Decomposition of Polycyclic Aromatic Hydrocarbon (PAHs) on Mineral Surface under Controlled Relative Humidity

The fate of Polycyclic Aromatic Hydrocarbons （PAHs） residing in the atmosphere has received enormous attention in recent years due to their mutagenic and carcinogenic risks on human health. In this context, the stability of pyrene （as a representative PAHs） on quartz, alumina, montmorillonite, kaolinite, humic acid and quartz coated with sorbed humic acid was investigated at controlled relative humidity （RH： i.e. 5% and 30%） without light irradiation in order to detect the presence of catalytic effect of mineral surface on PAHs decomposition. The stability of pyrene was found to depend strongly on the physicochemical properties of the substrates. Quartz showed a strong catalytic effect for the decomposition of pyrene even though it was coated with sorbed humic acid. Pyrene sorbed on montmorillonite and humic acid remained stable during the experimental period （i.e. 3 days）. Moisture in the experimental cell also affected the stability of pyrene in particular minerals. Especially, pyrene sorbed on alumina was rapidly decomposed at higher RH. However, there were almost no effect in the case of quartz, kaolinite and humic acid. Depending on the physicochemical properties of aerosols and RH, PAHs associated with minerals in the atmosphere would be decomposed and/or stably reside in the atmosphere.

Size distribution of particulate polycyclic aromatic hydrocarbons in fresh combustion smoke and ambient air: A review

Polycyclic aromatic hydrocarbons(PAHs) are ubiquitous in the atmosphere and they mostly stem from the imperfect combustion of fossil fuels and biofuels.PAHs are inherently associated with homogenous fine particles or distributed to different-sized particles during the aging of air masses.PAHs carried by fine particles undergo a long-range transport to remote areas while those adsorbed on coarse particles have a shorter lifetime in ambient air.More importantly, PAHs with higher molecular weights tend to be bound with finer particles and can deeply enter the lungs, posing severe health risks to humans.Thus, the environmental fate and health effects of particulate PAHs are strongly size-dependent.This review summarizes the size distributions of particulate PAHs freshly emitted from combustion sources as well as the distribution patterns of PAHs in ambient particles.It was found that PAHs from stationary sources are primarily bound to fine particles, which are slightly larger than particles to which PAHs from mobile sources are bound.In ambient air, particulate PAHs are distributed in larger size modes than those in the combustion fume, and the particle size decreases with PAH molecular weight increasing.The relevant mechanisms and influencing factors of particle size distribution changes are illustrated in this article, which are essentially attributed to combustion and ambient temperature as well as the physical and chemical properties of PAHs.Overall, the study on the particle size distribution of PAHs will contribute for a full understanding of the origin, atmospheric behaviors and health effects of particulate PAHs.

DISTRIBUTION AND CHARACTERIZATION OF POLYCYCLIC AROMATIC HYDROCARBON COMPOUNDS IN AIRBORNE PARTICULATES OF EAST ASIA

A review is presented on the distribution and characterization of polycyclic aromatic hydrocarbons （PAHs） and their derivatives, including nitro-PAHs and hydro-PAHs, on atmospheric particulates of East Asia. Generally, PAH compounds with two or three aromatic rings are released mainly into the gas phase, while those containing three or more aromatic rings are associated with particulate matter （PM） emission. Particle-associated PAHs are primarily adsorbed on fine particles, and little associated with coarse particles. Investigation into the concentration level of PAHs in different areas can serve not only to reflect the pollutant status and sources but also to lead to the formulation of control strategies. The results of the present study show that China has more severe PAH pollution than such East Asian countries as Japan and Korea.

Yearly variation in character istics and health risk of polycyclic aromatic hydrocarbons and nitro-PAHs in urban shanghai from 2010-2018

