methylated PAHs). The deposition fluxes of ƩPAHs and ƩPAH-derivatives were in the same range and averaged 530 and 500 ng m2 day−1, respectively. The fluxes were found to be higher with a factor of 2.5 for ƩPAHs and a factor of 3 for ƩPAH-derivatives during cold (<0 °C) in comparison to warm (>10 °C) periods. PAHs and PAH-derivatives showed similar seasonal patterns, which suggests that these two compound classes have similar sources and deposition mechanisms, and that the source strength of the PAH-derivatives in air follows that of the PAHs. The terrestrial export of PACs via the outlet of the catchment stream was estimated to be 1.1% for ƩPAHs and 1.7% for ƩPAH-derivatives in relation to the annual amounts deposited to the catchment, which suggests that boreal forests are sinks for PACs derived from the atmosphere. Some individual PACs showed higher export than others (i.e. chrysene, cyclopenta(c,d)pyrene, carbazole, quinoline, and benzo(f)quinoline), with high export PACs mostly characterized by low molecular weight and low hydrophobicity (2–3 benzene rings; log K ow <6.0). [Display omitted] • Deposition fluxes of ƩPAHs and ƩPAH-derivatives were in the same range. • Seasonal trends were similar for 19 PAHs and 15 PAH-derivatives. • Deposition fluxes were 3–5 times higher during cold (<0 °C) periods. • The terrestrial export of PACs was low: 1.1% for ƩPAHs and 1.7% for Ʃderivatives. • PACs with low MW and hydrophobicity showed higher export (>1%). [ABSTRACT FROM AUTHOR]

The organic matter in coal contains polycyclic aromatic compounds (PACs) of varying quantities in diverse soluble and insoluble forms. PACs in coal are of special interest for organic geochemical studies because they have been successfully used as biological marker compounds (biomarkers) and indicators of thermal maturity. In addition, they could provide critical information to understand the structural and compositional evolution of the coal organic matters during coalification, and to predict PAC releasing characteristics during coal utilization. The main purpose of this paper is to provide a critical review on the current state of knowledge on the potential use of PAC composition to understand the underlying biogeochemical factors that control PAC occurrence and distribution in coal. The published PAC data of world coal are first compiled according to their ranks (natural coke, anthracite, semi-anthracite, bituminous coal, low volatile bituminous coal, medium volatile bituminous coal, high volatile bituminous coal, sub-bituminous coal, lignite), countries (Brazil, Canada, China, France, Germany, Japan, USA), formation periods (Carboniferous, Permian, Jurassic, Cretaceous, Early-Middle Cenozoic). Then, the biogeochemical factors affecting the occurrence and distribution of PACs in coal, including biogenic precursor materials, coal rank, maceral composition, depositional environment, and geological settings, are comprehensively reviewed. The results show that the geochemical parameters of PACs in coal are robust tools to trace the coalification processes from the molecular perspectives, and to understand the corresponding biogeochemical process (e.g. depositional environment, geological settings, igneous intrusion) occurring during coal formation. [ABSTRACT FROM AUTHOR]

Biological degradation is the main process for oil degradation in a subsurface oil plume. There is, however, little information on the biodegradation potential of Arctic, marine subsurface environments. We therefore investigated oil biodegradation in microcosms at 2 °C containing Arctic subsurface seawater from the Disko Bay (Greenland) and crude oil at three concentrations of 2.5–10 mg/L. Within 71 days, the total petroleum hydrocarbon concentration decreased only by 18 ± 18% for an initial concentration of 5 mg/L. The saturated alkanes n C13- n C30 and the isoprenoids i C18- i C21 were biodegraded at all concentrations indicating a substantial potential for biodegradation of these compound classes. Polycyclic aromatic compounds (PACs) disappeared from the oil phase, but dissolution was the main process of removal. Analysis of diagnostic ratios indicated almost no PAC biodegradation except for the C1-naphthalenes. To conclude, the marine subsurface microorganisms from the Disko Bay had the potential for biodegradation of n -alkanes and isoprenoids while the metabolically complex and toxic PACs and their alkylated homologs remained almost unchanged. [ABSTRACT FROM AUTHOR]

Promising results of an efficient and convenient strategy for the annulation of polycyclic aromatic compounds (PACs), employing orthoquinones as starting material and comprising allylation, pinacol rearrangement, ring-closing metathesis (RCM), and one-pot reduction followed by Wagner-Meerwein rearrangement, are presented. The strategy involves introducing triallylborane prepared in situ in the allylation step. Moreover, a novel expedient method for the preparation of 9,10-diallylphenanthrene was introduced.

