Polycyclic Aromatic Hydrocarbons Fingerprints Research Articles

Chemical fingerprints and implicated cancer risks of Polycyclic aromatic hydrocarbons (PAHs) from fine particulate matter deposited in human lungs

Exposure to fine particles (PM2.5) and associated PAHs are frequently linked with lung cancer, which makes the understanding of their occurrence and health risk in human lungs urgently important. Using the ultrasonic treatment and sequencing centrifugation (USC) extraction method coupled with gas chromatography-tandem mass spectrometry (GC - MS/MS) analysis, we revealed the molecular fingerprints of PM-accumulated PAHs in human lungs from a cohort of 68 patients with lung cancer in a typical air-polluted region, China. Sixteen priority PAHs can be grouped by concentrations as ∼ 1 × 104 ng/g (ANT/BkF/ACE/DBA/BgP/PHN/PYR), 2–5 × 103 ng/g (BaP/FLE/NaP/BbF), and ∼ 1 × 103 ng/g (IND/Acy/CHR/FLT/BaA). The sum concentration of 16 PAHs was approximately equaled to 13% of those in atmospheric PM2.5, suggesting significant pulmonary leaching of PAHs deposited in lungs. Low- and high-molecular weight PAHs accounted for ∼ 41.8% and ∼ 45.1% of the total PAHs, respectively, which indicated that atmospheric PM2.5, tobacco and cooking smoke were likely to be important sources of pulmonary PAHs. The evident increasing concentrations of NaP and FLE in pulmonary PM were significantly correlated with smoking history among smokers. The implicated carcinogenic potency of PM-accumulated PAHs among the participants aged 70–80 was 17 times that among participants aged 40–50 on the basis of BaP equivalent concentration (BaPeq) evaluation. The particulate enrichment factor (EFP), the PAH content in pulmonary PM relative to the bulk lung tissue, was equaled to 54 ∼ 835 and averaged at 436. The high value of EFP suggested that PAHs were essentially accumulated in pulmonary PM and exhibited a pattern of “hotspot” distribution in the lungs, which would likely increase the risk of monoclonal tumorigenesis. The chemical characteristics of PM-accumulated PAHs in human lungs together with their implicated lung cancer risks could provide significant information for understanding health effects of particulate pollution in the human body.

A Versatile SERS Sensor for Multiple Determinations of Polycyclic Aromatic Hydrocarbons and Its Application Potential in Analysis of Fried Foods.

Polycyclic aromatic hydrocarbons (PAHs), due to their high hydrophobicity, have low affinity for metallic SERS-active surfaces, which leads to their low SERS detection sensitivity. Various functional groups have been used to improve the affinity of metallic substrates towards the target PAHs. However, a large portion of the signals generated from the “first-layer effect” of the functionalized substrates may complicate the spectrum, leading to a distortion in the assignment of the intrinsic SERS fingerprints of PAHs. In this study, a SERS sensor composed of Au nanoparticles (AuNPs) and reoxidized graphene oxide (rGO) was developed for the simultaneous determination of 16 EPA priority PAHs. The synthesis of the rGO/AuNP substrate can be realized without a complicated modification process. All the 16 PAHs could be identified based on their characteristic peaks in the presence of the composited substrate, with estimated LOD as low as 0.2–2 ng·mL−1. The binary linear regression was optimized as the fitting model for all PAHs except for benzo(k)fluoranthene, with the linear correlation coefficient ranging from 0.9889 to 0.9997. Based on the developed SERS substrates and sample pretreatment, the characteristic SERS peaks of four PAHs in Chinese traditional fried food (youtiao) were identified without any background interference. The whole detection process only takes approximately 15 minutes. The results demonstrate the potential of the multicomponent on-field detection of PAHs.

Concentrations and fingerprints of PAHs and PCBs adsorbed onto marine plastic debris from the Indonesian Cilacap coast and theNorth Atlantic gyre

We investigated the contamination of marine plastic debris from the Indonesian Cilacap coast and the North Atlantic gyre by polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). The mean concentrations of 15 PAHs in gyre were 58 and 142 ng/g in polyethylene (PE) and polyethylene terephthalate (PET) debris, respectively, while PE and polypropylene (PP) Indonesian debris exhibited an average content of 552 ng/g (mainly naphthalene). The mean concentration of 61 PCBs in open ocean debris was 12.2 ng/g, while coastal debris showed a worryingly high mean value of 1.4×104 ng/g, with the notable presence of CB6, 101 and 173. PE gyre debris contained mostly high molecular weight PAHs such as benzo(g,h,i)perylene and indeno(1,2,3-cd)pyrene and low-chlorinated PCBs such as CB52, 77 and 105, whereas PET debris contained low molecular weight PAHs (mainly acenaphthylene and phenanthrene) and high-chlorinated PCBs such as CB204.

