Parent Polycyclic Aromatic Hydrocarbons Research Articles

Insights into the Formation of Chlorinated Polycyclic Aromatic Hydrocarbons Related to Chlorine in Salt-Tolerant Rice: Profiles in Market Samples, Effects of Saline Cultivation, and Household Cooking.

Halogenated polycyclic aromatic hydrocarbons (XPAHs) present potential risk owing to their greater toxicity than PAHs. This study aimed to explore their profiles in commercial salt-tolerant rice, effects of saline cultivation (0‰ and 3‰ saline conditions), and formation during home cooking. A validated SPE-GC-MS/MS method was used to analyze PAHs and XPAHs in 16 commercial salt-tolerant rice samples. The PAH24 and XPAH18 concentrations were 6.95-32.73 μg kg-1 and 0.013-0.593 μg kg-1, respectively. Chlorinated PAHs (ClPAHs) were significantly greater in salt-tolerant rice (0.14 μg kg-1) than in normal rice (0.048 μg kg-1). During cooking, a notable increase (210-1120%) in ClPAHs and a significant correlation (r = 0.70-0.81, p < 0.05) between newly formed ClPAHs and their parent PAHs were observed, suggesting cooking-induced chlorination of PAHs. Moreover, chlorine radical-induced chlorination of PAHs may be the primary mechanism involved. These findings highlight increased exposure to ClPAHs due to saline cultivation and cooking and provide new insight into ClPAH formation from household cooking.

A comprehensive Review into Emission Sources, Formation Mechanisms, Ecological Effects, and Biotransformation Routes of Halogenated Polycyclic Aromatic Hydrocarbons (HPAHs)

Halogenated polycyclic aromatic hydrocarbons (HPAHs, H = F, Cl, Br) are a new class of PAHs derivatives that mainly originate from the incomplete combustion of halogen-laden materials and via metallurgical operations. These compounds circulate extensively in various environmental matrices. This survey provides a comprehensive review on governing synthesis routes of HPAHs, their environmental occurrence, and their health and ecological effects. The review comprehensively enlists and presents emission sources of these emerging organic pollutants into the air that serves as their main reservoir. The formation of HPAHs ensues through successive addition reactions of related precursors accompanied by ring cyclization steps; in addition to direct unimolecular fragmentation of parents halogenated. Halogenation of parent PAHs rapidly occurs in saline ecosystems, thus multiplying the availability of these notorious compounds in the environment. Certain HPAHs appear to be more carcinogenic than dioxins. Transmission routes of HPAHs from their emission sources to water bodies, soil, aquatic life, plants, terrestrial animals, and humans are well-documented. Later, the direct and indirect diffusion of HPAHs from air to the biotic (plants, animals, humans) and abiotic components (soil, water, sediments) are described in detail. The study concludes that HPAHs are permeable to the carbon matrices resulting in the alleviation of the source-to-sink interface. As a potential future perspective, understanding the transmission interfaces lays a foundation to intervene in the introduction of these toxicants into the food chain.

Machine learning models to predict the bioaccessibility of parent and substituted polycyclic aromatic hydrocarbons (PAHs) in food: Impact on accurate health risk assessment

Food intake is the primary pathway for polycyclic aromatic hydrocarbons (PAHs) to enter the human body. Once ingested, PAHs tend to accumulate, posing health risks. To accurately assess the risk of PAHs from food, concentrations of 10 parent PAHs (PPAHs) and 15 substituted PAHs (SPAHs) were detected across 34 commonly consumed foods. Results indicated that SPAHs concentrations (3.89–11.6 ng/g dw) were higher than PPAH concentrations (1.66–3.43 ng/g dw) in shrimp and shellfish and freshwater fish. Four machine learning algorithms were used to predict the bioaccessibility of PAHs in foods, with the random forest model performing the best (R2 =0.987, RMSE=5.99). Feature variable importance analysis revealed that lipid and protein contents in food are critical variables influencing PAH bioaccessibility. Subsequently, the bioaccessibility of 25 PAHs in various foods was predicted to explore its impact on health risk assessment. Consequently, the carcinogenic risks considering bioaccessibility (5.62 ×10−5-7.12 ×10−5) was about an order of magnitude lower than that ignoring bioaccessibility (1.52 ×10−4-1.69 ×10−4), yet it still exceeded 10⁻6, indicating potential carcinogenic risks. Although PPAHs and alkylated PAHs were predominant in foods, 6-nitrochrysene was the main compound inducing both non-carcinogenic and carcinogenic risks owing to its high toxicity. This study developed a novel method for assessing pollutant bioaccessibility and evaluating its impact on health risk assessment, which provides a valuable model for managing massive hazardous pollutants and is essential for improving the accuracy of health risk assessment.

