Polycyclic aromatic hydrocarbons in commercial brands of dry whole soybeans for direct human consumption.

PubMed

Garcia, Laura Pereira; Gomes, Fernanda M L; Tfouni, Silvia; Vicente, Eduardo; Savi, Geovana D; Santos, Karolina; Scussel, Vildes M

2017-03-01

A total of 13 polycyclic aromatic hydrocarbons (PAHs) were surveyed in dry whole soybeans (Glycine max L.) sold for human consumption. The analysed samples were commercialised in vegetarian shops and food stores in Southern Brazil regions. The determination of PAHs levels was carried out by high performance liquid chromatography (HPLC)with fluorescence detection. PAHs were present in 89.7% of the samples. Chrysene (Chy) and 5 methyl chrysene (5MeChy) were the main PAHs detected (76.9% and 71.8%, respectively) followed by dibenzo(ai)pyrene (DaiP), however in a much less percentage of samples (23.1%). Apart from those PAHs, also benzo(a)antracene (BaA), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF) and benzo(a)pyrene(BaP) were found. The ΣPAH levels in the positive samples ranged from 0.80 to 38.78 µg kg -1 , with exception of one sample that reached 204.46 µg kg -1 (ΣPAHs of six compounds). Despite the present contamination there are no maximum limits set for PAHs in soybeans.

The anharmonic quartic force field infrared spectra of five non-linear polycyclic aromatic hydrocarbons: Benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene

NASA Astrophysics Data System (ADS)

Mackie, Cameron J.; Candian, Alessandra; Huang, Xinchuan; Maltseva, Elena; Petrignani, Annemieke; Oomens, Jos; Mattioda, Andrew L.; Buma, Wybren Jan; Lee, Timothy J.; Tielens, Alexander G. G. M.

2016-08-01

The study of interstellar polycyclic aromatic hydrocarbons (PAHs) relies heavily on theoretically predicted infrared spectra. Most earlier studies use scaled harmonic frequencies for band positions and the double harmonic approximation for intensities. However, recent high-resolution gas-phase experimental spectroscopic studies have shown that the harmonic approximation is not sufficient to reproduce experimental results. In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs, showing the importance of including anharmonicities into the theoretical calculations. In this paper, we continue this work by extending the study to include five non-linear PAHs (benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene), thereby allowing us to make a full assessment of how edge structure, symmetry, and size influence the effects of anharmonicities. The theoretical anharmonic spectra are compared to spectra obtained under matrix isolation low-temperature conditions, low-resolution, high-temperature gas-phase conditions, and high-resolution, low-temperature gas-phase conditions. Overall, excellent agreement is observed between the theoretical and experimental spectra although the experimental spectra show subtle but significant differences.

Polycyclic aromatic hydrocarbons content and fatty acids profile in coconut, safflower, evening primrose and linseed oils.

PubMed

Silva, Simone Alves da; Torres, Elizabeth A F da Silva; Almeida, Adriana Palma de; Sampaio, Geni Rodrigues

2018-04-15

This study aimed at evaluating the polycyclic aromatic hydrocarbons (PAHs) contamination of commercial vegetable oils and examined the identity through the fatty acids profiles. Coconut, safflower, evening primrose, and linseed oils marketed in São Paulo (Brazil) were investigated totaling 69 samples. Four PAHs, benzo[a]anthracene (BaA), chrysene (Chr), benzo[b]fluoranthene (BbF), and benzo[a]pyrene (BaP), were detected in 96% of the samples at individual levels ranging from not detected to 14.99 μg kg -1 . Chrysene was the abundant hydrocarbon found among all types of oils, with the highest median values. The results of the fatty acid profiles revealed that 43% showed different profiles according to the ones on their labels, with a higher incidence of adulteration of evening primrose oils. The maximum tolerable limits by European Regulation No. 835/2011 were exceeded for BaP in 12%, and for total 4 PAHs in 28%, with a greater contribution of adulterated samples. Copyright © 2017. Published by Elsevier Ltd.

The anharmonic quartic force field infrared spectra of five non-linear polycyclic aromatic hydrocarbons: Benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene.

PubMed

Mackie, Cameron J; Candian, Alessandra; Huang, Xinchuan; Maltseva, Elena; Petrignani, Annemieke; Oomens, Jos; Mattioda, Andrew L; Buma, Wybren Jan; Lee, Timothy J; Tielens, Alexander G G M

2016-08-28

The study of interstellar polycyclic aromatic hydrocarbons (PAHs) relies heavily on theoretically predicted infrared spectra. Most earlier studies use scaled harmonic frequencies for band positions and the double harmonic approximation for intensities. However, recent high-resolution gas-phase experimental spectroscopic studies have shown that the harmonic approximation is not sufficient to reproduce experimental results. In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs, showing the importance of including anharmonicities into the theoretical calculations. In this paper, we continue this work by extending the study to include five non-linear PAHs (benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene), thereby allowing us to make a full assessment of how edge structure, symmetry, and size influence the effects of anharmonicities. The theoretical anharmonic spectra are compared to spectra obtained under matrix isolation low-temperature conditions, low-resolution, high-temperature gas-phase conditions, and high-resolution, low-temperature gas-phase conditions. Overall, excellent agreement is observed between the theoretical and experimental spectra although the experimental spectra show subtle but significant differences.

Chrysen-2-ol derivative from West Indian Wood Nettle Laportea aestuans (L.) Chew inhibits oxidation and microbial growth in vitro

PubMed Central

Oloyede, Ganiyat K.; Oyelola, Martha S.

2013-01-01

Bio-active compounds present in West Indian Wood Nettle Laportea aestuans (L.) Chew (Urticaceae), used in ethno medicine as antioxidant and antimicrobial were studied. The aim of this research work was to isolate and characterize the bio-active compounds in the n-hexane fraction of L. aestuans, determine the toxicity and subject it to in-vitro antimicrobial and free radical scavenging activities. The chemical constituents were isolated by gradient elution column chromatographic technique and Ultra Violet/visible (UV), Infrared (IR) and Nuclear Magnetic Resonance (NMR) spectroscopies were used for structural elucidation. The free radical scavenging activity of the isolate was assessed using three methods; scavenging effect on 2,2-diphenyl-1-picrylhydrazyl radical (DPPH), hydroxyl radical generated from hydrogen peroxide and ferric thiocynate method. Antimicrobial screening was done by agar well diffusion method while toxicity was determined by Brine shrimp lethality test. Structures were proposed for the white crystalline solids isolated; (4E)-3,6-dimethylhep-4-en-3-ol (AB) and 1,2,3,4,4a,4b,5,6,6a,7,8,9,10,10a,10b,11-hexadecahydro-1,1,6a,10b-tetramethyl-7-((E)-4,7-dimethyloct-5-enyl) chrysen-2-ol (AC). Percentage yield of AC was 91.2 and was non-toxic with LC50 (µg/ml) value of 1581233000.0. AC significantly scavenged free radical at 0.0625 mg/ml in the DPPH (64.73 %) and hydrogen peroxide (99.22 %) tests. It also showed 65.23 % inhibition at 1.0 mg/ml in the ferric thiocyanate test. AC also inhibited microbial growth significantly when compared with gentamicin and tioconazole which are antibacterial and antifungal standards respectively. The presence of Chrysen-2-ol derivative in L. aestuans which was non-toxic and possessed significant antimicrobial and antioxidant activities supports its ethno medicinal application. PMID:27092035

Identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons in a complex mixture of polycyclic aromatic hydrocarbons from coal tar.

PubMed

Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara; Wise, Stephen A

2016-04-15

A methodology for the characterization of groups of polycyclic aromatic hydrocarbons (PAHs) using a combination of normal phase liquid chromatography with ultraviolet-visible spectroscopy (NPLC/UV-vis) and gas chromatography with mass spectrometry (GC/MS) was used for the identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons, PAHs, in standard reference material (SRM) 1597a, complex mixture of PAHs from coal tar. The NPLC/UV-vis isolated the fractions based on the number of aromatic carbons and the GC/MS allowed the identification and quantification of five of the nine C26H14 PAH isomers; naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene using a retention time comparison with authentic reference standards. For the other four benzenoid isomers with no available reference standards the following two approaches were used. First, the annellation theory was used to achieve the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene, and second, the elution distribution in the GC fractions was used to support the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene and to reach the tentative identifications of dibenzo[a,ghi]perylene, naphtho[7,8,1,2,3-pqrst]pentaphene, and anthra[2,1,9,8-opqra]naphthacene. It is the first time that naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene are quantified, and the first time that benzo[qr]naphtho[3,2,1,8-defg]chrysene is potentially identified, in any sample, in any context. Copyright © 2016 Elsevier B.V. All rights reserved.

In vitro metabolism of benzo[a]pyrene-7,8-dihydrodiol and dibenzo[def,p]chrysene-11,12 diol in rodent and human hepatic microsomes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Jordan N.; Mehinagic, Denis; Nag, Subhasree

Polycyclic aromatic hydrocarbons (PAHs) are contaminants that are ubiquitously found in the environment, produced through combustion of organic matter or petrochemicals, and many of which are procarcinogens. The prototypic PAH, benzo[a]pyrene (B[a]P) and the highly carcinogenic dibenzo[def,p]chrysene (DBC) are metabolically activated by isoforms of the P450 enzyme superfamily producing benzo[a]pyrene-7,8-dihydrodiol (B[a]P diol), dibenzo[def,p]chrysene-11,12 diol (DBC diol). Each of these diols can be further metabolized by cytochrome P450 enzymes to highly reactive diol-epoxide metabolites that readily react with DNA or by phase II conjugation facilitating excretion. To complement prior in vitro metabolism studies with parent B[a]P and DBC, both phase Imore » metabolism and phase II glucuronidation of B[a]P diol and DBC diol were measured in hepatic microsomes from female B6129SF1/J mice, male Sprague-Dawley rats, and female humans. Metabolic parameters, including intrinsic clearance and Michaelis-Menten kinetics were calculated from substrate depletion data. Mice and rats demonstrated similar B[a]P diol phase I metabolic rates. Compared to rodents, human phase I metabolism of B[a]P diol demonstrated lower overall metabolic capacity, lower intrinsic clearance at higher substrate concentrations (>0.14 µM), and higher intrinsic clearance at lower substrate concentrations (<0.07 µM). Rates of DBC diol metabolism did not saturate in mice or humans and were highest overall in mice. Higher affinity constants and lower capacities were observed for DBC diol glucuronidation compared to B[a]P diol glucuronidation; however, intrinsic clearance values for these compounds were consistent within each species. Kinetic parameters reported here will be used to extend physiologically based pharmacokinetic (PBPK) models to include the disposition of B[a]P and DBC metabolites in animal models and humans to support future human health risk assessments.« less

40 CFR Appendix J to Part 122 - NPDES Permit Testing Requirements for Publicly Owned Treatment Works (§ 122.21(j))

Code of Federal Regulations, 2012 CFR

2012-07-01

...-ethylhexyl) phthalate 4-bromophenyl phenyl ether Butyl benzyl phthalate 2-chloronaphthalene 4-chlorophenyl phenyl ether Chrysene Di-n-butyl phthalate Di-n-octyl phthalate Dibenzo(a,h)anthracene 1,2-dichlorobenzene 1,3-dichlorobenzene 1,4-dichlorobenzene 3,3-dichlorobenzidine Diethyl phthalate Dimethyl phthalate...

PROPOSED PROCEDURE FOR DERIVATION OF REGULATORY VALUES FOR CARCINOGENIC AIRBORNE POLYCYCLIC AROMATIC HYDROCARBONS (PAHS) BASED ON COAL TAR PITCH (CTP) VOLATILES

EPA Science Inventory

A procedure for estimating upper bound lifetime human cancer risk from air levels of 6 common carcinogenic PAHs, termed "PAHs of concern", is proposed. These PAHs are benzo(a)pyrene, benz(a)anathracene, benzo(k)flouranthene, indeno(1,2,3-c,d)pyrene and chrysene. In application,...

Synthesis, crystal structure and photo physical properties of isomeric fluorinated s-shaped polyaromatic dibenzo[c,l]chrysene derivatives

NASA Astrophysics Data System (ADS)

Moriguchi, Tetsuji; Tabuchi, Daichi; Yakeya, Daisuke; Tsuge, Akihiko; Jalli, Venkataprasad; Yoza, Kenji

2018-01-01

Two s-shaped fluorinated isomeric polyaromatic dibenzo[c,l]chrysene derivatives have been synthesized by a two step process using the Wittig, Heck and iodine promoted cyclization reactions. These cyclized compounds were characterized by 1H NMR and EI-MS. Further, absolute configurations of isomeric 4a and 4b were determined by X-ray diffraction analysis. Compound 4a crystallized under monoclinic system with space group P21/c and compound 4b crystallized under monoclinic system with space group Cc. They have good solubility in common organic solvents such as dichloromethane, chloroform and THF. Photophysical properties of 4a and 4b were evaluated by using UV-Visible and Fluorescence spectrophotometer. Compounds 4a and 4b showed strong absorption maximum wavelength at 317 nm. The emission spectra of 4a and 4b displayed sharp peaks in the visible region from 417 to 441 nm. The shape of the UV-Visible and Fluorescence spectra of 4a and 4b looks almost identical. But compound 4a exhibited better fluorescence intensity than compound 4b. This difference may be due to the difference in the configuration of compounds 4a and 4b.

EU marker polycyclic aromatic hydrocarbons in food supplements: analytical approach and occurrence

PubMed Central

Zelinkova, Zuzana; Wenzl, Thomas

2015-01-01

Several food supplements comprising botanical, oil and bee products collected from retail markets in different countries were tested for the occurrence of 4 EU marker Polycyclic aromatic hydrocarbons (PAHs; benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene). A robust GC/MS-based stable-isotope dilution method was used taking into account the differences in the type of matrices. The accuracy of the results was assessed by implementing several quality control tools. Sixty-eight samples of 94 analysed products exceeded the level of 0.5 μg/kg for the sum of the four EU marker PAHs (ΣPAH4). Benzo[a]pyrene exceeded the limit of quantification in 49 samples. The PAH with the highest abundance in all products was chrysene. On average, propolis extracts and other bee products showed relatively high levels of ΣPAH4 (mean 188.2 μg/kg), whereas the contamination levels of fish oil supplements were very low or mostly undetectable. Considerably high ΣPAH4 amounts found in some samples could remarkably increase the daily exposure of consumers to PAHs, demonstrating the need for continuous monitoring of ΣPAH4 in food supplements. PMID:26467752

Multi-source apportionment of polycyclic aromatic hydrocarbons using simultaneous linear equations

NASA Astrophysics Data System (ADS)

Marinaite, Irina; Semenov, Mikhail

2014-05-01

A new approach to identify multiple sources of polycyclic aromatic hydrocarbons (PAHs) and to evaluate the source contributions to atmospheric deposition of particulate PAHs is proposed. The approach is based on differences in concentrations of sums of PAHs with the same molecular weight among the sources. The data on PAHs accumulation in snow as well as the source profiles were used for calculations. Contributions of aluminum production plant, oil-fired central heating boilers, and residential wood and coal combustion were calculated using the linear mixing models. The concentrations of PAH pairs such as Benzo[b]fluorantene + Benzo[k]fluorantene and Benzo[g,h,i]perylene + Indeno[1,2,3-c,d]pyrene normalized to Benzo[a]antracene + Chrysene were used as tracers in mixing equations. The results obtained using ratios of sums of PAHs were compared with those obtained using molecular diagnostic ratios such as Benzo[a]antracene/Chrysene and Benzo[g,h,i]perylene/Indeno[1,2,3-c,d]pyrene. It was shown that the results obtained using diagnostic ratios as tracers are less reliable than results obtained using ratios of sums of PAHs. Funding was provided by Siberian Branch of Russian Academy of Sciences grant No. 8 (2012-2014).

Distribution and sources of bioaccumulative air pollutants at Mezquital Valley, Mexico, as reflected by the atmospheric plant Tillandsia recurvata L.

NASA Astrophysics Data System (ADS)

Zambrano García, A.; Medina Coyotzin, C.; Rojas Amaro, A.; López Veneroni, D.; Martínez, L. Chang; Sosa Iglesias, G.

2009-09-01

Mezquital Valley (MV), a Mexican wastewater-based agricultural and industrial region, is a "hot spot" of regulated air pollutants emissions, but the concurrent unregulated ones, like hazardous metals and polycyclic aromatic hydrocarbons (PAH), remain undocumented. A biomonitoring survey with the epiphytic Tillandsia recurvata was conducted there to detect spatial patterns and potential sources of 20 airborne elements and 15 PAH. The natural δ13C and δ15N ratios of this plant helped in source identification. The regional mean concentration of most elements was two (Cr) to over 40 times (Ni, Pb, V) higher than reported for Tillandsia in other countries. Eleven elements, pyrene and chrysene had 18-214% higher mean concentration at the industrial south than at the agricultural north of MV. The total quantified PAH (mean, 572 ng g-1; range, 143-2568) were composed by medium (65%, phenanthrene to chrysene), low (28%, naphthalene to fluorene) and high molecular weight compounds (7%, Benzo(b)fluoranthene to indeno(1,2,3-cd)pyrene). The δ13C (mean, -14.6‰; range, -15.7‰ to -13.7‰) was consistently lower than -15‰ near the major petroleum combustion sources. The δ15N (mean, -3.0‰; range, -9.9‰ to 3.3‰) varied from positive at agriculture/industrial areas to negative at rural sites. Factor analysis provided a five-factor solution for 74% of the data variance: 1) crustal rocks, 39.5% (Al, Ba, Cu, Fe, Sr, Ti); 2) soils, 11.3%, contrasting contributions from natural (Mg, Mn, Zn) and saline agriculture soils (Na); 3) cement production and fossil fuel combustion, 9.8% (Ca, Ni, V, chrysene, pyrene); 4) probable agricultural biomass burning, 8.1% (K and benzo(g,h,i)perylene), and 5) agriculture with wastewater, 5.2% (δ15N and P). These results indicated high deposition of bioaccumulative air pollutants at MV, especially at the industrial area. Since T. recurvata reflected the regional differences in exposition, it is recommended as a biomonitor for comparisons within and among countries where it is distributed: southern USA to Argentina.

Distribution and sources of bioaccumulative air pollutants at Mezquital Valley, Mexico, as reflected by the atmospheric plant Tillandsia recurvata L.

NASA Astrophysics Data System (ADS)

Zambrano García, A.; Medina Coyotzin, C.; Rojas Amaro, A.; López Veneroni, D.; Martínez, L. Chang; Sosa Iglesias, G.

2009-03-01

Mezquital Valley (MV), a Mexican wastewater-based agricultural and industrial region, is a ''hot spot'' of regulated air pollutants emissions, but the concurrent unregulated ones, like hazardous metals and polycyclic aromatic hydrocarbons (PAH), remain undocumented. A biomonitoring survey with the epiphytic Tillandsia recurvata was conducted there to detect spatial patterns and potential sources of 20 airborne elements and 15 PAH. The natural δ13C and δ15N ratios of this plant helped in source identification. The regional mean concentrations of most elements was two (Cr) to over 40 times (Ni, Pb, V) higher than reported for Tillandsia in other countries. Eleven elements, pyrene and chrysene had 18-214% higher mean concentration at the industrial south than at the agricultural north of MV. The total quantified PAH (mean, 572 ng g-1; range, 142.6-2568) were composed by medium (65%, phenanthrene to chrysene), low (28%, naphthalene to fluorene) and high molecular weight compounds (7%, Benzo(b)fluoranthene to indeno(1,2,3-cd)pyrene). The δ13C (mean, -14.6‰; range, -5.7 to -13.7‰) was lower (<-15‰) near the major petroleum combustion sources. The δ15N (mean, -3.0‰; range, -9.9 to 3.3‰) varied from positive at agriculture/industrial areas to negative at rural sites. Factor analysis provided a five-factor solution for 74% of the data variance: (1) crustal rocks, 39.5% (Al, Ba, Cu, Fe, Sr, Ti); (2) soils, 11.3%, contrasting contributions from natural (Mg, Mn, Zn) and saline agriculture soils (Na); (3) cement production and fossil fuel combustion, 9.8% (Ca, Ni, V, chrysene, pyrene); (4) probable agricultural biomass burning, 8.1% (K and benzo(g,h,i)perylene), and (5) agriculture with wastewater, 5.2% (δ15N and P). These results indicated high deposition of bioaccumulative air pollutants at MV, especially at the industrial area. Since T. recurvata reflected the regional differences in exposition, it is recommended as a biomonitor for comparisons within and among countries where it is distributed: southern USA to Argentina.

Polycyclic aromatic hydrocarbons as skin carcinogens: Comparison of benzo[a]pyrene, dibenzo[def,p]chrysene and three environmental mixtures in the FVB/N mouse

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siddens, Lisbeth K.; Larkin, Andrew; Superfund Research Center, Oregon State University

2012-11-01

The polycyclic aromatic hydrocarbon (PAH), benzo[a]pyrene (BaP), was compared to dibenzo[def,p]chrysene (DBC) and combinations of three environmental PAH mixtures (coal tar, diesel particulate and cigarette smoke condensate) using a two stage, FVB/N mouse skin tumor model. DBC (4 nmol) was most potent, reaching 100% tumor incidence with a shorter latency to tumor formation, less than 20 weeks of 12-O-tetradecanoylphorbol-13-acetate (TPA) promotion compared to all other treatments. Multiplicity was 4 times greater than BaP (400 nmol). Both PAHs produced primarily papillomas followed by squamous cell carcinoma and carcinoma in situ. Diesel particulate extract (1 mg SRM 1650b; mix 1) did notmore » differ from toluene controls and failed to elicit a carcinogenic response. Addition of coal tar extract (1 mg SRM 1597a; mix 2) produced a response similar to BaP. Further addition of 2 mg of cigarette smoke condensate (mix 3) did not alter the response with mix 2. PAH-DNA adducts measured in epidermis 12 h post initiation and analyzed by {sup 32}P post‐labeling, did not correlate with tumor incidence. PAH‐dependent alteration in transcriptome of skin 12 h post initiation was assessed by microarray. Principal component analysis (sum of all treatments) of the 922 significantly altered genes (p < 0.05), showed DBC and BaP to cluster distinct from PAH mixtures and each other. BaP and mixtures up-regulated phase 1 and phase 2 metabolizing enzymes while DBC did not. The carcinogenicity with DBC and two of the mixtures was much greater than would be predicted based on published Relative Potency Factors (RPFs). -- Highlights: ► Dibenzo[def,p]chrysene (DBC), 3 PAH mixtures, benzo[a]pyrene (BaP) were compared. ► DBC and 2 PAH mixtures were more potent than Relative Potency Factor estimates. ► Transcriptome profiles 12 hours post initiation were analyzed by microarray. ► Principle components analysis of alterations revealed treatment-based clustering. ► DBC gave a unique pattern of gene alterations compared to BaP and PAH mixtures.« less

Preliminary physiologically based pharmacokinetic models for benzo[a]pyrene and dibenzo[def,p]chrysene in rodents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crowell, Susan Ritger, E-mail: Susan.crowell@pnnl.gov; Amin, Shantu G.; Anderson, Kim A.

2011-12-15

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants generated as byproducts of natural and anthropogenic combustion processes. Despite significant public health concern, physiologically based pharmacokinetic (PBPK) modeling efforts for PAHs have so far been limited to naphthalene, plus simpler PK models for pyrene, nitropyrene, and benzo[a]pyrene (B[a]P). The dearth of published models is due in part to the high lipophilicity, low volatility, and myriad metabolic pathways for PAHs, all of which present analytical and experimental challenges. Our research efforts have focused upon experimental approaches and initial development of PBPK models for the prototypic PAH, B[a]P, and the more potent, albeitmore » less studied transplacental carcinogen, dibenzo[def,p]chrysene (DBC). For both compounds, model compartments included arterial and venous blood, flow limited lung, liver, richly perfused and poorly perfused tissues, diffusion limited fat, and a two compartment theoretical gut (for oral exposures). Hepatic and pulmonary metabolism was described for both compounds, as were fractional binding in blood and fecal clearance. Partition coefficients for parent PAH along with their diol and tetraol metabolites were estimated using published algorithms and verified experimentally for the hydroxylated metabolites. The preliminary PBPK models were able to describe many, but not all, of the available data sets, comprising multiple routes of exposure (oral, intravenous) and nominal doses spanning several orders of magnitude. Supported by Award Number P42 ES016465 from the National Institute of Environmental Health Sciences. -- Highlights: Black-Right-Pointing-Pointer We present PBPK models for benzo[a]pyrene (B[a]P) and dibenzo[def,p]chrysene (DBC). Black-Right-Pointing-Pointer B[a]P model accurately predicts data from multiple sources over a wide dose range. Black-Right-Pointing-Pointer DBC model was based on the B[a]P model as less chemical specific data is available. Black-Right-Pointing-Pointer DBC model accurately predicted preliminary pharmacokinetic data. Black-Right-Pointing-Pointer DBC model underscored data gaps on metabolism, binding and pharmacokinetics.« less

In vitro metabolism of benzo[a]pyrene-7,8-dihydrodiol and dibenzo[def,p]chrysene-11,12 diol in rodent and human hepatic microsomes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Jordan N.; Mehinagic, Denis; Nag, Subhasree

Polycyclic aromatic hydrocarbons (PAHs) are contaminants that are ubiquitously found in the environment, produced through combustion of organic matter or petrochemicals, and many of which are procarcinogens. The prototypic PAH, benzo[a]pyrene (B[a]P) and the highly carcinogenic dibenzo[def,p]chrysene (DBC) are metabolically activated by isoforms of the P450 enzyme superfamily producing benzo[a]pyrene-7,8-dihydrodiol (B[a]P diol), dibenzo[def,p]chrysene-11,12 diol (DBC diol). Each of these diols can be further metabolized by cytochrome P450 enzymes to highly reactive diol-epoxide metabolites that readily react with DNA or by phase II conjugation facilitating excretion. To complement prior in vitro metabolism studies with parent B[a]P and DBC, both phase Imore » metabolism and phase II glucuronidation of B[a]P diol and DBC diol were measured in this paper in hepatic microsomes from female B6129SF1/J mice, male Sprague-Dawley rats, and female humans. Metabolic parameters, including intrinsic clearance and Michaelis-Menten kinetics were calculated from substrate depletion data. Mice and rats demonstrated similar B[a]P diol phase I metabolic rates. Compared to rodents, human phase I metabolism of B[a]P diol demonstrated lower overall metabolic capacity, lower intrinsic clearance at higher substrate concentrations (>0.14 μM), and higher intrinsic clearance at lower substrate concentrations (<0.07 μM). Rates of DBC diol metabolism did not saturate in mice or humans and were highest overall in mice. Higher affinity constants and lower capacities were observed for DBC diol glucuronidation compared to B[a]P diol glucuronidation; however, intrinsic clearance values for these compounds were consistent within each species. Finally, kinetic parameters reported here will be used to extend physiologically based pharmacokinetic (PBPK) models to include the disposition of B[a]P and DBC metabolites in animal models and humans to support future human health risk assessments.« less

In vitro metabolism of benzo[a]pyrene-7,8-dihydrodiol and dibenzo[def,p]chrysene-11,12 diol in rodent and human hepatic microsomes

DOE PAGES

Smith, Jordan N.; Mehinagic, Denis; Nag, Subhasree; ...

2017-01-21

Polycyclic aromatic hydrocarbons (PAHs) are contaminants that are ubiquitously found in the environment, produced through combustion of organic matter or petrochemicals, and many of which are procarcinogens. The prototypic PAH, benzo[a]pyrene (B[a]P) and the highly carcinogenic dibenzo[def,p]chrysene (DBC) are metabolically activated by isoforms of the P450 enzyme superfamily producing benzo[a]pyrene-7,8-dihydrodiol (B[a]P diol), dibenzo[def,p]chrysene-11,12 diol (DBC diol). Each of these diols can be further metabolized by cytochrome P450 enzymes to highly reactive diol-epoxide metabolites that readily react with DNA or by phase II conjugation facilitating excretion. To complement prior in vitro metabolism studies with parent B[a]P and DBC, both phase Imore » metabolism and phase II glucuronidation of B[a]P diol and DBC diol were measured in this paper in hepatic microsomes from female B6129SF1/J mice, male Sprague-Dawley rats, and female humans. Metabolic parameters, including intrinsic clearance and Michaelis-Menten kinetics were calculated from substrate depletion data. Mice and rats demonstrated similar B[a]P diol phase I metabolic rates. Compared to rodents, human phase I metabolism of B[a]P diol demonstrated lower overall metabolic capacity, lower intrinsic clearance at higher substrate concentrations (>0.14 μM), and higher intrinsic clearance at lower substrate concentrations (<0.07 μM). Rates of DBC diol metabolism did not saturate in mice or humans and were highest overall in mice. Higher affinity constants and lower capacities were observed for DBC diol glucuronidation compared to B[a]P diol glucuronidation; however, intrinsic clearance values for these compounds were consistent within each species. Finally, kinetic parameters reported here will be used to extend physiologically based pharmacokinetic (PBPK) models to include the disposition of B[a]P and DBC metabolites in animal models and humans to support future human health risk assessments.« less

The Predictive Power of the Annellation Theory: The Case of the C26H16 Cata-Condensed Benzenoid Polycyclic Aromatic Hydrocarbons.

PubMed

Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara

2015-10-22

The Annellation Theory was applied to establish the locations of maximum absorbance for the p and β bands in the UV-vis spectra of eight benzenoid cata-condensed polycyclic aromatic hydrocarbons (PAHs) with molecular formula C26H16 and no available syntheses procedures. In this group of eight isomers, there are seven compounds with potential carcinogenic properties due to geometrical constraints. In addition, crude oil and asphaltene absorption spectra exhibit similar properties, and the PAHs in heavier crude oils and asphaltenes are known to be the source of the color of heavy oils. Therefore, understanding the electronic bands of PAHs is becoming increasingly important. The methodology was validated using information for the remaining 29 isomers with available UV-vis spectra. The results satisfactorily agree with the results from semiempirical calculations made using the ZINDO/S approach. The locations of maximum absorbance for the p and β bands in the UV-vis spectra of the eight C26H16 cata-condensed isomers dibenzo[c,m]tetraphene, naphtho[1,2-c]chrysene, dibenzo[c,f]tetraphene, benzo[f]picene, naphtho[2,1-a]tetraphene, naphtho[2,1-c]tetraphene, dibenzo[c,l]chrysene, and naphtho[1,2-a]tetraphene were established for the first time.

Combination of Liquid Chromatography with Multivariate Curve Resolution-Alternating Least-Squares (MCR-ALS) in the Quantitation of Polycyclic Aromatic Hydrocarbons Present in Paprika Samples.

PubMed

Monago-Maraña, Olga; Pérez, Rocío L; Escandar, Graciela M; Muñoz de la Peña, Arsenio; Galeano-Díaz, Teresa

2016-11-02

This work presents a strategy for quantitating polycyclic aromatic hydrocarbons (PAHs) in smoked paprika samples. For this, a liquid chromatographic method with fluorimetric detection (HPLC-FLD) was optimized. To resolve some interference co-eluting with the target analytes, the second-order multivariate curve resolution-alternating least-squares (MCR-ALS) algorithm has been employed combined with this liquid chromatographic method. Among the eight PAHs quantified (fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene) by HPLC-FLD, only in the case of fluorene, pyrene, and benzo[b]fluoranthene was it necessary to apply the second-order algorithm for their resolution. Limits of detection and quantitation were between 0.015 and 0.45 mg/kg and between 0.15 and 1.5 mg/kg, respectively. Good recovery results (>80%) for paprika were obtained via the complete extraction procedure, consisting of an extraction from the matrix and the cleanup of the extract by means of silica cartridges. Higher concentrations of chrysene, benzo[a]anthracene, benzo[b]fluoranthene, and benzo[a]pyrene were found in the paprika samples, with respect to the maximal amounts allowed for other spices that are under European Regulation (EU) N° 2015/1933.

An In Silico Study on the Isomers of Pentacene: The Case for Air-Stable and Alternative C22H14 Acenes for Organic Electronics.

PubMed

Jones, Leighton; Lin, Long

2017-04-13

Pentacene is one of the most investigated candidates for organic thin film transistor (OTFT) applications over the last few decades even though it unstable in air (E g = 1.80 eV), owing in part to its planar nature and high charge-transfer mobilities as both a single crystal (35 cm 2 V -1 s -1 ) and as a thin-film (3.0 cm 2 V -1 s -1 ). Until now, picene is the only isomer of pentacene to be investigated for organic electronic applications, due to its greater stability (E g = 4.21 eV) and high-charge transfer mobility (3.0 cm 2 V -1 s -1 ); even benefiting from oxygen doping. In the present study, a total of 12 fused-ring isomers (including pentacene, picene and ten other structures) of the formula C 22 H 14 were analyzed and investigated for their electronic and optical properties for worth in OTFT applications. We screened several pure and hybrid DFT functionals against the experimental frontier molecular orbitals (FMOs) of pentacene, then deployed Marcus Theory, Koopmans' Theorem and Green's function with the P3 electron propagator variant, for the internal hole reorganization energy, the hole transfer integral (via the "splitting-in-dimer method" at d = 3.0, 3.5, and 4.0 Å), the charge transfer rate constant, and vertical ionization energies. Using these as a basis, we studied pentacene's isomers and found that the four nonplanar structures, namely, benzo[g]chrysene (3), naphtho[c]phenanthrene (7), benzo[c]chrysene (11) and dibenzo[c,c']phenthrene (12), are (I) more stable than pentacene, by up to 2 eV, and (II) have relatively similar ionization energies (7.5-7.6 eV) to those of picene's experimental value (7.51 eV). The largest charge transfer rates at 3.5 Å dimer separations were given by the isomers benzo[b]chrysene 4, naphtha[c]phenanthrene 7, dibenzo[a,c]anthracene 8 and benzo[a]tetracene 10 and found to be 2.92, 1.72, 1.30, and 3.09 × 10 14 s -1 respectively. In comparison to that of pentacene (K CT = 3.97 × 10 14 s -1 ), these unusual isomers are thus promising air-stable and alternative candidates for organic electronic applications.

Hydroxypropyl cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimers as effective carbohydrate-solubilizers for polycyclic aromatic hydrocarbons.

PubMed

Choi, Jae Min; Jeong, Daham; Piao, Jinglan; Kim, Kyoungtea; Nguyen, Andrew Bao Loc; Kwon, Nak-Jung; Lee, Mi-Kyung; Lee, Im Soon; Yu, Jae-Hyuk; Jung, Seunho

2015-01-12

The removal of polycyclic aromatic hydrocarbons by soil washing using water is extremely difficult due to their intrinsic hydrophobic nature. In this study, the effective aqueous solubility enhancements of seven polycyclic aromatic hydrocarbons by chemically modified hydroxypropyl rhizobial cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimer have been investigated for the first time. In the presence of hydroxypropyl cyclic β-(1 → 2)-D-glucans, the solubility of benzo[a]pyrene is increased up to 38 fold of its native solubility. The solubility of pyrene and phenanthrene dramatically increased up to 160 and 359. Coronene, chrysene, perylene, and fluoranthene also show an increase of 11, 23, 23, and 97 fold, respectively, of enhanced solubility by complexation with synthetic epichlorohydrin β-cyclodextrin dimer. The physicochemical properties of the complex are characterized by Fourier-transform infrared spectra and differential scanning calorimetry. Utilizing a scanning electron microscopy, the morphological structures of native benzo[a]pyrene, pyrene, phenanthrene, coronene, chrysene, perylene, fluoranthene and their complex with novel carbohydrate-solubilizers are studied. These results elucidate that polycyclic aromatic hydrocarbons are able to form an efficient complex with hydroxypropyl cyclic β-(1 → 2)-D-glucans and β-cyclodextrin dimer, suggesting the potential usage of chemically modified novel carbohydrate-solubilizers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Distribution of polycyclic aromatic hydrocarbons in riverine waters after Mediterranean forest fires.

PubMed

Olivella, M A; Ribalta, T G; de Febrer, A R; Mollet, J M; de Las Heras, F X C

2006-02-15

Extensive forest fires occurred in Catalonia, northern Spain, in 1994. In our study, concentrations and profiles of 12 parent polycyclic aromatic hydrocarbons (PAHs) were determined in riverine waters, ash and sediment samples at nine sampling sites (W1-W9) and at three sampling dates from Llobregat hydrographic basin: in August, 1994, one month after the extensive forest fires; in September, 1994, after the first heavy autumn rainfalls and in January, 1995, six months after forest fires. In August 1994, the total concentrations of 12 PAHs measured in riverine waters varied from 2 ng/l to 336 ng/l. In September 1994, the total PAH concentrations decreased to 0.2-31 ng/l and in January 1995, from 9 ng/l to 73 ng/l. In August, the composition pattern of PAHs showed a distribution dominated by 4-ring PAHs (pyrene, chrysene+triphenylene, benzo(a)anthracene) at W3-W6, W8 and W9 and 3-ring PAHs (phenanthrene) at W1, W2 and W7. In September, a preference by 3-ring PAHs (phenanthrene) at all sampling sites except W5 was shown and in January was clearly dominated by 4-ring PAHs (chrysene+triphenylene, pyrene, benzo(a)anthracene) at all sampling sites. In ash and sediment samples, the total concentrations of 12 PAHs ranged from 1.3 ng/g to 19 ng/g. The dominant compound was phenanthrene.

Characterization of polycyclic aromatic hydrocarbons in fugitive PM10 emissions from an integrated iron and steel plant.

PubMed

Khaparde, V V; Bhanarkar, A D; Majumdar, Deepanjan; Rao, C V Chalapati

2016-08-15

Fugitive emissions of PM10 (particles <10μm in diameter) and associated polycyclic aromatic hydrocarbons (PAHs) were monitored in the vicinity of coking unit, sintering unit, blast furnace and steel manufacturing unit in an integrated iron and steel plant situated in India. Concentrations of PM10, PM10-bound total PAHs, benzo (a) pyrene, carcinogenic PAHs and combustion PAHs were found to be highest around the sintering unit. Concentrations of 3-ring and 4-ring PAHs were recorded to be highest in the coking unit whereas 5-and 6-ring PAHs were found to be highest in other units. The following indicatory PAHs were identified: indeno (1,2,3-cd) pyrene, dibenzo (a,h) anthracene, benzo (k) fluoranthene in blast furnace unit; indeno (1,2,3-cd) pyrene, dibenzo (a,h) anthracene, chrysene in sintering unit; Anthracene, fluoranthene, chrysene in coking unit and acenaphthene, fluoranthene, fluorene in steel making unit. Total-BaP-TEQ (Total BaP toxic equivalent quotient) and BaP-MEQ (Total BaP mutagenic equivalent quotient) concentration levels ranged from 2.4 to 231.7ng/m(3) and 1.9 to 175.8ng/m(3), respectively. BaP and DbA (dibenzo (a,h) anthracene) contribution to total-BaP-TEQ was found to be the highest. Copyright © 2016 Elsevier B.V. All rights reserved.

Embryotoxic and teratogenic effects of petroleum hydrocarbons in mallards (Anas platyrhynchos)

USGS Publications Warehouse

Hoffman, D.J.

1979-01-01

Egg surface applications of microliter quantities of crude and refined oils of high aromatic content are embryotoxic to mallards (Anas platyrhynchos) and other avian species; applications of aliphatic hydrocarbons have virtually no effect. Mallard eggs at 72 h of development were exposed to a mixture of aromatic hydrocarbons or to aromatic compounds representative to those present in crude oil to assess their toxicity. The class composition of the mixture was similar to that of South Louisiana crude oil, an American Petroleum Institute reference oil. Application of 20 microliter of the mixture reduced embryonic survival by nearly 70%. The temporal pattern of embryonic death was similar to that after exposure to South Louisiana crude oil. Embryonic growth was stunted, as reflected by weight, crown-rump length, and bill length, and there was a significant increase in the incidence of abnormal survivors. When individual classes of aromatic hydrocarbons were tested, tetracyclics caused some embryonic death at the concentrations in the mixture. When classes were tested in all possible combinations of two, no combination appeared to be as toxic as the entire mixture. Addition of the tetracyclic compound chrysene to the aromatic mixture considerably enhanced embryotoxicity, but could not completely account for the toxicity of the crude oil. The presence of additional unidentified polycyclic aromatic hydrocarbons as well as methylated derivatives of polycyclic aromatic compounds such as chrysene may further account for the embryotoxicity of the crude oil.

Synthesis of Potential Metaboliters in the 1,2,3,4, and 5,6,7,8 Benzo Ring Positions of the Polycyclic Aromatic Hydrocarbon Benzo(G)Chrysene.

DTIC Science & Technology

1986-01-01

biological activity. Pullman, in 1945 , noted that active compounds contained angular benzo rings. She introduced the terminology "K- region" to refer to...Figure 1.6) give .... ~~~~~. .. .. .. . ........ . _............ . _.-.•.-•.. . ..... ... ,. 12 .xcellent correlation when measured reactivity ( hydrolysis ...molecular plane, the diol epoxide is trans or series 2. Early studies indicated that isomer 1 is the more reactive diol epoxide in hydrolysis reactions

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

PubMed Central

Tian, Zhenyu; Pitz, William J.; Fournet, René; Glaude, Pierre-Alexander; Battin-Leclerc, Frédérique

2013-01-01

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C4 + C2 species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C6H4CH3 radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C6H4CH3 radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics. PMID:23762016

Nanoparticle Self-Assembled Grain Like Curcumin Conjugated ZnO: Curcumin Conjugation Enhances Removal of Perylene, Fluoranthene, and Chrysene by ZnO

PubMed Central

Moussawi, Rasha N.; Patra, Digambara

2016-01-01

Curcumin conjugated ZnO, referred as Zn(cur)O, nanostructures have been successfully synthesized, these sub-micro grain-like structures are actually self-assemblies of individual needle-shaped nanoparticles. The nanostructures as synthesized possess the wurtzite hexagonal crystal structure of ZnO and exhibit very good crystalline quality. FT-Raman and TGA analysis establish that Zn(cur)O is different from curcumin anchored ZnO (ZnO@cur), which is prepared by physically adsorbing curcumin on ZnO surfaces. Chemically Zn(cur)O is more stable than ZnO@cur. Diffuse reflectance spectroscopy indicates Zn(cur)O have more impurities compared to ZnO@cur. The solid-state photoluminescence of Zn(cur)O has been investigated, which demonstrates that increase of curcumin concentration in Zn(cur)O suppresses visible emission of ZnO prepared through the same method, this implies filling ZnO defects by curcumin. However, at excitation wavelength 425 nm the emission is dominated by fluorescence from curcumin. The study reveals that Zn(cur)O can remove to a far extent high concentrations of perylene, fluoranthene, and chrysene faster than ZnO. The removal depends on the extent of curcumin conjugation and is found to be faster for PAHs having smaller number of aromatic rings, particularly, it is exceptional for fluoranthene with 93% removal after 10 minutes in the present conditions. The high rate of removal is related to photo-degradation and a mechanism has been proposed. PMID:27080002

Potential Metabolic Activation of a Representative C2-Alkylated Polycyclic Aromatic Hydrocarbon 6-Ethylchrysene Associated with the Deepwater Horizon Oil Spill in Human Hepatoma (HepG2) Cells

PubMed Central

2016-01-01

Exposure to polycyclic aromatic hydrocarbons (PAHs) is the major human health hazard associated with the Deepwater Horizon oil spill. C2-Chrysenes are representative PAHs present in crude oil and could contaminate the food chain. We describe the metabolism of a C2-chrysene regioisomer, 6-ethylchrysene (6-EC), in human HepG2 cells. The structures of the metabolites were identified by HPLC-UV-fluorescence detection and LC-MS/MS. 6-EC-tetraol isomers were identified as signature metabolites of the diol-epoxide pathway. O-Monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and N-acetyl-l-cysteine(NAC)-6-EC-ortho-quinone were discovered as signature metabolites of the ortho-quinone pathway. Potential dual metabolic activation of 6-EC involving the formation of bis-electrophiles, i.e., a mono-diol-epoxide and a mono-ortho-quinone within the same structure, bis-diol-epoxides, and bis-ortho-quinones was observed as well. The identification of 6-EC-tetraol, O-monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and NAC-6-EC-ortho-quinone supports potential metabolic activation of 6-EC by P450 and AKR enzymes followed by metabolic detoxification of the ortho-quinone through interception of its redox cycling capability by catechol-O-methyltransferase and sulfotransferase enzymes. The tetraols and catechol conjugates could be used as biomarkers of human exposure to 6-EC resulting from oil spills. PMID:27054409

Contamination of agricultural lands by polycyclic aromatic hydrocarbons (Tver region, Russia)

NASA Astrophysics Data System (ADS)

Zhidkin, Andrey; Koshovskii, Timur; Gennadiev, Alexander

2016-04-01

It is important to study sources and concentrations of polycyclic aromatic hydrocarbons (PAHs) in the agriculture soils within areas without intensive contaminations. Our studied object was soil and snow cover in the taiga zone (Tver region, Russia). A total of 52 surface (0-30 cm) and 31 subsurface (30-50 cm) soil samples, and 13 snow samples were collected in 35 soil pits, located in forest, crop and layland soils. Studied concentrations of the following 11 individual compounds: two-ring compounds (diphenyl and naphthalene homologues); three-ring compounds (fluorene, phenanthrene, anthracene); four-ring compounds (chrysene, pyrene, tetraphene); five-ring compounds (perylene, benzo[a]pyrene); and six-ring compounds (benzo[ghi]perylene). Analyses made by specrtofluorometry method at the temperature of liquid nitrogen. The total concentrations of all PAHs in soil samples ranged from 9 to 770 ng*g-1 with a median of 96 ng*g-1. The sum of high molecular weight PAHs was significantly lower than the sum of low molecular weight PAHs in the studied soils. The phenanthrene concentration was highest and ranged from 1.2 to 720 ng*g-1 (medium 72 ng*g-1). Compared PAHs reserves in snow cover (μg*m-2) with the reserves in topsoil layer (μg*m-2 in the upper 30 cm). Low molecular weight PAHs (fluorene, phenanthrene, diphenyl, naphthalene) reserves in snow was less than 20% from the reserves in the soil surface layer. High molecular weight PAHs (benzo[a]pyrene, chrysene, perylene, pyrene and tetraphene) reserves in snow was about 50-70% from the reserves in soil surface layer. High molecular weight PAHs (benzo[ghi]perylene and anthracene) reserves in snow was more than in topsoil. PAHs vertical distribution in soil profiles was statistically examined. The total concentration of all PAHs decreased with depth in all studied forest soils. In the arable soils was no significant trend in domination of PAHs total concentrations in the plowing and subsoil layers. The ratio of topsoil to subsoil concentrations of PAHs is different for differ congeners. Contents of phenanthrene and fluorene predominantly increase with the depth. Content of high molecular weight PAHs (benzo[a]pyrene, anthracene, tetraphene, perylene and pyrene) predominantly decreased with the depth. Other PAHs congeners have indistinct profile distributions in studied pits. Based on studied results PAHs divided to associations with different concentrations, sources and vertical distribution in soils: a) phenanthrene and fluorine; b) naphthalene, diphenyl; c) pyrene, benzo(a)pyrene, tetraphene, perylene, chrysene; d) anthracene and benzo(ghi)perylene. Research is funded by Russian Science Foundation (Project 14-27-00083).

