nitro-PAHs Research Articles

Characteristics, sources, and health risks of PAHs and their derivatives in indoor dust in Zhengzhou

The occurrence, source, and health risk of polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and oxy-PAHs (OPAHs) in indoor dust collected from three types of microenvironments (offices, classrooms, and dormitories) at a university campus in Zhengzhou were analysed. The results showed that the average concentration of the total PAHs was 2403.21 ± 981.99 ng g−1, with PHE (20.06% of Σ18PAHs) and BkF (15.46%) being the dominant species. The average concentrations of total NPAHs and OPAHs were 11.09 ± 5.12 and 385.80 ± 255.27 ng g−1, with 2+3N-FLT (39.15%) and 9-FLO (39.76%) as the most abundant species of NPAHs and OPAHs, respectively. The average concentrations of total PAHs, NPAHs, and OPAHs in different microenvironments displayed obvious spatial specificity with the highest values in dormitories. The main source of PAHs, as identified by diagnostic ratios, was petroleum combustion, coal/biomass combustion and vehicle exhaust emissions. The average incremental lifetime cancer risk (ILCR) for undergraduates exposed to dust in classrooms and dormitories exceeded 10−6, indicating a potential cancer risk. The most important exposure pathway was dermal contact, while the inhalation route was negligible.

Emission characteristic, spatial distribution, and health risk of polycyclic aromatic compounds (PAHs, NPAHs, and OPAHs) from light-duty gasoline and diesel vehicles based on on-road measurements

Vehicle exhaust is the primary source of polycyclic aromatic compounds (PACs). Real road tests using a portable vehicle measurement system on light-duty gasoline vehicles and light-duty diesel trucks were conducted to investigate gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and oxy-PAHs (OPAHs) in vehicle exhaust with different emission standards, fuel types, and altitudes. The results showed that with the tightening of emission standards, the overall emission factors (EFs) of PACs decreased. Compared with China V diesel vehicles, the emissions of PAHs, OPAHs, and NPAHs from China VI diesel vehicles were 75.1 %, 84.4 %, and 61.2 % lower, respectively. With a ∼100 m increase in altitude, the EFs of PAHs, OPAHs, and NPAHs of diesel vehicles increased 1.88, 1.92, and 1.59 times due to incomplete combustion. In addition, the EFs of PAHs and OPAHs in gasoline vehicles were lower than those in diesel vehicles. In contrast, the proportion of PAHs with highly toxic components, such as dibenzo[a,h]anthracene (DahA) and benzo[a]pyrene (BaP), and the EFs of gas-phase NPAHs in gasoline vehicles were higher than those in diesel vehicles. Furthermore, the emissions of 1,8-DNP from diesel vehicles cannot be disregarded. 1,8-DNP was the main gas-phase NPAHs emitted by China VI and China V diesel vehicles, accounting for 49.3 % and 26.0 %, respectively. Moreover, gas-phase PACs contributed more to the EFs than particle-phase PACs, whereas particle-phase PACs have greater toxic effects. Although the EFs of PAHs are more than 100 times those of NPAHs, the toxic equivalent concentrations (TEQBaP) of PAHs in diesel and gasoline vehicles were approximately 6.5 times and 35 times those of NPAHs. The spatial distribution characteristics revealed that PACs emissions were mainly concentrated in urban areas and highways, and the differences in the toxicity of PACs emissions between different cities depended on the proportion of diesel vehicles. The average TEQBaP of PAHs and NPAHs in Haidong, Haibei, Huangnan, Hainan, Guoluo, and Yushu was 8.42 μg/m3 and 0.36 μg/m3, respectively, while those of Xining and Haixi were 0.24–0.29 μg/m3 and 0.09–0.108 μg/m3 higher, respectively. This study provides a comprehensive understanding of the emission characteristics, health risks, and spatial distribution of PACs from diesel and gasoline vehicle PACs in urban areas.

Differential Occupational Health Risks between Methylated PAHs and PAHs: Monitoring 126 PAHs and 6 Oxidative Stress Markers in Paired Serum-Urine Samples.

