Nitrated Polycyclic Aromatic Hydrocarbons Research Articles

Evaluation of Orthotrichum lyellii moss as a biomonitor of diesel exhaust

Exhaust from diesel combustion engines is an important contributor to urban air pollution and poses significant risk to human health. Diesel exhaust contains a chemical class known as nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and is enriched in 1-nitropyrene (1-NP), which has the potential to serve as a marker of diesel exhaust. The isomeric nitro-PAHs 2-nitropyrene (2-NP) and 2-nitrofluoranthene (2-NFL) are secondary pollutants arising from photochemical oxidation of pyrene and fluoranthene, respectively. Like other important air toxics, there is not extensive monitoring of nitro-PAHs, leading to gaps in knowledge about relative exposures and urban hotspots. Epiphytic moss absorbs water, nutrients, and pollutants from the atmosphere and may hold potential as an effective biomonitor for nitro-PAHs. In this study we investigate the suitability of Orthotrichum lyellii as a biomonitor of diesel exhaust by analyzing samples of the moss for 1-NP, 2-NP, and 2-NFL in the Seattle, WA metropolitan area. Samples were collected from rural parks, urban parks, residential, and commercial/industrial areas (N = 22 locations) and exhibited increasing concentrations across these land types. Sampling and laboratory method performance varied by nitro-PAH, but was generally good. We observed moderate to moderately strong correlation between 1-NP and select geographic variables, including summer normalized difference vegetation index (NDVI) within 250 m (r = −0.88, R2 = 0.77), percent impervious surface within 50 m (r = 0.83, R2 = 0.70), percent high development land use within 500 m (r = 0.77, R2 = 0.60), and distance to nearest secondary and connecting road (r = −0.75, R2 = 0.56). The relationships between 2-NP and 2-NFL and the geographic variables were generally weaker. Our results suggest O. lyellii is a promising biomonitor of diesel exhaust, specifically for 1-NP. To our knowledge this pilot study is the first to evaluate using moss concentrations of nitro-PAHs as biomonitors of diesel exhaust.

Pressurized liquid extraction and gas chromatography/mass spectrometry for determination of nitrated polycyclic aromatic hydrocarbons adsorbed on refractory diesel particles

A pressurized liquid extraction (PLE) technique was evaluated in this study and optimized using response surface methodology (RSM) for the determination of polycyclic aromatic hydrocarbons and their nitro derivatives from diesel particulate matter. A central composite design (CCD) was applied for the study of three parameters (temperature, nature of solvent and static time) and the optimal conditions were determined for a time of 9 min and a temperature of 145 °C and dichloromethane as extraction solvent. With the GC/MS analytical technique, the limits of detection (LOD) obtained range from 0.3 to 1.5 µg.L-1 for PAHs and from 4.6 to 8 µg.L-1 for nitrated PAHs. Also, this method allowed excellent recoveries of NPAH adsorbed on diesel soot particles (R ≥ 90%) using a mixture of solvents (1% acetic acid in pyridine). The PLE process developed in this research is quantitative and reproducible while using much less solvent than conventional extraction methods.

The Genotoxicity of Organic Extracts from Particulate Emissions Produced by Neat Gasoline (E0) and a Gasoline-Ethanol Blend (E15) in BEAS-2B Cells.

Emissions from modern gasoline engines represent an environmental and health risk. In this study, we aimed to compare the toxicity of organic compound mixtures extracted from particulate matter (PM extracts) produced by neat gasoline (E0) and a blend containing 15% ethanol (E15), which is offered as an alternative to non-renewable fossil fuels. Human lung BEAS-2B cells were exposed to PM extracts, and biomarkers of genotoxicity, such as DNA damage evaluated by comet assay, micronuclei formation, levels of phosphorylated histone H2AX, the expression of genes relevant to the DNA damage response, and exposure to polycyclic aromatic hydrocarbons (PAHs), were determined. Results showed that both PM extracts significantly increased the level of oxidized DNA lesions. The E0 extract exhibited a more pronounced effect, possibly due to the higher content of nitrated PAHs. Other endpoints were not substantially affected by any of the PM extracts. Gene expression analysis revealed mild but coordinated induction of genes related to DNA damage response, and a strong induction of PAH-inducible genes, indicating activation of the aryl hydrocarbon receptor (AhR). Our data suggest that the addition of ethanol into the gasoline diminished the oxidative DNA damage, but no effect on other genotoxicity biomarkers was observed. Activated AhR may play an important role in the toxicity of gasoline PM emissions.

