Much attention is drawn to polycyclic aromatic hydrocarbons (PAHs) as an air pollutant due to their toxic, mutagenic and carcinogenic properties. Therefore, to understand the levels, seasonality, sources and potential health risk of PAHs in two distinct geographical locations at Karachi and Mardan in Pakistan, total suspended particle (TSP) samples were collected for over one year period. The average total PAH concentrations were 31.5 +/- 24.4 and 199 +/- 229 ng/m(3) in Karachi and Mardan, respectively. The significantly lower concentration in Karachi was attributed to diffusion and dilution of the PAHs by the influence of clean air mass from the Arabian sea and high temperature, enhancing the volatilization of the particle phase PAHs to the gas phase. Conversely, the higher concentration (6 times) in Mardan was due to large influence from local and regional emission sources. A clear seasonality was observed at both the sites, with the higher values in winter and post-monsoon due to higher emissions and less scavenging, and lower values during monsoon season due to the dilution effect. Diagnostic ratios and principal component analysis indicated that PAHs in both sites originated from traffic and mixed combustion sources (fossil fuels and biomass). The average total BaP equivalent concentrations (BaPeq) in Karachi and Mardan were 3.26 and 34 ng/m(3) , respectively, which were much higher than the WHO guideline of 1 ng/m(3) . The average estimates of incremental lifetime cancer risk from exposure to airborne BaPeq via inhalation indicated a risk to human health from atmospheric PAHs at both sites. (C) 2021 The Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V.

With the recent rapid development of urbanization, atmospheric pollutants such as polycyclic aromatic hydrocarbons (PAHs) have attracted wide attention, particularly in remote regions. The Tibetan Plateau (TP), known as the third pole is adjacent to areas with heavy atmospheric pollution, such as South and East Asia. However, the spatial distribution and sources of PAHs on the TP remain unclear. Thus, we investigated the sources and spatio-temporal distributions of PAHs on the TP by combining aerosol sample data from six sites, including Ngari (NG), Laohugou (LHG), Beiluhe (BLH), Nam Co (NMC), Everest (EV), and Yulong (YL), in 2014 and 2016. The average concentrations of 15 PAHs at the six sites ranged from 3.4 to 15.2 ng m(-3), with a decreasing trend from the marginal to inner areas of the plateau. The highest concentration was that in YL in the southeastern part of the TP, with an average of 15.2 ng m(-3). The PAH concentrations in NG, NMC, and YL were higher in autumn and winter and lower in summer. High molecular weight PAHs usually exists in the particulate phase whereas tricyclic PAHs can change from particulate to gaseous phase, therefore it can indicate long-range transport. Tricyclic PAHs were the dominant PAHs on the TP (44%-58%), indicating long-range atmospheric transport as the major source of PAHs. Principal component analysis (PCA) and diagnostic ratio analysis showed that biomass and coal combustion were the major sources of PAHs in inland areas of the TP; however, marginal plateau areas were affected by fossil fuel emissions. Compared with levels in Beijing and other urban sites, the toxic equivalent quantity (TEQ) was low (0.36-1.06 ng m(-3)), suggesting a low risk to human and ecosystem health. (C) 2020 Elsevier Ltd. All rights reserved.

