Polycyclic Aromatic Hydrocarbons Isomers Research Articles

Distribution, sources and health risk assessment of polycyclic aromatic hydrocarbons in urban soils under different landform conditions of Taiyuan, China

Public concern about polycyclic aromatic hydrocarbons (PAHs) is rising due to their potential carcinogenic, teratogenic, and mutagenic effects. This study assessed PAHs in Taiyuan City’s plain and mountain soil, investigating concentrations, distribution, sources, and carcinogenic risk. Σ21PAHs concentrations in plain topsoil ranged from 133.2 to 6,410.6 ng/g (mean 1,444.7 ng/g), and in mountain soil from 66.5 to 2,250.2 ng/g (mean 585.5 ng/g). Approximately 55.1% of plain and 19.0% of mountain soil samples had contamination levels exceeding 600 ng/g. In plain soil, 4-ring and 5-ring PAHs dominated, while 2-ring and 3-ring PAHs were prevalent in mountain soil. Polluted areas in Taiyuan were primarily centered in the central-north, with higher content closer to industrial or business districts. PAH isomer ratios and principal component analysis/multiple linear regression (PCA/MLR) indicated coal combustion as the main PAH source, followed by coke production, vehicle emissions, and biomass combustion. Incremental lifetime cancer risks (ILCRs) showed Taiyuan’s PAH-related cancer risks were generally low, though heavily contaminated areas exhibited moderate risks. Plain regions had three times higher cancer risk than mountains, with children facing higher risk than adults. These findings highlight the need to consider PAH pollution while enhancing urban environmental quality.

Core-shell silica@pyridyl conjugated microporous polymer as a stationary phase for high performance liquid chromatography

BackgroundBecause of the advantages of good selectivity, high sensitivity, and fast analysis, high performance liquid chromatography (HPLC) has become one of the modern analytical techniques in wide application range, such as biological analysis, environmental detection, pharmaceutical and food inspection, agriculture and other fields. The stationary phase greatly decides the chromatographic separation performance, so the development of novel stationary phase is most important for HPLC. ResultsPyridyl conjugated microporous polymers (P-CMP) with one to four layers were modified on the surface of amino silica to obtain a novel core-shell material (SiO2@P-CMP) by the layer-by-layer assembly strategy and Chichibabin reaction. The relationship between the structure of SiO2@P-CMP and chromatographic performance was carefully investigated, and the retention mechanism was revealed. The interactions including π-π stacking, hydrophobic effect and hydrogen bond gradually enhanced with the increase of P-CMP layers on the silica surface. Compared with C18 column, SiO2@P-CMP columns displayed better separation selectivity for polycyclic aromatic hydrocarbons (PAHs). According to the relative retention values (α), the separation performance of SiO2@P-CMP columns (α = 1.144–1.884) for PAH isomers and other analytes was obviously better than that of C18 column (α = 0.998–1.487). Furthermore, the SiO2@P-CMP column with four layers was selected to separate different types of analytes (eight PAHs, four bisphenols, four estrogens and nine phthalates), and the peak order of analytes was different from that on the C18 column due to the influence of hydrogen-bonding and π-π interactions. The relative standard deviations (n = 10) of retention time and peak area on SiO2@P-CMP column were between 0.28 % and 1.98 %. Significance and noveltyPyridyl conjugated microporous polymer was introduced as the stationary phase for the first time in HPLC. The proposed column displayed better separation characteristics compared to Zorbax SB-C18 column. It provided a new idea for the separation of small molecules and the development of chromatographic packing or extraction material.

Immobilization of two dendritic organic phases onto silica and their molecular shape recognition for polycyclic aromatic hydrocarbons, tocopherols and carotenoid isomers