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.

Gas–particle partitioning and dry deposition of atmospheric parent, alkylated, nitrated and hydroxyl polycyclic aromatic hydrocarbons over the Bohai sea and northern Yellow sea in autumn

To elucidate the gas–particle partitioning characteristics and dry deposition contributions of polycyclic aromatic hydrocarbons (PAHs) in the marine environment, 23 integrated air samples were collected during a research cruise in the northern Yellow Sea (NYS) and Bohai Sea (BS) in mid-autumn 2020. The atmospheric concentrations of 23 parent PAHs (PPAHs), 18 alkylated PAHs (APAHs), five nitrated PAHs (NPAHs), and seven hydroxyl PAHs (OPAHs) in gaseous and particulate phases were measured simultaneously. The total concentrations of 53 PAHs varied from 8.77 to 348 ng/m3. The 2-ring and 3-ring PPAHs and APAHs had lower particle-bound fractions than those of the NPAHs and OPAHs. For the gas–particle partitioning of the PAHs, the gas–particle partitioning coefficients (Kp) estimated using an octanol–air partition coefficient (KOA)–based model and KOA/soot–air partition coefficient (KSA) dual model (KOA–KSA dual model) were lower than the Kp measured in the field. Underestimation of the Kp commonly occurred with these models, but the KOA–KSA dual model was more suitable than the KOA–based model for gas–particle partitioning of the 53 atmospheric PAHs in the BS and NYS. The estimated atmospheric dry deposition fluxes of the 53 PAHs ranged from 631 to 14,345 ng/m2/day. The BS receives a PAHs load of up to 117 tons/year. The study provides background information on the occurrence and environmental fate of PAHs and could be vitally important for environmental safety management for the Northwest Pacific Ocean.

Correlation analysis between the in vivo bioavailability and in vitro bioaccessibility of nitro PAHs in soil: Application of simplified FOREhST in vitro methods based on the Chinese pharmacopoeia

In this study, the relative bioavailability (RBA) of nitrated polycyclic aromatic hydrocarbons (NPAHs) in soil samples (n = 30) was assessed using an in vivo mouse model. Based on the correlation between the bioaccessibility data obtained from the Tenax improved traditional Fed ORganic Estimation human Simulation Test (FOREhST) in vitro method (TITF) and the bioavailability data obtained from in vivo experiments, the TITF method was further optimized and simplified by referring to the “Pharmacopoeia of the People's Republic of China: Volume IV, 2020” to adjust the formulation and parameters of the gastrointestinal fluid (GIF) in order to establish a simpler and lower cost in vitro method for the determination of the bioaccessibilities of NPAHs. The dose-accumulation relationship of the in vivo experiment showed that the linear dose-response was better in adipose tissue (R2 = 0.77–0.93), and the accumulation of NPAHs in adipose tissue was higher than that in kidney or liver tissue. Depending on the mouse adipose model, the NPAHs-RBA ranged from 1.88 % to 73.92 %, and a strongly significant negative relationship (R2 = 0.94, p < 0.05) was found between the NPAHs-RBA and Log Kow. The simplified experiment of the TITF showed that the composition of the GIF medium had a significant effect on the bioaccessibilities of NPAHs. The NPAH bioaccessibilities measured by the Tenax improved simplified FOREhST method (TISF) (9.0–36.5 %) were higher than that of the traditional FOREhST method (6.8–22.8 %) but significantly lower than that of the TITF method (16.8–55.2 %). With an increase in the bile concentration in the GIF (from 6 to 10 g/L), the bioaccessibilities of NPAHs increased from 9.0 to 36.5 % to 12.9–42.4 %. The accuracies of the four in vitro methods for predicting the bioavailabilities of NPAHs was in the following order: Tenax improved simplified FOREhST method with increased bile concentration (TITF-IB) (R2 = 0.54–0.87) ≈ TITF (R2 = 0.55–0.85) > TISF (R2 = 0.41–0.77) > FOREhST (R2 = 0.02–0.68). These results indicated that the simple in vitro method could also effectively predict the bioavailabilities of NPAHs.

