Occurrence and spatiotemporal distribution of PAHs and OPAHs in urban agricultural soils from Guangzhou City, China.

The occurrence of polycyclic aromatic hydrocarbon (PAH) derivatives in the environment is of growing concern because they exhibit higher toxicity than their parent PAHs. This study evaluated the large-scale occurrence and spatiotemporal distribution of 16 PAHs and 14 oxygenated PAHs (OPAHs) in urban agricultural soils from seven districts of Guangzhou City, China. Linear correlation analysis was conducted to explore the relationship between PAH and OPAH occurrence and a series of parameters. The compositional analysis, principal component analysis, diagnostic ratios, and principal component analysis coupled with a multiple linear regression model were used to identify the sources of PAHs and OPAHs in the soils. The average concentrations of ΣPAHs and ΣOPAHs (59.6 ± 31.1-213 ± 115.5 µg/kg) during the flood season were significantly higher than those during the dry season (42.1 ± 13.3-157.2 ± 98.2 µg/kg), which were due to relatively strong wet deposition during the flood season and weak secondary reactions during the dry season. Linear correlation analysis showed that soil properties, industrial activities, and agricultural activities (r = 0.27-0.96, p < 0.05) were responsible for the spatial distribution of PAHs during the dry season. The PAH distribution was mainly affected by precipitation during the flood season. The concentrations of ΣOPAHs were only related to the soil properties during the dry season because their occurrence was sensitive to secondary reactions, climate and meteorological conditions, and their water solubility. Our results further showed that coal combustion and traffic emissions were the dominant origins of PAHs and OPAHs during both the seasons. Wet deposition and runoff-induced transport also contributed to PAH and OPAH occurrence during the flood season. The results of this study can improve our understanding of the environmental risks posed by PAHs and OPAHs.

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 comparative study of the sorption of O-PAHs and PAHs onto soils to understand their transport in soils and groundwater.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated derivates (O-PAHs) are identified in soils and groundwater of industrialized sites and contribute to the risk for Humans and the Environment. Nevertheless, data are scarce in literature concerning their retention and transfer in soils and no soil - water partition coefficients are available for these compounds. Sorption of two PAHs, fluorene and acenaphthene and two O-PAHs, 9H-fluorenone and dibenzofuran onto two soils with different organic carbon contents was evaluated and compared by determining their sorption isotherms. Effect of ionic strength and liquid to solid ratio, on fluorene and fluorenone sorption was also evaluated. Sorption equilibrium is achieved within less than 24 hr of mixing and linear sorption models best fit the isotherm data. Acenaphthene and dibenzofuran are similarly sorbed onto the soil. KD of fluorene is higher than the one of fluorenone, showing a smaller affinity of fluorenone towards the solid phase. This means that O-PAH could form larger contamination plumes in groundwater than PAHs. Decreasing the L/S ratio from 100 to 50 and 30, increases the sorption of fluorenone onto the soil by 56% and 67% respectively, while the sorption of fluorene is slightly increased. Increasing the ionic strength of the aqueous phase also modifies the sorption of fluorenone, contrary to the sorption of fluorene which is slightly affected.

Seasonal variations of NPAHs and OPAHs in PM2.5 at heavily polluted urban and suburban sites in North China: Concentrations, molecular compositions, cancer risk assessments and sources.

16 nitrated polycyclic aromatic hydrocarbons (NPAHs) and 5 oxygenated polycyclic aromatic hydrocarbons (OPAHs) in PM2.5 at two locations in Northern China were analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). Sampling was conducted at an urban site in Shandong University in Jinan (SDU) and a suburban site in Qixingtai in Jinan (QXT) in March, June, September and December in 2016. Overall, the concentrations of NPAHs and OPAHs were higher at SDU (1.88 and 9.49 ng/m3, respectively) than QXT (1.57 and 6.90 ng/m3, respectively), and the NPAHs and OPAHs concentrations were significantly higher during the winter than the other seasons at both sites. The incremental lifetime cancer risk (ILCR) values were lower than 10-6 for all sites, seasons and age groups (ranging between 1.85E-08 and 2.56E-07), so there was no risk of carcinogenesis due to exposure to these pollutants. Total cancer risk at SDU was higher than QXT and NPAHs have the highest carcinogenic risk for adults aged from 30 to 70 years. The positive matrix factorization (PMF) results revealed that coal/biomass combustion, diesel vehicle emissions, gasoline vehicle emissions and secondary formation were the main sources of NPAHs and OPAHs at SDU and QXT. Coal/biomass combustion contributed more in spring, autumn and winter; diesel vehicle emission contributed the most in summer; secondary formation made greatest contributions in winter; the contributions of gasoline vehicle emission were similar in summer, autumn and winter. Diagnostic ratios clearly demonstrated that secondary formation is more active in winter than in other seasons, and the reactions of PAHs and OH radical were the dominant secondary formation pathway at both SDU and QXT. In addition, the potential source contribution function (PSCF) identified that the Beijing-Tianjin-Hebei region, Shandong province, Bohai Sea, Yellow Sea, Anhui province and Henan province were the main source regions of NPAHs and OPAHs in Jinan.

