Polycyclic Aromatic Hydrocarbons (PAHs) Occurrence and Toxicity in Camellia sinensis and Herbal Tea

ABSTRACT

This study describes a survey of polycyclic aromatic hydrocarbon (PAH) concentrations in 23 green, herbal, and black tea brands widely consumed in Nigeria by determining the levels of benzo[a]pyrene, chrysene (PAH2), benzo[a]pyrene, chrysene, benz[a]anthracene, benzo[b]fluoranthene (PAH4), benzo[a]pyrene, benz[a]anthracene, benzo[k]fluoranthene, chrysene, benzo[b]fluoranthene, dibenz[ah]anthracene, benzo[ghi]per-ylene and indeno[1,2,3-cd]pyrene (PA-H8). Toxic equivalence factor and mutagenic equivalence factor were applied to evaluate the toxic equivalence and mutagenic equivalence quotients relative to benzo[a]pyrene. The concentrations of PAHs indicate that Regulation 835/2011/EC was not fulfilled by benzo[a]anthracene, B[a]A, benzo[a]pyrene, B[a]P, benzo[b]fluoranthene, B[b]F, and chrysene, CHR. The PAH4 levels ranged from 1.28 to 44.57, 4.34 to 11.20, and 0.76 to 34.82 µg/kg in green, black, and herbal tea products, respectively. On the other hand, the PAH8 concentration varied between 1.63 and 65.73, 5.02 and 68.83, and 12.43 and 24.92 µg/kg in green, herbal, and black tea samples. The PAH4 and PAH8 provide more reliable indicators for determination of PAH contamination and risk characterization in food than PAH2.     

Determination of volatile N-nitroso compounds in various samples of edible vegetable oils and margarine (commercially available products)

The examination of samples of various commer-cially available vegetable oils (olive oil, sunflower oil, thistle oil, linseed oil, plant germ oil, etc.) and of various samples of margarine for the presence of vola-tile N-nitroso-compounds yielded the following results. By means of the above mentioned procedure (gas liquid chromatography — AFID gas liquid chromatography — TEA), N-nitrosodimethylamine (NDMA) was found to be present in 21 of 61 dif-ferent samples of vegetable oil, in concentrations ranging from < 1 μg/kg to 23 μg/kg. 18 samples con-tained N-nitrosodiethylamine (NDEA) in concentra-tions varying between < 1μg/kg and 27.8 μg/kg. 37 out of 107 different samples of margarine were shown to contain N-nitroso compounds. N-nitroso-dimethylamine was found to be present in 15 samples. The range of concentrations determined was between < 1 μg/kg and 5.8 μg/kg. 33 samples con-tained N-nitrosodiethylamine in concentrations varying between < 1 μg/kg and 7.5 μg/kg.     

Extraction of Polycyclic Aromatic Hydrocarbons in Barn Owls ( Tyto Alba ) from Northwest Spain by SFE and HPLC-FL Analysis

Supercritical fluid extraction (SFE) and high-performance liquid chromatography-fluorescence detection (HPLC-FL) were used to determine concentration of anthracene, benzo[ a ]anthracene, benzo[ a ]pyrene, benzo[ b ]fluoranthene, benzo[ ghi ]perylene, benzo[ k ]fluoranthene, chrysene, fluoranthene, pyrene, and indeno[1,2,3- cd ]pyrene in six classes of tissue (heart, liver, intestine, muscle, lung, and kidney) of 11 barn owls from Galicia (northwest Spain). We have detected fluoranthene and pyrene in >40.0% of samples, anthracene in 35.4%, and benzo[ a ]anthracene in 12.3%. Mean concentrations were between 0.398 w g/kg dry weight for anthracene and 4.855 w g/kg dry weight for fluoranthene. Lung and intestine tissues were more polluted than the other tissues.     