Nitro substituent caused negative impact on occurrence and development of atherosclerotic plaque by PM2.5-bound polycyclic aromatic compounds

PM2.5 exposure is a significant risk factor for the occurrence and development of atherosclerosis. Polycyclic aromatic hydrocarbons (PAHs) play prominent roles in PM2.5-related toxicity. However, the nitrated derivatives of PAHs, nitrated polycyclic aromatic hydrocarbons (NPAHs), have strong oxidizing properties due to the nitro substituents. Thus, the in vivo and in vitro experiments exposure to benzo[a]pyrene (BaP) and 6-nitro benzo[a]pyrene (NBaP) were conducted to evaluate the effect of nitro substituent on the atherosclerosis due to (or attributable to) PAHs. The results showed that NBaP exposure induced the inhibition of human umbilical vein endothelial cells (HUVECs) viability and cell morphology damage via more severe oxidative stress than BaP exposure. Furthermore, exposure to PM2.5-bound NBaP caused dyslipidemia in the Apolipoprotein E-deficient (ApoE−/−) mice, including the increment of total cholesterol, triglycerides, low-density lipoprotein cholesterol, and malondialdehyde levels, and the decrement of high-density lipoprotein cholesterol levels, superoxide dismutase and glutathione peroxidase levels in serum and aorta. Furthermore, histology showed atherosclerotic plaque in the aorta of ApoE−/− mice. However, there were no significant differences of the physiological and pathological changes between BaP and control groups. Thus, NPAHs induced endothelial dysfunction and dyslipidemia via severe oxidative stress, and further accelerated the occurrence and development of atherosclerosis compared with the parent PAHs. Our findings provide the first evidence that nitro substituent caused much severer negative health impact of polycyclic aromatic compounds, which highlight the significance of NPAHs in health risk estimation of polycyclic aromatic compounds.

Insight into personal exposure characteristics and health effects of PM2.5 and PM0.25-bound PAHs and their derivatives with different heating ways in the Fenwei Plain, China

Personal exposure (PE) to polycyclic aromatic hydrocarbons (PAHs) and their derivatives in particulate matter with two aerodynamic sizes of 2.5 and 0.25 μm (PM2.5 and PM0.25) from rural housewives was studied in the Fenwei Plain, China. A total of 15 households were divided into five different groups based on the type of solid fuel and heating device used, including biomass briquette-furnace (BBF), biomass-elevated Kang (BEK), outdoor lump coal-boiler (OLC), indoor briquette coal-stove (IBC), and electricity (ELE). The PE concentrations of the PAHs and biomarkers in urine collected from the participants were determined. The results showed that the PE concentrations of total quantified PAHs in the biomass group (i.e., BBF and BEK) were 2.2 and 2.0 times higher than those in the coal groups (i.e., OLC and IBC) in PM2.5 and PM0.25, respectively. The housewives who used biomass as fuel suffered from higher potential health impacts than the coal fuel users. The incremental lifetime cancer risk for the PAHs in PM2.5 in the BBF and BEK groups exceeded the international safety threshold. Furthermore, the PE concentrations of oxygenated PAH (o-PAHs) in PM2.5 and PM0.25 in the biomass groups and the nitrated PAHs (n-PAHs) in PM0.25 in the coal groups showed strong correlations with the biomarkers. The results of this study proved the associations between exposure to the different classes of PAHs and health hazards. The findings could also serve as a guideline in establishing efficient measures for using solid fuels for cooking and household warming in northern China.