It's time to reevaluate the list of priority polycyclic aromatic compounds: Evidence from a large urban shallow lake.

Monitoring only 16 priority PAHs (Pri-PAHs) may greatly underestimate the pollutant load and toxicity of polycyclic aromatic compounds (PACs) in aquatic environments. There is an urgent need to reevaluate the list of priority PACs. To determine which PACs deserve priority monitoring, the occurrence, sources, and toxicity of 78 PACs, including 24 parent PAHs (Par-PAHs), 49 alkylated PAHs (Alk-PAHs), 3 oxygenated PAHs (OPAHs), carbazole, and dibenzothiophene were investigated for the first time in Lake Chaohu sediments, China. Concentrations of ∑Par-PAHs, ∑Alk-PAHs, and ∑OPAHs ranged from 35 to 165, 3.4-26, and 7.7-26 ng g-1, respectively. Concentrations of 16 Pri-PAHs have decreased by 1-2 orders of magnitude compared to a decade ago, owing to the effective implementation of PAHs emission control measures. Comparisons with the sediment quality guidelines indicated that 16 Pri-PAHs have negligible adverse effects on benthic organisms. Positive matrix factorization (PMF) model results showed that coal combustion was the major source of PACs (accounting for 23.5 %), followed by traffic emissions (23.4 %), petroleum volatilization (21.9 %), wood/biomass combustion (18.2 %), and biological/microbial transformation (13.1 %). The toxicity of PACs was assessed by calculating the BaP toxic equivalent concentrations (TEQBaP) and toxic units. It was found that Par-PAHs were the predominant toxic substances. In addition, monomethyl-BaPs, OPAHs, BeP, and 7,12-DMBaA should be prioritized for monitoring due to their noticeable contributions to overall toxicity. The contributions of different sources to the toxicity of PACs were determined based on PMF model results and TEQBaP values, which revealed that combustion sources mainly contributed to the comprehensive toxicity of PACs in Lake Chaohu sediments.

Influence of oil extraction on concentration distributions, migration, secondary formation and carcinogenic risk of NPAHs and OPAHs in air and soil in an oilfield development area in China.

Oil extraction leads to environmental pollution from the oilfields and dweller activities, however, knowledge of the concentration distributions, migration, secondary formation and toxicity of nitrated/oxygenated polycyclic aromatic hydrocarbons (N/OPAHs) in oilfield regions is limited. In this research, atmospheric and soil samples in 7 different location types in an important oil industrial base in China were gathered. The ΣNPAHs and ΣOPAHs in the air ranged from 0.05 to 2.47 ng/m3 and 0.14-22.72 ng/m3, respectively, and in soil ranged from 0.22 to 17.81 ng/g and 9.69-66.86 ng/g, respectively. Both NPAHs and OPAHs in the atmosphere exhibited higher concentrations during winter. The atmospheric NPAH concentrations decreased exponentially with distance from urban area especially in the summer, revealing the impact of vehicles on the air in the Yellow River Delta area. High NPAH and OPAH concentrations were found only in soil near oil extraction facilities, indicating that the impact of oil extraction is limited to the soil near the extraction facilities. The air-soil exchanges of N/OPAHs were assessed through fugacity fraction analysis, and NPAHs were in the equilibrium-deposition state and OPAHs were in the net-deposition state in the winter. Higher incremental lifetime cancer risk (ILCR) occurred at the urban, industrial, and oilfield sites in the atmospheric samples, and the soil samples had the largest ILCR values in the oilfield sites. However, ILCR values for both air and soil did not exceed the threshold of 10-6.