8,9-DIHYDROXY-8,9-DIHYDRODIBENZO[A,L]PYRENE IS A POTENT MORPHOLOGICAL CELL-TRANSFORMING AGENT IN C3H10T1/2C18 MOUSE EMBRYO FIBROBLASTS IN THE ABSENCE OF DETECTABLE STABLE COVALENT DNA ADDUCTS

EPA Science Inventory

The comparative genotoxic effects of racemic trans-8,9dihydroxy-8,9-dihydrodibenzo[a,l]pyrene (trans- DB[a,l]P8,9-diol), the metabolic K-region dihydrodiol of dibenzo[a,l] pyrene (DB[a,l]P) (dibenzo[def,p]chrysene) and DB[a,l]P in transformable mouse embryo C3HIOT1/2C18 (C3HIOT1/...

PAH concentrations simulated with the AURAMS-PAH chemical transport model over Canada and the USA

NASA Astrophysics Data System (ADS)

Galarneau, E.; Makar, P. A.; Zheng, Q.; Narayan, J.; Zhang, J.; Moran, M. D.; Bari, M. A.; Pathela, S.; Chen, A.; Chlumsky, R.

2013-07-01

The off-line Eulerian AURAMS chemical transport model was adapted to simulate the atmospheric fate of seven PAHs: phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene + triphenylene, and benzo[a]pyrene. The model was then run for the year 2002 with hourly output on a~grid covering southern Canada and the continental USA with 42 km horizontal grid spacing. Model predictions were compared to ~ 5000 24 h average PAH measurements from 45 sites, eight of which also provided data on particle/gas partitioning which had been modelled using two alternative schemes. This is the first known regional modelling study for PAHs over a North American domain and the first modelling study at any scale to compare alternative particle/gas partitioning schemes against paired field measurements. Annual average modelled total (gas + particle) concentrations were statistically indistinguishable from measured values for fluoranthene, pyrene and benz[a]anthracene whereas the model underestimated concentrations of phenanthrene, anthracene and chrysene + triphenylene. Significance for benzo[a]pyrene performance was close to the statistical threshold and depended on the particle/gas partitioning scheme employed. On a day-to-day basis, the model simulated total PAH concentrations to the correct order of magnitude the majority of the time. Model performance differed substantially between measurement locations and the limited available evidence suggests that the model spatial resolution was too coarse to capture the distribution of concentrations in densely populated areas. A more detailed analysis of the factors influencing modelled particle/gas partitioning is warranted based on the findings in this study.

Passive Sampling of Nonpolar Compounds in Sediments

DTIC Science & Technology

2010-12-02

Example 1: pore water sniffing PAHs/PCBs/HCB in harbor sediments ES&T 37: 4213-4220,2003 LDPE strips in sediment slurries and stagnant sediments...slurry stagnant ~160 g sediment (1-4% oc) ~120 mL water 0.5 g LDPE (30x2.5 cm) 50 d exposure chrysene msed Kd ≈1000 L ms Ksw ≈ 300 L ( or ) Koc from...silicone ! SPME! POG! LDPE ! Chemcatcher ! SPMD! POCIS! Mesco I 300 200 100 2 3 4 5 6 7 8 N ( n g ) log Kow Cw = 1 ng / L week 123456 Evolution of peak pattern

The influence of smoking in traditional conditions on content of polycyclic aromatic hydrocarbons in Petrovská klobása

NASA Astrophysics Data System (ADS)

Škaljac, S.; Petrović, Lj; Jokanović, M.; Tomović, V.; Tasić, T.; Ivić, M.; Šojić, B.; Ikonić, P.; Džinić, N.

2017-09-01

The aim of this study was to determine the content of 13 polycyclic aromatic hydrocarbons (acenaphthylene, fluorene, phenanthrene, anthracene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene, dibenz[a,h]anthracene and benzo[ghi]perylene) the from Environmental Protection Agency list (US-EPA PAH) in traditional dry fermented sausage Petrovská klobása. Sausages were smoked in traditional conditions and samples for analyses were taken on day 0 of production (0), at the end of drying (T1) and at the end of the storage period (T2). The highest total content of 13 US-EPA PAHs was determined in sausages at the end of the storage period (73.5 μg/kg). Phenanthrene was the most abundant of the PAHs in all examined sausage samples (0-4.90 μg/kg T1-18.0 μg/kg and T2-26.3 μg/kg). Benzo[a]pyrene, with a maximum allowed content in smoked meat products of 2 µg/kg (EC No. 835/2011), was below the limit of detection in all examined samples. Also, PAH4 (the total content of benz[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) with a maximum allowed content in smoked meat products of 12 µg/kg (EC No. 835/2011), was below the limit of detection in all examined sausage samples. According to the results obtained in this study, and in regard to the European regulation on PAHs content, the dry fermented sausage Petrovská klobása, smoked in traditional conditions, was safe for consumers.

Comparative study of bioconcentration and EROD activity induction in the Japanese flounder, red sea bream, and Java medaka exposed to polycyclic aromatic hydrocarbons.

PubMed

Cheikyula, J Orkuma; Koyama, Jiro; Uno, Seiichi

2008-06-01

Japanese flounder (Paralichthys olivaceus), red sea bream (Pagrus major), and Java medaka (Oryzias javanicus) were exposed to water borne polycyclic aromatic hydrocarbons (PAHs) for 10 days to compare PAH bioconcentration and P450 enzyme induction by ethoxyresorufin-O-deethylase (EROD) activity for use in oil spill biomonitoring in Asian waters. Target exposure concentration for phenanthrene, pyrene, and chrysene were 30 microg/L each, while benzo[a]pyrene was 3.0 microg/L. Phenanthrene and pyrene were accumulated in the flounder and red sea bream; chrysene was found only in the livers of the red sea bream, while Java medaka accumulated the high molecular weight benzo[a]pyrene along with the other PAHs. Total PAH concentrations increased with duration of exposure in the red sea bream from 184+/-37 ng/g wet weight (w.w.) in day 2 to 572+/-72 ng/g (w.w.) in day 10; It, however, decreased in the other two species. Among the three fish species, Java medaka had the highest initial total PAH concentration of 388+/-62 ng/g (w.w.); this was, however, reduced to the lowest final concentration of 52.3+/-3 ng/g (w.w.). It also had the highest EROD activity of 4.2+/-2.8 n mol/min/mg protein compared to the lowest of 0.11+/-0.03 n mol/min/mg protein in the Japanese flounder. Java medaka with high EROD activity induction and bioaccumulation of all PAHs will be suitable for PAH biomonitoring in Asian waters. Due to its high PAH bioconcentration red sea bream is also recommended for consideration for biomonitoring and PAH chronic toxicity tests.

Modeling of experimental data on trace elements and organic compounds content in industrial waste dumps.

PubMed

Smoliński, Adam; Drobek, Leszek; Dombek, Václav; Bąk, Andrzej

2016-11-01

The main objective of the study presented was to investigate the differences between 20 mine waste dumps located in the Silesian Region of Poland and Czech Republic, in terms of trace elements and polycyclic aromatic hydrocarbons contents. The Principal Component Analysis and Hierarchical Clustering Analysis were applied in exploration of the studied data. Since the data set was affected by outlying objects, the employment of a relevant analysis strategy was necessary. The final PCA model was constructed with the use of the Expectation-Maximization iterative approach preceded by a correct identification of outliers. The analysis of the experimental data indicated that three mine waste dumps located in Poland were characterized by the highest concentrations of dibenzo(g,h,i)anthracene and benzo(g,h,i)perylene, and six objects located in Czech Republic and three objects in Poland were distinguished by high concentrations of chrysene and indeno (1.2.3-cd) pyrene. Three of studied mine waste dumps, one located in Czech Republic and two in Poland, were characterized by low concentrations of Cr, Ni, V, naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthen, benzo(a)anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo(a)pyrene, dibenzo(g,h,i)anthracene, benzo(g,h,i)perylene and indeno (1.2.3-cd) pyrene in comparison with the remaining ones. The analysis contributes to the assessment and prognosis of ecological and health risks related to the emission of trace elements and organic compounds (PAHs) from the waste dumps examined. No previous research of similar scope and aims has been reported for the area concerned. Copyright © 2016 Elsevier Ltd. All rights reserved.

Conversion of polycyclic aromatic hydrocarbons on diesel particulate matter upon exposure to ppm levels of ozone

NASA Astrophysics Data System (ADS)

Van Vaeck, L.; Van Cauwenberghe, K.

Diesel exhaust particlulate matter samples were collected from a dilution tunnel using a Hi-Vol cascade impactor. The fraction of the aerosol with aerodynamic diameter below 0.5 μm, retained on the glass fiber back-up filter, was exposed to a flow of ozonised particle free air for periods of 0.5-4 h (1.5 ppm of O 3, flow rate about 40 m 3 h -1). Both exposed and non-exposed reference niters were Soxhlet-extracted with benzene and methanol, and the polycyclic aromatic hydrocarbon fraction (PAH) was isolated by a liquid-liquid partition procedure described in the literature, using cyclohexane and dimethylformamid-water as solvents, modified for quantitative recovery of PAH. The conversion yields of PAH upon exposure to O 3 were determined by single ion monitoring mass spectrometry using a fused silica capillary column for their separation. Significant conversion was observed for PAH from molecular weight 226 to 276. Approximate half lives are of the order of 0.5-1 h for most PAH measured. This high reactivity of PAH on a carbonaceous matrix is probably related to the large specific surface of soot particles as well as to their high adsorptive capacity for gaseous compounds. Lower molecular weight PAH up to chrysene also undergo important physical losses by volatilisation and the extent to which chemical transformations occurred could not be determined accurately. Different reactivities are observed for several isomeric pairs of PAH: benzo(a)pyrene is much faster converted than benzo(e)pyrene, benz(a)anthracene reacts faster than chrysene. The benzo-fluoranthenes are most resistant toward O 3 attack. The implications of these results with respect to atmospheric degradation of PAH, as well as to the occurrence of artefactual conversion upon Hi-Vol sampling are discussed.

Field measurements of the atmospheric dry deposition fluxes and velocities of polycyclic aromatic hydrocarbons to the global oceans.

PubMed

González-Gaya, Belén; Zúñiga-Rival, Javier; Ojeda, María-José; Jiménez, Begoña; Dachs, Jordi

2014-05-20

The atmospheric dry deposition fluxes of 16 polycyclic aromatic hydrocarbons (PAHs) have been measured, for the first time, in the tropical and subtropical Atlantic, Pacific, and Indian Oceans. Depositional fluxes for fine (0.7-2.7 μm) and coarse (>2.7 μm) aerosol fractions were simultaneously determined with the suspended aerosol phase concentrations, allowing the determination of PAH deposition velocities (vD). PAH dry deposition fluxes (FDD) bound to coarse aerosols were higher than those of fine aerosols for 83% of the measurements. Average FDD for total (fine + coarse) Σ16PAHs (sum of 16 individual PAHs) ranged from 8.33 ng m(-2)d(-1) to 52.38 ng m(-2)d(-1). Mean FDD for coarse aerosol's individual PAHs ranged between 0.13 ng m(-2)d(-1) (Perylene) and 1.96 ng m(-2)d(-1) (Methyl Pyrene), and for the fine aerosol fraction these ranged between 0.06 ng m(-2)d(-1) (Dimethyl Pyrene) and 1.25 ng m(-2)d(-1) (Methyl Chrysene). The estimated deposition velocities went from the highest mean vD for Methyl Chrysene (0.17-13.30 cm s(-1)), followed by Dibenzo(ah)Anthracene (0.29-1.38 cm s(-1)), and other high MW PAHs to minimum values of vD for Dimethyl Pyrene (<0.04 cm s(-1)) and Pyrene (<0.06 cm s(-1)). Dry depositional processes depend on the concentration of PAHs in the suspended aerosol, but also on physicochemical properties and environmental variables (vapor pressure, wind speed, and on the affinity of aerosols for depositing to the sea surface). Empirical parametrizations are proposed to predict the dry depositional velocities of semivolatile organic compounds to the global oceans.

[Polycyclic aromatic hydrocarbons and soluble organic fraction in fine particles from solid fraction of biodiesel exhaust fumes].

PubMed

Szewczyńska, Małgorzata; Pośniak, Małgorzata

2012-01-01

This paper presents the results of investigations into the distribution of fine particles in the biodiesel exhaust fumes (bio-DEP), as well as into the content of polycyclic aromatic hydrocarbons (PAHs) and soluble organic fraction (SOF) in the study fractions. Samples of biodiesel B20 and B40 exhaust combustion fumes were generated at the model station composed of a diesel engine from Diesel TDI 2007 Volkswagen. Sioutas personal cascade impactor (SPCI) with Teflon filters and low-pressure impactor ELIPI (Dekati Low Pressure Impactor) were used for sampling diesel exhaust fine particles. The analysis of PAHs adsorbed on particulate fractions was performed by high performance liquid chromatography with fluorescence detection (HPLC/FL). For the determination of dry residue soluble organic fraction of biodiesel exhaust particles the gravimetric method was used. The combustion exhaust fumes of 100% ON contained mainly naphthalene, acenaphthalene, fluorene, phenanthrene, fluoranthene, pyrene, benzo(a)anthracene and chrysene, whilst the exhaust of B40-single PAHs of 4 and 5 rings, such as chrysene, benzo(k)fluoranthene, dibenzo (ah)anthracene and benzo(ghi)perylene. The total content of PAHs in diesel exhaust particles averaged 910 ng/m3 for 100% ON and 340 ng/m3 for B40. The concentrations of benzo(a)antarcene were at the levels of 310 ng/m3 (100% ON) and 90 ng/m3 (B40). The investigations indicated that a fraction < 025 microm represents the main component of diesel exhaust particles, regardless of the used fuel. Bioester B 100 commonly added to diesel fuel (ON) causes a reduction of the total particulates emission and thus reduces the amount of toxic substances adsorbed on their surface.

In vitro biotransformation rates in fish liver S9: effect of dosing techniques.

PubMed

Lee, Yung-Shan; Lee, Danny H Y; Delafoulhouze, Maximilien; Otton, S Victoria; Moore, Margo M; Kennedy, Chris J; Gobas, Frank A P C

2014-08-01

In vitro biotransformation assays are currently being explored to improve estimates of bioconcentration factors of potentially bioaccumulative organic chemicals in fish. The present study compares thin-film and solvent-delivery dosing techniques as well as single versus multiple chemical dosing for measuring biotransformation rates of selected polycyclic aromatic hydrocarbons in rainbow trout (Oncorhynchus mykiss) liver S9. The findings show that biotransformation rates of very hydrophobic substances can be accurately measured in thin-film sorbent-dosing assays from concentration-time profiles in the incubation medium but not from those in the sorbent phase because of low chemical film-to-incubation-medium mass-transfer rates at the incubation temperature of 13.5 °C required for trout liver assays. Biotransformation rates determined by thin-film dosing were greater than those determined by solvent-delivery dosing for chrysene (octanol-water partition coefficient [KOW ] =10(5.60) ) and benzo[a]pyrene (KOW  =10(6.04) ), whereas there were no statistical differences in pyrene (KOW  =10(5.18) ) biotransformation rates between the 2 methods. In sorbent delivery-based assays, simultaneous multiple-chemical dosing produced biotransformation rates that were not statistically different from those measured in single-chemical dosing experiments for pyrene and benzo[a]pyrene but not for chrysene. In solvent-delivery experiments, multiple-chemical dosing produced biotransformation rates that were much smaller than those in single-chemical dosing experiments for all test chemicals. While thin-film sorbent-phase and solvent delivery-based dosing methods are both suitable methods for measuring biotransformation rates of substances of intermediate hydrophobicity, thin-film sorbent-phase dosing may be more suitable for superhydrophobic chemicals. © 2014 SETAC.

Differential modulation of dibenzo[def,p]chrysene transplacental carcinogenesis: Maternal diets rich in indole-3-carbinol versus sulforaphane

PubMed Central

Shorey, Lyndsey E.; Madeen, Erin P.; Atwell, Lauren L.; Ho, Emily; Löhr, Christiane V.; Pereira, Clifford B.; Dashwood, Roderick H.; Williams, David E.

2014-01-01

Cruciferous vegetable components have been documented to exhibit anticancer properties. Targets of action span multiple mechanisms deregulated during cancer progression, ranging from altered carcinogen metabolism to the restoration of epigenetic machinery. Furthermore, the developing fetus is highly susceptible to changes in nutritional status and to environmental toxicants. Thus, we have exploited a mouse model of transplacental carcinogenesis to assess the impact of maternal dietary supplementation on cancer risk in offspring. In this study, transplacental and lactational exposure to a maternal dose of 15 mg/Kg B.W. of dibenzo[def,p]chrysene (DBC) resulted in significant morbidity of offspring due to an aggressive T-cell lymphoblastic lymphoma. As in previous studies, indole-3-carbinol (I3C, feed to the dam at 100, 500 or 1000 ppm), derived from cruciferous vegetables, dose-dependently reduced lung tumor multiplicity and also increased offspring survival. Brussels sprout and broccoli sprout powders, selected for their relative abundance of I3C and the bioactive component sulforaphane (SFN), respectively, surprisingly enhanced DBC-induced morbidity and tumorigenesis when incorporated into the maternal diet at 10% wt/wt. Purified SFN, incorporated in the maternal diet at 400 ppm, also decreased the latency of DBC-dependent morbidity. Interestingly, I3C abrogated the effect of SFN when the two purified compounds were administered in equimolar combination (500 ppm I3C and 600 ppm SFN). SFN metabolites measured in the plasma of neonates positively correlated with exposure levels via the maternal diet but not with offspring mortality. These findings provide justification for further study of the safety and bioactivity of cruciferous vegetable phytochemicals at supplemental concentrations during the perinatal period. PMID:23566957

Installation Restoration Program. Phase 2. Confirmation/Quantification, Stage 2 for Seymour Johnson Air Force Base, North Carolina. Volume 4

DTIC Science & Technology

1988-11-01

BENZIDINE 400 81)1 5 BENZO (a) ANTHRACENE 400 ODL 6 BENZ0 (a) PYRENE 400 61 )1 7 BENZO (b) FLUORANTHENE 400 61 )1 a BENZO (ghl) PERYLENE 1003 61 )1 9...BENZO (k) FLUIORANTHENE 400 61 )1 10 815 (2-CHOROEThOXY) METHANE 400 81)1 11 815 (2-CHOROETIIYL) ETHER 400 BDL 12 8(5 (2-CHLOROISOPROPYL) ETHER 400 BDL 13...CHOROPHENYL PHENYL ETHER 400 61 )1 18 CHRYSENE 400 B1)L - 19 DIBEIQO (ah) ANTHRACENE 400 81)1 20 1,2-DICHOROBENZENE 400 81)1 21 1 ,3-DICHLOROBENZENE

Concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) in Urban Stormwater, Madison, Wisconsin, 2005-08

USGS Publications Warehouse

Selbig, William R.

2009-01-01

Concentrations of 18 PAH compounds were characterized from six urban source areas (parking lots, feeder street, collector street, arterial street, rooftop, and strip mall) around Madison, Wisconsin. Parking lots were categorized into those that were or were not sealed. On average, chrysene, fluoranthene, and pyrene were the dominant PAH compounds in all urban stormwater samples. Geometric mean concentrations for most individual PAH compounds were significantly greater for a parking lot that was sealed than for lots that were not sealed. Results from this study are consistent with similar studies that measured PAH concentrations in urban stormwater samples in Marquette, Mich., and Madison, Wis.

Long-term monitoring data to describe the fate of polycyclic aromatic hydrocarbons in Deepwater Horizon oil submerged off Alabama's beaches.

PubMed

Yin, Fang; John, Gerald F; Hayworth, Joel S; Clement, T Prabhakar

2015-03-01

The 2010 Deepwater Horizon (DWH) catastrophe had considerable impact on the ∼ 50 km long sandy beach system located along the Alabama shoreline. We present a four-year dataset to characterize the temporal evolution of various polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologs trapped in the residual oil buried along the shoreline. Field samples analyzed include the first arrival oil collected from Perdido Bay, Alabama in June 2010, and multiple oil spill samples collected until August 2014. Our field data show that, as of August 2014, DWH oil is still trapped along Alabama's beaches as submerged oil, predominately in the form of surface residual oil balls (SRBs). Chemical characterization data show that various PAHs present in the spilled oil (MC252 crude) weathered by about 45% to 100% when the oil was floating over the open ocean system in the Gulf of Mexico. Light PAHs, such as naphthalenes, were fully depleted, whereas heavy PAHs, such as chrysenes, were only partially depleted by about 45%. However, the rate of PAH weathering appears to have decreased significantly once the oil was buried within the partially-closed SRB environment. Concentration levels of several heavy PAHs have almost remained constant over the past 4 years. Our data also show that evaporation was most likely the primary weathering mechanism for PAH removal when the oil was floating over the ocean, although photo-degradation and other physico-chemical processes could have contributed to some additional weathering. Chemical data presented in this study indicate that submerged oil containing various heavy PAHs (for example, parent and alkylated chrysenes) is likely to remain in the beach system for several years. It is also likely that the organisms living in these beach environments would have an increased risk of exposure to heavy PAHs trapped in the non-recoverable form of buried DWH oil spill residues. Copyright © 2014 Elsevier B.V. All rights reserved.

PAH concentrations simulated with the AURAMS-PAH chemical transport model over Canada and the USA

NASA Astrophysics Data System (ADS)

Galarneau, E.; Makar, P. A.; Zheng, Q.; Narayan, J.; Zhang, J.; Moran, M. D.; Bari, M. A.; Pathela, S.; Chen, A.; Chlumsky, R.

2014-04-01

The offline Eulerian AURAMS (A Unified Regional Air quality Modelling System) chemical transport model was adapted to simulate airborne concentrations of seven PAHs (polycyclic aromatic hydrocarbons): phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene + triphenylene, and benzo[a]pyrene. The model was then run for the year 2002 with hourly output on a grid covering southern Canada and the continental USA with 42 km horizontal grid spacing. Model predictions were compared to ~5000 24 h-average PAH measurements from 45 sites, most of which were located in urban or industrial areas. Eight of the measurement sites also provided data on particle/gas partitioning which had been modelled using two alternative schemes. This is the first known regional modelling study for PAHs over a North American domain and the first modelling study at any scale to compare alternative particle/gas partitioning schemes against paired field measurements. The goal of the study was to provide output concentration maps of use to assessing human inhalation exposure to PAHs in ambient air. Annual average modelled total (gas + particle) concentrations were statistically indistinguishable from measured values for fluoranthene, pyrene and benz[a]anthracene whereas the model underestimated concentrations of phenanthrene, anthracene and chrysene + triphenylene. Significance for benzo[a]pyrene performance was close to the statistical threshold and depended on the particle/gas partitioning scheme employed. On a day-to-day basis, the model simulated total PAH concentrations to the correct order of magnitude the majority of the time. The model showed seasonal differences in prediction quality for volatile species which suggests that a missing emission source such as air-surface exchange should be included in future versions. Model performance differed substantially between measurement locations and the limited available evidence suggests that the model's spatial resolution was too coarse to capture the distribution of concentrations in densely populated areas. A more detailed analysis of the factors influencing modelled particle/gas partitioning is warranted based on the findings in this study.

Continuous catalytic hydrogenation of polyaromatic hydrocarbon compounds in hydrogen-supercritical carbon dioxide.

PubMed

Yuan, Tao; Fournier, Anick R; Proudlock, Raymond; Marshall, William D

2007-03-15

A continuous hydrogenation device was evaluated for the detoxification of selected tri-, tetra-, or pentacyclic polyaromatic hydrocarbon (PAH) compounds {anthracene, phenanthrene, chrysene, and benzo[a]pyrene (B[a]P)} by hydrogenation. A substrate stream in hexane, 0.05-1.0% (w/v), was mixed with hydrogen-carbon dioxide (H2-CO2, 5-30% v/v) and delivered to a heated reactor column (25 cm x 1 cm) containing palladium supported on gamma alumina (Pd0/gamma-Al2O3) that was terminated with a capillary restrictor. The flow rate from the reactor, approximately 800 mL min(-1) decompressed gas, corresponded to 4 mL min(-1) fluid under the operating conditions of the trials. Reaction products were recovered by passing the reactor effluent through hexane. At 90 degrees C, the anthracene or phenanthrene substrate was hydrogenated only partially to octahydro and dodecahydro species and contained only a minor quantity of totally hydrogenated products. For substrates with increasing numbers of fused aromatic rings, the hydrogenation efficiency was decreased further. However, at an increasing temperature (90-150 degrees C) and increasing mobile phase flow rate (20.68 MPa corresponding to 2100 mL min(-1) decompressed gas), B[a]P and chrysene were hydrogenated, virtuallytotally, to their corresponding perhydro analogues (eicosahydrobenzo[a]pyrenes and octadecahydrochrysenes), respectively. That this approach might be useful for decontaminating soil extracts was supported by companion in vitro trials in which the substrate and products were assayed for mutagenic activity with five bacterial strains that are auxotrophic for histidine (Salmonella typhimurium TA98, TA100, TA1535, and TA1537) or tryptophan (Escherichia coliWP2 uvrA), using the bacterial reverse mutation assay (modified Ames test). Generally, substantial increases in revertant colony counts were not observed with any of the strains following exposure to the hydrogenation products in the absence or presence of the 10 or 30% S9 mix, which is consistent with the loss of mutagenic activity from these hydrogenation products.

Homology modeling, simulation and molecular docking studies of catechol-2, 3-Dioxygenase from Burkholderia cepacia: Involved in degradation of Petroleum hydrocarbons.

PubMed

Ajao, At; Kannan, M; Yakubu, Se; Vj, Umoh; Jb, Ameh

2012-01-01

Catechol 2, 3-dioxygenase is present in several types of bacteria and undergoes degradation of environmental pollutants through an important key biochemical pathways. Specifically, this enzyme cleaves aromatic rings of several environmental pollutants such as toluene, xylene, naphthalene and biphenyl derivatives. Hence, the importance of Catechol 2, 3-dioxygenase and its role in the degradation of environmental pollutants made us to predict the three-dimensional structure of Catechol 2, 3-dioxygenase from Burkholderia cepacia. The 10ns molecular dynamics simulation was carried out to check the stability of the modeled Catechol 2, 3- dioxygenase. The results show that the model was energetically stable, and it attains their equilibrium within 2000 ps of production MD run. The docking of various petroleum hydrocarbons into the Catechol 2,3-dioxygenase reveals that the benzene, O-xylene, Toluene, Fluorene, Naphthalene, Carbazol, Pyrene, Dibenzothiophene, Anthracene, Phenanthrene, Biphenyl makes strong hydrogen bond and Van der waals interaction with the active site residues of H150, L152, W198, H206, H220, H252, I254, T255, Y261, E271, L276 and F309. Free energy of binding and estimated inhibition constant of these compounds demonstrates that they are energetically stable in their binding cavity. Chrysene shows positive energy of binding in the active site atom of Fe. Except Pyrene all the substrates made close contact with Fe atom by the distance ranges from 1.67 to 2.43 Å. In addition to that, the above mentioned substrate except pyrene all other made π-π stacking interaction with H252 by the distance ranges from 3.40 to 3.90 Å. All these docking results reveal that, except Chrysene all other substrate has good free energy of binding to hold enough in the active site and makes strong VdW interaction with Catechol-2,3-dioxygenase. These results suggest that, the enzyme is capable of catalyzing the above-mentioned substrate.

Homology modeling, simulation and molecular docking studies of catechol-2, 3-Dioxygenase from Burkholderia cepacia: Involved in degradation of Petroleum hydrocarbons

PubMed Central

Ajao, AT; Kannan, M; Yakubu, SE; VJ, Umoh; JB, Ameh

2012-01-01

Catechol 2, 3-dioxygenase is present in several types of bacteria and undergoes degradation of environmental pollutants through an important key biochemical pathways. Specifically, this enzyme cleaves aromatic rings of several environmental pollutants such as toluene, xylene, naphthalene and biphenyl derivatives. Hence, the importance of Catechol 2, 3-dioxygenase and its role in the degradation of environmental pollutants made us to predict the three-dimensional structure of Catechol 2, 3-dioxygenase from Burkholderia cepacia. The 10ns molecular dynamics simulation was carried out to check the stability of the modeled Catechol 2, 3- dioxygenase. The results show that the model was energetically stable, and it attains their equilibrium within 2000 ps of production MD run. The docking of various petroleum hydrocarbons into the Catechol 2,3-dioxygenase reveals that the benzene, O-xylene, Toluene, Fluorene, Naphthalene, Carbazol, Pyrene, Dibenzothiophene, Anthracene, Phenanthrene, Biphenyl makes strong hydrogen bond and Van der waals interaction with the active site residues of H150, L152, W198, H206, H220, H252, I254, T255, Y261, E271, L276 and F309. Free energy of binding and estimated inhibition constant of these compounds demonstrates that they are energetically stable in their binding cavity. Chrysene shows positive energy of binding in the active site atom of Fe. Except Pyrene all the substrates made close contact with Fe atom by the distance ranges from 1.67 to 2.43 Å. In addition to that, the above mentioned substrate except pyrene all other made π-π stacking interaction with H252 by the distance ranges from 3.40 to 3.90 Å. All these docking results reveal that, except Chrysene all other substrate has good free energy of binding to hold enough in the active site and makes strong VdW interaction with Catechol-2,3-dioxygenase. These results suggest that, the enzyme is capable of catalyzing the above-mentioned substrate. PMID:23144539

Electron-intramolecular-vibration interactions in positively charged phenanthrene-edge-type hydrocarbons

NASA Astrophysics Data System (ADS)

Kato, Takashi; Yamabe, Tokio

2004-02-01

Electron-phonon interactions in positively charged phenanthrene-edge-type hydrocarbons such as phenanthrene, chrysene, and picene are studied. The C-C stretching modes around 1500 cm-1 and the low-frequency modes around 500 cm-1 strongly couple to the highest occupied molecular orbitals (HOMO) in phenanthrene-edge-type hydrocarbons. The total electron-phonon coupling constants for the monocations (lHOMO) of 0.251, 0.135, and 0.149 eV for phenanthrene, chrysene, and picene, respectively, are estimated to be larger than those of 0.130, 0.107, and 0.094 eV for anthracene, tetracene, and pentacene, respectively. The phase patterns difference between the HOMO localized on carbon atoms which are located at the molecular edge in acene-edge-type hydrocarbons and the delocalized HOMO in phenanthrene-edge-type hydrocarbons is the main reason for the result. Strengths of orbital interactions between two neighboring carbon atoms in the HOMO become weaker with an increase in molecular size because the electron density on each carbon atom in the HOMO becomes smaller with an increase in molecular size in phenanthrene-edge-type hydrocarbons. On the other hand, the frontier orbitals of acene-edge-type hydrocarbons have somewhat nonbonding characters and thus cannot strongly couple to the totally symmetric vibrational modes compared with the frontier orbitals of phenanthrene-edge-type hydrocarbons. This is the reason why the lHOMO value for phenanthrene-edge-type hydrocarbons decreases with an increase in molecular size more significantly than that for acene-edge-type hydrocarbons, and the reason why the lHOMO value for polyphenanthrene with C2v geometry (0.033 eV) is estimated to be similar to that for polyacene (0.036 eV). The reorganization energies between the neutral molecules and the corresponding monocations for phenanthrene-edge-type hydrocarbons with large molecular size are estimated to be larger than those for acene-edge-type hydrocarbons with large molecular size.

Effects of Crude Oil Exposure on Bioaccumulation of Polycyclic Aromatic Hydrocarbons and Survival of Adult and Larval Stages of Gelatinous Zooplankton

PubMed Central

Almeda, Rodrigo; Wambaugh, Zoe; Chai, Chao; Wang, Zucheng; Liu, Zhanfei; Buskey, Edward J.

2013-01-01

Gelatinous zooplankton play an important role in marine food webs both as major consumers of metazooplankton and as prey of apex predators (e.g., tuna, sunfish, sea turtles). However, little is known about the effects of crude oil spills on these important components of planktonic communities. We determined the effects of Louisiana light sweet crude oil exposure on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in adult stages of the scyphozoans Pelagia noctiluca and Aurelia aurita and the ctenophore Mnemiopsis leidyi, and on survival of ephyra larvae of A. aurita and cydippid larvae of M. leidyi, in the laboratory. Adult P. noctiluca showed 100% mortality at oil concentration ≥20 µL L−1 after 16 h. In contrast, low or non-lethal effects were observed on adult stages of A. aurita and M. leidyi exposed at oil concentration ≤25 µL L−1 after 6 days. Survival of ephyra and cydippid larva decreased with increasing crude oil concentration and exposition time. The median lethal concentration (LC50) for ephyra larvae ranged from 14.41 to 0.15 µL L−1 after 1 and 3 days, respectively. LC50 for cydippid larvae ranged from 14.52 to 8.94 µL L−1 after 3 and 6 days, respectively. We observed selective bioaccumulation of chrysene, phenanthrene and pyrene in A. aurita and chrysene, pyrene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, and benzo[a]anthracene in M. leidyi. Overall, our results indicate that (1) A. aurita and M. leidyi adults had a high tolerance to crude oil exposure compared to other zooplankton, whereas P. noctiluca was highly sensitive to crude oil, (2) larval stages of gelatinous zooplankton were more sensitive to crude oil than adult stages, and (3) some of the most toxic PAHs of crude oil can be bioaccumulated in gelatinous zooplankton and potentially be transferred up the food web and contaminate apex predators. PMID:24116004

The biodegradation of crude oil in the deep ocean.

PubMed

Prince, Roger C; Nash, Gordon W; Hill, Stephen J

2016-10-15

Oil biodegradation at a simulated depth of 1500m was studied in a high-pressure apparatus at 5°C, using natural seawater with its indigenous microbes, and 3ppm of an oil with dispersant added at a dispersant:oil ratio of 1:15. Biodegradation of the detectable hydrocarbons was prompt and extensive (>70% in 35days), although slower by about a third than under otherwise identical conditions equivalent to the surface. The apparent half-life of biodegradation of the total detectable hydrocarbons at 15MPa was 16days (compared to 13days at atmospheric pressure), although some compounds, such as the four-ring aromatic chrysene, were degraded rather more slowly. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantity and quality of stormwater collected from selected stormwater outfalls at industrial sites, Fort Gordon, Georgia, 2012

USGS Publications Warehouse

Nagle, Doug D.

2013-01-01

Samples from sites SWR11–3, SWR11–4, and SWR11–5 were analyzed for 83 volatile and semivolatile organic compounds. Eight polycyclic aromatic hydrocarbon compounds, benzo[a]pyrene, benzo[b]fluoranthene, benzo[ghi]perylene, benzo[k]fluoranthene, chrysene, indeno[1,2,3-cd]pyrene, phenanthrene, and pyrene, were detected at all three sites. Of the 86 volatile and semivolatile organic compounds that were analyzed in stormwater samples from heating and cooling sites, 15 (18 percent) were detected at site SWR11–3, 12 (14 percent) were detected at site SWR11–4, and 17 (20 percent) were detected at site SWR11–5.

PAHs in corn grains submitted to drying with firewood.

PubMed

de Lima, Rafael Friedrich; Dionello, Rafael Gomes; Peralba, Maria do Carmo Ruaro; Barrionuevo, Simone; Radunz, Lauri Lourenço; Reichert Júnior, Francisco Wilson

2017-01-15

Grain drying using firewood as fuel for air heating, with direct fire, is still widely used in Brazil. The combustion of organic material, such as wood, can generate polycyclic aromatic hydrocarbons (PAHs) which are known to have carcinogenic potential. In the present work corn grain drying was carried out at three drying air temperatures: 60°C, 60/80°C and 80°C. Following the drying process, the presence and quantification of PAH in the corn grains was investigated. After extracting the PAHs of the matrix, the material was subjected to analysis by gas chromatography with mass detector. he results showed the presence of seven compounds: fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene and chrysene. Copyright © 2016 Elsevier Ltd. All rights reserved.

Priority PAHs in orthodox black tea during manufacturing process.

PubMed

Grover, Inderpreet Singh; Singh, Satnam; Pal, Bonamali

2013-08-01

Orthodox black tea is obtained from fresh leaves followed by withering, rolling, fermentation and drying. The presence of 16 priority polycyclic aromatic hydrocarbons (PAHs) was studied in fresh leaves and at various stages of manufacturing. Benzo(a)pyrene (2A: probable human carcinogen) was found in dried tea leaves only whereas, naphthalene (2B: probable human carcinogen) was present during all the stages of manufacturing. Dry tea leaves showed higher content of total 16 PAHs (∑PAHs) about 3 and 211 times than present in withered and dried leaves, respectively. Chrysene, benzo[g,h,i]perylene, indendo[1,2,3-c,d]pyrene, dibenzo[a,h]pyrene and benzo[a]antracene were not found during manufacturing stages of tea.

Sediments from stormwater drainage system as sorbents of organic and inorganic pollutants

NASA Astrophysics Data System (ADS)

Sałata, Aleksandra; Dąbek, Lidia

2017-11-01

The study presents the results of tests aimed at determining variations in concentrations of polycyclic aromatic hydrocarbons (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a, h]anthracene, benzo[g, h, i]perylene and indeno[1, 2, 3-c, d]pyrene) and heavy metals (copper, cadmium, chromium, nickel, lead and zinc) in the sediments from the stormwater sewer system. Results of this study were then compared to Polish regulations and established ecological screening values to determine their potential risk to environment. The results suggest that stormwater sediments are moderately contaminated with PAHs and heavy metals according to domestic regulations and highly contaminated according to ecological benchmarks.

Environmental assessment of aromatic hydrocarbons-contaminated sediments of the Mexican Salina Cuz Bay.

PubMed

González-Macías, C; Schifter, I; Lluch-Cota, D B; Méndez-Rodríguez, L; Hernández-Vázquez, S

2007-10-01

Concentrations of total aromatic hydrocarbons and extractable organic matter in the water column and sediment were determined in samples collected in the course of the last 20 years from the Salina Cruz Harbor, México, to assess the degree of organic contamination. In sediments, organic compounds accumulate in shallow areas mostly associated with extractable organic matter and fine fractions. Calculated geocumulation index and enrichment factors suggest that contamination could be derived from anthropogenic activities attributed to harbor and ship scrapping activities, as well as transboundary source. Concentration of total aromatic hydrocarbons (as chrysene equivalents) ranged from 0.01 to 534 microg l(-1) in water, and from 0.10 to 2,160 microg g(-1) in sediments. Total aromatic concentration of 5 microg g(-1) is proposed as background concentration.

The IR emission features - Emission from PAH molecules and amorphous carbon particles

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

1987-01-01

Techniques for the assessment of the importance of the various forms of PAHs, and recent infrared observations concerning the PAH problem, are considered. Spectroscopic data suggest that the observed interstellar spectrum is due to both free molecule-sized PAHs producing the narrow features, and amorphous carbon particles contributing to the broad underlying components. Explanations for the multicomponent emission spectrum are discussed. A model of the emission mechanism for the example of chrysene is presented, and an exact treatment of the IR fluorescence from highly vibrationally excited large molecules shows that species containing 20-30 carbon atoms are responsible for the narrow features, although the spectra more closely resemble those of amorphous carbon particles. It is suggested that future emphasis should be placed on the spatial characteristics of the component spectra.

Synthesis and identification of major metabolites of environmental pollutant dibenzo[c,mno]chrysene.

PubMed

Sharma, Arun K; Amin, Shantu

2005-09-01

Dibenzo[c,mno]chrysene commonly known as naphtho[1,2-a]pyrene (N[1,2-a]P) is an environmental pollutant, recently identified in coal tar extract, in air-borne particulate matter, in marine sediment, and in cigarette-smoke condensate. We recently reported an efficient synthesis of N[1,2-a]P and examined its in vitro metabolism by male Sprague Dawley rat liver S9 fraction, which resulted in a number of dihydrodiol and phenolic metabolites. The synthesis of 10-hydroxy-N[1,2-a]P and fjord region N[1,2-a]P trans-9,10-dihydrodiol, which were identified among the various metabolites, was assigned earlier by comparing with the synthetic standards. The other major metabolites were separated by HPLC and, based on the 1H NMR analysis, were tentatively suggested to be the two K-region dihydrodiols, that is, N[1,2-a]P trans-4,5-dihydrodiol (6) and N[1,2-a]P trans-7,8-dihydrodiol (7), and the hydroxy derivatives of N[1,2-a]P. To unequivocally assign the structure to each of the peaks and to have them in larger amounts for toxicological studies, we have now synthesized the two K-region dihydrodiols and the 1-/3-hydroxy-N[1,2-a]P, short-listed based on the proton NMR of the collected peaks. The K-region dihydrodiols 6 and 7 were prepared by the treatment of N[1,2-a]P with OsO(4) to give a mixture of cis dihydrodiols 2 and 3, followed by pyridinium chlorochromate-assisted oxidation to quinones 4 and 5, and finally reduction with NaBH(4) to afford the dihydrodiols 6 and 7 with the desired trans stereochemistry. The 1-hydroxy-N[1,2-a]P (22) and 3-hydroxy-N[1,2-a]P (23) were synthesized using a photochemical approach. As expected, all the synthesized dihydrodiol and phenolic derivatives of N[1,2-a]P identified with those obtained from in vitro metabolism enabling the assignment of all the major metabolites.

Human in Vivo pharmacokinetics of [ 14C]Dibenzo[ def,p]chrysene by accelerator mass spectrometry following oral microdosing

DOE PAGES

Madeen, Erin; Corley, Richard A.; Crowell, Susan; ...

2014-11-24

Dibenzo( def,p)chrysene (DBC), (also known as dibenzo[a,l]pyrene), is a high molecular weight polycyclic aromatic hydrocarbon (PAH) found in the environment, including food, produced by the incomplete combustion of hydrocarbons. DBC, classified by IARC as a 2A probable human carcinogen, has a relative potency factor (RPF) in animal cancer models 30-fold higher than benzo[ a]pyrene. No data are available describing the disposition of high molecular weight (>4 rings) PAHs in humans to compare to animal studies. Pharmacokinetics of DBC was determined in 3 female and 6 male human volunteers following oral microdosing (29 ng, 5 nCi) of [ 14C]-DBC. This studymore » was made possible with highly sensitive accelerator mass spectrometry (AMS), capable of detecting [ 14C]-DBC equivalents in plasma and urine following a dose considered of de minimus risk to human health. Plasma and urine were collected over 72 h. The plasma C max was 68.8 ± 44.3 fg·mL –1 with a T max of 2.25 ± 1.04 h. Elimination occurred in two distinct phases: a rapid (α)-phase, with a T 1/2 of 5.8 ± 3.4 h and an apparent elimination rate constant (K el) of 0.17 ± 0.12 fg·h –1, followed by a slower (β)-phase, with a T 1/2 of 41.3 ± 29.8 h and an apparent K el of 0.03 ± 0.02 fg·h –1. In spite of the high degree of hydrophobicity (log Kow of 7.4), DBC was eliminated rapidly in humans, as are most PAHs in animals, compared to other hydrophobic persistent organic pollutants such as, DDT, PCBs and TCDD. Preliminary examination utilizing a new UHPLC-AMS interface, suggests the presence of polar metabolites in plasma as early as 45 min following dosing. Finally, this is the first in vivo data set describing pharmacokinetics in humans of a high molecular weight PAH and should be a valuable addition to risk assessment paradigms.« less

Differential modulation of dibenzo[def,p]chrysene transplacental carcinogenesis: Maternal diets rich in indole-3-carbinol versus sulforaphane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shorey, Lyndsey E.; Madeen, Erin P.; Linus Pauling Institute, Oregon State University, Corvallis, OR, 97331

2013-07-01

Cruciferous vegetable components have been documented to exhibit anticancer properties. Targets of action span multiple mechanisms deregulated during cancer progression, ranging from altered carcinogen metabolism to the restoration of epigenetic machinery. Furthermore, the developing fetus is highly susceptible to changes in nutritional status and to environmental toxicants. Thus, we have exploited a mouse model of transplacental carcinogenesis to assess the impact of maternal dietary supplementation on cancer risk in offspring. In this study, transplacental and lactational exposure to a maternal dose of 15 mg/Kg B.W. of dibenzo[def,p]chrysene (DBC) resulted in significant morbidity of offspring due to an aggressive T-cell lymphoblasticmore » lymphoma. As in previous studies, indole-3-carbinol (I3C, feed to the dam at 100, 500 or 1000 ppm), derived from cruciferous vegetables, dose-dependently reduced lung tumor multiplicity and also increased offspring survival. Brussels sprout and broccoli sprout powders, selected for their relative abundance of I3C and the bioactive component sulforaphane (SFN), respectively, surprisingly enhanced DBC-induced morbidity and tumorigenesis when incorporated into the maternal diet at 10% wt/wt. Purified SFN, incorporated in the maternal diet at 400 ppm, also decreased the latency of DBC-dependent morbidity. Interestingly, I3C abrogated the effect of SFN when the two purified compounds were administered in equimolar combination (500 ppm I3C and 600 ppm SFN). SFN metabolites measured in the plasma of neonates positively correlated with exposure levels via the maternal diet but not with offspring mortality. These findings provide justification for further study of the safety and bioactivity of cruciferous vegetable phytochemicals at supplemental concentrations during the perinatal period. - Highlights: • Dietary supplementation may modulate cancer risk in a mouse model of lymphoma. • Cruciferous vegetables may not contain sufficient I3C for transplacental protection. • SFN is abundant in cruciferous vegetables and may enhance risk in this model. • SFN and its mercapturic acid metabolites were measurable in neonatal plasma.« less

Human Microdosing with Carcinogenic Polycyclic Aromatic Hydrocarbons: In Vivo Pharmacokinetics of Dibenzo[ def,p ]chrysene and Metabolites by UPLC Accelerator Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madeen, Erin P.; Ognibene, Ted J.; Corley, Richard A.