Distributions of PAHs, NPAHs, OPAHs, BrPAHs, and ClPAHs in air, bulk deposition, soil, and water in the Shandong Peninsula, China: Urban-rural gradient, interface exchange, and long-range transport

A systematic study of the movement of PAHs (Polycyclic aromatic hydrocarbons) and their derivatives through air, soil, and water is key to understanding the exchange and transport mechanisms of these pollutants in the environment and for ultimately improving environmental quality. PAHs and their derivatives, such as nitrated PAHs (NPAHs), oxygenated PAHs (OPAHs), brominated PAHs (BrPAHs) and chlorinated PAHs (ClPAHs), were analyzed in air, bulk deposition, soil, and water samples collected from urban, rural, field, and background sites on the eastern coast of China. The goal was to investigate and discuss their spatiotemporal variations, exchange fluxes, and transport potential. The concentrations of PAHs and their derivatives in the air and bulk deposition displayed distinct seasonal patterns, with higher concentrations observed during the winter and spring and lower concentrations during the summer and autumn. NPAHs exhibited the opposite trend. Significant urban-rural gradients were observed for most of the PAHs and their derivatives. According to the air-soil fugacity calculations, 2–3 ring PAHs, BrPAHs, and ClPAHs were found to volatilize from the soil into the air, while 4–7 ring PAHs, OPAHs, and NPAHs deposited from the air into the soil. The air-water fugacity of the PAHs and their derivatives indicated that surface water was an important source for the ambient atmosphere in Qingdao. The characteristic travel distances (CTDs) and persistence (Pov) for atmospheric transport were much lower than that for the water samples, which may be due to the longer half-lives of PAHs and their derivatives in water. NPAHs and ClPAHs with long transport distances and strong persistence in water could lead to a significant impact on marine pollution.

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.

Atmospheric occurrences and health risk assessment of polycyclic aromatic hydrocarbons and their derivatives in a typical coking facility and surrounding areas

Coking facilities release large quantities of polycyclic aromatic hydrocarbons (PAHs) and their derivatives into the ambient air. Here we examined the profiles, spatial distributions, and potential sources of atmospheric PAHs and their derivatives in an industrial coking plant and its surrounding environment (gaseous and particulate). The mean concentrations of PAHs, nitrated PAHs (NPAHs), chlorinated PAHs (ClPAHs), and brominated PAHs (BrPAHs) in the air of the coking facility were 923, 23.8, 16.7 and 4.25 ng m−³, respectively, 1–2 orders of magnitude higher than those in the surrounding area and the control area. Linear regressions between contaminant concentrations and distance from the coking facility suggested that the concentrations of PAHs (r2 = 0.82, p < 0.05), NPAHs (r2 = 0.77, p < 0.01), and BrPAHs (r2 = 0.62, p < 0.01) were negatively correlated with distance. Additionally, the particle-bound fractions of PAHs and their derivatives were significantly correlated with their molecular weights (p < 0.01). Based on the calculation of the gas/particle partitioning coefficients (log KP) for PAHs and their derivatives and the corresponding subcooled liquid vapor pressures (log PL), the slope values for PAHs, NPAHs, ClPAHs, and BrPAHs ranged from −1 to −0.6, indicating that deposition of PAHs and their derivatives occurred through both adsorption and absorption. Five emissions sources were identified by positive matrix factorization (PMF), including coking emissions, oil pollution, industrial and combustion sources, secondary formation, and traffic emissions, with coking emissions accounting for more than 50% of total emissions. Furthermore, the results of the health risks assessment suggested that atmospheric PAHs and their derivatives in the coke plant and surrounding area negatively impacted human health.

