Unsubstituted Polycyclic Aromatic Hydrocarbons Research Articles

Geochemical implications of uranium-bearing thucholite aggregates in the Upper Permian Kupferschiefer shale, Lubin district, Poland

AbstractNew inorganic and organic geochemical data from thucholite in the Upper Permian (Wuchiapingian) Kupferschiefer (T1) shale collected at the Polkowice-Sieroszowice Cu-Ag mine in Poland are presented. Thucholite, which forms spherical or granular clusters, appears scattered in the T1 dolomitic shale at the oxic-anoxic boundary occurring within the same shale member. The composition of thucholite concretions and the T1 shale differs by a higher content of U- and REE-enriched mineral phases within the thucholite concretions compared to the T1 shale, suggesting a different mineralising history. The differences also comprise higher Ntot, Ctot, Htot, Stot contents and higher C/N, C/S ratios in thucholite than in the T1 shale. The hydrocarbon composition of the thucholite and the surrounding T1 shale also varies. Both are dominated by polycyclic aromatic compounds and their phenyl derivatives. However, higher abundances of unsubstituted polycyclic aromatic hydrocarbons in the thucholite are indicative of its pyrogenic origin. Pyrolytic compounds such as benz[a]anthracene or benzo[a]pyrene are more typical of the thucholite than the T1 shale. Microscopic observations of the thucholite and its molecular composition suggest that it represents well-rounded small charcoal fragments. These charcoals were formed during low-temperature combustion, as confirmed by semifusinite reflectance values, indicating surface fire temperatures of about 400 °C, and the absence of the high-temperature pyrogenic polycyclic aromatic hydrocarbons. Charred detrital particles, likely the main source of insoluble organic matter in the thucholite, migrated to the sedimentary basin in the form of spherical carbonaceous particulates, which adsorbed uranium and REE in particular, which would further explain their different contents and sorption properties in the depositional environment. Finally, the difference in mineral content between thucholite and the T1 shale could also have been caused by microbes, which might have formed biofilms on mineral particles, and caused a change in the original mineral composition.

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.

Atmospheric emissions estimation of polycyclic aromatic compounds from an oil sands tailings pond using passive air samplers

A mapping study targeting emissions of polycyclic aromatic compounds (PACs) from an oil sands tailings pond was undertaken in the Athabasca Oil sands Region (AOSR). Ten passive air samplers comprising polyurethane foam (PUF) disks were deployed around the perimeter of Suncor Tailings Pond 2/3 for a five-week period to generate time-integrated concentrations in air for PACs, which included ∑unsubstituted polycyclic aromatic hydrocarbons (PAHs), ∑alkylated PAHs (alk-PAHs), and ∑dibenzothiophenes (DBTs) (both unsubstituted and alkylated). Concentrations in air ranged from 13 to 70, 220–970, and 30–210 ng/m3, respectively, and were elevated in samplers downwind of the tailings pond. PAC emissions to air from the pond were estimated using only the air-side concentration information by applying a simplified Gaussian dispersion model and found to be 896 μg/m2/day. ∑alk-PAHs and ∑DBTs had the highest contribution to the total PAC fluxes (79% and 16%, respectively). This flux estimate for PACs is equivalent to 460 kg on an annual basis and 35 000 kg/year when scaled to represent all tailings ponds in the region. The results generally agree with fluxes estimated from coupled high volume air sampling data and tailings pond water concentrations from the same field study but which are complicated due to uncertainties associated with the use of pure water Henry's Law values for tailings pond water as well as the potential for surface oily films on the tailings ponds to impact water-air exchange of PACs. Overall, these findings support the use of relatively simple and electricity-free PUF disk samplers for mapping and estimating emissions from area sources such as tailings ponds, using only air-side concentration information.

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.

Polycyclic Aromatic Hydrocarbons in Air and Dust Samples from Vietnamese End-of-life Vehicle Processing Workshops: Contamination Status, Sources, and Exposure Risks.

