Polycyclic Aromatic Hydrocarbons Derivatives Research Articles

Application of High-Performance Liquid Chromatography with Fluorescence Detection for Non-Polar Heterocyclic Aromatic Amines and Acridine Derivatives Determination in Pork Loin Roasted in a Roasting Bag.

Heat treatment of meat can lead to the formation of carcinogenic organic compounds. The influence of dried fruits on the formation of non-polar heterocyclic aromatic amines (carbolines) and nitrogen derivatives of polycyclic aromatic hydrocarbons (azaarenes) in roasted pork loin was elucidated. Two hundred grams of fruit per 1 kg of meat were used as stuffing. Carbolines, derivatives of pyridoimidazole and pyridoindole, and azaarenes (benzoacridines and dibenzoacridines) were determined by means of high-performance liquid chromatography with fluorescence detection. The total concentration of six δ-, γ- and α-carbolines in roasted pork loin was 1.3 ng/g. This content decreased by 64%, 58%, and 54% in pork loin stuffed with prunes, apricots, and cranberries, respectively. Concentrations of β-carbolines (harmane and norharmane) increased under the influence of added fruits. The norharmane content increased the most, from 2.2 ng/g in the control sample to 12.3 ng/g in meat prepared with cranberries. The harmane content increased from 1.0 ng/g to 3.6 ng/g in meat with prunes. The total concentration of azaarenes (two benzoacridines and dibenzo[a,c]acridine), which was close to 0.1 ng/g, decreased in dishes with prunes and apricots by 54% and 12%, respectively. Azaarenes were not found in samples of meat stuffed with cranberries.

Presence of Halogenated Polycyclic Aromatic Hydrocarbons in Milk Powder and the Consequence to Human Health.

Recent reports of the presence of halogenated derivatives of polycyclic aromatic hydrocarbons (PAHs) in human foods of animal origin, such as chlorinated (ClPAHs) and brominated (BrPAHs) PAHs, suggest that their contamination in dairy products may also pose a human health risk. This study used GC/Orbitrap-MS to analyze 75 congeners of halogenated PAHs and parent PAHs in milk and creaming powder samples commonly found in grocery stores in Sri Lanka and Japan. Our investigation revealed a total of 31 halogenated PAHs (HPAHs) in the samples. The concentrations of total parent PAHs in the samples from Sri Lanka and Japan ranged from not detected (n.d.)–0.13 and <0.001–16 ng/g dry weight (d.w.). Total ClPAHs and BrPAHs in the samples ranged from 0.01–3.35 and 1.20–5.15 ng/g (d.w.) for Sri Lanka, and 0.04–2.54 and n.d.–2.03 ng/g d.w. for Japan, respectively. The ClPAHs were dominated by chlorinated-pyrene, -fluoranthene, and -benzo[a]pyrene congeners, whereas the BrPAHs were dominated by brominated-naphthalene and -pyrene congeners. The toxic assessment estimated based on the intake of toxic equivalency quotients (TEQs) for target compounds in milk powders revealed that HPAHs might contribute additively to the PAHs-associated health risk to humans, indicating that more research is needed.

Microplastics-sorbed phenanthrene and its derivatives are highly bioaccessible and may induce human cancer risks.

Microplastics (MPs) are ubiquitous in environmental media and human diets and can enrich organic contaminants, including polycyclic aromatic hydrocarbons (PAHs) and their derivatives. The bioaccessibilities and triggering cancer risks of MP-sorbed PAHs and PAH derivatives are closely linked with human health, which, however, were rarely focused on. This study explored the sorption behaviors of phenanthrene (PHE) and PHE derivatives on polyethylene (PE), polypropylene (PP), and polystyrene (PS) MPs, and assessed their bioaccessibilities in gastrointestinal fluids as well as their inducing human cancer risks. PE MPs harbored the highest sorption capacity, secondly the PP MPs, then the PS ones. Sorption of PHE and PHE derivatives on MPs was positively correlated with their hydrophobicities. The bioaccessibilities of sorbed PHE and PHE derivatives could reach 53.59%±0.46%-90.28%±0.92% in gastrointestinal fluids and 81.34%±0.77%-98.72%±1.44% in gastrointestinal fluids with the addition of Tenax (more close to the bioavailability). The hydrophobicities also controlled the bioaccessibilities of PHE and PHE derivatives in gastric fluids, and those in intestinal fluids with Tenax for PS MPs. The incremental lifetime cancer risk (ILCR) values for PHE, PHE-Cl, and PHE-NO2 on MPs at tested concentrations were all higher than the USEPA-suggested safety limit (10-6), and most of them were even higher than 10-4, which thus indicates serious cancer risks. This study promoted our understanding of the potential health threats posed by organic pollutant-bearing MPs in the environment.