Complex polycyclic aromatic compound mixtures in PM2.5 in a Chinese megacity: Spatio-temporal variations, toxicity, and source apportionment

Polycyclic aromatic compounds (PACs) are important toxic organic components in fine particulate matter (PM2.5), whereas the links between PM2.5 toxicity and associated PACs in ambient air are poorly understood. This study investigated the spatial–temporal variations of PACs in PM2.5 collected from 11 sampling sites across a Chinese megacity and characterized the reactive oxygen species (ROS) generation and cytotoxicity induced by organic extracts of PM2.5 based on cellular assays. The extra trees regression model based on machine learning and ridge regression were used to identify the key toxicants among complex PAC mixtures. The total concentrations of these PACs varied from 2.12 to 71.7 ng/m3 across the study city, and polycyclic aromatic hydrocarbons (PAHs) are the main PACs. The spatial variations of the toxicological indicators generally resembled those of the PAC concentrations, and the PM2.5 related to waste treatment facilities exhibited the strongest toxic potencies. The ROS generation was highly correlated with high molecular weight PAHs (MW302 PAHs), followed by PAHs with MW<302 amu and oxygenated PAHs, but not with nitrated PAHs and the plastics additives. The cell mortality showed weak correlations with these organic constituents. The associations between the biological endpoints and these PM2.5-bound contaminants were further confirmed by exposure to authentic chemicals. Four primary sources of PACs were identified, among which coal and biomass combustion sources (30.2% of the total PACs) and industrial sources (31.0%) were predominant. PACs emitted from industrial sources were highly associated with ROS generation in this city. Our findings highlight the potent ROS-generating potential of MW302 PAHs and the importance of industrial sources contributing to PM2.5 toxicity in this megacity, raising public concerns and further administration.

Urinary Amino-PAHs in relation to diesel engine emissions and urinary mutagenicity

Diesel exhaust has long been of health concern due to established toxicity including carcinogenicity in humans. However, the precise components of diesel engine emissions that drive carcinogenesis are still unclear. Limited work has suggested that nitrated polycyclic aromatic hydrocarbons (NPAHs) such as 1-nitropyrene and 2-nitrofluorene may be more abundant in diesel exhaust. The present study aimed to examine whether urinary amino metabolites of these NPAHs were associated with high levels of diesel engine emissions and urinary mutagenicity in a group of highly exposed workers including both smokers and nonsmokers. Spot urine samples were collected immediately following a standard work shift from each of the 54 diesel engine testers and 55 non-tester controls for the analysis of five amino metabolites of NPAHs, and cotinine (a biomarker of tobacco smoke exposure) using liquid chromatography–mass spectrometry. An overnight urine sample was collected in a subgroup of non-smoking participants for mutagenicity analysis using strain YG1041 in the Salmonella (Ames) mutagenicity assay. Personal exposure to fine particles (PM2.5) and more-diesel-specific constituents (elemental carbon and soot) was assessed for the engine testers by measuring breathing-zone concentrations repeatedly over several full work shifts. Results showed that it was 12.8 times more likely to detect 1-aminopyrene and 2.9 times more likely to detect 2-aminofluorene in the engine testers than in unexposed controls. Urinary concentrations of 1-aminopyrene were significantly higher in engine testers (p < 0.001), and strongly correlated with soot and elemental carbon exposure as well as mutagenicity tested in strain YG1041 with metabolic activation (p < 0.001). Smoking did not affect 1-aminopyrene concentrations and 1-aminopyrene relationships with diesel exposure. In contrast, both engine emissions and smoking affected 2-aminofluorene concentrations. The results confirm that urinary 1-aminopyrene may serve as an exposure biomarker for diesel engine emissions and associated mutagenicity.

Assessment of atmospheric pollution by oxygenated and nitrated derivatives of polycyclic aromatic hydrocarbons in two regions of the Czech Republic