Levels, enrichment characteristics, and health risks of halogenated and parent polycyclic aromatic hydrocarbons in traditional smoked pork

Chinese traditional smoked pork was contaminated with polycyclic aromatic hydrocarbons (PAHs) and chlorinated and brominated PAHs (ClPAHs and BrPAHs; XPAHs) during the smoking process. Therefore, our study investigated the concentrations, enrichment characteristics, and health risks associated with PAHs, as well as ClPAHs and BrPAHs in Chinese traditional smoked pork. The total concentrations of PAHs, ClPAHs and BrPAHs in traditional smoked pork ranged from 90.0 to 79200 ng/g fat weight (fw), 23.6–2340 pg/g fw and 0.550–200 pg/g fw, respectively, which were significantly higher than their levels found in raw pork. Additionally, the concentrations of PAHs and XPAHs in the surface of smoked pork were higher than those in the inner parts. High-ring PAHs exhibited a greater enrichment compared to low-ring PAHs, and BrPAHs exhibited greater enrichment ability than ClPAHs in smoked pork. Furthermore, the ability of individual congeners to migrate from the surface to the inner parts of the smoked pork were varied. When the smoking fuels were similar, a longer smoking time resulted in higher concentrations of PAHs and XPAHs in smoked pork, while casing effectively reduced their concentrations. The correlation between XPAH and parent PAH concentrations indicated that chlorination of PAHs was one of the primary formation mechanisms of some monochlorinated PAHs. Over half of the smoked pork samples posed a potential carcinogenic risk, particularly the surface samples. It is recommended to remove the surface parts when consuming smoked pork and to improve traditional smoking methods to mitigate the health risks.

Enrichment characteristics of polycyclic aromatic hydrocarbons in coal gangue of the Huaibei Coalfield, China

Coal gangue, a by-product of coal mining, deteriorates and oxidizes, causing environmental pollution. Despite extensive research on polycyclic aromatic hydrocarbon (PAHs) pollution in soil, aerosols, and water, studies on PAHs in coal gangue remain limited. This study aimed to fill this research gap by analyzing gangue samples from three areas in Huaibei. Sixteen priority parent polycyclic aromatic hydrocarbons (16PAHs) and alkyl polycyclic aromatic hydrocarbons (aPAHs) in the samples were analyzed qualitatively and quantitatively via gas chromatography-triple quadrupole mass spectrometry. The results showed that PAHs existed naturally in coal gangue. The aPAHs concentration of multiple samples from the same area (587.88 ng/g, 2972.73 ng/g, and 13528.29 ng/g from Liuqiao, Suntan, and Tongting, respectively) was higher than the 16PAHs concentration (528.79 ng/g, 570.16 ng/g, and 2818.79 ng/g from Liuqiao, Suntan, and Tongting, respectively). Among the 39 samples, the aPAHs concentration after weathering was 7732.78 ng/g, which was higher than the value in the fresh state of 4765.43 ng/g. 16PAHs with low ring number were dominant in the fresh state, but aPAHs with high ring number were dominant after weathering. The diagnostic ratios revealed that traditional diagnostic ratios may confuse sources of PAHs and that gangue should be considered as a single class of source materials. Additionally, there was no significant difference in the ratio between the weathered and fresh state. TEQBaP analysis showed that there was a certain environmental risk in the area and that TEQBaP(weathered) > TEQBaP(fresh). Therefore, the pollution attributable to PAHs in coal gangue, especially weathered gangue, warrants attention.