This study encompassed the regular observation of nine polycyclic aromatic hydrocarbons(PAHs)and three nitro-PAHs(NPAHs)in particulate matter(PM)in Shanghai in summer and winter from 2010 to 2018.The results showed that the mean concentrations of∑PAHs in summer decreased by 24.7%in 2013 and 18.1%in 2017 but increased by 10.2%in 2015 compared to the data in 2010.However,the mean concentrations of∑PAHs in winter decreased by 39.7%from 2010(12.8±4.55 ng/m^3)to 2018(7.72±3.33 ng/m^3),and the mean concentrations of 1-nitropyrene in winter decreased by 79.0%from 2010(42.3±16.1 pg/m^3)to 2018(8.90±2.09 pg/m^3).Correlation analysis with meteorological conditions revealed that the PAH and NPAH concentrations were both influenced by ambient temperature.The diagnostic ratios of PAHs and factor analysis showed that they were mainly affected by traffic emissions with some coal and/or biomass combustion.The ratio of 2-nitrofluoranthene to 2-nitropyrene was near 10,which indicated that the OH radical-initiated reaction was the main pathway leading to their secondary formation.Moreover,backward trajectories revealed different air mass routes in each sampling period,indicating a high possibility of source effects from the northern area in winter in addition to local and surrounding influences.Meanwhile,the mean total benzo[a]pyrene-equivalent concentrations in Shanghai in winter decreased by 50.8%from 2010(1860±645 pg/m^3)to 2018(916±363 pg/m^3).These results indicated the positive effects of the various policies and regulations issued by Chinese authorities.

Nitro-PAH exposures of occupationally-exposed traffic workers and associated urinary 1-nitropyrene metabolite concentrations

The assessment of occupational exposure to diesel exhaust（DE） is important from an epidemiological perspective. Urinary biomarkers of exposure have been proposed as a novel approach for measuring exposure to DE. In this study, we measured the concentrations of two urinary metabolites of 1-nitropyrene（1NP）, a nitrated polycyclic aromatic hydrocarbon that has been suggested as a molecular marker of diesel particulate matter. These two metabolites, 6-hydroxy-1-nitropyrene and 8-hydroxy-1-nitropyrene, were determined in urine samples（10 m L） from a small group of workers who were occupationally-exposed to vehicle exhaust in Trujillo, Peru, before and after their workshifts. Workshift exposures to1 NP, as well as PM_（2.5）, 2-nitropyrene and 2-nitrofluoranthene, were also measured.Exposures to 1NP were similar in all studied workers, averaging 105 ± 57.9 pg/m^3（±standard deviation）. Median urinary concentrations of the average of the pre- and post-exposure samples for 6-hydroxy-1-nitropyrene and 8-hydroxy-1-nitropyrene, were found to be 3.9 and 2.3 pg metabolite/mg creatinine, respectively in the group of occupationally-exposed subjects（n = 17） studied. A direct relationship between workshift exposure to 1NP and urinary 1NP metabolites concentrations was not observed. However,the 1NP exposures and the creatinine-corrected urinary concentrations of the hydroxynitropyrene metabolites in these Peruvian traffic workers were similar to occupationally-exposed taxi drivers in Shenyang, China, and were higher than biomarker levels in office workers from Trujillo without occupational exposure to vehicle exhaust.This study provides further evidence that urinary metabolites of 1NP are associated with exposure to DE and may serve as a useful exposure biomarker.

Variations in traffic-related polycyclic aromatic hydrocarbons in PM2.5 in Kanazawa, Japan, after the implementation of a new vehicle emission regulation

A three-year sampling campaign was conducted at a roadside air pollution monitoring station in the urban area of Kanazawa, Japan. Due to a new emission regulation, PAHs levels decreased over the sampling campaign, exhibiting values of 706 ± 413 pg/m^(3) in 2017, 559 ±384 pg/m^(3) in 2018, and 473 ± 234 pg/m^(3) in 2019. In each year, similar seasonal variations in PAHs levels were observed, with higher levels observed in winter and lower levels in summer. Among the PAHs isomer ratios, we observed that the ratio of benzo[b]fluoranthene(BbF) and benzo[k]fluoranthene(BkF), [Bb F]/([BbF] + [BkF]), and the ratio of indeno[1,2,3-cd]pyrene(IDP) and benzo[ghi]perylene(BgPe), [IDP]/([BgPe] + [IDP]), showed stability over the sampling campaign and were less affected by the new emission regulation, seasonal variations, and regional characteristics. When using the combined ratio ranges of 0.66-0.80([Bb F]/[BbF] + [BkF]) and 0.26-0.49([IDP]/[Bg Pe] + [IDP]), traffic emissions were clearly distinguished from other PAHs emission sources. Principal component analysis(PCA) and positive matrix factorization(PMF) were also performed to further analyse the characteristics of traffic-related PAHs. Overall, this study affirmed the effectiveness of the new emission regulation in the reduction of PAHs emissions and provided a combined range for identifying PAHs traffic emission sources.