POLYCYCLIC AROMATIC HYDROCARBON REFERENCE RANGE LEVELS IN THE U.S. POPULATION BY MEASUREMENT OF URINARY MONO-HYDROXY METABOLITES

We developed a gas chromatography/ isotope dilution high resolution mass spectrometry (GC/ID-HRMS) method for measuring 18 PAH metabolites representing 8 parent PAHs in 3 mL of urine at low part-per-trillion levels. We applied this method to the analysis of urine specimens from approximately 2400 people who participated in the National Health and Nutrition Examination Survey for the years 1999 and 2000 to determine levels for 14 PAH hydroxy metabolites of 7 parent compounds. Using this GC/ID-HRMS method, we found detectable concentrations for monohydroxy metabolite isomers of fluorene, phenanthrene, fluoranthene, and pyrene, and for chrysene, benzo[c]phenanthrene, and benz[a]anthracene. Some mono-hydroxy metabolite isomers of chrysene, benzo[c]phenanthrene, and benz[a]anthracene exhibitedlow detection frequencies which did not allow for geometric mean calculations. From our study, we established a reference range for the targeted PAHs in the general U.S. population.     

Quality of Wood-Pressed Rapeseed Oil

This study is the first report on the quality indices of Chinese wood‐pressed rapeseed oil. Nineteen representative wood‐pressed rapeseed oil samples (representing 80% of the factories that produce this oil in China) were collected and investigated for their physicochemical properties (acid value, peroxide value, color value, and oxidative stability index), fatty acid composition, as well as contents of tocopherols, phytosterols, polycyclic aromatic hydrocarbons (PAH), aflatoxin B₁, arsenic, and lead. Significant differences were observed in the quality results of 19 wood‐pressed rapeseed oil samples. The acid value, peroxide value, and color values, as well as the oxidative stability index were found in the ranges of 1.10–3.04 mg KOH/g, 0.84–9.34 mequiv O₂/kg, 3.50–5.30 (Y = 35, R), and 4.43–10.34 h (120 °C), respectively. Sixteen of the analyzed oil samples had greater than 2% erucic acid. Tocopherols content ranged from 50.93 to 97.54 mg/100 g and phytosterols content ranged from 453.86 to 735.65 mg/100 g. Meanwhile, benzo[a]pyrene and PAH4 were 1.00–13.57 and 7.47–33.55 μg/kg, respectively. Fourteen samples exceeded the maximum allowable limit of benzo[a]pyrene and PAH4 (chrysene, benz[a]anthracene, benzo[b]fluroranthene, and benzo[a]pyrene) according to the European Union (EU) standards. However, the contents of aflatoxin B₁, arsenic, and lead of the tested oil samples were all in conformance with the EU, Codex Alimentarius, and China national standards. Results showed that more attention should be paid to the problem of high PAH4 contents in wood‐pressed rapeseed oil. The inspection and monitoring of raw materials and processing equipment, as well as the establishment of quality standards for the production of high‐quality wood‐pressed rapeseed oil are necessary.     

Levels of 15 + 1 EU Priority Polycyclic Aromatic Hydrocarbons in Different Edible Oils Available in the Syrian Market

ABSTRACT

The levels of 15 + 1 EU priority polycyclic aromatic hydrocarbons (15 + 1 EU PAHs) have been determined in different edible oils (extra virgin olive oil, virgin olive oil, sunflower oil, corn oil, and soybean oil) available in the Syrian market. The samples have been prepared by donor–acceptor complex chromatography and subsequently characterized by high-pressure liquid chromatography coupled with fluorescence and ultraviolet detection for quantification purposes. Variable levels of contamination have been found within different kinds of edible oil samples, and only chrysene has been detected in all the studied samples. Moreover, the mean total sum of 15 + 1 EU PAHs has shown variation from 29.8 µg/kg (corn oil) to 63.7 µg/kg (virgin olive oil). A total of 11 samples out of 38 samples (28.9%) have not fulfilled the European Union (EU) food law requirements. Nine samples have exceeded the EU legislation limit of benzo[a]pyrene (BaP) (2 µg/kg) and only two samples have exceeded the EU legislation limit of PAH4 (10 µg/kg) and had acceptable level of BaP. Finally, the mean and maximum dietary exposures of PAHs through consumption of edible oils have been estimated.     