Insights into the variations of polycyclic aromatic hydrocarbons and their nitrated and oxygenated derivatives in urban airborne PM2.5

Polycyclic aromatic hydrocarbons (PAHs) can be transformed into more toxic species in the atmosphere, but field evidence for their transformation remains rare. Here, polycyclic aromatic compounds (PACs), including PAHs and their nitrated and oxygenated derivatives (NPAHs and OPAHs), in fine particulate matter (PM2.5) were measured in the seasons at multiple locations in a megacity (Guangzhou, China). Molecular diagnostic ratios (MDRs), meteorological factors, and atmospheric oxidant measurements were employed to understand the atmospheric behaviors of PM2.5-bound PACs. The results indicated that similarities/differences in the short-term variations of PAC concentrations between the locations depended on their sources and seasons. The temporal trends in MDRs were more distinct than those in concentrations among the locations. Meteorological factors affected PAC concentrations through a similar pathway (demodulating loadings on PM). Their influence on the ratios can be explained by compounds’ atmospheric half-life, vapor pressure, or particle-size distribution. Temperature was the most powerful factor for both the concentrations and MDRs. Relative humidity was minor, but its positive influence on the reaction to OH radicals was appreciable. The dependence on PM2.5 concentrations suggests that PM plays a more significant role in the sorption or formation of N/OPAHs than in their parent compounds. The OH radical-initiated reaction is the major formation mechanism of N/OPAHs throughout the year, but substantial reactions to NO3 radical in autumn were observed due to high ozone levels. Multiple linear regression revealed that parent PAHs, NO2, and/or O3 are significant contributing factors to the secondary formation of N/OPAHs. Partial least squares-discriminant analysis showed the distinguishing characteristics of summer and autumn PM2.5-bound PACs. This study provides field evidence for the gaseous and heterogeneous reactions of PAHs.

Pollution Characteristics and Ecological Impact of Screening Analysis of Fishing Port Sediments from Dalian, North China.

Environmental pollution from synthetic chemical mixtures has significant adverse impacts on marine ecosystems. However, identifying the main constituents of chemical mixtures that pose ecological threats is challenging due to the necessity of an integrated workflow for comprehensive identification and toxicological prioritization of pollutants. Here, an all-in-one mass spectrometric strategy integrating target, suspect, and nontarget analysis was used to investigate organic pollutants of concern in fishing port sediments, with 355 pollutants (32 from target analysis, 118 from suspect screening and 205 from nontarget analysis) identified in 11 categories. The chemical classes of polycyclic aromatic hydrocarbons (PAHs), pesticides, and intermediates were the extensively detected chemical classes. The ecological risks of absolutely quantified pollutants (i.e., 16 parent PAHs, 7 organophosphate esters (OPEs), 10 pesticides and 4 benzotriazole ultraviolet absorbers) were assessed using toxicity-weighted concentration ranking, with o,p'-DDT being the major contributor. Under the toxicological priority index (ToxPi) framework, an extended ranking of all identified pollutants was achieved by combining instrument response and detection frequency, with a priority control list of 15 pollutants obtained, of which benzo[ghi]perylene (BghiP) and p,p'-DDE had the highest risk priority. Due to frequent detection rates and significant environmental risks, routine monitoring of petroleum pollutants is considered essential. This study presents a general workflow that includes comprehensive identification and prioritization of pollutants, facilitating chemical management and ecological risk assessment.

