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.

Interactions between polycyclic aromatic hydrocarbons (PAHs) and phospholipids cause PAH migration into wet gums during the oil degumming process.

The refining process can reduce PAH contamination levels in vegetable oils, but the safety of byproducts requires further attention. We hypothesize that interactions between PAHs and phospholipids could contribute to PAH migration into the wet gums and subsequently evaluated the distribution of PAHs during different degumming processes. Enzymatic degumming achieved over 99.90 % removal of phospholipids from soybean oil and sunflower seed oil and minimized the toxic equivalency quotient of PAHs in wet gums (approximately 0.05 µg/kg). Notably, greater PAH reduction was correlated with greater phospholipid removal in degummed soybean oil. Quantum chemical calculations indicated that van der Waals forces between PAHs and phospholipids could cause PAH migration, with higher phospholipid contents and PAH contamination in soybean oil providing more favourable conditions than in sunflower seed oil. This study will help to improve the quality of edible oils and provide information on the mechanisms underlying PAH migration.

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%.

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.

Pyrene and its derivatives increase lung adverse effects by activating aryl hydrocarbon receptor transcription.

Derivatives of polycyclic aromatic hydrocarbons (PAHs) pose significant threat to environment and human health due to their widespread and potential hazards. However, adverse effects and action mechanisms of PAH derivatives on human health have not been attempted yet. Herein, we chose pyrene and its derivatives (1-hydroxypyrene, 1-nitropyrene, and 1-methylpyrene) to investigate adverse effect mechanism to human lungs using in vitro and in vivo methods. Results showed that pyrene derivatives have higher lung health risks than original pyrene. They can activate AhR, subsequently affecting expression of downstream target genes CYP1A1 and CYP1B1. The binding energies of pyrene and its derivatives ranged from -16.07 to -27.25 kcal/mol by molecular dynamics simulations, implying that pyrene and its derivatives acted as agonists of AhR and increased adverse effects on lungs. Specifically, 1-nitropyrene exhibited stabler binding conformation and stronger AhR expression. In addition, sensitivity of pyrene and its derivatives to AhR activation was attributed to type and number of key amino acids in AhR, that is, pyrene (Leu293), 1-nitropyrene (Cys333, Met348, and Val381), 1-hydroxypyrene (Leu293 and Phe287), and 1-methylpyrene (Met348). In summary, we provide a universal approach for understanding action mechanisms of PAH derivatives on human health, and their adverse effects should be taken seriously.

Increased concentration of PAH derivatives in biochar-amended soil observed in a long-term experiment.

During biochar preparation or application some toxic substances may be formed. The established limitations of the content of polycyclic aromatic hydrocarbons (PAHs) aim to monitor the fate of PAHs in the life cycle of biochar. The latest studies have revealed that besides PAHs, some of their derivatives with confirmed toxicity are formed. There has been no policy regards PAH derivatives in biochar yet. The aim of the presented studies was the estimation the changes in the content of PAHs and their derivatives during the agricultural application of biochar. A pot experiment with grass revealed that in a short time, both the content of PAHs and their derivatives was reduced. Similarly, when biochar was added to soil in a long-term experiment, the content of determined derivatives was below the limit of detection, whereas interestingly, the content of pristine PAHs increased with time. Co-addition of biochar and sewage sludge increased the content of PAHs and their derivatives indicating potential environmental hazard due to their presence. However, the key point is the estimation of the bioavailability of PAHs and their derivatives as only the bioavailable fraction is revealing the environmental hazard.

The occurrence and sources of PAHs, oxygenated PAHs (OPAHs), and nitrated PAHs (NPAHs) in soil and vegetation from the Antarctic, Arctic, and Tibetan Plateau.