Metabolism is a key health risk factor following exposures to pro-carcinogenic polycyclic aromatic hydrocarbons (PAHs) such as dibenzo[def,p]chrysene (DBC), an IARC classified 2A probable human carcinogen. Human exposure to PAHs occurs primarily from the diet in non-smokers. However, little data is available on the metabolism and pharmacokinetics in humans of high molecular weight PAHs (≥4 aromatic rings), including DBC. We previously determined the pharmacokinetics of DBC in human volunteers orally administered a micro-dose (29 ng; 5 nCi) of [14C]-DBC by accelerator mass spectrometry (AMS) analysis of total [14C] in plasma and urine. In the current study, we utilized a novelmore » “moving wire” interface between ultra-performance liquid chromatography (UPLC) and AMS to detect and quantify parent DBC and its major metabolites. The major [14C] product identified in plasma was unmetabolized [14C]-DBC itself, (Cmax= 18.5 ± 15.9 fg/mL, Tmax= 2.1 ± 1.0 h), whereas the major metabolite was identified as [14C]-(+/-)-DBC-11,12-diol (Cmax= 2.5 ± 1.3 fg/mL, Tmax= 1.8 h). Several minor species of [14C]-DBC metabolites were also detected for which no reference standards were available. Free and conjugated metabolites were detected in urine with [14C]-(+/-)-DBC-11,12,13,14-tetraol isomers identified as the major metabolites, 56.3% of which were conjugated (Cmax= 35.8 ± 23.0 pg/pool, Tmax= 6-12 h pool). [14C]-DBC-11,12-diol, of which 97.5% was conjugated, was also identified in urine (Cmax= 29.4 ± 11.6 pg/pool, Tmax= 6-12 h pool). Parent [14C]-DBC was not detected in urine. This is the first dataset to assess metabolite profiles and associated pharmacokinetics of a carcinogenic PAH in human volunteers at an environmentally relevant dose, providing the data necessary for translation of high dose animal models to humans for translation of environmental health risk assessment.« less

Human Micro-Dosing with Carcinogenic Polycyclic Aromatic Hydrocarbons: In Vivo Pharmacokinetics of Dibenzo[def,p]chrysene and Metabolites by UPLC Accelerator Mass Spectrometry

PubMed Central

Madeen, Erin P.; Ognibene, Ted J.; Corley, Richard A.; McQuistan, Tammie J.; Baird, William M.; Bench, Graham; Turteltaub, Ken W.; Williams, David E.

2017-01-01

Metabolism is a key health risk factor for exposures to pro-carcinogenic polycyclic aromatic hydrocarbons (PAHs) such as dibenzo[def,p]chrysene (DBC), an IARC classified 2A probable human carcinogen. Human exposure to PAHs occurs primarily from the diet in non-smokers. However, little data is available on the metabolism and pharmacokinetics in humans of high molecular weight PAHs (≥4 aromatic rings), including DBC. We previously determined the pharmacokinetics of DBC in human volunteers orally administered a micro-dose (29 ng; 5 nCi) of [14C]-DBC by accelerator mass spectrometry (AMS) analysis of total [14C] in plasma and urine. In the current study, we utilized a novel “moving wire” interface between ultra-performance liquid chromatography (UPLC) and the AMS to detect and quantify parent DBC and its major metabolites. The major [14C] product identified in plasma was unmetabolized [14C]-DBC itself, (Cmax= 18.5 ± 15.9 fg/mL, Tmax= 2.1 ± 1.0 h), whereas the major metabolite was identified as [14C]-(+/−)-DBC-11,12-diol (Cmax= 2.5 ± 1.3 fg/mL, Tmax= 1.8 h). Several minor species of [14C]-DBC metabolites were also detected for which no reference standards were available. Deconjugated and conjugated metabolites were detected in urine with [14C]-(+/−)-DBC-tetraol identified as the major metabolite, 88.7% of which was detected upon enzymatic deconjugation (Cmax= 35.8 ± 23.0 pg/pool, Tmax= 6–12 h pool). [14C]-DBC-11,12-diol, of which 94.4% was conjugated and identified in urine (Cmax= 29.4 ± 11.6 pg/pool, Tmax= 6–12 h pool). Parent [14C]-DBC was not detected in the urine. This is the first dataset to assess metabolite profiles and associated pharmacokinetics of a carcinogenic PAH in human volunteers at an environmentally relevant dose, providing the data necessary for translation of high dose laboratory animal models to human translation for environmental health risk assessment. PMID:27494294

Human in Vivo pharmacokinetics of [ 14C]Dibenzo[ def,p]chrysene by accelerator mass spectrometry following oral microdosing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Madeen, Erin; Corley, Richard A.; Crowell, Susan

Dibenzo( def,p)chrysene (DBC), (also known as dibenzo[a,l]pyrene), is a high molecular weight polycyclic aromatic hydrocarbon (PAH) found in the environment, including food, produced by the incomplete combustion of hydrocarbons. DBC, classified by IARC as a 2A probable human carcinogen, has a relative potency factor (RPF) in animal cancer models 30-fold higher than benzo[ a]pyrene. No data are available describing the disposition of high molecular weight (>4 rings) PAHs in humans to compare to animal studies. Pharmacokinetics of DBC was determined in 3 female and 6 male human volunteers following oral microdosing (29 ng, 5 nCi) of [ 14C]-DBC. This studymore » was made possible with highly sensitive accelerator mass spectrometry (AMS), capable of detecting [ 14C]-DBC equivalents in plasma and urine following a dose considered of de minimus risk to human health. Plasma and urine were collected over 72 h. The plasma C max was 68.8 ± 44.3 fg·mL –1 with a T max of 2.25 ± 1.04 h. Elimination occurred in two distinct phases: a rapid (α)-phase, with a T 1/2 of 5.8 ± 3.4 h and an apparent elimination rate constant (K el) of 0.17 ± 0.12 fg·h –1, followed by a slower (β)-phase, with a T 1/2 of 41.3 ± 29.8 h and an apparent K el of 0.03 ± 0.02 fg·h –1. In spite of the high degree of hydrophobicity (log Kow of 7.4), DBC was eliminated rapidly in humans, as are most PAHs in animals, compared to other hydrophobic persistent organic pollutants such as, DDT, PCBs and TCDD. Preliminary examination utilizing a new UHPLC-AMS interface, suggests the presence of polar metabolites in plasma as early as 45 min following dosing. Finally, this is the first in vivo data set describing pharmacokinetics in humans of a high molecular weight PAH and should be a valuable addition to risk assessment paradigms.« less

Sources of sedimentary PAHs in tropical Asian waters: differentiation between pyrogenic and petrogenic sources by alkyl homolog abundance.

PubMed

Saha, Mahua; Togo, Ayako; Mizukawa, Kaoruko; Murakami, Michio; Takada, Hideshige; Zakaria, Mohamad P; Chiem, Nguyen H; Tuyen, Bui Cach; Prudente, Maricar; Boonyatumanond, Ruchaya; Sarkar, Santosh Kumar; Bhattacharya, Badal; Mishra, Pravakar; Tana, Touch Seang

2009-02-01

We collected surface sediment samples from 174 locations in India, Indonesia, Malaysia, Thailand, Vietnam, Cambodia, Laos, and the Philippines and analyzed them for polycyclic aromatic hydrocarbons (PAHs) and hopanes. PAHs were widely distributed in the sediments, with comparatively higher concentrations in urban areas (Sigma PAHs: approximately 1000 to approximately 100,000 ng/g-dry) than in rural areas ( approximately 10 to approximately 100g-dry), indicating large sources of PAHs in urban areas. To distinguish petrogenic and pyrogenic sources of PAHs, we calculated the ratios of alkyl PAHs to parent PAHs: methylphenanthrenes to phenanthrene (MP/P), methylpyrenes+methylfluoranthenes to pyrene+fluoranthene (MPy/Py), and methylchrysenes+methylbenz[a]anthracenes to chrysene+benz[a]anthracene (MC/C). Analysis of source materials (crude oil, automobile exhaust, and coal and wood combustion products) gave thresholds of MP/P=0.4, MPy/Py=0.5, and MC/C=1.0 for exclusive combustion origin. All the combustion product samples had the ratios of alkyl PAHs to parent PAHs below these threshold values. Contributions of petrogenic and pyrogenic sources to the sedimentary PAHs were uneven among the homologs: the phenanthrene series had a greater petrogenic contribution, whereas the chrysene series had a greater pyrogenic contribution. All the Indian sediments showed a strong pyrogenic signature with MP/P approximately 0.5, MPy/Py approximately 0.1, and MC/C approximately 0.2, together with depletion of hopanes indicating intensive inputs of combustion products of coal and/or wood, probably due to the heavy dependence on these fuels as sources of energy. In contrast, sedimentary PAHs from all other tropical Asian cities were abundant in alkylated PAHs with MP/P approximately 1-4, MPy/Py approximately 0.3-1, and MC/C approximately 0.2-1.0, suggesting a ubiquitous input of petrogenic PAHs. Petrogenic contributions to PAH homologs varied among the countries: largest in Malaysia whereas inferior in Laos. The higher abundance of alkylated PAHs together with constant hopane profiles suggests widespread inputs of automobile-derived petrogenic PAHs to Asian waters.

Separation and characterization of gall bladder bile metabolites from speckled trout, Salvelinus fontinalis, exposed to individual polycyclic aromatic compounds.

PubMed

Leonard, J D; Hellou, J

2001-03-01

Speckled trout, Salvelinus fontinalis, were orally exposed to individual polycyclic aromatic compounds (PACs) represented by benzo[a]pyrene, carbazole, chrysene, dibenzofuran, dibenzothiophene, fluorene, phenanthrene, and pyrene. Fish were sacrificed 7 d after exposure and the gall bladder removed for bile analysis. High pressure liquid chromatography (HPLC) with fluorescence (F) and ultraviolet (UV) detection was used to determine the presence of PAC derivatives in the bile without pretreatment. Glucuronide conjugates were predominant in all exposures with variable amounts (0-53%) of phenols and starting material. Identification of compounds was confirmed by selective extraction of less polar nonconjugated PACs and enzymatic hydrolysis of water-soluble material. This was followed by HPLC and/or gas chromatography-mass spectrometry (GCMS) characterization of the produced phenols. Total metabolite levels varied widely among compounds.

Photodegradation of PAHs in passive water samplers.

PubMed

Allan, Ian J; Christensen, Guttorm; Bæk, Kine; Evenset, Anita

2016-04-15

Losses of deuterated polycyclic aromatic hydrocarbons (PAHs) used as performance reference compounds (PRCs) in semipermeable membrane devices deployed at fifteen coastal sampling sites near Harstad harbour in Northern Norway were used to investigate photodegradation of these photosensitive compounds. Unusual PRC dissipation profiles, especially for samplers exposed <5m below the water surface are indicative of photodegradation. A strong correlation between loss rates for d12-chrysene and d12-benzo[e]pyrene with consistently higher losses of the latter was found. The observed photodegradation rates may be sufficiently high to impact PAH masses absorbed by a factor of two. This study demonstrates that photodegradation during exposure of passive water samplers needs to be taken into account, particularly with deployments close to the water surface, when using SPMD canisters, or when sampling in the Arctic. Copyright © 2016 Elsevier Ltd. All rights reserved.

Illinois basin coal fly ashes. 1. Chemical characterization and solubility

USGS Publications Warehouse

Roy, W.R.; Griffin, R.A.; Dickerson, D.R.; Schuller, R.M.; Martin, S.M.C.

1984-01-01

Twelve precipitator-collected fly ash samples (nine derived from high-sulfur Illinois Basin coals and three from Western U.S. coals) were found to contain a variety of paraffins, aryl esters, phenols, and polynuclear aromatic hydrocarbons including phenanthrene, pyrene, and chrysene but all at very low concentrations. Less than 1% of the organic carbon in the samples was extractable into benzene. Solubility studies with a short-term (24-h) extraction procedure and a long-term (20-week) procedure indicate that the inorganic chemical composition of some types of fly ash effluent is time dependent and may be most toxic to aquatic ecosystems when initially mixed with water and pumped to disposal ponds. Some acidic, high-Cd fly ashes would be classified as hazardous wastes if coal ash was included in this waste category by future RCRA revisions. ?? 1984 American Chemical Society.

Infrared fluorescence from PAHs in the laboratory

NASA Technical Reports Server (NTRS)

Cherchneff, Isabelle; Barker, John R.

1989-01-01

Several celestial objects, including UV rich regions of planetary and reflection nebulae, stars, H II regions, and extragalactic sources, are characterized by the unidentified infrared emission bands (UIR bands). A few years ago, it was proposed that polycyclic aromatic hydrocarbon species (PAHs) are responsible for most of the UIR bands. This hypothesis is based on a spectrum analysis of the observed features. Comparisons of observed IR spectra with lab absorption spectra of PAHs support the PAH hypothesis. An example spectrum is represented, where the Orion Bar 3.3 micron spectrum is compared with the absorption frequencies of the PAHs Chrysene, Pyrene, and Coronene. The laser excited 3.3 micron emission spectrum is presented from a gas phase PAH (azulen). The infrared fluorescence theory (IRF) is briefly explained, followed by a description of the experimental apparatus, a report of the results, and discussion.

Biodegradation of naphthalene and anthracene by chemo-tactically active rhizobacteria of populus deltoides

PubMed Central

Bisht, Sandeep; Pandey, Piyush; Sood, Anchal; Sharma, Shivesh; Bisht, N. S.

2010-01-01

Several naphthalene and anthracene degrading bacteria were isolated from rhizosphere of Populus deltoides, which were growing in non-contaminated soil. Among these, four isolates, i.e. Kurthia sp., Micrococcus varians, Deinococcus radiodurans and Bacillus circulans utilized chrysene, benzene, toluene and xylene, in addition to anthracene and naphthalene. Kurthia sp and B. circulans showed positive chemotactic response for naphthalene and anthracene. The mean growth rate constant (K) of isolates were found to increase with successive increase in substrate concentration (0.5 to 1.0 mg/50ml). B. circulans SBA12 and Kurthia SBA4 degraded 87.5% and 86.6% of anthracene while, Kurthia sp. SBA4, B. circulans SBA12, and M. varians SBA8 degraded 85.3 %, 95.8 % and 86.8 % of naphthalene respectively after 6 days of incubation as determined by HPLC analysis. PMID:24031572

[PAH Cations as Viable Carriers of DIBs

NASA Technical Reports Server (NTRS)

Snow, Ted

1998-01-01

This report is intended to fill in the blanks in NASA's file system for our lab astro study of molecular ions of astrophysical interest. In order to give NASA what it needs for its files, I attach below the text of the section from our recent proposal to continue this work, in which we describe progress to date, including a large number of publications. Our initial studies were focused on PAH cations, which appear to be viable candidates as the carriers of the DIBs, an idea that has been supported by laboratory spectroscopy of PAH cations in inert matrices. Beginning with the simplest aromatic (benzene; C6H6) and moving progressively to larger species (naphthalene, C10OH8; pyrene, C16H10; and most recently chrysene, C18H12), we have been able to derive rate coefficients for reactions with neutral spices that are abundant in the diffuse interstellar medium.

Polycyclic aromatic hydrocarbon levels and risk assessment for food from service facilities in Korea.

PubMed

Park, Shin-Woong; Jeong, Jun-Hyun; Her, Jae-Young; Kim, Mina K; Lee, Kwang-Geun

2017-06-01

In this study, levels of benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene (BaP), dibenzo[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]pyrene in 412 food items collected from food service facilities in Korea were analysed. The concentrations of the eight polycyclic aromatic hydrocarbons (PAHs) ranged 0.13-0.48 μg/kg. The concentrations of benzo[a]pyrene in all food samples were <1 μg/kg, which is the lowest maximum limit in foods regulated by European Union legislation. PAH contents were employed to conduct exposure and risk assessment. The chronic daily intake of PAHs from 412 food samples was 5.48 × 10 -6 -4.70 ×x 10 -4  µg-TEQ BaP /kg/day with margins of exposure of 1.04 × 10 9 -1.16 × 10 11 .

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

NASA Technical Reports Server (NTRS)

Sagan, Carl; Khare, B. N.; Thompson, W. R.; Mcdonald, G. D.; Wing, Michael R.; Bada, Jeffrey L.; Vo-Dinh, Tuan; Arakawa, E. T.

1993-01-01

PAHs are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites, are identified, with a net abundance of about 0.0001 g/g (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bence, A.E.; Burns, W.A.

A procedure has been developed that discriminates Exxon Valdez crude from other sources of hydrocarbons found in Prince Williams Sound and the Gulf of Alaska. The procedure uses polycyclic aromatic hydrocarbon (PAH) distributions, measured by gas chromatography/mass spectrometry (GC/MS), to fingerprint sample extracts. The relative abundances of alkylated phenanthrenes, dibenzothiophenes, and chrysenes are used to differentiate Exxon Valdez crude and its weathering products from other hydrocarbons. Saturate fraction distributions are used to confirm the PAH identification whenever possible. The procedure has been applied to the more than 1,500 PAH analyses of tissues reported by the Oil Spill Health Task Force,more » formed after the spill to assess subsistence food safety, and nearly 4,700 PAH analyses of biological samples in PWSOIL, the government`s damage-assessment chemistry database. These two datasets constitute the largest collection of hydrocarbon analyses of biological samples form the spill-impact zone. 70 refs., 14 figs., 8 tabs.« less

Biomonitoring of atmospheric pollution by moss bags: Discriminating urban-rural structure in a fragmented landscape.

PubMed

Capozzi, F; Giordano, S; Di Palma, A; Spagnuolo, V; De Nicola, F; Adamo, P

2016-04-01

In this paper we investigated the possibility to use moss bags to detect pollution inputs - metals, metalloids and polycyclic aromatic hydrocarbons (PAHs) - in sites chosen for their different land use (agricultural, urban/residential scenarios) and proximity to roads (sub-scenarios), in a fragmented conurbation of Campania (southern Italy). We focused on thirty-nine elements including rare earths. For most of them, moss uptake was higher in agricultural than in urban scenarios and in front road sites. Twenty PAHs were analyzed in a subset of agricultural sites; 4- and 5-ringed PAHs were the most abundant, particularly chrysene, fluoranthene and pyrene. Overall results indicated that investigated pollutants have a similar spatial distribution pattern over the entire study area, with road traffic and agricultural practices as the major diffuse pollution sources. Moss bags proved a very sensitive tool, able to discriminate between different land use scenarios and proximity to roads in a mixed rural-urban landscape. Copyright © 2016 Elsevier Ltd. All rights reserved.

Study of the plasma proteome of Atlantic cod (Gadus morhua): Effect of exposure to two PAHs and their corresponding diols.

PubMed

Skogland Enerstvedt, Karianne; Sydnes, Magne O; Pampanin, Daniela M

2017-09-01

Occurrence of polycyclic aromatic hydrocarbon (PAH) contamination in the marine environment represents a risk to marine life and humans. In this study, plasma samples from Atlantic cod (Gadus morhua) were analysed by shotgun mass spectrometry to investigate the plasma proteome in response to exposure to single PAHs (naphthalene or chrysene) and their corresponding metabolites (dihydrodiols). In total, 369 proteins were identified and ranked according to their relative abundance. The levels of 12 proteins were found significantly altered in PAH exposed fish and are proposed as new biomarker candidates. Eleven proteins were upregulated, primarily immunoglobulin components, and one protein was downregulated (antifreeze protein type IV.) The uniformity of the upregulated proteins suggests a triggered immune response in the exposed fish. Overall, the results provide valuable knowledge for future studies of the Atlantic cod plasma proteome and generate grounds for establishing new plasma protein biomarkers for environmental monitoring of PAH related exposure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Preparation of stir bars for sorptive extraction using sol-gel technology.

PubMed

Liu, Wenmin; Wang, Hanwen; Guan, Yafeng

2004-08-06

A sol-gel coating method for the preparation of extractive phase on bars used in sorptive microextraction is described. The extraction phase of poly(dimethylsiloxane) is partially crosslinked with the sol-gel network, and the most part is physically incorporated in the network. Three aging steps at different temperatures are applied to complete the crosslinking process. Thirty-micrometer-thick coating layer is obtained by one coating process. The improved coating shows good thermal stability up to 300 degrees C. Spiked aqueous samples containing n-alkanes, polycyclic aromatic hydrocarbons and organophosphorus pesticides were analyzed by using the sorptive bars and GC. The results demonstrate that it is suitable for both aploar and polar analytes. The detection limit for chrysene is 7.44 ng/L, 0.74 ng/L for C19 and 0.9 ng/L for phorate. The extraction equilibration can be reached in less than 15 min by supersonic extraction with the bars of 30 microm coating layer.

Comparison of polycyclic aromatic hydrocarbons level between suspended solid and sediment samples of Pengkalan Chepa River, Kelantan state, Malaysia

NASA Astrophysics Data System (ADS)

Muslim, Noor Zuhartini Md; Babaheidari, Seyedreza Hashemi; Zakaria, Mohamad Pauzi

2015-09-01

Sixteen type of common Polycyclic Aromatic Hydrocarbons (PAHs) which consist of naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]-perylene, indeno[1,2,3-cd]-pyrene and dibenz[a,h]-anthracene in suspended solid and sediment samples of Pengkalan Chepa River, Kelantan state, Malaysia were investigated. The analysis samples were taken from six different sites of Pengkalan Chepa River during sunny day. The samples were subjected to a series of pre-treatment before the level of PAHs can be determined. A Gas Chromatography-Mass Spectrometry (GC-MS) was the prime method for the analysis of PAHs level. A total of 16 PAHs concentration in suspended solid of the whole Pengkalan Chepa River was found to be 2144.6 ng/g dry weights. This concentration was about eight times more than 16 PAHs concentration in sediment which found to be 266.5 ng/g dry weights.

Polycyclic Aromatic Hydrocarbons in drinking water of Tehran, Iran

PubMed Central

2013-01-01

Distribution and seasonal variation of sixteen priority polycyclic aromatic hydrocarbons (PAHs) were investigated in the drinking water of Tehran, the capital of Iran. Detected single and total PAHs concentrations were in the range of 2.01-38.96 and 32.45-733.10 ng/L, respectively, which were quite high compared to the values recorded in other areas of the world. The average occurrence of PAHs with high molecular weights was 79.55%; for example, chrysene occurred in 60.6% of the samples, with a maximum concentration of 438.96 ng/L. In addition, mean carcinogen to non-carcinogen PAHs ratio was 63.84. Although the concentration of benzo[a]pyrene, as an indicator of water pollution to PAHs, was lower than the guideline value proposed by World Health Organization (WHO) as well as that of Iranian National Drinking Water Standards for all of the samples, the obtained results indicated that carcinogen PAHs present in the drinking water of Tehran can cause threats to human health. PMID:24499505

Particulate polycyclic aromatic hydrocarbons (PAH) in the atmosphere of Bizerte city, Tunisia.

PubMed

Ben Hassine, S; Hammami, B; Ben Ameur, W; El Megdiche, Y; Barhoumi, B; Driss, M R

2014-09-01

The particle-phase concentrations of polycyclic aromatic hydrocarbons (PAH) were determined in 13 air samples collected in an urban area of Bizerte (Tunisia) during 2009-2010. Atmospheric particulate samples were extracted by ultrasonic bath and analyzed by high-performance liquid chromatography with fluorescence detection. PAH were found in all the analyzed air samples and the most abundant compounds were pyrene, fluoranthene, benzo[g,h,i]perylene, benzo[b]fluoranthene, chrysene and benzo[a]pyrene. ∑14-PAH concentrations ranging from 9.38 to 44.81 ng m(-3) with mean value of 25.39 ng m(-3). PAH diagnostic ratio source analysis revealed gasoline and diesel vehicular emissions as major sources. The mean total benzo[a]pyrene toxicity equivalent calculated for samples was 3.66 ng m(-3) and the mean contribution of the carcinogenic potency of benzo[a]pyrene was determined to be 55.8 %. Concentrations of particulate PAH in Bizerte city atmosphere were approximately eight times greater than sampled at a nearby rural site.

Synthesis, microsome-mediated metabolism, and identification of major metabolites of environmental pollutant naphtho[8,1,2-ghi]chrysene.

PubMed

Sharma, Arun K; Gowdahalli, Krishnegowda; Gimbor, Melissa; Amin, Shantu

2008-05-01

Naphtho[8,1,2- ghi]chrysene, commonly known as naphtho[1,2- e]pyrene (N[1,2- e]P) is a widespread environmental pollutant, identified in coal tar extract, air borne particulate matter, marine sediment, cigarette smoke condensate, and vehicle exhaust. Herein, we determined the ability of rat liver microsomes to metabolize N[1,2- e]P and an unequivocal assignment of the metabolites by comparing them with independently synthesized standards. We developed the synthesis of both the fjord region and the K-region dihydrodiols and various phenolic derivatives for metabolite identification. The 12-OH-N[1,2- e]P, fjord region dihydrodiol 14 and diol epoxide 15 were synthesized using a Suzuki cross-coupling reaction followed by the appropriate manipulation of the functional groups. The K-region trans-4,5-dihydrodiol ( 18) was prepared by the treatment of N[1,2- e]P with OsO 4 to give cis-dihydrodiol 16, followed by pyridinium chlorochromate oxidation to quinone 17, and finally reduction with NaBH 4 to afford the dihydrodiol 18 with the desired trans stereochemistry. The 9-OH-N[1,2- e]P ( 30) and N[1,2- e]P trans-9,10-dihydrodiol ( 32) were also synthesized following a Suzuki cross-coupling approach starting from 1,2,3,6,7,8-hexahydropyrene-4-boronic acid. The metabolism of N[1,2- e]P with rat liver microsomes led to several dihydrodiol and phenolic metabolites as assessed by the HPLC trace. The 11,12-dihydrodiol and 4,5-dihydrodiol were identified as major dihydrodiol metabolites. The synthesized 9,10-dihydrodiol, on the other hand, did not match with any of the peaks in the metabolism trace. Among the phenols, only 12-OH-N[1,2- e]P was identified in the metabolism. The other phenolic derivatives synthesized, that is, the 4-/5-, 9-, 10-, and 11-hydroxy derivatives, were not detected in the metabolism trace. In summary, N[1,2- e]P trans-11,12-dihydrodiol was the major metabolite formed along with N[1,2- e]P 4,5- trans-dihydrodiol and 12-OH-N[1,2- e]P on exposure of rat liver microsomes to N[1,2- e]P. The presence of N[1,2- e]P in the environment and formation of fjord region dihydrodiol 14 as a major metabolite in in vitro metabolism studies strongly suggest the role of N[1,2- e]P as a potential health hazard.

Cytochrome P450 1b1 in polycyclic aromatic hydrocarbon (PAH)-induced skin carcinogenesis: Tumorigenicity of individual PAHs and coal-tar extract, DNA adduction and expression of select genes in the Cyp1b1 knockout mouse

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siddens, Lisbeth K.; Superfund Research Center, Oregon State University, Corvallis, OR 97331; Bunde, Kristi L.

FVB/N mice wild-type, heterozygous or null for Cyp 1b1 were used in a two-stage skin tumor study comparing PAH, benzo[a]pyrene (BaP), dibenzo[def,p]chrysene (DBC), and coal tar extract (CTE, SRM 1597a). Following 20 weeks of promotion with TPA the Cyp 1b1 null mice, initiated with DBC, exhibited reductions in incidence, multiplicity, and progression. None of these effects were observed with BaP or CTE. The mechanism of Cyp 1b1-dependent alteration of DBC skin carcinogenesis was further investigated by determining expression of select genes in skin from DBC-treated mice 2, 4 and 8 h post-initiation. A significant reduction in levels of Cyp 1a1,more » Nqo1 at 8 h and Akr 1c14 mRNA was observed in Cyp 1b1 null (but not wt or het) mice, whereas no impact was observed in Gst a1, Nqo 1 at 2 and 4 h or Akr 1c19 at any time point. Cyp 1b1 mRNA was not elevated by DBC. The major covalent DNA adducts, dibenzo[def,p]chrysene-(±)-11,12-dihydrodiol-cis and trans-13,14-epoxide-deoxyadenosine (DBCDE-dA) were quantified by UHPLC-MS/MS 8 h post-initiation. Loss of Cyp1 b1 expression reduced DBCDE-dA adducts in the skin but not to a statistically significant degree. The ratio of cis- to trans-DBCDE-dA adducts was higher in the skin than other target tissues such as the spleen, lung and liver (oral dosing). These results document that Cyp 1b1 plays a significant role in bioactivation and carcinogenesis of DBC in a two-stage mouse skin tumor model and that loss of Cyp 1b1 has little impact on tumor response with BaP or CTE as initiators. - Highlights: • Cyp1b1 null mice exhibit lower skin cancer sensitivity to DBC but not BaP or CTE. • Cyp1b1 expression impacts expression of other PAH metabolizing enzymes. • cis/trans-DBCDE-dA ratio significantly higher in the skin than the spleen, lung or liver • Potency of DBC and CTE in mouse skin is higher than predicted by RPFs.« less

Profile distribution of polycyclic aromatic hydrocarbons in soils of drained peatlands after wildfires (Moscow region, Russia)

NASA Astrophysics Data System (ADS)

Tsibart, Anna; Gennadiev, Alexander; Koshovskii, Timur; Kovach, Roman

2014-05-01

Polycyclic aromatic compounds (PAHs) are formed in different natural and anthropogenic processes and could be found in many landscape components. These compounds are carcinogenic and belong to the group of persistent organic pollutants. The anthropogenic sources of PAHs are well-studied, but insufficient data are available on the hightemperature production of PAHs in natural processes. For example, natural fires are frequently related to the PAHs sources in landscapes, but very little factual data are on this topic. The soils of drained peatlands affected by catastrophic wildfires of 2010 and 2002 were studied in the Eastern part of Moscow Region (Russia). A total of 14 profiles of histosols and histic podsols were investigated. These series included soils of plots subjected to fires of different intensities and age, as well as soils of the background plots. Soil samples were taken from genetic horizons and from every 10 cm. The samples were analyzed for the contents of 14 prevailing individual compounds: fluorene, naphthalene, phenanthrene, chrysene, pyrene, anthracene, tetraphene, benz[a]pyrene, benzo[ghi]perylene, benzo[e]pyrene, coronene, dibenztiophene, triphenilene, benz(k)fluorantene. Morfological properties of soils after wildfires on drained peatlands were changed dramatically, the horizons of ash and char instead of organic layers were formed. These new horizons differ in the capability of PAHs accumulation. The char horizons have the highest concentrations of PAHs - up to 300 ng/g because of incomplete burning of organic matter in this sites, and the ash horizons, where the complete burning occured, contain only 10 ng/g PAHs. The highest concentrations of PAHs in soil profiles were detected after recent fires, and in cases of thick peat layers. After the combustion of peat chrysene, benz[a]pyrene, benz[e]pyrene, benzo[ghi]perylene, benz(k)fluorantene and tetraphene accumulated in soils. This is mainly the group of 4-6-nuclear compounds. The formation of high-molecular weight compounds is possible during smoldering process under a low oxygen supply. The oxygen deficit acts as a factor of the organic fragments recombination and PAHs production; therefore, relatively large amounts of PAHs are formed in peat fires. Moreover the peat fires occur directly in the soil layer; therefore, larger amounts of the resulting PAHs remain in the soils of the fire sites. The migration of low-molecular weight compounds occures in histic podsols, in histosols PAHs accumalate only in upper organic horizons. The research was conducted with the support of Russian Geographical Society.

Assessment of Fish Habitat, Water Quality, and Selected Contaminants in Streambed Sediments in Noyes Slough, Fairbanks, Alaska, 2001-2002

USGS Publications Warehouse

Kennedy, Ben W.; Whitman, Matthew S.; Burrows, Robert L.; Richmond, Sharon A.

2004-01-01

During 2001-2002, the U.S. Geological Survey sampled streambed sediment at 23 sites, measured water quality at 26 sites, and assessed fish habitat for the entire length of Noyes Slough, a 5.5-mile slough of the Chena River in Fairbanks, Alaska. These studies were undertaken to document the environmental condition of the slough and to provide information to the public for consideration in plans to improve environmental conditions of the waterway. The availability of physical habitat for fish in the slough does not appear to be limited, although some beaver dams and shallow water may restrict movement, particularly during low flow. Elevated water temperatures in summer and low dissolved-oxygen concentrations are the principle factors adversely affecting water quality in Noyes Slough. Increased flow mitigated poor water-quality conditions and reduced the number of possible fish barriers. Flow appears to be the most prominent mechanism shaping water quality and fish habitat in Noyes Slough. Streambed sediment samples collected at 23 sites in 2001 were analyzed for 24 trace elements. Arsenic, lead, and zinc were the only trace elements detected in concentrations that exceed probable effect levels for the protection of aquatic life. The background concentration for arsenic in Noyes Slough is naturally elevated because of significant concentrations of arsenic in local bedrock and ground water. Sources of the zinc and lead contamination are uncertain, however both lead and zinc are common urban contaminants. Streambed-sediment samples from 12 sites in 2002 were analyzed for organochlorine pesticides, polychlorinated biphenyls (PCBs), and semivolatile organic compounds (SVOCs). The concentration of bis(2-ethylhexyl)phthalate of 2,600 micrograms per kilogram (?g/kg) for one sample from the site above Aurora Drive approached the aquatic-life criterion of 2,650 ?g/kg. Low concentrations of p-cresol, chrysene, and fluoranthene were detected in most of the sediment samples. The presence of these compounds in Noyes Slough sediment was expected because cresols are emitted to the atmosphere in the exhaust from motor vehicles and chrysene and fluoranthene are formed during the incomplete burning of coal, oil, gas, wood, garbage, or other organic substances. Low-level concentrations of DDT or its degradation products DDD and DDE were detected in all samples collected during 2002. However, total DDT (DDT+DDD+DDE) concentrations are less than the effects range median aquatic-life criterion of 46.1 ?g/kg. In general, total DDT concentrations were less than 10 ?g/kg, except for samples from two sites that have estimated concentrations of about 14 and 20 ?g/kg.

PAH composition of Water Based Drilling Mud and drill cuttings in the offshore region, east coast of India.

PubMed

Jagwani, Devaanshi; Kulkarni, Atul; Shukla, Parth; Ramteke, Dilip S; Juneja, Harjeet D

2011-11-01

As a consequence of offshore drilling, used Water Based Drilling Muds (WBMs) are typically disposed off, by discharging into the sea; such a disposal does not fully eliminate the environmental hazards. Hence, in this study, 2, 3, 4 and 5 ringed polycyclic aromatic hydrocarbons (PAHs i.e. naphthalene, fluorene, phenanthrene, fluoranthene, chrysene and benzo (a) pyrene) were determined from the WBMs and associated drill cuttings obtained from varying depths(viz. 150, 300 and 600 m) from three offshore wells present in East coast of India. In both WBMs and drill cuttings, concentration of naphthalene was maximum i.e. 81.59 ± 2.73 and 39.87 ± 2.40 mg/kg respectively, while benzo (a) pyrene was minimum i.e. 0.19 ± 0.07 and 0.12 ± 0.03 mg/kg respectively. The WBMs contained significantly (p < 0.05) higher PAH concentration than drill cuttings. The individual PAH concentration significantly (p < 0.01) increased with increasing depth in each well.

Polymers imprinted with PAH mixtures--comparing fluorescence and QCM sensors.

PubMed

Lieberzeit, Peter A; Halikias, Konstantin; Afzal, Adeel; Dickert, Franz L

2008-12-01

Molecular imprinting with binary mixtures of different polycyclic aromatic hydrocarbons (PAH) is a tool for design of chemically highly sensitive layers for detection of these analytes. Sensor responses increase by one order of magnitude compared with layers imprinted with one type of template. Detection limits, e.g. for pyrene, reach down to 30 ng L(-1) in water, as could be observed with a naphthalene and pyrene-imprinted polyurethane. Comparing sensor characteristics obtained by QCM and fluorescence reveals different saturation behaviours indicating that, first, single PAH molecules occupy the interaction centres followed by gradual excimer incorporation at higher concentrations finally leading to substantial quenching, when all accessible cavities are occupied. The plateau in the mass-sensitive measurements suggests that up to 80% of the cavities generated in the MIP are re-occupied. Displacement measurements between chrysene and pyrene revealed that for imprinted layers with very high pyrene sensitivities the signals of both PAH are additive, whereas in materials with lower pyrene uptake the two analytes replace each other in the interaction sites of the polymer.

Quantitation of polycyclic aromatic hydrocarbons (PAH4) in cocoa and chocolate samples by an HPLC-FD method.

PubMed

Raters, Marion; Matissek, Reinhard

2014-11-05

As a consequence of the PAH4 (sum of four different polycyclic aromatic hydrocarbons, named benzo[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) maximum levels permitted in cocoa beans and derived products as of 2013, an high-performance liquid chromatography with fluorescence detection method (HPLC-FD) was developed and adapted to the complex cocoa butter matrix to enable a simultaneous determination of PAH4. The resulting analysis method was subsequently successfully validated. This method meets the requirements of Regulation (EU) No. 836/2011 regarding analysis methods criteria for determining PAH4 and is hence most suitable for monitoring the observance of the maximum levels applicable under Regulation (EU) No. 835/2011. Within the scope of this work, a total of 218 samples of raw cocoa, cocoa masses, and cocoa butter from several sample years (1999-2012), of various origins and treatments, as well as cocoa and chocolate products were analyzed for the occurrence of PAH4. In summary, it is noted that the current PAH contamination level of cocoa products can be deemed very slight overall.

A simple methodological validation of the gas/particle fractionation of polycyclic aromatic hydrocarbons in ambient air

NASA Astrophysics Data System (ADS)

Kim, Yong-Hyun; Kim, Ki-Hyun

2015-07-01

The analysis of polycyclic aromatic hydrocarbons (PAH) in ambient air requires the tedious experimental steps of both sampling and pretreatment (e.g., extraction or clean-up). To replace pre-existing conventional methods, a simple, rapid, and novel technique was developed to measure gas-particle fractionation of PAH in ambient air based on ‘sorbent tube-thermal desorption-gas chromatograph-mass spectrometer (ST-TD-GC-MS)’. The separate collection and analysis of ambient PAHs were achieved independently by two serially connected STs. The basic quality assurance confirmed good linearity, precision, and high sensitivity to eliminate the need for complicated pretreatment procedures with the detection limit (16 PAHs: 13.1 ± 7.04 pg). The analysis of real ambient PAH samples showed a clear fractionation between gas (two-three ringed PAHs) and particulate phases (five-six ringed PAHs). In contrast, for intermediate (four ringed) PAHs (fluoranthene, pyrene, benz[a]anthracene, and chrysene), a highly systematic/gradual fractionation was established. It thus suggests a promising role of ST-TD-GC-MS as measurement system in acquiring a reliable database of airborne PAH.

Optimization and validation of a method using UHPLC-fluorescence for the analysis of polycyclic aromatic hydrocarbons in cold-pressed vegetable oils.

PubMed

Silva, Simone Alves da; Sampaio, Geni Rodrigues; Torres, Elizabeth Aparecida Ferraz da Silva

2017-04-15

Among the different food categories, the oils and fats are important sources of exposure to polycyclic aromatic hydrocarbons (PAHs), a group of organic chemical contaminants. The use of a validated method is essential to obtain reliable analytical results since the legislation establishes maximum limits in different foods. The objective of this study was to optimize and validate a method for the quantification of four PAHs [benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene] in vegetable oils. The samples were submitted to liquid-liquid extraction, followed by solid-phase extraction, and analyzed by ultra-high performance liquid chromatography. Under the optimized conditions, the validation parameters were evaluated according to the INMETRO Guidelines: linearity (r2 >0.99), selectivity (no matrix interference), limits of detection (0.08-0.30μgkg -1 ) and quantification (0.25-1.00μgkg -1 ), recovery (80.13-100.04%), repeatability and intermediate precision (<10% RSD). The method was found to be adequate for routine analysis of PAHs in the vegetable oils evaluated. Copyright © 2016. Published by Elsevier Ltd.

Petroleum hydrocarbons in water from a Brazilian tropical estuary facing industrial and port development.

PubMed

Lemos, Rafael Thompson de Oliveira; de Carvalho, Paulo Sérgio Martins; Zanardi-Lamardo, Eliete

2014-05-15

A fast paced industrial and port development has occurred at Suape Estuary, Northeast Brazil, but no information about hydrocarbon concentrations in water is available to this area. Considering that, the contamination level of Suape was determined by UV-Fluorescence in terms of dissolved and/or dispersed petroleum hydrocarbons (DDPHs), during wet and dry seasons. DDPHs ranged between 0.05 and 4.59 μg L(-1) Carmópolis oil equivalents and 0.01-1.39 μg L(-1) chrysene equivalents, indicating DDPHs close to a baseline contamination level. Some relatively high concentrations (>1 μg L(-1)) were probably associated with shipyard operations (hull paintings and ship docking), pollutants remobilization by dredging operations, occasional industrial discharges and oil derivatives released by vessels. DDPHs concentrations were lower in the wet season suggesting that the increased dilution rates caused by rainfall dominated upon the wet deposition of atmospheric combustion-derived PAHs process. Results in this study may be used as baseline to further studies in this area. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis of extended polycyclic aromatic hydrocarbons by oxidative tandem spirocyclization and 1,2-aryl migration

NASA Astrophysics Data System (ADS)

Zhang, Xuan; Xu, Zhanqiang; Si, Weili; Oniwa, Kazuaki; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan

2017-04-01

The extended polycyclic aromatic hydrocarbons (PAHs) have received significant interdisciplinary attention due to their semiconducting applications in diverse organic electronics as well as intriguing structural interests of well-defined graphene segments. Herein, a highly efficient oxidative spirocyclization and 1,2-aryl migration tandem synthetic method for the construction of extended polyaromatic hydrocarbons (PAHs) has been developed. The CuCl-catalyst/PhCO3 tBu or DDQ oxidation system in the presence of trifluoroacetic acid enables the selective single-electron oxidation to take place preferentially at the more electron-rich alkene moiety of o-biphenylyl-substituted methylenefluorenes, giving rise to the subsequent tandem process. A variety of structurally diverse extended PAHs including functionalized dibenzo[g,p]chrysenes, benzo[f]naphtho[1,2-s]picene, hexabenzo[a,c,fg,j,l,op]tetracene, tetrabenzo[a,c,f,m]phenanthro[9,10-k]tetraphene, tetrabenzo[a,c,f,k]phenanthro[9,10-m]tetraphene, tetrabenzo[a,c,f,o]phenanthro[9,10-m]picene and S-type helicene have been readily synthesized.

Electron affinities of polycyclic aromatic hydrocarbons by means of B3LYP/6-31+G* calculations.

PubMed

Modelli, Alberto; Mussoni, Laura; Fabbri, Daniele

2006-05-25

The gas-phase experimental adiabatic electron affinities (AEAs) of the polycyclic aromatic hydrocarbons (PAHs) anthracene, tetracene, pentacene, chrysene, pyrene, benzo[a]pyrene, benzo[e]pyrene, and fluoranthene are well reproduced using the hybrid density functional method B3LYP with the 6-31+G* basis set, indicating that the smallest addition of diffuse functions to the basis set is suitable for a correct description of the stable PAH anion states. The calculated AEAs also give a very good linear correlation with available reduction potentials measured in solution. The AEAs (not experimentally available) of the isomeric benzo[ghi]fluoranthene and cyclopenta[cd]pyrene, commonly found in the environment, are predicted to be 0.817 and 1.108 eV, respectively, confirming the enhancement of the electron-acceptor properties associated with fusion of a peripheral cyclopenta ring. The calculated localization properties of the lowest unoccupied MO of cyclopenta[cd]pyrene, together with its relatively high electron affinity, account for a high reactivity at the ethene double bond of this PAH in reductive processes.