BackgroundMolecular shape selectivity, based on the size and shape parameters of the molecule, such as length and planarity, is a separation process that can be used for compounds with restricted shapes, such as isomers. The separation of geometric isomers is challenging because these compounds have similar physicochemical properties but differ slightly in molecular shape. The ability to separate and quantify these isomers is important in high performance liquid chromatography (HPLC), which is one of the most widely used techniques in separation science today, because the shape of the molecule has a strong influence on biological processes. ResultsWe prepared symmetrical discoidal dendrimeric organomolecule gelators (GSDM) and o-phenylenediamine-derived low-molecular-weight dendrimeric organomolecule gelators (G1) and bonded them to silica surfaces. The dendritic organic compound-grafted silica (SiO2@GSDM and SiO2@G1) was used as HPLC stationary phases for the separation of shape-restricted isomers of polycyclic aromatic hydrocarbons (PAHs), carotenoids and tocopherols. The two phases exhibit a very high molecular shape selectivity compared to the commercially available alkyl phases. There are differences in molecular shape selectivity between the two stationary phases. Changes in the chemical structure of dendritic organic compounds can alter the orientation of the molecules, as well as changes in the molecular recognition ability. It was found that SiO2@GSDM has high molecular linear selectivity for PAHs at different temperatures, even at 50 °C. The planar selectivity of SiO2@GSDM was better for triphenylene and o-terphenyl benzenes compared to SiO2@G1. SignificanceThis separation behavior may be attributed to the combined effect of weak interaction centers, which allowed the effective separation of bioactive and shape-restricted isomers through multiple interactions. Furthermore, SiO2@GSDM showed better separation of tocopherols and carotenoids, suggesting that the backbone and ordered structure of organic molecular gelators is an effective way to improve the shape selectivity of the molecules, whereas the molecular orientation of the functional groups influences the separation mechanism of the shape-restricted isomers.

Occurrence and Sources of Polycyclic Aromatic Hydrocarbons and Factors Influencing Their Accumulation in Surface Sediment of a Deep-Sea Depression, Namely, the Tatar Trough (Tatar Strait, the Sea of Japan)

The concentrations of 14 polycyclic aromatic hydrocarbons (PAHs) in the sediment of the Tatar Trough were studied. Despite the increase in PAH concentrations over recent decades, which is likely the result of the handling and transportation of fossil fuels, PAH levels and ecological risk were found to be low. The spatial pattern revealed that higher PAH concentrations were mainly in the deeper water sites, suggesting that trough slope failure transported the PAHs to the deeper part of the basin. There was no correlation between the PAHs and grain size or the PAHs and organic carbon that is related to the PAH input from a variety of sources and the heterogeneity of organic matter. The PAH composition, isomer ratio, and PCA identified two areas with different PAH sources. The most northern part of the Tatar Trough received petrogenic PAHs that are probably transported downslope from the northern Tatar Strait where fossil fuels are handled in some ports. Another trough part was polluted by the PAHs from the combustion of coal and biomass and the exhaust of marine vehicles. The minor presence of genes responsible for aerobic PAH destruction can be explained by the anaerobic degradation of PAHs or the spontaneous creation of favorable conditions that promote bacterial PAH oxidation.

Genotoxicity by rapeseed methyl ester and hydrogenated vegetable oil combustion exhaust products in lung epithelial (A549) cells.

Biofuel is an attractive substitute for petrodiesel because of its lower environmental footprint. For instance, the polycyclic aromatic hydrocarbons (PAH) emission per fuel energy content is lower for rapeseed methyl ester (RME) than for petrodiesel. This study assesses genotoxicity by extractable organic matter (EOM) of exhaust particles from the combustion of petrodiesel, RME, and hydrogenated vegetable oil (HVO) in lung epithelial (A549) cells. Genotoxicity was assessed as DNA strand breaks by the alkaline comet assay. EOM from the combustion of petrodiesel and RME generated the same level of DNA strand breaks based on the equal concentration of total PAH (i.e. net increases of 0.13 [95% confidence interval (CI): 0.002, 0.25, and 0.12 [95% CI: 0.01, 0.24] lesions per million base pairs, respectively). In comparison, the positive control (etoposide) generated a much higher level of DNA strand breaks (i.e. 0.84, 95% CI: 0.72, 0.97) lesions per million base pairs. Relatively low concentrations of EOM from RME and HVO combustion particles (<116 ng/ml total PAH) did not cause DNA strand breaks in A549 cells, whereas benzo[a]pyrene and PAH-rich EOM from petrodiesel combusted using low oxygen inlet concentration were genotoxic. The genotoxicity was attributed to high molecular weight PAH isomers with 5-6 rings. In summary, the results show that EOM from the combustion of petrodiesel and RME generate the same level of DNA strand breaks on an equal total PAH basis. However, the genotoxic hazard of engine exhaust from on-road vehicles is lower for RME than petrodiesel because of lower PAH emission per fuel energy content.