Although the fate of PAHs in the three polar regions (Antarctic, Arctic, and Tibetan Plateau) has been investigated, the occurrence and contamination profiles of PAH derivatives such as oxygenated PAHs (OPAHs) and nitrated PAHs (NPAHs) remain unclear. Some of them are more toxic and can be transformed from PAHs in environment. This study explored and compared the concentrations composition profiles and potential sources of PAHs, OPAHs, and NPAHs in soil and vegetation samples from the three polar regions. The total PAH, OPAH, and NPAH concentrations were 3.55-519, n.d.-101, and n.d.-1.10 ng/g dry weight (dw), respectively. The compounds were dominated by three-ring PAHs, and the most abundant individual PAH and OPAH were phenanthrene (PHE) and 9-fluorenone (9-FO), respectively. The sources of PAHs and their derivatives were qualitatively analyzed by the diagnostic ratios and quantified using the positive matrix factorization (PMF) model. The ratios of PAH derivatives to parent PAHs (9-FO/fluorene and 9,10-anthraquinone/anthracene) were significantly higher in the Antarctic samples than in the Arctic and TP samples, implying a higher occurrence of secondary OPAH and NPAH formation in the Antarctic region. To our knowledge, this is the first comparative study that simultaneously investigated the contamination profiles of PAHs and their derivatives in the three polar regions. The findings of this study provide a scientific basis for the development of risk assessment and pollution control strategies in these fragile regions.

A Systematic Review of Polycyclic Aromatic Hydrocarbon Derivatives: Occurrences, Levels, Biotransformation, Exposure Biomarkers, and Toxicity.

Polycyclic aromatic hydrocarbon (PAH) derivatives constitute a significant class of emerging contaminants that have been ubiquitously detected in diverse environmental matrixes, with some even exhibiting higher toxicities than their corresponding parent PAHs. To date, compared with parent PAHs, fewer systematic summaries and reanalyses are available for PAH derivatives with great environmental concerns. This review summarizes the current knowledge on the chemical species, levels, biotransformation patterns, chemical analytical methods, internal exposure routes with representative biomarkers, and toxicity of PAH derivatives, primarily focusing on nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), halogenated PAHs (XPAHs), and alkylated PAHs (APAHs). A collection of 188 compounds from four categories, 44 NPAHs, 36 OPAHs, 56 APAHs, and 52 XPAHs, has been compiled from 114 studies that documented the environmental presence of PAH derivatives. These compounds exhibited weighted average air concentrations that varied from a lower limit of 0.019 pg/m3 to a higher threshold of 4060 pg/m3. Different analytical methods utilizing comprehensive two-dimensional gas chromatography coupled with high-resolution time-of-flight mass spectrometry (GC × GC-TOF-MS), gas chromatography coupled to time-of-flight mass spectrometry (GC-TOF-MS), comprehensive two-dimensional gas chromatography coupled to quadrupole mass spectrometry (GC × GC-QQQ-MS), and Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS), that adopted untargeted strategies for the identification of PAH derivatives are also reviewed here. Additionally, an in-depth analysis of biotransformation patterns for each category is provided, including the likelihood of specific biotransformation reaction types. For the toxicity, we primarily summarized key metabolic activation pathways, which could result in the formation of reactive metabolites capable of covalently bonding with DNA and tissue proteins, and potential health outcomes such as carcinogenicity and genotoxicity, oxidative stress, inflammation and immunotoxicity, and developmental toxicity that might be mediated by the aryl hydrocarbon receptor (AhR). Finally, we pinpoint research challenges and emphasize the need for further studies on identifying PAH derivatives, tracking external exposure levels, evaluating internal exposure levels and associated toxicity, clarifying exposure routes, and considering mixture exposure effects. This review aims to provide a broad understanding of PAH derivatives' identification, environmental occurrence, human exposure, biotransformation, and toxicity, offering a valuable reference for guiding future research in this underexplored area.

Seasonal trends and retention of polycyclic aromatic compounds (PACs) in a remote sub-Arctic catchment.

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

The Levels of Polycyclic Aromatic Hydrocarbons and Their Derivatives in Plasma and Their Effect on Mitochondrial DNA Methylation in the Oilfield Workers.

