Toxic equivalency factors (TEFs) for polycyclic aromatic hydrocarbons (PAHs).

The polycyclic aromatic hydrocarbons (PAHs; also referred to as the polynuclear aromatic hydrocarbons or PNAs) are commonly encountered at hazardous waste sites and are often the focus of site remediation activities. However, toxicity criteria are not available for all the PAHs. In the past, EPA has assessed risks posed by mixtures of PAHs by assuming that all carcinogenic PAHs are as potent as benzo[a]pyrene (B[a]P), one of the most potent PAHs. The available information on the toxicity of the PAHs suggests that most are considerably less potent than B[a]P and therefore, the EPA approach is likely to overestimate risks. Several approaches have been developed to allow the relative potency of the different PAHs to be considered in a site-specific risk assessment. This paper evaluates these approaches and presents a modified version that we feel more accurately reflects the state of knowledge on the relative potency of these compounds.     

Evaluation of polycyclic aromatic hydrocarbons (PAHs) in fish: a review and meta-analysis

Abstract

Polycyclic aromatic hydrocarbons (PAHs) are a group of pollutants which occur in considerable amounts in the environment and food. In this study, a meta-analysis study was conducted on PAHs concentrations in fish in different parts of the world. The results showed that the PAHs were observed and quantified in fish in the most considered studies. The maximum and minimum concentration of PAHs was found in Cynoglossus Bilineatus fish of Persian Gulf (3970?ng/kg) and Cyprinus Carpio fish of Caspian Sea (0.004?ng/kg), respectively. These values are below the maximum value currently allowed by European Union regulations (12.0?μg/kg wet weight).     

Toxicity and EROD-inducing potency of 24 polycyclic aromatic hydrocarbons (PAHs) in chick embryos

The toxicities (embryolethality) of 24 polycyclic aromatic hydrocarbons (PAHs) were determined in chick embryos using a 72-h test. The substances, dissolved in peanut oil, were injected into the air sacs of eggs preincubated for 7 days. LD₅₀ values were determined for the four most toxic of the 24 compounds. Benzo [k] fluoranthene proved to be the most potent, with an LD₅₀ of 14 g (56 nmol)/kg egg. Dibenz[a,h]anthracene, benz[a]anthracene and benzo[b]naphtho[2,3-d]thiophene were a few times less toxic [LD₅₀=39 g (140 nmol)/kg, 79 g (349 nmol)/kg and 82 g (350 nmol)/kg, respectively]. The LD₅₀ of benzo [k] fluoranthene was only about 5 times higher than that previously found for the most potent coplanar polychlorinated biphenyl (PCB), 3,3,4,4,5-pentachlorobiphenyl [LD₅₀=3.1 g (9.4 nmol)/kg], in the same kind of test. The toxicities of 18 of the PAHs in this study have also been evaluated previously using a 2-week test in chick embryos. Dibenz[a,h]anthracene, which had not been studied earlier in the 2-week test, proved to be almost as toxic as previously found for benzo [k] fluoranthene in that test. Several of the PAHs studied induced EROD activity in chick embryos, and, in general, the most toxic PAHs were also the most potent inducers of EROD. The highest enzyme activities were found after treatment with indeno[1,2,3-c,d]pyrene (12 times the control value) and dibenz[a,h]anthracene (8 times the control value). However, due to the high toxicity of dibenz[a,h]anthracene, the dose used was 7 times lower than that of indeno [1,2,3-c,d]pyrene. Following injection of PAHs on day 7, the EROD activities on day 10 were considerably lower than those obtained after a corresponding treatment with coplanar PCBs in an earlier study. Of the PAHs studied, some exhibited very high embryotoxicity. The most toxic PAHs induced EROD activity, suggesting that their toxicity was at least partly mediated via binding to the Ah receptor.     