The hazards of polycyclic aromatic hydrocarbons (PAHs) on occupationally exposed population have been widely acknowledged. However, the occupational exposure risks associated their derivatives, methylated PAHs, remain poorly understood. This study conducted a screen of 126 PAHs and 6 oxidative stress biomarkers (OSBs) in paired serum-urine samples from 110 petrochemical workers to assess the risk associated with different PAHs exposure. The results showed that the median concentrations of unmetabolized 16 priority PAHs (p-PAHs), 16 regular PAHs (R-PAHs), 50 methyl-PAHs (Me-PAHs), and 30 nitro-PAHs (N-PAHs) in serum (urine) were 97.98 (66.46), 11.02 (0.00), 77.76 (31.77), and 1.93 (0.10) ng/mL, respectively. The median concentration of metabolized hydroxy PAHs (OH-PAHs) in urine was 12.00 ng/mL (9.49 ng/mg creatinine). OSBs indicate that the hazards of Me-PAHs on exposed populations manifest as protein damage, while the hazards of p-PAHs mainly result in lipid and DNA damage. Results from common diseases and PAH exposure demonstrate a correlation between liver damage and PAH exposure, and Me-PAHs are more difficult to metabolize through urine due to their stronger lipophilicity. This study suggests that traditional health screenings targeting p-PAHs may be insufficient and likely underestimate the exposure risks for occupational populations.

Autumn and spring observations of PM2.5-bound polycyclic aromatic hydrocarbons and nitro-polycyclic aromatic hydrocarbons in China and Japan

The transboundary transport of polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) aggravated by the East Asian winter monsoon is a major atmospheric environmental issue in East Asia. To thoroughly elucidate the role of the East Asian monsoon on regional PAH and NPAH pollution in East Asia, PM2.5-bound PAHs and NPAHs were investigated concurrently at five sites in Beijing and Shenyang in China and Tsukuba, Kanazawa, and Wajima in Japan in autumn (November 2018) and spring (March 2019). During both autumn and spring sampling periods, the concentrations of PM2.5, PAHs, and NPAHs at sites in China were 1–2 orders of magnitude higher than those at sites in Japan, and showed an opposite temporal variation, with higher concentrations during the autumn sampling period due to intensive emissions and unfavourable weather conditions. During the sampling periods, PAHs at the Beijing and Shenyang sites had mixed sources of traffic emissions and coal and biomass combustion, while those at the Tsukuba, Kanazawa, and Wajima sites were mainly characterized by domestic traffic emissions. In addition, NPAHs at the five sites were jointly affected by primary combustion sources and atmospheric generation, with a greater contribution of atmospheric generation to the Beijing and Shenyang sites. Based on backwards trajectory clustering and concentration-weighted trajectory analysis, external contributions to PM2.5, PAHs, and NPAHs at each site were relatively stable during the two sampling periods, and potential source areas were mainly distributed in domestic cities and nearby sea areas. Therefore, the apparent temporal differences in the characteristics and sources of pollutants between sites in the two countries indicate that transboundary pollution dominated by the East Asian winter monsoon was unobvious in autumn and spring. The results of the study provide a time-specific solution for the effective management of regional air pollution during the East Asian winter monsoon.

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.

Main Emission Sources and Health Risks of Polycyclic Aromatic Hydrocarbons and Nitro-Polycyclic Aromatic Hydrocarbons at Three Typical Sites in Hanoi

Particulate matter-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) were first systematically studied in downtown (XT), suburban (GL) and rural (DA) sites in winter and summer in Hanoi, Vietnam, from 2019 to 2022. The mean concentrations of PAHs and NPAHs ranged from 0.76 ng m−3 to 50.2 ng m−3 and 6.07 pg m−3 to 1.95 ng m−3, respectively. The concentrations of PAHs and NPAHs in winter were higher than in summer, except for NPAHs in XT. We found the benzo[a]pyrene (BaP)/benzo[ghi]perylene (BgPe) ratio could effectively identify biomass burning in this study, in which a higher [BaP]/[BgPe] value indicates a greater effect of biomass burning on PAHs and NPAHs. The results indicated that atmospheric PAHs and NPAHs were mainly affected by motor vehicles (especially the unique motorcycles in Southeast Asia) in the summer in Hanoi. In winter, all sites were affected by the burning of rice straw to varying degrees, especially DA. The incremental lifetime cancer risk (ILCR) in Hanoi was first determined through ingestion, inhalation and dermal absorption. The results showed that residents in Hanoi faced high health risks, while females experienced higher health risks than males. The ingestion and dermal pathways indicated higher exposure risks than the usually considered inhalation pathway.