This study focuses on the components and levels of polycyclic aromatic hydrocarbons (PAHs) and their derivatives (MPAHs and OPAHs) in plasma samples from 19 oil workers, pre- and post-workshift, and their exposure-response relationship with mitochondrial DNA (mtDNA) methylation. PAH, MPAH, OPAH, and platelet mtDNA methylation levels were determined using a gas chromatograph mass spectrometer (GC-MS) and a pyrosequencing protocol, respectively. The total plasma concentrations of PAHs in mean value were, respectively, 31.4 ng/mL and 48.6 ng/mL in pre- and post-workshift, and Phe was the most abundant (13.3 ng/mL in pre-workshift and 22.1 ng/mL in post-workshift, mean value). The mean values of total concentrations of MPAHs and OPAHs in the pre-workshift were 2.7 ng/mL and 7.2 ng/mL, while in the post-workshift, they were 4.5 ng/mL and 8.7 ng/mL, respectively. The differences in the mean MT-COX1, MT-COX2, and MT-COX3 methylation levels between pre- and post-workshift were 2.36%, 5.34%, and 0.56%. Significant (p < 0.05) exposure-response relationships were found between PAHs and mtDNA methylation in the plasma of workers; exposure to Anthracene (Ant) could induce the up-regulation of the methylation of MT-COX1 (ß = 0.831, SD = 0.105, p < 0.05), and exposure to Fluorene (Flo) and Phenanthrene (Phe) could induce the up-regulation of methylation of MT-COX3 (ß = 0.115, SD = 0.042, p < 0.05 and ß = 0.036, SD = 0.015, p < 0.05, respectively). The results indicated that exposure to PAHs was an independent factor influencing mtDNA methylation.

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.

Association between mitochondrial DNA methylation and internal exposure to polycyclic aromatic hydrocarbons (PAHs), nitrated-PAHs (NPAHs) and oxygenated-PAHs (OPAHs) in young adults from Tianjin, China.

Polycyclic aromatic hydrocarbons (PAHs), nitrated-PAHs (NPAHs) and oxygenated-PAHs (OPAHs) are environmental pollutants with adverse effects on human health. The correlation between the concentrations of PAHs, NPAHs and OPAHs in human plasma and the methylation level of mitochondrial DNA (mtDNA) was investigated using data from 110 plasma samples collected in Tianjin, China. The median concentrations of PAHs, NPAHs and OPAHs were 16.0 (IQR: 14.4-20.7) ng/mL, 82.2 (IQR: 63.1-97.6) ng/mL and 49.6 (IQR: 28.6-53.8) ng/mL, and the mean proportions were 13.4%, 56.5% and 30.1%, respectively. Bisulfite-PCR pyrosequencing was used to measure the methylation level of MT-CO1 and tRNA-Leu. The methylation levels of two mitochondrial genes (MT-CO1, tRNA-Leu) including four CpG sites (MT-CO1-P1, MT-CO1-P2, tRNA-Leu-P1 and tRNA-Leu-P2) were 0.67% ± 1.38%, 13.54% ± 2.59%, 7.23% ± 5.35% and 1.64% ± 2.94%, respectively. To the best of our knowledge, this is the first time that significant correlations were found between PAHs and their derivatives exposure and mtDNA methylation levels.

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 1196.6 µg/kg to 14980.9 µg/kg and decreased with depth at all sites. PAHs were the most abundant PACs, with a mean concentration of 6640.7 µg/kg, followed by oxygenated PAHs (mean 156.3 µg/kg) and nitrated PAHs (mean 33.4 µg/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 (2-6 m in depth) than in deep soil (8-10 m 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.

Temporal profiles, source analysis, and health risk assessments of parent polycyclic aromatic hydrocarbons (PPAHs) and their derivatives (NPAHs, OPAHs, ClPAHs, and BrPAHs) in PM2.5 and PM1.0 from the eastern coastal region of China: Urban coastal area versus coastal background area.