Zinc-Based Metal-Organic Framework with MLCT Properties as an Efficient Electrochemiluminescence Probe for Trace Detection of Trenbolone.

In this work, we utilized polycyclic aromatic hydrocarbon (PAH) derivatives as ligands to develop a zinc-based metal-organic framework (Zn-MOF) as an effective detection probe to construct an electrochemiluminescence (ECL) sensor for trenbolone detection. As traditional ECL emitters, PAHs and their derivatives have limited luminescence efficiency because of the aggregation-induced quenching (ACQ) effect. Therefore, Zn-PTC was designed by the coordination of 3,4,9,10-perylenetetracarboxylic (PTC) in the MOF to eliminate the ACQ effect. Meanwhile, Zn-PTC formed based on an aromatic ligand possessed the metal-to-ligand charge-transfer (MLCT) effect, which could transfer the energy of Zn2+ to the aromatic ligand for strong luminescence. The ECL efficiency of Zn-PTC was calculated to be approximately 2.2 times that of the ligand (K4PTC). Second, the Ag@Fe core-shell bimetallic nanocrystal was prepared for efficient activation of persulfate (S2O82-), thereby generating more sulfate radicals (SO4•-) to further promote ECL emission. According to ECL characterizations, UV-vis and fluorescence spectra, and density functional theory calculations, the luminescence and signal amplification mechanisms were investigated. In addition, NKFRGKYKC (NKF) was introduced as an affinity ligand to directionally immobilize the target antibodies, thus releasing specific sites in their Fab fragment to enhance binding activity. Based on the above strategies, the constructed biosensor exhibited high sensitivity, realizing trace detection of TBE with a wide detection range (10 fg/mL-100 ng/mL) and a low detection limit (3.28 fg/mL). This study provided an important reference for sensitive monitoring of steroid pollutants in the environment.

Prediction study on the distribution of polycyclic aromatic hydrocarbons and their halogenated derivatives in the atmospheric particulate phase

Polycyclic aromatic hydrocarbons (PAHs) and their halogenated derivatives (X-PAHs), which generally produced from photochemical and thermal reactions of parent PAHs, widely exist in the environment. They are semi-volatile organic chemicals (SVOCs) and the partitioning between gas/particulate phases affects their environmental migration, transformation and fate, which further impacts their toxicity and health risk to human. However, there is a large data missing of the experimental distribution ratio in the atmospheric particulate phase (f), especially for X-PAHs. In this study, we first checked the correlation between experimental f values of 53 PAH derivatives and their octanol-air partitioning coefficients (log KOA), which is frequently used to characterize the distribution of chemicals in organic phase, and yielded R2 = 0.803. Then, quantum chemical descriptors derived from molecular structural optimization by M06–2X/6–311 +G (d,p) method were further employed to develop Quantitative Structure-Property Relationship (QSPR) model. The model contains two descriptors, the average molecular polarizability (α) and the equilibrium parameter of molecular electrostatic potential (τ), and yields better performance with R2 = 0.846 and RMSE = 0.122. The mechanism analysis and validation results by different strategies prove that the model can reveal the molecular properties that dominate the distribution between gas and particulate phases and it can be used to predict f values of other PAHs/X-PAHs, providing basic data for their environmental ecological risk assessment.