Concentrations of 18 unsubstituted polycyclic aromatic hydrocarbons (PAHs) and 11 methylated derivatives (Me-PAHs) were measured in polyurethane foam-based passive air (PUF-PAS) and settled dust samples collected from end-of-life vehicle (ELV) processing workshops in northern Vietnam. Concentrations of total 29 PAHs ranged from 42 to 95 (median 57) ng/m3 and from 860 to 18,000 (median 5700) ng/g in air and dust samples, respectively. PAH levels in ELV air and dust samples were 1.5 ± 0.4 and 9.4 ± 7.9 times higher than levels found in a control house, suggesting ELV processing as potential PAH emission sources. Concentrations and proportions of Me-PAHs in total PAHs of the ELV air (26% ± 7%) and dust (41% ± 14%) were higher than those found in control house (18% in both air and dust). The occurrence of PAHs and Me-PAHs in the ELV workshops are attributed to not only pyrogenic but also petrogenic sources (i.e., improper treatment and management of fuels, lubricants, and vehicle oils).

Unexpected Structural Effects on the Onset of Thermal Reactions of Aromatic Hydrocarbons

This work aims to study the reactivity of a broad range of aromatic hydrocarbons to better understand the reactivities of more complex hydrocarbon mixtures. A set of closed-system pyrolysis experiments were conducted on a diverse range of ∼30 polycyclic aromatic hydrocarbons (PAHs) at the thermal onset reaction temperature of 400 °C to understand structural effects on reactivities and shed light on the early events of thermal reaction mechanisms. Thermal transformations, including methyl transfer (alkylation/dealkylation), rearrangement, condensation, molecular growth, and other chemical transformations, are often indicated by dark carbon materials composed of complex mixtures. Thermal transformation was confirmed by phenomenological changes (color and solubility) and chemical analysis using nuclear magnetic resonance, thermogravimetric analysis, gas chromatography, and electron spin resonance. Unsubstituted PAHs (e.g., phenanthrene, anthracene, pyrene, chrysene, etc.) were unaffected by heating at this temperature, with the exception of tetracene and pentacene which readily transformed into dark and insoluble materials. The reactivity of these unsubstituted PAHs is consistent with aromaticity predicted by the Clar theory. On the contrary, most alkyl-substituted PAHs can be transformed into carbon materials at 400 °C; however, alkyl-substituted phenanthrenes (2,7-dimethyl, 2-ethyl, or 7-ethyl) and benzenes (xylenes and pentamethylbenzene) were unreactive. CH2-containing PAH molecules were unreactive if in a five-membered ring (e.g., fluorene and benzofluorene) but became reactive if in a six-membered ring (9,10-dihydroanthracene), likely as a result of aromatization of the latter. The reactivity of the aryl–aryl linkage depends upon the aromatic moieties to which it is connected. While it is unreactive when connecting phenyl groups, such as in p-terphenyl, it is reactive when connecting pyrenes, such as in 1,1′-bispyrene. These results were unexpected and challenge the conventional thinking about hydrocarbon reactivities. Explanations and possible hypotheses are proposed, but more questions remain unanswered to understand the structural effects on reactivities. These findings are conducive to the sustainable use of aromatic hydrocarbons for higher value carbon materials and relevant to numerous pyrolysis studies on oil shale kerogens, biomass, and waste plastics.

Influence on the levels of PAHs and methylated PAHs in surface soil from pollution control in China: Evidence in 2019 data compared with 2005 and 2012 data

To comprehensively clarify the pollution characteristics of persistent toxic substances, the Soil and Air Monitoring Program Phase III (SAMP-III) was conducted in 2019 in China. In total, 154 surface soil samples were collected across China, and 30 unsubstituted polycyclic aromatic hydrocarbons (U-PAHs) and 49 methylated PAHs (Me-PAHs) were analyzed in this study. The mean concentrations of total U-PAHs and Me-PAHs were 540 ± 778 and 82.0 ± 132 ng/g dw, respectively. Northeastern China and Eastern China are the two regions of concern with high PAH and BaP equivalency levels. Compared with SAMP-I (2005) and SAMP-II (2012), an obvious upward temporal trend followed by a downward trend of PAH levels was observed in the past 14 years for the first time. The mean concentrations of 16 U-PAHs were 377 ± 716, 780 ± 1010, and 419 ± 611 ng/g dw in surface soil across China for the three phases, respectively. Considering rapid economic growth and energy consumption, an increasing trend from 2005 to 2012 was expected. From 2012 to 2019, the PAH levels in soils across China decreased by 50 %, which was consistent with the decline in PAH emissions. The period of reduction of PAHs in surface soil coincided with the implementation of Air and Soil Pollution Control Actions in China after 2013 and 2016, respectively. Along with the pollution control actions in China, the pollution control of PAHs and the increase in soil quality can be expected in the near future.