The Suntuan mining area of Huaibei is a typical coal resource mining base in the Huainan-Huaibei areas in North China. Previous environmental studies related to surface dust in coal mining areas mainly focused on heavy metals and water-soluble ions, with little research on polycyclic aromatic compounds (PACs). In this study, gas chromatography-triple tandem quadrupole mass spectrometry (GC-MS/MS) was used to determine the contents of 16 parent polycyclic aromatic hydrocarbons (16PAHs), alkyl polycyclic aromatic hydrocarbons (aPAHs), and some oxygenated polycyclic aromatic hydrocarbons (OPAHs) in surface dust from the Suntuan mining area and surrounding environment. The results showed that the ΣPACs concentration range of surface dust in the Suntuan mining area was 283.8-36852.5 μg·kg -1 (mean:4114.2 μg·kg -1 ). ΣaPAHs (mean:2593.8 μg·kg -1 ) was 2.4 times higher than Σ16PAHs (mean:1074.9 μg·kg -1 ), which was the main contributor to PAC pollution. The composition of 16PAHs and aPAHs in surface dust was dominated by low molecular polycyclic aromatic hydrocarbons. The average OPAH content was 445.6 μg·kg -1 . At the same time, PAC pollution was mainly concentrated around the mining area and near the road of a coal gangue landfill. Based on the positive matrix factor (PMF) analysis, it was inferred that the study area was mainly affected by petroleum sources, followed by coal and biomass combustion, and traffic sources and petroleum product leakage accounted for a relatively small proportion. Based on the ratio and distribution pattern of 16PAHs and aPAHs, it was inferred that when Σ16PAHs/ΣPACs<0.25, it was mainly polluted by the coal mining area. The results of PMF combined with lifetime carcinogenic risk (ILCR) showed that there were potential carcinogenic risks for children near the study area, mainly from coal and biomass burning and coal mining. There are many coal mining areas in Huaihe River Basin in China. The results of this study can provide reference for pollution prevention and control of PACs in these coal mining areas.

In former coal transformation plants (coking and gas ones), the major organic contamination of soils is coal tar, mainly composed of polycyclic aromatic compounds (PACs). Air oxidation of a fresh coal tar was chosen to simulate the abiotic natural attenuation impact on PAC-contaminated soils. Water-leaching experiments were subsequently performed on fresh and oxidized coal tars to study the influence of oxidation on dissolved organic matter (DOM) quality and quantity. The characterization of the DOM was performed using a combination of molecular and spectroscopic techniques (high-performance liquid chromatography-size-exclusion chromatography (HPLC-SEC), 3D fluorescence, and gas chromatography coupled with mass spectrometry (GC-MS)) and compared with the DOM from contaminated soils sampled on the field exposed to natural attenuation for several decades. An increase in the oxygenated polycyclic aromatic compound concentrations was observed with abiotic oxidation both in the coal tar and the associated DOM. Polycyclic aromatic hydrocarbon concentrations in the leachates exceeded pure water solubility limits, suggesting that co-solvation with other soluble organic compounds occurred. Furthermore, emission excitation matrix analysis combined with synchronous fluorescence spectra interpretation and size-exclusion chromatography suggests that oxidation induced condensation reactions which were responsible for the formation of higher-molecular weight compounds and potentially mobilized by water. Thus, the current composition of the DOM in aged soils may at least partly result from (1) a depletion in lower-molecular weight compounds of the initial contamination stock and (2) an oxidative condensation leading to the formation of a higher-molecular weight fraction. Abiotic oxidation and water leaching may therefore be a significant combination contributing to the evolution of coal tar-contaminated soils under natural attenuation. [ABSTRACT FROM AUTHOR]