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions.

PubMed

Zhou, Hui; Wu, Chunfei; Onwudili, Jude A; Meng, Aihong; Zhang, Yanguo; Williams, Paul T

2015-02-01

The formation of 2-4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. The results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock. Copyright © 2014 Elsevier Ltd. All rights reserved.

Influence of fuel composition on polycyclic aromatic hydrocarbon emissions from a fleet of in-service passenger cars

NASA Astrophysics Data System (ADS)

Lim, McKenzie C. H.; Ayoko, Godwin A.; Morawska, Lidia.; Ristovski, Zoran D.; Jayaratne, E. Rohan

The composition of exhaust emissions from eight in-service passenger cars powered by liquefied petroleum gas (LPG) and unleaded petrol (ULP) were measured on a chassis dynamometer at two driving speeds (60 and 80 km h -1) with the aims of evaluating their polycyclic aromatic hydrocarbon (PAH) contents and investigating the effects of the type of fuel on vehicle performance, ambient air quality and associated health risks. Naphthalene, fluorene, phenanthrene, anthracene, pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene were the most prominent PAHs emitted by both ULP and LPG powered cars. The total emission factors of PAHs from LPG cars were generally lower than (but statistically comparable with) those of ULP cars. Similarly, the total BAP eq of the PAHs emitted by LPG cars were lower than those from ULP cars. Multi-criteria decision making (MCDM) methods showed that cars powered by LPG fuel performed better than those powered by ULP fuel in term of PAH levels. The implications of these observations on the advantages and disadvantages of using ULP and LPG fuels are discussed.

Polycyclic aromatic hydrocarbons and the unidentified infrared emission bands - Auto exhaust along the Milky Way

NASA Technical Reports Server (NTRS)

Allamandola, L. J.; Tielens, A. G. G. M.; Barker, J. R.

1985-01-01

The unidentified infrared emission features (UIR bands) are attributed to a collection of partially hydrogenated, positively charged polycyclic aromatic hydrocarbons (PAHs). This assignment is based on a spectroscopic analysis of the UIR bands. Comparison of the observed interstellar 6.2 and 7.7-micron bands with the laboratory measured Raman spectrum of a collection of carbon-based particulates (auto exhaust) shows a very good agreement, supporting this identification. The infrared emission is due to relaxation from highly vibrationally and electronically excited states. The excitation is probably caused by UV photon absorption. The infrared fluorescence of one particular, highly vibrationally excited PAH (chrysene) is modeled. In this analysis the species is treated as a molecule rather than bulk material and the non-thermodynamic equilibrium nature of the emission is fully taken into account. From a comparison of the observed ratio of the 3.3 to 11.3-micron UIR bands with the model calculations, the average number of carbon atoms per molecule is estimated to be about 20. The abundance of interstellar PAHs is calculated to be about 2 x 10 to the -7th with respect to hydrogen.

Identification of polycyclic aromatic hydrocarbons in mutagenic adsorbates to a copper-phthalocyanine derivative recovered from municipal river water.

PubMed

Sayato, Y; Nakamuro, K; Ueno, H; Goto, R

1993-08-01

A study was made to identify polycyclic aromatic hydrocarbons (PAHs) in the mutagenic adsorbate to blue cotton recovered from the water of the Katsura River which is a tributary of the Yodo River, a typical municipal river. As blue cotton bears a covalently bound copper-phthalocyanine derivative which can adsorb PAHs over 3 rings, PAHs in the adsorbate were separated into 4 fractions (I-IV) by Sephadex LH-20 gel chromatography. Fractions III and IV showed high direct and indirect frameshift mutagenicity in strains YG1021 and YG1024, the nitroreductase- and O-acetyltransferase-overproducing derivatives of TA98, especially in YG1024 with S9 mix, whereas these fractions showed less mutagenicity in TA98NR or TA98/1,8-DNP6. These results suggest that mutagenic nitroarenes and aminoarenes are present in both fractions. The retention times of some peaks separated from both fractions using high performance liquid chromatography (HPLC) with a fluorescence detector were identical with those of authentic PAHs. Gas chromatography-mass spectrometry of some HPLC fractions demonstrated that anthraquinone, azulene derivative, quinoline derivative, chrysene and benzo[b]fluoranthene are probably contained in these fractions.

Electromagnetic plasmon propagation and coupling through gold nanoring heptamers: a route to design optimized telecommunication photonic nanostructures.

PubMed

Ahmadivand, Arash; Golmohammadi, Saeed

2014-06-20

In this work, a configuration of bulk gold nanorings with certain geometrical sizes has been utilized for designing efficient photonic subwavelength nanostructures. We verify that adjacent heptamers based on gold nanorings are able to couple and transport magnetic plasmon resonance along a nanoring array in chrysene and triphenylene molecule orientations. This magnetic resonance transmission is caused by an antiphase circular current through the heptamer arrays. An orientation model of nanoring heptamers helps us to provide efficient optical structures with a remarkable decay length and a trivial ratio of destructive interferences. Exploiting the robust magnetic plasmon resonance coupling effect between heptamers arrays, we would be able to propose a practical plasmonic waveguide, a Y-shaped optical power divider (splitter), and an ON/OFF router that is operating based on destructive and constructive interferences. The quality of power splitting has been discussed comprehensively and also, the effect of undesirable occasions on the functioning performance of the proposed router has been investigated numerically. Ultimately, we verify that employing heptamers based on gold nanorings leads us to propose efficient plasmonic nanostructures and devices that are able to work in the telecommunication spectrum.

Degradation of polycyclic aromatic hydrocarbons in crumb tyre rubber catalysed by rutile TiO2 under UV irradiation.

PubMed

Yu, Kai; Huang, Linyue; Lou, Lan-Lan; Chang, Yue; Dong, Yanling; Wang, Huan; Liu, Shuangxi

2015-01-01

The polycyclic aromatic hydrocarbons (PAHs) in crumb tyre rubber were firstly degraded under UV irradiation in the presence of rutile TiO2 and hydrogen peroxide. The effects of light intensity, catalyst amount, oxidant amount, initial pH value, co-solvent content, and reaction time on degradation efficiency of typical PAHs in crumb tyre rubber were studied. The results indicated that UV irradiation, rutile TiO2, and hydrogen peroxide were beneficial to the degradation of PAHs and co-solvent could accelerate the desorption of PAHs from crumb tyre rubber. Up to 90% degradation efficiency of total 16 PAHs could be obtained in the presence of rutile TiO2 (1 wt%) and hydrogen peroxide (1.0 mL) under 1800 µW cm(-2) UV irradiation for 48 h. The high molecular weight PAHs (such as benz(a)pyrene) were more difficult to be degraded than low molecular weight PAHs (such as phenanthrene, chrysene). Moreover, through the characterization of reaction solution and degradation products via GC-MS, it was proved that the PAHs in crumb tyre rubber were successfully degraded.

Input and behavior of polycyclic aromatic hydrocarbons in arable, fallow, and forest soils of the taiga zone (Tver oblast)

NASA Astrophysics Data System (ADS)

Zhidkin, A. P.; Gennadiev, A. N.; Koshovskii, T. S.

2017-03-01

Contents of 11 most prevalent polycyclic aromatic hydrocarbons (PAHs) in snow and soils of arable, fallow, and forest areas significantly remote from impact technogenic sources of polyarenes have been examined in the Torzhok district of Tver oblast. From the analysis of snow samples, the volumes and composition of PAHs coming from the atmosphere onto the areas of different land use have been determined. Light hydrocarbons prevail in PAHs. They make up 65-70% of total PAHs; their share in soils reaches almost 95%. An increase in the content of PAHs is revealed in fallow soils compared to arable and afforested areas. A direct relationship is revealed between the lateral distribution of total PAHs and the content of organic carbon. The distribution of total PAHs is surface-accumulative in forest soils, mainly uniform in arable soils, and deepaccumulative in fallow soils. PAH groups characterized by similar radial distributions and ratios between their reserves in snow and soils are distinguished: (1) fluorene and phenanthrene, (2) biphenyl and naphthalene, (3) benzo(a)anthracene, chrysene, perylene, and benzo[ a]pyrene, and (4) anthracene and benzo[ ghi]pyrene.

Effects of polycyclic aromatic compounds in fine particulate matter generated from household coal combustion on response to EGFR mutations in vitro.

PubMed

Ho, Kin-Fai; Chang, Chih-Cheng; Tian, Linwei; Chan, Chi-Sing; Musa Bandowe, Benjamin A; Lui, Ka-Hei; Lee, Kang-Yun; Chuang, Kai-Jen; Liu, Chien-Ying; Ning, Zhi; Chuang, Hsiao-Chi

2016-11-01

Induction of PM 2.5 -associated lung cancer in response to EGFR-tyrosine kinase inhibitors (EGFR-TKI) remains unclear. Polycyclic aromatic hydrocarbons (PAHs) and their polar derivatives (oxygenated PAHs: OPAHs and azaarenes: AZAs) were characterized in fine particulates (PM 2.5 ) emitted from indoor coal combustion. Samples were collected in Xuanwei (Yunnan Province), a region in China with a high rate of lung cancer. Human lung adenocarcinoma cells A549 (with wild-type EGFR) and HCC827 (with EGFR mutation) were exposed to the PM 2.5 , followed by treatment with EGFR-TKI. Two samples showed significant and dose-dependent reduction in the cell viability in A549. EGFR-TKI further demonstrated significantly decreased in cell viability in A549 after exposure to the coal emissions. Chrysene and triphenylene, dibenzo[a,h]anthracene, benzo[ghi]perylene, azaarenes and oxygenated polycyclic aromatic hydrocarbons (carbonyl-OPAHs) were all associated with EGFR-TKI-dependent reduced cell viability after 72-h exposure to the PM 2.5 . The findings suggest the coal emissions could influence the response of EGFR-TKI in lung cancer cells in Xuanwei. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of particulate polycyclic aromatic hydrocarbons in an urban atmosphere of central-southern Spain.

PubMed

Villanueva, Florentina; Tapia, Araceli; Cabañas, Beatriz; Martínez, Ernesto; Albaladejo, José

2015-12-01

Over 1-year period, 13 polycyclic aromatic hydrocarbons (PAHs) associated with particulate matter PM10 have been monitored for the first time in the atmosphere of Ciudad Real, situated at the central-southern Spain. PM10-bound PAHs were collected using a high-volume sampler from autumn 2012 to summer 2013 and were analyzed by HPLC with fluorescence detector. The most abundant PAHs were pyrene, chrysene, benzo[b]fluoranthene, dibenzo[a,h]anthracene and benzo[g,h,i]perylene. The ∑PAH concentrations in Ciudad Real were 888, 368, 259 and 382 pg m(-3) for winter, spring, summer and autumn seasons, respectively. The diurnal variation of PAH was also investigated presenting the highest concentrations during the evening (19:00-23:00). Benzo[a]pyrene concentrations ranged from 2.4 to 110 pg m(-3), these values are lower than the target value proposed by the European legislation, 1 ng m(-3). Diagnostic ratios were used to identify potential sources of PAHs. Results suggest that vehicle emissions are the major source of identified PAHs, with a higher contribution of diesel engines although other anthropogenic sources could also have an impact on the PAH levels.

Polycyclic aromatic hydrocarbons in Bangladeshi vegetables and fruits.

PubMed

Hossain, M Amzad; Hoque, Mohammad Zahirul

2011-01-01

Polycyclic aromatic hydrocarbons (PAHs) occur as contaminants in different types of food predominantly from environmental pollution, food packaging and food processing and the levels found depend on the source of the contamination. PAHs emissions from automobile traffic and industry activities were shown to influence the PAHs levels and profiles in vegetables and fruits grown nearby. The present study was carried out to determine the levels of PAHs in samples of tomato, cabbage and apple, collected from six different places of urban and rural areas of plantation in Dhaka city. Eight PAHs listed in the priority pollutant of US Environment Protection Agency and regarded as carcinogens were analyzed in this study. The analytical method involved saponification with methanolic KOH, liquid-liquid extraction with cyclohexane, clean-up on silica gel column and determination by Gas chromatography and mass spectrometry. The mean levels of total PAHs were 9.50 μg/kg in tomato, 8.86 μg/kg in cabbage and 4.05 μg/kg in apple. Of the carcinogenic PAHs, benzo(a)anthracene was the most representative, being found in 89% of all samples analysed. Chrysene was not detected in any sample. Copyright © 2010 Elsevier Ltd. All rights reserved.

Fate and Transport of Polycyclic Aromatic Hydrocarbons in Upland Irish Headwater Lake Catchments

PubMed Central

Scott, Heidi E. M.; Aherne, Julian; Metcalfe, Chris D.

2012-01-01

Polycyclic aromatic hydrocarbons (PAHs) are a concern due to their carcinogenicity and propensity for transboundary atmospheric transport. Ireland is located on the western periphery of Europe and assumed to receive clean Atlantic air. As such, it has been used as an atmospheric reference for comparison to other regions. Nonetheless, few studies have evaluated concentrations of PAHs within the Irish environment. In the current study, PAHs were measured at five upland (500–800 masl) headwater lake catchments in coastal regions around Ireland, remote from industrial point source emissions. Semipermeable membrane devices were deployed in lakes for a 6-month period in July 2009, and topsoils were sampled from each catchment during October 2010. The concentrations of PAHs were low at most study sites with respect to other temperate regions. Homologue groups partitioned between lake and soil compartments based on their molecular weight were: “lighter” substances, such as Phenanthrene and Fluorene, were found in higher proportions in lakes, whereas “heavier” compounds, such as Chrysene and Benz[a]anthracene, were more prominent in soils. Concentrations of PAHs were highest at the east coast sites, potentially due to contributions from historical transboundary and regional combustion sources. PMID:23346024

Influence of infrared final cooking on polycyclic aromatic hydrocarbon formation in ohmically pre-cooked beef meatballs.

PubMed

Kendirci, Perihan; Icier, Filiz; Kor, Gamze; Onogur, Tomris Altug

2014-06-01

Effects of infrared cooking on polycyclic aromatic hydrocarbon (PAH) formation in ohmically pre-cooked beef meatballs were investigated. Samples were pre-cooked in a specially designed-continuous type ohmic cooking at a voltage gradient of 15.26V/cm for 92s. Infrared cooking was applied as a final cooking method at different combinations of heat fluxes (3.706, 5.678, 8.475kW/m(2)), application distances (10.5, 13.5, 16.5cm) and application durations (4, 8, 12min). PAHs were analyzed by using high performance liquid chromatography (HPLC) equipped with a fluorescence detector. The total PAH levels were detected to be between 4.47 and 64μg/kg. Benzo[a] pyrene (B[a]P) and PAH4 (sum of B[a]P, chrysene (Chr), benzo[a]anthracene (B[a]A) and benzo[b]fluoranthene (B[b]F)) levels detected in meatballs were below the EC limits. Ohmic pre-cooking followed by infrared cooking may be regarded as a safe cooking procedure of meatballs from a PAH contamination point of view. Copyright © 2014 Elsevier Ltd. All rights reserved.

Quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair by HPLC with fluorescence detection: a biological monitoring method to evaluate the exposure to PAHs.

PubMed

Toriba, Akira; Kuramae, Yayoi; Chetiyanukornkul, Thaneeya; Kizu, Ryoichi; Makino, Tsunehisa; Nakazawa, Hiroyuki; Hayakawa, Kazuichi

2003-01-01

A high-performance liquid chromatographic (HPLC) method with fluorescence detection was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs) in human hair. Fifteen kinds of PAHs classified as priority pollutants by the US EPA were quantified with four perdeuterated PAHs as internal standards. After 50 mg hair samples were washed with n-hexane to remove external contamination of PAHs, the samples were digested in 2.5 M sodium hydroxide. The digests were extracted with n-hexane and then analyzed by HPLC. Eleven kinds of PAHs were identified in hair samples of 20 subjects, and 10 kinds of PAHs were eventually quantified using the internal standards. For anthracene, chrysene and benzo[k]fluoranthene, significant differences were observed between smokers and non-smokers. Although benzo[b]fluoranthene, dibenz[a,h]anthracene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene were observed in the particulates of indoor and outdoor air, they were not detected in all hair samples. The analysis of PAHs in human hair should be useful as a new biomarker to evaluate the exposure to PAHs.

Removal of polycyclic aromatic hydrocarbons from soil: a comparison between bioremoval and supercritical fluids extraction.

PubMed

Amezcua-Allieri, M A; Ávila-Chávez, M A; Trejo, A; Meléndez-Estrada, J

2012-03-01

Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic substances which are resistant to environmental degradation due to their highly hydrophobic nature. Soils contaminated with PAHs pose potential risks to human and ecological health, therefore concern over their adverse effects have resulted in extensive studies on their removal from contaminated soils. The main purpose of this study was to compare experimental results of PAHs removal, from a natural certified soil polluted with PAHs, by biological methods (using bioaugmentation and biostimulation in a solid-state culture) with those from supercritical fluid extraction (SFE), using supercritical ethane as solvent. The comparison of results between the two methods showed that maximal removal of naphthalene, acenaphthene, fluorene, and chrysene was performed using bioremediation; however, for the rest of the PAHs considered (fluoranthene, pyrene, and benz(a)anthracene) SFE resulted more efficient. Although bioremediation achieved higher removal ratios for certain hydrocarbons and takes advantage of the increased rate of natural biological processes, it takes longer time (i.e. 36 d vs. half an hour) than SFE and it is best for 2-3 PAHs rings. Copyright © 2011 Elsevier Ltd. All rights reserved.

Validation of analytical conditions for determination of polycyclic aromatic hydrocarbons in roasted coffee by gas chromatography-mass spectrometry.

PubMed

Guatemala-Morales, Guadalupe María; Beltrán-Medina, Elisa Alejandra; Murillo-Tovar, Mario Alfonso; Ruiz-Palomino, Priscilla; Corona-González, Rosa Isela; Arriola-Guevara, Enrique

2016-04-15

Polycyclic aromatic hydrocarbons (PAHs) are of significant interest due to their genotoxicity in humans. PAHs quantification in coffee is complex since some of its compounds interfere in the chromatographic analysis, which hinders the reliable determination of the PAHs. Analytical conditions for the ultrasound extraction, purification and quantification of 16 PAHs in roasted coffee were studied. The better extraction efficiency of benzo[a]pyrene (68%) from ground-roasted coffee was achieved with a solvent ratio of Hex:MC (9:1 v/v) and three extraction periods of 20 min, followed by alkaline saponification and purification of the extracts. The detection limits were 0.85-39.32 ng mL(-1), and the quantification limits from 2.84 to 131.05 ng mL(-1), obtained for fluoranthene and chrysene, respectively. The extraction was effective for most of the analytes, with recoveries of 39.8% dibenzo[ah]anthracene and 69.0% benzo[b]fluoranthene. For coffee roasted in a spouted bed reactor, the summation of the 16 PAHs ranged from 3.5 to 16.4 μg kg(-1). Copyright © 2015 Elsevier Ltd. All rights reserved.

Regional modelling of polycyclic aromatic hydrocarbons: WRF-Chem-PAH model development and East Asia case studies

NASA Astrophysics Data System (ADS)

Mu, Qing; Lammel, Gerhard; Gencarelli, Christian N.; Hedgecock, Ian M.; Chen, Ying; Přibylová, Petra; Teich, Monique; Zhang, Yuxuan; Zheng, Guangjie; van Pinxteren, Dominik; Zhang, Qiang; Herrmann, Hartmut; Shiraiwa, Manabu; Spichtinger, Peter; Su, Hang; Pöschl, Ulrich; Cheng, Yafang

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRF-Chem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

Versatile peroxidase of Bjerkandera fumosa: substrate and inhibitor specificity.

PubMed

Pozdnyakova, Natalia; Makarov, Oleg; Chernyshova, Marina; Turkovskaya, Olga; Jarosz-Wilkolazka, Anna

2013-01-10

The inhibitor and substrate specificities of versatile peroxidase from Bjerkandera fumosa (VPBF) were studied. Two different effects were found: NaN(3), Tween-80, anthracene, and fluorene decreased the activity of VPBF, but p-aminobenzoic acid increased it. A mixed mechanism of effector influence on the activity of this enzyme was shown. The catalytic properties of VPBF in the oxidation of mono- and polycyclic aromatic compounds were studied also. 2,7-Diaminofluorene, ABTS, veratryl alcohol, and syringaldazine can be oxidized by VPBF in two ways: either directly by the enzyme or by diffusible chelated Mn(3+) as an oxidizing agent. During VPBF oxidation of 2,7-diaminofluorene, both with and without Mn(2+), biphasic kinetics with apparent saturation in both micromolar and millimolar ranges were obtained. In the case of ABTS, inhibition of VPBF activity by an excess of substrate was observed. Direct oxidation of p-aminobenzoic acid by versatile peroxidase was found for the first time. The oxidation of three- and four-ring PAHs by VPBF was investigated, and the oxidation of anthracene, phenanthrene, fluorene, pyrene, chrysene, and fluoranthene was shown. The products of PAH oxidation (9,10-anthraquinone, 9,10-phenanthrenequinone, and 9-fluorenone) catalyzed by VPBF were identified. Copyright © 2012 Elsevier Inc. All rights reserved.

Sample preparation of sewage sludge and soil samples for the determination of polycyclic aromatic hydrocarbons based on one-pot microwave-assisted saponification and extraction.

PubMed

Pena, M Teresa; Pensado, Luis; Casais, M Carmen; Mejuto, M Carmen; Cela, Rafael

2007-04-01

A microwave-assisted sample preparation (MASP) procedure was developed for the analysis of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and soil samples. The procedure involved the simultaneous microwave-assisted extraction of PAHs with n-hexane and the hydrolysis of samples with methanolic potassium hydroxide. Because of the complex nature of the samples, the extracts were submitted to further cleaning with silica and Florisil solid-phase extraction cartridges connected in series. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[e]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene, and indeno[1,2,3-cd]pyrene, were considered in the study. Quantification limits obtained for all of these compounds (between 0.4 and 14.8 microg kg(-1) dry mass) were well below of the limits recommended in the USA and EU. Overall recovery values ranged from 60 to 100%, with most losses being due to evaporation in the solvent exchange stages of the procedure, although excellent extraction recoveries were obtained. Validation of the accuracy was carried out with BCR-088 (sewage sludge) and BCR-524 (contaminated industrial soil) reference materials.

Evolution of potential ecological impacts of the bottom sediment from the Gulf of Gemlik; Marmara Sea, Turkey.

PubMed

Unlü, Selma; Alpar, Bedri

2009-12-01

The eastern and southern coasts of the Gulf of Gemlik, a resort in the Sea of Marmara, Turkey, are under the influence of rapid ecotourism development, direct domestic and industrial discharges via rivers and outfalls, surface run-off, drainage from ports and shipping. According to sediment quality criteria in use around the world, sediment quality in the gulf shows a broad spectrum. It is more related by direct input, rather than by the type of sediment, and excluding inner port and southern coasts, it does not exert adverse biological effects yet. The total PAH concentrations range from 51 to 13,482 ng/g dry weight with the mean value of 1,850 ng/g dry weight (n = 61). The elevated values of the total toxic Benzo[a]pyrene equivalency (TEQcarc), with a maximum of 1,838 ng/g dry weight, were found at the inner harbor of Gemlik, possibly posing hazard to benthic organisms. Among the different PAHs, the contribution to the total TEQcarc decreased as the following order: Benzo[a]pyrene (43.6%) > Benzo[k]fluoranthene (36.0%) > Indeno[1,2,3-cd]pyrene (35.1%) > Benzo[b]fluoranthene (20.0%) > Chrysene + Triphenylene (18.9%) > Benzo[a]anthracene (12.5%).

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: environmental legacy after twelve years of the Gulf war oil spill.

PubMed

Bejarano, Adriana C; Michel, Jacqueline

2010-05-01

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU(FCV,43)). Samples were assigned to risk categories according to ESBTU(FCV,43) values: no-risk (< or = 1), low (>1 - < or = 2), low-medium (>2 - < or = 3), medium (>3 - < or = 5) and high-risk (>5). Sixty seven percent of samples had ESBTU(FCV,43) > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30 - <60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War. Copyright 2009 Elsevier Ltd. All rights reserved.

Identification of mammalian cell genotoxins in respirable diesel exhaust particles by bioassay-directed chemical analysis.

PubMed

Oh, Seung-Min; Chung, Kyu-Hyuck

2006-03-01

A bioassay-directed chemical analysis which consists of mammalian cell bioassays (comet assay, CBMN assay and EROD-microbioassay) in conjunction with analytical measurements was performed to identify the most biologically active compounds of the diesel exhaust particulate matters (DEPs) on mutagenic activity. These bioassay systems were suitable to estimate the mammalian genotoxic potentials of pollutants present in low concentrations in limited environmental samples, as is the case with DEPEs. The results from mutagenic assay showed that the aromatic and slightly polar fraction of DEPs induced chromosomal damage and DNA breakage in a non-cytotoxic dose. It was also revealed that indirect-acting mutagens may mainly contribute to the mutagenic effect of aromatic fraction via the enzyme metabolism system. In the aromatic fraction, several indirect-acting mutagenic PAHs such as dibenzo(a,h)anthracene, chrysene, and 1,2-benzanthracene were detected by GC-MS and the complex mixture effect of this fraction was quantified in terms of its biological-TCDD equivalent concentration (bio-TEQ) which was 32.82 bio-TEQ ng/g-DEPs by EROD-microbioassay. Conclusively, we confirmed that indirect-acting mutagens contained in aromatic fraction may be important causatives of the genotoxicity of extracts of DEPs by integrating the results obtained from a mammalian cell bioassay-directed fractionation.

Reconnaissance of water quality at a US Department of Energy site, Pinellas County, Florida

USGS Publications Warehouse

Fernandez, Mario

1985-01-01

Sanitary and industrial wastes at the Pinellas Plant of the U.S. Department of Energy, prior to December 1982, were combined, treated, and disposed of by ponding and spray irrigation on a 10-acre tract within the plant site. Prior to 1972, the treated wastes were released to surface drainage features. An electromagnetic survey for ground conductivity was made to identify changes in the ground conductivity that may be due to the spray irrigation disposal operations. Water samples from four test wells drilled into the surficial aquifer and the two disposal ponds and bottom material from the ponds were analyzed for priority and nonpriority pollutants, total organic carbon, volatile organic carbon, herbicides, insecticides, trace metals, nutrients, and major constituents. Overall, concentrations of constituents in the water samples were (1) less than the detection limits, (2) within U.S. Environmental Protection Agency quality criteria for water, or (3) within the range of results for a designated background water-quality site. Concentrations of 12 priority pollutants were found to be considerably above detection limits. Concentrations of these compounds, mostly coal-tar derivatives, ranged from 220 to 5,500 micrograms per kilogram; the detection limit for these compounds is 10 micrograms per kilogram. Included in these compounds were anthracene, pyrenes, and chrysene. (USGS)

Influence of Cadmium and Mercury on Activities of Ligninolytic Enzymes and Degradation of Polycyclic Aromatic Hydrocarbons by Pleurotus ostreatus in Soil

PubMed Central

Baldrian, Petr; in der Wiesche, Carsten; Gabriel, Jiří; Nerud, František; Zadražil, František

2000-01-01

The white-rot fungus Pleurotus ostreatus was able to degrade the polycyclic aromatic hydrocarbons (PAHs) benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, and benzo[ghi]perylene in nonsterile soil both in the presence and in the absence of cadmium and mercury. During 15 weeks of incubation, recovery of individual compounds was 16 to 69% in soil without additional metal. While soil microflora contributed mostly to degradation of pyrene (82%) and benzo[a]anthracene (41%), the fungus enhanced the disappearance of less-soluble polycyclic aromatic compounds containing five or six aromatic rings. Although the heavy metals in the soil affected the activity of ligninolytic enzymes produced by the fungus (laccase and Mn-dependent peroxidase), no decrease in PAH degradation was found in soil containing Cd or Hg at 10 to 100 ppm. In the presence of cadmium at 500 ppm in soil, degradation of PAHs by soil microflora was not affected whereas the contribution of fungus was negligible, probably due to the absence of Mn-dependent peroxidase activity. In the presence of Hg at 50 to 100 ppm or Cd at 100 to 500 ppm, the extent of soil colonization by the fungus was limited. PMID:10831426

Key high molecular weight PAH-degrading bacteria in a soil consortium enriched using a sand-in-liquid microcosm system.

PubMed

Tauler, Margalida; Vila, Joaquim; Nieto, José María; Grifoll, Magdalena

2016-04-01

A novel biphasic system containing mineral medium and sand coated with a biologically weathered creosote-PAH mixture was developed to specifically enrich the high molecular weight polycyclic aromatic hydrocarbon (HMW PAH)-degrading community from a creosote-polluted soil. This consortium (UBHP) removed 70% of the total HMW PAHs and their alkyl-derivatives in 12 weeks. Based on a combined culture-dependent/independent approach, including clone library analysis, detection of catabolic genes, metabolomic profiles, and characterization of bacterial isolates, 10 phylotypes corresponding to five major genera (Sphingobium, Sphingomonas, Achromobacter, Pseudomonas, and Mycobacterium) were pointed out as key players within the community. In response to exposure to different single PAHs, members of sphingomonads were associated to the utilization of phenanthrene, fluoranthene, benzo[a]anthracene, and chrysene, while the degradation of pyrene was mainly associated to low-abundance mycobacteria. In addition to them, a number of uncultured phylotypes were detected, being of special relevance a group of Gammaproteobacteria closely related to a group previously associated with pyrene degradation that were here related to benzo(a)anthracene degradation. The overall environmental relevance of these phylotypes was confirmed by pyrosequencing analysis of the microbial community shift in the creosote-polluted soil during a lab-scale biostimulation.

A proposed procedure for derivation of regulatory values for carcinogenic airborne polycyclic aromatic hydrocarbons (PAHs) based on coal tar pitch (CTP) volatiles.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Foureman, G.L.; Smith, R.L.

A procedure for estimating upper bound lifetime human cancer risk from air levels of six common carcinogenic polycyclic aromatic hydrocarbons (PAHs), termed APAHs of concern, is proposed. These PAHs are benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene, benzo(k)fluoranthene, indeno(1,2,3-c,d)pyrene, and chrysene. In application, this proposed procedure would regard any given air level obtained for a APAH of concern to originate from a standard mixture of coal tar pitch (CTP). The given air level for the APAHs of concern is then related to a corresponding air level of CTP and thence, to an inhalation unit cancer risk calculated for CTP. Reference values for the proceduremore » are the relative and absolute PAH composition of a CTP standard (SRM-1597) and the inhalation unit cancer risk. Qualitative characterization of the results are a vital part of the procedure especially when more than one APAH of concern{at} is being considered. Toxic equivalency factors (TEFs) may be used as an evaluative tool in characterization of the procedure and outcome. Limitations of this proposed procedure include the uneven database for the reference values and the inability to consider air samples inclusive of another common carcinogenic PAH, dibenz(a,h)anthracene, due to its lack of documentation in CTP and high TEF« less

A survey on polycyclic aromatic hydrocarbon concentrations in soil in Chiang-Mai, Thailand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amagai, Takashi; Takahashi, Yukari; Matsushita, Hidetsuru

Soil samples were collected at 30 sampling sites along roadsides in the city of Chiang-Mai, Thailand, in February 1996, and concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) were determined. The distribution of PAH concentration in the soil samples was almost log-normal for all PAHs. Concentrations of pyrene (Py) and fluoranthene (Fluor) were the highest, followed by those of benzo[ghi]perylene and coronene (Cor). Since PAH concentrations were highest on the roadside where the traffic density was high, vehicles were the main determinants of PAH concentration in soil in Chiang-Mai. Significant correlations among PAH concentrations were found for almost all PAHs. PAHmore » profiles in the air were different from those in the soil. For example, relative benzo[a]pyrene (BaP) concentration in the soil was significantly lower than that in the air. Relative concentrations of Fluor, Py, chrysene, and Cor in the soil were considerably higher than those in the air, due presumably to their difference in photochemical reactivities and in sources. The sampling of soil has advantages relative to that of air: (1) collection of soil is easy; (2) it needs no special equipment and electricity; (3) it takes little time; and (4) it can be collected anywhere. Therefore PAH analysis in soil was useful as a proxy-screening tool for air pollution levels with consideration of compositional differences between soil and air samples.« less

Trends in polycyclic aromatic hydrocarbon concentrations in the great lakes atmosphere.

PubMed

Sun, Ping; Blanchard, Pierrette; Brice, Kenneth A; Hites, Ronald A

2006-10-15

Atmospheric polycyclic aromatic hydrocarbon (PAHs) concentrations were measured in both the vapor and particle phases at seven sites near the Great Lakes as a part of the Integrated Atmospheric Deposition Network. Lower molecular weight PAHs, including fluorene, phenanthrene, fluoranthrene, and pyrene, were dominant in the vapor phase, and higher molecular weight PAHs, including chrysene, benzo[a]pyrene, and coronene, were dominant in the particle phase. The highest PAH concentrations in both the vapor and particle phases were observed in Chicago followed by the semiurban site at Sturgeon Point, NY. The spatial difference of PAH concentrations can be explained by the local population density. Long-term decreasing trends of most PAH concentrations were observed in both the vapor and particle phases at Chicago, with half-lives ranging from 3-10 years in the vapor phase and 5-15 years in the particle phase. At Eagle Harbor, Sleeping Bear Dunes, and Sturgeon Point, total PAH concentrations in the vapor phase showed significant, but slow, long-term decreasing trends. At the Sturgeon Point site, which was impacted by a nearby city, particle-phase PAH concentrations also declined. However, most particle-phase PAH concentrations did not show significant long-term decreasing trends at the remote sites. Seasonal trends were also observed for particle-phase PAH concentrations, which were higher in the winter and lower in the summer.

Impact of pyrolysis conditions on polycyclic aromatic hydrocarbons (PAHs) formation in particulate matter (PM) during sewage sludge pyrolysis.

PubMed

Ko, Jae Hac; Wang, Jingchen; Xu, Qiyong

2018-05-21

Polycyclic aromatic hydrocarbons (PAHs) not only present a risk to human health when released into the air, but also can be precursors to form particulate matter (PM) during sewage sludge pyrolysis. In this study, 16 EPA PAHs in PM (ΣPAH PM ) during sewage sludge pyrolysis were investigated with increasing temperature (200 o C-1000 °C) and holding time under different operation conditions [inert gas flow rate (IGFR) (200-800 mL/min) and heating rate (5-20 °C/min)]. ΣPAH PM varied with temperature, IGFR, and heating rate, and ranged from 597 (±41) μg/g to 3240 (±868) μg/g. ΣPAH PM decreased with increasing IGFR but increased with rapid heating rate. Among PAHs species in PM, naphthalene (Nap) was commonly detected at low temperature ranges in all tested conditions. Chrysene (CHR), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), indeno[1,2,3-cd] pyrene (IND), and benzo[g,h,i]perylene (BghiP) in PM became abundant at high temperature with a low IGFR. At high temperature ranges with high volatile conditions (rapid heating rate and low IGFR), PAH formation and growth reactions were considerable, resulting in the formation of heavy PAHs in PM. Copyright © 2018 Elsevier Ltd. All rights reserved.

DNA methylation in lung tissues of mouse offspring exposed in utero to polycyclic aromatic hydrocarbons.

PubMed

Fish, Trevor J; Benninghoff, Abby D

2017-11-01

Polycyclic aromatic hydrocarbons (PAHs) comprise an important class of environmental pollutants that are known to cause lung cancer in animals and are suspected lung carcinogens in humans. Moreover, evidence from cell-based studies points to PAHs as modulators of the epigenome. The objective of this work was to assess patterns of genome-wide DNA methylation in lung tissues of adult offspring initiated in utero with the transplacental PAH carcinogens dibenzo [def,p]chrysene (DBC) or benzo [a]pyrene (BaP). Genome-wide methylation patterns for normal (not exposed), normal adjacent and lung tumor tissues obtained from adult offspring were determined using methylated DNA immunoprecipitation (MeDIP) with the NimbleGen mouse DNA methylation CpG island array. Lung tumor incidence in 45-week old mice initiated with BaP was 32%, much lower than that of the DBC-exposed offspring at 96%. Also, male offspring appeared more susceptible to BaP as compared to females. Distinct patterns of DNA methylation were associated with non-exposed, normal adjacent and adenocarcinoma lung tissues, as determined by principal components, hierarchical clustering and gene ontology analyses. From these methylation profiles, a set of genes of interest was identified that includes potential important targets for epigenetic modification during the process of lung tumorigenesis in animals exposed to environmental PAHs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Assessment of the bioavailability and phytotoxicity of sediment spiked with polycyclic aromatic hydrocarbons.

PubMed

Rončević, Srđan; Spasojević, Jelena; Maletić, Snežana; Jazić, Jelena Molnar; Isakovski, Marijana Kragulj; Agbaba, Jasmina; Grgić, Marko; Dalmacija, Božo

2016-02-01

Large amounts of sediment are dredged globally every year. This sediment is often contaminated with low concentrations of metals, polycyclic aromatic hydrocarbons, pesticides and other organic pollutants. Some of this sediment is disposed of on land, creating a need for risk assessment of the sediment disposal method, to minimize the degradation of environmental quality and prevent risks to human health. Evaluating the available fractions of certain polycyclic aromatic hydrocarbons is very important, as in the presence of various organisms, they are believed to be easily subject to the processes of bioaccumulation, biosorption and transformation. In order to determine the applicability of applying these methods for the evaluation of pollutant bioavailability in sediments, the desorption kinetics from the sediment of various polycyclic aromatic hydrocarbons in the presence of Tenax and XAD4 were examined over the course of 216 h. Changes in the PAH concentrations in dredged sediments using five different seed plants during a short time of period (10 days) were also followed. Using chemical extraction techniques with Tenax and XAD4, a time of around 24 h is enough to achieve equilibrium for all four PAHs. Results showed good agreement between the seed accumulation and PAH extraction methods with both agents. If we compare the two extraction techniques, XAD4 gave better results for phenanthrene, pyrene and benzo(a)pyrene, and Tenax gave better results for chrysene.

Symmetrized density matrix renormalization group algorithm for low-lying excited states of conjugated carbon systems: Application to 1,12-benzoperylene and polychrysene

NASA Astrophysics Data System (ADS)

Prodhan, Suryoday; Ramasesha, S.

2018-05-01

The symmetry adapted density matrix renormalization group (SDMRG) technique has been an efficient method for studying low-lying eigenstates in one- and quasi-one-dimensional electronic systems. However, the SDMRG method had bottlenecks involving the construction of linearly independent symmetry adapted basis states as the symmetry matrices in the DMRG basis were not sparse. We have developed a modified algorithm to overcome this bottleneck. The new method incorporates end-to-end interchange symmetry (C2) , electron-hole symmetry (J ) , and parity or spin-flip symmetry (P ) in these calculations. The one-to-one correspondence between direct-product basis states in the DMRG Hilbert space for these symmetry operations renders the symmetry matrices in the new basis with maximum sparseness, just one nonzero matrix element per row. Using methods similar to those employed in the exact diagonalization technique for Pariser-Parr-Pople (PPP) models, developed in the 1980s, it is possible to construct orthogonal SDMRG basis states while bypassing the slow step of the Gram-Schmidt orthonormalization procedure. The method together with the PPP model which incorporates long-range electronic correlations is employed to study the correlated excited-state spectra of 1,12-benzoperylene and a narrow mixed graphene nanoribbon with a chrysene molecule as the building unit, comprising both zigzag and cove-edge structures.

Heterologous Expression of Polycyclic Aromatic Hydrocarbon Ring-Hydroxylating Dioxygenase Genes from a Novel Pyrene-Degrading Betaproteobacterium

PubMed Central

Hu, Jing; Aitken, Michael D.

2012-01-01

A betaproteobacterium within the family Rhodocyclaceae previously identified as a pyrene degrader via stable-isotope probing (SIP) of contaminated soil (designated pyrene group 1 or PG1) was cultivated as the dominant member of a mixed bacterial culture. A metagenomic library was constructed, and the largest contigs were analyzed for genes associated with polycyclic aromatic hydrocarbon (PAH) metabolism. Eight pairs of genes with similarity to the α- and β-subunits of ring-hydroxylating dioxygenases (RHDs) associated with aerobic bacterial PAH degradation were identified and linked to PG1 through PCR analyses of a simplified enrichment culture. In tandem with a ferredoxin and reductase found in close proximity to one pair of RHD genes, six of the RHDs were cloned and expressed in Escherichia coli. Each cloned RHD was tested for activity against nine PAHs ranging in size from two to five rings. Despite differences in their predicted protein sequences, each of the six RHDs was capable of transforming phenanthrene and pyrene. Three RHDs could additionally transform naphthalene and fluorene, and these genotypes were also associated with the ability of the E. coli constructs to convert indole to indigo. Only one of the six cloned RHDs was capable of transforming anthracene and benz[a]anthracene. None of the tested RHDs were capable of significantly transforming fluoranthene, chrysene, or benzo[a]pyrene. PMID:22427500

The relative abundance and seasonal distribution correspond with the sources of polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of Chenab River, Pakistan.

PubMed

Hussain, Imran; Syed, Jabir Hussain; Kamal, Atif; Iqbal, Mehreen; Eqani, Syed-Ali-Mustjab-Akbar-Shah; Bong, Chui Wei; Taqi, Malik Mumtaz; Reichenauer, Thomas G; Zhang, Gan; Malik, Riffat Naseem

2016-06-01

Chenab River is one of the most important rivers of Punjab Province (Pakistan) that receives huge input of industrial effluents and municipal sewage from major cities in the Central Punjab, Pakistan. The current study was designed to evaluate the concentration levels and associated ecological risks of USEPA priority polycyclic aromatic hydrocarbons (PAHs) in the surface sediments of Chenab River. Sampling was performed from eight (n = 24) sampling stations of Chenab River and its tributaries. We observed a relatively high abundance of ∑16PAHs during the summer season (i.e. 554 ng g(-1)) versus that in the winter season (i.e. 361 ng g(-1)), with an overall abundance of two-, five- and six-ring PAH congeners. Results also revealed that the nitrate and phosphate contents in the sediments were closely associated with low molecular weight (LMW) and high molecular weight (HMW) PAHs, respectively. Source apportionment results showed that the combustion of fossil fuels appears to be the key source of PAHs in the study area. The risk quotient (RQ) values indicated that seven PAH congeners (i.e. phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)pyrene, chrysene and benzo(a)anthracene) could pose serious threats to the aquatic life of the riverine ecosystem in Pakistan.

Distributions of Polycyclic Aromatic Hydrocarbons, Aromatic Ketones, Carboxylic Acids, and Trace Metals in Arctic Aerosols: Long-Range Atmospheric Transport, Photochemical Degradation/Production at Polar Sunrise.

PubMed

Singh, Dharmendra Kumar; Kawamura, Kimitaka; Yanase, Ayako; Barrie, Leonard A

2017-08-15

The distributions, correlations, and source apportionment of aromatic acids, aromatic ketones, polycyclic aromatic hydrocarbons (PAHs), and trace metals were studied in Canadian high Arctic aerosols. Nineteen PAHs including minor sulfur-containing heterocyclic PAH (dibenzothiophene) and major 6 carcinogenic PAHs were detected with a high proportion of fluoranthene followed by benzo[k]fluoranthene, pyrene, and chrysene. However, in the sunlit period of spring, their concentrations significantly declined likely due to photochemical decomposition. During the polar sunrise from mid-March to mid-April, benzo[a]pyrene to benzo[e]pyrene ratios significantly dropped, and the ratios diminished further from late April to May onward. These results suggest that PAHs transported over the Arctic are subjected to strong photochemical degradation at polar sunrise. Although aromatic ketones decreased in spring, concentrations of some aromatic acids such as benzoic and phthalic acids increased during the course of polar sunrise, suggesting that aromatic hydrocarbons are oxidized to result in aromatic acids. However, PAHs do not act as the major source for low molecular weight (LMW) diacids such as oxalic acid that are largely formed at polar sunrise in the arctic atmosphere because PAHs are 1 to 2 orders of magnitude less abundant than LMW diacids. Correlations of trace metals with organics, their sources, and the possible role of trace transition metals are explained.

The contribution of particles washed from rooftops to contaminant loading to urban streams.

PubMed

Van Metre, P C; Mahler, B J

2003-09-01

Rooftops are both a source of and a pathway for contaminated runoff in urban environments. To investigate the importance of particle-associated contamination in rooftop runoff, particles washed from asphalt shingle and galvanized metal roofs at sites 12 and 102 m from a major expressway were analyzed for major and trace elements and PAHs. Concentrations and yields from rooftops were compared among locations and roofing material types and to loads monitored during runoff events in the receiving urban stream to evaluate rooftop sources and their potential contribution to stream loading. Concentrations of zinc, lead, pyrene, and chrysene on a mass per mass basis in a majority of rooftop samples exceeded established sediment quality guidelines for probable toxicity of bed sediments to benthic biota. Fallout near the expressway was greater than farther away, as indicated by larger yields of all contaminants investigated, although some concentrations were lower. Metal roofing was a source of cadmium and zinc and asphalt shingles a source of lead. The contribution of rooftop washoff to watershed loading was estimated to range from 6 percent for chromium and arsenic to 55 percent for zinc. Estimated contributions from roofing material to total watershed load were greatest for zinc and lead, contributing about 20 and 18 percent, respectively. The contribution from atmospheric deposition of particles onto rooftops to total watershed loads in stormwater was estimated to be greatest for mercury, contributing about 46 percent.