Sequential One-Pot Carbene-Catalyzed Intramolecular Stetter Reaction and Acid-Mediated Condensation: Access to Heteroatom Analogues of π-Extended Polyaromatic Hydrocarbons.

In this Letter, we disclose a simple and effective method to access a variety of phenanthro[9,10-b]furan and 1H-dibenzo[e,g]indole derivatives based on the design of a carbene-catalyzed intramolecular Stetter reaction followed by a Paal-Knorr reaction in one-pot. These compounds are a class of π-extended polycyclic aromatic hydrocarbon (PAH) derivatives containing an oxygen/nitrogen atom. The practical utility of the developed transformation was demonstrated on the gram scales and postsynthetic transformations thereof.

Nitrated and oxygenated polycyclic aromatic hydrocarbons emissions from solid fuel combustion in rural China: Database of 12 real-world scenarios for residential cooking and heating activities

Polycyclic aromatic hydrocarbons (PAHs) derivatives such as oxygenated PAHs (oPAHs) and nitrated PAHs (nPAHs), are receiving raising concerns due to their high toxic potential. Incomplete solid fuel combustion can release large quantities of PAHs derivatives, especially in low-efficiency domestic stoves. In this study, field measurements were conducted in rural Chinese homes to determine emissions of nPAHs and oPAHs from solid fuel combustion. A total of 12 fuel-stove combinations including cooking and space heating activities were investigated. Emission factors (EFs) of total nPAHs and oPAHs were in the range of 1.0–682.1 μg/kg and 0.01–131.7 mg/kg, respectively, with arithmetic means and stand deviations of 53.5 ± 72.5 μg/kg and 13.9 ± 24.4 mg/kg, respectively. The EFs of nPAHs and oPAHs for coal combustion (including honeycomb briquette, coal chunk, and peat tested in this study) were 30.2 ± 28.1 μg/kg and 1.5 ± 2.9 mg/kg, respectively, much lower than that for biomass burning (p < 0.05). The combustion phase could significantly affect the PAHs derivative emissions with higher emissions at initial phase than that at stable phase. Fuel type was found to affect the EFs, composition profiles, and ratios of PAHs derivatives to parent PAHs. This study tries to have an insight of PAHs derivative emissions from various solid fuel combustion, which would be useful in understanding the atmospheric PAHs derivative pollutions in China.

Long-term physical and chemical aging of biochar affected the amount and bioavailability of PAHs and their derivatives

Biochar applied into the soil is recommended as an effective tool for increasing its properties and crop productivity. However, biochar can contain some potentially toxic compounds such as polycyclic aromatic hydrocarbons (PAHs). Moreover, during biochar production or environmental application (e.g. as soil fertilizer), more toxic PAHs derivatives containing nitrogen, oxygen or sulfur can be formed. There is a lack of information on how the environmental factors affect the bioavailability of such compounds during the long-term application of BC into the soil. In the presented studies the effects of physical (freeze-thaw cycles) and chemical aging (temperatures 60 °C and 90 °C) on the total and bioavailable content of PAHs and their derivatives were estimated. The results indicate that long-term (6 months) aging affected the physicochemical characteristic of biochars promoting the formation of new C and O-containing species on the BC surface increasing their polarity and hydrophilicity. Physical and chemical aging promoted the formation of compounds with higher molecular weight and a significant (up to 550 %) increase in the bioavailability of PAHs and their derivatives. The results of this study highlight the importance of the bioavailable fraction of PAHs and their derivatives for evaluation of the toxicity of aged biochar.