Cooling dynamics of energized naphthalene and azulene radical cations.

Naphthalene and azulene are isomeric polycyclic aromatic hydrocarbons (PAHs) and are topical in the context of astrochemistry due to the recent discovery of substituted naphthalenes in the Taurus Molecular Cloud-1 (TMC-1). Here, the thermal- and photo-induced isomerization, dissociation, and radiative cooling dynamics of energized (vibrationally hot) naphthalene (Np+) and azulene (Az+) radical cations, occurring over the microsecond to seconds timescale, are investigated using a cryogenic electrostatic ion storage ring, affording "molecular cloud in a box" conditions. Measurement of the cooling dynamics and kinetic energy release distributions for neutrals formed through dissociation, until several seconds after hot ion formation, are consistent with the establishment of a rapid (sub-microsecond) Np+ ⇌ Az+ quasi-equilibrium. Consequently, dissociation by C2H2-elimination proceeds predominantly through common Az+ decomposition pathways. Simulation of the isomerization, dissociation, recurrent fluorescence, and infrared cooling dynamics using a coupled master equation combined with high-level potential energy surface calculations [CCSD(T)/cc-pVTZ], reproduce the trends in the measurements. The data show that radiative cooling via recurrent fluorescence, predominately through the Np+ D0 ← D2 transition, efficiently quenches dissociation for vibrational energies up to ≈1eV above dissociation thresholds. Our measurements support the suggestion that small cations, such as naphthalene, may be more abundant in space than previously thought. The strategy presented in this work could be extended to fingerprint the cooling dynamics of other PAH ions for which isomerization is predicted to precede dissociation.

Assessing the effects of heavy metals and polycyclic aromatic hydrocarbons on benthic foraminifera: The case of Houshui and Yangpu Bays, Hainan Island, China

This work aimed to investigate the distribution of benthic foraminiferal assemblages in Houshui and Yangpu Bays, Hainan Island, and assess the relative effects of heavy metals, total organic carbon (TOC), and polycyclic aromatic hydrocarbons (PAHs) on foraminiferal assemblages. A total of 30 sites were sampled and analyzed for benthic foraminiferal assemblages, heavy metals, TOC, and PAHs. The organic matter in the study was derived primarily from algae according to the C/N ratios, and PAHs were generated by petroleum and combustion of petroleum products, as inferred from the diagnostic ratios of PAH isomers. Two-way hierarchical cluster analysis was used to classify the 35 common species into two species groups, and the 30 sites were classified based on their geographical location. CCA was used to investigate the effects of pollution on foraminiferal assemblages. The results showed that the effects of pollution on foraminiferal assemblages were in the order of heavy metals &amp;gt; TOC &amp;gt; PAHs. Furthermore, the species group I, which consisted of agglutinated taxa including Bigenerina nodosaria, Ammobaculites agglutinans, Textularia spp., T. foliacea, Haplophragmoides canariensis, and several tolerant species of hyaline forms, including Ammonia beccarii, Elphidium advenum, E. hispidulum, Quinqueloculina laevigata, and Q. seminula, was found to be positively influenced by heavy metals. In contrast, species group II, primarily composed of porcelaneous taxa such as Massilina laevigata, Spiroloculina communis, and some hyaline taxa including E. crispum and Elphidium spp., was found to be positively influenced by TOC and PAHs. This work suggest that heavy metal pollution is the main factor influencing foraminiferal assemblages in the study area. The observed positive effect of heavy metals on species group I may indicate the presence of metal-tolerant taxa, whereas the positive effect of TOC and PAHs on species group II suggests that these taxa may be more tolerant of organic pollution. The study highlights the potential of specific foraminiferal assemblages as bioindicators for assessing the impact of different types of pollution on marine ecosystems.