Development of Quantitative Chemical Ionization Using Gas Chromatography/Mass Spectrometry and Gas Chromatography/Tandem Mass Spectrometry for Ambient Nitro- and Oxy-PAHs and Its Applications

The concentration of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere has been continually monitored since their toxicity became known, whereas nitro-PAHs (NPAHs) and oxy-PAHs (OPAHs), which are derivatives of PAHs by primary emissions or secondary formations in the atmosphere, have gained attention more recently. In this study, a method for the quantification of 18 NPAH and OPAH congeners in the atmosphere based on combined applications of gas chromatography coupled with chemical ionization mass spectrometry is presented. A high sensitivity and selectivity for the quantification of individual NPAH and OPAH congeners without sample preparations from the extract of aerosol samples were achieved using negative chemical ionization (NCI/MS) or positive chemical ionization tandem mass spectrometry (PCI-MS/MS). This analytical method was validated and applied to the aerosol samples collected from three regions in Northeast Asia-namely, Noto, Seoul, and Ulaanbaatar-from 15 December 2020 to 17 January 2021. The ranges of the method detection limits (MDLs) of the NPAHs and OPAHs for the analytical method were from 0.272 to 3.494 pg/m3 and 0.977 to 13.345 pg/m3, respectively. Among the three regions, Ulaanbaatar had the highest total mean concentration of NPAHs and OPAHs at 313.803 ± 176.349 ng/m3. The contribution of individual NPAHs and OPAHs in the total concentration differed according to the regional emission characteristics. As a result of the aerosol samples when the developed method was applied, the concentrations of NPAHs and OPAHs were quantified in the ranges of 0.016~3.659 ng/m3 and 0.002~201.704 ng/m3, respectively. It was concluded that the method could be utilized for the quantification of NPAHs and OPAHs over a wide concentration range.

Spatial distribution, source identification, and human health risk assessment of PAHs and their derivatives in soils nearby the coke plants

The coking industry can generate large amounts of polycyclic aromatic hydrocarbons (PAHs) and their derivatives, which may negatively impact the environment and human health. In this study, soils nearby a typical coking plant were sampled to assess the impact of coke production on the surrounding residential areas and human health. The mean concentration of PAHs and their derivatives in residential area soils nearby the coke plant was 4270 ng/g dw, which was 1 order of magnitude higher than that observed in areas far from the coke plant and approximately 4 times lower than that revealed the coke plant. In addition, the results showed that coking processing area was the most contaminant area of the coke plant (mean: 74.4 μg/g dw), where was also the main source of pollutants in residential areas. In terms of vertical soils in coking plant, the maximum levels of chemicals (mean: 205 μg/g dw) were presented at the leakage of underground pipelines, where were much higher than those in surface soils, and decreased with the increase of depth. The analysis of variance (ANOVA) results showed obvious differences in the concentrations of 6-nitrochrysene between the plant, residential areas and control areas. Meanwhile, 6-nitrochrysene had potential cancer risk (CR) for human in the coking site. Thus, 6-nitrochrysene was the most noteworthy PAH derivatives. Furthermore, the CR (mean: 5.94 × 10−5) and toxic equivalent quantities (TEQs) (mean: 14.8 μg·TEQ/g) of PAHs and their derivatives was assessed in this study. This finding suggested that PAHs and their derivatives especially those extremely toxic chemicals (Nitro-PAHs (NPAHs) and Br/Cl-PAHs (XPAHs)) might pose a potential health risk to residents nearby the coke plant. The current study provides further insights into the pollution characteristics of PAHs and their derivatives in coke plants and potential risks to the workers and surrounding residents.