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

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

Analysis of Micro-Contaminants in Solid Particles from Direct Injection Gasoline Vehicles

Exhaust emissions from vehicles are the subject of numerous studies and legal acts. In the European Union, exhaust emissions are regulated by “Euro” emission standards, which limit emissions of gaseous pollutants such as CO, CO2, HC, and NOx, as well as the particulate matter (PM) and particle number (PN). Solid particles consist of a number of micro-contaminants, inter alia polycyclic aromatic hydrocarbons (PAHs) and their nitrated and oxygenated derivatives. Despite their highly mutagenic and carcinogenic character, these micro-contaminants are not regulated in Euro emissions standards. This paper presents both a general discussion of the phenomenon of particulate formation in and emission from direct injection gasoline engines, as well as a wide range of results on the subject. The subject of the micro-contaminants in solid particles from modern gasoline vehicles is explored. The samples of solid particles were collected from 11 groups of vehicles according to the WLTP test methodology. Solid particles from gasoline vehicles were analyzed via various analytical techniques, including ion chromatography (IC) to measure selected anion concentrations, gas chromatography with mass spectroscopy (GC-MS) to study 16 PAHs and selected PAH derivatives, scanning electron microscopy with energy-dispersive spectroscopy (SEM/EDS) for images and elemental composition, and microwave plasma atomic emission spectroscopy (MP-AES) for qualitative screening analysis of 19 elements. The study of non-regulated compounds is crucial in efforts to establish the influence of solid particles on health and the environment. Furthermore, extended studies can provide a basis for further research on vehicle emissions or other fields, such as medicine or material engineering.

Vertical distribution characteristics and interactions of polycyclic aromatic compounds and bacterial communities in contaminated soil in oil storage tank areas.

Polycyclic aromatic compound (PAC) contamination in soil as a result of oil spills is a serious issue because of the huge global demand for fossil energy. This study assessed the vertical variation in polycyclic aromatic hydrocarbons (PAHs), derivatives of PAHs (dPAHs) and bacterial community structure in deep soil with long-term contamination by oil spillage. Our results suggest that the content of total PACs ranged from 1196.6μg/kg to 14980.9μg/kg and decreased with depth at all sites. PAHs were the most abundant PACs, with a mean concentration of 6640.7μg/kg, followed by oxygenated PAHs (mean 156.3μg/kg) and nitrated PAHs (mean 33.4μg/kg). PAHs are mainly low molecular weight PACs such as naphthalene, fluorene and phenanthrene, while derivatives of PAHs are all low molecular weight PACs and mainly oxygenated PAHs. Low molecular weight PAHs were an important source of dPAHs under specific conditions. The bacterial community structure showed higher bacterial diversity and lower bacterial richness in shallow soil (2-6m in depth) than in deep soil (8-10m in depth). Spearman's analysis confirmed that dramatic bacterial community shifts are a response to contamination. At the genus level, the presence of PACs highly selected for Pseudomonas, belonging to Proteobacteria. Moreover, functional predictions based on Tax4Fun revealed that soil with long-term contamination had a strong potential for PAC degradation. In addition, statistical analysis showed that oxidation-reduction potential (Eh) was closely related to variations of bacterial community composition and function. Finally, Ramlibacter, Pseudomonas, Pseudonocardia, c_MB-A2-108, f_Amb-16S-1323, and Qipengyuania were identified by cooccurrence network analysis as keystone taxa contributing to the maintenance of bacterial ecological function. Together, our results provide evidence of tight bacterial effects of PAHs and dPAHs and a more complete understanding of the fate of PACs in deep contaminated soils.

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated, nitrated and oxygenated derivatives in the atmosphere over the Mediterranean and Middle East seas

