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A large portion of organic pollutants (OPs) represent a potential hazard to humans and living beings due to their toxic properties. For several years, birds have been used as biomonitor species of environmental pollution. Polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated biphenyl ethers (PBDEs), organophosphate pesticides (OPPs), polycyclic aromatic hydrocarbons (PAHs) and pyrethroids (PYRs) were assessed in body feather samples of 71 feral pigeons (Columba livia domestica) collected from Asturias and Galicia (NW Spain). The percentage of detection for all chemical groups were above 90% in studied birds. The general pattern was dominated by PAHs (mean value ± standard deviation (SD) 32 ± 15 ng/g) followed by OCPs (3.8 ± 1.1 ng/g), PYRs (3.4 ± 3.8 ng/g), PCBs (1.6 ± 1.0 ng/g), OPPs (1.3 ± 0.70 ng/g) and PBDEs (0.80 ± 0.30 ng/g). Significant differences were observed between age, location and gender suggesting different sources of exposure and accumulation pathways., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic hydrocarbons (PAHs) are a family of toxicants that are ubiquitous in the environment. These contaminants generate considerable interest, because some of them are highly carcinogenic in laboratory animals and have been implicated in breast, lung, and colon cancers in humans. Dietary intake of PAHs constitutes a major source of exposure in humans. Factors affecting the accumulation of PAHs in the diet, their absorption following ingestion, and strategies to assess risk from exposure to these hydrocarbons following ingestion have received very little attention. This review, therefore, focuses on concentrations of PAHs in widely consumed dietary ingredients along with gastrointestinal absorption rates in humans. Metabolism and bioavailability of PAHs in animal models and the processes, which influence the disposition of these chemicals, are discussed. Finally, based on intake, disposition, and tumorigenesis data, the exposure risk to PAHs from diet is presented. This information is expected to provide a framework for refinements in risk assessment of PAHs.

Fish oils are one of the main sources of health promoting nutrients such as n-3 fatty acids in animal and human diet. Nevertheless, they could be an important source of persistent organic pollutants (POPs). Different strategies of decontamination processes to reduce polycyclic aromatic hydrocarbon (PAH) levels in fish oils, such as solvent extraction (ethanol) and adsorbent extraction using commercially available (activated carbon) and sustainable adsorbents (mussel shell and wood ashes), were compared. Adsorption conditions were evaluated and optimized by an experimental design and the experimental results were adjusted to response surfaces. In this way, PAH removals increased with increasing of individual PAH molecular weight and they range from 80% to 100% using activated carbon and from 10% to 100% using wood ashes. Pine wood ashes showed similar removal rates to activated carbon (87%-100%) excluding F (51%) and P (42%). No PAH removal was observed using mussel shell ashes. Ethanol extraction was also optimized and showed a good performance in the extraction of PAHs. However, it does affect their ω-3 fatty acid contents. Finally, real oil samples from different fishing areas: Spain, South America, and North Europe were selected for the decontamination experiments under experimental conditions previously optimized., (© 2013.)