The eastern coastal region of China is the area with the highest emission of PAHs in China. Therefore, understanding the sources and health risk of parent polycyclic aromatic hydrocarbons (PPAHs) and their derivatives in eastern coastal cities of China is the main basis for air pollution control. In this study, we measured the concentrations of 18 parent PAHs, 17 nitrated PAHs, 7 oxygenated PAHs, 8 chlorinated PAHs, and 13 brominated PAHs in PM1.0 and PM2.5 samples collected at an urban coastal city site and a coastal background site in 2019. We analyzed the temporal distribution, molecular composition, and sources and performed health risk assessments for both winter and summer samples. The average concentration of the PPAHs and their derivatives (all 63 compounds combined) in the PM1.0 samples accounted for 75.57% of the PAHs concentration in PM2.5 samples. The average concentration of PM2.5- and PM1.0- bound PPAHs in winter was 114.70 times higher than in summer, and their derivatives was 27.51 times. Both the combined concentrations of the 18 PPAHs and the combined concentrations of the 45 derivatives were higher in the coastal city compared to the background site during the winter (1.90 and 1.48 times, respectively), but they were comparable during the summer. The positive matrix factorization analysis indicated that the compounds mainly originated from coal/biomass combustion, industrial sources, vehicle emissions, and secondary formation. In addition, the concentration-weighted trajectories model revealed that the PAHs were mainly emitted locally in Shandong Province and surrounding areas, such as Hebei Province, Henan Province, and Bohai Sea. The compounds 1-NPYR, 2+9-BrPHE, 9,10-Cl2PHE, and 1-ClPYR dominantly contributed to the derivatives of TEQ during the winter due to their high concentrations or the high TEFs of these compounds.

Atmospheric wet and dry depositions of polycyclic aromatic compounds in a megacity of Southwest China.

The dry and wet depositions of polycyclic aromatic hydrocarbons (PAHs) and related derivatives have rarely been characterized separately. Parent, oxygenated and nitrated PAHs (PAHs, OPAHs and NPAHs) have been measured in monthly-averaged wet and dry deposition samples collected from January to December 2019 in urban Chongqing. The annual average concentrations of Æ©17PAHs, Æ©9OPAHs and Æ©9NPAHs in wet deposition samples were 457 ± 375, 1311 ± 1416 and 8.25 ± 10.2 ng/L, respectively, with significant monthly variations introduced by rainfall and air-borne particle deposition. Most PAHs species were associated with the particulate phase in wet deposition, while OPAHs and NPAHs were mainly distributed in the dissolved phase, probably due to the lower octanol-water partitioning coefficient of N/OPAHs than that of PAHs. Annual deposition fluxes of PAHs, OPAHs and NPAHs in dry deposition were 25264, 25310 and 388 ng/m2/yr, respectively, higher than those in wet deposition (9869, 24083 and 207 ng/m2/yr). This indicates that PACs, especially PAHs, were removed from the atmosphere mainly via dry deposition. The contributions of wet deposition to total deposited PACs were larger for months with higher precipitation and for PACs with higher molecular weight. Composition pattern and temporal variation results indicated that wet deposition fluxes were mainly affected by precipitation-related particle deposition and chemical properties (e.g., water solubility), while dry deposition fluxes were affected more by factors such as gas/particle partitioning, particle size distribution and physicochemical properties of PACs. Principle component analysis combined with diagnostic ratios revealed that PACs in atmospheric deposition samples were from vehicle emission (48.6%), coal combustion (13.4%), petrogenic source (5.9%) and secondary formation (32.1%).

Occurrence and fate of polycyclic aromatic hydrocarbons from electronic waste dismantling activities: A critical review from environmental pollution to human health.