Source apportionment of particle-bound polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (OPAHs), and their associated long-term health risks in a major European city.

Many studies have drawn attention to the associations of oxygenated polycyclic aromatic hydrocarbons (OPAHs) with harmful health effects, advocating for their systematic monitoring alongside simple PAHs to better understand the aerosol carcinogenic potential in urban areas. To address this need, this study conducted an extensive PM2.5 sampling campaign in Athens, Greece, at the Thissio Supersite of the National Observatory of Athens, from December 2018 to July 2021, aiming to characterize the levels and variability of polycyclic aromatic compounds (PACs), perform source apportionment, and assess health risk. Cumulative OPAH concentrations (Σ-OPAHs) were in the same range as Σ-PAHs (annual average 4.2 and 5.6 ng m-3, respectively). They exhibited a common seasonal profile with enhanced levels during the heating seasons, primarily attributed to residential wood burning (RWB). The episodic impact of biomass burning was also observed during a peri-urban wildfire event in May 2021, when PAH and OPAH concentrations increased by a factor of three compared to the monthly average. The study period also included the winter 2020-2021 COVID-19 lockdown, during which PAH and OPAH levels decreased by >50 % compared to past winters. Positive matrix factorization (PMF) source apportionment, based on a carbonaceous aerosol speciation dataset, identified PAC sources related to RWB, local traffic (gasoline vehicles) and urban traffic (including diesel emissions), as well as an impact of regional organic aerosol. Despite its seasonal character, RWB accounted for nearly half of Σ-PAH and over two-thirds of Σ-OPAH concentrations. Using the estimated source profiles and contributions, the source-specific carcinogenic potency of the studied PACs was calculated, revealing that almost 50 % was related to RWB. These findings underscore the urgent need to regulate domestic biomass burning at a European level, which can provide concrete benefits for improving urban air quality, towards the new stricter EU standards, and reducing long-term health effects.

A free radical interlocking co-deposition strategy based on the oxidative pyrolysis mechanism of polyethylene terephthalate to achieve green energy recovery.

Accidental combustion and energy recovery of polyethylene terephthalate (PET) result in the formation of harmful organic substances and excessive emissions of CO2 and CO. This paper presents our recent efforts to unravel the formation mechanism of these harmful substances during the PET combustion process using thermal analysis and simulation calculations (DFT, CDFT, and ReaxFF). Our findings reveal that PET oxidative pyrolysis produces free radicals, harmful small molecule gases, and CO2. The interaction between aromatic free radicals and oxygen initiates unstable peroxy bonds, triggering uncontrollable chain exothermic reactions and producing oxygenated polycyclic aromatic hydrocarbon (OPAH) precursors. We propose a straightforward and eco-friendly free radical interlocking co-deposition inhibition strategy for PET by incorporating polycarbonate (PC). This strategy aims to facilitate green energy recovery by curbing OPAH formation and reducing CO2 and CO emissions during PET waste combustion. Our investigation into the oxidative pyrolysis of PET challenges conventional wisdom dominated by C-H bond fracture, paving the way for efficient, low-pollution green energy recovery.

[Effect of Low-density Polyethylene Microplastics on Natural Attenuation of Oxygenated Polycyclic Aromatic Hydrocarbons in Soil].

The continuous accumulation of microplastics in agricultural soils may affect the natural attenuation of oxygen-containing polycyclic aromatic hydrocarbons (OPAHs). The effects of low-density polyethylene (LDPE) microplastics with the spiking proportion of 1 % and 0.01 % in soils on the natural attenuation of OPAHs were investigated via soil microcosm experiments. The relation between the response of bacterial communities and OPAHs dissipation was also explored. The initial content of OPAHs in the soil was 34.6 mg·kg-1. The dissipation of OPAHs in the soil on day 14 was inhibited by LDPE. The contents of OPAHs in LDPE groups were higher than that in the control by 0.9-1.6 mg·kg-1, and the inhibition degree increased with the proportion of LDPE. The contents of OPAHs were not significantly different among groups on day 28, indicating that the inhibitory effect of LDPE disappeared. LDPE did not change the composition of the dominant taxa in the OPAHs-contaminated soil community but influenced the relative abundances of some dominant taxa. LDPE increased the relative abundance of Proteobacteria and Actinobacteria at the phylum level and decreased that of Bacillus and increased those of Micromonospora, Sphingomonas, and Nitrospira (potential degrading bacteria of LDPE and endogenous substances) at the genus level, all four of which were the main genera dominating intergroup community differences. LDPE changed the α and ß diversity of bacterial communities, but the extents were not significant. LDPE affected the function of the bacterial community, reducing the total abundance of PAHs-degrading genes and some degrading enzymes, inhibiting the growth of PAHs-degrading bacteria and thus interfering with the natural decay of OPAHs.