Abundance, Source Apportionment and Health Risk Assessment of Polycyclic Aromatic Hydrocarbons and Nitro-Polycyclic Aromatic Hydrocarbons in PM2.5 in the Urban Atmosphere of Singapore

In this study, the levels of fine particulate matter (PM2.5), polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in PM2.5 samples were determined from 2020 to 2021 in Singapore. For analysis convenience, the sampling period was classified according to two monsoon periods and the inter-monsoon period. Considering Singapore’s typically tropical monsoon climate, the four seasons were divided into the northeast monsoon season (NE), southwest monsoon season (SW), presouthwest monsoon season (PSW) and prenortheast monsoon season (PNE)). The PM2.5 concentration reached 17.1 ± 8.38 μg/m3, which was slightly higher than that in 2015, and the average PAH concentration continuously declined during the sampling period compared to that reported in previous studies in 2006 and 2015. This is the first report of NPAHs in Singapore indicating a concentration of 13.1 ± 10.7 pg/m3. The seasonal variation in the PAH and NPAH concentrations in PM2.5 did not obviously differ owing to the unique geographical location and almost uniform climate changes in Singapore. Diagnostic ratios revealed that PAHs and NPAHs mainly originated from local vehicle emissions during all seasons. 2-Nitropyrene (2-NP) and 2-nitrofluoranthene (2-NFR) in Singapore were mainly formed under the daytime OH-initiated reaction pathway. Combined with airmass backward trajectory analysis, the Indonesia air mass could have influenced Singapore’s air pollution levels in PSW. However, these survey results showed that no effect was found on the concentrations of PAHs and NPAHs in PM2.5 in Indonesia during SW because of Indonesia’s efforts in the environment. It is worth noting that air masses from southern China could impact the PAH and NPAH concentrations according to long-range transportation during the NE. The results of the total incremental lifetime cancer risk (ILCR) via three exposure routes (ingestion, inhalation and dermal absorption) for males and females during the four seasons indicated a low long-term potential carcinogenic risk, with values ranging from 10−10 to 10−7. This study systematically explains the latest pollution conditions, sources, and potential health risks in Singapore, and comprehensively analyses the impact of the tropical monsoon system on air pollution in Singapore, providing a new perspective on the transmission mechanism of global air pollution.

Inherent and external factors influencing the distribution of PAHs, hydroxy-PAHs, carbonyl-PAHs and nitro-PAHs in urban road dust

The distribution and fate of hazardous polycyclic aromatic hydrocarbons (PAHs) and their associated transformed PAHs products (TPPs) notably carbonyl-PAHs (CPAHs), hydroxy-PAHs (HoPAHs), and nitro-PAHs (NPAHs) on urban road surfaces are influenced by diverse factors to varying extent. The pollutants are eventually transported to urban receiving waters via stormwater runoff posing risks to human and ecosystem health. In order to formulate an effective mitigation strategy, it is essential to comprehensively examine the role of both inherent and external factors in the distribution and fate of these hazardous pollutants, and thus, the need for this study. The research study showed that commercial land use has the highest cumulative concentration of PAHs and TPPs. Antecedent dry days (ADDs) has an inverse influence on the distribution of the total concentrations of low-molecular weight PAHs (LMW-PAHs), PAHs, and (PAHs + TPPs) irrespective of the type of land use, whilst there was no major influence on the total concentrations of high molecular weight PAHs (HMW-PAHs), and TPPs. The high volatility of LMW-PAHs compared to HMW-PAHs is considered to account for the decreasing concentration of LMW-PAH with increasing ADD. Particle size range has significant inverse influence on the cumulative concentration of pollutants across all land uses, since smaller particles are characteristically associated with larger surface area leading to the higher sorption of pollutants. Multivariate analysis of the influential factors indicated that two particle size ranges (0.45–150 μm and 150–425 μm) constitute the major influential factors on the distribution and fate of PAHs and TPPs in urban road dust. Greater quantum of pollutants are sorbed to the 0.45–150 μm particles due to the relatively higher specific surface area (SSA), concentration of total organic carbon (TOC) and total suspended solids (TSS) concentration. Therefore, it is critical to effectively remove finer particles from road surfaces in order to reduce exposure to hazardous pollutants.