Abstract. Polycyclic aromatic hydrocarbons (PAHs) and their alkylated (RPAHs), nitrated (NPAHs) and oxygenated (OPAHs) derivatives are air pollutants. Many of these substances are long-lived, can undergo long-range atmospheric transport and adversely affect human health upon exposure. However, the occurrence and fate of these air pollutants have hardly been studied in the marine atmosphere. In this study, we report the atmospheric concentrations over the Mediterranean Sea, the Red Sea, the Arabian Sea, the Gulf of Oman and the Arabian Gulf, determined during the AQABA (Air Quality and Climate Change in the Arabian Basin) project, a comprehensive ship-borne campaign in summer 2017. The average concentrations of ∑26PAHs, ∑19RPAHs, ∑11OPAHs and ∑17NPAHs, in the gas and particulate phases, were 2.99 ± 3.35 ng m−3, 0.83 ± 0.87 ng m−3, 0.24 ± 0.25 ng m−3 and 4.34 ± 7.37 pg m−3, respectively. The Arabian Sea region was the cleanest for all substance classes, with concentrations among the lowest ever reported. Over the Mediterranean Sea, we found the highest average burden of ∑26PAHs and ∑11OPAHs, while the ∑17NPAHs were most abundant over the Arabian Gulf (known also as the Persian Gulf). 1,4-Naphthoquinone (1,4-O2NAP) followed by 9-fluorenone and 9,10-anthraquinone were the most abundant studied OPAHs in most samples. The NPAH composition pattern varied significantly across the regions, with 2-nitronaphthalene (2-NNAP) being the most abundant NPAH. According to source apportionment investigations, the main sources of PAH derivatives in the region were ship exhaust emissions, residual oil combustion and continental pollution. All OPAHs and NPAHs except 2-nitrofluoranthene (2-NFLT), which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-NFLT and 2-nitropyrene (2-NPYR) were highly abundant in aged shipping emissions due to secondary formation. Apart from 2-NFLT and 2-NPYR, benz(a)anthracene-7,12-dione and 2-NNAP also had significant photochemical sources. Another finding was that the highest concentrations of PAHs, OPAHs and NPAHs were found in the sub-micrometre fraction of particulate matter (PM1).

Atmospheric occurrences of nitrated and hydroxylated polycyclic aromatic hydrocarbons from typical e-waste dismantling sites

Primitive electronic waste (e-waste) dismantling activities have been shown to be an important emissions source for a variety of toxic organic compounds, including carcinogenic polycyclic aromatic hydrocarbons (PAHs). Previous studies have found that some nitrated PAHs (NPAHs) are more toxic than their parent PAHs, however, little attention has been paid to the formation of PAH derivatives during e-waste processing and there is a lack of comprehensive data from field observations. In this study, the spatial distribution, temporal trends and atmospheric fate of NPAHs and hydroxylated PAHs (OH-PAHs) were investigated at typical e-waste dismantling sites, with monitoring data collected over three consecutive years. Compared to background levels, higher levels of NPAHs and OH-PAHs were found in air samples from an e-waste dismantling industrial park, with their seasonal and annual changes shown to be affected by e-waste dismantling activities. Atmospheric PM2.5 particles were found to have high relative abundances of NPAHs (76.9%–95.1%) and OH-PAHs (73.3%–91.6%), with particle-bound concentrations ranging from 20.1 to 88.8 and 37.1 to 107 pg m−3, respectively. The most abundant NPAH isomers were found to be 9-Nitroanthracene and 2-Nitrofluoranthene, while OH-PAH isomers containing 2–4 rings were predominant. Source identification was performed based on the specific diagnostic ratios of NPAH isomers, confirming that NPAH and OH-PAH emissions have multiple sources, including emissions related to the e-waste dismantling process, atmospheric photochemical reactions and traffic emissions. Further research on the fate of such derivatives and their potential use as markers for source identification, is urgently required.

Low bioavailability of derivatives of polycyclic aromatic hydrocarbons in biochar obtained from different feedstock