PAH Metabolism in Cultured Mammalian Lung Epithelial Cells

In vitro cultures of mammalian cells have an advantage over animal experiments in that human cells can be directly compared with various other mammalian cells. In this study we compared the metabolism of several polycyclic aromatic hydrocarbons (PAH) (benzo[a]pyrene, chrysene, pyrene, phenanthrene, benz[a]anthracene) in epithelial cells from hamster, rat and human lung.

The cells investigated in our system yielded more or less qualitatively similar metabolic profiles for all PAH mentioned above except benz[a]anthracene in the three species. Additionally, species-specific differences were prominent between human and rodent cells with regard to the ratio of phase I and phase II metabolites.

Indications have been obtained that monooxygenase induction is required in fetal cells prior to metabolic conversion of those PAH which lack an inductive potential for CYP450.     

Frying Quality Characteristics of French Fries Prepared in Refined Olive Oil and Palm Olein

The objective of this study was to compare two oils with different polyunsaturated/saturated (P/S) fatty acid ratios, refined olive oil (P/S 0.75) and palm olein (P/S 0.25), in frying French fries. The chemical qualities of the oil residues extracted from the French fries were assayed for five consecutive batches fried at 1-h intervals. The levels of total polar compounds, free fatty acids, p-anisidine value and phytosterol oxidation products (POPs) were elevated in French fries fried in both oils. The level of total polar compounds increased from 4.6 in fresh refined olive oil to 7.3% in final batches of French fries. The corresponding figures for palm olein were 9.8–13.8%. The level of free fatty acid in fresh refined olive oil increased from 0.06 to 0.11% in final products. These figures for palm olein were 0.04–0.13%. The p-anisidine value increased from 3.7 to 32.8 and 2.5 to 53.4 in fresh oils and in final batches of French fries in refined olive oil and palm olein, respectively. The total amount of POPs in fresh refined olive oil increased from 5.1 to 9.6 μg/g oil in final products. These figures were 1.9 to 5.3 μg/g oil for palm olein.     

POLYCYCLIC AROMATIC HYDROCARBONS (PAH) IN DANISH SMOKED FISH AND MEAT PRODUCTS

Twenty seven PAH were detected in 45 selected smoked food samples produced in Denmark, including mackerel, herring, trout, small sausages, salami, and bacon. The sum of PAH in smoked meat products ranged from 24 μg/kg for salami to 64 μg/kg in bacon, while those in fish products ranged from 22 μg/kg in smoked mackerel prepared in an electric oven to 1387 μg/kg in herring smoked by direct smoking. The concentration of benzo[a]pyrene for all sample types were below the maximum level of 5 μg/kg for smoked fish and meat set by the European Commission. Results from this survey confirm that the actual level of individual PAH in fish products is dependent on variables such as the type of wood used in the smoking process. Furthermore, the use of the benzo[a]pyrene approach for estimation of the carcinogenicity of PAH in food is confirmed. The Danish intake of benzo[a]pyrene from these smoked products is 2 to 4 ng/person/day.     

Association of Polycyclic Aromatic Hydrocarbons (PAHs) with Different Sizes of Atmospheric Particulate in Hisar City and its Health Aspects