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 297.9-1158.3 ng/L, 281.1-587.2 ng/L, and 65.7-269.1 ng/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.

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.

PM-bound polycyclic aromatic compounds (PACs) in two large-scale petrochemical bases in South China: Spatial variations, sources, and risk assessment.

Polycyclic aromatic compounds (PACs) are potential pollutants emitted from the petrochemical industry, whereas their occurrence and sources in petrochemical regions are still poorly known. The present study revealed the spatial variations, compositional profiles, sources and contributions, and health risks of PM-bound PACs in two large-scale petrochemical bases (GDPB and HNPB) in South China. The concentrations of parent polycyclic aromatic hydrocarbons (PAHs) were 7.14 ± 3.16 ng/m3 for ∑18PAHs and 0.608 ± 0.294 ng/m3 for the PAHs with molecular weight of 302 amu (MW302 PAHs) in the GDPB base and 2.55 ± 1.26 ng/m3 and 0.189 ± 0.088 ng/m3 in the HNPB base. Oxygenated PAHs (OPAHs) showed comparable concentrations to the parent PAHs in both the bases and nitrated PAHs (NPAHs) had the lowest mean levels (260 pg/m3 and 59.4 pg/m3 in the two regions). Coronene, 2,8-dinitrodibenzothiophene, and dibenzo[a,e]fluoranthene showed remarkably higher contributions to the PAC and can be PAC markers of the petrochemical industry source. Five sources of PACs were identified respectively in both petrochemical bases by the positive matrix factorization (PMF) model. The vehicle (and ship) traffic exhaust was the primary source of PACs (contributed 33% to the ∑PACs), and the sources related to the coking of coal and heavy petroleum and refinery exhaust were identified in both bases, with contributions of 10-20%. PACs in GDPB also contributed from secondary atmospheric reactions (17.3%) and the usage of sulfur-containing fuels (20.9%), while the aromatics industry made a significant contribution (20.1%) to the PACs in the HNPB region. The cumulative incremental lifetime cancer risks (ILCRs) induced by inhalation of PM-bound PACs in both petrochemical bases were low (10-8-10-6). For the sources related to the petrochemical industry, coking activities and the aromatic industry were the significant contributors to the ∑ILCRs in GDPB and HNPB, respectively. This research has implications for further source-targeted control and health risk reduction of PACs in petrochemical regions.

The antioxidant defense responses of Hordeum vulgare L. to polycyclic aromatic hydrocarbons and their derivatives in biochar-amended soil.

The recent studies indicated that the biochar (BC) may be a source of polycyclic aromatic hydrocarbons (PAHs) as well as their oxygen, nitrogen, or sulfur-containing derivatives that are considered as more toxic pollutants than their parent compounds. Here, the assessment of the impact of various biochars addition (1% wt.) to soil on barley Hordeum vulgare L. growth was presented. The concentrations of bioavailable PAHs and their derivatives in biochar were determined. PAHs increased reactive oxygen species generation resulting in oxidative stress in organisms. In this study, the response of soil-grown plants was examined in terms of the activity of the antioxidative enzymes (superoxide dismutase, catalase, peroxidase), lipid peroxidation, and the expression of genes related to oxidative stress. The results indicate that despite low content of a bioavailable fraction of parent compounds and their derivatives (up to 4.45 ± 0.24 ng gbiochar-1 and 0.83 ± 0.03 ng L-1, respectively) the biochemical response of plant was present, the activity of superoxide dismutase increased up to 2 times, but the activity of the other enzymes was lowered. The transcript level values support the studies on enzymatic activity. The presence of PAHs and their derivatives induced oxidative stress slightly but the plant was able to mitigate it.

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.

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.

Occurrence and toxicity of polycyclic aromatic hydrocarbons derivatives in environmental matrices.