Organic‐Inorganic Interaction Recorded by Polycyclic Aromatic Steranes in Continental Epithermal Ore Deposits

AbstractContinental epithermal ore deposits are commonly associated with sedimentary organic matter, oils or solid bitumen. These organics embedded in mineral deposits can convey valuable information of the ore genesis. However, the extent to which the formation of ore minerals was recorded by organic compounds remains largely unknown, as also is how metal‐rich ores interfere with the molecular proxies in the temperature regime envisaged for hydrothermal activity. The molecular compositional changes of various polycyclic aromatic steranes and polycyclic aromatic hydrocarbons and compounds derived from the Jinding Pb/Zn deposit, SW China provide new data. Aliphatic regular steranes are present as traces. The transformation from polycyclic aromatic steranes to unsubstituted polycyclic aromatic hydrocarbons is observed to show an increased trend with increasing hydrothermal alteration levels; this is consistent with the transformation from unsubstituted polycyclic aromatic hydrocarbons to heterocyclic compounds. Dehydrocyclization (aromatization) of polycyclic biological compounds and hydrodecyclization (dearomatization) of polycyclic aromatic compounds are two important reaction pathways in hydrothermal systems with moderate temperature. This detailed investigation of organic‐inorganic interactions of two groups of polycyclic compounds with metal‐rich ores provides insights into the questions on how and to what extent the formation of Pb/Zn deposits can be recorded by organics. This work will improve our understanding of carbon reduction, oxidation or condensation in the deep Earth and the carbon exchange between the Earth's crust and mantle, and may shed light on the processes for ultra‐deep hydrocarbon exploration.

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.

Assessment of environmental risk related to the polycyclic aromatic hydrocarbons (PAH) in the sediments along the eastern Adriatic coast

Polycyclic aromatic hydrocarbons (PAH) were investigated in the sediments at 24 locations in the coastal area of Adriatic Sea. Total PAH concentrations ranged from 14,98 to 26145,62 µg kg-1, with the highest levels determined in the sediments of Šibenik Bay and the lowest in the sediment near Island of Pag. Unsubstituted PAH were prevailing PAH group in the sediments from the Šibenik Bay and in the Coastal area, while methyl-substituted PAH were dominant group in the sediments of the Kaštela Bay. In order to estimate the possible toxicological significance of PAH concentrations, Sediment Quality Assessment was done according to three different sets of sediment quality guidelines. A high environmental risk was calculated for each station in Šibenik Bay; for the station in vicinity of the Industrial port of Split and for the two stations in Coastal zone. Low environmental risk was determined in less urbanised areas such as Island of Pag. Sediment extracts were further analysed for acute toxicity by measurements of decrease in bioluminescence upon exposure to sediment extracts. Obtained results show disagreement between sediment toxicity predicted upon PAH levels in sediment and experimentally obtained sediment toxicity. Sediment extracts in which low PAH levels were measured showed high acute toxicity indicating that concentrations of PAH alone are a poor indicator of sediment toxicity. Correlation analysis between concentrations of specific PAH compounds and toxicity revealed the strongest association between acute sediment toxicity and sulphur-containing PAH suggesting the S-PAH should be considered in sediment toxicity assessment.