Determination of 123 polycyclic aromatic hydrocarbons and their derivatives in atmospheric samples

Polycyclic aromatic hydrocarbons (PAHs) are a class of toxic organic pollutants. Until now, they have been detected in many regions and various environmental matrix. However, not all PAHs are usually detected by researchers, and no methods is established to analyze systematically hundreds of PAHs. In this study, 123 PAHs were identified and quantified using gas chromatography−tandem triple-quadrupole mass spectrometry (GC-MS/MS), which were divided into 3 groups: 32 regular PAHs (R-PAHs), 50 methyl-PAHs (Me-PAHs), 30 Nitro-PAHs (N-PAHs) and 11 hydroxyl-PAHs (OH-PAHs). The developed method was applied to detect the target PAHs in 6 marine gaseous samples and 6 particulate samples collected on board the research vessel Snow Dragon. Limits of detection (LOD) and limits of quantification (LOQ) were determined from 0.009 to 2.50 and 0.03–8.33 pg/m3, respectively. Recoveries of the internal standards in atmosphere were from 88% to 112%, 70%–104%, and 72%–102% for R-PAHs、Me-PAHs、N-PAHs and OH-PAHs, respectively, which showed the reliability of the experimental method. The total concentrations of 123 PAHs in marine air and particle samples were from 1532 to 7877 and 206–1022 pg/m3, respectively.

Emission characteristics and assessment of potential health risks on PM2.5-bound organics from incense burning

Incense burning is a nonnegligible indoor air pollution source in many Asian countries, particularly in China. There is a lack of regulation on the formations of incense and its emissions. Herein, the emission factors (EFs) of important particulate phase toxic compounds, parent polycyclic aromatic hydrocarbons (pPAHs), alkylated PAHs (APAHs), oxygenated PAHs (OPAHs), nitro PAHs (NPAHs), and cyclohexanes were determined from the burning of the most representative types of Chinese incenses (i.e., five Nimu Tibetan incenses [NTI], one ordinary smoke incense [SI], and one smoke-free incense [SFI]). The total EFs of the quantified organic species (EFΣorganics) for NTI was 7.44 ± 2.72 μg g−1 on average, within the levels of SI to SFI. The pPAHs showed the largest proportion (41.5%–63.7%) of the total quantified organics. The total cancer risks for all examined incenses severely exceeded the health risk threshold value of 1 × 10−4, verifying that incense burning poses certain extent damage to human health. Notably, the organic compositions of NTI and SFI burnings were similar, with lower EFs and inhalation lifetime cancer risks than SI. The present results suggest that the advanced types of incenses of NTI or SFI should be better choices than SI while the incense burning is necessary. This acts as a guide for the residents, visitors, and workers in the selections of incenses that offer lower toxic substances emissions in dwellings or temples. In addition, the high health risks for incense emissions alert the establishment of more restrictive regulations on incense production and emission are compulsory.

Characteristics and Health Risks of Polycyclic Aromatic Hydrocarbons and Nitro-PAHs in Xinxiang, China in 2015 and 2017

Fine particulate matter (PM2.5) samples were collected in the summer and winter of 2015 and 2017 in Xinxiang, China. Nine polycyclic aromatic hydrocarbons (PAHs) and three nitro-PAHs (NPAHs) in PM2.5 were detected via high-performance liquid chromatography (HPLC). The PAHs concentration in summer and winter decreased from 6.37 ± 1.30 ng/m3 and 96.9 ± 69.9 ng/m3 to 4.89 ± 2.67 ng/m3 and 49.8 ± 43.4 ng/m3 from 2015 to 2017. NPAHs decreased in winter (from 1707 ± 708 pg/m3 to 1192 ± 1113 pg/m3), but increased in summer from 2015 (336 ± 77.2 pg/m3) to 2017 (456 ± 312 pg/m3). Diagnostic ratios of PAHs indicated that petroleum combustion was the main emission source in summer, and pollutants originating from the combustion of petroleum, coal and biomass dominated in winter. The 2-nitrofluoranthene (2-NFR)/2-nitropyrene (2-NP) ratio in this study demonstrated that the OH radical pathway was the main pathway for the formation of 2-NP and 2-NFR. The mean total benzo[a]pyrene-equivalent concentrations (BaPeq) and incremental lifetime cancer risk (ILCR) values decreased from 2013 to 2017. The high value of total BaPeq in the winter of 2017 in Xinxiang revealed that a high-risk of cancer remained for residents. The results of this study demonstrate that the decreases in PAHs and NPAHS concentrations from 2015 to 2017. Combined with reducing gaseous pollutants concentration, the reduction in this study might be attributable to emissions reductions by implementing the air pollution control regulations in Xinxiang city in 2016.