Novel insights into the predominant factors affecting the bioavailability of polycyclic aromatic hydrocarbons in industrial contaminated areas using PLS-developed model

Bioavailability is recognized as a useful technical standard for risk assessment and pollution rehabilitation. However, knowledge on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) in contaminated site soils is still limited, especially concerning the influential mechanism. With an abundance of soil collections from nine industrial areas in China, the bioavailabilities, as conceptually defined as bioconcentration factors (BCFs) of PAHs were analyzed using biomimetic extraction of hydroxypropyl-β-cyclodextrin (HPCD). Apart from the total content of PAHs varying with the different pyrogenic sources, the BCFs were greatly dependent on the soil physicochemical properties from the spatial scale and inversely proportional to the number of rings. Pearson correlation analysis indicated a weak relationship between bioavailability and the soil dissolved organic matter (DOM), pH and particle size. To incorporate the soil physicochemical properties and structural characteristics of PAHs determined by density functional theory (DFT), the optimum model for bioavailability was developed for BCFs by partial least square (PLS) analysis. The PLS-derived model was shown to be predictive within the applicability domain (AD). The structural characteristics, e.g., molecular polarizability and frontier orbital energy level that favor the soil adsorption of PAH isomers via dispersion interactions, and electron exchanges were indicated to be more impactful on bioavailability than soil environmental factors. However, soil factors should not be neglected, because the pH, DOM, etc. were significantly influential. It makes sense that the higher DOM causes greater bioavailability via increasing the free-dissolved fractions of PAHs. Interestingly, the effect of pH on bioavailability was spectrally validated by excitation-emission matrix (EEM) fluorescence, showing that the interaction between DOM and pyrene strengthened the fluorescence quenching of chromophores with the decline in pH.

A multi-criteria approach to investigate spatial distribution, sources, and the potential toxicological effect of polycyclic aromatic hydrocarbons (PAHs) in sediments of urban retention tanks

Bottom sediments deposited in retention tanks (RTs) located on two urban streams (Oliwski and Strzyza) in the central part of Gdansk (Poland) were analysed for polycyclic aromatic hydrocarbons’ (PAHs) content. PAHs were extracted from samples with methylene chloride, then the extracts were subjected to clean-up applying the solid phase extraction (SPE) method. Quantitative and qualitative determination of 16 PAHs was performed with the use of gas chromatography/mass spectrometry technique. A multi-dimensional approach was applied to analyse PAHs’ spatial distribution, source, and contamination status. Potential sources of PAHs were verified using isomer ratios supported by a statistical approach. The Σ16PAHs (in mg/kg d.w.) ranged from 1.95 ± 0.64 to 20.4 ± 6.8 for RTs located on the Oliwski Stream and from 0.50 ± 0.17 to 8.6 ± 2.9 for RTs located on the Strzyza Stream. PAHs detected in bottom sediments were mainly composed of 4- and 5-ring compounds. PAH isomer ratios such as Phen/Anth, Flth/Pyr, B(a)A/B(a)A + Chry, Inpy/Inpy + B(ghi)P, Flth/Flth + Pyr, Anth/Anth + Phen, and Flth/Flth + Pyr suggested delivery pathways for biomass, coal, and petroleum combustion. Petrogenic PAHs related to fuel leaks from cars were not detected. Statistical analyses confirmed traffic and heating system sources, while factor analysis (FA) pointed out the abrasion of wasting parts of vehicles. Based on threshold levels presented in sediment quality guidelines (SQGs), in most cases, PAHs were at low levels with occasional negative biological effects on organisms. Only sediments deposited in two RTs located on the Oliwski Stream presented harmful features for sediment-dwelling organisms. The risk assessment performed accordingly to the Σ16PAHs presented a moderate and high risk for biota. This study not only reflects the direct threat related to PAH content in bottom sediments, but also highlights the overall pollution of an area, considered to be a recreational part of the city (Oliwski Stream catchment). The findings of this study highlight the need to launch preventative methods to protect the area against pollution from heating system emission and traffic.