Paleo-wildfire signatures revealing co-occurrence of angiosperm-gymnosperm in the early Paleogene: Evidences from woody charcoal and biomarker analysis from the Gurha lignite mine, Rajasthan, India

Charcoal, a common product of wildfire, is abundant in many sedimentary rocks deposited in a wide range of environments, from terrestrial to marine. The analysis of paleofloras and the related paleoecological conditions is of great importance for the understanding of past environmental and paleoclimatic events. Woody charcoal is identified from the early Paleogene sediments of the Gurha lignite mine (Palana Formation), Bikaner, Rajasthan. This evidence is in the form of fragments of tracheids and vessels that show homogenized cell walls and well-preserved anatomical details, like pitting on cell walls, characteristic features of charcoal. These charcoal remains, most of which belong to angiosperms, represent the first verified occurrence of paleo-wildfires in this region during the early Paleogene. Moreover, a gymnospermous taxonomic affinity can be established for some of the charred woods and a relationship with conifers is likely, thus providing additional evidence for the taxonomic composition of early Paleogene floras in this region. Consecutively, the presence of diterpenoid compounds together with the occurrence of (mega-)sporinite in the lignite samples also shows the presence of gymnosperm vegetation (conifers).Furthermore, the petrographic composition reveals that the lignite samples are dominated and sub-dominated by the huminite (av. 43.2 vol%) and inertinite (av. 39 vol%) groups, respectively, followed by liptinite (av. 13.9 vol%) group of macerals. Fusinite, semifusinite (and inertodetrinite) macerals are commonly considered as fossil charcoal. The relatively higher content of these macerals in the studied lignite indicates the regular events of palaeofire during the deposition. Subsequently, the presence of unsubstituted polycyclic aromatic hydrocarbon (PAH) compounds identified in samples further suggests the occurrence of fire. Additionally, the inertinite (fusinite) reflectance indicates that the charcoal/inertinite was formed at a temperature above 300 °C, while the highest reflectance value suggests a burning temperature of ∼800 °C.

Important But Overlooked Potential Risks of Substituted Polycyclic Aromatic Hydrocarbon: Looking Below the Tip of the Iceberg

Substituted polycyclic aromatic hydrocarbons (PAHs) are PAH derivatives in which substituents replace hydrogen atoms on the aromatic benzene ring, or N/S/O atoms replace carbon atoms in aromatic rings. Compared to unsubstituted PAHs, some substituted PAHs have higher pollution levels and more significant toxicity than their parent PAHs (p-PAHs), and the International Agency for Research on Cancer (IARC) lists them as possible human carcinogens, which harm human health but lack sufficient examination. This paper summarizes and discusses the environmental occurrence and distribution, toxicity, and impacts of substituted PAHs on human health and compares with the 16 representative priority-controlled PAHs (PAHs16). According to occurrence of PAHs in various environmental media, it is shown that the mean concentration of individual substituted PAH in the air is higher than that of individual PAH16. The mean concentration of individual substituted PAH in the soil varies widely among different countries, with a difference of 100,000 times between the lowest level (Italy) and the highest level (USA). The mean individual alkylated PAH (APAHs) and oxygenated PAH (OPAHs) are the most abundant in surface water and sediments. In the aspect of toxicity effects, some substituted PAHs have been proved to have similar or identical toxicity as PAHs16. We summarize existing problems and propose future priority research areas through the analysis of the occurrence and toxicity of substituted PAHs in the environment, which is important for further research and regulation of substituted PAHs.Graphical Abstract

Assessment and Characterization of Alkylated PAHs in Selected Sites across Canada

Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs), dibenzothiophenes (DBTs), and unsubstituted polycyclic aromatic hydrocarbons (PAHs) are naturally present in fossil fuels. Thus, they can be considered as candidates for markers of pollution from petrogenic emissions such as those from traffic. Consequently, ambient air concentrations of alkyl-PAHs, DBTs, and PAHs at selected ambient air monitoring sites of various types (residential, near-road, urban-industrial, agricultural) in Montréal, Toronto, Hamilton, Edmonton, and Simcoe, were evaluated from 2015 to 2016 to study their profiles, trends, and assess potential primary emission source types. Alkyl-PAHs were the prevailing species at all sites and were most elevated at the high-traffic impacted near-road site in Toronto which was also accompanied by the highest unsubstituted PAH concentrations. Comparison of relative abundance ratios of alkyl-PAH and PAH groupings suggests that the profile differences amongst sites were small. Source attribution with cluster grouping suggested similar emission sources of alkyl-PAH and PAH at all sites, with the exception of Hamilton which was particularly impacted by additional emission sources of PAHs. The Principal Component Analysis further indicated distinct PAC profiles at HWY401 and HMT that have the same variability of “heavy PACs” but differ in “medium mass PAHs” sources. Seasonality affected the bulk species trends (alkylated naphthalenes, fluorenes, and phenanthrenes/anthracenes), especially at sites with lower concentrations of these species. This study findings confirm a notable contribution of traffic emissions to alkyl-PAH levels in urban ambient air at the studied Canadian sites, and show that enhanced speciation of alkyl-PAHs provides more data on ambient air quality and additional health risks, and can also help distinguish petrogenic-influenced sources from other sources.