Fish oil has been identified as one of the most important contributors to the level of Persistent Organic Pollutants (POPs) in feed products. The determination of polycyclic aromatic hydrocarbons (PAHs) in fish oils is complicated due to the fat matrix, which affects both extraction efficiency and analytical quality. This article reviews and addresses two of the most relevant analytical methods for determining 11 mutagenic and carcinogenic PAHs, as well as two EPA indicator PAHs in fish oils. We discuss and critically evaluate two different extraction procedures, such as ultrasound-assisted solvent extraction (USAE) and ultrasound-assisted emulsification-microextraction (USAEME). Clean-up of extracts was performed by solid-phase extraction using C18 and glass columns containing silica gel and florisil for USAE or only C18 for USAEME. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted and recoveries ranged from 70% to 100% by USAE and from 70% to 108% by USAEME with estimated quantification limits between 0.020 and 2.6 μg/kg were achieved. Moreover, the applicability of the selected methods was evaluated by the analysis of real samples. To our knowledge, this is the first time that USAEME has been applied to the determination of PAHs in food matrices, such as oil fish samples. The methods proposed were applied to the determination of the target PAHs in fish samples from different countries, and it was found that the low PAH contamination of the selected fish oils could mainly occur by atmospheric sources., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The primary aim of the proposed work is to propose the potential sources of pollution by polycyclic aromatic hydrocarbons (PAHs) in feeds and ingredients. To reach this propose the development of a simple, fast, quantitative and economic method for determining PAHs using liquid-liquid extraction (LLE), clean-up and detection by liquid chromatography with fluorescence detection (LC-FD) in polluting feeds and ingredients was developed. The overall method quantification limits range from 0.020 to 4.0μg/kg and analyte recoveries are between 70% and 105% with relative standard deviations (RSD) lower than 20%. Molecular patterns of PAHs were used to study their distribution in the selected samples by cluster analysis, separating them in two groups: contaminated by atmospheric or pyrolytic sources. In order to find a relationship between the nutritional composition (protein, fibre, ash and fat content), and the hypothetical toxicity of selected feeds, a partial least squared (PLS) analysis was used, showing that fibre was a major contributor. Moreover, the complete data set of 27 feed samples and 25 feed ingredients x 13 PAH concentrations were analysed by PCA to find out what ingredients were controlling PAH pollution., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Studies on the temporal deposition of polycyclic aromatic hydrocarbons (PAHs) in peatlands are scarce, and none have been carried out in the Iberian Peninsula. To address this gap, ten PAHs were determined in a short peat core (spanning the last 1000 years) sampled in NW Iberian Peninsula, by HPLC-fluorescence. Fluoranthene, pyrene, benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene predominated in the upper layers (10 cm), whereas fluoranthene and pyrene were the most abundant in the lower layers (40 cm), which showed an absence of high molecular weight PAHs (benzo[ghi]perylene and Indeno[1,2,3-cd]pyrene). Although increased PAH contents have been detected since 1700 A.D., coinciding with the beginning of the Metallurgical and Industrial Revolution, high levels of fluoranthene and pyrene were present in peat samples dating back to the 12th century A.D. The results suggest that changes in sources, type of emission (global or local) and transport could be responsible for the different PAH content and composition of the peat core. These changes are consistent with the history of the use of natural resources in the NW of the Iberian Peninsula., (Copyright © 2012 Elsevier Inc. All rights reserved.)

Polycyclic aromatic hydrocarbons (PAHs) can be formed during the refinery processes of crude petroleum. Their removal is of great importance. The same happens with other organic solvents used for the extraction of PAHs (hexane, acetonitrile...), which can be polluted with PAHs. Kinetic and equilibrium batch sorption tests were used to investigate the effect of wood ashes wastes as compared to activated carbon on the sorption of three representative PAHs from n-hexane and acetonitrile. Mussel shell ashes were discarded for batch sorption experiments because they were the only ashes containing PAHs. The equilibrium time was reached at 16 h. Physical sorption caused by the aromatic nature of the compounds was the main mechanism that governed the PAHs removal process. Our investigation revealed that wood ashes obtained at lower temperature (300 degrees C) did not show any PAHs sorption, while ashes obtained at higher temperature (>500 degrees C) have adsorbent sites readily available for the PAH molecules. An increase in the molecular weight of PAHs has a strong effect on sorption wood ashes wastes. As low the wood ashes particle size as high the sorption of PAHs, as a result of differences in adsorbent sites. The performance of wood ash wastes vs. activated carbon to remove 10 PAHs from organic solvents is competitive in price, and a good way for waste disposal., (Copyright 2010 Elsevier B.V. All rights reserved.)

The assessment of historical trends in atmospheric deposition of organic contaminants by using peat samples has been reported on several occasions because these samples represent an almost ideal medium for recording temporal changes in organic contaminant deposition rates. The determination of polycyclic aromatic hydrocarbons (PAHs) in peat samples is complicated due to the high content of organic matter in peat, which affects both extraction efficiency and analytical quality. A rapid and simple method is proposed for the determination of 10 US Environmental Protection Agency indicator PAHs in complex matrices such as peat. This article reviews and addresses the most relevant analytical methods for determining PAHs in peat. We discuss and critically evaluate three different extraction procedures, such as ultrasound-assisted solvent extraction (UASE), shaking and pressurized liquid extraction (PLE). Clean-up of extracts was performed by solid-phase extraction using silica cartridges. Detection of the selected PAHs was carried out by high-performance liquid chromatography coupled with fluorescence detection for determination. Optimization of the variables affecting extraction by the selected extraction techniques was conducted, concluding that the UASE extraction method using hexane:dichloromethane (80:20) as extractant was robust enough to determine the selected PAHs in peat samples with estimated quantification limits between 0.050 and 3.5 microg/kg depending on the PAH. UASE did not demand sophisticated equipment and long extraction times. PLE involved sophisticated equipment and showed important variations in the results. The method proposed was applied to the determination of PAHs in peat samples from Xistral Mountains (Galicia, Spain).