In this study, a method for monitoring 16 representatives of nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) and six oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) in airborne particulate matter (PM) was developed and validated. Soxhlet extraction, followed by solid phase extraction (SPE) on silica, was used to isolate the target compounds. Instrumental analysis was performed by gas chromatography coupled with (tandem) mass spectrometry (GC-MS(/MS)) operated in electron impact (EI) and negative ion chemical ionization (NICI) modes. GC-EI-MS/MS was selected for further experiments due to its higher selectivity of measurement and ability to measure derivatives simultaneously with 20 commonly analyzed PAHs (EU + US EPA priority list). This is the first study documenting the simultaneous analysis of OPAHs, NPAHs, and parent PAHs in a single run. This analysis strategy was successfully validated at two concentration levels of artificial contamination, i.e., 0.8 and 4 ng per filter, with recoveries in the 70–104% range and less than 23% repeatability. The newly developed method was used for the analysis of 45 air samples from two cities in the Czech Republic, namely Ceske Budejovice and Most (a place with heavy industry), and two sampling seasons (February vs. May 2017). Five representatives were found in all samples from the oxy-PAH group, with 9,10-anthraquinone (9,10-ANTQ) being the most abundant (0.010–2.49 ng m−3 air). Three major nitro-PAHs, namely 9-nitroanthracene (9-nANT), 2-nitrofluoranthene (2-nFA), and 1-nitropyrene (1-nPYR), were found in 89%, 96%, and 33% of the samples, respectively, found in concentration ranges of <0.60–902, <0.60–276, and <0.60–117 pg m−3 air. Slightly higher levels of oxy- and nitro-PAHs were found in Ceske Budejovice compared to Most, but the difference was not statistically significant (p-value >0.05). A statistically significant difference was observed between February and May, where the concentrations in February were up to 20 and 50 times higher for individual oxy- and nitro-PAHs, respectively, in both regions. The diagnostic ratio 2-nFA/1-nPYR >5 showed that indirect emissions were the primary nitro-PAH source in Most of nitro-PAHs in Most and in both sampling campaigns. In Ceske Budejovice, the opposite trend was observed in winter, i.e. 2-nFA/1-nPYR <5, indicating direct emissions as the main source. In summary, direct emissions of OPAHs and NPAHs originate from fossil (transportation-related) and solid fuel (heating-related) combustion. In contrast, indirect emissions are related to atmospheric reactions of PAHs with OH radicals (spring, winter) and NO3 radicals (winter). The total TEQB[a]P was higher in winter than spring, with higher inhalation cancer risk.

Characterization and Risk Assessment of PM2.5-Bound Polycyclic Aromatic Hydrocarbons and their Derivatives Emitted from a Typical Pesticide Factory in China.

Polycyclic aromatic hydrocarbons (PAHs) and their derivatives have received extensive attention due to their negative effects on the environment and on human health. However, few studies have performed comprehensive assessments of PAHs emitted from pesticide factories. This study assessed the concentration, composition, and health risk of 52 PM2.5-bound PAHs during the daytime and nighttime in the vicinity of a typical pesticide factory. The total concentration of 52 PAHs (Σ52PAHs) ranged from 53.04 to 663.55 ng/m3. No significant differences were observed between daytime and nighttime PAH concentrations. The average concentrations of twenty-two parent PAHs, seven alkylated PAHs, ten oxygenated PAHs, and twelve nitrated PAHs were 112.55 ± 89.69, 18.05 ± 13.76, 66.13 ± 54.79, and 3.90 ± 2.24 ng/m3, respectively. A higher proportion of high-molecular-weight (4-5 rings) PAHs than low-molecular-weight (2-3 rings) PAHs was observed. This was likely due to the high-temperature combustion of fuels. Analysis of diagnostic ratios indicated that the PAHs were likely derived from coal combustion and mixed sources. The total carcinogenic equivalent toxicity ranged from 15.93 to 181.27 ng/m3. The incremental lifetime cancer risk from inhalation, ingestion, and dermal contact with the PAHs was 2.33 × 10-3 for men and 2.53 × 10-3 for women, and the loss of life expectancy due to the PAHs was 11,915 min (about 0.023 year) for men and 12,952 min (about 0.025 year) for women. These results suggest that long-term exposure to PM2.5 emissions from a pesticide factory has significant adverse effects on health. The study results support implementing the characterization of PAH emissions from pesticide factories and provides a scientific basis for optimizing the living environment around pesticide factories.

Overlooked Transformation of Nitrated Polycyclic Aromatic Hydrocarbons in Natural Waters: Role of Self-Photosensitization.