Polycyclic aromatic hydrocarbons (PAHs) in sediments from a typical urban impacted river: application of a comprehensive risk assessment.

Soweto and Lenasia, the most densely populated area of South Africa, is simultaneously a thriving metropolis, with a fair share of people still living in squalor conditions directly dependant on the natural resources. Because of industrialisation the populace and environment in this urban area are exposed to various pollutants. The aquatic environment was selected as a proxy to study the effect of industrial pollution in this area. The concentrations, source identification, and various environmental risks of polycyclic aromatic hydrocarbons (PAHs) were determined in sediments of the upper reaches of the Klip River. Composite sediment samples collected in low-flow conditions in 2013 and 2014 ranged from 270-5400 ng/g. The PAHs in this aquatic ecosystem were dominated by 4-ring congeners and could be attributed to combustion of organic fuels by chemical mass balance. Heavy traffic and industrial complexes in the northern part of the study area were responsible for the PAH fingerprints. Probable adverse effects such as toxicity to benthic biota were proven after comparison with international sediment quality guidelines (SQG) both survey years. Toxic equivalence quotients (TEQs) calculated for the sediments using fish potency factors (FPFs) were up to 30 times greater than the Canadian guideline for dioxin-like compounds, indicating high probability of carcinogenic effect to fish mediated through the aryl-hydrocarbon receptor. Finally, sediments in the area posed moderate to high ecological risk, which corroborates the other toxicity assessments. The advantage of investigating multiple risk endpoints, is the comprehensive results obtained that allows for a more realistic representation of the study area. Consequently more aspects are kept into account that results in better conclusions.

Forensic assessment of polycyclic aromatic hydrocarbons at the former Sydney Tar Ponds and surrounding environment using fingerprint techniques

Polycyclic aromatic hydrocarbons (PAHs) were assessed spatially and temporally within and adjacent to a former coking and steel manufacturing facility in Sydney, Nova Scotia, Canada. Concentrations of PAHs were measured in surface soils, marine and estuary sediments prior to and during remediation of the Sydney Tar Ponds (STPs) site which was contaminated by nearly a century of coking and steel production. Previous studies identified PAHs in surficial marine sediments within Sydney Harbour, which were considered to be derived from STP discharges. Numerous PAH fingerprint techniques (diagnostic ratios, principal component analysis, quantitative and qualitative analysis) were applied to soil and sediment samples from the STPs and surrounding area to identify common source apportionment of PAHs. Results indicate coal combustion (from historical residential, commercial and industrial uses) and coal handling (from historic on-site stockpiling and current coal transfer and shipment facilities) are likely the principal source of PAHs found in urban soils and marine sediments, consistent with current and historical activities near these sites. However, PAH fingerprints associated with STP sediments correlated poorly with those of urban soils and marine sediments, but were similar to coal tar, historically consistent with by-products produced by the former coking operations. This study suggests PAH contamination of Sydney Harbour sediments and urban soils is largely unrelated to historic coking operations or recent remediation of the STPs site, but rather a legacy of extensive use of coal for a variety of activities.

Burial and degradation of Rena oil within coastal sediments of the Bay of Plenty

ABSTRACTDuring the Rena oil spill, no data existed for New Zealand conditions on the likely depth of burial and the expected degradation of oil deposited on sandy beaches. Sediment cores were taken from 12 locations along the Bay of Plenty coastline c. 1 year after the Rena oil spill. No visible oil was detected in cores and trenches dug within the beaches. Chemical extraction was performed on 20 cm slices from the upper 40 cm of 26 cores, and the elutriates were analysed for the presence of polycyclic aromatic hydrocarbons (PAHs). The results were compared with known PAH fingerprints of Rena oil and its degradation products. Only seven samples contained some marker PAHs, and none had a complete Rena profile, indicating stormwater contamination. Despite extensive deposition of Rena oil on beaches, no evidence of ongoing contamination could be located, indicating that the clean-up and degradation were effective at removing the oil.