The influence of oxychlorine phases on the flash pyrolysis of polycyclic aromatic hydrocarbons and implications for mars

A variety of chlorine-bearing hydrocarbons have been detected in the chemical analyses of soil and rock samples performed on Mars with the GCMS instruments onboard the Viking landers and the SAM instrument suite onboard the Curiosity rover. These aromatic and aliphatic chlorohydrocarbons are most likely produced by chemical reactions between salts (e.g., perchlorates, chlorates) and organic molecules of martian origin either during the thermal processing of the samples in flight or generated through radiation processes happening in Mars’ near surface. To understand the influence of salts on the organic molecules during pyrolysis and identify the potential precursors of the chlorohydrocarbons detected on Mars, we performed a systematic study and pyrolyzed three polycyclic aromatic hydrocarbons (PAHs)—naphthalene, phenanthrene, and benzanthracene—in the presence of six perchlorate and chlorate salts that have been identified or are most likely present on Mars—calcium perchlorate, iron perchlorate, sodium perchlorate, magnesium perchlorate, sodium chlorate, and potassium chlorate. Iron perchlorate had the strongest (oxy)chlorination power on the PAHs of all the salts tested whereas magnesium perchlorate and potassium chlorate were the most destructive ones. Despite the presence of these caustic salts, PAHs were highly chemically and thermally stable, suggesting they would likely be detectable natively if present in a martian sample. In addition, chlorohydrocarbons that are characteristic of the parent PAH were formed and could be used to help identify the nature of a PAH. This investigation underlines that PAHs could be the precursors of aromatic chlorohydrocarbons detected on Mars, but a definitive identification will require the detection of the parent PAHs and their respective pyrolyzates, molecules that were not yet detected on Mars likely because of the flight operating constraints of the SAM instrument.

Identification and seasonal variation of specific particulate bound (halogenated) polycyclic aromatic hydrocarbons in air from different metal industrial parks in Northwest China.

During the process of industrial heating, a large amount of polycyclic aromatic hydrocarbons (PAHs) and their halogenated compounds (Cl/Br-PAHs) can be formed. However, there is still limited understanding of the chemicals from different metal smelting industrial parks. This study evaluated the seasonal variations, composition profiles, and source allocations of the atmospheric particulate-bound PAHs and Cl/Br-PAHs in different metal industrial parks in a typical industrial city in northwest China. The results showed that the main PAHs produced by metal smelting were low molecular weight isomers, and the concentrations of Cl-PAHs were lower compared to Br-PAHs. The main Br-PAHs were 1-Br-Pyr and 4-Br-Pyr, while 9-Cl-Fle, 1-Cl-Pyr, and 6-Cl-BaP were the dominated Cl-PAH isomers. No significant difference was found in the concentrations among the sites, whereas the levels of the target chemicals were higher during cold months compared to warm months. The main source of PAHs was coal combustion and gasoline vehicle emission during metal smelting, and that of Cl/Br-PAHs was also industrial coal burning. In addition to the primary source, the secondary chlorination of parent PAHs was also a significant source of Cl-PAHs in the production of high purity aluminum. This study suggests that Cl-PAHs and Br-PAHs may behave differently in the atmosphere.

Exploring avian exposure to parent polycyclic aromatic hydrocarbons (PAHs): Using the common eider Somateria mollissima in a global context

Compared to other organic contaminants, birds are rarely studied for their exposure to polycyclic aromatic hydrocarbons (PAHs), mainly due to their effective metabolization of parent PAHs. However, as some studies suggest, exposure to PAHs may result in adverse health effects including decreased survival, especially following oil spills. In the present study, we analyzed samples from a sea duck, the common eider Somateria mollissima including feathers, preen oil, blood, liver and bile, to evaluate whether non- lethally collected samples could be reliably used for avian biomonitoring strategies. Phenanthrene was the only individual PAH detected across sample types, with the highest concentration found in preen gland and the lowest in blood. Significant differences in concentrations were observed between bile vs preen gland and liver vs preen gland, while for most compounds neither blood nor feathers showed detectable levels of parent PAHs. Therefore, the utility of those sample types for PAH exposure assessment may be limited and should be interpreted with caution, moreover as several physiological factors may affect them. Additionally, we also provide a comparison with the available literature to review current avian PAH exposure assessment and outline future research focused needs.

Particulate Matter (PM) and Parent, Nitrated and Oxygenated Polycyclic Aromatic Hydrocarbon (PAH) Emissions of Emulsified Heavy Fuel Oil in Marine Low-Speed Main Engine.