Electronic waste (e-waste) is one of the fastest-growing solid wastes and has become an urgent issue due to the potential adverse consequences of exposure to emitted toxic pollutants, especially for these occupational exposed workers and local residents. In this review, the environmental occurrences, emission characteristics, sources, and possible adverse effects of polycyclic aromatic hydrocarbons (PAHs) emitted from primitive e-waste dismantling activities are summarized. In general, the atmospheric levels of PAHs at typical e-waste sites, e.g., in Guiyu, China, have substantially decreased by more than an order of magnitude compared with levels a decade ago. The PAH concentrations in soil from old e-waste sites in China are also generally lower than those at newly emerged e-waste sites in India, Pakistan and Ghana. However, elevated concentrations of PAHs have been reported in human milk, hair and urine from the populations near these e-waste sites. Source apportionment both from bench-scale studies to field observations has demonstrated that the pyrolysis and combustion processing of electronic circuit board are mainly responsible for the emissions of various PAHs. In addition, some specific PAHs and their derivatives, such as triphenylbenzene, halogenated and oxygenated PAHs, have frequently been identified and could be considered as indicators in routine analysis in addition to the 16 U.S. EPA priority PAHs currently used.

Spatiotemporal variations and source identification of atmospheric nitrated and oxygenated polycyclic aromatic hydrocarbons in the coastal cities of the Bohai and Yellow Seas in northern China.

Gaseous and particulate nitrated polycyclic aromatic hydrocarbons (NPAHs, 12 species) and oxygenated polycyclic aromatic hydrocarbons (OPAHs, 4 species) in seven coastal cities of the Bohai and Yellow Seas were determined throughout the year. The annual arithmetical mean concentrations of ΣNPAH12 and ΣOPAH4 were 737 ± 475 pg/m3 and 35.3 ± 26.8 ng/m3. NPAHs and OPAHs existed mainly in the gaseous phase, accounted for 88.5% and 95.2% of the total concentrations. Air concentrations of ΣNPAH12 and ΣOPAH4 in the coastal cities of the Yellow Sea were significantly lower (p < 0.05) than those of the Bohai Sea. Air concentrations of ΣNPAH12 and ΣOPAH4 were significantly higher (p < 0.01) in winter than in summer. Strong secondary formation of atmospheric NPAHs and OPAHs occurred in all of the studied cities. The sequence of annual contribution of the emission sources of airborne NPAHs determined by positive matrix factorization was traffic exhaust > combustion of solid fuels (coal and biomass) > secondary formation, while for OPAHs, it was combustion of solid fuels > secondary formation > traffic exhaust. The combustion of solid fuels served as the main source of NPAHs and OPAHs in winter, while secondary formation was the predominant source in summer. Interregional transport may exert an important effect on the local atmospheric NPAHs and OPAHs by potential source contribution function analysis. The estimated incremental lifetime cancer risk (ILCR) due to inhalation exposure to specific NPAHs ranged from 2.9 × 10-12 to 6.2 × 10-6 (median at 4.8 × 10-9) was mainly attributed to exposure before the age of 16.

Simultaneous Determination of Typical Chlorinated, Oxygenated, and European Union Priority Polycyclic Aromatic Hydrocarbons in Milk Samples and Milk Powders.

An increasing number of studies have suggested that PAH contamination in dairy products demands high concern. This study established an efficient determination method for the European Union 15 + 1 PAHs and four PAH derivatives in dairy samples using a QuEChERS method coupled with GC-QqQ-MS. The optimized method obtained a recovery of 63.38-109.17% with a precision of 3.82-15.62%, and the limit of detection and limit of quantification were 0.08-0.78 and 0.27-2.59 µg/kg, respectively. The validated method was then successfully applied to identify the 20 PAHs in 82 dairy samples, including 43 commercial milk samples and 39 milk powders. The total PAH concentrations ranged from 2.37 to 11.83 µg/kg, and benzo[a]pyrene was only quantified in one milk and one milk powder sample at 0.35 and 0.42 µg/kg, respectively. The concentrations of PAH4 in milk samples and milk powders were not quantified (nq)-3.99 and nq-4.51 µg/kg, respectively. The results confirmed the appreciable occurrence of PAHs in dairy products, especially in infant formula. The data in this study provide a scientific basis for assessment on origin tracing, dietary exposure, and health risk of PAHs and their derivatives.