The concentration of polycyclic aromatic hydrocarbons (PAHs) associated with different particulate sizes of suspended particulate matter (SPM) was studied in Hisar city with the help of a MOUDI-NR 10-stage (18 μm to 0.056 μm) cascade impactor. The vehicular-cum-commercial, vehicular, commercial, and institutional/residential locations had the average concentration (ng/g) of 11.39, 10.39/10.22 (NH 10/Bus Terminus), 8.89, and 8.93, respectively. Vehicular emission was the chief source and diesel-vehicle dominated areas represented higher concentration of PAHs associated with coarse fraction. An increase in PAH associated with fine fraction was observed with an increase in vehicular density. Maximum average concentration (11.26 ng/g) was found to be associated in particle range of <0.56–0.32 μm. It was followed by particle range (μm) of <18–10, <1.8–1, <0.18–0.1, <1–0.56, <5.6–3.2, <0.32–0.18, <3.2–1.8 <0.1–0.056, and <10–5.6 with average values (ng/g) of 10.75, 10.35, 10.22, 10.16, 10.06, 9.50, 9.18, 9.18, and 9.00, respectively. Among the PAHs studied, maximum levels were observed for pyrene, followed by Benzo(b)fluoranthene, Benzo(e)pyrene, benzo(k)fluoranthene, fluoranthene, phenanthrene, benzo(ghi)perylene, anthracene, and naphthalene. With respect to the percent fraction of PAHs studied, the vehicular-cum-commercial area represented maximum fraction (22%) followed by vehicular area (21% each for NH-10 and Bus Terminus), institutional/residential area (18%), and commercial area (18%). The isomeric ratios revealed that most of the PAHs originate from combustion of diesel, gasoline, used engine oil, and coal/wood. The association of PAHs with fine fraction of health concern since it can penetrate and get accumulated in deep respiratory regions.     

Antioxidant capacity of extra-virgin olive oils

In this study, the oxygen radical absorbance capacity (ORAC) of vegetable oils was investigated using a spectrofluorometric method, which measures the protection of the phenolic substances of the oil on the β-phycoerythrin fluorescence decay in comparison with Trolox. More than 97% of the phenolic substances was extracted from the oil using methanol, and the methanolic extract was then used for the ORAC and the total phenolics assay. We found a significant correlation between ORAC values of different olive oils and the total amount of phenolics. For extra-virgin olive oils, maximal ORAC values reached 6.20±0.31 μmol Trolox equivalent/g, while refined and seed oils showed values in the 1–1.5 μmol Trolox equivalent/g range. Our method is useful to assess the quality of olive oils and to predict, in combination with the rancidity tests, their stability against oxidation.     

Contamination of Soil by Polycyclic Aromatic Hydrocarbons in Some Urban Areas

The contamination by 16 polycyclic aromatic hydrocarbons (PAHs) in surface soils, sampled at a 0-5 cm depth in the urban areas of Tallinn, Helsinki, Vilnius, Chicago, London is reported. All samples were analyzed using the same protocol. The median concentrations ( w g/kg) were found to be 117, 539, 127, 3,263, 1,728 for pyrene; 62, 236, 43, 1,634, 1,652 for benzo[ a ]pyrene; 86, 304, 92, 2,295, 2,068 for benzo[ a ]pyrene toxic equivalents, calculated using the benzo[ a ]pyrene toxic equivalency factors; 467, 1,471, 392, 8,981, 6,837 for a total of seven probable human carcinogenic PAHs: benzo[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, dibenz[ ah ]anthracene, indeno[1,2,3- cd ]pyrene; 911, 2,941, 672, 16,183, 13,718 for the total of 16 PAHs, recommended by the U.S. Environmental Protection Agency: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, dibenz[ ah ]anthracene, benzo[ ghi ]perylene, indeno[1,2,3- cd ]pyrene in Tallinn ( n = 3), Helsinki ( n = 3), Vilnius ( n = 15), Chicago ( n = 4), London ( n = 3), respectively. The size of the population is a statistically significant factor in urban soil contamination by high-molecular-mass PAHs.     