In the last years, there is great progress in the field of studies on the thermal transformation of wastes into valuable materials such as biochar. High-temperature processes, however, are connected with the formation of polycyclic aromatic hydrocarbons (PAHs) with confirmed toxicity. However, during pyrolysis, some derivatives containing oxygen, nitrogen, or sulfur can also be formed. Their toxicity is expected to be higher than parent PAHs. However, the key parameter in the agricultural application of carbonaceous materials is PAHs’ bioavailability. The aim of the presented studies was the determination of the effect of various feedstock (wheat straw (Triticum L.), willow (Salix viminalis), sunflower, residues from softwood and hardwood, sewage sludges, and residues from biogas production) on the formation of PAHs and their derivatives (O-, N-PAHs) in biochar and their bioavailability. The results indicated that the content of total and bioavailable PAHs in obtained biochar was rather low. The concentration of total PAHs in plant-derived biochar reached 57 ± 3 ng g−1 - 181 ± 8 ng g−1, whereas sewage sludge-derived biochar contained from 121 ± 6 ng g−1 to 188 ± 9 ng g−1 of PAHs. The highest concentration of PAHs was noted in biochar obtained from residues from biochar production – up to 202 ± 9 ng g−1. The total concentration of bioavailable PAHs was lower and reached 2–4.45 ng L−1 for plant-derived biochar, 3–40 ng L−1 for sewage sludge-derived biochar. The highest content of bioavailable PAHs was noted in biochar obtained from residues from biogas production: 9–42 ng L−1 indicating that increased attention should be paid to using this type of biochar. Among PAHs derivatives, nitronaphthalene, 1-methyl-5-nitronaphthalene, 1-methyl-6-nitronaphthalene, 9,10-anthracenedione, 4H-cyclopenta(def)phenanthrene, nitropyrene were determined at various levels and their concentrations were from below the limit of detection (LOD) to 28 ng L−1 for plant-derived biochar, 3–16 ng L−1 for biochar obtained from residues from biogas production, and 5–45 ng L−1 for sewage sludge-derived biochar. The content of bioavailable PAHs derivatives was, generally, one order of magnitude lower than parent PAHs derivatives, and reached from below LOD up to almost 1 ng L−1 for plant-derived biochar, from 0.5 to 2 ng L−1 for biochar obtained from residues from biogas production, and from 0.2 to almost 5 ng L−1 for sewage sludge-derived biochar confirming the safety of agricultural usage of biochar.

A step towards the application of molecular plasmonic-like excitations of PAH derivatives in organic electrochromics

Polycyclic aromatic hydrocarbons (PAHs), are regarded as molecular fragments of graphene and are facilely available through chemical synthesis. Recently, it is found collective charge density oscillations with strong induced electromagnetic field display in PAH derivatives. This phenomenon, analogue to plasmonic excitation in metal, called molecular plasmonics, arise the significant interest of physicists. Instead of discussing its rich physics, this work aims at the application of molecular plasmon-like excitations in electrochromics and optoelectronics. We found that the energy and the intensity of plasmonic-like oscillation could be largely tuned by increasing the conjugation size along both the longitude/transverse axis in PAHs. Besides, the dimeric PAH demonstrates the possibility that molecular plasmonics could be designed using PAHs as building blocks for integration into larger molecular systems. Moreover, this work straightforwardly extends the molecular plasmonic-like property from CH composed PAHs to much more versatile planar conjugation systems with heteroatoms, achieving transferring between p-type and n-type organic semiconductors. Therefore, with the natural abundance, low cost, easily chemical synthesis of PAH derivatives, we believe this work paves the way for the application of molecular plasmonic-like properties in optoelectronics.

Polycyclic aromatic hydrocarbons and their oxygenated derivatives in urban aerosol: levels, chemical profiles, and contribution to PM2.5 oxidative potential

The concentrations of polycyclic aromatic hydrocarbons (PAHs) and quinones, a subgroup of oxygenated PAHs (oxy-PAHs), were measured in PM2.5 samples collected during warm (May–June 2019) and cold (February–March 2020) seasons in the city of Bologna, Italy. Total PAHs concentration was nearly double in winter (6.58 ± 1.03 ng m−3) compared with spring (3.16 ± 0.53 ng m−3), following the trend of the PM2.5 mass concentration. Molecular diagnostic ratios suggested that, together with traffic, biomass burning was the dominant emission source contributing to the peaks of concentration of PM2.5 registered in the cold season. Quinone level was constant in both seasons, being 1.44 ± 0.24 ng m−3, that may be related to the increased secondary formation during warm season, as confirmed by the higher Σoxy-PAHs/ΣPAHs ratio in spring than in winter. The oxidative potential (OP) of the PM2.5 samples was assessed using acellular dithiothreitol (DTT) and ascorbic acid (AA) assays. The obtained responses showed a strong seasonality, with higher volume-normalized (OPV) values in winter than in spring, i.e., OPVDTT: 0.32 ± 0.15 nmol min−1 m−3 vs. 0.08 ± 0.03 nmol min−1 m−3 and OPVAA: 0.72 ± 0.36 nmol min−1 m−3 vs. 0.28 ± 0.21 nmol min−1 m−3. Both OPVDTT and OPVAA responses were significantly associated with total PAHs, as a general descriptor of redox-active PAH derivatives, associated with co-emission from burning sources or secondary atmospheric oxidation of parent PAHs. Otherwise, only winter OPVDTT responses showed a significant correlation with total Ʃoxy-PAHs concentration.