Air pollution increases human health risks of PM2.5-bound PAHs and nitro-PAHs in the Yangtze River Delta, China

Identifying the nature and extent of atmospheric PM2.5-bound toxic organic pollutants is beneficial to evaluate human health risks of air pollution. Seasonal observations of PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in the Yangtze River Delta (YRD) were investigated, along with criteria air pollutants and meteorological parameters. With the elevated PM2.5 level, the percentage of 4-ring PAHs and typical NPAH including 3-Nitrobiphenyl (3-NBP) and 2-Nitrofluoranthene (2-NFLT) increased by 19–40%. PM2.5-bound 2-NFLT was positively correlated with O3 and NO2, suggesting the contribution of atmospheric oxidation capacity to enhance the secondary formation of NPAHs in the atmosphere. Positive matrix factorization (PMF) analysis indicated that traffic emissions (44.9–48.7%), coal and biomass combustion (27.6–36.0%) and natural gas and volatilization (15.3–27.5%) were major sources of PAHs, and secondary formation (39.8–53.8%) was a predominant contributor to total NPAH concentrations. Backward trajectory analysis showed that air masses from North China transported to the YRD region increased PAH and NPAH concentrations. Compare to clean days, the BaP equivalent concentrations of total PAHs and NPAHs during haze pollution days were enhanced by 10–25 and 2–6 times, respectively. The Incremental Lifetime Cancer Risks (ILCRs) of PAHs by inhalation exposure also indicated high potential health risks in the YRD region. The results implied that the health risks of PM2.5-bound PAHs and NPAHs could be sharply enhanced with the increase of PM2.5 concentrations.

Characteristics and unique sources of polycyclic aromatic hydrocarbons and nitro-polycyclic aromatic hydrocarbons in PM2.5at a highland background site in northwestern China☆.

Polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) in PM2.5 were first observed at a background site (Yuzhong site: YZ site) in the northwestern highlands of China in five seasonal campaigns. Compared with major northwestern cities, PAHs and NPAHs at the YZ site were at a lower level but showed consistent seasonal differences. The PAH and NPAH concentrations peaked in the winter campaigns, which were 36.11±6.54ng/m3 and 418.11±123.55pg/m3, respectively, in winter campaign 1 and 28.97±10.07ng/m3 and 226.89±133.54pg/m3, respectively, in winter campaign 2. These values were approximately a dozen times larger those in other campaigns. The diagnostic ratios indicate that vehicle emissions were the primary source of the PAHs throughout the five campaigns, and coal and biomass combustion also contributed during the winter, summer, and fall campaigns. Among NPAHs, 2-nitrofluoranthene and 2-nitropyrene were generated through OH radical-initiated reactions during atmospheric transport, while 1-nitropyrene came from combustion sources. There is an observation worth pondering, which is that the ratio between pyrene and fluoranthene increased abnormally in the spring and fall campaigns, which is presumably caused by the burning of Tibetan barley straw in the northwestern highlands. The backward trajectories over Tibetan areas in Qinghai and southwestern Gansu are consistent with this hypothesis. In addition, this study reported for the first time that the burning of Tibetan barley straw has become a seasonal contributor to air pollution in northwestern China and is participating in the atmospheric transport of air pollutants driven by the monsoon in East Asia, which urgently requires further research.

Influence of photolysis on source characterization and health risk of polycyclic aromatic hydrocarbons (PAHs), and carbonyl-, nitro-, hydroxy- PAHs in urban road dust.