Abstract: We evaluated the effects of soil properties and climate on concentrations of parent and oxygenated polycyclic aromatic compounds (PAHs and OPAHs) and azaarenes (AZAs) in topsoil and subsoil at 20 sites along a 2100-km north (N)–south (S) transect in Argentina. The concentrations of Σ29PAHs, Σ15OPAHs and Σ4AZAs ranged 2.4–38ngg−1, 0.05–124ngg−1 and not detected to 0.97ngg−1, respectively. With decreasing anthropogenic influence from N to S, low molecular weight PAHs increasingly dominated. The octanol–water partitioning coefficients correlated significantly with the subsoil to topsoil concentration ratios of most compounds suggesting leaching as the main transport process. Organic C concentrations correlated significantly with those of many compounds typical for atmosphere–soil partitioning. Lighter OPAHs were mainly detected in the S suggesting biological sources and heavier OPAHs in the N suggesting a closer association with parent-PAHs. Decreasing alkyl-naphthalene/naphthalene and 9,10-anthraquinone (9,10-ANQ)/anthracene ratios from N to S indicated that 9,10-ANQ might have originated from low-temperature combustion. [Copyright &y& Elsevier]

Highlights: [•] The CHEMSIC method is an accurate tool for assessing the bioremediation efficiency. [•] Bacterial enrichment and addition of nutrients enhance removal of TPHs in soil. [•] Bacterial enrichment increases the degradation of n-alkanes and some PACs. [•] Chemometrics is a comprehensive approach for monitoring of the degradation of petroleum hydrocarbons. [ABSTRACT FROM AUTHOR]

Abstract: A chemometric method based on principal component analysis (PCA) of pre-processed and combined sections of selected ion chromatograms (SICs) is used to characterise the hydrocarbon profiles in soil and sediment from Araucária, Guajuvira, General Lúcio and Balsa Nova Municipalities (Iguaçu River Watershed, Paraná, Brazil) and to indicate the main sources of hydrocarbon pollution. The study includes 38 SICs of polycyclic aromatic compounds (PACs) and four of petroleum biomarkers in two separate analyses. The most contaminated samples are inside the Presidente Getúlio Vargas Refinery area. These samples represent a petrogenic pattern and different weathering degrees. Samples from outside the refinery area are either less or not contaminated, or contain mixtures of diagenetic, pyrogenic and petrogenic inputs where different proportions predominate. The locations farthest away from industrial activity (Balsa Nova) contains the lowest levels of PAC contamination. There are no evidences to conclude positive matches between the samples from outside the refinery area and the Cusiana spilled oil. [Copyright &y& Elsevier]

In this work, the binding of 2-hydroxy-3-nitro-9-fluorenone (HNF; a new reagent with antitumour activity) to human serum albumin (HSA) was investigated by fluorescence spectroscopy combined with UV-Vis absorption, circular dichroism (CD), and Fourier transform infrared (FT-IR) spectrophotometric techniques under simulative physiological conditions for the first time. A strong fluorescence quenching reaction of HNF to HSA was observed and the quenching mechanism was suggested as static quenching according to the Stern–Volmer (S–V) equation. The binding constants of HNF with HSA at 300, 310 and 320 K were calculated as 6.08×105, 3.80×105 and 2.79×105 M-1, respectively, and corresponding numbers of binding sites (n) were 1.1, 1.0 and 1.0. Experimental results observed showed that the binding of HNF to HSA induced conformational change of HSA. The quantitative analysis data of CD spectra from that of the α-helix 60.3% in free HSA to 56.5% in the HNF–HSA complex further confirmed that the secondary structure of the protein was modified by HNF. The thermodynamic parameters, standard enthalpy change (ΔH°) and the standard entropy change (ΔS°), were obtained to be -31.10 kJ mol-1 and 6.87 J mol-1 K-1, respectively, which indicated that a hydrophobic force played a major role in the interaction of HNF with HSA. All these experimental results and theoretical data clarified that HNF could bind to HSA and be effectively transported and eliminated in body, which could be a useful guideline for further drug design. [Copyright &y& Elsevier]