PAHs from a polluted atmosphere are generally transferred to plants by particle-phase deposition on the waxy leaf cuticle or by uptake in the gas phase through stomata. Thus, they are also present in ingredients for animal feed. Generally, toxic substances are metabolized before or after absorption through the intestinal tract. This is the case of 3-hydroxybenzo[a]pyrene, which can be found free or in its glucuronide and/or sulphate conjugate forms. This article develops a procedure to monitor the carry-over of PAHs from feed to food of animal origin based on the analysis of animal manure. Eleven PAHs and 3-hydroxybenzo[a]pyrene were measured in four animal manures (cow, horse, rabbit and pig) by liquid chromatography with fluorescence detection. benzo[a]pyrene, benzo[b]fluoranthene and benzo[k]fluoranthene were found in all the selected samples, but their total levels were not alarming (benzo[a]pyrene equivalents (microg/kg)<3.1). 3-hydroxybenzo[a]pyrene was quantified in all the samples exempting rabbit manure. The highest total PAH levels were detected in cow manure (9.0 microg/kg), while the highest 3-OH-B[a]P level was determined in horse samples (13 microg/kg).

Little is known of the fate of polycyclic aromatic hydrocarbons (PAHs) in soils under burnt woodland. It is not clear what the behavior of the overlying wood ash layer will be along months. In this study, the levels of eight representative PAHs in the 1-5 cm layer of a periurban woodland soil that had undergone wildfire were compared with those measured in nearby and distant unburnt periurban woodland soils and in a distant unburnt rural woodland soil, and the levels at the burnt site were monitored during some 10 months. The analytical method optimized for the purpose afforded recoveries of 74-111% (depending on PAH) and repeatabilities (RSDs) better than 9%, with limits of detection ranging from 1 to 7 microg/kg. PAH levels in the 1-5 cm layer of the burnt periurban soil were very similar to those of distant unburnt periurban soil (188 vs 173 microg/kg), about seven times the 26 microg/kg measured in unburnt rural soil, which furthermore contained no detectable quantities of the highest molecular weight PAHs typical of traffic and other urban sources, as the periurban soils did. At the burnt site, PAH levels fell along the months (the total PAH level from 188 to 119 microg/kg), apparently as the result of rainfall and the prevention of further input from the atmosphere by the overlying layer of wood ash, which had a very high PAH adsorption capacity (1169 microg/kg) and did not itself appear to act as a source of PAHs. PAH transport may have been assisted by increased mobilization of PAHs associated with dissolvable organic matter due to an increase in soil pH due to alkaline ash components.

Some polycyclic aromatic hydrocarbons (PAHs), particularly those with a high molecular mass, have been classified as probably being carcinogenic to humans by the International Agency for Research on Cancer (IARC). The significance of the determination of PAHs is reflected by the special attention the European Union is paying to regulating their maximum allowed levels in various types of foodstuffs. Like tobacco and smoked meats, alcoholic drinks can also contain these carcinogenic chemicals, as the latter have been detected in the charred insides of barrels, some ingredients such as caramel or the smoke released during the drying of germinated barley in beer or whisky. This paper determined the contents of seven PAHs in alcoholic beverages of variable alcoholic strength that had been aged in charred barrels for different times (months, years). The aim was to elucidate the dependence of the formation of seven PAHs on the type of charring (traditional or convective) used and the charring intensity (light, medium or heavy). Based on the results, the way the tree raw material is toasted strongly influences PAH levels in alcoholic drinks; thus, traditional charring produces increased amounts of PAHs from the wood relative to convective toasting. The sum of the analysed PAH concentrations in the aged alcoholic beverages studied ranged from zero for a white wine to 172 ng l(-1) for a 'brandy de jerez solera'. The carcinogenic indicator benzo[a]pyrene was found at concentrations below 10 ng l(-1). These PAH concentrations in alcoholic beverages are very low relative to those in smoked and char-broiled foodstuffs. Any health hazards, however, can be minimized by using convective toasting to manufacture the barrels where the drinks are to be aged.

Polycyclic aromatic hydrocarbons (PAHs), at least those with high molecular mass, are classified as probable human carcinogens by the US Environmental Protection Agency. The importance of the material used to generate smoke is indicated by the attention that the European Union is paying to list the wood that can be used to produce smoking flavour agents. The paper examines the dependence on the nature of the wood used for smoking on the formation of eight PAHs (selected as markers of PAHs) and transfer of these PAHs into traditional Spanish smoked chorizo sausages with collagen and tripe casings. The results showed that the kind of combustion performed on different materials seriously affected the PAH levels in the smoke generated. Ignition and firing of the material with a flame compared with heating produced more PAHs in the smoke. The levels of PAHs found in the meat and in the collagen and tripe casings of the smoked chorizo samples suggest that the collagen-based casings behave as a better barrier to PAHs.