Identification of molecular signatures predicting the carcinogenicity of polycyclic aromatic hydrocarbons (PAHs)

There are multiple lines of evidence showing that environmental toxicants including pesticides may contribute to neuronal cell death. Fipronil (FPN) is a phenylpyrazole insecticide that acts on insect GABA receptors. Although the action of FPN is restricted to insect neuronal or muscular transmitter systems, a few studies have assessed the effects of this neurotoxicant on neuronal cell death distinct from an insect. To determine the mechanisms underlying FPN-induced neuronal cell death, we evaluated the ability of this chemical to induce oxidative stress and studied the involvement of mitogen activated protein kinases (MAPKs) in FPN-induced apoptosis stress in human neuroblastoma SH-SY5Y (SH-SY5Y) cells. Exposure of SH-SY5Y cells to FPN led to the production of reactive oxygen species (ROS) and apoptotic cell death via activation of caspase-9 and caspase-3. Interestingly, the antioxidant, N-acetyl-cysteine (NAC) attenuated apoptotic cell death and ROS production induced by FPN. These results indicated that oxidative stress plays a central role in FPN-induced cytotoxicity. Mitochondrial complex I activity was also inhibited by FPN treatment. These finding indicate that FPN triggers intrinsic apoptosis via the mitochondrial signaling pathway that is initiated by the generation of ROS. Furthermore, FPN treatment induced phosphorylation of MAPK members. Activation of these protein kinases by FPN was involved in the onset of apoptosis as inhibitors specific to these kinases protect against FPN-induced cell death as well as ROS generation. Our data indicate that FPN-induced apoptosis is mediated primarily by the generation of ROS and activation of MAPK members followed by activation of the intrinsic apoptotic pathway.     

Comparison of polycyclic aromatic hydrocarbons (PAHs) between smoked marc spirits and whiskies.

The presence of polycyclic aromatic hydrocarbons (PAHs) in three brands of smoked marc spirits, the only actually on the market, was studied and compared with literature PAHs concentrations reported for whiskies. In two brands of smoked marc spirit the higher-molecular-weight PAHs concentrations (5 and 6 rings PAHs) resulted higher (0.09-0.3 microg L (-1)) than in whiskies (0.00-0.02 microg L(-1)) and consequently higher resulted the carcinogenic potential expressed using the toxicity equivalent factor (TEF).     

Environmental polycyclic aromatic hydrocarbons (PAHs) enhance allergic inflammation by acting on human basophils

Diesel exhaust particles (DEPs) have been implicated in the worldwide increased incidence of allergic airway diseases over the past century. There is growing evidence that DEP-associated polycyclic aromatic hydrocarbons (PAHs) participate in the development and maintenance of immunoglobulin (Ig) E-mediated allergic diseases. To address this issue we investigated the impact of U.S. Environmental Protection Agency (EPA) priority PAHs as well as of PAH-containing airborne extracts on antigen-induced CD63 upregulation and mediator release from human basophils. Whole blood samples from birch pollen allergic and control subjects were incubated in the presence of organic extracts of urban aerosol (AERex) or EPA-PAH standard with or without rBet v 1. Basophils were analyzed for CD63 expression as a measure of basophil activation by using multiparameter flow cytometry. In addition, purified basophils from birch pollen allergic donors were incubated for 2 h in the presence of 1 muM benzo[a]pyrene (BaP) or phenanthrene (Phe) and then stimulated with rBet v 1 for 45 min. Supernatants were assayed for histamine, interleukin (IL)-4, and IL-8 by means of enzyme-linked immunosorbent assay (ELISA). Basophils exposed in vitro simultaneously to AERex or EPA-PAH standard and rBet v 1 expressed CD63 significantly more than with antigen alone. PAHs synergized with rBet v 1 dose dependently, but did not activate basophils from nonallergic donors. BaP and Phe significantly enhanced cytokine secretion (IL-4, IL-8) and histamine release from purified basophils without antigen added, and secretion was not further enhanced by rBet v 1 stimulation. In conclusion, PAHs from roadside emissions can directly activate sensitized basophils to cytokine secretion and drive proallergic processes through enhanced Fcepsilon RI-coupled mediator release from human basophils.     