Photochemical transformation is an important process that involves trace organic contaminants (TrOCs) in sunlit surface waters. However, the environmental implications of their self-photosensitization pathway have been largely overlooked. Here, we selected 1-nitronaphthalene (1NN), a representative nitrated polycyclic aromatic hydrocarbon, to study the self-photosensitization process. We investigated the excited-state properties and relaxation kinetics of 1NN after sunlight absorption. The intrinsic decay rate constants of triplet (31NN*) and singlet (11NN*) excited states were estimated to be 1.5 × 106 and 2.5 × 108 s-1, respectively. Our results provided quantitative evidence for the environmental relevance of 31NN* in waters. Possible reactions of 31NN* with various water components were evaluated. With the reduction and oxidation potentials of -0.37 and 1.95 V, 31NN* can be either oxidized or reduced by dissolved organic matter isolates and surrogates. We also showed that hydroxyl (•OH) and sulfate (SO4•-) radicals can be generated via the 31NN*-induced oxidation of inorganic ions (OH- and SO42-, respectively). We further investigated the reaction kinetics of 31NN* and OH- forming •OH, an important photoinduced reactive intermediate, through complementary experimental and theoretical approaches. The rate constants for the reactions of 31NN* with OH- and 1NN with •OH were determined to be 4.22 × 107 and 3.95 ± 0.01 × 109 M-1 s-1, respectively. These findings yield new insights into self-photosensitization as a pathway for TrOC attenuation and provide more mechanistic details into their environmental fate.

Trace analysis of nitrated polycyclic aromatic hydrocarbons based on two-color femtosecond laser ionization mass spectrometry

Nitrated polycyclic aromatic hydrocarbons (nitro-PAHs) are suspected to be highly carcinogenic and mutagenic compounds that are present in the environment. Gas chromatography combined with mass spectrometry (GC-MS) is the most frequently used technique for trace analysis. The electron ionization techniques that are currently used in MS, however, typically do not result in the formation of a molecular ion, thus making the determination of these compounds more difficult. In this study, we report on the use of a compact highly-repetitive (low-pulse-energy) ultraviolet (UV) femtosecond laser as the ionization source in combination with a miniature time-of-flight mass analyzer and a time-correlated ion counting system. The UV laser pulses emitted at 343, 257, and 206 nm were produced by harmonic generations of a femtosecond Yb laser emitting at 1030 nm and were utilized for single-color multiphoton ionization. A combination of the 343-nm and 257-nm pulses was further employed to achieve two-color two-photon ionization. This technique was found to be more useful for sensitive detection and also resulted in the formation of a molecular ion. A pump-and-probe technique using these pulses was examined in a proof-of-concept study to measure the femtosecond lifetimes of the nitro-PAHs separated by GC, providing additional information for use in the characterization of the analyte. The developed technique was applied in the analysis of an authentic sample, an organic solvent extract from diesel exhaust particulates. The nitro-PAHs contained in a standard reference material (SRM1975) were determined on a two-dimensional GC-MS display, suggesting that this technique would be useful for the practical trace analysis of nitro-PAHs in environmental samples.

Distribution, sources, and health risk of polycyclic aromatic hydrocarbons and their derivatives in the watershed: the case of Yitong River, China

Polycyclic aromatic hydrocarbons (PAHs) and substituted PAHs (SPAHs) are persistent organic pollutants prevalent globally, and SPAHs have received widespread attention in recent years due to their stronger toxicity and carcinogenicity compared to PAHs. There is a lack of systematic examination of PAHs and their derivatives in watersheds. Thus, to clarify the current status, possible sources, and potential risks of PAHs and their derivatives in watersheds, a study was conducted on Yitong River in China. The results showed that the concentrations of ∑PAHs, ∑OPAHs, and ∑NPAHs ranged from 297.9-1158.3ng/L, 281.1-587.2ng/L, and 65.7-269.1ng/L, respectively. Diagnostic ratio analysis showed that the PAHs were mainly derived from petroleum sources, agricultural waste, and coal combustion. Nitrated PAHs (NPAHs) were mainly derived from liquid combustion sources, and oxygenated PAHs (OPAHs) were derived mainly from petroleum source emissions and atmospheric deposition. The exposure risk model of PAHs revealed that 86% of the studied sites would pose carcinogenic risks after dermal contact. The contaminant causing a major carcinogenic risk was DahA, and none of the sites produced non-carcinogenic risks. The lifetime carcinogenic risk of NPAHs was 8.85 × 10-10-1.44 × 10-4, and some surface waters presented with potential carcinogenic risks.