Identification and Quantification of Six-Ring C26H16 Cata-Condensed Polycyclic Aromatic Hydrocarbons in a Complex Mixture of Polycyclic Aromatic Hydrocarbons from Coal Tar

PubMed Central

Oña-Ruales, Jorge O.; Sharma, Arun K.; Wise, Stephen A.

2015-01-01

We applied a combination of normal-phase liquid chromatography (NPLC) with ultraviolet-visible spectroscopy and gas chromatography with mass spectrometry (GC/MS) for the fractionation, identification, and quantification of six ring C26H16 cata-condensed polycyclic aromatic hydrocarbons, PAHs, in the Standard Reference Material 1597a, Complex Mixture of PAHs from Coal Tar. For the characterization analysis, we calculated the GC retention indices of 17 C26H16 PAH authentic reference standards using the Rxi-PAH and DB-5 GC columns. Then, we used NPLC with ultraviolet-visible spectroscopy to isolate the fractions containing the C26H16 PAHs, and subsequently, we used GC/MS to establish the identity and quantity of the C26H16 PAHs using authentic reference standards. Following this procedure, 12 C26H16 cata-condensed PAHs benzo[c]pentaphene, dibenzo[f,k]tetraphene, benzo[h]pentaphene, dibenzo[a,l]tetracene, dibenzo[c,k]tetraphene, naphtho[2,3-c]tetraphene, dibenzo[a,c]tetracene, benzo[b]picene, dibenzo[a,j]tetracene, naphtho[2,1-a]tetracene, dibenzo[c,p]chrysene, and dibenzo[a,f]tetraphene were identified and quantified for the first time, and benzo[c]picene was quantified for the first time in an environmental combustion sample. PMID:26449848

Distribution, characterization, and exposure of MC252 oil in the supratidal beach environment.

PubMed

Lemelle, Kendall R; Elango, Vijaikrishnah; Pardue, John H

2014-07-01

The distribution and characteristics of MC252 oil:sand aggregates, termed surface residue balls (SRBs), were measured on the supratidal beach environment of oil-impacted Fourchon Beach in Louisiana (USA). Probability distributions of 4 variables, surface coverage (%), size of SRBs (mm(2) of projected area), mass of SRBs per m(2) (g/m(2)), and concentrations of polycyclic aromatic hydrocarbons (PAHs) and n-alkanes in the SRBs (mg of crude oil component per kg of SRB) were determined using parametric and nonparametric statistical techniques. Surface coverage of SRBs, an operational remedial standard for the beach surface, was a gamma-distributed variable ranging from 0.01% to 8.1%. The SRB sizes had a mean of 90.7 mm(2) but fit no probability distribution, and a nonparametric ranking was used to describe the size distributions. Concentrations of total PAHs ranged from 2.5 mg/kg to 126 mg/kg of SRB. Individual PAH concentration distributions, consisting primarily of alkylated phenanthrenes, dibenzothiophenes, and chrysenes, did not consistently fit a parametric distribution. Surface coverage was correlated with an oil mass per unit area but with a substantial error at lower coverage (i.e., <2%). These data provide probabilistic risk assessors with the ability to specify uncertainty in PAH concentration, exposure frequency, and ingestion rate, based on SRB characteristics for the dominant oil form on beaches along the US Gulf Coast. © 2014 SETAC.

Polycyclic aromatic hydrocarbons (PAH) formation from the pyrolysis of different municipal solid waste fractions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hui; Energy Research Institute, University of Leeds, Leeds LS2 9JT; Wu, Chunfei, E-mail: c.wu@leeds.ac.uk

2015-02-15

Highlights: • PAH from pyrolysis of 9 MSW fractions was investigated. • Pyrolysis of plastics released more PAH than that of biomass. • Naphthalene was the most abundant PAH in the tar. • The mechanism of PAH release from biomass and plastics was proposed. - Abstract: The formation of 2–4 ring polycyclic aromatic hydrocarbons (PAH) from the pyrolysis of nine different municipal solid waste fractions (xylan, cellulose, lignin, pectin, starch, polyethylene (PE), polystyrene (PS), polyvinyl chloride (PVC), and polyethylene terephthalate (PET)) were investigated in a fixed bed furnace at 800 °C. The mass distribution of pyrolysis was also reported. Themore » results showed that PS generated the most total PAH, followed by PVC, PET, and lignin. More PAH were detected from the pyrolysis of plastics than the pyrolysis of biomass. In the biomass group, lignin generated more PAH than others. Naphthalene was the most abundant PAH, and the amount of 1-methynaphthalene and 2-methynaphthalene was also notable. Phenanthrene and fluorene were the most abundant 3-ring PAH, while benzo[a]anthracene and chrysene were notable in the tar of PS, PVC, and PET. 2-ring PAH dominated all tar samples, and varied from 40 wt.% to 70 wt.%. For PS, PET and lignin, PAH may be generated directly from the aromatic structure of the feedstock.« less

Assessment of hydrocarbons concentration in marine fauna due to Tasman Spirit oil spill along the Clifton beach at Karachi coast.

PubMed

Siddiqi, Hina A; Ansari, Fayyaz A; Munshi, Alia B

2009-01-01

On 27 July 2003, Tasman Spirit spilled 31,000 tonnes of crude oil into the sea at the Karachi coast. This disaster badly affected the marine life (Flora and Fauna.) Present research has been proposed to ascertain the level of Polycyclic Aromatic hydrocarbons (PAHs) contamination in different fisheries including Fishes, Crustaceans; Crabs and Shrimps, Mollusks and Echinoderms along with passing time. Heavier components of crude oil such as Polycyclic Aromatic Hydrocarbons (PAHs) appear to cause most damages as these are relatively unreactive and persist in water. High concentrations of toxic PAHs were observed in all the fisheries and shellfishes caught form oil-impacted area. In this study fishes were found most contaminated than shellfishes i.e. summation operator 16 PAH = 1821.24 microg/g and summation operator 1164.34 microg/g, respectively. Naphthalene was found in the range of 0.042-602.23 microg/g. Acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene were detected in the range 0.008-80.03 microg/g, fluoranthene, pyrene, benzo(a)anthracene and chrysene 0.0008-221.32 microg/g, benzo(b) fluoranthene, benzo(k)fluoranthene and benzo(a) pyrene 0.0005-7.71 microg/g, benzo(g,h,i)perylene and indeno(1,2,3-c,d)pyrene 0.02-503.7 microg/g. Dibenzo(a,h)anthracenre was not detected in any specie.

Endocrine disrupting potential of PAHs and their alkylated analogues associated with oil spills.

PubMed

Lee, Sangwoo; Hong, Seongjin; Liu, Xiaoshan; Kim, Cheolmin; Jung, Dawoon; Yim, Un Hyuk; Shim, Won Joon; Khim, Jong Seong; Giesy, John P; Choi, Kyungho

2017-09-20

Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs are known to be major toxic contaminants in spills of petroleum hydrocarbons (oil). Spilled oil undergoes weathering and over time, PAHs go through a series of compositional changes. PAHs can disrupt endocrine functions, and the type of functions affected and associated potencies vary with the type and alkylation status of PAH. In this study, the potential of five major PAHs of crude oil, i.e., naphthalene, fluorene, dibenzothiophene, phenanthrene, and chrysene, and their alkylated analogues (n = 25), to disrupt endocrine functions was evaluated by use of MVLN-luc and H295R cell lines. In the MVLN-luc bioassay, seven estrogen receptor (ER) agonists were detected among 30 tested PAHs. The greatest ER-mediated potency was observed for 1-methylchrysene (101.4%), followed by phenanthrene and its alkylated analogues (range of %-E2max from 1.6% to 47.3%). In the H295R bioassay, significantly greater syntheses of steroid hormones were observed for 20 PAHs. For major PAHs and their alkylated analogues, disruption of steroidogenesis appeared to be more significant than ER-mediated effects. The number and locations of alkyl-moieties alone could not explain differences in the types or the potencies of toxicities. This observation shows that disruption of endocrine functions by some constituents of oil spills could be underestimated if only parent compounds are considered in assessments of hazard and risk.

Areal distribution and concentrations of contaminants of concern in surficial streambed and lakebed sediments, Lake Erie-Lake Saint Clair Drainages, 1990-97

USGS Publications Warehouse

Rheaume, S.J.; Button, D.T.; Myers, Donna N.; Hubbell, D.L.

2001-01-01

Concerns about elevated concentrations of contaminants such as polychlorinated biphenyls and mercury in aquatic bed sediments throughout the Great Lakes Basin have resulted in a need for better understanding of the scope and severity of the problem. Various organochlorine pesticides, polychlorinated biphenyls, trace metals, and polycyclic aromatic hydrocarbons are a concern because of their ability to persist and accumulate in aquatic sediments and their association with adverse aquatic biological effects. The areal distribution and concentrations in surficial bed sediments of 20 contaminants of concern with established bed-sediment-toxicity guidelines were examined in relation to their potential effects on freshwater aquatic biota. Contaminants at more than 800 sampling locations are characterized in this report. Surficial bed-sediment-quality data collected from 1990 to 1997 in the Lake Erie?Lake Saint Clair Drainages were evaluated to reflect recent conditions. In descending order, concentrations of total polycyclic aromatic hydrocarbons, phenanthrene, total polychlorinated biphenyls, chrysene, benz[a]anthracene, benzo[a]pyrene, cadmium, lead, zinc, arsenic, and mercury were the contaminants that most commonly exceeded levels associated with probable adverse effects on aquatic benthic organisms. The highest concentrations of most of these contaminants in aquatic bed sediments are confined to the 12 specific geographic Areas of Concern identified in the 1987 Revisions to the Great Lakes Water Quality Agreement of 1972. An exception is arsenic, which was detected at concentrations exceeding threshold effect levels at many locations outside Areas of Concern.

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3-micrometers Region: Role of Periphery

NASA Technical Reports Server (NTRS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2017-01-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3-micrometers absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 per cm range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3-micrometers region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3-micrometers band, and on features such as the two-component emission character of this band and the 3-micrometers emission plateau.

Three-peak standard white organic light-emitting devices for solid-state lighting

NASA Astrophysics Data System (ADS)

Guo, Kunping; Wei, Bin

2014-12-01

Standard white organic light-emitting device (OLED) lighting provides a warm and comfortable atmosphere and shows mild effect on melatonin suppression. A high-efficiency red OLED employing phosphorescent dopant has been investigated. The device generates saturated red emission with Commission Internationale de l'Eclairage (CIE) coordinates of (0.66, 0.34), characterized by a low driving voltage of 3.5 V and high external quantum efficiency of 20.1% at 130 cd m-2. In addition, we have demonstrated a two-peak cold white OLED by combining with a pure blue emitter with the electroluminescent emission of 464 nm, 6, 12-bis{[N-(3,4-dimethylpheyl)-N-(2,4,5-trimethylphenyl)]} chrysene (BmPAC). It was found that the man-made lighting device capable of yielding a relatively stable color emission within the luminance range of 1000-5000 cd m-2. And the chromaticity coordinates, varying from (0.25, 0.21) to (0.23, 0.21). Furthermore, an ultrathin layer of green-light-emitting tris (2-phenylpyridinato)iridium(Ⅲ) Ir(ppy)3 in the host material was introduced to the emissive region for compensating light. By appropriately controlling the layer thickness, the white light OLED achieved good performance of 1280 cd m-2 at 5.0 V and 5150 cd m-2 at 7.0 V, respectively. The CIE coordinates of the emitted light are quite stable at current densities from 759 cd m-2 to 5150 cd m-2, ranging from (0.34, 0.37) to (0.33, 0.33).

[Simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter by gas chromatography-tandem mass spectrometry].

PubMed

Zhang, Xiaotao; Zhang, Li; Ruan, Yibin; Wang, Weiwei; Ji, Houwei; Wan, Qiang; Lin, Fucheng; Liu, Jian

2017-10-08

A method for the simultaneous determination of 15 polycyclic aromatic hydrocarbons in cigarette filter was developed by isotope internal standard combined with gas chromatography-tandem mass spectrometry. The cigarette filters were extracted with dichloromethane, and the extract was filtered with 0.22 μm organic phase membrane. The samples were isolated by DB-5MS column (30 m×0.25 mm, 0.25 μm) and detected using multiple reaction monitoring mode of electron impact source under positive ion mode. The linearities of the 15 polycyclic aromatic hydrocarbons (acenapthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, ben[ a ]anthracene, chrysene, benzo[ b ]fluoranthene, benzo[ k ]fluoranthene, benzo[ a ]pyrene, dibenzo[ a,h ]anthracene, benzo[ g,h,i ]perylene and indeno[1,2,3- c,d ]pyrene) were good, and the correlation coefficients ( R 2 ) ranged from 0.9914 to 0.9999. The average recoveries of the 15 polycyclic aromatic hydrocarbons were 81.6%-109.6% at low, middle and high spiked levels, and the relative standard deviations were less than 16%, except that the relative standard deviation of fluorene at the low spiked level was 19.2%. The limits of detection of the 15 polycyclic aromatic hydrocarbons were 0.02 to 0.24 ng/filter, and the limits of quantification were 0.04 to 0.80 ng/filter. The method is simple, rapid, accurate, sensitive and reproducible. It is suitable for the quantitative analysis of the 15 polycyclic aromatic hydrocarbons in cigarette filters.

Molecular Tracers of Saturated and Polycyclic Aromatic Hydrocarbon Inputs into Central Park Lake, New York City

PubMed Central

YAN, BEIZHAN; ABRAJANO, TEOFILO A.; BOPP, RICHARD F.; CHAKY, DAMON A.; BENEDICT, LUCILLE A.; CHILLRUD, STEVEN N.

2011-01-01

Saturated hydrocarbons (SH) and polycyclic aromatic hydrocarbons (PAHs) have been quantified in a sediment core obtained from Central Park Lake, New York City. Radionuclides 210Pb and 137Cs were used to assign approximate dates to each individual section in the core. The dating profile based on 210Pb matches very well with the time constraints provided by 137Cs. Radionuclide-derived depositional dates are consistent with temporal information from the petroleum-indicator ratio U/R [the ratio of unresolved complex mixture (UCM) to saturated hydrocarbons in the aliphatic fraction] and the history of fuel use in the NYC area. Ratios of 1,7-dimethylphenanthrane (DMP) to 1,7-DMP plus 2,6-DMP [1,7/(1,7 + 2,6)-DMP], retene to retene plus chrysene [Ret/(Ret + Chy)], and fluoranthene to fluoranthene plus pyrene [Fl/(Fl + Py)] provide additional source discrimination throughout the core. Results show that the ratio U/R is sensitive to petroleum inputs and Ret/(Ret + Chy) is responsive to contributions from softwood combustion, whereas both Fl/(Fl + Py) and 1,7/(1,7 + 2,6)-DMP can be used to discriminate among wood, coal, and petroleum combustion sources. Combined use of these ratios suggests that in New York City, wood combustion dominated 100 years ago, with a shift to coal combustion occurring from the 1900s to the 1950s. Petroleum use began around the 1920s and has dominated since the 1940s. PMID:16201624

Contamination of Tea and Tea Infusion with Polycyclic Aromatic Hydrocarbons

PubMed Central

Zachara, Alicja; Gałkowska, Dorota; Juszczak, Lesław

2017-01-01

The aim of this work was to validate the method of determination of polycyclic aromatic hydrocarbons (PAHs), i.e., benzo(a)pyrene and sum of benzo(a)pyrene, benz(a)anthracene, benzo(b)fluoranthene and chrysene in different types of tea, as well as to assess the transfer of these contaminants from tea to tea infusion. The research materials were popular types of black, green, red and white tea. Quantitative and qualitative determination of PAHs was performed by High Performance Liquid Chromatography with fluorimetric detection (HPLC-FLD). The samples were prepared by QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) technique followed by cleaning-up by dispersion solid-phase extraction (d-SPE). Values of limit of detection and limit of quantification obtained in the validation of the method were lower than the respective maximum values given in Commission Regulation (EU) No. 836/2011. The level of contamination of popular teas commercially available on the Polish market with PAHs is similar to that of teas available in other countries, with a very large variation in the concentration of each of the compounds. The highest benzo(a)pyrene and Σ4PAHs contents (209 ± 42 μg/kg and 756 ± 151 μg/kg, respectively) were found for black tea leaves. The transfer of Σ4PAHs from black tea to tea infusions was 0.48%, while it was 1.55–1.72% for red, white and green teas. PMID:29283369

Removal Capacities of Polycyclic Aromatic Hydrocarbons (PAHs) by a Newly Isolated Strain from Oilfield Produced Water

PubMed Central

Qi, Yi-Bin; Wang, Chen-Yu; Lv, Cheng-Yuan; Lun, Zeng-Min; Zheng, Cheng-Gang

2017-01-01

The polycyclic aromatic hydrocarbon (PAH)-degrading strain Q8 was isolated from oilfield produced water. According to the analysis of a biochemical test, 16S rRNA gene, house-keeping genes and DNA–DNA hybridization, strain Q8 was assigned to a novel species of the genus Gordonia. The strain could not only grow in mineral salt medium (MM) and utilize naphthalene and pyrene as its sole carbon source, but also degraded mixed naphthalene, phenanthrene, anthracene and pyrene. The degradation ratio of these four PAHs reached 100%, 95.4%, 73.8% and 53.4% respectively after being degraded by Q8 for seven days. A comparative experiment found that the PAHs degradation efficiency of Q8 is higher than that of Gordonia alkaliphila and Gordonia paraffinivorans, which have the capacities to remove PAHs. Fourier transform infrared spectra, saturate, aromatic, resin and asphaltene (SARA) and gas chromatography–mass spectrometry (GC–MS) analysis of crude oil degraded by Q8 were also studied. The results showed that Q8 could utilize n-alkanes and PAHs in crude oil. The relative proportions of the naphthalene series, phenanthrene series, thiophene series, fluorene series, chrysene series, C21-triaromatic steroid, pyrene, and benz(a)pyrene were reduced after being degraded by Q8. Gordonia sp. nov. Q8 had the capacity to remediate water and soil environments contaminated by PAHs or crude oil, and provided a feasible way for the bioremediation of PAHs and oil pollution. PMID:28241412

Emission of polycyclic aromatic hydrocarbons from diesel engine in a bus station, Londrina, Brazil

NASA Astrophysics Data System (ADS)

Tavares, Moacir; Pinto, Jurandir P.; Souza, Alexandre L.; Scarmínio, Ieda S.; Cristina Solci, Maria

2004-09-01

The concentrations of vapor phase polycyclic aromatic hydrocarbons (PAHs) were measured at the Central Bus Station of Londrina, where only diesel-powered vehicles circulate. The samples were collected within a period of 24 h for 14 consecutive days in January 2002. The semi-volatile PAHs were collected using a cartridge packed with XAD-2 resin, extracted under sonication and subsequently analyzed by gas chromatograph equipped with the flame ionization and mass spectrometer detectors (GC-FID and GC/MS). Ten PAH compounds were found (naphthalene, acenapthylene, acenapthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo(a)anthracene and chrysene). The average concentrations ranged from 1.4±0.3 ng m-3 for benzo(a)anthracene to 348.0±32.7 ng m-3 for phenanthrene. The species that presented higher concentration were phenanthrene (348.0±32.7 ng m-3), fluorene (140.2±17.3 ng m-3) and naphthalene (97.7±10.3 ng m-3). The PAHs with two and three rings were responsible by 90.2% of the total concentration among 10 PAHs. The concentrations of PAHs were lower on Sunday in comparison with the workdays, due to the reduction of bus traffic in the station. Correlations and principal component analysis with Varimax rotation were used to estimate the local PAH emission source profile originating from the diesel exhaust. The ratio PHEN/FLU of 2.5 calculated from the results is suggested as indication from diesel combustion exhaust.

Molecular tracers of saturated and polycyclic aromatic hydrocarbon inputs into Central Park Lake, New York City.

PubMed

Yan, Beizhan; Abrajano, Teofilo A; Bopp, Richard F; Chaky, Damon A; Benedict, Lucille A; Chillrud, Steven N

2005-09-15

Saturated hydrocarbons (SH) and polycyclic aromatic hydrocarbons (PAHs) have been quantified in a sediment core obtained from Central Park Lake, New York City. Radionuclides 210Pb and 137Cs were used to assign approximate dates to each individual section in the core. The dating profile based on 210Pb matches very well with the time constraints provided by 137Cs. Radionuclide-derived depositional dates are consistent with temporal information from the petroleum-indicator ratio U/R [the ratio of unresolved complex mixture (UCM)to saturated hydrocarbons in the aliphatic fraction] and the history of fuel use in the NYC area. Ratios of 1,7-dimethylphenanthrane (DMP) to 1,7-DMP plus 2,6-DMP [1,7/(1,7 + 2,6)-DMP], retene to retene plus chrysene [Ret/(Ret + Chy)], and fluoranthene to fluoranthene plus pyrene [FI/(FI + Py)] provide additional source discrimination throughoutthe core. Results show that the ratio U/R is sensitive to petroleum inputs and Ret/(Ret + Chy) is responsive to contributions from softwood combustion, whereas both FI/(FI + Py) and 1,7/ (1,7 + 2,6)-DMP can be used to discriminate among wood, coal, and petroleum combustion sources. Combined use of these ratios suggests that in New York City, wood combustion dominated 100 years ago, with a shift to coal combustion occurring from the 1900s to the 1950s. Petroleum use began around the 1920s and has dominated since the 1940s.

High-resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons in the 3 μm Region: Role of Periphery

NASA Astrophysics Data System (ADS)

Maltseva, Elena; Petrignani, Annemieke; Candian, Alessandra; Mackie, Cameron J.; Huang, Xinchuan; Lee, Timothy J.; Tielens, Alexander G. G. M.; Oomens, Jos; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau.

Polycyclic aromatic hydrocarbon exposure and burden of outdoor workers in Budapest.

PubMed

Szaniszló, J; Ungváry, G

2001-03-09

Polycyclic aromatic hydrocarbons exposure (PAHs: (benz[a]anthracene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, indeno[1,2,3-cd]-pyrene, fluoranthene, chrysene, pyrene) of policemen on street duty in downtown Budapest and workers repairing the road (asphalting) at a traffic junction and their excretion of PAH metabolites (1-hydroxypyrene, 3-hydroxybenz[a]anthracene, and 3-hydroxybenzo[a]pyrene) were determined. As controls, health-care workers were investigated. In addition PAH pollution of the air of a factory processing asphalt was also measured. The measurements were performed on air samples gained using personal samplers and from urine of end-shift samples using a high-performance liquid chromatography method. It was found that PAH pollution of the most crowded and busy center of Budapest was similar to that of several other cities in the world. PAH exposure of road builders was actually not higher than that of policemen; the slight difference resulted from diverging life-styles. PAH metabolite excretion of smoking health-care workers, road builders, or policemen significantly exceeded that of the nonsmokers. The PAH metabolite values of the three groups engaged in various activities did not show any difference. It was concluded that cancer-related risk due to PAH compounds in the case of policemen on street duty and road builders (asphalting) does not exceed significantly that of workers not exposed occupationally to PAHs in the ambient air, but that smoking is a decisive factor.

Concentration dependence of biotransformation in fish liver S9: Optimizing substrate concentrations to estimate hepatic clearance for bioaccumulation assessment.

PubMed

Lo, Justin C; Allard, Gayatri N; Otton, S Victoria; Campbell, David A; Gobas, Frank A P C

2015-12-01

In vitro bioassays to estimate biotransformation rate constants of contaminants in fish are currently being investigated to improve bioaccumulation assessments of hydrophobic contaminants. The present study investigates the relationship between chemical substrate concentration and in vitro biotransformation rate of 4 environmental contaminants (9-methylanthracene, pyrene, chrysene, and benzo[a]pyrene) in rainbow trout (Oncorhynchus mykiss) liver S9 fractions and methods to determine maximum first-order biotransformation rate constants. Substrate depletion experiments using a series of initial substrate concentrations showed that in vitro biotransformation rates exhibit strong concentration dependence, consistent with a Michaelis-Menten kinetic model. The results indicate that depletion rate constants measured at initial substrate concentrations of 1 μM (a current convention) could underestimate the in vitro biotransformation potential and may cause bioconcentration factors to be overestimated if in vitro biotransformation rates are used to assess bioconcentration factors in fish. Depletion rate constants measured using thin-film sorbent dosing experiments were not statistically different from the maximum depletion rate constants derived using a series of solvent delivery-based depletion experiments for 3 of the 4 test chemicals. Multiple solvent delivery-based depletion experiments at a range of initial concentrations are recommended for determining the concentration dependence of in vitro biotransformation rates in fish liver fractions, whereas a single sorbent phase dosing experiment may be able to provide reasonable approximations of maximum depletion rates of very hydrophobic substances. © 2015 SETAC.

Collection-efficient, axisymmetric vacuum sublimation module for the purification of solid materials.

PubMed

May, Michael; Paul, Elizabeth; Katovic, Vladimir

2015-11-01

A vacuum sublimation module of axisymmetric geometry was developed and employed to purify solid-phase materials. The module provides certain practical advantages and it comprises: a metering valve, glass collector, glass lower body, main seal, threaded bushing, and glass internal cartridge (the latter to contain starting material). A complementary process was developed to de-solvate, sublime, weigh, and collect solid chemical materials exemplified by oxalic acid, ferrocene, pentachlorobenzene, chrysene, and urea. The oxalic acid sublimate was analyzed by titration, melting range, Fourier Transform Infrared (FT-IR) Spectroscopy, cyclic voltammetry, and its (aqueous phase) electrolytically generated gas. The analytical data were consistent with a high-purity, anhydrous oxalic acid sublimate. Cyclic voltammograms of 0.11 mol. % oxalic acid in water displayed a 2.1 V window on glassy carbon electrode beyond which electrolytic decomposition occurs. During module testing, fifteen relatively pure materials were sublimed with (energy efficient) passive cooling and the solid-phase recovery averaged 95 mass %. Key module design features include: compact vertical geometry, low-angle conical collector, uniformly compressed main seal, modest power consumption, transparency, glovebox compatibility, cooling options, and preferential conductive heat transfer. To help evaluate the structural (module) heat transfer, vertical temperature profiles along the dynamically evacuated lower body were measured versus electric heater power: for example, an input of 18.6 W generated a temperature 443-K at the bottom. Experimental results and engineering calculations indicate that during sublimation, solid conduction is the primary mode of heat transfer to the starting material.

Polycyclic aromatic hydrocarbons in the leaves of twelve plant species along an urbanization gradient in Shanghai, China.

PubMed

Liang, Jing; Fang, Hailan; Zhang, Taolin; Wang, Xingxiang

2017-04-01

Plants, particularly their leaves, play an important role in filtering both gas-phase and particle-phase polycyclic aromatic hydrocarbons (PAHs). However, many studies have focused on the accumulation and adsorption functions of plant leaves, possibly underestimating the effects that plants have on air quality. Therefore, eight tree species from different locations in Shanghai were selected to assess PAH filtering (via adsorption and capture) using washed and unwashed plant leaves. The differences in the total PAH contents in the washed leaves were constant for the different species across the different sampling sites. The PAH levels decreased in the following order: industrial areas > traffic areas > urban areas > background area. The PAH compositions in the different plant leaves were dominated by fluorene (Fle), phenanthrene (Phe), anthracene (Ant), chrysene (Chr), fluoranthene (Flu), and pyrene (Pyr); notably, Phe accounted for 49.4-76.7% of the total PAHs. By comparing the PAH contents in the washed leaves with the PAH contents in the unwashed leaves, Pittosporum tobira (P. tobira), Ginkgo biloba (G. biloba), and Platanus acerifolia (P. acerifolia) were found to be efficient species for adsorbing PAHs, while Osmanthus fragrans (O. fragrans), Magnolia grandiflora (M. grandiflora), and Prunus cerasifera Ehrh. (P. cerasifera Ehrh.) were efficient species for capturing PAHs. The efficiencies of the plant leaves for the removal of PAHs from air occurred in the order of low molecular weight > medium molecular weight > high molecular weight PAHs.

A rhodium(III) complex for high-affinity DNA base-pair mismatch recognition

PubMed Central

Junicke, Henrik; Hart, Jonathan R.; Kisko, Jennifer; Glebov, Oleg; Kirsch, Ilan R.; Barton, Jacqueline K.

2003-01-01

A rhodium(III) complex, rac-[Rh(bpy)2phzi]3+ (bpy, 2,2′-bipyridine; phzi, benzo[a]phenazine-5,6-quinone diimine) has been designed as a sterically demanding intercalator targeted to destabilized mismatched sites in double-helical DNA. The complex is readily synthesized by condensation of the phenazine quinone with the corresponding diammine complex. Upon photoactivation, the complex promotes direct strand scission at single-base mismatch sites within the DNA duplex. As with the parent mismatch-specific reagent, [Rh(bpy)2(chrysi)]3+ [chrysene-5,6-quinone diimine (chrysi)], mismatch selectivity depends on the helix destabilization associated with mispairing. Unlike the parent chrysi complex, the phzi analogue binds and cleaves with high affinity and efficiency. The specific binding constants for CA, CC, and CT mismatches within a 31-mer oligonucleotide duplex are 0.3, 1, and 6 × 107 M−1, respectively; site-specific photocleavage is evident at nanomolar concentrations. Moreover, the specificity, defined as the ratio in binding affinities for mispaired vs. well paired sites, is maintained. The increase in affinity is attributed to greater stability in the mismatched site associated with stacking by the heterocyclic aromatic ligand. The high-affinity complex is also applied in the differential cleavage of DNA obtained from cell lines deficient in mismatch repair vs. those proficient in mismatch repair. Agreement is found between photocleavage by the mismatch-specific probes and deficiency in mismatch repair. This mismatch-specific targeting, therefore, offers a potential strategy for new chemotherapeutic design. PMID:12610209

Ft. McHenry tunnel study: Source profiles and mercury emissions from diesel and gasoline powered vehicles

NASA Astrophysics Data System (ADS)

Landis, Matthew S.; Lewis, Charles W.; Stevens, Robert K.; Keeler, Gerald J.; Dvonch, J. Timothy; Tremblay, Raphael T.

During the fall of 1998, the US Environmental Protection Agency and the Florida Department of Environmental Protection sponsored a 7-day study at the Ft. McHenry tunnel in Baltimore, MD with the objective of obtaining PM 2.5 vehicle source profiles for use in atmospheric mercury source apportionment studies. PM 2.5 emission profiles from gasoline and diesel powered vehicles were developed from analysis of trace elements, polycyclic aromatic hydrocarbons (PAH), and condensed aliphatic hydrocarbons. PM 2.5 samples were collected using commercially available sampling systems and were extracted and analyzed using conventional well-established methods. Both inorganic and organic profiles were sufficiently unique to mathematically discriminate the contributions from each source type using a chemical mass balance source apportionment approach. However, only the organic source profiles provided unique PAH tracers (e.g., fluoranthene, pyrene, and chrysene) for diesel combustion that could be used to identify source contributions generated using multivariate statistical receptor modeling approaches. In addition, the study found significant emission of gaseous elemental mercury (Hg 0), divalent reactive gaseous mercury (RGM), and particulate mercury (Hg(p)) from gasoline but not from diesel powered motor vehicles. Fuel analysis supported the tunnel measurement results showing that total mercury content in all grades of gasoline (284±108 ng L -1) was substantially higher than total mercury content in diesel fuel (62±37 ng L -1) collected contemporaneously at local Baltimore retailers.

Profiles, sources, and transport of polycyclic aromatic hydrocarbons in soils affected by electronic waste recycling in Longtang, south China.

PubMed

Huang, De-Yin; Liu, Chuan-Ping; Li, Fang-Bai; Liu, Tong-Xu; Liu, Cheng-Shuai; Tao, Liang; Wang, Yan

2014-06-01

We studied the profiles, possible sources, and transport of polycyclic aromatic hydrocarbons (PAHs) in soils from the Longtang area, which is an electronic waste (e-waste) recycling center in south China. The sum of 16 PAH concentrations ranged from 25 to 4,300 ng/g (dry weight basis) in the following order: pond sediment sites (77 ng/g), vegetable fields (129 ng/g), paddy fields (180 ng/g), wastelands (258 ng/g), dismantling sites (678 ng/g), and former open burning sites (2,340 ng/g). Naphthalene, phenanthrene, fluoranthene, pyrene, chrysene, and benzo[b]fluoranthene were the dominant PAHs and accounted for approximately 75 % of the total PAHs. The similar composition characteristics of PAHs and the significant correlations among individual, low molecular weight, high molecular weight, and total PAHs were found in all six sampling site types, thus indicating that PAHs originated from similar sources. The results of both isomeric ratios and principal component analyses confirmed that PAHs were mainly derived from the incomplete combustion of e-waste. The former open burning sites and dismantling sites were the main sources of PAHs. Soil samples that were taken closer to the point sources had high PAH concentrations. PAHs are transported via different soil profiles, including those in agricultural fields, and have been detected not only in 0- to 40-cm-deep soil but also in 40 cm to 80 cm-deep soil. PAH concentrations in soils in Longtang have been strongly affected by primitive e-waste recycling, particularly by former open burning activities.

Trends in polycyclic aromatic hydrocarbon concentrations in the Great Lakes atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ping Sun; Pierrette Blanchard; Kenneth A. Brice

2006-10-15

Atmospheric polycyclic aromatic hydrocarbon (PAHs) concentrations were measured in both the vapor and particle phases at seven sites near the Great Lakes as a part of the Integrated Atmospheric Deposition Network. Lower molecular weight PAHs, including fluorene, phenanthrene, fluoranthrene, and pyrene, were dominant in the vapor phase, and higher molecular weight PAHs, including chrysene, benzo(a)pyrene, and coronene, were dominant in the particle phase. The highest PAH concentrations in both the vapor and particle phases were observed in Chicago followed by the semiurban site at Sturgeon Point, NY. The major sources of PAHs in and around Chicago are vehicle emissions, coalmore » and natural gas combustion, and coke production. The spatial difference of PAH concentrations can be explained by the local population density. Long-term decreasing trends of most PAH concentrations were observed in both the vapor and particle phases at Chicago, with half-lives ranging from 3-10 years in the vapor phase and 5-15 years in the particle phase. At Eagle Harbor, Sleeping Bear Dunes, and Sturgeon Point, total PAH concentrations in the vapor phase showed significant, but slow, long-term decreasing trends. At the Sturgeon Point site, which was impacted by a nearby city, particle-phase PAH concentrations also declined. However, most particle-phase PAH concentrations did not show significant long-term decreasing trends at the remote sites. Seasonal trends were also observed for particle-phase PAH concentrations, which were higher in the winter and lower in the summer. 36 refs., 4 figs., 1 tab.« less

[Characterization of PAHs in fly ashes from coke production].

PubMed

Mu, Ling; Peng, Lin; Liu, Xiao-Feng; Bai, Hui-Ling; Zhang, Jian-Qiang

2013-03-01

In order to investigate the characteristics of polycyclic aromatic hydrocarbons (PAHs) in ashes from coking, PAHs in ashes from three coke production plants were analyzed with GC-MS, and the distribution characteristics of PAHs and potential toxicity risk were discussed. The sum of 16 EPA prior PAHs varied from 8.17 x 10(2) to 5.17 x 10(3) microg x g(-1). PAH contents from the coke oven (stamp charging) with the height of 3.2 m were two times higher than those from the one (top charging) with the height of 6.0 m, and PAHs in ashes from coal charging were significantly higher than those from coke pushing in the same plant. Four-ring and five-ring PAHs were the dominant species in ashes from coking and the sum of them accounted for more than 80.00% of total PAHs. Chrysene (Chr), benzo [a] anthracene (BaA) and benzo [b] fluoranthene (BbF) were abundant in all ash samples. The content of total BaP-based toxic equivalency (BaPeq) ranged from 1.64 x 10(2) to 9.57 x 10(2) microg x g(-1). From the carcinogenic point of view, besides benzo [a] pyrene (BaP), dibenz [a,h] anthracene (DbA) contributed most to the overall toxicity of PAHs, followed by BaA and BbF. BaPeq concentration from coal charging was 5.21-fold higher than that from coke pushing, indicating that different reuse ways should be considered based on their specific toxicity profiles of PAHs.

Polycyclic aromatic hydrocarbons (PAHs) skin permeation rates change with simultaneous exposures to solar ultraviolet radiation (UV-S).

PubMed

Hopf, Nancy B; Spring, Philipp; Hirt-Burri, Nathalie; Jimenez, Silvia; Sutter, Benjamin; Vernez, David; Berthet, Aurelie

2018-05-01

Road construction workers are simultaneously exposed to two carcinogens; solar ultraviolet (UV-S) radiation and polycyclic aromatic hydrocarbons (PAHs) in bitumen emissions. The combined exposure may lead to photogenotoxicity and enhanced PAH skin permeation rates. Skin permeation rates (J) for selected PAHs in a mixture (PAH-mix) or in bitumen fume condensate (BFC) with and without UV-S co-exposures were measured with in vitro flow-through diffusion cells mounted with human viable skin and results compared. Possible biomarkers were explored. Js were greater with UV-S for naphthalene, anthracene, and pyrene in BFC (0.08-0.1 ng/cm 2 /h) compared to without (0.02-0.26 ng/cm 2 /h). This was true for anthracene, pyrene, and chrysene in the PAH-mix. Naphthalene and benzo(a)pyrene (BaP) in the PAH-mix had greater Js without (0.97-13.01 ng/cm 2 /h) compared to with UV-S (0.40-6.35 ng/cm 2 /h). Time until permeation (T lags ) in the PAH-mix were generally shorter compared to the BFC, and they ranged from 1 to 13 h. The vehicle matrix could potentially be the reason for this discrepancy as BFC contains additional not identified substances. Qualitative interpretation of p53 suggested a dose-response with UV-S, and somewhat with the co-exposures. MMP1, p65 and cKIT were not exploitable. Although not statistically different, PAHs permeate human viable skin faster with simultaneous exposures to UV. Copyright © 2018 Elsevier B.V. All rights reserved.

Single-laboratory validation of a saponification method for the determination of four polycyclic aromatic hydrocarbons in edible oils by HPLC-fluorescence detection.

PubMed

Akdoğan, Abdullah; Buttinger, Gerhard; Wenzl, Thomas

2016-01-01

An analytical method is reported for the determination of four polycyclic aromatic hydrocarbons (benzo[a]pyrene (BaP), benz[a]anthracene (BaA), benzo[b]fluoranthene (BbF) and chrysene (CHR)) in edible oils (sesame, maize, sunflower and olive oil) by high-performance liquid chromatography. Sample preparation is based on three steps including saponification, liquid-liquid partitioning and, finally, clean-up by solid phase extraction on 2 g of silica. Guidance on single-laboratory validation of the proposed analysis method was taken from the second edition of the Eurachem guide on method validation. The lower level of the working range of the method was determined by the limits of quantification of the individual analytes, and the upper level was equal to 5.0 µg kg(-1). The limits of detection and quantification of the four PAHs ranged from 0.06 to 0.12 µg kg(-1) and from 0.13 to 0.24 µg kg(-1). Recoveries of more than 84.8% were achieved for all four PAHs at two concentration levels (2.5 and 5.0 µg kg(-1)), and expanded relative measurement uncertainties were below 20%. The performance of the validated method was in all aspects compliant with provisions set in European Union legislation for the performance of analytical methods employed in the official control of food. The applicability of the method to routine samples was evaluated based on a limited number of commercial edible oil samples.

Biodegradation of polycyclic aromatic hydrocarbons by Trichoderma species: a mini review.

PubMed

Zafra, German; Cortés-Espinosa, Diana V

2015-12-01

Fungi belonging to Trichoderma genus are ascomycetes found in soils worldwide. Trichoderma has been studied in relation to diverse biotechnological applications and are known as successful colonizers of their common habitats. Members of this genus have been well described as effective biocontrol organisms through the production of secondary metabolites with potential applications as new antibiotics. Even though members of Trichoderma are commonly used for the commercial production of lytic enzymes, as a biological control agent, and also in the food industry, their use in xenobiotic biodegradation is limited. Trichoderma stands out as a genus with a great range of substrate utilization, a high production of antimicrobial compounds, and its ability for environmental opportunism. In this review, we focused on the recent advances in the research of Trichoderma species as potent and efficient aromatic hydrocarbon-degrading organisms, as well as aimed to provide insight into its potential role in the bioremediation of soils contaminated with heavy hydrocarbons. Several Trichoderma species are associated with the ability to metabolize a variety of both high and low molecular weight polycyclic aromatic hydrocarbons (PAHs) such as naphthalene, phenanthrene, chrysene, pyrene, and benzo[a]pyrene. PAH-degrading species include Trichoderma hamatum, Trichoderma harzianum, Trichoderma reesei, Trichoderma koningii, Trichoderma viride, Trichoderma virens, and Trichoderma asperellum using alternate enzyme systems commonly seen in other organisms, such as multicooper laccases, peroxidases, and ring-cleavage dioxygenases. Within these species, T. asperellum stands out as a versatile organism with remarkable degrading abilities, high tolerance, and a remarkable potential to be used as a remediation agent in polluted soils.

Elimination of polycyclic aromatic hydrocarbons from smoked sausages by migration into polyethylene packaging.

PubMed

Semanová, Jana; Skláršová, Božena; Šimon, Peter; Šimko, Peter

2016-06-15

The objective of this work was a study of interactions between a smoked meat product and plastic packaging to find a possibility of elimination of polycyclic aromatic hydrocarbons (PAH) from smoked sausages by migration into the packaging. Smoked meat sausages were packed into o-polyamide/low density polyethylene laminated film and content of four PAH was determined at 0, 15, 30, 45, 60, 75, 90, 120, 150 and 180 min by HPLC. During this time, total PAH4 content decreased from 30.1 to 5.7 μg/kg, benzo[a]anthracene decreased from 11.5 to 2.1 μg/kg, chrysene from 9.4 to 1.9 μg/kg, benzo[b]fluoranthene from 5.3 to 0.6 μg/kg and benzo[a]pyrene from 3.9 to 1.1 μg/kg while PAH4 content in non-packed sausages remained at a constant level. So, while sausages did not meet European safety limits set for PAH4 content of 12 μg/kg and 2 μg/kg for benzo[a]pyrene before packaging, these limits were met at the end of the experiment. This decrease was brought about by migration of PAH4 from sausages into low density polyethylene packaging bulk and the measure of decrease can be predicted by a kinetic equation, making it possible to calculate PAH content equal to any time of experiment as well as the time of interaction necessary to fulfil EU legislative limits. Copyright © 2016 Elsevier Ltd. All rights reserved.

Atmospheric behaviors of polycyclic aromatic hydrocarbons at a Japanese remote background site, Noto peninsula, from 2004 to 2014

NASA Astrophysics Data System (ADS)

Tang, Ning; Hakamata, Mariko; Sato, Kousuke; Okada, Yumi; Yang, Xiaoyang; Tatematsu, Michiya; Toriba, Akira; Kameda, Takayuki; Hayakawa, Kazuichi

2015-11-01

Total suspended particulates were collected at a Japanese remote background site (Noto Air Monitoring Station; NAMS) on the Noto Peninsula from September 2004 to June 2014. Nine polycyclic aromatic hydrocarbons (PAHs) in the particulates (fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, benzo[ghi]perylene and indeno[1,2,3-cd]pyrene) were determined by HPLC with fluorescence detection. The mean total concentrations of the nine PAHs in the cold season (November to May for the years 2004-2014) was 670 pg m-3 (range 37-4100 pg m-3). The mean total concentration in the warm season (June to October for the same period) was 170 pg m-3 (range 31-960 pg m-3). The atmospheric PAH level at NAMS decreased in recent years, although no significant change was found in the warm season. An analysis of meteorological conditions showed that the atmospheric PAHs at NAMS were long range transported from Northeast China in the cold seasons and were contributed to by Japanese domestic sources in the warm seasons. Lower concentration ratios of reactive PAHs to their isomers at NAMS also supported these results. Activities associated with the Beijing Olympic and Paralympic Games in 2008 and reconstruction after the 2007 Noto Hanto earthquake may have contributed to the yearly variations of atmospheric PAH levels at NAMS during the period 2007-2009. Source control measures implemented by the Chinese and Japanese governments appear to have been effective in decreasing the atmospheric PAH levels at NAMS in recent years.