Determination of polycyclic aromatic hydrocarbons (PAHs) in cosmetic products by gas chromatography-tandem mass spectrometry

A gas chromatography coupled with tandem mass spectrometry (GC-MS/MS) method is developed to determine 18 representative polycyclic aromatic hydrocarbons (PAHs) in cosmetics, including Benzo[a]pyrene (BaP) and others. The method offers high sensitivity and selectivity under selected reaction monitoring (SRM) mode to satisfy the requirements of both quantitation and qualitation. The extraction solvent system used in this study is acetone/hexane 1:1 (v/v) and other purification procedure is unnecessary. The linearities of 18 PAHs are validated in different concentration in the range of 0.25–20 ng/mL individually with coefficient correlation (r) higher than 0.996. The recoveries for spiking 3 different concentrations are from 87.40% to 120.44% for 18 PAHs and the coefficient of variation (CV) are below 12.32%. Limit of quantification (LOQ) of 18 PAHs is in the range of 0.05–0.2 mg/kg. A matrix enhancement effect is observed and can be compensated with deuterated internal standard. The method has been successfully applied to 73 samples, over 40 of them are lipsticks. The results show none of the samples detect Benzo[a]pyrene (BaP) and Dibenzo[a,h]anthracene (DBA), both are classified as the most carcinogenic. 8 PAHs are detected and the average value between 0.08 and 0.27 mg/kg. This study offers a sensitive and simple method to analyze 18 representative PAHs successfully and can be applied to cosmetic products and raw materials.     

Potential effects of polycyclic aromatic hydrocarbons (PAHs) in marine foods on human health: a critical review

Marine pollution particularly oil pollution is a major threat to human and environmental health. Commercial species being suitable for consumption of marine environment such as fish, mollusks, invertebrates, etc. are demanded by consumers all around the world. Polycyclic aromatic hydrocarbons (PAHs) are one of the most widespread organic environmental pollutants that pose a potential risk to human health via marine biota. Toxic, carcinogenic and mutagenic properties of PAHs are studied in several researches. This paper reviews thoroughly the sources, potential risks and harmful health effects of PAHs in marine food according to the findings of published research studies.     

Effect of charcoal types and grilling conditions on formation of heterocyclic aromatic amines (HAs) and polycyclic aromatic hydrocarbons (PAHs) in grilled muscle foods

Grilling muscle foods involves high temperatures that lead to production of cooking toxicants, such as heterocyclic aromatic amines (HAs) and polycyclic aromatic hydrocarbons (PAHs). To obtain realistic exposure levels of these two groups of mutagens analyses of the same samples using similar separation/detection techniques were performed. HAs and PAHs were quantified in well-done meat and fish samples grilled with wood and coconut shell charcoal at 200 °C. Quantitative HAs and PAHs profiles were different for beef and salmon using the same type of charcoal. Higher levels of HAs and PAHs were found in salmon samples. No significant differences were observed for HAs and PAHs in beef samples grilled with both charcoal types, whereas salmon grilled with coconut shell charcoal presented significantly lower amounts of HAs and PAHs than salmon grilled with usual wood charcoal. Continuous barbecuing with the same charcoal shown that combustion of fat that dropped along the grilling period contributed to higher formation of HAs and PAHs. Special attention must be given to the intake of barbecued foods since high amounts of HAs and PAHs can be taken in a single meal.     

Study of polycyclic aromatic hydrocarbons (PAHs) in soil samples from Al-Ahdab oil field in Waset Region,Iraq

Levels of thirteen polycyclic aromatic hydrocarbons (PAHs) were studied in 24 soil samples collected from the Ahdab oil field in Waset region, Iraq. The whole analysis was carried out using the gas chromatography with mass spectrometry (GC/MS) in the single ion monitoring (SIM)-mode. The total PAHs concentrations were ranged between 19?μg/kg (Site 15) and 855?μg/kg (Site of 16). The results of these samples were compared among each other according to their toxicity equivalence in μg TEQ/g concentrations and with the results of other studies. The total estimated cancer risks of exposure to PAHs in soil samples were ranged from 1.02?×?10^?7 to 4.59?×?10^?6. By multiplying the estimated cancer risk values by 10⁶, then the estimated theoretical cancer cases per million is between 0.0 and 5. The total estimated cancer risks in this study were within the acceptable range of excess cancer risk speci?ed by the Environmental Protection Agency in the United States.     