Past, present, and future perspectives on the assessment of bioavailability/bioaccessibility of polycyclic aromatic hydrocarbons: A 20-year systemic review based on scientific econometrics.

Bioaccessibility/bioavailability (bioac-bioav) is an important criterion in the risk assessment of polycyclic aromatic hydrocarbons (PAHs), especially in the restoration of contaminated sites. Although, the bioac-bioav concept is widely employed in PAH risk assessment for both humans and wildlife, their growth and integration in risk assessment models are seldom discussed. Consequently, the relevant literature listed on Web of Science (WOS)™ was retrieved and analyzed using the bibliometric software Citespace in order to gain a comprehensive understanding of this issue. Due to the limitations of the literature search software, we manually searched the articles about PAHs bioac-bioav that were published before 2000. This stage focuses on research on the distribution coefficient of PAHs between different environmental phases and laid the foundation for the adsorption-desorption of PAHs in subsequent studies of the bioac-bioav of PAHs. The research progress on PAH bioac-bioav from 2000 to the present was evaluated using the Citespace software based on country- and discipline-wise publication volumes and research hotspots. The development stages of PAH bioac-bioav after 2000 were divided into four time segments. The first three segments (2000-2005, 2006-2010, and 2011-2015) focused on the degradation of PAHs and their in vivo (bioavailability)-in vitro (bioaccessibility) evaluation method and risk assessment. Meanwhile, the current (2016-present) research focuses on the establishment of analytical methods for assessing PAH derivatives at environmental concentrations and the optimization of various in vitro digestion methods, including chemical optimization (sorptive sink) and biological optimization (Caco-2 cell). The contents are aimed at supplying researchers with a deeper understanding of the development of PAH bioac-bioav.

Nano-MoO2 activates peroxymonosulfate for the degradation of PAH derivatives.

The rapid and efficient degradation of polycyclic aromatic hydrocarbon (PAH) derivatives with toxicological properties remains a substantial challenge. In this study, a cost-effective and eco-friendly catalyst, nano-MoO2 (0.05 g L-1), exhibited excellent performance in activating 4.0 mmol L-1 peroxymonosulfate (PMS) for the degradation of naphthalene derivatives with 1 mg L-1 in aqueous systems; these derivatives include 1-methylnaphthalene, 1-nitronaphthalene, 1-chloronaphthalene, 1-naphthylamine and 1-naphthol, with high degradation rates of 87.52%, 86.23%, 97.87%, 99.74%, and 77.16%. Nano-MoO2 acts as an electron donor by transferring an electron causing O-O bond of PMS to cleave producing SO4·-, and later ·OH. Electron paramagnetic resonance (EPR) analysis combined with free radical quenching research indicated that SO4·- and ·OH dominated the degradation of naphthalene derivatives, and O2·- and 1O2 participated in the processes. X-ray photoelectron spectroscopy (XPS) revealed the transformation of Mo(IV) to Mo(V) and Mo(VI), which suggested that the activation process proceeded via electron transfer from nano-MoO2 to PMS. The applicability of the nano-MoO2/PMS system in influencing parameters and stability was explored. The degradation pathways were primarily elucidated for each naphthalene derivative based on the intermediates identified in the systems. The -CH3, -NO2, -Cl, -OH substituents increased the positive electrostatic potential (ESP) on the molecular surface of 1-methylnaphthalene, 1-nitronaphthalene, 1-chloronaphthalene, and 1-naphthol, which reduced the electrophilic reaction and electron transfer between the reactive species and pollutants, leading to a lower degradation rate of naphthalene derivatives than the parent compound. However, the effect of -NH2 substituents is the opposite. These findings suggest that nano-MoO2 may aid as a novel catalyst in the future remediation of environments polluted with PAH derivatives.