To understand the influences of emulsified fuel on ship exhaust emissions more comprehensively, the emissions of particulate matter (PM), nitrated, oxygenated and parent polycyclic aromatic hydrocarbons (PAHs) were studied on a ship main engine burning emulsified heavy fuel oil (EHFO) and heavy fuel oil (HFO) as a reference. The results demonstrate that EHFO (emulsified heavy fuel oil) exhibits notable abilities to significantly reduce emissions of particulate matter (PM) and low molecular weight PAHs (polycyclic aromatic hydrocarbons) in the gas phase, particularly showcasing maximum reductions of 13.99% and 40.5%, respectively. Nevertheless, burning EHFO could increase the emission of high molecular weight PAHs in fine particles and pose a consequent higher carcinogenic risk for individual particles. The total average (gaseous plus particulate) ΣBEQ of EHFO exhausts (41.5 μg/m3) was generally higher than that of HFO exhausts (18.7 μg/m3). Additionally, the combustion of EHFO (extra-heavy fuel oil) can significantly alter the emission quantity, composition, and particle-size distribution of PAH derivatives. These changes may be linked to molecular structures, such as zigzag configurations in C=O bonds. Our findings may favor the comprehensive environmental assessments on the onboard application of EHFO.

Effective isolation and comprehensive quantification of EPA16 PAHs, EU15+1 PAHs, 17 halogenated PAHs, and 18 oxygenated PAHs in soybean oil

Halogenated and oxygenated polycyclic aromatic hydrocarbons (XPAHs and OPAHs) have attracted increasing attention due to their considerable or higher toxicity than the corresponding parent PAHs. However, only a few kinds of PAH derivatives were monitored in vegetable oils due to the difficulties in analysis. This study aimed to establish analytical methods for 24 PAHs, 17 XPAHs and 18 OPAHs in soybean oil. The modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) pretreatment followed by GC-MS/MS or UPLC-MS/MS analysis was applied in this study. The results showed that the modified QuEChERS pretreatment could successfully extract 56 PAHs and derivatives in soybean oil, which saved organic solvent to a great extent. Simultaneous determination of EPA16 PAHs, EU15 + 1 PAHs, 17 XPAHs, and 12 OPAHs in soybean oil was achieved by GC-MS/MS analysis, which had recoveries of 61.33–111.61% and relative standard deviations (RSDs) of 1.35–19.89%. UPLC-MS/MS analysis obtained recoveries from 51.61% to 109.45% and RSDs from 1.31% to 15.05% for 14 OPAHs. As a supplement to GC-MS/MS, UPLC-MS/MS exhibited high sensitivity to ortho-OPAHs and benzo[a]pyrene–quinone isomers. Through GC-MS/MS and UPLC-MS/MS analyses, the concentrations of two XPAHs and ten OPAHs in soybean oils were firstly reported. In short, this study offered guidance for comprehensive analyses of PAHs, XPAHs, and OPAHs in vegetable oils.

Pollution Characteristics and Health Risks of Polycyclic Aromatic Compounds (PACs) in Soils of a Coking Plant.

Coke production is an important source of environmental polycyclic aromatic compounds (PACs), including parent polycyclic aromatic hydrocarbons (PAHs) and their derivatives. The focus near coking plants has primarily been on parent-PAH contamination, with less attention given to highly toxic derivatives. In this study, soil samples were collected from both within and outside of a coking plant. The concentrations of parent-PAHs and their derivatives, including methylated-PAHs, oxygenated-PAHs, and nitrated-PAHs, were examined. Spatial interpolation was employed to determine their spatial distribution patterns. Methods for identifying potential sources and conducting incremental lifetime cancer risk analysis were used. This could achieve a comprehensive understanding of the status of PAC pollution and the associated health risks caused by coke production. The concentrations of total PACs inside the plant ranged from 7.4 to 115.8 mg/kg, higher than those outside (in the range of 0.2 to 65.7 mg/kg). The spatial distribution of parent-PAH concentration and their derivatives consistently decreased with increasing distance from the plant. A significant positive correlation (p < 0.05) among parent-PAHs and their derivatives was observed, indicating relatively consistent sources. Based on diagnostic ratios, the potential emission sources of soil PACs could be attributed to coal combustion and vehicle emissions, while principal component analysis-multiple linear regression further indicated that primary emissions and secondary formation jointly influenced the PAC content, accounting for 60.4% and 39.6%, respectively. The exposure risk of soil PACs was dominated by 16 priority control PAHs; the non-priority PAHs' contribution to the exposure risk was only 6.4%.