Assessment of Alkylated and Unsubstituted Polycyclic Aromatic Hydrocarbons in Air in Urban and Semi-Urban Areas in Toronto, Canada.

22 alkylated polycyclic aromatic hydrocarbons (alk-PAHs) were characterized in ambient air individually for the first time in urban and semi-urban locations in Toronto, Canada. Five unsubstituted PAHs were included for comparison. Results from the measurements were used to estimate benzo[a]pyrene equivalent toxicity (BaPeq) of individual compounds in order to investigate the significance of a single compound in contributing to the overall toxic equivalency (TEQ) of air mixtures. To determine which compounds merit further investigation, BaPeq values of individual compounds were compared to the measured BaP toxicity. Our results showed that both unsubstituted and alkylated PAHs were more abundant in the urban area (38 and 30%, respectively). Benzo[a]pyrene levels at the urban location exceeded Ontario's 24 h guideline (40% of the events), and on average, it was 5 times higher than that at the semi-urban area. Gas-phase two- and three-ring compounds contributed up to 39% (urban) and 76% (semi-urban) of the TEQ of all compounds analyzed. Some alk-PAHs such as 7,12-dimethylbenzo[a]anthracene had a huge impact on the toxicity of urban air, and its BaPeq was on average 8 times higher than that of BaP. We emphasize that the toxic impact of alkylated and gaseous PAHs, which is not routinely included in many air monitoring programs, is significant and should not be neglected.

Globalization-Driven Industry Relocation Significantly Reduces Arctic PAH Contamination.

Industry relocation under globalization has altered the origins and strength of emission sources of many air pollutants. We develop global emission inventories of polycyclic aromatic hydrocarbons (PAHs) embodied in the production and consumption of goods and services. We implement these inventories within a global atmospheric transport model and simulate spatial-temporal changes in atmospheric concentrations of benzo[α]pyrene (BaP), the most toxic congener in unsubstituted PAHs, and depositions across the Arctic subject to global trade and industry relocation. We show that interregional trade and industry relocation dramatically reduce the atmospheric levels and deposition of BaP in the Arctic. The most significant BaP decline occurs in the European and North American Arctic regions due to attenuated sources in the two well-developed continents proximate to the polar region induced by the relocation of high-PAH pollution industries to many developing countries far from the Arctic. Although BaP emissions embodied in industry relocations in China, India, and South and Southeast Asia resulted in increased BaP contamination in the Asian Arctic, such increases in pollution are minor compared to significant BaP reductions occurring in the European and North American Arctic regions. We find that "North-to-South" industry transfer could reduce trade-related BaP contamination by 60% in the Arctic.

Toxicity screening of air extracts representing different source sectors in the Greater Toronto and Hamilton areas: In vitro oxidative stress, pro-inflammatory response, and toxicogenomic analysis