Inventory, source and health risk assessment of nitrated and parent PAHs in agricultural soils over a rural river in Southeast China

Nitrated polycyclic aromatic hydrocarbons (NPAHs) have become a concerning topic because of their widespread occurrence and carcinogenicity. However, studies on NPAHs in soils, especially in agricultural soils, are still limited. In this study, a systematic monitoring campaign of 15 NPAHs and 16 polycyclic aromatic hydrocarbons (PAHs) was performed in agricultural soils from the Taige Canal basin in 2018, which is a typical agricultural activity area of the Yangtze River Delta. The total concentration of NPAHs and PAHs ranged from 14.4 to 85.5 ng g−1 and 118–1108 ng g−1, respectively. Among the target analytes, 1,8-dinitropyrene and fluoranthene were the most predominant congeners accounting for 35.0% of ∑15NPAHs and 17.2% of ∑16PAHs, respectively. Four-ring NPAHs and PAHs were predominant, followed by three-ring NPAHs and PAHs. NPAHs and PAHs had a similar spatial distribution pattern with high concentrations in the northeastern Taige Canal basin. The soil mass inventory of ∑16PAHs and ∑15NPAHs was evaluated to be 31.7 and 2.55 metric tons, respectively. Total organic carbon had a significant impact on the distribution of PAHs in soils. The correlation between PAH congeners in agricultural soils was higher than that between NPAH congeners. Based on diagnostic ratios and principal component analysis-multiple linear regression model, vehicle exhaust emission, coal combustion, and biomass combustion were the predominant sources of these NPAHs and PAHs. According to the lifetime incremental carcinogenic risk model, the health risk posed by NPAHs and PAHs in agricultural soils of the Taige Canal basin was virtually negligible. The total health risk in soils of the Taige Canal basin to adults was slightly higher than that to children.

Nitrated Polycyclic Aromatic Hydrocarbon (Nitro-PAH) Signatures and Somatic Mutations in Diesel Exhaust-Exposed Bladder Tumors.

Diesel exhaust is a complex mixture, including polycyclic aromatic hydrocarbons (PAH) and nitrated PAHs (nitro-PAH), many of which are potent mutagens and possible bladder carcinogens. To explore the association between diesel exposure and bladder carcinogenesis, we examined the relationship between exposure and somatic mutations and mutational signatures in bladder tumors. Targeted sequencing was conducted in bladder tumors from the New England Bladder Cancer Study. Using data on 797 cases and 1,418 controls, two-stage polytomous logistic regression was used to evaluate etiologic heterogeneity between bladder cancer subtypes and quantitative, lifetime estimates of respirable elemental carbon (REC), a surrogate for diesel exposure. Poisson regression was used to evaluate associations between REC and mutational signatures. We observed significant heterogeneity in the diesel-bladder cancer risk relationship, with a strong positive association among cases with high-grade, nonmuscle invasive TP53-mutated tumors compared with controls [ORTop Tertile vs.Unexposed, 4.8; 95% confidence interval (CI), 2.2-10.5; Ptrend<0.001; Pheterogeneity = 0.002]. In muscle-invasive tumors, we observed a positive association between diesel exposure and the nitro-PAH signatures of 1,6-dintropyrene (RR, 1.93; 95% CI, 1.28-2.92) and 3-nitrobenzoic acid (RR, 1.97; 95% CI, 1.33-2.92). The relationship between diesel exhaust and bladder cancer was heterogeneous based on the presence of TP53 mutations in tumors, further supporting the link between PAH exposure and TP53 mutations in carcinogenesis. Future studies that can identify nitro-PAH signatures in exposed tumors are warranted to add human data supporting the link between diesel and bladder cancer. This study provides additional insight into the etiology and possible mechanisms related to diesel exhaust-induced bladder cancer.