Evaluation of drum bioreactor performance used for decontamination of soil polluted with polycyclic aromatic hydrocarbons

A laboratory‐scale drum bioreactor system was used to study engineering aspects of soil bioremediation. Polycyclic aromatic hydrocarbons (PAHs) were chosen as contaminants in soil. In the operation of the reactor, different mixing strategies were applied according to the size of soil without separate washing of sand. The effect of the water content of the soil mixture on solid mixing time and phenanthrene degradation rate was of particular interest. At 20% water content, which was below the saturation level, the mixing efficiency of soil and the degradation rate of phenanthrene was lower than those at 30% or 40% water content. Optimal water content was variable according to the soil texture. The drum bioreactor was operated under optimal water content and PAH concentration (fluorene, phenanthrene, anthracene, pyrene) and microbial numbers were measured in each soil phase (sediment and suspension). Over 95% of PAHs with three or four rings (fluorene, phenanthrene, anthracene, pyrene) were degraded at 270 mg kg⁻¹ soil within 20 days. The degradation rate of PAHs in the suspension phase was higher than that in sediment phase. © 1999 Society of Chemical Industry     

THE SIGNIFICANCE OF POLYCYCLIC AROMATIC HYDROCARBONS AS ENVIRONMENTAL CARCINOGENS. 35 YEARS RESEARCH ON PAH—A RETROSPECTIVE

In vivo studies with laboratory animals as well as in vitro studies with bacteria and mammalian cell cultures have demonstrated that the mutagenic and/or carcinogenic properties of numerous PAHs require metabolic transformation. Metabolism of PAHs has been explored in vitro using cellular microsomal fractions, mammalian cell cultures and later genetically engineered cells expressing cytochromes P450 from several species including humans.

Balancing the carcinogenic potential of some environmental matrices (vehicle exhaust, condensate of hard coal combustion effluents, cigarette smoke condensate, used motor oil) after separation into sub-fractions evidenced that the carcinogenic effect may be attributed almost exclusively to PAH. Mixtures of well-known carcinogenic PAH in concentrations as present in these matrices, however, did not explain the total biological effect. Thus, it had been speculated that either very potent unknown carcinogens are still hidden in the PAH fraction, or that synergistic effects (enzyme induction) play a significant role.

In parallel to these carcinogenicity studies, the metabolism of various PAHs has been investigated in rat liver microsomes from untreated animals as well as from animals pre-treated with inducers of cytochrome P450. It was found that even non-carcinogenic PAHs possess a significant inducing potential. Moreover, in several mammals a highly species-specific metabolism of PAH could be observed allowing a critical view to the extrapolation from animal experiments to the human situation. This was further confirmed by experiments with mammalian cell cultures including human ones as well as by metabolic studies with genetically engineered Chinese hamster V79 cells singularly expressing various cytochrome P450 enzymes from a number of different species (human, rat, mouse, fish). With these cell lines metabolic studies were carried out with a larger number of PAHs as substrates including phenanthrene, pyrene, chrysene, benzo[a]anthracene, benzo[c]phenanthrene, benzo[a]pyrene, dibenzo[a,l]pyrene, and benzo[c]chrysene.

Based on the metabolism results, analytical methods have been developed to determine urinary biomarkers of human PAH exposure. Human biomonitoring studies have been performed with different occupationally exposed individuals as well as within smokers and non-smokers of the general population. Endogenous PAH exposure levels and changes in the urinary excreted metabolic profile depending on exposure level have been determined.     

Adulteration and Presence of Polycyclic Aromatic Hydrocarbons in Extra Virgin Olive Oil Sold on the Brazilian Market