Limnic and brackish aquatic sediments from contaminated locations in Sweden were analysed for polycyclic aromatic compounds (PACs) and tested for acute aquatic toxicity. The organic compounds were analysed in solvent-extractable and alkaline-treated fractions to complete the analysis of a set of priority pollutants according to the Swedish EPA. Additionally, the acute toxicity was measured by the solid phase Microtox test. The measured effects were correlated with sedimentological and chemical parameters. Analysis revealed no indication of a contribution of PACs to the acute sediment toxicity in highly contaminated sediments, with concentrations in the range of 11.3-307 μg SPAC37/39/g dry matter. Despite a high ranking of 3 to 5 within the Swedish EPA list for coastal sediments, the acute toxicity results indicate a very low bioavailability of the analysed PACs from the creosote and combustion-contaminated sediments. A correlation of acute toxicity to elemental sulfur was indicated. [ABSTRACT FROM AUTHOR]

Complex mixtures consist of homocyclic and heterocyclic polycyclic aromatic compounds (PACs) represented by benzo[ a ]pyrene (B a P) and 7 H -dibenzo[ c,g ]carbazole (DBC), respectively. To exert their biological effects, PACs are metabolized into reactive intermediates, which can form DNA adducts. In this preliminary report, male A/J mice were given a single intraperitoneal injection. Groups of three animals were treated with DBC (2 or 10 mg/kg) or B a P (10 or 100 mg/kg). Mixtures of DBC:B a P were given at doses of 2:10, 2:100, 10:10, or 10:100 mg/kg. DNA adduct levels in lungs collected three days posttreatment were determined by the 32 P-postlabeling method. The results indicate that, in the lungs, exposure to mixtures containing more B a P than DBC resulted in the absence of adduct 3 (DBC) and significantly higher total adduct levels. This suggests that B a P is being preferentially metabolized, resulting in less DBC adduction. [ABSTRACT FROM AUTHOR]

Rising global demand for energy promotes extensive mining of natural resources, such as oil sands extractions in Alberta, Canada. These extractive activities release hazardous chemicals into the environment, such as polycyclic aromatic compounds (PACs), which include the parent polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and sulfur-containing heterocyclic dibenzothiophenes (DBTs). In areas adjacent to industrial installations, Indigenous communities may be exposed to these PACs through the consumption of traditional foods. Our objective was to evaluate and compare the concentrations of total PACs (∑PAC), expressed as the sum of the 16 U.S. EPA priority PAHs (∑PAH), 49 alkylated PAHs (∑alkyl-PAH), and 7 DBTs (∑DBT) in plant and animal foods collected in 2015 by the Bigstone Cree Nation in Alberta, Canada. We analyzed 42 plant tissues, 40 animal muscles, 5 ribs, and 4 pooled liver samples. Concentrations of ∑PAC were higher in the lichen, old man's beard (Usnea spp.) (808 ± 116 ng g−1 w.w.), than in vascular plants, and were also higher in smoked moose (Alces alces) rib (461 ± 120 ng g−1 w.w.) than in all other non-smoked animal samples. Alkylated-PAHs accounted for between 63% and 95% of ∑PAC, while the concentrations of ∑PAH represented 4%–36% of ∑PAC. Contributions of ∑DBT to ∑PAC were generally lowest, ranging from <1% to 14%. While the concentrations of benzo(a)pyrene (B[a]P) and ∑PAH4 (∑benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and B[a]P) in all samples were below guideline levels for human consumption as determined by the European Commission, guideline levels for the more prevalent alkylated PAHs are not available. Given the predominance of alkylated PAHs in all food samples and the potentially elevated toxicity relative to parent PAHs of this class of PACs, it is critical to consider a broader range of PACs other than just parent PAHs in research conducted close to oil sands mining activities. Image 1 • Benzo[a]pyrene (B[a]P) was not detected in most of the plant and animal samples. • Alkylated PAHs were the dominant PAC class in all plant and animal samples. • Old man's beard (a lichen) and smoked moose rib had the highest levels of alkylated PAHs. • Levels of dibenzothiophenes (DBTs) were minor contributors to the total PACs. Alkylated PAHs were the dominant class of PACs relative to parent PAHs and DBTs in traditional foods of the Bigstone Cree Nation near the Athabasca oil sands in Alberta, Canada. [ABSTRACT FROM AUTHOR]