QSAR study using acute toxicity of Daphnia magna and Hyalella azteca through exposure to polycyclic aromatic hydrocarbons (PAHs)

Polycyclic aromatic hydrocarbons are organic chemicals consisting of a small number of benzene rings. PAHs are exposed to the environment by events such as Crude oil spills, even though they are substances present in the environment. Exposure of PAHs to the environment will affect not only the environment, but also the living organisms and the ecosystem as a whole. The effects of PAHs vary widely depending on the type of PAHs and have been studied for a long time. However, there are only 16 kinds of PAHs defined by US EPA, and there are more kinds of PAHs present in the environment. Therefore, it is time- and space-limited to judge the toxicity of all kinds of PAHs by evaluating them. In all cases, the tendency of research is shifting toward predicting toxicity evaluation through modeling rather than the direction of toxicity evaluation. In this study, we constructed a quantitative structure-activity relationship (QSAR) model, one of the molecular structure activation models, and predicted the correlation between the toxicity value and the logKow value of PAHs. Basically, as the logKow value increases, the median effective concentration (EC50) tends to decrease. Compared with the previous studies, Hyalella azteca showed this tendency, but Daphnia magna showed different results when exposed to Naphthalene. The RMSE(Root Mean Square Error) values of Daphnia magna and Hyalella azteca were 6.0049 and 5.9980, respectively, when the QSAR model was constructed using the toxicity data for PAHs. We confirmed the validity of the QSAR model in this study by comparing the results of exposing Daphnia magna to PAHs and the ECOSAR data, one of the existing models. The R² value was found to be 0.9356. This study suggests that it may be helpful to predict the toxicity evaluation and to prepare countermeasures for accidents such as Crude oil spill. It is thought that if more data base is created by using additional types of PAHs and species in the same way as this study in the future, it will help to construct the modeling.

     

Microbial degradation of polycyclic aromatic hydrocarbons and polycyclic aromatic nitrogen heterocyclics

Fermentor studies were conducted to examine the microbial degradation of polycyclic aromatic hydrocarbons (PAHs; naphthalene, phenanthrene, anthracene) and a polycyclic aromatic nitrogen heterocyclic (quinoline) using a mixed bacterial culture capable of utilizing these compounds as the sole carbon and energy source for growth. Half-lives for the three PAHs in the cyclone fermentor system ranged from 1 day for naphthalene to 4 days for anthracene. Several major metabolites during the biodegradation of PAHs were also identified. These included 2-hydroxybenzoic acid and 1-naphthalenol (for naphthalene); 1-phenanthrenol and 1-hydroxy-2-naphthalenecarboxylic acid (for phenanthrene); and 3-hydroxy-2-naphthalenecarboxylic acid (for anthracene). Thus our bacterial culture biodegraded the three PAHs by initial hydroxylation of the molecule followed by the eventual cleavage of the ring to yield the ortho- or meta-cleavage intermediates, which would be further metabolized via conventional metabolic pathways. However, biodegradation of the nitrogen-containing polycyclic aromatic hydrocarbon compound quinoline by our culture resulted in the accumulation of 4–5 metabolites, one of which has been identified as 2-quinolinol. Work is in progress to identify the other metabolites from quinoline degradation. © 1992 John Wiley & sons, Inc.     

Determination of benzo[a]pyrene and other polycyclic aromatic hydrocarbons (PAHs) at trace levels in human tissues

A sensitive and rugged gas chromatographic-mass spectrometric (GC-MS) method was developed for determining 11 polycyclic aromatic hydrocarbons (PAHs) in 4-g specimens of human lung, breast, and liver tissue. The method quantitation limit (MQL) was 0.01-0.02 ng/g for benzo[a]pyrene (BaP) and six other five- and six-ring PAHs. The MQL was higher for four-ring PAHs because of their presence at trace levels in method blanks. The average MQLs for pyrene and chrysene were 0.05 and 0.03 ng/g, respectively. The method was applied to 200 human tissue specimens (89 lung, 68 breast, and 43 liver) obtained from patients during surgery. Quality-control results demonstrated average recoveries of 80% or better from reagent controls spiked at the 0.2-ng level and average recoveries from tissue fortified at the 0.25-ng/g level of 66-95%. The precision of the method was determined from duplicate analyses of specimens (16-38% RSD) and from duplicate GC-MS analysis of tissue extracts (8-17%RSD). Benzo[a]pyrene was detected at measurable levels in 87% of the lung specimens. This method makes possible the measurement of ambient levels of PAHs in small samples of human tissue such as those obtained by biopsy.     

Evaluation of estrogenic activities of hydroxylated polycyclic aromatic hydrocarbons in cigarette smoke condensate.