Seventy samples sold in the Brazilian market as extra virgin olive oil (EVOO) were evaluated for the presence of the 13 polycyclic aromatic hydrocarbons (PAH) classified as carcinogenic and genotoxic by the Joint FAO/WHO Expert Committee on Food Additives (JECFA), to verify if the products were adulterated and to evaluate if there is a correlation between PAH presence and adulteration. PAH were detected in 93% of the samples, with summed levels varying from not detected to 41.10 μg/kg. Five samples showed BaP concentration above acceptable levels set by European legislation and by Brazilian regulation (2.0 μg/kg) and 7 presented PAH4 levels above the limit set by European legislation (10.0 µg/kg). The levels of fatty acid composition, sterols content, stigmastadiene and specific extinction did not comply with both Brazilian and International Olive Council (IOC) standards in 18, 31, 30 and 21% of the samples, respectively. The tolerance levels for these analyses in the Brazilian standards are 55.0–83.0 g/100 g (oleic acid), 3.5–21.0 g/100 g (linoleic acid), ≤0.05 g/100 g (trans-oleic acid), ≤0.05 g/100 g (trans-linoleic + trans-linolenic acid), ≤0.15 mg/kg (stigmastadiene), ≤2.50 (K232), ≤0.22 (K270), ≤0.01 (?K), 1000–1600 mg/kg (Σ sterols). Results indicate that 19 samples were adulterated. According to principal component analysis, samples were distinguished as: (1) EVOO with addition of vegetable oil from another source, (2) EVOO with addition of refined oil and (3) samples possibly not adulterated. The variable ΣPAH was related mainly to samples of EVOO with addition of vegetable oil from another source.     

Bioaccumulation of PAHs and Their Hydroxylated Metabolites in Common Carp (Cyprinus Carpio Linnaeus 1758) in Controlled Environment

Abstract

This study aimed to determine the incorporation of PAHs into muscle of Cyprinus carpio. Three model compounds (phenanthrene, pyrene and benzo[a]pyrene) were orally administered during 56 days, in a series of three increasing doses (0, 100, 500 μg of each PAHs per kg of fish). PAHs and their hydroxylated metabolites were analyzed by a HPLC-Fluorimetry method. Results of this study showed a significant increase of phenanthrene and pyrene in muscle. Benzo[a]pyrene incorporation to muscle was not effective. Concerning hydroxylated metabolites, they were not detected in muscle of carp. Steady states for phenanthrene and pyrene were obtained after 28 days of exposure. Low incorporation to muscle was observed at equilibrium for phenanthrene (6% and 3%) and pyrene (3% and 1%), depending of the dose tested.     

Major gaseous and PAH emissions from a fluidized-bed combustor firing rice husk with high combustion efficiency

This experimental work investigated major gaseous (CO and NO_x) and PAH emissions from a 400 kW_th fluidized-bed combustor with a cone-shaped bed (referred to as ‘conical FBC’) firing rice husk with high, over 99%, combustion efficiency. Experimental tests were carried out at the fuel feed rate of 80 kg/h for different values of excess air (EA). As revealed by the experimental results, EA had substantial effects on the axial CO and NO_x concentration profiles and corresponding emissions from the combustor. The concentration (mg/kg-ash) and specific emission (μg/kW h) of twelve polycyclic aromatic hydrocarbons (PAHs), acenaphthylene, fluorene, phenanthrene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene and indeno[1,2,3-cd]pyrene, were quantified in this work for different size fractions of ash emitted from the conical FBC firing rice husk at EA = 20.9%. The total PAHs emission was found to be predominant for the coarsest ash particles, due to the effects of a highly developed internal surface in a particle volume. The highest emission was shown by acenaphthylene, 4.1 μg/kW h, when the total yield of PAHs via fly ash was about 10 μg/kW h.     

POLYCYCLIC AROMATIC HYDROCARBONS ANALYZED IN RAINWATER COLLECTED ON TWO SITES IN EAST OF FRANCE (STRASBOURG AND ERSTEIN)

Polycyclic Aromatic Hydrocarbons (naphtalene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[j]fluoranthene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylène, indeno[1,2,3-c,d]pyrene and coronene) have been consecutively analyzed in rainwater sampled in Strasbourg (urban site) and Erstein (rural site) between January 2002 and June 2003 and between April 2002 and June 2003 on a weekly basis respectively. For the sampling of rainwater, a wet-only rainwater sampler was used together with an open collector to take the measurements of precipitation.