In the last years, there is great attention paid to the determination of polycyclic aromatic hydrocarbons (PAHs) in different environmental matrices. Extensive reviews on PAHs presence and toxicity were published recently. However, PAHs formation and transformation in the environment lead to the production of PAHs derivatives containing oxygen (O-PAHs), nitrogen (N-PAHs and aazarenes AZA) or sulfur (PASHs) in the aromatic ring. The development of new analytical methods enabled the determination of these novel contaminants. The presence of oxygen, nitrogen, or sulfur in PAHs aromatic rings increased their toxicity. The most common primary sources of PAHs derivatives are biological processes such as microbial activity (in soil, water, and wastewater treatment plants (O-PAHs)) and all processes involving combustion of fuel, coal, and biomass (O-PAHs, N-PAHs, AZA, PASHs). The secondary resources involved i) photochemical (UV light), ii) radical-mediated (OH, NO3), and iii) reactions with oxidants (O3, NOx) (O-PAHs, N-PAHs, AZA). Furthermore, N-PAHs were able to transform to their corresponding O-PAHs, while other derivatives were not. It indicated that N-PAHs are more vulnerable to photooxidation in the environment. 85% of O- and N-PAHs were detected with particle matter below 2.5 µm suggesting their easier bioaccessibility. More than 90% of compounds with four and more aromatic cycles were present in the particle phase in the air. Although the concentrations of N-PAHs or O-PAHs may be similar to PAHs concentration or even 1000 times lower than parent PAHs, PAHs derivatives accounted for a significant portion of the total mutagenicity. The present review is describing the results of the studies on the determination of PAHs derivatives in different environmental matrices including airborne particles, sediments, soil, and organisms. The mechanisms of their formation and toxicity were assessed.

Insights into sources and occurrence of oxy- and nitro-PAHs in the alberta oil sands region using a network of passive air samplers.

Mining-related activities in the Alberta Oil Sands Region (AOSR) are known to emit polycyclic aromatic hydrocarbons (PAHs) and related compounds to ambient air. This is a concern due to the toxicity of PAHs, including their transformation products such as nitrated (NPAHs) and oxygenated (OPAHs) PAHs. This is the first study that provided a more extensive outlook into the sources, occurrence in air, and spatial and seasonal patterns of NPAHs and OPAHs in the AOSR by using passive air sampling. A sampling campaign from 2013 to 2016 revealed concentrations of NPAHs that were much lower than those of OPAHs. The highest concentrations of NPAHs were concentrated in the region associated with extensive mining activities, with ∑NPAH concentrations ranging from 20 to 250 pg/m3. Within the oil sands (OS) mineable area, NPAHs associated with primary release appear more commonly, while NPAHs produced via oxidative transformation are predominant outside of this area. The concentrations of ∑OPAH ranged from 400 to 2400 pg/m3, with the highest air concentrations in the region located south of the main OS activity zone, with peak concentrations attributed to a 2016 forest fire event. Uptake of PAHs from ambient air and their subsequent conversion to generate OPAHs is believed to play an important role in wildfire emissions of OPAHs. The seasonal trend investigation was inconclusive, with NPAHs slightly higher during the winter, while OPAHs were slightly elevated during summer. A preliminary comparison of ambient concentrations of OPAHs and NPAHs in the AOSR to measurements in the Greater Toronto Area revealed a similar range of concentrations, but also a unique presence of certain NPAHs such as 4-nitrobiphenyl, 2-nitrodibenzothiophene, 2,8-dinitrodibenzothiophene and 6-nitrobenzo-(a)-pyrene. This indicates that AOSR might have its own NPAH profile - creating the need to better understand associated NPAH toxicity and propensity for long range transport.

Three years of atmospheric concentrations of nitrated and oxygenated polycyclic aromatic hydrocarbons and oxygen heterocycles at a central European background site.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs, OPAHs) are abundant in the atmosphere and contribute significantly to the health risk associated with inhalation of polluted air. Despite the health hazard they pose, NPAHs and OPAHs were rarely included in monitoring. The aim of this study is to provide the first multi-year temporal trends of the concentrations, composition pattern and fate of NPAHs and OPAHs in air from a site representative of background air quality conditions in central Europe. Samples were collected every second week at a rural background site in the Czech Republic during 2015-2017. Concentrations ranged from 1.3 to 160 pg m-3 for Σ17NPAHs, from 32 to 2600 pg m-3 for Σ10OPAHs and from 5.1 to 4300 pg m-3 for Σ2O-heterocycles. The average particulate mass fraction (θ) ranged from 0.01 ± 0.02 (2-nitronaphthalene) to 0.83 ± 0.22 (1-nitropyrene) for individual NPAHs and from <0.01 ± 0.01 (dibenzofuran) to 0.96 ± 0.08 (6H-benzo (c,d)pyren-6-one) for individual OPAHs and O-heterocycles. The multiyear variations showed downward trends for a number of targeted compounds. This suggests that on-going emission reductions of PAHs are effective also for co-emitted NPAHs and OPAHs.