Brown carbon (BrC), an organic aerosol, plays an important role in radiative forcing. Polycyclic aromatic hydrocarbons (PAHs) and their derivatives such as oxygenated and nitrated polycyclic aromatic hydrocarbons (OPAHs & NPAHs) are the major constituents of BrC and are persistent environmental pollutants. Our strategy here is to utilize time dependent-density functional theory (TD-DFT) to model the absorption spectra of PAHs and their derivatives in two Chinese industrial sites: Qingcheng district (site A) and Longtang town of Qingyuan (site B). These data are corrected for Real-world experimental concentrations of PAHs over these cities. For the first time, nocturnal/diurnal and seasonal variations of PAHs are being simultaneously studied under a theoretical framework. These findings show that the absorptions at site A and B take place mainly due to PAHs while OPAHs and NPAHs have negligible contribution. The site A is highly affected by climate forcing caused by these PAHs. The absorption in winter is higher as compared to that of in summer. Our theoretical modeling approach remarkably identifies the most relevant PAHs for climate forcing in both Chinese regions.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAHs) and nitrated (NPAHs) derivatives are main chromophores of the carbonaceous aerosol brown carbon (BrC), which is linked with radiative forcing. Here, we investigated the atmospheric absorption spectra of 64 PAHs, OPAHs, and NPAHs directly over the Chinese megacity of Xi'an, by employing a time-dependent density functional theory (TD-DFT) computational approach and correcting the results for the experimentally determined atmospheric concentration of the studied molecules. The obtained data showed that these molecules contribute more to radiative forcing by absorbing light in the UVA and (sub)visible region of the spectrum. Investigating daily absorption spectra revealed major seasonal variation in the intensity of light absorption, but little changes in the shape of the absorption spectra. The observed light absorption can be explained mainly by contributions from PAHs and to a lesser extent by carbonyl-OPAHs, with relatively low contributions of the other OPAHs and NPAHs. Among them, benzo[b+j+k] fluoranthenes, benzo[e]pyrene, benzo[a]pyrene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, 6H-benzo[cd] pyren-6-one, 7H-benz[de]anthracen-7-one, and benz[a]anthracene-7,12-dione are highlighted as potentially problematic contributors for radiative forcing over Xi'an.

Brown carbon is a type of strong light-absorbing carbonaceous aerosol associated with radiative forcing. Nevertheless, the difficulty in correlating the chemical composition of brown carbon with its light absorption properties impairs the proper elucidation of its role in radiative forcing. Here, we have used a time-dependent density functional theory (TD-DFT)-based procedure to revisit the real-world absorption spectra of polycyclic aromatic hydrocarbons (PAHs) over the city of Porto, in Portugal, while correcting the spectra for their quantity in PM10 particulate matter. Our aim is to, by comparing these new results with those obtained previously regarding PM2.5 data, evaluate the role of different groupings of particulate matter in the light absorption of brown carbon. The results indicate that irrespective of the absorption spectra corresponding to their PM10 or PM2.5 data, the studied PAHs should contribute to radiative forcing by light absorption at UVA and (sub)visible wavelengths. However, the identity of the individual PAH species that contribute the most for the considered wavelengths can be quite different. Thus, different groupings of particulate matter appear to provide distinct contributions to light absorption and radiative forcing over the same location, even when considering the same class of molecular compounds.

The composition and radiative forcing of light-absorbing brown carbon (BrC) aerosol remain poorly understood. Polycyclic aromatics (PAs) are BrC chromophores with fused benzene rings. Understanding the occurrence and significance of PAs in BrC is challenging due to a lack of standards for many PAs. In this study, we quantified polycyclic aromatic carbon (PAC), defined as the carbon of fused benzene rings, based on molecular markers (benzene polycarboxylic acids, BPCAs). Open biomass burning aerosols (OBBAs) of 22 rainforest plants were successively extracted with water and methanol for the analysis of water- and methanol-soluble PAC (WPAC and MPAC, respectively). PAC is an important fraction of water- and methanol-soluble organic carbon (WSOC and MSOC, respectively). WPAC/WSOC ranged from 0.03 to 0.18, and MPAC/MSOC was even higher (range: 0.16-0.80). The priority polycyclic aromatic hydrocarbons contributed less than 1% of MPAC. The mass absorption efficiency (MAE) of MSOC showed a strong linear correlation with MPAC/MSOC (r = 0.60-0.95, p < 0.01). The absorption Angstrom exponent (AAE) of methanol-soluble BrC showed a strong linear correlation with the degree of aromatic condensation of MPAC, which was described by the average number of carboxylic groups of BPCA (r = -0.79, p < 0.01). This result suggested that PAC was a key fraction determining the light absorption properties (i.e., light absorptivity and wavelength dependence) of methanol-soluble BrC in OBBAs.