Development and Field Application of a Diffusive Gradients in Thin-Films Passive Sampler for Monitoring Three Polycyclic Aromatic Hydrocarbon Derivatives and One Polycyclic Aromatic Hydrocarbon in Waters

Polycyclic aromatic hydrocarbon (PAH) derivatives are widely present in the environment, and some are more hazardous than their parent PAHs. However, compared to PAHs, PAH derivatives are less studied due to challenges in monitoring as a result of their low concentrations in environmental matrixes. Here, we developed a new passive sampler based on diffusive gradients in thin films (DGT) to monitor PAH derivatives and PAHs in waters. In the laboratory study, the XAD18-DGT device exhibited high adsorption rates and was demonstrated to be suitable for deployment in environmental waters on the timescale of months. The diffusion coefficients, D, were 5.30 × 10−6 cm2 s−1, 4.51 × 10−6 cm2 s−1, 4.03 × 10−6 cm2 s−1 and 3.34 × 10−6 cm2 s−1 for 9-fluorenone (9-FL), 1-chloroanthraquinone (1-CLAQ), 9-nitroanthracene (9-NA) and phenanthrene (Phe), respectively, at 25 °C. The DGT device’s performance was independent of pH, ionic strength, deployment time and storage time, indicating it can be widely used in natural waters. In the field study, the target pollutant concentrations measured by the DGT are in good accordance with those determined via grab sampling. Then, the DGT devices were utilized to quantify PAH derivatives and PAHs in several rivers in Hefei, China. This work demonstrates the feasibility of using the DGT technique to detect trace PAH derivatives and PAHs in waters.

Air-soil cycling of oxygenated, nitrated and parent polycyclic aromatic hydrocarbons in source and receptor areas

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives, OPAHs and NPAHs, are semivolatile air pollutants which are distributed and cycling regionally. Subsequent to atmospheric deposition to and accumulation in soils they may re-volatilise, a secondary source which is understudied.We studied the direction of air-soil mass exchange fluxes of 12 OPAHs, 17 NPAHs, 25 PAHs and one alkylated PAH in two rural environments being influenced by the pollutant concentrations in soil and air, by season, and by land cover. The OPAHs and NPAHs in samples of topsoil, of ambient air particulate and gas phases and in the gas-phase equilibrated with soil were analysed by GC-APCI-MS/MS. The pollutants soil burdens show a pronounced seasonality, a winter maximum for NPAHs and PAHs and a summer maximum for OPAHs. One order of magnitude more OPAH and parent PAH are found stored in forest soil than in nearby grassland soil. Among a number of 3–4 ring PAHs, the OPAHs benzanthrone and 6H-benzo(c,d)pyren-6-one, and the NPAHs 1- and 2-nitronaphthalene, 9-nitrophenanthrene and 7-nitrobenz(a)anthracene are found to re-volatilise from soils at a rural background site in central Europe in summer. At a receptor site in northern Europe, net deposition of polycyclic aromatic compounds (PACs) prevails and re-volatilisation occurs only sporadic.Re-volatilisation of a number of PACs, including strong mutagens, from soils in summer and even in winter indicates that long-range atmospheric transport of primary PAC emissions from central Europe to receptor areas might be enhanced by secondary emissions from soils.