Improved identification of pollution source attribution by using PAH ratios combined with multivariate statistics

Polycyclic aromatic hydrocarbons (PAHs) are contaminants introduced by different pathways in the marine ecosystem, affecting both aquatic and sediment bodies. Identification of their sources is of vital importance for protecting the marine ecosystem. The attribution of the pollution sources is usually made by using diagnostic molecular ratios of PAHs isomers. The reliability of this approach diminishes when PAHs contents are measured far from their original source, for example in water bodies or in bottom sediments. Conventionally the source attribution is based on time consuming univariate methods. In the present work coupling of molecular ratios with advanced supervised statistical techniques was used to increase the accuracy of the PAH source attribution in bottom sediments. Data on PAHs distribution within 5 port areas, with known pattern port activity, were collected. Evaluation of multiple PAHs ratios at once by means of supervised OPLS-DA technique was performed. A robust descriptive and predictive model was set up and successfully validated. The proposed methodology helps identify PAH transport pathways, highlighting interactions between pollution patterns, port activities and coastal land-use supporting decision makers in defining monitoring and mitigation procedures.

Non-separative determination of isomeric polycyclic aromatic hydrocarbons by electrospray Ag(I) cationization mass spectrometry and multivariate calibration

A new approach for the determination of isomeric polycyclic aromatic hydrocarbons using a stand-alone mass spectrometry method is proposed. The aim of the work is to study quantitative possibilities of multivariate calibration and electrospray Ag(I) cationization mass spectrometry for the non-separative determination of polycyclic aromatic hydrocarbons isomers. The method is based on flow injection analysis, electrospray ionization and tandem mass spectrometry (FIA-ESI-MS/MS). No chromatographic column was included into the instrumental configuration and the analysis time was 1.7 min. Seven polycyclic aromatic hydrocarbons were selected as test compounds and the ionization was achieved by forming complexes with Ag (I). Individual quantification of all the isomers was carried out by using PLS multivariate calibration and experimental design for calibration modeling. The PLS models were used to predict the concentration of the analytes in a set of external validation samples and satisfactory results were obtained. RMSE, expressed as a relative value, were found to be between 23 and 34 %. Results obtained with multivariate analysis were compared with those corresponding to univariate calibration to show its high potential.

Contamination level, sources, and health risk of polycyclic aromatic hydrocarbons in suburban vegetable field soils of Changchun, Northeast China

Polycyclic aromatic hydrocarbons (PAHs) are a class of persistent organic pollutants. With the expansion of the city, the suburban environment is being increasingly polluted by PAHs, which pose a huge potential risk for suburban agriculture. Therefore, we conducted a survey focusing on the pollution level, sources, and risk of PAHs in Changchun suburban vegetable soils, Northeast China. The total concentrations of 16 PAHs (Σ16PAHs) in soils were between 2338.2 and 15,200 ng g−1 (mean 6778.1 ng g−1), which were significantly higher than those in most other cities. High molecular weight PAHs were the major components, which occupied over 85.63% of all PAHs. Seven potential carcinogenic PAHs accounted for 56.96% of the Σ16PAHs. Source apportionment results based on the ratio of PAH isomers and principal components analysis showed that PAHs were primarily derived from pyrolysis sources, such as biomass/coal combustion, traffic emissions, and petroleum. Ecological risk values of PAHs were between effects range-low (ERL) and effects range-median (ERM), which might cause occasionally ecological risks in the suburbs. According to the incremental lifetime cancer risk assessment results, the health risks to the exposed population were in the acceptable level, with dermal contact and ingestion being the predominant exposure pathway.

Cryoconites as biogeochemical markers of anthropogenic impact in high mountain regions: analysis of polyaromatic pollutants in soil-like bodies

The globalisation and omnidirectional character of anthropogenic processes has challenged scientists around the world to estimate the harmful effects of these processes on ecosystems and human health. Polycyclic aromatic hydrocarbons (PAHs) is one the most infamous group of contaminants, originated both from natural and anthropogenic processes. They could transport to high latitudes and altitudes through atmospheric long-distance transfer and further enter ecosystems of these vulnerable regions by deposition on terrestrial surfaces. An interesting object for tracking transboundary contamination processes in high mountain ecosystems is called cryoconite. Cryoconite, a dark-coloured supraglacial sediment which is abundant in polar and mountain environments, is considered as a storage of various pollutants, including PAHs. Thus, it may pose a risk for local human health and ecosystem through short-distance transfer. Studied cryoconite sediments were collected at the surface of Skhelda and Garabashi glaciers, Central Caucasus high-mountain region, as well as mudflow, moraine material and local soils at the Baksan Gorge in order to examine levels of their contamination. We analysed the content of 15 priority polyaromatic compounds from the US EPA list and used the method of calculation of PAHs isomer ratios with the purpose of identifying their source. To estimate their potential toxicity, Benzo[a]pyrene (BaP) equivalents were calculated. Maximum concentration was defined for NAP (84 ng×g-1), PHE (40 ng×g-1) and PYR (47 ng×g-1), with the minimum concentration for ANT (about 1 ng×g-1). The most polluted material is a cryoconite from Garabashi glacier because of local anthropogenic activities and long-distance transfer. High-molecular weight PAHs are dominated in PAHs composition of almost all samples. The most common sources of PAHs in studied materials are combustion processes and mixed pyrolytic/petrogenic origin. Toxicity levels of separate PAHs did not exceed the maximum permissible threshold concentrations values in most cases. However, the sum of PAHs in BaP equivalents exceed the threshold values in all samples, in some of them more than twice.