Estrogenic activities of cigarette smoke condensates obtained from the extraction of particulate matters from mainstream and sidestream cigarette smoke with benzene/ethanol were evaluated by using a yeast two-hybrid assay system expressing human estrogen receptor alpha (hERalpha). To identify the constituents of the cigarette smoke condensate which are responsible for the estrogenic activity, the condensate was fractionated into eleven fractions by liquid-liquid extractions. Among these fractions, the neutral fractions of mainstream and sidestream smoke showed the strongest estrogen receptor-mediated activity by the yeast two-hybrid assay. Then the neutral fractions were fractionated by medium-pressure liquid chromatography with silica gel column. In the fractions that showed strong estrogenic activity, 2-hydroxyfluorene (2-OHFle), 2- and 3-hydroxyphenanthrene (2- and 3-OHPhe), 1-hydroxypyrene (1-OHPyr) and n-propyl-p-hydroxybenzoate (n-PHB) were identified by LC- and GC-MS and HPLC with fluorescence detection. 2-OHFle, 2-OHPhe and n-PHB exhibited estrogenic activity, whereas weak activity was observed with 3-OHPhe and 1-OHPyr. Several other hydroxylated polycyclic aromatic hydrocarbons having no activity were also identified. This is a first study to identify estrogenic hydroxylated PAHs in cigarette smoke condensate. The present findings points out the necessity for detailed investigation of exposure to aerosols containing apparently estrogenic compounds.     

Human exposure to polycyclic aromatic hydrocarbons (PAHs) using data from a duplicate diet study in Catalonia,Spain

In this study, the dietary intake of 16 polycyclic aromatic hydrocarbons (PAHs) by the population of Tarragona County (Catalonia, Spain) was assessed using the duplicate diet approach. Duplicate diet samples, prepared as per consumption, were collected during September 2010 in various restaurants offering a variety of daily menus (breakfast, lunch, and dinner). For analysis of PAHs, a total of 90 composite samples were prepared. Analytical procedure of PAHs was performed by means of gas chromatography/mass spectrometry. Intake calculations were made for the standard male adult population. The highest intakes corresponded to acenaphthylene (12.7 μg/day), acenaphthene (12.4 μg/day), and fluorene (11.9 μg/day), while the lowest intake corresponded to dibenz[a,h]anthracene (0.12 μg/day), being also comparatively low those of pyrene, benzo[b]fluoranthene + benzo[j]fluoranthene, benzo[a]pyrene and benzo[ghi]perylene (0.13 μg/day in all cases). The results were compared with data from previous total diet studies (TDS) recently performed in the same geographical area. In the present study, the estimated mean dietary intake for a standard male adult living in Catalonia was 59.2 μg/day, a value notably higher than that found in our recent TDS (6.72 μg/day). However, it is essential to remark that important methodological differences exist between both surveys, reflecting that calculation methods should be similar when the purpose is to compare results from different surveys. In general terms, we conclude that for PAHs, duplicate diet studies may be a good alternative to total diet studies, especially when there are important economical limitations to perform a suitable TDS. The costs associated to the former may be notably lower, as they do not require such an extensive number of samples for chemical analysis. Moreover, a duplicate diet approach may even be more realistic, as cooked foodstuffs are used for dietary exposure assessment.     

The source apportionment of polycyclic aromatic hydrocarbons (PAHs) in the topsoil in Xiaodian sewage irrigation area,North of China

31 topsoil samples were collected by grid method in Xiaodian sewage irrigation area, Taiyuan City, North of China. The concentrations of 16 kinds of polycyclic aromatic hydrocarbons (PAHs) were determined by gas chromatograph coupled with mass spectrum. Generally speaking, the distribution order of PAHs in the area is: those with five and six rings > those with four rings > those with two and three rings. Source apportionment shows a significant zonation of the source of PAHs: the civil coal pollution occurred in the north part, the local and far factory pollution happened in the middle area and the mixed pollution sources from coal and wood combustion, automotive emission, presented in the south area. The distribution of PAHs has a definite relationship with the sewage water flow and soil adsorption. The related coefficient between PAHs and physicochemical property showed there was a negative correlation between pH, silt, clay and PAHs while there was a positive correlation between total organic carbon, sand and PAHs.     