PAHs in rainwater were extracted by using SPE cartridges and analyzed by HPLC-fluorescence following a method developed in the laboratory.

Mean concentrations of all PAHs (Σ 16 HAPs) varied between 0.15 and 79.60 ng·L^?1 in Erstein, and between 3.70 and 1596.45 ng·L^?1 in Strasbourg. Naphtalene, phenanthrene, fluoranthene, pyrene, chrysene, benzo[j]fluoranthne and benzo[a]pyrene were the most concentrated PAHs analyzed. Benzo[a]pyrene was frequently detected. Seasonal effects were observed with a maximum of concentrations of PAHs during cold periods. Some spatial influences were also reported. The calculation of some PAH ratios show that diesel exhaust could be the main source of PAHs in rainwater on the two sites.     

POLYCYCLIC AROMATIC HYDROCARBON REFERENCE RANGE LEVELS IN THE U.S. POPULATION BY MEASUREMENT OF URINARY MONOHYDROXY METABOLITES

We developed a gas chromatography/isotope dilution high- resolution mass spectrometry (GC/ID-HRMS) method for measuring 18 PAH metabolites representing 8 parent PAHs in 3 mL of urine at low part-per-trillion levels. We applied this method to the analysis of urine specimens from approximately 2400 people who participated in the National Health and Nutrition Examination Survey for the years 1999 and 2000 to determine levels for 14 PAH hydroxy metabolites of 7 parent compounds. Using this GC/ID-HRMS method, we found detectable concentrations for monohydroxy metabolite isomers of fluorene, phenanthrene, fluoranthene, and pyrene, and for chrysene, benzo[c]phenanthrene, and benz[a]anthracene. Some monohydroxy metabolite isomers of chrysene, benzo[c]phenanthrene, and benz[a]anthracene exhibited low detection frequencies which did not allow for geometric mean calculations. From our study, we established a reference range for the targeted PAHs in the general U.S. population.     

DETERMINATION OF DIBENZO[A,L]PYRENE AND OTHER FJORD-REGION PAH ISOMERS WITH MW 302 IN ENVIRONMENTAL SAMPLES

Polycyclic aromatic hydrocarbons (PAHs) occur in the environment as complex mixtures including compounds with mutagenic and carcinogenic activity. The PAH profile routinely determined in environmental samples at present encompasses isomers with molecular weight (MW) not greater than 300. However, PAHs with MW >300 have been demonstrated for several matrices to contribute up to 50% of the total activity when tested for carcinogenicity in experimental animals. Recent studies indicate that among the dibenzopyrenes with MW 302 dibenzo[a,l]pyrene, possessing a fjord region, is by far the most carcinogenic PAH hitherto identified. To further elucidate the environmental relevance of this compound we have applied the isotope dilution GC/MS technique as analytical procedure to determine this compound and the related fjord region PAH naphtho[1,2-a]- and naphtho[1,2-e]pyrene in various matrices. Identification was based on comparison of UV and mass spectra as well as retention times of authentic reference materials. Determination of these PAHs was achieved after clean-up by several chromatographic steps including fractionation on a modified TABA-silica gel column. Quantitative data for matrices such as two cigarette smoke condensates, motor vehicle exhaust condensate (Otto-type engines), and tar-cork are reported. Based on toxic equivalent factors the relative contribution of dibenzo[a,l]pyrene (5.4–42.3%) to the total carcinogenic activity of a PAH profile will be discussed comprising 14 selected isomers (benzo[b]naphtho[2,1-d]thiophene; cyclopenta[cd]pyrene; benz[a]anthracene; chrysene/triphenylene; sum of benzo[b]-, benzo[k]-, and benzo[j]fluoranthene; benzo[a]pyrene; indeno[1,2,3-cd]pyrene; dibenz[a,h]anthracene; benzo[ghi]perylene; anthanthrene; dibenzo[a,l]pyrene determined in these matrices.