Formation of the acenaphthylene cation as a common C2H2-loss fragment in dissociative ionization of the PAH isomers anthracene and phenanthrene.

Polycyclic aromatic hydrocarbons (PAHs) are thought to be a major constituent of astrophysical environments, being the carriers of the ubiquitous aromatic infrared bands (AIBs) observed in the spectra of galactic and extra-galactic sources that are irradiated by ultraviolet (UV) photons. Small (2-cycles) PAHs were unambiguously detected in the TMC-1 dark cloud, showing that PAH growth pathways exist even at low temperatures. The processing of PAHs by UV photons also leads to their fragmentation, which has been recognized in recent years as an alternative route to the generally accepted bottom-up chemical pathways for the formation of complex hydrocarbons in UV-rich interstellar regions. Here we consider the C12H8+ ion that is formed in our experiments from the dissociative ionization of the anthracene and phenanthrene (C14H10) molecules. By employing the sensitive action spectroscopic scheme of infrared pre-dissociation (IRPD) in a cryogenic ion trap instrument coupled to the free-electron lasers at the FELIX Laboratory, we have recorded the broadband and narrow line-width gas-phase IR spectra of the fragment ions (C12H8+) and also the reference spectra of three low energy isomers of C12H8+. By comparing the experimental spectra to those obtained from quantum chemical calculations we have identified the dominant structure of the fragment ion formed in the dissociation process to be the acenaphthylene cation for both isomeric precursors. Ab initio molecular dynamics simulations are presented to elucidate the fragmentation process. This result reinforces the dominant role of species containing a pentagonal ring in the photochemistry of small PAHs.

Liquid-liquid extraction combined with online cleanup for the simultaneous determination of PAHs by GC–MS/MS and their hydroxylated metabolites by LC-MS/MS in human fingernails

A method was developed for the simultaneous determination of polycyclic aromatic hydrocarbons (PAHs) and their hydroxylated metabolites (OH-PAHs) in human fingernails using liquid–liquid extraction and online purification. After surface decontamination by rinsing with acetone, the fingernails were digested with sodium hydroxide and subjected to liquid–liquid extraction with a mixture of n-hexane and methyl tertbutyl ether. The organic extract was then fractionated using a silica-based solid-phase extraction (SPE) cartridge to obtain a PAH fraction eluted with n-hexane/dichloromethane (v/v, 95:5) and an OH-PAH fraction eluted with dichloromethane/ethyl acetate (v/v, 50:50). The PAH fraction was directly injected into an online gel permeation chromatography-gas chromatography-triple quadrupole tandem mass spectrometry (GPC-GC–MS/MS) system, enabling rapid determination of 16 PAHs. A parallel online SPE liquid chromatography tandem mass spectrometry (LC-MS/MS) method was used to determine 12 OH-PAHs. Validation experiments showed that the recovery of PAH and OH-PAH were within range of 67.4%−105.1% (RSD ≤ 10.1%) and 72.8%−102.3% (RSD ≤ 10.9%), respectively, with limits of quantitation (LOQ) of 0.06–0.8 ng/g and 0.15–3.1 ng/g, respectively. Forty-two human fingernail samples from residents of Southern China were analyzed to establish background PAH and OH-PAH levels in this region. Several PAHs and OH-PAHs were detected, at concentrations of 97.5 to 3,687 ng/g for PAHs and 24.2 to 767 ng/g for OH-PAHs. The dominant homologues were two- and three-ring PAH isomers, notably naphthalene (Nap), fluorene (Flu), and phenanthrene (Phe), as well as the corresponding hydroxylated metabolites 2-OH-Nap, OH-Flu, and OH-Phe. Smoking, consuming barbecued food, and age had no significant effects on PAH exposure, but a larger sample would be required to confirm this finding. The online purification strategy presented here expedites cleanup and purification during analysis of human fingernails and should facilitate non-invasive biomonitoring of PAHs in humans, particularly when analyzing large numbers of samples.