Simple, rapid, and inexpensive methods have been developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in drinking waters without interferences from other chemical contaminants by use of two different extraction techniques and analysis by an optimized reverse-phase (RP) high-performance liquid chromatography followed by fluorescence detection (HPLC-FLD) method. The feasibility of SPE (solid-phase extraction) and SPME (solid-phase microextraction) for the determination of PAH in drinking water samples has been evaluated. Several parameters have been studied and optimized for both extraction procedures. The relationship between the nature of the fibers and the quantity of extracted compounds and the effects of organic solvent, salt addition, sampling temperature, and sampling time was studied for SPME. Acetonitrile percentage added to the sample, sample storage conditions (temperature and time), and type of organic elution solvent and elution volume were evaluated for SPE. The results show that both extraction procedures can be used to determine PAHs in drinking waters, but SPE gives better performance (recovery, precision, and quantification limits) for the determination of PAHs in drinking water at the levels established by the legislation.

Before wood ash can be safely used as a fertilizer in soils, possible negative effects such as input of organic contaminants or remobilization of contaminants already stored in the soil must be investigated. The objective of this study was to optimize and characterize extraction methods to isolate and quantitatively measure polycyclic aromatic hydrocarbons (PAHs) concentrations in wood ash that can be used as amendment of soils. It will be then possible to examine the effects of wood ash application on PAHs concentrations in the washing waters with the aim of evaluating their distribution by storage in the different compartments and what influences their stability and persistence. Simple, rapid and inexpensive methods have been set up for the determination of seven polycyclic aromatic hydrocarbons (PAHs) in wood ashes and ash aqueous extracts without interferences from other chemical contaminants using organic solvent extraction and/or SPE techniques and analyzed by an optimized RP-HPLC-FLD method. The feasibility of extraction for the determination of PAHs in wood ashes has been evaluated because PAHs are strongly sorbed to such a matrix, which explains why the PAHs content in ash was seldom studied. The method resulted to be of recoveries ranging from 81 to 97% for the different PAHs, with repeatabilities (RSDs%) better than 6%. Detection levels were from 0.2 to 2.2 microg/kg, while quantification limits were from 0.7 to 5.6 microg/kg, low enough to evaluate the presence of PAHs in wood ashes.

The application of a new extraction technique which is known as stir bar sorptive extraction (SBSE), followed by high-performance liquid chromatography with a fluorescence detector, was assessed for determining eight polycyclic aromatic hydrocarbons (PAHs) in water samples. The extraction conditions such as acetonitrile addition; effects of temperature and salt; and finally, extraction and desorption time profiles were studied. Once SBSE was optimized, analytical method parameters such as linearity (r(2)>0.991), precision (<9%), detection (0.5-7.3 ng/L) and quantitation (1.0-22 ng/L) limits were estimated. To correct for the 43-57% absolute recovery depending on the PAH, calibration was done with a line obtained submitting standard-spiked blank tap waters to the complete sample treatment and analysis. Consequently, relative recovery was about 100% because all water samples (those for calibration purposes and those for recovery estimation) were processed in the same way and the absolute recovery remained constant. SBSE method characteristics were checked with the analysis of real drinking waters in the search for PAHs.

The objective of this study was to optimize and characterise extraction methods to examine the effects of wood ash application on polycyclic aromatic hydrocarbons (PAHs) concentrations in run-off waters for the evaluation of their distribution by storage in the different compartments (free and bound to dissolved organic matter, DOM), what influence their stability and persistence. The feasibility of solid phase extraction (SPE) and stir bar sorptive extraction (SBSE) for the determination of eight PAHs in run-off water samples has been evaluated. Both are appropriate to determine PAHs in run-off waters, but SPE is suitable for the determination of overall PAHs, while SBSE is used for the determination of free PAHs. The combination of both extraction techniques can then be used to estimate PAHs bound to DOM. Another approach based in the only use of SBSE is proposed for the estimation of all PAHs fractions (free, bound to DOM, and overall), once we are able to estimate the fraction percentage the free concentration represents. The percentage of free fraction was variable in the run-off waters with medium levels of DOM depending on the number of aromatic rings, molecular weight and water solubility of PAHs. [Copyright &y& Elsevier]