Twenty-five years after the first look at polycyclic aromatic compounds (PACs) in Canada, this article presents current knowledge on Canadian PAC emission sources. The analysis is based on national inventories (the National Pollutant Release Inventory (NPRI) and the Air Pollutant Emissions Inventory (APEI)), an analysis of Canadian forest fires, and several air quality model-ready emissions inventories. Nationally, forest fires continue to dominate PAC emissions in Canada, however there is uncertainty in these estimates. Though forest fire data show a steady average in the total annual area burned historically, an upward trend has developed recently. Non-industrial sources (home firewood burning, mobile sources) are estimated to be the second largest contributor (∼6-8 times lower than forest fires) and show moderate decreases (25%–65%) in the last decades. Industrial point sources (aluminum production, iron/steel manufacturing) are yet a smaller contributor and have seen considerable reductions (90% +) in recent decades. Fugitive emissions from other industrial sources (e.g. disposals by the non-conventional oil extraction and wastewater sectors, respectively) remain a gap in our understanding of total PAC emissions in Canada. Emerging concerns about previously unrecognized sources such as coal tar-sealed pavement run-off, climate change are discussed elsewhere in this special issue. Results affirm that observations at the annual/national scale are not always reflective of regional/local or finer temporal scales. When determining which sources contribute most to human and ecosystem exposure in various contexts, examination at regional and local scales is needed. There is uncertainty overall in emissions data stemming in part from various accuracy issues, limitations in the scope of the various inventories, and inventory gaps, among others. Image 1 • PACs in Canada are from forest fires, home firewood burning, vehicles and industry. • Priority sources at regional scales often differ from national/provincial scales. • PAC inventories are shaped by scope, timing, inputs, and granularity, among others. • Future directions to improve understanding of PAC sources are suggested. Capsule: This review assesses emission sources and trends of polycyclic aromatic compounds (PACs) in Canada. [ABSTRACT FROM AUTHOR]

Ecological risk assessments (ERAs) of polycyclic aromatic compounds (PACs), as single congeners or in mixtures, present technical challenges that raise concerns about their accuracy and validity for Canadian environments. Of more than 100,000 possible PAC structures, the toxicity of fewer than 1% have been tested as individual compounds, limiting the assessment of complex mixtures. Because of the diversity in modes of PAC action, the additivity of mixtures cannot be assumed, and mixture compositions change rapidly with weathering. In vertebrates, PACs are rapidly oxygenated by cytochrome P450 enzymes, often to metabolites that are more toxic than the parent compound. The ability to predict the ecological fate, distribution and effects of PACs is limited by toxicity data derived from tests of a few responses with a limited array of test species, under optimal laboratory conditions. Although several models are available to predict PAC toxicity and rank species sensitivity, they were developed with data biased by test methods, and the reported toxicities of many PACs exceed their solubility limits. As a result, Canadian Environmental Quality Guidelines for a few individual PACs provide little support for ERAs of complex mixtures in emissions and at contaminated sites. These issues are illustrated by reviews of three case studies of PAC-contaminated sites relevant to Canadian ecosystems. Interactions among ecosystem characteristics, the behaviour, fate and distribution of PACs, and non-chemical stresses on PAC-exposed species prevented clear associations between cause and effect. The uncertainties of ERAs can only be reduced by estimating the toxicity of a wider array of PACs to species typical of Canada's diverse geography and environmental conditions. Improvements are needed to models that predict toxicity, and more field studies of contaminated sites in Canada are needed to understand the ecological effects of PAC mixtures. Image 1 • ERAs for PACS in Canada are hampered by a lack of relevant data. • ERAs must deal with a diverse array of >100,000 PACs; the toxicity of <1% is known. • The sensitivity to PACs has been assessed for <1% of global species. • PACs occur in complex mixtures of compounds with multiple modes of action. • Research is needed on MOAs, mixture interactions and models of PAC toxicity. This review assesses the challenges of ecological risk assessments for polycyclic aromatic compounds due to complex interactions among a diversity of PAC structures, exposures, and environmental receptors in Canadian ecosystems. [ABSTRACT FROM AUTHOR]

Promising results of an efficient and convenient strategy for the annulation of polycyclic aromatic compounds (PACs), employing orthoquinones as starting material and comprising allylation, pinacol rearrangement, ring-closing metathesis (RCM), and one-pot reduction followed by Wagner-Meerwein rearrangement, are presented. The strategy involves introducing triallylborane prepared in situ in the allylation step. Moreover, a novel expedient method for the preparation of 9,10-diallylphenanthrene was introduced. [ABSTRACT FROM AUTHOR]