In this study, PAHs and their transformed PAH products (TPPs) in road dust were subjected to UV driven photolysis, and then extracted using simultaneous pressurized fluid extraction, and analysed using Shimadzu Triple Quadrupole GC/MS. The results of the analysis were used to investigate the robustness and reliability of 14 existing diagnostic ratios (DRs) and two newly proposed molecular DRs that are relevant for characterizing the sources of PAHs and TPPs. The influence of photolysis on the carcinogenic health risk posed to humans by these hazardous pollutants was then assessed. The findings indicated that the DRs segregated into stable, moderately stable and non-stable classes of source characteristics under the influence of photolysis. Only two of the existing DRs, namely, benzo(a)pyrene/benzo(ghi)perylene (BaP/BghiP) and total index exhibited consistent stability to photolysis, whilst fluoranthene/(fluoranthene+pyrene) (FRT/(FRT+PYR)) showed moderate stability. The two newly proposed DRs, naphthalene/1-nitronaphthalene (NAP/NNAP) and pyrene/(1-nitropyrene+1-hydroxypyrene) (PYR/(1NPY+HPY)) were found to be highly reliable in post-emission source characterization. The cross-plots of the most stable DRs showed that traffic emissions is the primary source of PAHs, whilst post-emission photolysis is the secondary source of nitro-PAH (NPAH) TPPs. The percent resonance energy thermodynamic stability of the PAH pollutants does not exert any direct influence on the source characteristics of the DRs. Adults are more vulnerable to potential carcinogenic risks as a result of PAH and TPPs photolysis whereas negligible risk exist for children. This study contributes to a more reliable diagnosis of PAH and TPP sources and thus, to the regulatory mitigation of these hazardous pollutants thereby, promoting enhanced protection of human health and the environment.

Polycyclic and nitro-polycyclic aromatic hydrocarbon pollution characteristics and carcinogenic risk assessment of indoor kitchen air during cooking periods in rural households in North China.

Medium-flow atmospheric samplers were used to collect particulate (PM2.5) and gaseous samples from the indoor kitchen of each of 35 randomly selected rural houses in North China while a meal was being cooked. The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) and 9 nitro-PAHs (NPAHs) in the samples were quantified by high-performance liquid chromatography (HPLC). This study provided the real PAH and NPAH pollution characteristics and carcinogenic risk produced by cooking in rural indoor kitchens in North China. The mean PAH and NPAH concentrations in air in the indoor kitchens during cooking periods were 4049.1 and 1741.6 ng/m3, respectively. The PAH and NPAH concentrations were lower in the particulate phase than the gaseous phase. The mean PAH and NPAH concentrations were much higher for cooking using coal than for cooking using liquefied petroleum gas (LPG) or electricity. The PAH and NPAH benzo[a]pyrene toxic equivalent (TEQBaP) concentrations for cooking using coal were 1823.3 and 2760.9 ng/m3, respectively. Lower PAH and NPAH concentrations were found in kitchens with than without range hoods. Range hoods decreased the PAH and NPAH TEQBaP concentrations by 68.8% and 61.9%, respectively. Appropriate fuel and ventilation choice will improve air pollution in indoor kitchens during cooking. The results provide important evidence for changing cooking habits and developing policies for cooking in rural China.

Atmospheric degradation of chrysene initiated by OH radical: A quantum chemical investigation

Chrysene, a four-ring polycyclic aromatic hydrocarbon (PAH), is recalcitrant to biodegradation and persistent in the environment due to its low water solubility. Here, we investigated the atmospheric degradation process of chrysene initiated by OH radical in the presence of O2 and NOX using quantum chemical calculations. The reaction mechanisms were elucidated by density functional theory (DFT) at M06–2X/6–311++G(3df,2p)//M06–2X/6-311+G(d,p) level, and the kinetics calculations were conducted with Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results show that the oxidation products of atmospheric chrysene are oxygenated PAHs (OPAHs) and nitro-PAHs (NPAHs), including nitro-chrysene, hydroxychrysene, hydroxychrysenone, 11-benzo[a]fluorenone and dialdehydes. Most of the products have deleterious effects on the environment and human beings due to their acute toxicity, carcinogenicity and mutagenicity. The overall rate constant for the reaction of chrysene with OH radical is 4.48 × 10−11 cm3 molecule−1 s−1 and the atmospheric lifetime of chrysene determined by OH radical is 6.4 h. The present work provided a comprehensive understanding on the degradation mechanisms and kinetics of chrysene, which could help to clarify its atmospheric fate and environmental risks.