Indoor air levels of polycyclic aromatic compounds (PAC) in public buildings with creosote impregnated constructions – A pilot case study using passive samplers

Creosote has been used in Sweden as a wood preservative in buildings since the 19th century. These buildings can function as workplaces, homes, and cultural buildings to which the public has access. Creosote contains polycyclic aromatic hydrocarbons (PAH) which are well known carcinogens. To understand exposure and risks in an indoor environment, it is important to determine air levels of parent PAHs as well as the more toxic nitrated and oxygenated PAH derivatives (NPAH, OPAH).This study aims to investigate indoor air levels of polycyclic aromatic compounds (PACs) e.g., PAH, NPAH, OPAH and dibenzothiophenes in buildings containing creosote sources and whether these levels pose a health risk.Four cultural buildings were studied, all located within a radius of 130 m. Two were known to have creosote sources, and two had not. Polyurethane foam passive air samplers (PUF-PAS) were used to indicate possible point sources. PUF-PAS measurements were performed for one month in each building winter and summer. Simultaneously, PAC outdoor level measurements were performed.Buildings with creosote impregnated constructions had notably higher indoor air levels of PAC (31–1200 ng m−3) compared to the two buildings without creosote sources (14–45 ng m−3). The PAH cancer potency (sum of benzo[a]pyrene equivalents (BaPeq)) was more than one order of magnitude higher in the buildings containing creosote impregnated wood compared to reference buildings. The highest value was 5.1 BaPeq ng m−3 which was significantly higher than the outdoor winter measurement (1.3 BaPeq ng m−3). Fluoranthene and phenanthrene, with significant distribution in gas phase, but also several particulate NPAHs contributed significantly to the total cancer risk. Thus, creosote containing buildings can still contaminate the indoor air with PACs despite being over a hundred years old. The PUF-PAS was shown to be a good tool providing quantitative/semiquantitative measures of PACs exposure in indoor microenvironments.

Hazardous implications of halogenated polycyclic aromatic hydrocarbons in feedstuff: Congener specificity and toxic levels in feed ingredients and feeds

Studies have shown that halogenated polycyclic aromatic hydrocarbons (HPAHs), including chlorinated (ClPAHs) and brominated PAHs (BrPAHs), could be hazardous pollutants due to their pervasive occurrence in the environment. However, their accumulation properties and toxic potentials in animal feedstuffs remain unclear. This study investigated 75 congeners of parent PAHs, ClPAHs, and BrPAHs in animal-based feed ingredients and fish and swine feeds in Japan using a GC/Orbitrap MS system. The total parent PAHs ranged from below the method detection limit (<MDL) to 2700 ng/g lipid weight (l.w.), with the highest concentration found in fish oil. The total ClPAHs and BrPAHs were in the ranges of <MDL to 104.55 and 0.21–54.38 ng/g l.w., respectively, with their highest concentrations detected in fish meal. The maximum detection frequencies for parent PAHs, ClPAHs, and BrPAHs were detected for fluorene (75 %), trichloropyrene (86 %), and 2-bromonaphthalene (97 %), respectively. The highest ClPAH concentrations were dominated by dichloropyrene (61.92 ng/g l.w., fish meal). The BrPAHs were mostly contributed by 1-bromonaphthalene (33.94 ng/g l.w., animal fat) and 2-bromonaphthalene (22.37 ng/g l.w., fish meal). The toxic assessment estimated for target compounds in various feed ingredients and feed based on the toxic equivalency quotients (TEQs) revealed that HPAHs could additively contribute (up to 100 %) to PAH-like toxic effects. Despite their high detection frequencies and concentrations, several ClPAHs and BrPAHs had no relative toxic potency values. Thus, the TEQs were underestimated, indicating that urgent in-depth research is required to obtain toxicological data for predominant HPAHs.