The formation and evolution of parent and oxygenated polycyclic aromatic hydrocarbons during a severe winter haze-fog event over Xi'an, China.

In this study, 3- or 4-h high time-resolved PM2.5 was observed during a severe winter haze-fog event (1 to 6 January 2017) to investigate the formation and evolution of parent polycyclic aromatic hydrocarbons (pPAHs) and oxygenated polycyclic aromatic hydrocarbons (OPAHs) in Xi'an, a typical city in northwestern China. Three episodes (episode I, episode II, and rainy day (EI, EII, and RD)) have been identified during this haze-fog event. Nine water-soluble ions, 8 carbonaceous fractions, 18 pPAHs, and 3 OPAHs in PM2.5 were measured. pPAHs showed two peaks at around 12:00 local standard time (LST) and 24:00 LST and two troughs at around 2:00 LST and 18:00 LST during EI. However, the OPAHs presented highest at around 18:00 LST and lowest at around 2:00 LST. During EII, pPAHs and OPAHs displayed similar diurnal variations with the highest values at noon but lowest values at around 2:00-5:00 LST. In addition, no obvious diurnal variations of pPAHs and OPAHs were observed during RD were absent during RD. Diurnal variations of pPAH ring distributions demonstrated coal combustion, and vehicle emissions contributed to pPAHs for three episodes, which is further confirmed by diagnostic ratio results. High oxygenation (Ro) rates were found during the sampling time, which favored OPAH formation. The study herein indicates that OPAH formation through complex atmospheric reactions provides us new insights into the severe haze-fog events.

Polycyclic aromatic compounds (PAHs, oxygenated PAHs, nitrated PAHs, and azaarenes) in air from four climate zones of China: Occurrence, gas/particle partitioning, and health risks.

Polycyclic aromatic compounds (PACs) such as polycyclic aromatic hydrocarbons (PAHs) and their derivatives [oxygenated PAHs (OPAHs), nitrated PAHs (NPAHs), and azaarenes (AZAs)] are toxic and ubiquitous air pollutants. In this study, the concentrations of these PACs were determined in air obtained in spring and autumn of 2012 from urban and rural areas of the Tibetan Plateau, temperate, subtropical, and tropical climate zones in China. Average concentrations (gaseous + particulate) of ∑29PAHs, ∑15OPAHs, ∑11NPAHs, and ∑4AZAs were 928 ± 658, 54 ± 45, 5.3 ± 4.4, 14 ± 11 ng m-3 and 995 ± 635, 67 ± 38, 8.4 ± 6.1, 24 ± 16 ng m-3 in spring and autumn, respectively. Various C fractions and latitude correlated significantly with the concentrations and ratios of PACs. The slopes of the regression of gas-particle partition coefficients (Kp) of PACs on their sub-cooled liquid vapor pressures (PL0), indicated both adsorption and absorption to total suspended particles (TSP) for PAHs, OPAHs, and NPAHs in the four studied climatic zones. This result was further supported by comparing the fractions of PACs in TSP calculated from field data with those predicted by the Junge-Pankow adsorption and KOA absorption models. The concentration ratios of most OPAHs or NPAHs to their parent PAHs and of benzo[e]pyrene/benzo[a]pyrene were higher in autumn than in spring and increased with remoteness from point sources. This suggests enhanced secondary formation of PAH derivatives due to the elevated photochemical activity in autumn and longer ageing of air and associated transformation of PACs during their long-distance transport from source regions (urban sites) to rural sites. Lifetime lung cancer risk estimated from PACs ranged from 0.8 ± 0.6 to 3.1 ± 1.0 (×10-3), exceeding the value (10-5) recommended by the WHO. Gaseous PACs contributed substantially to the estimated cancer risks and their contributions increased with decreasing latitude in China.