In the present study, the suitability and sensitivity of different in vitro toxicity endpoints were determined to evaluate and distinguish the specific contributions of polycyclic aromatic carbon (PAC) mixtures from various sites in Toronto (Canada), to pulmonary toxicity. Air samples were collected for two-month periods from April 2014 to March 2015 from one location, and from August 2016 to August 2017 from multiple locations reflecting different geographical areas in Toronto, and the Greater Toronto Area, with varying source emissions including background, traffic, urban, industrial and residential sites. Relative concentrations of PACs and their derivatives in these air samples were characterised. In vitro cytotoxicity, pro-inflammatory, and oxidative stress assays were employed to assess the acute pulmonary effects of urban-air-derived air pollutants. In addition, global transcriptional profiling was utilized to understand how these chemical mixtures exert their harmful effects. Lastly, the transcriptomic data and the chemical profiles for each site and season were used to relate the biological response back to individual constituents. Site-specific responses could not be derived; however, the Spring season was identified as the most responsive through benchmark concentration analysis. A combination of correlational analysis and principal component analysis revealed that nitrated and oxygenated polycyclic aromatic hydrocarbons (PAHs) drive the response at lower concentrations while specific PAHs drive the response at the highest concentration tested. Unsubstituted PAHs are the current targets for analysis as priority pollutants. The present study highlights the importance of by-products of PAH degradation in the assessment of risk. The study also demonstrates the usefulness of in vitro toxicity assays to derive meaningful data in support of risk assessment.

Quantitative Assessment of Organic and Inorganic Contaminants in Charcoal

Thirty-one batches of commercial charcoal from various regions of Poland and Germany were tested for the presence of 20 toxic elements and polycyclic aromatic hydrocarbons (PAHs) using gas chromatography-mass spectrometry (GC-MS). Elements that are toxic to living organisms were determined using atomic absorption spectroscopy (AAS). They were classified as elements representing a very high degree of hazard (As, Cd, Cu, Hg, and Pb), high degree of hazard (Zn, Ba, Cr, Mn, and Mo), moderate degree of hazard (Co, Ni, Sn, and Te), and a low degree of hazard for living organisms and the environment (Ag, Bi, Ce, Se, Sr, and Zr). In regard to the most toxic elements, the highest concentration in the whole tested material was recorded for Cu. In addition, considerable amounts of Ba, Mn, and Sr, i.e., elements representing a high or moderate degree of hazard, were found in the tested charcoals. Moreover, all charcoals contained a wide range of PAHs, from naphthalene to benzo(ghi)perylene, with concentrations in a range between 12.55 and 3554.11 ng/g charcoal. In total, 25 unsubstituted PAHs were identified in the charcoal extracts. PAHs distributions were dominated by five-ring PAHs. The results indicate high carcinogenicity with ∑PAHcarc/∑PAHtot close to 1, as well as high TEQ and MEQ values. Thus, prolonged exposure to charcoal and charcoal dust might cause serious health problems. This applies to employees actively involved in the production and transport of charcoal and, to a lesser extent, users of this fuel.

Hydrothermal catalytic conversion and metastable equilibrium of organic compounds in the Jinding Zn/Pb ore deposit

Hydrothermal organic reactions in the presence of mineral catalysts have been well established by laboratory experiments. However, little is documented about hydrothermal catalytic conversion (HTCC) and the metastable existence of complex molecules in continental hydrothermal systems. Five freshly mined ores containing oil and solid bitumen and associated unmineralised host sediment were sampled from the Beichang mine, Jinding Zn/Pb ore deposit, Lanping, near the Indo-Eurasian collisional margin, southeastern Tibetan Plateau. Here we show evidence for a wide range of mineral (ZnS/PbS) catalysis of polycyclic aromatic compounds in the natural subsurface.An interpretation of hydrothermal alteration (non-biodegradation) was made for the unresolved complex mixture. From unmineralised host sediment through oils to the solid bitumen, a stepwise interaction of organic compounds with metal-bearing hydrothermal fluids was demonstrated by the transformation of polycyclic aromatic hydrocarbons (PAHs) and phenyl/sulfur/oxygen-containing compounds that are thought to be generated through HTCC. Thermodynamically-unstable phenyl derivatives (ortho- or α-substituted) resulted from hydrothermal alteration (ring opening) of the middle and naphthenic (low energy) rings of peri-condensed parent PAHs, as supported by the dominance of 1-phenyldibenzothiophene, 1-phenyldibenzofuran, triphenyleno[1,12-bcd]thiophene, triphenyleno[1,12-bcd]furan, 9-phenylphenanthrene, 1,1′:2′,1′′:2′′,1′′′-quaterphenyl, and the corresponding thiophenes or furans over other isomers. Heteroatom addition to phenyl-derivatives generates abundant heterocyclic compounds, which can undergo further dehydrocyclisation. In the presence of ZnS/PbS, the abundance of three compound classes (unsubstituted PAHs, ‘aryl-aryl’ linked phenyl-derivatives, and S/O atom-containing compounds) is mainly hydrothermally controlled, rather than thermodynamically controlled. Various phenyl/sulfur/oxygen-containing compounds are the metastable equilibrium products of a series of complex redox reactions under specific hydrothermal conditions. We hypothesise that the ubiquitous triphenyleno[1,12-bcd]furan is an important marker for hydrothermal organic–inorganic interactions in the Zn/Pb deposit. The relative abundance of 9-phenylphenanthrene provides a measure of the degree of hydrothermal alteration and HTCC. Our data is consistent with a close interaction of ascending metalliferous hydrothermal fluids with indigenous organic matter/compounds. Hydrothermal fluids, in the presence of sphalerite (and/or galena), are highly effective for activation of the carbon–carbon bonds in PAHs.