Atmospheric oxidation mechanism of acenaphthene initiated by OH radicals

Gas-phase oxidation of PAHs can result in formation of oxygenated PAHs (OPAHs) and nitro-PAH (NPAHs) as well as a series of secondary pollutants which contribute to formation of SOA. Acenaphthene (ACE) is one of the PAHs with three rings which exists mainly as gaseous form in the atmosphere, where the oxidation is mainly initiated by reaction with OH radical. In this study, the atmospheric oxidation mechanism of ACE initiated by OH radical is investigated using high level quantum chemistry (at the ROCBS-QB3 level) and kinetic calculations, and the overall rate coefficient obtained here is in good agreement with previous experimental values. The reaction starts with OH radical additions to the C3-, C5-site and H atom abstraction from C1/C2 of ACE, and the fates of main adducts formed as ACE-n-OH (ACE3 and ACE5 in short) and R2 are further considered. ACE3 and ACE5 would react with O2 at different sites, of which all the additions are reversible. An overall effective removal rate of ~9 s−1 for ACE5 with O2 are calculated here using steady state approximately, which allows their reaction with NO2 to a relative significant extent in the atmosphere. We predicted significant 4-NACE formation from ACE5. Reaction of ACE3 with O2 is fast enough of ~107 s−1 that 9-NACE is expected to form in smaller quantities. Additionally, a number of cyclic OPAHs and multifunctional compounds are formed in the oxidation of ACE3, ACE5 and R2 under the high/low NOx concentration as observed in previous investigations.

PM2.5 source profiles from typical Chinese commercial cooking activities in northern China and its influences on bioreactivity of vascular smooth muscle cells (VSMCs)

Abstract Fine particulate matter (PM2.5) emitted from commercial cooking activities can lead cardiovascular diseases to humans. In this study, PM2.5 filter samples were collected from the exhausts of six typical and commercial cuisines including Sichuan cuisine, Shaanxi Cuisine, Northeast Chinese cuisine, Shaanxi snacks, hotpot and Chinese barbecue (BBQ) in the Northern China. Chemical components of carbonaceous fractions, water-soluble inorganic ions, elements, and polycyclic aromatic hydrocarbons [including parent PAHs (pPAHs), alkylated PAHs (aPAHs), oxygenated PAHs (oPAHs) and nitro PAHs (nPAHs)] were quantified. The bioreactivities in vascular smooth muscle cells (VSMCs) induced by the exposures to the PM2.5 were also measured. The PM2.5 concentration levels in the kitchen exhausts ranged from the lowest of 290 ± 104 μg m−3 for the Northeast Chinese cuisine to the highest of 3400 ± 978 μg m−3 for the Chinese BBQ. The PM2.5 composition was predominantly comprised of organic carbon (OC), especially for Sichuan and Shaanxi cuisines. The highest PAHs concentration was shown in the Chinese BBQ, followed by the stir-fry-dominated cuisines (i.e., Sichuan, Shaanxi and Northeast Chinese cuisines), and boiling-dominated cuisines (i.e., Shaanxi snacks and hotpot). The pPAH was the most dominated PAHs group. Our results demonstrated that higher cooking temperatures and larger oil consumptions could promote the PAHs formations. The levels of PM2.5 cytotoxicity for the examined cuisines showed a descending order of the Chinese BBQ > stir-fry-dominated cuisines > boiling-dominated cuisines. In addition, the Person's correlations demonstrated that the cooking emitted PM2.5 were much interrelated with the inflammation induction (R > 0.80) than the oxidative stress (R > 0.60) due to the toxic chemical compositions. Using the stepwise regression model, the bioreactivities in VSMCs were found to be conquered by the concentration levels of 12 key chemical components such as chromium (Cr) and 9-methylanthracene. The regression formula explained nearly 100% of the variations on the induced bioreactivities (R2 = 1.00), suggesting that the suppression of emissions of Cr (or 9-methylanthracene) could be efficient in reducing the cytotoxicity induced by cooking emitted PM2.5.