Brown carbon is a type of carbonaceous aerosol with strong light absorption in the ultraviolet and visible wavelengths that leads to radiative forcing. However, it is difficult to correlate the chemical composition of brown carbon with its atmospheric light absorption properties, which translates into significant uncertainty. Thus, a time-dependent density functional theory (TD-DFT) approach was used to model the real-world absorption properties of 14 polycyclic aromatic hydrocarbons (PAHs) over three regions of the Basque Country (Spain): Bilbao, Urretxu, and Azpeitia. The data were corrected for atmospheric concentration. The results show that the absorption spectra over each region are qualitatively identical, with the absorption intensities being significantly higher over Bilbao than over Azpeitia and Urretxu. Furthermore, it was found that the light absorption by PAHs should be more relevant for radiative forcing when it occurs at UVA and (sub)visible wavelengths. Finally, among the 14 studied PAHs, benzo[b]fluoranthene, pyrene, fluoranthene, benzo[a]pyrene, and benzo[k]fluoranthene and benzoperylene were identified as the molecules with larger contributions to radiative forcing.

A range of polycyclic aromatic hydrocarbons has been identified, and regularities of their vertical distribution in the peatland of hummock-hollow complexes in the southern tundra - forest tundra and northern tundra - southern tundra ecotones of the European Arctic zone have been determined. Benzo[ghi]perylene, naphthalene, pyrene, fluorene, phenanthrene, benzo[b]fluoranthene and benzo[a]pyrene are displayed most in the peatlands under study. Regarding the peatland profile the vertical polyarene distribution is similar - in 150-175 cm permafrost layers (site 1) and 50(70)-210(250) cm layers (site 2), and on the border between the active layer and permafrost 35-50(60) cm (site 1) and 30(42) - 50 cm (site 2) a significant increase of HCO-accumulated PAHs weight fraction is observed. PAHs content maximums in tundra peatland horizons are associated both with 4-, 5- and 6-nuclear structures at both sites under the analysis, and with a larger amount of 2- and 3-nuclear polyarenes in the peatlands on the northern tundra-southern tundra ecotone. Aeration-exposed seasonally thawing peatland layers are subject to continuous formation of primarily light 2- and 3-nuclear PAHs of natural origin resulting from microbiological decomposition of plant residues, which are subsequently involved in equilibrium cycles of chemical and biochemical transformation, with their total capacity remaining almost unchanged and constituting ?200-500 ng/g. Owing to low productivity of plant communities and absence of tree vegetation in the seasonally thawed layer, accumulation of the sum of 4-, 5- and 6-nuclear PAHs weakens significantly. One can detect dependencies between individual PAHs and the botanic composition of peat through higher weight fraction of 4-, 5- and 6-nuclear polyarenes being lignin transformation products generated more as the share of tree vegetation grows. The PAHs composition is a paleoclimatic marker reflecting adequately both changing paleovegetation stages and the degree of peat decomposition.

This study was conducted in the Central Himalayan middle hills to understand the nature of polycyclic aromatic hydrocarbons (PAHs) embedded in aerosol particles, their sources and human health risk assessments. The level of sum of 15 particlephase PAHs was between 9 and 335 ng/m(3), with an average concentration of 73 +/- 66 ng/m(3). There were strong seasonal differences in total suspended particles (TSP) and particle-bound PAH concentrations with higher concentrations in winter, followed by premonsoon and lowest in monsoon. The main contributor to the suspended particles was 5-ring PAHs (32%), followed by 4-ring (29%), 6-ring (28%), and 3-ring PAHs (11%). Conversely, the gas-phase PAHs showed that 3-ring PAHs contributed utmost to the total particles. The molecular ratios and principal component analysis indicated that both petrogenic and pyrogenic sources, particularly fossil fuel combustion, biomass combustion, and car exhausts, were the major sources of PAHs. The overall average Benzo (a)pyrene equivalent concentration of particulate PAHs was 11.71 ng/m(3), which substantially exceeded the WHO guideline (1 ng/m(3)), and indicated the potential health risks for local residents. The average lifetime inhalation cancer risk (ILCR) estimates associated with carcinogenic PAHs was 8.78x 10(-6) for adults, suggesting the possible cancer risk and 2.47 x10(-5) for children, signifying extreme carcinogenic effects of PAHs on children's health. Therefore, strict measures should be taken to reduce PAHs emissions in the region.