Polycyclic aromatic hydrocarbons and their relationship to maturity and paleoenvironmental settings in lacustrine sediments of the Neogene Toplica Basin, Serbia

The study investigated the influence of maturity, biomass type, and depositional settings on the distribution and relative abundance of polycyclic aromatic hydrocarbons (PAHs) for lacustrine sediments collected from depths up to 1000 m of Prebreza and Čučale stratigraphic units (the northwest part of the Toplica Basin). A recently proposed benzo[ghi]perylene/(perylene + benzo[ghi]perylene) parameter, along with commonly used Phenanthrene Alkylation Index and benzo[e]pyrene/(perylene + benzo[e]pyrene) indices, pointed out differences in maturity levels between stratigraphic units by displaying a positive linear relationship with vitrinite reflectance. However, in several immature Prebreza sediments, a substantial presence of algae and/or anoxic, mesosaline/hypersaline conditions were suitable for forming β-substituted methylphenanthrenes and 6-ring benzo[ghi]perylene. Generally, high molecular weight unsubstituted PAHs (HMWPAHs), particularly perylene, predominated Prebreza sediments. Anoxic conditions appeared to be decisive for accumulating and preserving the perylene carbon skeleton in studied stratigraphic units. Besides, more intense volcanism in the Čučale unit favored combustion processes, which prompted the accumulation of low molecular weight unsubstituted PAHs (LMWPAHs), especially phenanthrene. A general prevalence of retene over cadalene in Prebreza sediments, in which alginite and liptodetrinite predominated, implied algae as retene precursor. Selective degradation of retene or hindered demethylation of 9-methylphenanthrene under anoxic and more saline environmental settings had occurred notably in the Prebreza unit, which led to the formation of 1-methylphenanthrene and/or pimanthrene (1,7-dimethylphenanthrene). Čučale sediments with substantial amounts of vitrinite macerals or saturated diterpenoids had a predominant simonellite derived from conifers. Non-degraded and well-preserved Pinaceae conifers predominated in Prebreza sediments deposited under semi-arid climatic conditions, whereas mixed degraded/non-degraded conifers characterized Čučale sediments deposited in a wide range of climatic conditions, from semi-arid to semi-humid.

Electrochemical Synthesis, Deposition, and Doping of Polycyclic Aromatic Hydrocarbon Films.

Polycyclic aromatic hydrocarbons (PAHs) are employed as organic semiconductors because their delocalized π-electron systems and strong intermolecular interactions endow them with an exceptional charge-transport ability. However, the deposition of PAHs from solution onto high-quality thin films is often difficult. Here, we report a one-step electrochemical method to synthesize and deposit unsubstituted PAHs, starting from twisted oligophenyl precursors. The cyclodehydrogenated products were analyzed by matrix-assisted laser-desorption time-of-flight mass spectrometry as well as Fourier transform infrared and Raman spectroscopy. With this electrosynthesis and deposition, the PAHs stack into compact and ordered supramolecular structures along the π-π direction to form thin films with controllable thicknesses and doping levels. The direct fabrication of PAH films opens new pathways toward PAH-based optoelectronic devices.