Assessment of PAHs levels in some fish and seafood from different coastal waters in the Niger Delta.

Levels of sixteen polycyclic aromatic hydrocarbons (PAHs) in 30 edible tissues of selected frequently-consumed fish and seafood collected from three coastal waters of Niger Delta, namely, Sime, Kporghor and Iko were investigated in 2014. Gas chromatographic analysis were employed for PAHs determination. Observed mean PAHs levels in the samples ranged from below detection limit (BD) of analytical instrument to 22.400 ± 0.050 μg kg−1 wet wt. in Littorina littorea, BD to 87.400 ± 0.030 μg kg−1 wet wt. in Crassostrea virginica and from BD to 171.000 ± 0.430 μg kg−1 wet wt. in Periophthalmus koeleuteri. The highest average concentration of 171.000 ± 0.430 μg kg−1 wet wt. was recorded for Indeno [1,2,3-cd]pyrene from Sime water. High molecular weight PAHs (HMW-PAHs) were generally predominant compared to low molecular weight PAHs (LMW-PAHs). The LMW- PAH/HMW-PAH ratio was <1 for all species, indicating anthropogenic origin of PAHs in the coastal waters of Niger Delta environment. Moreover, the study of the PAHs fingerprints, using specific ratios, suggests the predominance of a pyrolytic origin for observed PAHs.

Marine biodegradation of crude oil in temperate and Arctic water samples

Despite increased interest in marine oil exploration in the Arctic, little is known about the fate of Arctic offshore oil pollution. Therefore, in the present study, we examine the oil degradation potential for an Arctic site (Disko Bay, Greenland) and discuss this in relation to a temperate site (North Sea, Denmark). Biodegradation was assessed following exposure to Oseberg Blend crude oil (100mgL−1) in microcosms. Changes in oil hydrocarbon fingerprints of polycyclic aromatic hydrocarbons (PAHs), alkyl-substituted PAHs, dibenzothiophenes, n-alkanes and alkyltoluenes were measured by gas chromatography-mass spectrometry (GC–MS). In the Disko Bay sample, the degradation order was n-alkanes>alkyltoluenes (para->meta->ortho-isomers)>PAHs and dibenzothiophenes, whereas, the degradation order in the North Sea samples was PAHs and dibenzothiophenes>alkyltoluenes>n-alkanes. These differences in degradation patterns significantly affect the environmental risk of oil spills and emphasise the need to consider the specific environmental conditions when conducting risk assessments of Arctic oil pollution.

Regionalized concentrations and fingerprints of polycyclic aromatic hydrocarbons (PAHs) in German forest soils

Samples of 474 forest stands in Germany were analysed for concentrations of polycyclic aromatic hydrocarbons (PAHs) in three sampling depths. Enhanced concentrations were mainly found at spots relatively close to densely industrialized and urbanized regions and at some topographically elevated areas. Average enrichment factors between mineral soil and humic layer depend on humus type i.e. decrease from mull via moder to mor. Based on their compound-patterns, the observed samples could be assigned to three main clusters. For some parts of our study area a uniform assignment of samples to clusters over larger regions could be identified. For instance, samples taken at vicinity to brown-coal strip-mining districts are characterized by high relative abundances of low-molecular-weight PAHs. These results suggest that PAHs are more likely originated from local and regional emitters rather than from long-range transport and that specific source-regions can be identified based on PAH fingerprints.

Characterization of polycyclic aromatic hydrocarbons using Raman and surface‐enhanced Raman spectroscopy

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous atmospheric pollutants and food contaminants, which exhibit potent carcinogenicity, mutagenicity, and teratogenicity. Vibrational spectroscopy techniques, especially Raman spectroscopy and surface‐enhanced Raman spectroscopy (SERS), can be potentially used as an alternative technique to liquid and gas chromatography in PAH analysis. However, there is limited information on the intrinsic Raman and SERS fingerprints of PAHs. In this study, we have acquired the Raman and SERS spectra of seven PAH compounds and compared their experimental spectra with theoretical Raman spectra calculated by density function theory (DFT). The vibrational modes corresponding to the Raman peaks have also been assigned using DFT. Characteristic Raman and SERS peaks have been identified for five PAH compounds, and the limits of detection were estimated. Such information could be useful for developing SERS assays for simple and rapid PAH identification. Copyright © 2014 John Wiley &amp; Sons, Ltd.