Human Health and Ecological Risk Assessment of 16 Polycyclic Aromatic Hydrocarbons in Drinking Source Water from a Large Mixed-Use Reservoir

PubMed Central

Sun, Caiyun; Zhang, Jiquan; Ma, Qiyun; Chen, Yanan

2015-01-01

Reservoirs play an important role in living water supply and irrigation of farmlands, thus the water quality is closely related to public health. However, studies regarding human health and ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in the waters of reservoirs are very few. In this study, Shitou Koumen Reservoir which supplies drinking water to 8 million people was investigated. Sixteen priority PAHs were analyzed in a total of 12 water samples. In terms of the individual PAHs, the average concentration of Fla, which was 5.66 × 10−1 μg/L, was the highest, while dibenz(a,h)anthracene which was undetected in any of the water samples was the lowest. Among three PAH compositional patterns, the concentration of low-molecular-weight and 4-ring PAHs was dominant, accounting for 94%, and the concentration of the total of 16 PAHs was elevated in constructed-wetland and fish-farming areas. According to the calculated risk quotients, little or no adverse effects were posed by individual and complex PAHs in the water on the aquatic ecosystem. In addition, the results of hazard quotients for non-carcinogenic risk also showed little or no negative impacts on the health of local residents. However, it could be concluded from the carcinogenic risk results that chrysene and complex PAHs in water might pose a potential carcinogenic risk to local residents. Moreover, the possible sources of PAHs were identified as oil spills and vehicular emissions, as well as the burning of biomass and coal. PMID:26529001

Exposure to polycyclic aromatic hydrocarbons (PAHs) and bladder cancer: evaluation from a gene-environment perspective in a hospital-based case-control study in the Canary Islands (Spain)

PubMed Central

Boada, Luis D; Henríquez-Hernández, Luis A; Navarro, Patricio; Zumbado, Manuel; Almeida-González, Maira; Camacho, María; Álvarez-León, Eva E; Valencia-Santana, Jorge A; Luzardo, Octavio P

2015-01-01

Background: Exposure to polycyclic aromatic hydrocarbons (PAHs) has been linked to bladder cancer. Objective: To evaluate the role of PAHs in bladder cancer, PAHs serum levels were measured in patients and controls from a case-control study. Methods: A total of 140 bladder cancer patients and 206 healthy controls were included in the study. Sixteen PAHs were analyzed from the serum of subjects by gas chromatography–mass spectrometry. Results: Serum PAHs did not appear to be related to bladder cancer risk, although the profile of contamination by PAHs was different between patients and controls: pyrene (Pyr) was solely detected in controls and chrysene (Chry) was exclusively detected in the cases. Phenanthrene (Phe) serum levels were inversely associated with bladder cancer (OR = 0·79, 95%CI = 0·64–0·99, P = 0·030), although this effect disappeared when the allelic distribution of glutathione-S-transferase polymorphisms of the population was introduced into the model (multinomial logistic regression test, P = 0·933). Smoking (OR = 3·62, 95%CI = 1·93–6·79, P<0·0001) and coffee consumption (OR = 1·73, 95%CI = 1·04–2·86, P = 0·033) were relevant risk factors for bladder cancer. Conclusions: Specific PAH mixtures may play a relevant role in bladder cancer, although such effect seems to be highly modulated by polymorphisms in genes encoding xenobiotic-metabolizing enzymes. PMID:25291984

Oxidation kinetics of polycyclic aromatic hydrocarbons by permanganate.

PubMed

Forsey, Steven P; Thomson, Neil R; Barker, James F

2010-04-01

The reactivity of permanganate towards polycyclic aromatics hydrocarbons (PAHs) is well known but little kinetic information is available. This study investigated the oxidation kinetics of a selected group of coal tar creosote compounds and alkylbenzenes in water using permanganate, and the correlation between compound reactivity and physical/chemical properties. The oxidation of naphthalene, phenanthrene, chrysene, 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, carbazole isopropylbenzene, ethylbenzene and methylbenzene closely followed pseudo first-order reaction kinetics. The oxidation of pyrene was initially very rapid and did not follow pseudo first-order kinetics at early times. Fluoranthene was only partially oxidized and the oxidation of anthracene was too fast to be captured. Biphenyl, dibenzofuran, benzene and tert-butylbenzene were non-reactive under the study conditions. The oxidation rate was shown to increase with increasing number of polycyclic rings because less energy is required to overcome the aromatic character of a polycyclic ring than is required for benzene. Thus the rate of oxidation increased in the series naphthalene

HIGH-RESOLUTION IR ABSORPTION SPECTROSCOPY OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE 3 μ m REGION: ROLE OF PERIPHERY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maltseva, Elena; Petrignani, Annemieke; Buma, Wybren Jan

2016-11-01

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μ m absorption band. For this purpose, we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950–3150 cm{sup −1} range. The experimental spectra are compared with standard harmonic calculations and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μmore » m region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive data set of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μ m band, and on features such as the two-component emission character of this band and the 3 μ m emission plateau.« less

Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons.

PubMed

Kim, Pil-Gon; Roh, Ji-Yeon; Hong, Yongseok; Kwon, Jung-Hwan

2017-10-01

Passive sampling can be applied for measuring the freely dissolved concentration of hydrophobic organic chemicals (HOCs) in soil pore water. When using passive samplers under field conditions, however, there are factors that might affect passive sampling equilibrium and kinetics, such as soil water saturation. To determine the effects of soil water saturation on passive sampling, the equilibrium and kinetics of passive sampling were evaluated by observing changes in the distribution coefficient between sampler and soil (K sampler/soil ) and the uptake rate constant (k u ) at various soil water saturations. Polydimethylsiloxane (PDMS) passive samplers were deployed into artificial soils spiked with seven selected polycyclic aromatic hydrocarbons (PAHs). In dry soil (0% water saturation), both K sampler/soil and k u values were much lower than those in wet soils likely due to the contribution of adsorption of PAHs onto soil mineral surfaces and the conformational changes in soil organic matter. For high molecular weight PAHs (chrysene, benzo[a]pyrene, and dibenzo[a,h]anthracene), both K sampler/soil and k u values increased with increasing soil water saturation, whereas they decreased with increasing soil water saturation for low molecular weight PAHs (phenanthrene, anthracene, fluoranthene, and pyrene). Changes in the sorption capacity of soil organic matter with soil water content would be the main cause of the changes in passive sampling equilibrium. Henry's law constant could explain the different behaviors in uptake kinetics of the selected PAHs. The results of this study would be helpful when passive samplers are deployed under various soil water saturations. Copyright © 2017 Elsevier Ltd. All rights reserved.

Relationship between total polar components and polycyclic aromatic hydrocarbons in fried edible oil.

PubMed

An, Ke-Jing; Liu, Yu-Lan; Liu, Hai-Lan

2017-09-01

Deep-fried dough sticks (a Chinese traditional breakfast) were fried individually in peanut, sunflower, rapeseed, rice bran, soybean and palm oil without any time lag for 32 h (64 batches fried, each for 30 min) and fried oil samples were obtained every 2 h. The frying-induced changes in the levels of total polar compounds (TPC) and polycyclic aromatic hydrocarbons (PAHs) were investigated by edible oil polar compounds (EOPC) fast separation chromatographic system and gas chromatography-mass spectrometry (GC-MS), respectively. The correlations were analysed of TPC with benzo[a]pyrene (BaP), TPC and PAH4 (benzo[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) as well as TPC with PAH16 (USEPA 16 PAHs). The results revealed that the levels of TPC and PAHs in fried oil considerably increased with frying time, and the type of oil affected their formation, which could inform the choice of oil for frying. The total BaP equivalents (∑BaPeq) concentrations in fresh oil and in oil whose TPC exceeded 27% were 2.14-13.48 and 5.78-10.80 μg kg -1 , respectively, which means that the carcinogenic potency of frying oil was more pronounced than that of fresh oil. In addition, the TPC concentration was significantly correlated with the concentrations of the sum of the 16 PAHs, PAH4 and BaP, so that the levels of PAHs could be predicted according to the levels of TPC in fried oil. In European standards, the rejection point for TPC in frying oil should be recalculated when considered PAHs. In all, the concentration of PAHs is a vital factor for ensuring the safety of frying oil.

Conditions of persistent oil on beaches in Prince William Sound 26 years after the Exxon Valdez spill

NASA Astrophysics Data System (ADS)

Lindeberg, Mandy R.; Maselko, Jacek; Heintz, Ron A.; Fugate, Corey J.; Holland, Larry

2018-01-01

On March 24, 1989, the Exxon Valdez grounded on Bligh Reef in Prince William Sound, Alaska, spilling an estimated 10.8 million gallons of crude oil. Contrary to early projections, subsequent studies over several decades have shown subsurface oil persisting on impacted beaches. Here we present findings from a lingering oil survey conducted during the summer of 2015 at a small set of beaches in Prince William Sound known to have persistent subsurface Exxon Valdez oil. The objectives of the survey were to estimate how much oil remains at these sites, the oil composition, and oil retention rates compared to previous studies. Results from the survey found lingering oil was present at 8 of 9 sites that were revisited. Surveys revealed little evidence of change in oil area or mass over the last 14 years, nor has there been a change in the distribution of oiling intensities or their location on the beach. Detailed analysis of the oil indicated it has not weathered since 2001. Subsurface oils collected in 2015 have enriched concentrations of phenanthrenes and chrysenes relative to oil originating in the cargo hold indicating that buried oil has retained some toxic potential over the last two decades, but it is not currently bioavailable. Subsurface oil appears to be sequestered in sediments and protected from hydrological washing and low oxygen and nutrient levels inhibiting biodegradation. These findings are consistent with previous surveys and predictive geomorphic models suggesting the estimated 0.6% Exxon Valdez oil remaining is sequestered and not bioavailable unless disturbed and will likely persist in the environment on a decadal scale.

Toxicological and chemical characterization of the process stream materials and gas combustion products of an experimental low-btu coal gasifier.

PubMed

Benson, J M; Hanson, R L; Royer, R E; Clark, C R; Henderson, R F

1984-04-01

The process gas stream of an experimental pressurized McDowell-Wellman stirred-bed low-Btu coal gasifier, and combustion products of the clean gas were characterized as to their mutagenic properties and chemical composition. Samples of aerosol droplets condensed from the gas were obtained at selected positions along the process stream using a condenser train. Mutagenicity was assessed using the Ames Salmonella mammalian microsome mutagenicity assay (TA98, with and without rat liver S9). All materials required metabolic activation to be mutagenic. Droplets condensed from gas had a specific mutagenicity of 6.7 revertants/microgram (50,000 revertants/liter of raw gas). Methylnaphthalene, phenanthrene, chrysene, and nitrogen-containing compounds were positively identified in a highly mutagenic fraction of raw gas condensate. While gas cleanup by the humidifier-tar trap system and Venturi scrubber led to only a small reduction in specific mutagenicity of the cooled process stream material (4.1 revertants/microgram), a significant overall reduction in mutagenicity was achieved (to 2200 revertants/liter) due to a substantial reduction in the concentration of material in the gas. By the end of gas cleanup, gas condensates had no detectable mutagenic activity. Condensates of combustion product gas, which contained several polycyclic aromatic compounds, had a specific mutagenicity of 1.1 revertants/microgram (4.0 revertants/liter). Results indicate that the process stream material is potentially toxic and that care should be taken to limit exposure of workers to the condensed tars during gasifier maintenance and repair and to the aerosolized tars emitted in fugitive emissions. Health risks to the general population resulting from exposure to gas combustion products are expected to be minimal.

Polycyclic aromatic hydrocarbons in soil of the Canadian River floodplain in Oklahoma

USGS Publications Warehouse

Sartori, F.; Wade, T.L.; Sericano, J.L.; Mohanty, B.P.; Smith, K.A.

2010-01-01

The accumulation of polycyclic aromatic hydrocarbons (PAH) in soil, plants, and water may impart negative eff ects on ecosystem and human health. We quantified the concentration and distribution of 41 PAH (n = 32), organic C, total N, and S (n = 140) and investigated PAH sources using a chronosequence of floodplain soils under a natural vegetation succession. Soil samples were collected between 0- and 260-cm depth in bare land (the control), wetland, forest, and grassland areas near a closed municipal landfill and an active asphalt plant (the contaminant sources) in the north bank of the Canadian River near Norman, OK. Principal component, cluster, and correlation analyses were used to investigate the spatial distribution of PAH, in combination with diagnostic ratios to distinguish pyrogenic vs. petrogenic PAH suites. Total PAH concentration (??PAH) had a mean of 1300 ng g-1, minimum of 16 ng g-1, and maximum of 12,000 ng g-1. At 0- to 20-cm depth, ??PAH was 3500 ?? 1600 ng g-1 (mean ?? 1 SE) near the contaminant sources. The most common compounds were nonalkylated, high molecular weight PAH of pyrogenic origin, i.e., fluoranthene (17%), pyrene (14%), phenanthrene (9%), benzo(b)fluoranthene (7%), chrysene (6%), and benzo(a)anthracene (5%). ??PAH in the control (130 ?? 23 ng g -1) was comparable to reported concentrations for the rural Great Plains. Perylene had a unique distribution pattern suggesting biological inputs. The main PAH contamination mechanisms were likely atmospheric deposition due to asphalt production at the 0- to 20-cm depth and past landfill operations at deeper depths. Copyright ?? 2010 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Comment on: Negative ions, molecular electron affinity and orbital structure of cata-condensed polycyclic aromatic hydrocarbons by Rustem V. Khatymov, Mars V. Muftakhov and Pavel V. Shchukin.

PubMed

Chen, Edward S; Chen, Edward C M

2018-02-15

The anion mass spectral lifetimes for several aromatic hydrocarbons reported in the subject article were related to significantly different electron affinities. The different values are rationalized using negative ion mass spectral data. Electron affinities for polycyclic aromatic hydrocarbons are reported from the temperature dependence of unpublished electron capture detector data. These are compared with published values and the largest values are assigned to the ground state. The ground state adiabatic electron affinities: (eV) pentacene, 1.41 (3); tetracene, 1.058 (5); benz(a)pyrene, 0.82 (4); benz(a) anthracene, 0.69 (2) anthracene, 0.68 (2); and pyrene, 0.59 (1) are used to assign excited state adiabatic electron affinities: (eV) tetracene: 0.88 (4); anthracene 0.53 (1); pyrene, 0.41 (1); benz(a)anthracene, 0.39 (10); chrysene, 0.32 (1); and phenanthrene, 0.12 (2) and ground state adiabatic electron affinities: (eV) dibenz(a,j)anthracene, 0.69 (3); dibenz(a,h)anthracene, 0.68 (3); benz(e)pyrene, 0.60 (3); and picene, 0.59 (3) from experimental data. The lifetime of benz(a)pyrene is predicted to be larger than 150 μs and for benzo(c)phenanthrene and picene about 40 μs, from ground state adiabatic electron affinities. The assignments of adiabatic electron affinities of aromatic hydrocarbons determined from electron capture detector and mass spectrometric data to ground and excited states are supported by constant electronegativities. A set of consistent ground state adiabatic electron affinities for 15 polycyclic aromatic hydrocarbons is related to lifetimes from the subject article. Copyright © 2017 John Wiley & Sons, Ltd.

Characterization and distribution of polycyclic aromatic hydrocarbon contaminations in surface sediment and water from Gao-ping River, Taiwan.

PubMed

Doong, Ruey-An; Lin, Yu-Tin

2004-04-01

The concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in water and sediment samples collected from 12 locations in Gao-ping River, Taiwan were analyzed. Molecular ratios and principal component analysis (PCA) were used to characterize the possible pollution sources. Concentrations of total 16 PAHs (SigmaPAHs) in water samples ranged from below method detection limits (

Chemical Contaminants Found in the Gastrointestinal Tract of Loggerhead Sea Turtles (Caretta caretta)

NASA Astrophysics Data System (ADS)

Athey, S. N.; Seaton, P. J.; Mead, R. N.

2016-02-01

Plastic is becoming increasingly more abundant in the marine environment. Plastic ingestion has been shown to be a source of exposure to a variety of harmful compounds, such as polycyclic aromatic hydrocarbons (PAHs), bisphenol A (BPA), and phthalates, which are known for their negative physiological effects on the endocrine system as well as their ability to adsorb and leach from plastic into the bodies of marine organisms. The physiological effects of these compounds on loggerhead sea turtles (Caretta caretta) still remain unknown. This study investigated the presence of toxicants on marine plastic samples collected from Bermuda, the Sargasso Sea, and the North Atlantic Ocean. Gas chromatography/triple quadruple mass spectrometry (GC/MS) analysis showed PAHs were present on many plastic debris samples. Plastic additives such as phthalates and (BPA) were also found. ΣPAH concentrations for anthracene, chrysene, benzo[b]fluoranthene, and benzo[k]fluoranthene for 2013 environmental plastic samples averaged 26.7ng/g of plastic. This study also examined the presence of these compounds in fluids from the stomach, small intestine, and large intestine from two adult loggerhead turtles. GC/MS analysis also showed the presence of BPA and phthalates on plastic samples, as well as in two out of the six gastrointestinal fluids samples. Average ΣPAH concentration for GI fluids for the loggerheads in the study was 58.7 ng/mL. This study showed plastic could be a significant source of PAHs in sea turtles and the first to detect PAHs in sea turtle GI fluid. Loggerhead sea turtles are a long living species and could accumulate high concentrations of these endocrine-disrupting chemicals throughout their lifetime.

Polyphasic approach for assessing changes in an autochthonous marine bacterial community in the presence of Prestige fuel oil and its biodegradation potential.

PubMed

Jiménez, Núria; Viñas, Marc; Guiu-Aragonés, Cèlia; Bayona, Josep M; Albaigés, Joan; Solanas, Anna M

2011-08-01

A laboratory experiment was conducted to identify key hydrocarbon degraders from a marine oil spill sample (Prestige fuel oil), to ascertain their role in the degradation of different hydrocarbons, and to assess their biodegradation potential for this complex heavy oil. After a 17-month enrichment in weathered fuel, the bacterial community, initially consisting mainly of Methylophaga species, underwent a major selective pressure in favor of obligate hydrocarbonoclastic microorganisms, such as Alcanivorax and Marinobacter spp. and other hydrocarbon-degrading taxa (Thalassospira and Alcaligenes), and showed strong biodegradation potential. This ranged from >99% for all low- and medium-molecular-weight alkanes (C(15)-C(27)) and polycyclic aromatic hydrocarbons (C(0)- to C(2)- naphthalene, anthracene, phenanthrene, dibenzothiophene, and carbazole), to 75-98% for higher molecular-weight alkanes (C(28)-C(40)) and to 55-80% for the C(3) derivatives of tricyclic and tetracyclic polycyclic aromatic hydrocarbons (PAHs) (e.g., C(3)-chrysenes), in 60 days. The numbers of total heterotrophs and of n-alkane-, aliphatic-, and PAH degraders, as well as the structures of these populations, were monitored throughout the biodegradation process. The salinity of the counting medium affects the counts of PAH degraders, while the carbon source (n-hexadecane vs. a mixture of aliphatic hydrocarbons) is a key factor when counting aliphatic degraders. These limitations notwithstanding, some bacterial genera associated with hydrocarbon degradation (mainly belonging to α- and γ-Proteobacteria, including the hydrocarbonoclastic Alcanivorax and Marinobacter) were identified. We conclude that Thalassospira and Roseobacter contribute to the degradation of aliphatic hydrocarbons, whereas Mesorhizobium and Muricauda participate in the degradation of PAHs.

Characteristics of PAHs in farmland soil and rainfall runoff in Tianjin, China.

PubMed

Shi, Rongguang; Xu, Mengmeng; Liu, Aifeng; Tian, Yong; Zhao, Zongshan

2017-10-14

Rainfall runoff can remove certain amounts of pollutants from contaminated farmland soil and result in a decline in water quality. However, the leaching behaviors of polycyclic aromatic hydrocarbons (PAHs) with rainfall have been rarely reported due to wide variations in the soil compositions, rainfall conditions, and sources of soil PAHs in complex farmland ecosystems. In this paper, the levels, spatial distributions, and composition profiles of PAHs in 30 farmland soil samples and 49 rainfall-runoff samples from the Tianjin region in 2012 were studied to investigate their leaching behaviors caused by rainfall runoff. The contents of the Σ 16 PAHs ranged from 58.53 to 3137.90 μg/kg in the soil and 146.58 to 3636.59 μg/L in the runoff. In total, most of the soil sampling sites (23 of 30) were contaminated, and biomass and petroleum combustion were proposed as the main sources of the soil PAHs. Both the spatial distributions of the soil and the runoff PAHs show a decreasing trend moving away from the downtown, which suggested that the leaching behaviors of PAHs in a larger region during rainfall may be mainly affected by the compounds themselves. In addition, 4- and 5-ring PAHs are the dominant components in farmland soil and 3- and 4-ring PAHs dominate the runoff. Comparisons of the PAH pairs and enrichment ratios showed that acenaphthylene, acenaphthene, benzo[a]anthracene, chrysene, and fluoranthene were more easily transferred into water systems from soil than benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, and indeno[123-cd]pyrene, which indicated that PAHs with low molecular weight are preferentially dissolved due to their higher solubility compared to those with high molecular weight.

Exposure risk to carcinogenic PAHs in indoor-air during biomass combustion whilst cooking in rural India

NASA Astrophysics Data System (ADS)

Bhargava, Anuj; Khanna, R. N.; Bhargava, S. K.; Kumar, Sushil

In India, a vast majority of rural household burns unprocessed biomass, as an energy source, to cook food. The biomass is burnt indoors in conventionally homemade clay-stoves, called 'Chulha', which results in the generation of a variety of airborne products along with polycyclic aromatic hydrocarbons (PAHs) in an uncontrolled manner. We report here the concentrations and profile of carcinogenic PAHs, co-sampled with respirable suspended particulate matter, in rural indoors during burning of biomass vis-à-vis liquified petroleum gas as the energy source. There is a limited data on the subject in the literature. The seasonal variation has also been studied. Sampling was done in breathing zone and in surrounding areas concurrent with cooking on chulha. PAHs were extracted in methylene chloride and analyzed over HPLC after column clean up on silica gel. Our study revealed that the concentrations of carcinogenic PAHs were fairly high in breathing zone and in surrounding areas while cooking over chulha in rural India. PAHs concentrations increased substantially during biomass combustion. Concentrations were high during CDC combustion and low during LPG combustion or the non-cooking period. This trend was conserved in both the seasons. Concentrations of total PAHs were greater in winter as compared to summer and greatest in the breathing zone. Di-benz( a,h)anthracene, benzo( k)-fluoranthene and chrysene contributed maximum. Benzo( a)pyrene contributed moderately. Maximum concentrations of indoor air benzo( a)pyrene (>1.5 μg/m 3) were found in breathing zone in winter. The daily exposure to high concentrations of carcinogenic PAHs in indoor air environment while cooking food could be impacting for chronic pulmonary illnesses in rural Indian women.

Measurement and estimated health risks of semivolatile organic compounds (PCBs, PAHs, pesticides, and phthalates) in ambient air at the Hanford Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patton, G.W.; Cooper, A.T.; Blanton, M.L.

1997-09-01

Air samples for polychlorinated biphenyls (PCBs), chlorinated pesticides, phthalate plasticizers, and polycyclic aromatic hydrocarbons (PAHs) were collected at three Hanford Site locations (300-Area South Gate, southeast of 200-East Area, and a background location near Rattlesnake Springs). Samples were collected using high-volume air samplers equipped with a glass fiber filter and polyurethane foam plug sampling train. Target compounds were extracted from the sampling trains and analyzed using capillary gas chromatography with either electron capture detection or mass selective detection. Twenty of the 28 PCB congeners analyzed were found above the detection limits, with 8 of the congeners accounting for over 80%more » of the average PCB concentrations. The average sum of all individual PCB congeners ranged from 500-740 pg/m{sup 3}, with little apparent difference between the sampling locations. Twenty of the 25 pesticides analyzed were found above the detection limits, with endosulfan I, endosulfan II, and methoxychlor having the highest average concentrations. With the exception of the endosulfans, all other average pesticide concentrations were below 100 pg/m{sup 3}. There was little apparent difference between the air concentrations of pesticides measured at each location. Sixteen of the 18 PAHs analyzed were found above the detection limit. Phenanthrene, fluoranthene, pyrene, fluorene, chrysene, benzo(b)fluoranthene, and naphthalene were the only PAHs with average concentrations above 100 pg/m{sup 3}. Overall, the 300 Area had higher average PAH concentrations compared to the 200-East Area and the background location at Rattlesnake Springs; however, the air concentrations at the 300-Area also are influenced by sources on the Hanford Site and from nearby communities.« less

Human biomonitoring of polycyclic aromatic hydrocarbonsand metals in the general population residing near the municipal solid waste incinerator of Modena, Italy.

PubMed

Gatti, Maria Giulia; Bechtold, Petra; Campo, Laura; Barbieri, Giovanna; Quattrini, Giulia; Ranzi, Andrea; Sucato, Sabrina; Olgiati, Luca; Polledri, Elisa; Romolo, Michael; Iacuzio, Laura; Carrozzi, Giuliano; Lauriola, Paolo; Goldoni, Carlo A; Fustinoni, Silvia

2017-11-01

A cross-sectional biomonitoring study was carried out to investigate exposure to incinerator emission in relation to the body burden of selected biomarkers in the population living around the plant. Approximately 500 people, aged 18-69 yrs, living within 4 km from the incinerator were randomly selected form the population register. Exposure was measured through fall-out maps of particulate matter (PM), used as tracer for incinerator emissions. Ten metabolized polycyclic aromatic hydrocarbons (PAHs), from naphthalene to chrysene, 1-hydroxypyrene and twelve metals (Cd, Cr, Cu, Hg, Ni, Pb, Ni, Zn, V, Tl, As, Sn) were measured in spot urine samples. Confounders, such as diet, smoking, traffic, occupation and personal characteristics were assessed by questionnaires and objective measurements, and included into multivariate linear regression models. Metal concentrations in urine were in line with or higher than Italian reference limits, besides Cr and V with more than twofold concentrations. Metal levels did not show clear association to exposure categories. Most abundant PAHs were naphthalene (median 26.2 ng/L) and phenanthrene (7.4 ng/L). All PAHs, but benz[a]anthracene and 1-hydroxypyrene, were found in more than 52% of samples, and included in regression models. Significant associations between urinary PAHs and exposure were found, strong for fluorene, and weaker for naphthalene, fluoranthene and pyrene. Results were confirmed by sensitivity analyses. Correlation with variables reported in literature were observed. The study indicates that the emissions were very low and highlights that specific urinary PAHs provided useful information about the internal dose arising from incinerator emission. Copyright © 2017 Elsevier Ltd. All rights reserved.

Deposition flux of aerosol particles and 15 polycyclic aromatic hydrocarbons in the North China Plain.

PubMed

Wang, Xilong; Liu, Shuzhen; Zhao, Jingyu; Zuo, Qian; Liu, Wenxin; Li, Bengang; Tao, Shu

2014-04-01

The present study examined deposition fluxes of aerosol particles and 15 polycyclic aromatic hydrocarbons (PAHs) associated with the particles in the North China Plain. The annual mean deposition fluxes of aerosol particles and 15 PAHs were 0.69 ± 0.46 g/(m(2) ×d) and 8.5 ± 6.2 μg/(m(2) ×d), respectively. Phenanthrene, fluoranthene, pyrene, chrysene, benzo[b]fluoranthene, and benzo[k]fluoranthene were the dominant PAHs bound to deposited aerosol particles throughout the year. The total concentration of 15 PAHs in the deposited aerosol particles was the highest in winter but lowest in spring. The highest PAH concentration in the deposited aerosol particles in winter was because the heating processes highly increased the concentration in atmospheric aerosol particles. Low temperature and weak sunshine in winter reduced the degradation rate of deposited aerosol particle-bound PAHs, especially for those with low molecular weight. The lowest PAH concentration in deposited aerosol particles in spring resulted from the frequently occurring dust storms, which diluted PAH concentrations. The mean deposition flux of PAHs with aerosol particles in winter (16 μg/[m(2) ×d]) reached 3 times to 5 times that in other seasons (3.5-5.0 μg/[m(2) ×d]). The spatial variation of the deposition flux of PAHs with high molecular weight (e.g., benzo[a]pyrene) was consistent with their concentrations in the atmospheric aerosol particles, whereas such a phenomenon was not observed for those with low molecular weight (e.g., phenanthrene) because of their distinct hydrophobicity, Henry's law constant, and the spatially heterogeneous meteorological conditions. © 2013 SETAC.

Simulation of polycyclic aromatic hydrocarbons transport in multimedia

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, L.; Chu, C.J.

1999-07-01

Many studies have indicated that the threat from toxic air pollutants such as VOCs comes not through inhalation by humans while the pollutants are in a gaseous state but through absorption when the pollutants are in a solid state such as in an aerosol or particulate form. Pollutants such as Polycyclic Aromatic Hydrocarbons (PAHs) usually exist in a semi-volatile state. To assess the risk of the PAHs, one needs to estimate the dose of the pollutants to which a human would be exposed through various pathways. In this study, the authors modified a Spatial Multimedia Compartmental Model (SMCM) originally developedmore » by UCLA Professor Cohen to predict the PAHs distribution among multimedia such as air, water, soil and sediment in the Taipei metropolitan area. Three PAHs were considered in this study. They are Benzo(a)pyrene, Pyrene and Chrysene. When PAHs are emitted into atmosphere, physical and chemical mechanisms may redistribute the PAHs among multimedia. Five cases of PAHs distribution in multimedia were simulated: (1) PAHs distribution in a dry condition, (2) PAHs distribution when there are different dry deposition velocities, (3) PAHs distribution under a single rainfall event, (4) PAHs distribution when there are different soil properties, (5) PAHs distribution under a random rainfall case. The simulation results are concluded: (1) In the dry case, the PAHs accumulate mostly in soil and air compartments, (2) Different dry depositing velocities will affect the PAHs distribution among compartments. (3) Different soil properties affect the PAHs concentration in the soil and sediment compartments, (4) The soil PAHs concentrations usually increase for those PAHs with a high solid/gas ratio. (5) The random rainfall only affects the PAHs concentration in the soil.« less

Novel Palm Fatty Acid Functionalized Magnetite Nanoparticles for Magnetic Solid-Phase Extraction of Trace Polycyclic Aromatic Hydrocarbons from Environmental Samples.

PubMed

Rozi, Siti Khalijah Mahmad; Nodeh, Hamid Rashidi; Kamboh, Muhammad Afzal; Manan, Ninie Suhana Abdul; Mohamad, Sharifah

2017-07-01

A novel adsorbent, palm fatty acid coated magnetic Fe 3 O 4 nanoparticles (MNP-FA) was successfully synthesized with immobilization of the palm fatty acid onto the surface of MNPs. The successful synthesis of MNP-FA was further confirmed by X-Ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and Energy dispersive X-Ray spectroscopy (EDX) analyses and water contact angle (WCA) measurement. This newly synthesized MNP-FA was applied as magnetic solid phase extraction (MSPE) adsorbent for the enrichment of polycyclic aromatic hydrocarbons (PAHs), namely fluoranthene (FLT), pyrene (Pyr), chrysene (Cry) and benzo(a)pyrene (BaP) from environmental samples prior to High Performance Liquid Chromatography- Diode Array Detector (HPLC-DAD) analysis. The MSPE method was optimized by several parameters such as amount of sorbent, desorption solvent, volume of desorption solvent, extraction time, desorption time, pH and sample volume. Under the optimized conditions, MSPE method provided a low detection limit (LOD) for FLT, Pyr, Cry and BaP in the range of 0.01-0.05 ng mL -1 . The PAHs recoveries of the spiked leachate samples ranged from 98.5% to 113.8% with the RSDs (n = 5) ranging from 3.5% to 12.2%, while for the spiked sludge samples, the recoveries ranged from 81.1% to 119.3% with the RSDs (n = 5) ranging from 3.1% to 13.6%. The recyclability study revealed that MNP-FA has excellent reusability up to five times. Chromatrographic analysis demonstrated the suitability of MNP-FA as MSPE adsorbent for the efficient extraction of PAHs from environmental samples.

Characterization of a Naphthalene Dioxygenase Endowed with an Exceptionally Broad Substrate Specificity Toward Polycyclic Aromatic Hydrocarbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jouanneau,Y.; Meyer, C.; Jakoncic, J.

In Sphingomonas CHY-1, a single ring-hydroxylating dioxygenase is responsible for the initial attack of a range of polycyclic aromatic hydrocarbons (PAHs) composed of up to five rings. The components of this enzyme were separately purified and characterized. The oxygenase component (ht-PhnI) was shown to contain one Rieske-type [2Fe-2S] cluster and one mononuclear Fe center per {alpha} subunit, based on EPR measurements and iron assay. Steady-state kinetic measurements revealed that the enzyme had a relatively low apparent Michaelis constant for naphthalene (K{sub m} = 0.92 {+-} 0.15 {mu}M) and an apparent specificity constant of 2.0 {+-} 0.3 M{sup -1} s{sup -1}.more » Naphthalene was converted to the corresponding 1,2-dihydrodiol with stoichiometric oxidation of NADH. On the other hand, the oxidation of eight other PAHs occurred at slower rates and with coupling efficiencies that decreased with the enzyme reaction rate. Uncoupling was associated with hydrogen peroxide formation, which is potentially deleterious to cells and might inhibit PAH degradation. In single turnover reactions, ht-PhnI alone catalyzed PAH hydroxylation at a faster rate in the presence of organic solvent, suggesting that the transfer of substrate to the active site is a limiting factor. The four-ring PAHs chrysene and benz[a]anthracene were subjected to a double ring-dihydroxylation, giving rise to the formation of a significant proportion of bis-cis-dihydrodiols. In addition, the dihydroxylation of benz[a]anthracene yielded three dihydrodiols, the enzyme showing a preference for carbons in positions 1,2 and 10,11. This is the first characterization of a dioxygenase able to dihydroxylate PAHs made up of four and five rings.« less

Linear- and angular-shaped naphthodithiophenes: selective synthesis, properties, and application to organic field-effect transistors.

PubMed

Shinamura, Shoji; Osaka, Itaru; Miyazaki, Eigo; Nakao, Akiko; Yamagishi, Masakazu; Takeya, Jun; Takimiya, Kazuo

2011-04-06

A straightforward synthetic approach that exploits linear- and angular-shaped naphthodithiophenes (NDTs) being potential as new core structures for organic semiconductors is described. The newly established synthetic procedure involves two important steps; one is the chemoselective Sonogashira coupling reaction on the trifluoromethanesulfonyloxy site over the bromine site enabling selective formation of o-bromoethynylbenzene substructures on the naphthalene core, and the other is a facile ring closing reaction of fused-thiophene rings from the o-bromoethynylbenzene substructures. As a result, three isomeric NDTs, naphtho[2,3-b:6,7-b']dithiophene, naphtho[2,3-b:7,6-b']dithiophenes, and naphtho[2,1-b:6,5-b']dithiophene, are selectively synthesized. Electrochemical and optical measurements of the parent NDTs indicated that the shape of the molecules plays an important role in determining the electronic structure of the compounds; the linear-shaped NDTs formally isoelectronic with naphthacene have lower oxidation potentials and more red-shifted absorption bands than those of the angular-shaped NDTs isoelectronic with chrysene. On the contrary, the performance of the thin-film-based field-effect transistors (FETs) using the dioctyl or diphenyl derivatives were much influenced by the symmetry of the molecules; centrosymmetric derivatives tend to give higher mobility (up to 1.5 cm(2) V(-1) s(-1)) than axisymmetric ones (∼0.06 cm(2) V(-1) s(-1)), implying that the intermolecular orbital overlap in the solid state is influenced by the symmetry of the molecules. These results indicate that the present NDT cores, in particular the linear-shaped, centrosymmetric naphtho[2,3-b:6,7-b']dithiophene, are promising building blocks for the development of organic semiconducting materials. © 2011 American Chemical Society

Common y-intercept and single compound regressions of gas-particle partitioning data vs 1/T

NASA Astrophysics Data System (ADS)

Pankow, James F.

Confidence intervals are placed around the log Kp vs 1/ T correlation equations obtained using simple linear regressions (SLR) with the gas-particle partitioning data set of Yamasaki et al. [(1982) Env. Sci. Technol.16, 189-194]. The compounds and groups of compounds studied include the polycylic aromatic hydrocarbons phenanthrene + anthracene, me-phenanthrene + me-anthracene, fluoranthene, pyrene, benzo[ a]fluorene + benzo[ b]fluorene, chrysene + benz[ a]anthracene + triphenylene, benzo[ b]fluoranthene + benzo[ k]fluoranthene, and benzo[ a]pyrene + benzo[ e]pyrene (note: me = methyl). For any given compound, at equilibrium, the partition coefficient Kp equals ( F/ TSP)/ A where F is the particulate-matter associated concentration (ng m -3), A is the gas-phase concentration (ng m -3), and TSP is the concentration of particulate matter (μg m -3). At temperatures more than 10°C from the mean sampling temperature of 17°C, the confidence intervals are quite wide. Since theory predicts that similar compounds sorbing on the same particulate matter should possess very similar y-intercepts, the data set was also fitted using a special common y-intercept regression (CYIR). For most of the compounds, the CYIR equations fell inside of the SLR 95% confidence intervals. The CYIR y-intercept value is -18.48, and is reasonably close to the type of value that can be predicted for PAH compounds. The set of CYIR regression equations is probably more reliable than the set of SLR equations. For example, the CYIR-derived desorption enthalpies are much more highly correlated with vaporization enthalpies than are the SLR-derived desorption enthalpies. It is recommended that the CYIR approach be considered whenever analysing temperature-dependent gas-particle partitioning data.

Characterization of a Polycyclic Aromatic Hydrocarbon Degradation Gene Cluster in a Phenanthrene-Degrading Acidovorax Strain▿

PubMed Central

Singleton, David R.; Guzmán Ramirez, Liza; Aitken, Michael D.

2009-01-01

Acidovorax sp. strain NA3 was isolated from polycyclic aromatic hydrocarbon (PAH)-contaminated soil that had been treated in a bioreactor and enriched with phenanthrene. The 16S rRNA gene of the isolate possessed 99.8 to 99.9% similarity to the dominant sequences recovered during a previous stable-isotope probing experiment with [U-13C]phenanthrene on the same soil (D. R. Singleton, S. N. Powell, R. Sangaiah, A. Gold, L. M. Ball, and M. D. Aitken, Appl. Environ. Microbiol. 71:1202-1209, 2005). The strain grew on phenanthrene as a sole carbon and energy source and could mineralize 14C from a number of partially labeled PAHs, including naphthalene, phenanthrene, chrysene, benz[a]anthracene, and benzo[a]pyrene, but not pyrene or fluoranthene. Southern hybridizations of a genomic fosmid library with a fragment of the large subunit of the ring-hydroxylating dioxygenase gene from a naphthalene-degrading Pseudomonas strain detected the presence of PAH degradation genes subsequently determined to be highly similar in both nucleotide sequence and gene organization to an uncharacterized Alcaligenes faecalis gene cluster. The genes were localized to the chromosome of strain NA3. To test for gene induction by selected compounds, RNA was extracted from amended cultures and reverse transcribed, and cDNA associated with the enzymes involved in the first three steps of phenanthrene degradation was quantified by quantitative real-time PCR. Expression of each of the genes was induced most strongly by phenanthene and to a lesser extent by naphthalene, but other tested PAHs and PAH metabolites had negligible effects on gene transcript levels. PMID:19270134

Succession of Phenotypic, Genotypic, and Metabolic Community Characteristics during In Vitro Bioslurry Treatment of Polycyclic Aromatic Hydrocarbon-Contaminated Sediments

PubMed Central

Ringelberg, David B.; Talley, Jeffrey W.; Perkins, Edward J.; Tucker, Samuel G.; Luthy, Richard G.; Bouwer, Edward J.; Fredrickson, Herbert L.

2001-01-01

Dredged harbor sediment contaminated with polycyclic aromatic hydrocarbons (PAHs) was removed from the Milwaukee Confined Disposal Facility and examined for in situ biodegradative capacity. Molecular techniques were used to determine the successional characteristics of the indigenous microbiota during a 4-month bioslurry evaluation. Ester-linked phospholipid fatty acids (PLFA), multiplex PCR of targeted genes, and radiorespirometry techniques were used to define in situ microbial phenotypic, genotypic, and metabolic responses, respectively. Soxhlet extractions revealed a loss in total PAH concentrations of 52%. Individual PAHs showed reductions as great as 75% (i.e., acenapthene and fluorene). Rates of 14C-PAH mineralization (percent/day) were greatest for phenanthrene, followed by pyrene and then chrysene. There was no mineralization capacity for benzo[a]pyrene. Ester-linked phospholipid fatty acid analysis revealed a threefold increase in total microbial biomass and a dynamic microbial community composition that showed a strong correlation with observed changes in the PAH chemistry (canonical r2 of 0.999). Nucleic acid analyses showed copies of genes encoding PAH-degrading enzymes (extradiol dioxygenases, hydroxylases, and meta-cleavage enzymes) to increase by as much as 4 orders of magnitude. Shifts in gene copy numbers showed strong correlations with shifts in specific subsets of the extant microbial community. Specifically, declines in the concentrations of three-ring PAH moieties (i.e., phenanthrene) correlated with PLFA indicative of certain gram-negative bacteria (i.e., Rhodococcus spp. and/or actinomycetes) and genes encoding for naphthalene-, biphenyl-, and catechol-2,3-dioxygenase degradative enzymes. The results of this study suggest that the intrinsic biodegradative potential of an environmental site can be derived from the polyphasic characterization of the in situ microbial community. PMID:11282603

Pressurized liquid extraction of diesel and air particulate standard reference materials: effect of extraction temperature and pressure.

PubMed

Schantz, Michele M; McGaw, Elizabeth; Wise, Stephen A

2012-10-02

Four particulate matter Standard Reference Materials (SRMs) available from the National Institute of Standards and Technology (NIST) were used to evaluate the effect of solvent, number of static cycles and static times, pressure, and temperature when using pressurized liquid extraction (PLE) for the extraction of polycyclic aromatic hydrocarbons (PAHs) and nitrated-PAHs. The four materials used in the study were SRM 1648a Urban Particulate Matter, SRM 1649b Urban Dust, SRM 1650b Diesel Particulate Matter, and SRM 2975 Diesel Particulate Matter (Industrial Forklift). The results from the study indicate that the choice of solvent, dichloromethane compared to toluene and toluene/methanol mixtures, had little effect on the extraction efficiency. With three to five extraction cycles, increasing the extraction time for each cycle from 5 to 30 min had no significant effect on the extraction efficiency. The differences in extraction efficiency were not significant (with over 95% of the differences being <10%) when the pressure was increased from 13.8 to 20.7 MPa. The largest increase in extraction efficiency occurred for selected PAHs when the temperature of extraction was increased from 100 to 200 °C. At 200 °C naphthalene, biphenyl, fluorene, dibenzothiophene, and anthracene show substantially higher mass fractions (>30%) than when extracted at 100 °C in all the SRMs studied. For SRM 2975, large increases (>100%) are also observed for some other PAHs including benz[a]anthracene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, benzo[ghi]perylene, and benzo[b]chrysene when extracted at the higher temperatures; however, similar trends were not observed for the other diesel particulate sample, SRM 1650b. The results are discussed in relation to the use of the SRMs for evaluating analytical methods.

Application of a Fuzzy Neural Network Model in Predicting Polycyclic Aromatic Hydrocarbon- Mediated Perturbations of the Cyp1b1 Transcriptional Regulatory Network in Mouse Skin

PubMed Central

Larkin, Andrew; Siddens, Lisbeth K.; Krueger, Sharon K.; Tilton, Susan C.; Waters, Katrina M.; Williams, David E.; Baird, William M.

2013-01-01

Polycyclic aromatic hydrocarbons (PAHs) are present in the environment as complex mixtures with components that have diverse carcinogenic potencies and mostly unknown interactive effects. Non-additive PAH interactions have been observed in regulation of cytochrome P450 (CYP) gene expression in the CYP1 family. To better understand and predict biological effects of complex mixtures, such as environmental PAHs, an 11 gene input-1 gene output fuzzy neural network (FNN) was developed for predicting PAH-mediated perturbations of dermal Cyp1b1 transcription in mice. Input values were generalized using fuzzy logic into low, medium, and high fuzzy subsets, and sorted using k-means clustering to create Mamdani logic functions for predicting Cyp1b1 mRNA expression. Model testing was performed with data from microarray analysis of skin samples from FVB/N mice treated with toluene (vehicle control), dibenzo[def,p]chrysene (DBC), benzo[a]pyrene (BaP), or 1 of 3 combinations of diesel particulate extract (DPE), coal tar extract (CTE) and cigarette smoke condensate (CSC) using leave one out cross-validation. Predictions were within 1 log2 fold change unit of microarray data, with the exception of the DBC treatment group, where the unexpected down-regulation of Cyp1b1 expression was predicted but did not reach statistical significance on the microarrays. Adding CTE to DPE was predicted to increase Cyp1b1 expression, whereas adding CSC to CTE and DPE was predicted to have no effect, in agreement with microarray results. The aryl hydrocarbon receptor repressor (Ahrr) was determined to be the most significant input variable for model predictions using back-propagation and normalization of FNN weights. PMID:23274566

Accumulation trends of petroleum hydrocarbons in commercial shellfish from the Galician coast (NW Spain) affected by the Prestige oil spill.

PubMed

Viñas, L; Franco, M A; Soriano, J A; González, J J; Ortiz, L; Bayona, J M; Albaigés, J

2009-04-01

Aliphatic and aromatic hydrocarbons were determined in three species of commercial shellfish, namely razor shells (Ensis arcuatus and Ensis siliqua), goose barnacle (Pollicipes cornucopia) and sea urchin (Paracentrotus lividus), living in different habitats and exhibiting different feeding behaviors. The samples were collected monthly, from January 2003 to October 2004, in three stations of the Galicia coast (NW Spain), following the Prestige oil spill, with the aim of assessing their response to the spill and, therefore, their suitability for monitoring purposes. The aliphatic fractions were mostly dominated by biogenic hydrocarbons, reflecting the diet composition of the organisms and their low metabolic capacity. The presence of oil was assessed by the determination of chemical markers. The analysis of the aromatic fractions revealed the occurrence of 3-6 ring parent and alkylated PAHs, consistent with a mixed petrogenic-pyrolytic origin, with the common feature of the predominance of chrysene in all samples collected after the spill. However, the distributions exhibited both temporal and interspecies variations. The PAH concentrations (Sigma13) increased significantly after the spill and decreased 6-7 months later close to background levels for the region. One year after the accident, the median values were: 58 microg/kg for razor shells, 26 microg/kg for barnacles, and 25 microg/kg for sea urchins. The temporal evolution of the PAH concentrations along the survey period was used to estimate loss rates for bioavailable PAHs in barnacles and sea urchins after the spill. Half-life values were in the order of 30 and 60 d, respectively. The results of the study demonstrate that barnacles can be suitable species for oil spill monitoring.