Evidence for widespread wildfires and their environmental impact in the Late Cretaceous Canadian Arctic

Wildfires are important in modern ecology but the complex interplay between wildfires and vegetation or climate is less well understood in ancient environments, in particular those of the Arctic regions. This includes the impacts of paleo-wildfires on surrounding marine basins by affecting sedimentation rates and nutrient input via soil degeneration and intensification of continental run-off. The Late Cretaceous was an important time of global climate shift, with the rise of angiosperm vegetation marking a turning point in global flora, and globally abundant wildfires due to high atmospheric oxygen levels and elevated temperatures. This study investigates Late Cretaceous samples from the Canadian Arctic Islands to examine the evidence for widespread wildfires and how these wildfires may have influenced or been influenced by contemporaneous climate and vegetation shifts. Organic geochemical, and organic petrological data show evidence of enhanced wildfires beginning in the Turonian, including increases in semi-fusinite macerals and pyrogenic PAH (polycyclic aromatic hydrocarbon) indicators of natural combustion. This increasing wildfire influence corresponds with a rise in broad-leafed Arctic forests, as evidenced by angiosperm-derived terpenoid biomarkers, with both wildfire and angiosperm abundances peaking in the Early Campanian. Additionally, geochemical and petrographic data shows a shift in the type of organic matter deposited over time, correlating to the evidence of increased wildfire activity. This study proposes that the distance between wildfire region and marine depocenter is assessed via a new provenance method based on the degree of photo-oxic degradation of selected PAH isomers upon airborne transport. The increasing effects of wildfires on the Arctic ecosystem over the Turonian-Campanian were likely driven by relatively warm temperatures, elevated atmospheric oxygen, volcanism related to the High Arctic Large Igneous Province (HALIP), and abundant fuel availability. Widespread wildfires are proposed to have fostered the expansion of angiosperm vegetation into the Canadian Arctic in the Late Cretaceous by allowing them to outcompete gymnosperms in post-fire regrowth. Intensified erosion and continental run-off associated with the destruction of the vegetation cover by wildfires is thought to have acted as a driving force in the increasing terrigenous organic matter deposition in the Sverdrup Basin during the Late Cretaceous. Taken together, the results of this study suggest that increasing wildfires related to global climatic conditions in the Late Cretaceous contributed to the expansion of angiosperm flora in the Arctic, and had a substantial impact on the deposition of sediments in the surrounding Sverdrup Basin.

Calculating source contributions to urban atmospheric polycyclic aromatic hydrocarbons and nitropolycyclic aromatic hydrocarbons using 1-nitropyrene and pyrene: An application to an Asian dust event

A method to calculate source contributions to atmospheric polycyclic aromatic hydrocarbons (PAHs) and their nitrated congeners (NPAHs) is proposed, using pyrene (Pyr) and 1-nitropyrene (1-NP), as respective representatives of PAHs and NPAHs. This is based on the known increases in NPAH to PAH ratios as combustion temperatures increase. The fractions of 1-NP and Pyr from high temperature combustion sources in total 1-NP and Pyr are respectively calculated as a (0 <a <1) and b (0 <b < 1). By using atmospheric concentrations of Pyr and 1-NP obtained at monitoring sites, contributions of high and low temperature combustion sources were calculated. Using this method, the contributions of automobiles and coal combustion facilities/industries to atmospheric Pyr and 1-NP concentrations were calculated for atmospheric samples collected in Kanazawa, Japan during a seasonal Asian dust event. The results show that Pyr was almost entirely emitted from industries in China and transported long-range to Japan. By contrast, 1-NP was emitted primarily from automobiles in Kanazawa and its surrounding areas, with a small amount of 1-NP possibly transported from China. The proposed method can provide greater clarity on source identification compared to the typically used PAH isomer pairs.