Application of binary diagnostic ratios of polycyclic aromatic hydrocarbons for identification of Tsunami 2004 backwash sediments in Khao Lak, Thailand.

Identification of Tsunami deposits has long been a controversial issue among geologists. Although there are many identification criteria based on the sedimentary characteristics of unequivocal Tsunami deposits, the concept still remains ambiguous. Apart from relying on some conventional geological, sedimentological, and geoscientific records, geologists need some alternative “proxies” to identify the existence of Tsunami backwash in core sediments. Polycyclic aromatic hydrocarbons (PAHs) are a class of very stable organic molecules, which can usually be presented as complex mixtures of several hundred congeners; one can assume that the “Tsunami backwash deposits” possess different fingerprints of PAHs apart from those of “typical marine sediments.” In this study, three-dimensional plots of PAH binary ratios successfully identify the Tsunami backwash deposits in comparison with those of global marine sediments. The applications of binary ratios of PAHs coupled with HCA are the basis for developing site-specific Tsunami deposit identification criteria that can be applied in paleotsunami deposits investigations.

Particle-phase concentrations of polycyclic aromatic hydrocarbons in ambient air of rural residential areas in southern Germany.

An important source of polycyclic aromatic hydrocarbons (PAHs) in residential areas, particularly in the winter season, is the burning process when wood is used for domestic heating. The target of this study was to investigate the particle-phase PAH composition of ambient samples in order to assess the influence of wood combustion on air quality in residential areas. PM10 samples (particulate matter <10 μm) were collected during two winter seasons at two rural residential areas near Stuttgart in Germany. Samples were extracted using toluene in an ultrasonic bath and subsequently analysed by gas chromatography–mass spectrometry. Twenty-one PAH compounds were detected and quantified. The PAH fingerprints of different wood combustion emissions were found in significant amounts in ambient samples and high correlations between total PAHs and other wood smoke tracers were found, indicating the dominant influence of wood combustion on air quality in residential areas. Carcinogenic PAHs were detected in high concentrations and contributed 49% of the total PAHs in the ambient air. To assess the health risk, we investigated the exposure profile of individual PAHs. The findings suggest that attention should be focused on using the best combustion technology available to reduce emissions from wood-fired heating during the winter in residential areas.

Vertical distribution and environmental significance of PAHs in soil profiles in Beijing, China

Vertical distribution of both the concentration and composition of polycyclic aromatic hydrocarbons (PAHs) in ten profiles in Beijing has been investigated. The results showed that PAH concentrations and compositions in topsoil from different sampling sites were different. PAH concentrations were much higher in topsoil of the investigated urban area, industrial region, and paddy field with wastewater irrigation than in other areas. Moreover, PAH concentrations in topsoil were much higher than those at greater depth, where the concentrations were relatively consistent in most soil profiles. The fingerprints of PAHs in the samples from topsoil (0-30 cm) in the same profiles were similar and were obviously different from those at greater depth, suggesting that PAH sources were consistent in topsoil samples and were discriminating between topsoil and deeper soils. PAHs in topsoil mainly arose from mixed sources of combustion of liquid fuel, coal, and/or wood, as well as wastewater irrigation, while those at greater depth were derived from soil genesis and the process of soil formation.

Monitoring of polychlorinated dibenzo- p-dioxins and dibenzofurans, dioxin-like PCBs and polycyclic aromatic hydrocarbons in food and feed samples from Ismailia city, Egypt

Concentrations of polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyl (PCBs) and polycyclic aromatic hydrocarbons (PAHs) have been determined using GC/HRMS in food (butter, seafood and meat) and feed samples (chicken, cattle and fish) purchased from Ismailia city, Egypt. PCDD/F concentrations in food samples ranged between 0.12 and 3.35 pg WHO TEQ/g wet w, while those in feed samples were between 0.08 and 0.2 pg WHO TEQ/g dry w. Levels of PCB TEQ ranged from 0.14 to 3.2 pg/g wet w in the food samples. The feed samples have an average of 0.35 pg PCB TEQ /g dry w. In this study, butter samples showed the highest contamination levels of PCDD/Fs and PCBs. The PCBs contribution to the total TEQ was on average 63% in seafood and on average 49% for meat and butter. The highest contamination levels of PCDD/Fs and PCBs were found in butter samples. The butter TEQ content is several times higher than that reported in all EU countries and exceeded the EU limits, while the PCDD/F levels in seafood and the feed samples is far below the current EU limit. Generally, congener profiles in the food samples reflect the non-industrialized nature of the city and suggest solid waste burning as a significant source of emission. Nevertheless, the profiles for butter suggest an impact from various sources. In the case of the sum of 16 PAH contamination levels in food samples were in the range of 11.7–154.3 ng/g wet w and feed samples had a range of 116–393 ng/g dry w. Benzo( a)pyrene (B aP) has been detected in the range of 0.05–3.29 ng/g wet w in the food samples; butter showed the highest contamination which exceeded the EU standard set for fats and oil. Fingerprints of PAHs suggested both petrogenic and pyrolytic sources of contamination.