Size-dependent in vitro inhalation bioaccessibility of PAHs and O/N PAHs - Implications to inhalation risk assessment

Size segregated samples (<0.49, 0.49–0.95, 0.95–1.5, 1.5–3.0, 3.0–7.2 and > 7.2 μm) of atmospheric particulate matter (APM) were collected at a traffic site in the urban agglomeration of Thessaloniki, northern Greece, during the cold and the warm period of 2020. The solvent-extractable organic matter was analyzed for selected organic contaminants including polycyclic aromatic hydrocarbons (PAHs), and their nitro- and oxy-derivarives (NPAHs and OPAHs, respectively). Mean concentrations of ∑16PAHs, ∑6NPAHs and ∑10OPAHs associated to total suspended particles (TSP) were 18 ng m−3, 0.2 ng m−3 and 0.9 ng m−3, respectively, in the cold period exhibiting significant decrease (6.4, 0.2 and 0.09 ng m−3, respectively) in the warm period. The major amount of all compounds was found to be associated with the alveolar particle size fraction <0.49 μm. The inhalation bioaccessibility of PAHs and O/N PAHs was measured in vitro using two simulated lung fluids (SLFs), the Gamble's solution (GS) and the artificial lysosomal fluid (ALF). With both SLFs, the derived bioaccessible fractions (BAFs) followed the order PAHs > OPAHs > NPAHs. Although no clear dependence of bioaccessibility on particle size was obtained, increased bioaccessibility of PAHs and PAH derivatives in coarse particles (>7.2 μm) was evident. Bioaccessibility was found to be strongly related to the logKOW and the water solubility of individual compounds hindering limited mobilization of the most hydrophobic and less water-soluble compounds from APM to SLFs. The lifetime cancer risk due to inhalation exposure to bioaccessible PAHs, NPAHs and OPAHs was estimated and compared to those calculated from the particulate concentrations of organic contaminants.

Application of QuEChERS with GC/MS/MS for monitoring polycyclic aromatic hydrocarbon (PAHs) contaminants in Turkish flora honey produced in urban and rural areas

ABSTRACT Environmental pollution has been a problem waiting for solutions worldwide in recent years. Pollution with polycyclic aromatic hydrocarbon (PAHs), oil, and petroleum derivatives, may have long- and short-term environmental and health effects. Bee products are used as bioindicators to determine environmental pollution. In this work, 16 PAHs compounds were analyzed in honey samples from different Turkey regions by gas chromatography-tandem mass spectrometry (GC/MS/MS). In this work, the modern extraction method (QuEChERS) was selective and sensitive enough to extract 16 PAHs from honey samples. High amounts of naphthalene (22.5 µg kg−1), acenaphthylene (16.2 µg kg−1), acenaphthene (17.3 µg kg−1), fluorene (13.3 µg kg−1), phenanthrene (14.5 µg kg−1), fluoranthene (11.9 µg kg−1), benzo(b)fluoranthene (12.6 µg kg−1), benzo(k)fluoranthene (12.7 µg kg−1), and benzo(a)pyrene (11.7 µg kg−1) were detected. Besides, PAHs levels in the Marmara region were very high. The differences in PAHs content between honey from rural and urban areas could be related to atmospheric conditions such as exhaust gases, dust, and airborne particles or from soils in which the plants grow.