Identification of estrogenic and antiestrogenic activities of respirable diesel exhaust particles by bioassay-directed fractionation.

PubMed

Oh, Seung Min; Ryu, Byung Taek; Chung, Kyu Hyuck

2008-01-01

Bioassay-directed fractionation was performed to identify causative chemical groups of DEPs with estrogenic and antiestrogenic activities. Bioassay-directed fractionation consists of a cell bioassay (E-SCREEN) in conjunction with acid-base partitioning (F1 and F2) and silica gel column fractionation of neutral fractions (F3-F7). Crude extract (CE) of DEPs in dichloromethane (DCM) exhibited both estrogenic and antiestrogenic activity. Estrogenic activity of CE and some fractions (F1, F2, F3, F5 and F6) was induced through estrogen receptor (ER)-mediated pathways. In particular, the acid polar fraction (F2) of DEPs, which contains phenols, induced high levels of estrogenic activity compared to other fractions. The estrogenic activity of F2 (610.80 pg-bio-EEQ/g-DEPs) was higher than that of the total estrogenic activity of CE (222.22 pg-bio-EEQ/g-DEPs). This result indicates that the estrogenic activity induced by causative estrogenic fraction (F2) may be antagonized by unidentified chemicals in DEPs. On the other hand, non-polar fractions (F3 and F4) of DEPs include aliphatic and chlorinated hydrocarbon, polyaromatic hydrocarbons, and their alkyl derivatives, which play an important role in the antiestrogenic activity of DEPs. In particular, F4, which contains PAH and its derivatives, showed the highest antiestrogenic activity. Since in our previous study, dibenzo(a, h)anthracene and chrysene were identified in F4, and these chemicals have antiestrogenic activity, we assume that these chemicals are the major causative chemicals with antiestrogenic activity in DEPs. In contrast to the estrogenic activity of DEPs, antiestrogenic activity of CE was stronger than that of antiestrogenic fractions (F3 and F4) at non-cytotoxic concentrations, indicating that additive or synergistic effects by unidentified chemicals contained in DEPs occurred.

[Polycyclic aromatic hydrocarbons in ultrafine particles of diesel exhaust fumes--the use of ultrafast liquid chromatography].

PubMed

Małgorzata Szewczyńska; Małgorzata Pośniak

2014-01-01

The article presents the results of the determination of polycyclic aromatic hydrocarbons (PAHs) in the fine par ticles fraction emitted from 3 types of diesel fuels using ultra-high pressure liquid chromatography. Samples of diesel Eco, Verwa and Bio exhaust combustion fumes were generated at the model station which consisted of a diesel engine from the 2007 Diesel TDI 2.0. Personal Cascade Sioutas Impactor (IPCSI) with Teflon filters was used to collect samples of exhaust fume ultrafine particles. PAHs adsorbed on particulate fractions were analyzed by ultra-high pressure liquid chromatography with fluorescence detection (UHPLC/FL). Phenanthrene, fluoranthene, pyrene and chrysene present the highest concentration in the particulate matter emitted by an engine. The total contents of fine particles collected during engine operation on fuels Eco, Verwa and Bio were 134.2 μg/g, 183.8 μg/g and 153.4 μg/g, respectively, which makes 75%, 90% and 83% of the total PAHs, respectively. The highest content of benzo(a)pyrene determined in particles emitted during the combustion of fuels Eco and Bio was 1.5 μg/g and 1 μg/g, respectively. The study of the PAH concentration in the particles of fine fraction below 0.25 μm emitted from different fuels designed for diesel engines indicate that the exhaust gas content of carcinogens, including PAHs deposited on particulates, is still significant, regardless of the fuel. Application of ultrahigh pressure liquid chromatography with fluorescence detection for the analysis ofPAHs in the particles emitted in the fine fraction of diesel exhaust allowed to shorten the analysis time from 35 min to 8 min.

Polycyclic aromatic hydrocarbons in mountain soils of the subtropical Atlantic.

PubMed

Ribes, A; Grimalt, J O; Torres García, C J; Cuevas, E

2003-01-01

Surface soil samples from various altitudes on Tenerife Island, ranging from sea level up to 3400 m above mean sea level, were analyzed to study the distribution of 26 polycyclic aromatic hydrocarbons (PAHs) in a remote subtropical area. The stable atmospheric conditions in this island define three vertically stratified layers: marine boundary, trade-wind inversion, and free troposphere. Total PAH concentrations, 1.9 to 6000 microg/kg dry wt., were high when compared with those in tropical areas and in a similar range to those in temperate areas. In the marine boundary layer, fluoranthene (Fla), pyrene (Pyr), benz [a]anthracene (BaA), and chrysene (C + T) were largely dominant. The predominance of Fla over Pyr may reflect photo-oxidative processes during atmospheric transport, although coal combustion inputs cannot be excluded. The PAHs found in higher concentration in the soils from the inversion layer were benzo[b + j]fluoranthene (BbjF) + benzo[k]fluoranthene (BkF) > benzo[e]pyrene (BeP) approximately indeno[1,2, 3-cd]pyrene (Ind) > benzo[a]pyrene (BaP) approximately benzo[ghi]perylene (Bghi) > coronene (Cor) approximately dibenz[a,h]anthracene (Dib), reflecting that high temperatures and insolation prevent the accumulation of PAHs more volatile than BbjF in significant amounts. These climatic conditions involve a process of standardization that prevents the identification of specific PAH sources such as traffic, forest fires, or industrial inputs. Only soils with high total organic carbon (TOC) (e.g., 10-30%) preserve the more volatile compounds such as phenanthrene (Phe), methylphenanthrenes (MPhe), dimethylphenanthrenes (DMPhe), and retene (Ret). However, no relation between PAHs and soil TOC and black carbon (BC) was found. The specific PAH distributions of the free tropospheric region suggest a direct input from pyrolytic processes related to the volcanic emission of gases in Teide.

Mechanism-based classification of PAH mixtures to predict carcinogenic potential

DOE PAGES

Tilton, Susan C.; Siddens, Lisbeth K.; Krueger, Sharon K.; ...

2015-04-22

We have previously shown that relative potency factors and DNA adduct measurements are inadequate for predicting carcinogenicity of certain polycyclic aromatic hydrocarbons (PAHs) and PAH mixtures, particularly those that function through alternate pathways or exhibit greater promotional activity compared to benzo[ a]pyrene (BaP). Therefore, we developed a pathway based approach for classification of tumor outcome after dermal exposure to PAH/mixtures. FVB/N mice were exposed to dibenzo[ def,p]chrysene (DBC), BaP or environmental PAH mixtures (Mix 1-3) following a two-stage initiation/promotion skin tumor protocol. Resulting tumor incidence could be categorized by carcinogenic potency as DBC>>BaP=Mix2=Mix3>Mix1=Control, based on statistical significance. Gene expression profilesmore » measured in skin of mice collected 12 h post-initiation were compared to tumor outcome for identification of short-term bioactivity profiles. A Bayesian integration model was utilized to identify biological pathways predictive of PAH carcinogenic potential during initiation. Integration of probability matrices from four enriched pathways (p<0.05) for DNA damage, apoptosis, response to chemical stimulus and interferon gamma signaling resulted in the highest classification accuracy with leave-one-out cross validation. This pathway-driven approach was successfully utilized to distinguish early regulatory events during initiation prognostic for tumor outcome and provides proof-of-concept for using short-term initiation studies to classify carcinogenic potential of environmental PAH mixtures. As a result, these data further provide a ‘source-to outcome’ model that could be used to predict PAH interactions during tumorigenesis and provide an example of how mode-of-action based risk assessment could be employed for environmental PAH mixtures.« less

/sup 32/P-postlabeling analysis of DNA adducts in liver of wild English sole (Parophrys vetulus) and winter flounder (Pseudopleuronectes americanus)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Varanasi, U.; Reichert, W.L.; Stein, J.E.

The 1-butanol adduct enhancement version of the 32P-postlabeling assay was used to measure the levels of hepatic DNA adducts in the marine flatfish, English sole (Parophrys vetulus), sampled from the Duwamish Waterway and Eagle Harbor, Puget Sound, WA, where they are exposed to high concentrations of sediment-associated chemical contaminants and exhibit an elevated prevalence of hepatic neoplasms. Hepatic DNA was also analyzed from English sole from a reference area (Useless Bay, WA) and from reference English sole treated with organic-solvent extracts of sediments from the two contaminated sites. Autoradiograms of thin-layer chromatograms of 32P-labeled hepatic DNA digests from English solemore » from the contaminated sites exhibited up to three diagonal radioactive zones, which were not present in autoradiograms of thin-layer chromatogram maps of 32P-labeled DNA digests from English sole from the reference site. These diagonal radioactive zones contained several distinct spots as well as what appeared to be multiple overlapping adduct spots. The levels (nmol of adducts/mol of nucleotides) of total DNA adducts for English sole from Duwamish Waterway and Eagle Harbor were 26 +/- 28 (DS) and 17 +/- 9.6, respectively. All autoradiograms of DNA from fish from the contaminated sites exhibited a diagonal radioactive zone where DNA adducts of chrysene, benzo(a)pyrene, and dibenz(a,h)anthracene, formed in vitro using English sole hepatic microsomes, were shown to chromatograph. English sole treated with extracts of the contaminated sediments had adduct profiles generally similar to those for English sole from the respective contaminated sites.« less

Polycyclic Aromatic Hydrocarbons In Edible Mushrooms from Niger Delta, Nigeria: Carcinogenic and Non-Carcinogenic Health Risk Assessment

PubMed

Igbiri, Sorbari; Udowelle, Nnaemeka Arinze; Ekhator, Osazuwa Clinton; Asomugha, Rose Ngozi; Igweze, Zelinjo Nkeiruka; Orisakwe, Orish Ebere

2017-02-01

In the oil-rich Niger Delta, hydrocarbon pollution and oil spillages, gas flaring and sundry anthropogenic activities constitute sources of polycyclic aromatic hydrocarbons (PAHs), with food contamination playing a major role in human exposure. In this study we assessed PAH levels in wild and cultivated edible mushroom species consumed by the general population from the oil producing Niger Delta, Nigeria. The concentrations of USEPA-16 PAHs were determined by gas chromatography and carcinogenic and non-carcinogenic health risks were calculated. The concentrations of USEPA-16 PAHs ranged from 0.02 mg/kg – 3.37 mg/kg. The dietary intake of carcinogenic and non-carcinogenic USEPA-16 PAHs (Naphthalene, Acenaphthylene, Acenaphthene, Anthracene, Phenanthrene, Flourene, Flouranthene, Pyrene, Benzo[a]Anthracene, Chrysene, Benzo[a]Pyrene, Benzo[b]Flouranthene, Benzo[K]Flouranthene, Benzo[g,h,i] Perylene, Dibenz[a,h]Anthracene and Ideno[1,2,3-cd]Pyrene) for adults, adolescents and seniors ranged from 0.00 – 0.05 mg/kg/day, 0.00 – 0.06 mg/kg/day and 0.00 – 0.07 mg/kg/day. The BaPeq ranged from 0.02 – 2.76 with margin of exposure MOE values of BaP ranging from 3,500,000 to 700,000, 3,500,000 and 3,500,000 to 7,000,000 for adults, adolescents and seniors indicating very insignificant health risk. The incremental lifetime cancer risk was within the safe range of 1.56x10-8 – 1.73x10-6 with the highest calculated risk found for wild Pleurotus ostreatus mushroom species from the study area. Creative Commons Attribution License

Nonradiological chemical pathway analysis and identification of chemicals of concern for environmental monitoring at the Hanford Site

DOE Office of Scientific and Technical Information (OSTI.GOV)

Blanton, M.L.; Cooper, A.T.; Castleton, K.J.

1995-11-01

Pacific Northwest`s Surface Environmental Surveillance Project (SESP) is an ongoing effort tot design, review, and conducted monitoring on and off the Hanford site. Chemicals of concern that were selected are listed. Using modeled exposure pathways, the offsite cancer incidence and hazard quotient were calculated and a retrospective pathway analysis performed to estimate what onsite concentrations would be required in the soil for each chemical of concern and other detected chemicals that would be required to obtain an estimated offsite human-health risk of 1.0E-06 cancer incidence or 1.0 hazard quotient. This analysis indicates that current nonradiological chemical contamination occurring on themore » site does not pose a significant offsite human-health risk; the highest cancer incidence to the offsite maximally exposed individual was from arsenic (1.76E-10); the highest hazard quotient was chromium(VI) (1.48E-04). The most sensitive pathways of exposure were surfacewater and aquatic food consumption. Combined total offsite excess cancer incidence was 2.09E-10 and estimated hazard quotient was 2.40E-04. Of the 17 identified chemicals of concern, the SESP does not currently (routinely) monitor arsenic, benzo(a)pyrene, bis(2- ethylhexyl)phthalate (BEHP), and chrysene. Only 3 of the chemicals of concern (arsenic, BEHP, chloroform) could actually occur in onsite soil at concern high enough to cause a 1.0E-06 excess cancer incidence or a 1.0 hazard index for a given offsite exposure pathway. During the retrospective analysis, 20 other chemicals were also evaluated; only vinyl chloride and thallium could reach targeted offsite risk values.« less

Biodegradation in seawater of PAH and alkylphenols from produced water of a North Sea platform.

PubMed

Lofthus, Synnøve; Almås, Inger K; Evans, Peter; Pelz, Oliver; Brakstad, Odd Gunnar

2018-09-01

Operational planned discharges of produced water (PW) to the marine environment from offshore oil production installations, contain low concentrations of dispersed oil compounds, like polycyclic aromatic hydrocarbons (PAHs) and alkylated phenols (APs). Biotransformation in natural seawater (SW) of naphthalenes/PAHs and phenol/APs in field-collected PW from a North Sea platform was investigated in this biodegradation study. The PW was diluted in SW from a Norwegian fjord, and the biodegradation study was performed in slowly rotating carousels at 13 °C over a period of 62 days. Naphthalenes/PAHs and phenol/APs biotransformation was determined by first-order rate kinetics, after normalization against the recalcitrant biomarker 17α(H),21β(H)-Hopane. The results from this study showed total biotransformation half-lives ranging from 10 to 19 days for groups of naphthalenes and PAHs, while half-lives for APs (C0- to C9-alkylated) were 10-14 days. Biotransformation half-lives of single compounds ranged from 8 to >100 days for naphthalenes and PAHs (median 16 days), and from 5 to 70 days (median 15 days) for phenols and APs. Four of the tested PAHs (chrysene, benzo(b)fluoranthene, benzo(e)pyrene, benzo(g,h,i)perylene) and one AP (4-tert-butylphenol) showed biotransformation half-lives >50 days. This is one of a few studies that has investigated the potential for biodegradation of PW in natural SW. Methods and data from this study may be used as a part of Risk Based Approaches (RBA) for assessments of environmental fate of PW released to the marine environment and as part of the persistence related to risk. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.

Mechanism-Based Classification of PAH Mixtures to Predict Carcinogenic Potential.

PubMed

Tilton, Susan C; Siddens, Lisbeth K; Krueger, Sharon K; Larkin, Andrew J; Löhr, Christiane V; Williams, David E; Baird, William M; Waters, Katrina M

2015-07-01

We have previously shown that relative potency factors and DNA adduct measurements are inadequate for predicting carcinogenicity of certain polycyclic aromatic hydrocarbons (PAHs) and PAH mixtures, particularly those that function through alternate pathways or exhibit greater promotional activity compared to benzo[a]pyrene (BaP). Therefore, we developed a pathway-based approach for classification of tumor outcome after dermal exposure to PAH/mixtures. FVB/N mice were exposed to dibenzo[def,p]chrysene (DBC), BaP, or environmental PAH mixtures (Mix 1-3) following a 2-stage initiation/promotion skin tumor protocol. Resulting tumor incidence could be categorized by carcinogenic potency as DBC > BaP = Mix2 = Mix3 > Mix1 = Control, based on statistical significance. Gene expression profiles measured in skin of mice collected 12 h post-initiation were compared with tumor outcome for identification of short-term bioactivity profiles. A Bayesian integration model was utilized to identify biological pathways predictive of PAH carcinogenic potential during initiation. Integration of probability matrices from four enriched pathways (P < .05) for DNA damage, apoptosis, response to chemical stimulus, and interferon gamma signaling resulted in the highest classification accuracy with leave-one-out cross validation. This pathway-driven approach was successfully utilized to distinguish early regulatory events during initiation prognostic for tumor outcome and provides proof-of-concept for using short-term initiation studies to classify carcinogenic potential of environmental PAH mixtures. These data further provide a 'source-to-outcome' model that could be used to predict PAH interactions during tumorigenesis and provide an example of how mode-of-action-based risk assessment could be employed for environmental PAH mixtures. © The Author 2015. Published by Oxford University Press on behalf of the Society of Toxicology. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Toxicity of effluents from gasoline stations oil-water separators to early life stages of zebrafish Danio rerio.

PubMed

Alves, Romulo Nepomuceno; Mariz, Célio Freire; Paulo, Driele Ventura de; Carvalho, Paulo S M

2017-07-01

Used petroleum hydrocarbons and gasoline stations runoff are significant sources of polycyclic aromatic hydrocarbons (PAHs) to aquatic ecosystems. Samples of the final effluent of oil-water-separators were collected at gasoline stations in the metropolitan region of Recife, Brazil, before release to sewage or rainwater systems. Effluent soluble fractions (ESF) were prepared and bioassays were performed according to the Fish Embryo Toxicity Test. The test involved exposing zebrafish Danio rerio embryos to dilutions of the ESFs for 96 h, with daily examination of lethality and sublethal morphological effects integrated through the General Morphology Score (GMS), based on the achievement of developmental hallmarks. Frequencies of abnormalities were recorded after exposures. ESF LC50-96h (lethal concentration to 50% of exposed embryos) in the most toxic effluent achieved 8.9% (v/v), equivalent to 11 μg phenanthrene equivalents L -1 . GMS scores indicated significantly delayed embryo-larval development at ESF dilutions of 10% and 20% from effluents of all gas stations. Major abnormalities detected after the 96 h exposure included the presence of a yolk sac not fully absorbed coupled with the lack of an inflated swim bladder, lack of both pectoral fins, and the failure to develop a protruding mouth. Effective equivalent PAH concentrations that induce a 50% frequency of larvae without an inflated swim bladder (EC50) were 4.9 μg phenanthrene L -1 , 21.8 μg naphthalene L -1 , and 34.1 μg chrysene L -1 . This study shows that PAHs in ESFs from gas stations oil water separators are toxic to zebrafish, contributing to the toxicity of urban storm waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Time trends of polycyclic aromatic hydrocarbon exposure in New York City from 2001 to 2012: assessed by repeat air and urine samples.

PubMed

Jung, Kyung Hwa; Liu, Bian; Lovinsky-Desir, Stephanie; Yan, Beizhan; Camann, David; Sjodin, Andreas; Li, Zheng; Perera, Frederica; Kinney, Patrick; Chillrud, Steven; Miller, Rachel L

2014-05-01

Exposure to air pollutants including polycyclic aromatic hydrocarbons (PAH), and specifically pyrene from combustion of fuel oil, coal, traffic and indoor sources, has been associated with adverse respiratory health outcomes. However, time trends of airborne PAH and metabolite levels detected via repeat measures over time have not yet been characterized. We hypothesized that PAH levels, measured repeatedly from residential indoor and outdoor monitors, and children׳s urinary concentrations of PAH metabolites, would decrease following policy interventions to reduce traffic-related air pollution. Indoor PAH (particle- and gas-phase) were collected for two weeks prenatally (n=98), at age 5/6 years (n=397) and age 9/10 years (n=198) since 2001 and at all three age-points (n=27). Other traffic-related air pollutants (black carbon and PM2.5) were monitored indoors simultaneous with PAH monitoring at ages 5/6 (n=403) and 9/10 (n=257) between 2005 and 2012. One third of the homes were selected across seasons for outdoor PAH, BC and PM2.5 sampling. Using the same sampling method, ambient PAH, BC and PM2.5 also were monitored every two weeks at a central site between 2007 and 2012. PAH were analyzed as semivolatile PAH (e.g., pyrene; MW 178-206) (∑8PAH(semivolatile): Including pyrene (PYR), phenanthrene (PHEN), 1-methylphenanthrene (1-MEPH), 2-methylphenanthrene (2-MEPH), 3-methylphenanthrene (3-MEPH), 9-methylphenanthrene (9-MEPH), 1,7-dimethylphenanthrene (1,7-DMEPH), and 3,6-dimethylphenanthrene (3,6-DMEPH)) and the sum of eight nonvolatile PAH (∑8PAH(nonvolatile): Including benzo[a]anthracene (BaA), chrysene/iso-chrysene (Chry), benzo[b]fluoranthene (BbFA), benzo[k]fluoranthene (BkFA), benzo[a]pyrene (BaP), indeno[1,2,3-c,d]pyrene (IP), dibenzo[a,h]anthracene (DahA), and benzo[g,h,i]perylene (BghiP); MW 228-278). A spot urine sample was collected from children at child ages 3, 5, 7 and 9 between 2001 and 2012 and analyzed for 10 PAH metabolites. Modest declines were detected in indoor BC and PM2.5 levels between 2005 and 2012 (Annual percent change [APC]=-2.08% [p=0.010] and -2.18% [p=0.059] for BC and PM2.5, respectively), while a trend of increasing pyrene levels was observed in indoor and outdoor samples, and at the central site during the comparable time periods (APC=4.81%, 3.77% and 7.90%, respectively; p<0.05 for all). No significant time trend was observed in indoor ∑8PAH(nonvolatile) levels between 2005 and 2012; however, significant opposite trends were detected when analyzed seasonally (APC=-8.06% [p<0.01], 3.87% [p<0.05] for nonheating and heating season, respectively). Similarly, heating season also affected the annual trends (2005-2012) of other air pollutants: the decreasing BC trend (in indoor/outdoor air) was observed only in the nonheating season, consistent with dominating traffic sources that decreased with time; the increasing pyrene trend was more apparent in the heating season. Outdoor PM2.5 levels persistently decreased over time across the seasons. With the analyses of data collected over a longer period of time (2001-2012), a decreasing trend was observed in pyrene (APC=-2.76%; p<0.01), mostly driven by measures from the nonheating season (APC=-3.54%; p<0.01). In contrast, levels of pyrene and naphthalene metabolites, 1-hydroxypyrene and 2-naphthol, increased from 2001 to 2012 (APC=6.29% and 7.90% for 1-hydroxypyrene and 2-naphthol, respectively; p<0.01 for both). Multiple NYC legislative regulations targeting traffic-related air pollution may have led to decreases in ∑8PAH(nonvolatile) and BC, especially in the nonheating season. Despite the overall decrease in pyrene over the 2001-2012 periods, a rise in pyrene levels in recent years (2005-2012), that was particularly evident for measures collected during the heating season, and 2-naphthol, indicates the contribution of heating oil combustion and other indoor sources to airborne pyrene and urinary 2-naphthol. Copyright © 2014 Elsevier Inc. All rights reserved.

Multivariate analysis of mixed contaminants (PAHs and heavy metals) at manufactured gas plant site soils.

PubMed

Thavamani, Palanisami; Megharaj, Mallavarapu; Naidu, Ravi

2012-06-01

Principal component analysis (PCA) was used to provide an overview of the distribution pattern of polycyclic aromatic hydrocarbons (PAHs) and heavy metals in former manufactured gas plant (MGP) site soils. PCA is the powerful multivariate method to identify the patterns in data and expressing their similarities and differences. Ten PAHs (naphthalene, acenapthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]pyrene) and four toxic heavy metals - lead (Pb), cadmium (Cd), chromium (Cr) and zinc (Zn) - were detected in the site soils. PAH contamination was contributed equally by both low and high molecular weight PAHs. PCA was performed using the varimax rotation method in SPSS, 17.0. Two principal components accounting for 91.7% of the total variance was retained using scree test. Principle component 1 (PC1) substantially explained the dominance of PAH contamination in the MGP site soils. All PAHs, except anthracene, were positively correlated in PC1. There was a common thread in high molecular weight PAHs loadings, where the loadings were inversely proportional to the hydrophobicity and molecular weight of individual PAHs. Anthracene, which was less correlated with other individual PAHs, deviated well from the origin which can be ascribed to its lower toxicity and different origin than its isomer phenanthrene. Among the four major heavy metals studied in MGP sites, Pb, Cd and Cr were negatively correlated in PC1 but showed strong positive correlation in principle component 2 (PC2). Although metals may not have originated directly from gaswork processes, the correlation between PAHs and metals suggests that the materials used in these sites may have contributed to high concentrations of Pb, Cd, Cr and Zn. Thus, multivariate analysis helped to identify the sources of PAHs, heavy metals and their association in MGP site, and thereby better characterise the site risk, which would not be possible if one uses chemical analysis alone.

Water quality, organic chemistry of sediment, and biological conditions of streams near an abandoned wood-preserving plant site at Jackson, Tennessee

USGS Publications Warehouse

Bradfield, A.D.; Flexner, N.M.; Webster, D.A.

1993-01-01

An investigation of water quality, organic sediment chemistry, and biological conditions of streams near an abandoned wood-preserving plant site at Jackson, Tennessee, was conducted during December 1990. The study was designed to assess the extent of possible contamination of water and biota in the streams from creosote-related discharge originating at this Superfund site. Central Creek, adjacent to the plant, had degraded water quality and biological conditions. Water samples from the most downstream station on Central Creek contained 30 micrograms per liter of pentachlorophenol, which exceeds the State's criterion maximum concentrations of 9 micrograms per liter for fish and aquatic life. Bottom-sediment samples from stations on Central Creek contained concentrations of acenaphthene, napthalene, and phenanthrene ranging from 1,400 to 2,500 micrograms per kilogram. Chronic or acute toxicity resulted during laboratory experiments using test organisms exposed to creosote-related contaminants. Sediment elutriate samples from Central Creek caused slightly to highly toxic effects on Ceriodaphnia dubia. Pimephales promelas, and Photobacterium phosphoreum. Fish-tissue samples from this station contained concentrations of naphthalene. dibenzofuran, fluorene, and phenanthrene ranging from 1.5 to 3.9 micrograms per kilogram Blue-green algae at this station represented about 79 percent of the organisms counted, whereas diatoms accounted for only 11 percent. Benthic invertebrate and fish samples from Central Creek had low diversity and density. Sediment samples from a station on the South Fork Forked Deer River downstream from its confluence with Central Creek contained concentrations of acenaphthene, anthracene, chrysene, fluoranthene, fluorene, pyrere, and phenanthrene ranging from 2,800 to 69,000 micrograms per kilogram. Sediment elutriate samples using water as elutriate from this station contained concentrations of extractable organic compounds ranging from an estimated 43 to 420 micrograms per liter. Sediment elutriate samples were toxic to Ceriodaphnia dubta, Pimephales promelas, Photobacterium phosphoreum, and Salenastrum capricornulum.

SOURCE APPORTIONMENT OF POLYCYCLIC AROMATIC HYDROCARBONS (PAHs) INTO CENTRAL PARK LAKE, NEW YORK CITY, OVER A CENTURY OF DEPOSITION

PubMed Central

Yan, Beizhan; Bopp, Richard F.; Abrajano, Teofilo A.; Chaky, Damon; Chillrud, Steven N.

2014-01-01

Relative contributions of polycyclic aromatic hydrocarbons (PAHs) from combustion sources of wood, petroleum, and coal were computed in sediments from Central Park Lake in New York City (NY, USA) by chemical mass balance based on several reliable source indicators. These indicators are the ratio of retene to the sum of retene and chrysene, the ratio of 1,7-dimethylphenanthrene (DMP) to 1,7-DMP and 2,6-DMP, and the ratio of fluroanthene to fluroanthene and pyrene. The authors found that petroleum combustion–derived PAH fluxes generally followed the historical consumption data of New York State. Coal combustion-derived PAH flux peaked approximately in the late 1910s, remained at a relatively high level over the next 3 decades, then rapidly declined from the 1950s to the 1960s; according to historical New York State coal consumption data, however, there was a 2-peak trend, with peaks around the early 1920s and the mid-1940s. The 1940s peak was not observed in Central Park Lake, most likely because of the well-documented shift from coal to oil as the major residential heating fuel in New York City during the late 1930s. It was widely believed that the decreased PAH concentrations and fluxes in global sediments during the last century resulted from a major energy shift from coal to petroleum. The data, however, show that this shift occurred from 1945 through the 1960s and did not result in an obvious decline. The sharpest decrease, which occurred in the 1970s was not predominantly related to coal usage but rather was the result of multiple factors, including a decline in petroleum usage largely, the introduction of low sulfur–content fuel in New York City, and the introduction of emission-control technologies. PMID:24375577

Source apportionment of polycyclic aromatic hydrocarbons (PAHs) into Central Park Lake, New York City, over a century of deposition.

PubMed

Yan, Beizhan; Bopp, Richard F; Abrajano, Teofilo A; Chaky, Damon; Chillrud, Steven N

2014-05-01

Relative contributions of polycyclic aromatic hydrocarbons (PAHs) from combustion sources of wood, petroleum, and coal were computed in sediments from Central Park Lake in New York City (NY, USA) by chemical mass balance based on several reliable source indicators. These indicators are the ratio of retene to the sum of retene and chrysene, the ratio of 1,7-dimethylphenanthrene (DMP) to 1,7-DMP and 2,6-DMP, and the ratio of fluroanthene to fluroanthene and pyrene. The authors found that petroleum combustion-derived PAH fluxes generally followed the historical consumption data of New York State. Coal combustion-derived PAH flux peaked approximately in the late 1910s, remained at a relatively high level over the next 3 decades, then rapidly declined from the 1950s to the 1960s; according to historical New York State coal consumption data, however, there was a 2-peak trend, with peaks around the early 1920s and the mid-1940s. The 1940s peak was not observed in Central Park Lake, most likely because of the well-documented shift from coal to oil as the major residential heating fuel in New York City during the late 1930s. It was widely believed that the decreased PAH concentrations and fluxes in global sediments during the last century resulted from a major energy shift from coal to petroleum. The data, however, show that this shift occurred from 1945 through the 1960s and did not result in an obvious decline. The sharpest decrease, which occurred in the 1970s was not predominantly related to coal usage but rather was the result of multiple factors, including a decline in petroleum usage largely, the introduction of low sulfur-content fuel in New York City, and the introduction of emission-control technologies. © 2013 SETAC.

Bioremediation of a tropical clay soil contaminated with diesel oil.

PubMed

Chagas-Spinelli, Alessandra C O; Kato, Mario T; de Lima, Edmilson S; Gavazza, Savia

2012-12-30

The removal of polyaromatic hydrocarbons (PAH) in tropical clay soil contaminated with diesel oil was evaluated. Three bioremediation treatments were used: landfarming (LF), biostimulation (BS) and biostimulation with bioaugmentation (BSBA). The treatment removal efficiency for the total PAHs differed from the efficiencies for the removal of individual PAH compounds. In the case of total PAHs, the removal values obtained at the end of the 129-day experimental period were 87%, 89% and 87% for LF, BS and BSBA, respectively. Thus, the efficiency was not improved by the addition of nutrients and microorganisms. Typically, two distinct phases were observed. A higher removal rate occurred in the first 17 days (P-I) and a lower rate occurred in the last 112 days (P-II). In phase P-I, the zero-order kinetic parameter (μg PAH g(-1) soil d(-1)) values were similar (about 4.6) for all the three treatments. In P-II, values were also similar but much lower (about 0.14). P-I was characterized by a sharp pH decrease to less than 5.0 for the BS and BSBA treatments, while the pH remained near 6.5 for LF. Concerning the 16 individual priority PAH compounds, the results varied depending on the bioremediation treatment used and on the PAH species of interest. In general, compounds with fewer aromatic rings were better removed by BS or BSBA, while those with 4 or more rings were most effectively removed by LF. The biphasic removal behavior was observed only for some compounds. In the case of naphthalene, pyrene, chrysene, benzo[k]fluoranthene and benzo[a]pyrene, removal occurred mostly in the P-I phase. Therefore, the best degradation process for total or individual PAHs should be selected considering the target compounds and the local conditions, such as native microbiota and soil type. Copyright © 2012 Elsevier Ltd. All rights reserved.

Phthalates and polycyclic aromatic hydrocarbons (PAHs) in the indoor settled carpet dust of mosques, health risk assessment for public.

PubMed

Kadi, Mohammad W; Ali, Nadeem; Albar, Hussain Mohammed Salem Ali

2018-06-15

A number of studies have reported the occurrence of phthalates and polycyclic aromatic hydrocarbons (PAHs) in indoor settled dust from different occupational and residential settings around the world but limited studies are available from public and religious places. In recent decades Kingdom of Saudi Arabia (KSA) has experienced tremendous industrial growth especially in the petroleum industries, and as result environmental issues related with such industries have also increased but scientific data is still scarce to understand the impact on public health. Therefore, the main objective of this study was to report the phthalates and PAHs profile in the settled dust collected from various mosques of Jeddah, an important part of people living in the region, and to evaluate the health risk associated with these chemicals via dust ingestion, inhalation and dermal contact for the general public who attend mosques for prayers. Phenanthrene (500-3000 ng/g), pyrene (40-1220 ng/g), and chrysene (95-4590 ng/g) were the major PAHs and ∑ 12 PAHs concentrations ranged from 2550 to 9150 ng/g. Whereas, DEHP (

Emission factors of particulate matter, polycyclic aromatic hydrocarbons, and levoglucosan from wood combustion in south-central Chile.

PubMed

Jimenez, Jorge; Farias, Oscar; Quiroz, Roberto; Yañez, Jorge

2017-07-01

In south-central Chile, wood stoves have been identified as an important source of air pollution in populated areas. Eucalyptus (Eucalyptus globulus), Chilean oak (Nothofagus oblique), and mimosa (Acacia dealbata) were burned in a single-chamber slow-combustion wood stove at a controlled testing facility located at the University of Concepción, Chile. In each experiment, 2.7-3.1 kg of firewood were combusted while continuously monitoring temperature, exhaust gases, burn rate, and collecting particulate matter samples in Teflon filters under isokinetic conditions for polycyclic aromatic hydrocarbon and levoglucosan analyses. Mean particulate matter emission factors were 2.03, 4.06, and 3.84 g/kg dry wood for eucalyptus, oak, and mimosa, respectively. The emission factors were inversely correlated with combustion efficiency. The mean emission factors of the sums of 12 polycyclic aromatic hydrocarbons in particle phases were 1472.5, 2134.0, and 747.5 μg/kg for eucalyptus, oak, and mimosa, respectively. Fluoranthene, pyrene, benzo[a]anthracene, and chrysene were present in the particle phase in higher proportions compared with other polycyclic aromatic hydrocarbons that were analyzed. Mean levoglucosan emission factors were 854.9, 202.3, and 328.0 mg/kg for eucalyptus, oak, and mimosa, respectively. Since the emissions of particulate matter and other pollutants were inversely correlated with combustion efficiency, implementing more efficient technologies would help to reduce air pollutant emissions from wood combustion. Residential wood burning has been identified as a significant source of air pollution in populated areas. Local wood species are combusted for home cooking and heating, which releases several toxic air pollutants, including particulate matter, carbon monoxide, and polycyclic aromatic hydrocarbons. Air pollutant emissions depend on the type of wood and the technology and operational conditions of the wood stove. A better understanding of emissions from local wood species and wood stove performance would help to identify better biomass fuels and wood stove technologies in order to reduce air pollution from residential wood burning.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE PAGES

Geier, Mitra C.; James Minick, D.; Truong, Lisa; ...

2018-04-01

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.« less

Degradation of polycyclic aromatic hydrocarbons (PAHs) present in used motor oil and implications for urban runoff quality

NASA Astrophysics Data System (ADS)

Ferreira, M.; Stenstrom, M. K.; Lau, S.

2013-12-01

Polycyclic aromatic hydrocarbons (PAHs) are common organic pollutants of urban stormwater runoff due to atmospheric deposition, vehicle-related discharges, and coal tar pavement sealants. The US EPA lists sixteen PAHs as priority pollutants and seven of those are potential carcinogenic compounds. Due to their molecular structure, PAHs tend to attach to particles that will subsequently be deposited as sediments in waterways. This study focuses on the degradation of PAHs present in used motor oil. Four experimental setups were used to simulate volatilization and photooxidation in the degradation of sixteen PAHs as observed for up to 54 days. The volatilization-only experiment showed substantial reduction only in the concentration of Napthalene (Nap). However, photooxidation-only was more efficient in degrading PAHs. In this process, substantial reduction in the concentrations of Nap, Acenapthene (Anthe), Anthracene (ANT), Fluoranthene (FLT), Pyrene (PYR), Benz[a]anthracene (BaA), Benzo[a]pyrene (BaP), Indeno[1,2,3,cd]pyrene (INP), and Benz[g,h,i]perylene (BghiP) were observed as early as five days. The two volatilization-photooxidation experiments exhibited substantial reduction in the concentrations of Fluorene (FLU), Chrysene (CHR) and Benzo[b]fluoranthene (BbF), in addition to the PAHs reduced by photooxidation-only. Phenanthrene (PHE), Fluoranthene (FLT), and Benzo[b]fluoranthene (BbF) only exhibited substantial decreased concentrations after 20 days in the volatilization-photooxidation experiment. One PAH, acenapthylene (Anthy), was not detected in the original sample of used motor oil. The highest degradations were observed in the combined volatilization-photooxidation experiment. In regions with infrequent rainfall, such as Southern California, molecules of PAHs attached to highway particles will have time to undergo degradation prior to transport. Therefore, PAHs may be present in lower concentrations in highway runoff in dry climates than in rainy climates. To support this hypothesis, a review of highway-related PAHs concentrations is presented.

Pyrene and benzo[a]pyrene metabolism by the filamentous fungus, Penicillium janthinellum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Launen, L.; Pinto, L.; Kiehlmann, E.

1995-12-31

The incomplete combustion of fossil fuels generates polycyclic aromatic hydrocarbons (PAH). These include 4-5 ring PAH, of which many are potent carcinogens and mutagens that persist in soil for years. Fungi can oxidize these compounds via two mechanisms: (1) by extracellular peroxidases (Basidiomycete fungi), or (2) by a putative cytochrome P450 enzyme system. The authors have previously isolated Penicillium janthinellum from petroleum-contaminated soil and shown that it possesses high activity to oxidize pyrene, benzo(a)pyrene and chrysene in liquid culture. The purpose of this study was to evaluate the effect of changing growth condition glucose, nitrate and agitation levels, on pyrenemore » metabolism by P. janthinellum using a 3 x 2 x 2 factorial design. Spores were inoculated into minimal salts media amended with varying carbon or nitrogen concentrations and containing {sup 14}C-pyrene. The level of glucose and nitrate significantly affected the bioconversion: low glucose and nitrate levels increased the loss of parent PAH from the medium. However this effect was independent of biomass. Biometer flask experiments using {sup 14}C-pyrene showed that most pyrene became cell-associated within 7 days of incubation. Cell associated {sup 14}C-pyrene was inextractable by ethyl acetate but was recovered in methylene chloride. This result was confirmed by the mass balance result from a 10 day time course experiment using {sup 14}C-pyrene or {sup 14}C-BaP. Greater than 70% of the radiolabel in cultures containing live cells was strongly associated with the cell matter within 7 days, relative to < 1 % association with dead cells. The authors conclude that: (1) pyrene and BaP oxidation was affected by C and N levels in the growth medium independent of cell mass and (2) {sup 14}C-PAH became strongly associated with live but not dead cells within 7 days in liquid culture.« less

Usefulness of oxidative stress biomarkers evaluated in the snout scraping, serum and Peripheral Blood Cells of Crocodylus moreletii from Southeast Campeche for assessment of the toxic impact of PAHs, metals and total phenols.

PubMed

Dzul-Caamal, Ricardo; Hernández-López, Abigail; Gonzalez-Jáuregui, Mauricio; Padilla, Sergio E; Girón-Pérez, Manuel Ivan; Vega-López, Armando

2016-10-01

In this study, we assessed the effects of inorganic and organic pollutants [As, Cu, Fe, Mn, Pb, Zn, PAHs (11 compounds) and total phenols] from a panel of biomarkers [O2, H2O2, thiobarbituric acid reactive substances (TBARS), carbonyl proteins (RCO), superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx) and total cytochrome P450 activities] evaluated in the Snout Scraping (SS), Serum (S) and Peripheral Blood Cells (PBC) of the Morelet's crocodile (Crocodylus moreletii) inhabiting the reference locality (Lake Mocu) and polluted locality (Champoton River) using Principal Component Analysis (PCA). In male crocodiles from the reference site, only H2O2 in PBC was related to levels of fluoranthene on the Keel of Caudal Scales (KCS), but, in females, no association was detected. In contrast, a sex-linked response was detected in specimens from the polluted locality. Levels of benzo[a]pyrene, benzo[a]anthracene, chrysene, pyrene, phenanthrene, acenaphthene, Zn, Cu, and Pb in KCS of the female crocodil were related to the oxidative stress biomarkers on PBC, incluing the total CYP450 activity and levels of O2, H2O2 in serum. However, in male crocodiles, the oxidative stress in SS and in the serum (TBARS, RCO, CAT, GPx), and SOD in PBC was related to As, Pb, Cu, Fe, and benzo[a]pyrene water concentrations and to the burdens of As, Fe, Mn, indeno[1,2,3cd]pyrene in KCS. These results confirm the usefulness of minimal or non-invasive methods of evaluating the oxidative stress response for the environmental monitoring program on the wild Morelet's crocodile that is subject to special protection in Mexican guidelines. Copyright © 2016 Elsevier Inc. All rights reserved.

Ex(2)Box: interdependent modes of binding in a two-nanometer-long synthetic receptor.

PubMed

Juríček, Michal; Barnes, Jonathan C; Dale, Edward J; Liu, Wei-Guang; Strutt, Nathan L; Bruns, Carson J; Vermeulen, Nicolaas A; Ghooray, Kala C; Sarjeant, Amy A; Stern, Charlotte L; Botros, Youssry Y; Goddard, William A; Stoddart, J Fraser

2013-08-28

Incorporation of two biphenylene-bridged 4,4'-bipyridinium extended viologen units into a para-phenylene-based cyclophane results in a synthetic receptor that is ~2 nm long and adopts a box-like geometry. This cyclophane, Ex(2)Box(4+), possesses the ability to form binary and ternary complexes with a myriad of guest molecules ranging from long π-electron-rich polycyclic aromatic hydrocarbons, such as tetracene, tetraphene, and chrysene, to π-electron-poor 2,6-dinitrotoluene, 1,2,4-trichlorobenzene, and both the 9,10- and 1,4-anthraquinone molecules. Moreover, Ex(2)Box(4+) is capable of forming one-to-one complexes with polyether macrocycles that consist of two π-electron-rich dioxynaphthalene units, namely, 1,5-dinaphtho[38]crown-10. This type of broad molecular recognition is possible because the electronic constitution of Ex(2)Box(4+) is such that the pyridinium rings located at the "ends" of the cyclophane are electron-poor and prefer to enter into donor-acceptor interactions with π-electron-rich guests, while the "middle" of the cyclophane, consisting of the biphenylene spacer, is more electron-rich and can interact with π-electron-poor guests. In some cases, these different modes of binding can act in concert to generate one-to-one complexes which possess high stability constants in organic media. The binding affinity of Ex(2)Box(4+) was investigated in the solid state by way of single-crystal X-ray diffraction and in solution by using UV-vis and NMR spectroscopy for 12 inclusion complexes consisting of the tetracationic cyclophane and the corresponding guests of different sizes, shapes, and electronic compositions. Additionally, density functional theory was carried out to elucidate the relative energetic differences between the different modes of binding of Ex(2)Box(4+) with anthracene, 9,10-anthraquinone, and 1,4-anthraquinone in order to understand the degree with which each mode of binding contributes to the overall encapsulation of each guest.

Acute changes in pulse pressure in relation to constituents of particulate air pollution in elderly persons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jacobs, Lotte; Buczynska, Anna; Walgraeve, Christophe

An increased pulse pressure (difference between systolic and diastolic blood pressure) suggests aortic stiffening. The objective of this study was to examine the acute effects of both particulate matter (PM) mass and composition on blood pressure, among elderly persons. We carried out a panel study in persons living in elderly homes in Antwerp, Belgium. We recruited 88 non-smoking persons, 70% women with a mean age of 83 years (standard deviation: 5.2). Blood pressure was measured and a blood sample was collected on two time points, which were chosen so that there was an exposure contrast in ambient PM exposure. Themore » elemental content of the collected indoor and outdoor PM{sub 2.5} (particulate matter with an aerodynamic diameter <2.5 {mu}m) mass concentration was measured. Oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs) on outdoor PM{sub 10} (particulate matter with an aerodynamic diameter <10 {mu}m) were measured. Each interquartile range increase of 20.8 {mu}g/m Superscript-Three in 24-h mean outdoor PM{sub 2.5} was associated with an increase in pulse pressure of 4.0 mmHg (95% confidence interval: 1.8-6.2), in persons taking antihypertensive medication (n=57), but not in persons not using antihypertensive medication (n=31) (p for interaction: 0.02). Vanadium, iron and nickel contents of PM{sub 2.5} were significantly associated with systolic blood pressure and pulse pressure, among persons on antihypertensive medication. Similar results were found for indoor concentrations. Of the oxy-PAHs, chrysene-5,6-dione and benzo[a]pyrene-3,6-dione were significantly associated with increases in systolic blood pressure and pulse pressure. In elderly, pulse pressure was positively associated with acute increases in outdoor and indoor air pollution, among persons taking antihypertensive medication. These results might form a mechanistic pathway linking air pollution as a trigger of cardiovascular events.« less

Rapid determination of polycyclic aromatic hydrocarbons (PAHs) in tea using two-dimensional gas chromatography coupled with time of flight mass spectrometry.