Hydrocarbon pollution fixed to combined sewer sediment: a case study in Paris

Over a period of two years (2000–2001), sediment samples were extracted from 40 silt traps (STs) spread through the combined sewer system of Paris. All sediment samples were analysed for physico-chemical parameters (pH, organic matter content, grain size distribution), with total hydrocarbons (THs) and 16 polycyclic aromatic hydrocarbons (PAHs) selected from the priority list of the US-EPA. The two main objectives of the study were (1) to determine the hydrocarbon contamination levels in the sediments of the Paris combined sewer system and (2) to investigate the PAH fingerprints in order to assess their spatial variability and to elucidate the PAH origins. The results show that there is some important inter-site and intra-site variations in hydrocarbon contents. Despite this variability, TH and PAH contamination levels (50th percentile) in the Parisian sewer sediment are estimated at 530 and 18 μg g −1, respectively. The investigation of the aromatic compound distributions in all of the 40 STs has underlined that there is, at the Paris sewer system scale, a homogeneous PAH background pollution. Moreover, the study of the PAH fingerprints, using specific ratios, suggests the predominance of a pyrolytic origin for those PAHs fixed to the sewer sediment.

The Chemical Baseline as a Key to Defining Continuing Injury and Recovery of Prince William Sound

ABSTRACT Studies of records and data pertaining to anthropogenic and natural sources of petroleum, and specifically of the polycyclic aromatic hydrocarbons (PAH), have indicated a generally constant background, with episodic input spikes of bioavailable PAH to the marine environment of Prince William Sound (PWS), Alaska. The Exxon Valdez oil spill (EVOS) was one such PAH spike. However, hundreds of smaller spills, occurring prior to and since the EVOS, contribute a background of bioavailable petrogenic PAH to PWS. The widespread historical and contemporary uses of PWS by man have left chronic, sizeable, and widespread petrogenic and pyrogenic PAH fingerprints and bioavailable PAH at many locations in PWS. Evidence from mussel samples, taken both prior to and since EVOS, and from subtidal sediments, indicates that bioavailable PAH are a constant feature of the PWS system. While EVOS may continue to add some bioavailable PAH to highly localized areas, most PAH inputs to the PWS marine environment are unrelated to EVOS. Such findings indicate that biological, sublethal effects studies, which rely on tissue body burdens and biomarkers as leading indicators of continuing effects from EVOS (e.g. CYP1A-P450, etc.) may have been misinterpreted, as they are confounded by this easily detectable, significant, and continuing background of bioavailable PAH. Therefore measurements of exposure to PAH as indicating lingering effects from EVOS, 13 years after the spill, are speculative and ignore the baseline PAH from non-EVOS inputs.

Pyrogenic Polycyclic Aromatic Hydrocarbons in Sediments Record Past Human Activity: A Case Study in Prince William Sound, Alaska

Polycyclic aromatic hydrocarbons (PAH) are sensitive recorders of past human activities in Prince William Sound, Alaska. In the nearshore subtidal sediments of bays, the fingerprints of the pyrogenic (combustion-derived) PAH record numerous sites of both present and historical human activities including active settlements, fish hatcheries, fish camps and recreational campsites, in addition to abandoned settlements, canneries, sawmills, and mining camps. In instances, there are high levels of PAH attributable to past human activities even though there is little remaining visual evidence of these activities on the shorelines. Forest fires are also an important source of pyrogenic PAH in subtidal sediments at certain time periods and locations and pyrogenic PAH from atmospheric fallout forms part of the regional PAH background. These pyrogenic PAH fingerprints are superimposed on a regional background of natural petroleum hydrocarbons derived from seeps in the eastern Gulf of Alaska. In isolated locations, weathered traces of the Exxon Valdez oil spill were detected as a minor part of the total PAH present from all sources.