Understanding Polycyclic Aromatic Hydrocarbons (PAHs) and Derivatives: Sources, Properties, and Health Impacts

PAHs, persistent organic pollutants (POPs), composed of 2-7 fused aromatic rings, emerge from processes involving incomplete combustion of organic materials. Released into the ambient air as vapors or adsorbed onto airborne particulate matter, these compounds undergo complex photochemical reactions with atmospheric pollutants such as ozone, NOX, SOX, and OH radicals and result in the formation of its derivatives which possess remarkably higher toxicity and carcinogenicity than its parent PAHs. This chapter delves into the contemporary knowledge surrounding Polycyclic Aromatic Hydrocarbons (PAHs) and their derivatives, shedding light on their sources, formation mechanisms, and inherent properties. It also comprehensively reviews the global status.

Method Development for Quantitative Analysis of Polycyclic Aromatic Hydrocarbons, Nitrogen Heterocycles and Sulfur Heterocycles in Crude Oils Using Quadrupole Time-of-Flight Mass Spectrometry

An oil spill is a catastrophic event that results in various toxic polycyclic aromatic hydrocarbons (PAHs) entering the environment. Polycyclic aromatic nitrogen heterocycles (PANHs) are more toxic to the environment than their parent PAHs. The high cost and paucity of available PANH standards, the lower abundance of PANHs relative to PAHs, and the difficult separation due to co-elution with PAHs have all contributed to the scarcity of related published literature on the determination of these compounds. To overcome these challenges, a new quantitative method has been successfully developed and validated for the inclusion of 113 polycyclic aromatic carbon (PAC) compounds in a single injection. The 113 compounds consist of PAHs, nitrogen heterocycles, sulfur heterocycles, and alkylated equivalents. Distinct separation of the PANHs and their alkylated counterparts (APANHs) from PAHs was achieved using a gas chromatography quadrupole time-of-flight (GC-QToF) mass spectrometer. The instrument resolved compounds by the high-resolution extraction of monoisotopic masses, allowing response correction factors (RCFs) to be determined from available PANH standards and to calculate concentrations from PAH calibration standards. The developed method was applicable to crude oil samples, generating concentrations of PANHs and relevant information on compound stability for use in oil spill forensics investigation. Development of this practical PAC method provides a powerful tool for screening toxic contaminants, assessing environmental impact, and monitoring recovery following an oil spill.

Reactions of deoxyribonucleotide bases with sulfooxymethyl or halomethyl polycyclic aromatic hydrocarbons induce unwinding of DNA supercoils

Torsional stress in double-stranded DNA enables and regulates facets of chromosomal metabolism, replication, and transcription and requires regulatory enzymatic systems including topoisomerases and histone methyltransferases. As such, this machinery may be subject to deleterious effects from reactive mutagens, including ones from carcinogenic polycyclic aromatic hydrocarbon (PAH) adduct formation with DNA. Supercoiled plasmid DNA was investigated for its torsional responses to adducts formed in vitro from PAH benzylic carbocation reactive intermediates created spontaneously by release of leaving groups. PAH sulfate esters were found to (1) unwind DNA in a concentration dependent manner, and (2) provide maximum unwinding in a pattern consistent with known carcinogenicities of the parent PAHs, that is, 6-methylbenzo[a]pyrene > 7,12-methylbenz[a]anthracene > 3-methylcholanthrene > 9-methylanthracene > 7-methylbenz[a]anthracene > 1-methylpyrene. Supercoil unwinding was demonstrated to be dependent on the presence of sulfate or chloride leaving groups such that reactive carbocations were generated in situ by hydrolysis. In silico modeling of intercalative complex topology showed PAH benzylic carbocation reactive functional groups in alignment with target nucleophiles on guanine bases in a 5’-dCdG-3’ pocket in agreement with known formation of nucleotide adducts. Inhibitory or modulatory effects on PAH-induced supercoil unwinding were seen with ascorbic acid and an experimental antineoplastic agent Antineoplaston A10 in agreement with their known anticarcinogenic properties. In summary, the reactive PAH intermediates studied here undoubtedly participate in well-known mutational mechanisms such as frameshifts and apurinic site generation. However, they are also capable of random disruption of chromosomal supercoiling in a manner consistent with the known carcinogenicities of the parent compounds, and this mechanism may represent an additional detrimental motif worthy of further study for a more complete understanding of chemical carcinogenicity.