Spatial distributions and sources of PAHs in soil in chemical industry parks in the Yangtze River Delta, China

The Yangtze River Delta (YRD) is one of the fastest developing areas in eastern China and contains many chemical industry parks. The profiles and sources of polycyclic aromatic hydrocarbons (PAHs) in soil in chemical industry parks and surrounding areas in the YRD were investigated by analyzing soil samples (n = 64) were collected in the YRD and Rudong chemical park (RD), a typical chemical park in the Yangtze River Delta. The total concentrations of 19 PAHs in the YRD soil samples were 16.3–4694 ng g−1 (mean 688 ng g−1), and the total concentrations of PAHs in RD were 21.6–246 ng g−1 (mean 75.4 ng g−1). The PAHs in soil in YRD were dominated by four-ring and five-ring PAHs, and the PAHs in RD were dominated by two-ring and three-ring PAHs. It suggested that PAHs may have been supplied to soil in YRD predominantly through coal combustion and vehicle emissions, PAHs in the soil of RD may be due to the volatilization and leakage of chemical raw material. According to the different distribution characteristics of PAHs, the ratio (1.5) of (2 + 3) rings/4 rings was proposed to identify the chemical source of PAHs. The PAH isomer ratios and principal component analysis/multiple linear regression (PCA/MLRA) results indicated that PAHs concentrations in soil in the YRD and RD are mainly supplied by industrial and traffic emissions. Incremental lifetime cancer risks (ILCRs) indicated that PAHs in soil pose negligible cancer risks to children and adults, but much stronger risks to children than adults.

Mid-infrared spectroscopic signatures of dibenzopyrene cations – The effect of symmetry on PAH IR spectroscopy

In this work, we characterize – for the first time – in the gas phase infrared spectra of three isomeric Polycyclic Aromatic Hydrocarbon (PAH) cations of C24H14 composition that belong to distinctly different symmetry groups (C2h, Cs and C1). Mid-infrared (Mid-IR) spectra are recorded by means of infrared multiple photon dissociation (IRMPD) spectroscopy at the free electron laser for infrared experiments (FELIX) laboratory. The measured infrared (IR) band positions compare reasonably well with density functional theory (DFT) calculated values. The number of IR active bands increases as the symmetry of the molecule lowers. The IRMPD spectra of irregular PAHs are found to be dense and do not resemble the sharp signatures typical of astronomical IR bands, but rather look like the broad plateau on which these are perched. This lends credit to the GrandPAH hypothesis that suggests that small and irregular PAHs are weeded out by the strong interstellar radiation field and only large regular PAHs remain.

Distribution and Sources of n-Alkanes and Polycyclic Aromatic Hydrocarbons in Sediments Around Oil Production Facilities in the Escravos River Basin, Niger Delta, Nigeria.

This study provides data on the characteristic levels, spatial patterns, sources, and risk of n-alkanes (AHs) [octane, n-C8, totetracontane, n-C40] and polycyclic aromatic hydrocarbons (PAHs) in surficial sediments from the Escravos River Basin (ERB), Nigeria. The n-alkane and PAH concentrations in sediments were quantified by chromatographic methods. The concentrations of AHs and PAHs in the ERB sediments varied from 95 to 3430µgg-1 and from 0.75 to 213µgg-1, respectively. Both the concentrations of AHs and PAHs in ERB sediments exceeded their respective guideline values. The carbon preference index and other AH markers provide evidence that the AHs in the ERB sediments originated from petroleum sources. Ecological risk assessment indicated that the ecological risk relating to an organism's contact with PAHs in the ERB sediments was high. The possible carcinogenic risk arising from human exposure with PAHs in surface sediments through accidental oral ingestion and skin contact exceeded the safe level of 10-6, indicating a considerable probable cancer risk for fishermen and other inhabitants of the ERB. PAH isomer ratios and multivariate statistics suggested that the PAHs in sediments from the ERB originated from gas flaring inputs, discharges from oil drilling platforms, diesel engines, ships, and speed boats, and combustion of wood and other biomass.