Spatial and temporal variation, source identification, and toxicity evaluation of brominated/chlorinated/nitrated/oxygenated-PAHs at a heavily industrialized area in eastern China

Some derivatives of polycyclic aromatic hydrocarbons (PAHs) such as chlorinated and brominated PAHs (Cl/BrPAHs), nitrated and oxygenated PAHs (N/OPAHs) have attracted significant concern due to their high toxicity. Knowledge of the profiles, formation mechanisms, and potential sources of these toxic chemicals near the industrial complexes is essential for their pollution control and management. In this study, we monitored Cl/BrPAHs, N/OPAHs, and PAHs at 24 sampling sites near a heavily industrialized area (steel, chemical, and rubber plants) using passive air samplers during the heating period (7 December 2019 to 15 April 2020) and the non-heating period (2 June 2020 to 4 October 2020). The total average concentrations of 16 BrPAHs, 8 ClPAHs, 17 NPAHs, 6 OPAHs, and 18 PAHs during both sampling periods were 471 pg/m3, 229 pg/m3, 312 pg/m3, 2120 pg/m3, and 63.1 ng/m3, respectively. Except for NPAHs, BrPAHs, ClPAHs, OPAHs, and PAHs all showed higher levels during the heating period. The spatial distributions of Cl/BrPAHs, N/OPAHs, and PAHs exhibited a similar pattern, with the highest concentrations detected in the vicinity of the steel industry. Congener profiles of PAH derivatives indicated that mono-substituted low molecular weight compounds (2–3 rings) were dominant. The major formation mechanisms of halogenated PAHs were discussed by correlation analysis and relative Gibbs free energies, and direct bromination of parent PAHs could be the major formation mechanism of BrPAHs in this study. Diagnostic ratios showed that NPAHs were mainly derived from primary emissions, but the contribution of secondary formation was increased at heavily contaminated sites. The positive matrix factorization model extracted four Cl/BrPAHs, three N/OPAHs, and four PAHs factors, and the result showed that PAHs and their derivatives mainly derived from industrial and combustion sources, photochemical reactions, vehicle emissions, and crude oil volatilization, etc.

A comparative study of persistent DNA oxidation and chromosomal instability induced in vitro by oxidizers and reference airborne particles

Adverse health effects driven by airborne particulate matter (PM) are mainly associated with reactive oxygen species formation, pro-inflammatory effects, and genome instability. Therefore, a better understanding of the underlying mechanisms is needed to evaluate health risks caused by exposure to PM. The aim of this study was to compare the genotoxic effects of two oxidizing agents (menadione and 3-chloro-1,2-propanediol) with three different reference PM (fine dust ERM-CZ100, urban dust SRM1649, and diesel PM SRM2975) on monocytic THP-1 and alveolar epithelial A549 cells. We assessed DNA oxidation by measuring the oxidized derivative 8-hydroxy-2'-deoxyguanosine (8-OHdG) following short and long exposure times to evaluate the persistency of oxidative DNA damage. Cytokinesis-block micronucleus cytome assay was performed to assess chromosomal instability, cytostasis, and cytotoxicity. Particles were characterized by inductively coupled plasma mass spectrometry in terms of selected elemental content, the release of ions in cell medium and the cellular uptake of metals. PM deposition and cellular dose were investigated by a spectrophotometric method on adherent A549 cells. The level of lipid peroxidation was evaluated via malondialdehyde concentration measurement. Despite differences in the tested concentrations, deposition efficiency, and lipid peroxidation levels, all reference PM samples caused oxidative DNA damage to a similar extent as the two oxidizers in terms of magnitude but with different oxidative DNA damage persistence. Diesel SRM2975 were more effective in inducing chromosomal instability with respect to fine and urban dust highlighting the role of polycyclic aromatic hydrocarbons derivatives on chromosomal instability. The persistence of 8-OHdG lesions strongly correlated with different types of chromosomal damage and revealed distinguishing sensitivity of cell types as well as specific features of particles versus oxidizing agent effects. In conclusion, this study revealed that an interplay between DNA oxidation persistence and chromosomal damage is driving particulate matter-induced genome instability.