DNA‐adducts in subjects exposed to urban air pollution by benzene and polycyclic aromatic hydrocarbons (PAHs) in Cotonou,Benin

Air pollution effect on humans represents a major public health problem. Exposure to genotoxic compounds in the ambient air is evaluated using different biomarkers. In the present study we assessed DNA‐adducts levels in apparently healthy people living and working in the city of Cotonou (Benin) in which exposure to air pollutants such as benzene and polycyclic aromatic hydrocarbons (PAHs) mainly benzo(a)pyrene has been evidenced. Rural inhabitants were enrolled as control group. Taxi‐motorbike drivers, street food vendors, and gasoline salesmen were recruited in Cotonou whereas suburban residents were recruited in Godomey, 12 km from Cotonou. We found that taxi‐motorbike drivers, roadside residents, street vendors, taxi‐motor‐bike drivers and gasoline sellers had significantly higher levels of DNA‐adducts than suburban and village inhabitants (P < 0.001; post hoc, LSD). Means values were 24.6 ± 6.4, 23.78 ± 6.9, 34.7 ± 9.8, and 37.2 ± 8.1 in the exposed groups versus 2.1 ± 0.6 and 3.1 ± 0.8 adducts/10⁸ nucleotides, in the two control groups, respectively. We did not find any significant difference within the high exposuregroups and inside low exposure subgroups (namely suburban residents and villagers) because the mean individual exposure values to both PAHs and benzene were similar among subjects exposed in the city of Cotonou and those in suburban and village areas. However, there is significant interindividual variations in adducts levels that may reflect variation of genetic susceptibility factors. Ranges of adduct level/10⁸ nucleotides were: 1–69, 1–76, 3–169, 4–124, 0–9, 0–8 adducts/10⁸ for taxi‐motorbike drivers, roadside residents, street vendors, gasoline sellers, suburban and village inhabitants, respectively. Our study demonstrated a clear‐cut elevated level of DNA adducts in city residents than in none exposed people (or very low exposure levels people) and designate these city residents groups as people at risks for the chronic diseases possibly caused by benzene and PAHs. © 2009 Wiley Periodicals, Inc. Environ Toxicol 26: 93‐102, 2011.     

Measurement of polycyclic aromatic hydrocarbons and other pollutants

A single point study of atmospheric pollution has been carried out in Granada (Spain); suspended particulate matter, sulphur oxides, ammoniac, nitrogen dioxide and polycyclic aromatic hydrocarbons were determined. There were variations in relation to the month and the day of the week. The PAHs have been determined through HPLC, with a mobile phase of acetonitrile-water (75-25). The results of measurements of benzo(a)pyrene were between 1.006 and 0.485 micrograms m-3 in two different periods of sampling.     

Gas/particle partitioning and yield levels of polycyclic aromatic hydrocarbons and n-alkanes in the mainstream cigarette smoke of commercial cigarette brands.

The gas/particle partitioning of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes was investigated in the mainstream smoke (MSS) from 59 commercial cigarette brands classified according to the existence of filter tip, the tar yield indicated on the packet, and the cigarette length and diameter, into 15 cigarette classes: non filter (NF), high (H), medium (M), light (L), super light (SL), ultra light (UL), one-tar yield (O), 100-mm long (H-100, L-100, SL-100, UL-100, O-100), and slim (SL-SLIM, UL-SLIM, O-SLIM). The gas/particle partitioning constant, Kp, was determined and its relationship with the subcooled liquid vapour pressure pL degrees of individual compounds was investigated. A good linear relationship was obtained for both chemical classes following the equation log Kp=mr log pL degrees+br. In all cigarette classes, PAHs were found to sorb more strongly on MSS particles than n-alkanes. Carcinogenic PAHs were detectable only in the total particulate matter (TPM) of MSS and their yields increased linearly with the TPM yield. However, when normalized against TPM, the yields of carcinogenic PAHs were quite similar in all cigarette classes with a slight drop from low tar- to high tar-yield brands suggesting probably lower biological activity per mg TPM for the latter. The nicotine-normalized PAH yields were also similar among the different cigarette classes suggesting that, if smokers adjust their smoking behavior to achieve a consistent nicotine intake, they will be exposed to an equivalent amount of carcinogenic PAHs regardless of whether they smoke full-flavored, light, or ultralight varieties.