PubMed

Drabova, Lucie; Pulkrabova, Jana; Kalachova, Kamila; Tomaniova, Monika; Kocourek, Vladimir; Hajslova, Jana

2012-10-15

A simple, fast, and cost effective sample preparation procedure has been developed and validated for the determination of 15+1 European Union Polycyclic Aromatic Hydrocarbons (15+1 EU PAHs) in dried tea leave samples. Based on a critical assessment of several sample extraction/clean-up approaches, the method based on the ethyl acetate extraction followed by the use of PAHs dedicated cartridges with molecularly imprinted polymers (MIPs) has been found as an optimal alternative in terms of time demands and obtained good extract purity. For the final identification/quantification of target PAHs, two dimensional gas chromatography coupled to a time-of-flight mass spectrometry (GC×GC-TOFMS) was used. The performance characteristics of the overall analytical method for individual PAHs determined at three spiking levels (0.5, 2.5 and 5 μg kg(-1)) were in following ranges: limits of quantitation (LOQs) 0.05-0.2 μg kg(-1), repeatabilities 2-9%, and recoveries 73-103%. The recoveries achieved by the newly developed sample preparation procedure when employed for naturally contaminated sample ("incurred" PAHs) were comparable to those obtained by other routinely used approaches employing sonication and/or pressurised liquid extraction for sample analytes isolation. The validated method was subsequently used for the determination of selected genotoxic PAHs in 36 samples of black and green tea obtained from the Czech retail market. The levels of ΣPAH4 (sum of benzo[a]anthracene (BaA), chrysene (CHR), benzo[b]fluoranthene (BbFA) and benzo[a]pyrene (BaP)) in black and green tea leaves ranged from 7.4 to 700 μg kg(-1) and from 4.5 to 102 μg kg(-1), respectively. Contamination of tested tea samples by BaP was in the range of 0.2-152 μg kg(-1). Copyright © 2012 Elsevier B.V. All rights reserved.

Concentration characteristics, source apportionment, and oxidative damage of PM2.5-bound PAHs in petrochemical region in Xinjiang, NW China.

PubMed

Turap, Yusan; Talifu, Dilinuer; Wang, Xinming; Aierken, Tuergong; Rekefu, Suwubinuer; Shen, Hao; Ding, Xiang; Maihemuti, Mailikezhati; Tursun, Yalkunjan; Liu, Wei

2018-05-30

Polycyclic aromatic hydrocarbons (PAHs) are of considerable concern due to their potential as human carcinogens. Thus, determining the characteristics, potential source, and examining the oxidative capacity of PAHs to protect human health is essential. This study investigated the PM 2.5 -bound PAHs at Dushanzi, a large petrochemical region in Xinjiang as well as northwest China. A total of 33 PM 2.5 samples with 13 PAHs, together with molecular tracers (levoglucosan, and element carbon), were analyzed during the non-heating and heating periods. The results showed that the PM 2.5 concentrations were 70.22 ± 22.30 and 95.47 ± 61.73 μg/m 3 , while that of total PAHs were 4.07 ± 2.03 and 60.33 ± 30.80 ng/m 3 in sampling period, respectively. The fluoranthene, pyrene, chrysene, benzo[b]fluoranthene, and benzo[k]fluoranthene were the most abundant (top five) PAHs, accounting for 71.74 and 72.80% of total PAH mass during non-heating and heating periods. The BaP equivalent (BaPeq) concentration exceeded 1 ng/m 3 as recommended by National Ambient Air Quality Standards during heating period. The diagnostic ratios and positive matrix factorization indicated that oil industry, biomass burning, coal combustion, and vehicle emissions are the primary sources. The coal combustion remarkably increased during heating period. The plasmid scission assay (PSA) results showed that higher DNA damage rate was observed during heating period. PAHs in PM 2.5 such as Chr, BaP, and IcdP were found to have significantly positive correlations with the plasmid DNA damage rates. Additionally, the relationship among BaPeq and DNA damage rate suggested that synergistic reaction may modify the toxicity of PAHs.

Appraisement, source apportionment and health risk of polycyclic aromatic hydrocarbons (PAHs) in vehicle-wash wastewater, Pakistan.

PubMed

Qamar, Zahir; Khan, Sardar; Khan, Anwarzeb; Aamir, Muhammad; Nawab, Javed; Waqas, Muhammad

2017-12-15

Vehicle-wash wastewater (VWW) contains elevated concentrations of different petrochemicals including polycyclic aromatic hydrocarbons (PAHs), a carcinogenic group of organic compounds. This study investigates the discharge of PAHs present in the untreated wastewater of vehicle-wash stations (VWS) located in district Peshawar, Pakistan. The data obtained was being novel with the detection of 16 USEPA PAHs (both individuals and total) and compared with earlier studies and international standards. The ∑16PAHs in wastewater from light vehicle-wash stations (LVWS) and heavy vehicle-wash stations (HVWS) ranged from 245-429μg/l and 957-1582μg/l, respectively. A significant difference (p<0.01) was observed in PAHs discharged from LVWS and HVWS. The projected ∑16PAHs discharge from both HVWS (92% of total generated PAHs) and LVWS (8%) was about 5109.9 g per annum. According to PAH diagnostic ratios, PAHs were both petrogenic (chrysene/benz(a)anthracene, low molecular weight/high molecular weight) and pyrogenic (phenanthrene/anthracene, fluoranthene/pyrene, fluoranthene/fluoranthene+pyrene) in origin. The highest toxic equivalent quotient (TEQ) value was shown by benzo(a)pyrene (21.6μg/l) followed by dibenz(ah)anthracene (9.81μg/l) in wastewater from HVWS. However, in LVWS the case was reversed with highest value (7.54μg/l) for dibenz(ah)anthracene followed by benzo(a)pyrene (3.54μg/l). The lowest TEQ value was indicated for phenanthrene (0.007μg/l) in wastewater of LVWS, while pyrene showed the lowest value (0.007μg/l) in wastewater of HVWS. The results indicated that VWS contribute significant amount of PAHs each year, which is of great concern regarding water quality, ecological and human health risk. This is the first systematic and comprehensive research related with generation of PAHs load per day, week, month and annum from VWS, their source apportionment and health effects in Pakistan. Copyright © 2017 Elsevier B.V. All rights reserved.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geier, Mitra C.; James Minick, D.; Truong, Lisa

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. Here, we constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilizationmore » (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.« less

Distributions and potential sources of polycyclic aromatic hydrocarbons in surface sediments from an emerging industrial city (Xinxiang).

PubMed

Feng, Jinglan; Xi, Nannan; Zhang, Fei; Zhao, Jiahui; Hu, Pengtuan; Sun, Jianhui

2016-01-01

To investigate the distributions, degree, and possible sources of polycyclic aromatic hydrocarbons (PAHs) in bed sediments from four rivers of Xinxiang, 18 sediment samples were analyzed. The concentrations ranged from 4.45 × 10(3) to 29.0 × 10(3) ng/g for ∑15PAHs (sum of US Environmental Protection Agency (EPA) priority PAHs apart from naphthalene (Nap)) and 3.37 × 10(3) to 23.5 × 10(3) ng/g for ∑7carPAHs (including benzo[a]anthracene (BaA), chrysene (Chr), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DBA), and indeno[1,2,3-cd]pyrene (InP)) with average concentrations of 10.7 × 10(3) and 7.99 × 10(3) ng/g, respectively. Compared with those from other rivers in China, sediments from four rivers of Xinxiang were severely polluted with PAHs. Pearson correlation analysis showed that ∑15PAHs concentrations had a significant positive correlation with black carbon content. Four- to six-ring PAHs accounted for 83.4 % of total PAHs, which indicated that the main source of PAHs in the studied area could be pyrogenic contamination. Source apportionment using PCA/MLR and UNMIX revealed that coal and biomass combustion contributed 64.4-67.1 %, gasoline vehicle 23.2-27.2 %, and diesel vehicle 5.70-12.4 % of the total PAHs, respectively. The effects range low/effects range median (ERL/ERM) values showed that there was a high level of toxicity risk for BaA. The ecological risk assessment by mean effects range median quotients (mERMQ) revealed a medium ecological risk of ∑15PAHs in sediments from four rivers of Xinxiang, manifesting that a close attention should be paid to pollution of PAHs in the studied area.

Exposure of children to air pollution in the industrial zone of Metropolitan Area of Mexico City

NASA Astrophysics Data System (ADS)

Mugica-Alvarez, Violeta; Quintanilla-Vega, Betsabé; De Vizcaya-Ruiz, Andrea; Alvarado-Cruz, Isabel

2016-04-01

An air quality monitoring in three schools located in the most important industrial zone at the Northeast of the Metropolitan Area of Mexico City (MAMC) was conducted in order to determine the exposure of children to toxics contained in PM10. Particles were analyzed for metals, polycyclic aromatic hydrocarbons (PAH), organic and elemental carbon by ICP-AES, GC-MS and TOT (Sunset lab) respectively. Average concentration of PM10 was 108.4±11.6 μg/m3. Most abundant metals were Fe, Zn and Pb with concentrations ranged by 1.1-5.4 μg/m3, 0.3-2 μg/m3, and 0.18-0.63 μg/m3 respectively; the sum of the seventeen PAHs varied from 1.4 to 3.3 ng/m3 where most abundant PAH were indene[1,2,3-c,d]pyrene, benzo[b]fluoranthene, benzo[a]anthracene, chrysene, and benzo[a]pyrene. The sum of the seven carcinogenic PAH contributed in average with the 48% of the total mixture. Carcinogenic potential of PAH were obtained using toxic equivalent factors determined by Nisbet and La Goy which varied from 0.3 to 0.6 ng/ m3 of benzo[a]pyrene equivalent (BAPeq), this value is lower than the standard proposed for the European Community of 1 ng/ m3, but higher than the standard from the United Kingdom of 0.25 ng/ m3. Principal component analysis for source apportionment showed that vehicular and industrial emissions are the main sources of PM in the zone. In general, the concentrations of particles as well as concentration of metals and PAHs are lower than concentrations measured six year before, showing that the established measures have improved the air quality. Nevertheless these PM10 concentrations exceeded frequently the Mexican Standard and children are especially susceptible due to the higher risk to develop diseases if the exposure occurs at early age.

Modified ion source triple quadrupole mass spectrometer gas chromatograph for polycyclic aromatic hydrocarbon analyses

PubMed Central

Anderson, Kim A.; Szelewski, Michael J.; Wilson, Glenn; Quimby, Bruce D.; Hoffman, Peter D.

2015-01-01

We describe modified gas chromatography electron-impact/triple-quadrupole mass spectrometry (GC–EI/MS/MS) utilizing a newly developed hydrogen-injected self-cleaning ion source and modified 9 mm extractor lens. This instrument, with optimized parameters, achieves quantitative separation of 62 polycyclic aromatic hydrocarbons (PAHs). Existing methods historically limited rigorous identification and quantification to a small subset, such as the 16 PAHs the US EPA has defined as priority pollutants. Without the critical source and extractor lens modifications, the off-the-shelf GC–EI/MS/MS system was unsuitable for complex PAH analysis. Separations were enhanced by increased gas flow, a complex GC temperature profile incorporating multiple isothermal periods, specific ramp rates, and a PAH-optimized column. Typical determinations with our refined GC–EI/MS/MS have a large linear range of 1–10,000 pg μl−1 and detection limits of <2 pg μl−1. Included in the 62 PAHs, multiple-reaction-monitoring (MRM) mode enabled GC-EI/MS/MS identification and quantitation of several constituents of the MW 302 PAHs isomers. Using calibration standards, values determined were within 5% of true values over many months. Standard curve r2 values were typically >0.998, exceptional for compounds which are archetypally difficult. With this method benzo[a]fluorene, benzo[b]fluorene, benzo[c]fluorene were fully separated as was benzo[b]fluoranthene, benzo[k]fluoranthene, and benzo[j]fluoranthene. Chrysene and triphenylene, were sufficiently separated to allow accurate quantitation. Mean limits of detection (LODs) across all PAHs were 1.02 ± 0.84 pg μl−1 with indeno[1,2,3-c,d] pyrene having the lowest LOD at 0.26 pg μl−1 and only two analytes above 2.0 pg μl−1; acenaphthalene (2.33 pg μl−1) and dibenzo[a,e]pyrene (6.44 pg μl−1). PMID:26454790

Interactions between Zooplankton and Crude Oil: Toxic Effects and Bioaccumulation of Polycyclic Aromatic Hydrocarbons

PubMed Central

Almeda, Rodrigo; Wambaugh, Zoe; Wang, Zucheng; Hyatt, Cammie; Liu, Zhanfei; Buskey, Edward J.

2013-01-01

We conducted ship-, shore- and laboratory-based crude oil exposure experiments to investigate (1) the effects of crude oil (Louisiana light sweet oil) on survival and bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) in mesozooplankton communities, (2) the lethal effects of dispersant (Corexit 9500A) and dispersant-treated oil on mesozooplankton, (3) the influence of UVB radiation/sunlight exposure on the toxicity of dispersed crude oil to mesozooplankton, and (4) the role of marine protozoans on the sublethal effects of crude oil and in the bioaccumulation of PAHs in the copepod Acartia tonsa. Mortality of mesozooplankton increased with increasing oil concentration following a sigmoid model with a median lethal concentration of 32.4 µl L−1 in 16 h. At the ratio of dispersant to oil commonly used in the treatment of oil spills (i.e. 1∶20), dispersant (0.25 µl L−1) and dispersant- treated oil were 2.3 and 3.4 times more toxic, respectively, than crude oil alone (5 µl L−1) to mesozooplankton. UVB radiation increased the lethal effects of dispersed crude oil in mesozooplankton communities by 35%. We observed selective bioaccumulation of five PAHs, fluoranthene, phenanthrene, pyrene, chrysene and benzo[b]fluoranthene in both mesozooplankton communities and in the copepod A. tonsa. The presence of the protozoan Oxyrrhis marina reduced sublethal effects of oil on A. tonsa and was related to lower accumulations of PAHs in tissues and fecal pellets, suggesting that protozoa may be important in mitigating the harmful effects of crude oil exposure in copepods and the transfer of PAHs to higher trophic levels. Overall, our results indicate that the negative impact of oil spills on mesozooplankton may be increased by the use of chemical dispersant and UV radiation, but attenuated by crude oil-microbial food webs interactions, and that both mesozooplankton and protozoans may play an important role in fate of PAHs in marine environments. PMID:23840628

3,3′-Diindolylmethane Induces G1 Arrest and Apoptosis in Human Acute T-Cell Lymphoblastic Leukemia Cells

PubMed Central

Shorey, Lyndsey E.; Hagman, Amanda M.; Williams, David E.; Ho, Emily; Dashwood, Roderick H.; Benninghoff, Abby D.

2012-01-01

Certain bioactive food components, including indole-3-carbinol (I3C) and 3,3′-diindolylmethane (DIM) from cruciferous vegetables, have been shown to target cellular pathways regulating carcinogenesis. Previously, our laboratory showed that dietary I3C is an effective transplacental chemopreventive agent in a dibenzo[def,p]chrysene (DBC)-dependent model of murine T-cell lymphoblastic lymphoma. The primary objective of the present study was to extend our chemoprevention studies in mice to an analogous human neoplasm in cell culture. Therefore, we tested the hypothesis that I3C or DIM may be chemotherapeutic in human T-cell acute lymphoblastic leukemia (T-ALL) cells. Treatment of the T-ALL cell lines CCRF-CEM, CCRF-HSB2, SUP-T1 and Jurkat with DIM in vitro significantly reduced cell proliferation and viability at concentrations 8- to 25-fold lower than the parent compound I3C. DIM (7.5 µM) arrested CEM and HSB2 cells at the G1 phase of the cell cycle and 15 µM DIM significantly increased the percentage of apoptotic cells in all T-ALL lines. In CEM cells, DIM reduced protein expression of cyclin dependent kinases 4 and 6 (CDK4, CDK6) and D-type cyclin 3 (CCND3); DIM also significantly altered expression of eight transcripts related to human apoptosis (BCL2L10, CD40LG, HRK, TNF, TNFRSF1A, TNFRSF25, TNFSF8, TRAF4). Similar anticancer effects of DIM were observed in vivo. Dietary exposure to 100 ppm DIM significantly decreased the rate of growth of human CEM xenografts in immunodeficient SCID mice, reduced final tumor size by 44% and increased the apoptotic index compared to control-fed mice. Taken together, our results demonstrate a potential for therapeutic application of DIM in T-ALL. PMID:22514694

Risks to human health and estuarine ecology posed by pulling out creosote-treated timber on oyster farms.

PubMed

Smith, Paul T

2008-01-31

Five oyster farms in Port Stephens, Australia were studied to identify consequences of using creosote-treated posts and the risks posed by removing the posts. Gas chromatography coupled with mass spectrometry (GC/MS) was used to measure polycyclic aromatic hydrocarbons (PAHs) and phenols in sediments, timber, water and oyster tissue. Before posts were removed, the total PAHs in surface sediment on farms was 24.1 mgkg(-1) dry weight. This increased to 45.5 mgkg(-1) dry weight after the posts were pulled out and remained significantly higher 6 months later at 59.7 mgkg(-1) dry weight. A similar increase was found in deeper sediments. The sediment attached to creosote-treated posts had a total concentration of PAHs of 484-2642 mgkg(-1) dry weight, while the corresponding value for the sediment on tar-treated posts was only 30.7 mgkg(-1) dry weight. The surface timber of creosote-treated posts had high levels of PAHs and an average post contained 43 g of PAHs. The total PAHs dispersed to the environment when a creosote-treated post was pulled out was at least 0.67 g. The main species were PAHs with low-molecular weights: fluoranthene, phenanthrene, pyrene, acenaphthylene and chrysene. Benzo(a)pyrene represented 1-10% of PAHs in most samples. Bioassays with creosote-contaminated sediment revealed that Sydney rock oysters (Saccostrea glomerate) and Pacific oysters (Crassostrea gigas) accumulated PAHs at (mgkg(-1) wet tissue weight): 11.3-15.3 and 35.5-47.9, respectively, when exposed for 5 days to water with < 1 microgl(-1) PAHs. Wild oysters growing on creosote-treated posts had high levels of phenols (0.09-6.92 mgkg(-1) wet weight) and PAHs (0.59-1.01 mgkg(-1) wet weight). The dilemma posed by removing creosote-treated posts and dispersing carcinogenic, bioavailable contaminants needs to be managed in light of risks to human health and estuarine ecology.

Study on the fate of petroleum-derived polycyclic aromatic hydrocarbons (PAHs) and the effect of chemical dispersant using an enclosed ecosystem, mesocosm.

PubMed

Yamada, Mihoko; Takada, Hideshige; Toyoda, Keita; Yoshida, Akihiro; Shibata, Akira; Nomura, Hideaki; Wada, Minoru; Nishimura, Masahiko; Okamoto, Ken; Ohwada, Kouichi

2003-01-01

Polycyclic Aromatic Hydrocarbons (PAHs) are one of the components found in oil and are of interest because some are toxic. We studied the environmental fate of PAHs and the effects of chemical dispersants using experimental 500 l mesocosm tanks that mimic natural ecosystems. The tanks were filled with seawater spiked with the water-soluble fraction of heavy residual oil. Water samples and settling particles in the tanks were collected periodically and 38 PAH compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Low molecular weight (LMW) PAHs with less than three benzene rings disappeared rapidly, mostly within 2 days. On the other hand, high molecular weight (HMW) PAHs with more than four benzene rings remained in the water column for a longer time, up to 9 days. Also, significant portions (10-94%) of HMW PAHs settled to the bottom and were caught in the sediment trap. The addition of chemical dispersant accelerated dissolution and biodegradation of PAHs, especially HMW PAHs. The dispersant amplified the amounts of PAHs found in the water column. The amplification was the greater for the more hydrophobic PAHs, with an enrichment factor of up to six times. The increased PAHs resulting from dispersant use overwhelmed the normal degradation and, as a result, higher concentrations of PAHs were observed in water column throughout the experimental period. We conclude that the addition of the dispersant could increase the concentration of water column PAHs and thus increase the exposure and potential toxicity for organisms in the natural environment. By making more hydrocarbon material available to the water column, the application of dispersant reduced the settling of PAHs. For the tank with dispersant, only 6% of chrysene initially introduced was detected in the sediment trap whereas 70% was found in the trap in the tank without dispersant.

Evolution of organic molecules under Mars-like UV radiation with EXPOSE-R2, a photochemistry experiment outside the International Space Station

NASA Astrophysics Data System (ADS)

Rouquette, Laura; Stalport, Fabien; Cottin, Hervé; Coll, Patrice; Szopa, Cyril; Saiagh, Kafila; Poch, Olivier; Khalaf, Diana; Chaput, Didier; Grira, Katia; Chaouche, Naila; Dequaire, Tristan

2016-10-01

The detection and identification of organic molecules on Mars are of prime importance, as some of these molecules are life precursors and components. While in situ planetary missions are searching for them, it is essential to understand how organic molecules evolve and are preserved at the surface of Mars. Indeed the harsh conditions of the environment of Mars such as ultraviolet (UV) radiation or oxidative processes could explain the low abundance and diversity of organic molecules detected by now.The EXPOSE R2 facility has been placed in low Earth orbit (LEO) under solar radiation, outside the International Space Station (ISS) in 2014. One of the EXPOSE R2 experiment, called PSS (Photochemistry on the Space Station), is dedicated to astrobiology- and astrochemistry-related studies. Part of PSS samples have been dedicated to the study of the evolution of organic molecules under Mars-like surface radiation conditions. Indeed, UV radiation above 200 nm reaches the surface of Mars and could degrade organic matter. Organic samples have been exposed directly to the Sun under KBr filters (>200 nm) from November 2014 to February 2016, mimicking the UV radiation conditions of the surface of Mars. Four types of samples were exposed as thin layers of solid molecules: adenine, adenine with nontronite (a kind of clay mineral detected on Mars), chrysene and glycine with nontronite.To characterize the evolution of our samples under irradiation, infrared (IR) transmission analyses were performed, before the launch of EXPOSE R2 to the ISS in 2014, and after the exposure in space and the return on Earth, this year. These analyses allowed determining whether each molecule is preserved or photodegraded, and if so, its photolysis rate. The effect of nontronite on organic molecules preservation has been investigated as well. We also compared these results from LEO with laboratory data, obtained by irradiating organic samples under a UV lamp.

Separation of {sup 32}P-postlabeled DNA adducts of polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons by HPLC

DOE Office of Scientific and Technical Information (OSTI.GOV)

King, L.C.; Gallagher, J.E.; Lewtas, J.

The {sup 32}P-postlabeling assay, thin-layer chromatography, and reverse-phase high-pressure liquid chromatography (HPLC) were used to separate DNA adducts formed from 10 polycyclic aromatic hydrocarbons (PAHs) and 6 nitrated polycyclic aromatic hydrocarbons (NO{sub 2}-PAHs). The PAHs included benzo[j]fluoranthene, benzo[k]fluoranthene, indeno[1,2,3-cd]pyrene, benzo[a]pyrene, chrysene, 6-methylchrysene, 5-methylchrysene, and benz[a]anthracene. The NO{sub 2}-PAHs included 1-nitropyrene, 2-nitrofluoranthene, 3-nitrofluoranthene, 1,6-dinitropyrene, 1,3-dinitropyrene, and 1,8-dinitropyrene. Separation of seven of the major PAH-DNA adducts was achieved by an initial PAH HPLC gradient system. The major NO{sub 2}-PAH-DNA adducts were not all separated from each other using the initial PAH HPLC gradient but were clearly separated from the PAH-DNA adducts. Amore » second NO{sub 2}-PAH HPLC gradient system was developed to separate NO{sub 2}-PAH-DNA adducts following one-dimensional TLC and HPLC analysis. HPLC profiles of NO{sub 2}-PAH-DNA adducts were compared using both adduct enhancement versions of the {sup 32}P-postlabeling assay to evaluate the use of this technique on HPLC to screen for the presence of NO{sub 2}-PAH-DNA adducts. To demonstrate the application of these separation methods to a complex mixture of DNA adducts, the chromatographic mobilities of the {sup 32}P-postlabeled DNA adduct standards (PAHs and NO{sub 2}-PAHs) were compared with those produced by a complex mixture of polycyclic organic matter (POM) extracted from diesel emission particles. The diesel-derived adducts did not elute with the identical retention time of any of the PAH or NO{sub 2}-PAH standards used in this study. HPLC analyses of the NO{sub 2}-PAH-derived adducts (butanol extracted) revealed the presence of multiple DNA adducts.« less

Occurrence, sources and health risk of polycyclic aromatic hydrocarbons in soils around oil wells in the border regions between oil fields and suburbs.

PubMed

Fu, Xiao-Wen; Li, Tian-Yuan; Ji, Lei; Wang, Lei-Lei; Zheng, Li-Wen; Wang, Jia-Ning; Zhang, Qiang

2018-08-15

The Yellow River Delta (YRD) is a typical region where oil fields generally overlap cities and towns, leading to complex soil contamination from both the oil fields and human activities. To clarify the distribution, speciation, potential sources and health risk of polycyclic aromatic hydrocarbons (PAHs) in soils of border regions between oil fields and suburbs of the YRD, 138 soil samples (0-20 cm) were collected among 12 sampling sites located around oil wells with different extraction histories. The 16 priority control PAHs (16PAHs), as selected by the United States Environmental Protection Agency (USEPA), were extracted via an accelerated solvent extraction and detected by GC-MS. The results showed that soils of the study area were generally polluted by the 16PAHs. Among these pollutions, chrysene and phenanthrene were the dominant components, and 4-ring PAHs were the most abundant. A typical temporal distribution pattern of the 16PAHs was revealed in soils from different sampling sites around oil wells with different exploitation histories. The concentrations of total 16PAHs and high-ring PAHs (HPAHs) both increased with the extraction time of the nearby oil wells. Individual PAH ratios and PCA method revealed that the 16PAHs in soil with newly developed oil wells were mainly from petroleum pollutants, whereas PAHs in soils around oil wells with a long exploitation history were probably from petroleum contamination; combustion of petroleum, fuel, and biomass; and degradation and migration of PAHs from petroleum. Monte Carlo simulation was used to evaluate the health risks of the 7 carcinogenic PAHs and 9 non-carcinogenic PAHs in the study area. The results indicated that ingestion and dermal contact were the predominant pathways of exposure to PAH residues in soils. Both the carcinogenic and non-carcinogenic burden of the 16PAHs in soils of the oil field increased significantly with exploitation time of nearby oil wells. Copyright © 2018 Elsevier Inc. All rights reserved.

Cumulative health risk assessment of halogenated and parent polycyclic aromatic hydrocarbons associated with particulate matters in urban air.

PubMed

Sun, Jian-Lin; Jing, Xin; Chang, Wen-Jing; Chen, Zheng-Xia; Zeng, Hui

2015-03-01

Halogenated polycyclic aromatic hydrocarbons (HPAHs) have been reported to occur widely in urban air. Nevertheless, knowledge about the human health risk associated with inhalation exposure to HPAHs is scarce so far. In the present study, nine HPAHs and 16 PAHs were determined in atmospheric particulate matter (PM) collected from Shenzhen, China to address this issue. Concentrations of Σ9HPAHs varied from 0.1 to 1.5 ng/m(3) and from 0.09 to 0.4 ng/m(3) in PM10 and PM2.5 samples, respectively. As for individuals, 9-bromoanthracene, 7-bromobenz(a)anthracene, and 9,10-dibromoanthracene were the dominant congeners. Levels of Σ16PAHs in PM10 and PM2.5 samples ranged from 3.2 to 81 ng/m(3) and from 2.8 to 85 ng/m(3), respectively. Among individual PAHs, chrysene, benzo[b]fluoranthene, and indeno[1,2,3-c,d]pyrene were the main congeners. According to the season, concentrations of HPAHs and PAHs in atmospheric PM10/PM2.5 samples show a similar decreasing trend with an order: winter>autumn>spring>summer. The daily intake (DI) of PM10/PM2.5-bound HPAHs and PAHs were estimated. Our results indicated that children have the highest DI levels via inhalation exposure. The incremental lifetime cancer risk (ILCR) induced by PM10/PM2.5-bound HPAHs and PAHs were calculated. The ILCR values showed a similar decreasing trend with an order: adults>children>seniors>adolescent. Overall, the ILCR values induced by HPAHs and PAHs were far below the priority risk level (10(-4)), indicating no obvious cancer risk. To our knowledge, this is the first study to investigate the human health risk associated with inhalation exposure to PM10/PM2.5-bound HPAHs. Copyright © 2014 Elsevier Inc. All rights reserved.

Biogenic polycyclic aromatic hydrocarbons in sediments of the San Joaquin River in California (USA), and current paradigms on their formation.

PubMed

Wakeham, Stuart G; Canuel, Elizabeth A

2016-06-01

Biogenic perylene and higher plant pentacyclic triterpenoid-derived alkylated and partially aromatized tetra- and pentacyclic derivatives of chrysene (3,4,7-trimethyl- and 3,3,7-trimethyl-1,2,3,4-tetrahydrochrysene, THC) and picene (1,2,9-trimethyl- and 2,2,9-trimethyl-1,2,3,4-tetrahydropicene, THP) were two- to four-fold more abundant than pyrogenic PAH in two sediment cores from the San Joaquin River in Northern California (USA). In a core from Venice Cut (VC), located in the river, PAH concentrations varied little downcore and the whole-core PAH concentration (biogenics + pyrogenics) was 250.6 ± 73.7 ng g(-1) dw; biogenic PAH constituted 67 ± 4 % of total PAH. THC were 26 ± 9 % of total biogenic PAH, THP were 36 ± 7 %, and perylene was 38 ± 7 %. PAH distributions in a core from Franks Tract (FT), a former wetland that was converted to an agricultural tract in the late 1800s and flooded in 1938, were more variable. Surface sediments were dominated by pyrogenic PAH so that biogenic PAH were only ~30 % of total PAH. Deeper in the core, biogenic PAH constituted 60-93 % of total PAH; THC, THP and perylene were 31 ± 28 %, 24 ± 32 %, and 45 ± 36 % of biogenic PAH. At 100-103 cm depth, THP constituted 80 % of biogenic PAH and at 120-123 cm perylene was 95 % of biogenic PAH. Current concepts related to precursors and transformation processes responsible for the diagenetic generation of perylene and triterpenoid-derived PAH are discussed. Distributions of biogenic PAH in VC and FT sediments suggest that they may not form diagenetically within these sediments but rather might be delivered pre-formed from the river's watershed.

Seasonal variation, sources and gas/particle partitioning of polycyclic aromatic hydrocarbons in Guangzhou, China.

PubMed

Yang, Yunyun; Guo, Pengran; Zhang, Qian; Li, Deliang; Zhao, Lan; Mu, Dehai

2010-05-15

Air samples were collected weekly at an urban site and a suburban site in Guangzhou City, China, from April 2005 to March 2006, to measure the concentrations of polycyclic aromatic hydrocarbons (PAHs) in the ambient air and study their seasonal variations, gas/particle partitioning, origins and sources. The concentrations of summation Sigma16-PAHs (particle+gas) were 129.9+/-73.1 ng m(-)(3) at the urban site and 120.4+/-48.5 ng m(-)(3) at the suburban site, respectively. It was found that there was no significant difference in PAH concentrations between the urban and suburban sites. Seasonal variations of PAH concentrations at the two sampling sites were similar, with higher levels in the winter that gradually decreased to the lowest levels in the summer. The average concentrations of summation Sigma16-PAHs in the winter samples were approximately three times higher than those of the summer samples because in the summer local emissions dominated, and in the winter the contribution from outside sources or transported PAHs is increased. The plot of logK(p) versus logP(L)(0) for the data sets of summer and winter season samples had significantly different slopes at both sampling sites. The slopes for the winter samples were steeper than those for the summer samples. It was also observed that gas/particle partitioning of PAHs showed different characteristics depending on air parcel trajectories. Steeper slopes were obtained for an air parcel that traveled across the continent to the sampling site from the northern or northeastern sector, whereas shallower slopes were obtained for air masses that traveled across the sea from the southern or eastern sector. Diagnostic ratio analytical results imply that the origins of PAHs were mainly from petroleum combustion and coal/biomass burning. The anthracene/phenanthrene and benzo[a]anthracene/chrysene ratios in the winter were significantly lower than those in the summer, which indicate that there might be long-range transported PAH input to Guangzhou in the winter. Copyright 2010 Elsevier B.V. All rights reserved.

Heat and PAHs Emissions in Indoor Kitchen Air and Its Impact on Kidney Dysfunctions among Kitchen Workers in Lucknow, North India.

PubMed

Singh, Amarnath; Kamal, Ritul; Mudiam, Mohana Krishna Reddy; Gupta, Manoj Kumar; Satyanarayana, Gubbala Naga Venkata; Bihari, Vipin; Shukla, Nishi; Khan, Altaf Hussain; Kesavachandran, Chandrasekharan Nair

2016-01-01

Indoor air quality and heat exposure have become an important occupational health and safety concern in several workplaces including kitchens of hotels. This study investigated the heat, particulate matter (PM), total volatile organic compounds (TVOCs) and polycyclic aromatic hydrocarbons (PAHs) emissions in indoor air of commercial kitchen and its association with kidney dysfunctions among kitchen workers. A cross sectional study was conducted on 94 kitchen workers employed at commercial kitchen in Lucknow city, North India. A questionnaire-based survey was conducted to collect the personal and occupational history of the kitchen workers. The urine analysis for specific gravity and microalbuminuria was conducted among the study subjects. Indoor air temperature, humidity, wet/ dry bulb temperature and humidex heat stress was monitored during cooking activities at the kitchen. Particulate matter (PM) for 1 and 2.5 microns were monitored in kitchen during working hours using Hazdust. PAHS in indoor air was analysed using UHPLC. Urinary hydroxy-PAHs in kitchen workers were measured using GC/MS-MS. Higher indoor air temperature, relative humidity, PM1 and PM2.5 (p<0.001) was observed in the kitchen due to cooking process. Indoor air PAHs identified are Napthalene, fluorine, acenaphthene, phenanthrene, pyrene, chrysene and indeno [1,2,3-cd) pyrene. Concentrations of all PAHs identified in kitchen were above the permissible OSHA norms for indoor air. Specific gravity of urine was significantly higher among the kitchen workers (p<0.001) as compared to the control group. Also, the prevalence of microalbuminuria was higher (p<0.001) among kitchen workers. Urinary PAH metabolites detected among kitchen workers were 1-NAP, 9-HF, 3-HF, 9-PHN and 1-OHP. Continuous heat exposure in kitchens due to cooking can alter kidney functions viz., high specific gravity of urine in kitchen workers. Exposure to PM, VOCs and PAHs in indoor air and presence of urinary PAHs metabolites may lead to inflammation, which can cause microalbuminuria in kitchen workers, as observed in the present study.

Assessment of contamination source and quality control approach for polycyclic aromatic hydrocarbons in wood-pressed rapeseed oil.

PubMed

Liu, Ruijie; Zhang, Youfeng; Wang, Jun; Pan, Qiqi; Luo, Yingqi; Sun, Yujie; Jin, Qingzhe; Wang, Xingguo

2018-03-14

Contamination sources of polycyclic aromatic hydrocarbons (PAHs) in the raw material, oil production and storage processes of wood-pressed rapeseed oil were investigated in this study. The results showed that benzo[a]pyrene (BaP) and PAH4 (sum of BaP, benzo[a]fluoranthene, benzo[b]fluoranthene and chrysene) were unevenly distributed in the kernel (0.56-0.98 and 2.84-8.64 μg/kg, respectively) and hull (1.53-3.17 and 13.49-22.31 μg/kg, respectively) of the rapeseed raw materials. The contents of BaP and PAH4 continuously increased during the process of wood-pressed rapeseed oil, ranging from 2.21 to 10.93 and 9.36 to 40.03 μg/kg, thus demonstrating that a wide range of pollution sources of PAHs existed for the test wood-pressed rapeseed oils. The initial temperature and time of roasting should be controlled at <210°C and <60 min, due to the generation of PAHs in rapeseed by over-roasting. In addition, contact tools and substance such as lubricating oil (from the mill), heat-transfer oil (from roasting machine), rubber gaskets and straws should be properly screened. The BaP and PAH4 of rapeseed placed in the roasting area increased from 0.5 to 2.24 and from 2.08 to 9.03 μg/kg, respectively. Therefore, roasting fume control and treatment systems are necessary and the roasting section should be strictly isolated from the other stages. Storage can slightly lower the PAHs amounts in the rapeseed oil, which made the contents of BaP and PAH4 decrease from 27.00 to 24.70 and from 138.63 to 117.58 μg/kg, respectively. Quality control measures of PAHs in wood-pressed rapeseed oil were proposed and implemented, and the final oil products' BaP and PAH4 were kept below 2 and 10 μg/kg, respectively, which meets the European Commission Regulation No. 835/2011.

PCDD/F, PAH and heavy metals in the sewage sludge from six wastewater treatment plants in Beijing, China.

PubMed

Dai, Jiayin; Xu, Muqi; Chen, Jiping; Yang, Xiangping; Ke, Zhenshan

2007-01-01

In order to better understand land application of sewage sludge, the characterization of heavy metals, PCDD/F and PAHs in sewage sludge was investigated from six different wastewater treatment plants (WWTP) in Beijing City, China. It was found that the total concentrations of Zn in Wujiacun (WJC) sewage sludge, and Cd and Hg in sewage sludge generated from all of the six different places are higher than Chinese regulation limit of pollutants for sludge to be used for agriculture (GB18918-2002). The levels of 16 PAHs that have been categorized as priority pollutants by US EPA in the sewage sludge samples varied from 2467 to 25923 microg/kg (dry weight), the highest values of 25923 microg/kg being found in WJC WWTP. The concentrations of Benzo[a]pyrene were as high as 6.1mg/kg dry weight in WJC sewage sludge, exceeding the maximum permitted content by GB18918-2002. Individual PAH content varies considerably with sewage samples. The ratios of anthracene to anthracene plus phenanthrene (An/178), benz[a]anthracene to benz[a]anthracene plus chrysene (BaA/228), indene[1,2,3-cd]pyrene to indene[1,2,3-cd]pyrene plus benzo[g,h,i]perylene (In/In+BP), and fluoranthene to fluoranthene plus pyrene (Fl/Fl+Py) suggest that petroleum and combustion of fossil fuel were the dominant contributions for the PAHs in sewage sludge. The concentrations of total PCDD/F in the sewage sludge ranged from 330 to 4245 pg/g d.w. The toxicity equivalent concentrations is between 3.47-88.24 pg I-TEQ according to NATO/CCMS, which is below Chinese legislation limit value proposed for land application. The PCDD/F congener/homologue profiles found in the Beijing samples indicated that the high chlorinated PCDD/F contamination might originate mainly from PCP-related source and depositional sources while the low chlorinated PCDD/F homologues could be originating from incineration or coal combustion. The major source of PCDD/Fs in Beijing sludge is still unclear.

Heat and PAHs Emissions in Indoor Kitchen Air and Its Impact on Kidney Dysfunctions among Kitchen Workers in Lucknow, North India

PubMed Central

Singh, Amarnath; Kamal, Ritul; Mudiam, Mohana Krishna Reddy; Gupta, Manoj Kumar; Satyanarayana, Gubbala Naga Venkata; Bihari, Vipin; Shukla, Nishi; Khan, Altaf Hussain; Kesavachandran, Chandrasekharan Nair

2016-01-01

Indoor air quality and heat exposure have become an important occupational health and safety concern in several workplaces including kitchens of hotels. This study investigated the heat, particulate matter (PM), total volatile organic compounds (TVOCs) and polycyclic aromatic hydrocarbons (PAHs) emissions in indoor air of commercial kitchen and its association with kidney dysfunctions among kitchen workers. A cross sectional study was conducted on 94 kitchen workers employed at commercial kitchen in Lucknow city, North India. A questionnaire-based survey was conducted to collect the personal and occupational history of the kitchen workers. The urine analysis for specific gravity and microalbuminuria was conducted among the study subjects. Indoor air temperature, humidity, wet/ dry bulb temperature and humidex heat stress was monitored during cooking activities at the kitchen. Particulate matter (PM) for 1 and 2.5 microns were monitored in kitchen during working hours using Hazdust. PAHS in indoor air was analysed using UHPLC. Urinary hydroxy-PAHs in kitchen workers were measured using GC/MS-MS. Higher indoor air temperature, relative humidity, PM1 and PM2.5 (p<0.001) was observed in the kitchen due to cooking process. Indoor air PAHs identified are Napthalene, fluorine, acenaphthene, phenanthrene, pyrene, chrysene and indeno [1,2,3-cd) pyrene. Concentrations of all PAHs identified in kitchen were above the permissible OSHA norms for indoor air. Specific gravity of urine was significantly higher among the kitchen workers (p<0.001) as compared to the control group. Also, the prevalence of microalbuminuria was higher (p<0.001) among kitchen workers. Urinary PAH metabolites detected among kitchen workers were 1-NAP, 9-HF, 3-HF, 9-PHN and 1-OHP. Continuous heat exposure in kitchens due to cooking can alter kidney functions viz., high specific gravity of urine in kitchen workers. Exposure to PM, VOCs and PAHs in indoor air and presence of urinary PAHs metabolites may lead to inflammation, which can cause microalbuminuria in kitchen workers, as observed in the present study. PMID:26871707

PAH distributions in sediments in the oil sands monitoring area and western Lake Athabasca: Concentration, composition and diagnostic ratios.

PubMed

Evans, Marlene; Davies, Martin; Janzen, Kim; Muir, Derek; Hazewinkel, Rod; Kirk, Jane; de Boer, Dirk

2016-06-01

Oil sands activities north of Fort McMurray, Alberta, have intensified in recent years with a concomitant debate as to their environmental impacts. The Regional Aquatics Monitoring Program and its successor, the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring (JOSM), are the primary aquatic programs monitoring this industry. Here we examine sediment data (collected by Ekman grabs) to investigate trends and sources of polycyclic aromatic hydrocarbons (PAHs), supplementing these data with sediment core studies. Total PAH (ΣPAH) concentrations were highest at Shipyard Lake (6038 ± 2679 ng/g) in the development center and lower at Isadore's Lake (1660 ± 777 ng/g) to the north; both lakes are in the Athabasca River Valley and lie below the developments. ΣPAH concentrations were lower (622-930 ng/g) in upland lakes (Kearl, McClelland) located further away from the developments. ΣPAH concentrations increased at Shipyard Lake (2001-2014) and the Ells River mouth (1998-2014) but decreased in nearshore areas at Kearl Lake (2001-2014) and a Muskeg River (2000-2014) site. Over the longer term, ΣPAH concentrations increased in Kearl (1934-2012) and Sharkbite (1928-2010) Lakes. Further (200 km) downstream in the Athabasca River delta, ΣPAH concentrations (1029 ± 671 ng/g) increased (1999-2014) when %sands were included in the regression model; however, 50 km to the east, concentrations declined (1926-2009) in Lake Athabasca. Ten diagnostic ratios based on anthracene, phenanthrene, fluoranthene, pyrene, benz[a]anthracene, chrysene, indeno[123-cd]pyrene, dibenz[a,h]anthracene, dibenzothiophene and retene were examined to infer spatial and temporal trends in PAH sources (e.g., combustion versus petrogenic) and weathering. There was some evidence of increasing contributions of unprocessed oil sands and bitumen dust to Shipyard, Sharkbite, and Isadore's Lakes and increased combustion sources in the Athabasca River delta. Some CCME interim sediment quality guidelines were exceeded, primarily in Shipyard Lake and near presumed natural bitumen sources. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish.

PubMed

Geier, Mitra C; James Minick, D; Truong, Lisa; Tilton, Susan; Pande, Paritosh; Anderson, Kim A; Teeguardan, Justin; Tanguay, Robert L

2018-04-06

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. We constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilization (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures. Copyright © 2018 Elsevier Inc. All rights reserved.

Long term observations of PM2.5-associated PAHs: Comparisons between normal and episode days

NASA Astrophysics Data System (ADS)

Wang, Jia; Li, Xiao; Jiang, Nan; Zhang, Wenkai; Zhang, Ruiqin; Tang, Xiaoyan

2015-03-01

The pollution characteristic of fine particular matter (PM2.5) and associated polycyclic aromatic hydrocarbons (PAHs) are currently drawing a great deal of interest because of their influence on environment and health. In this study, PM2.5 was collected from 2011 to 2013 (n = 188) in a suburban area of Zhengzhou, China. 16-PAHs were analyzed to determine the concentration, seasonal variation and potential sources during normal days and episode events. The total mass of 16 PAHs and PM2.5 were in the range of 7-961 ng m-3 and 55-697 μg m-3, with a 3-year average of 174 ng m-3 and 194 μg m-3 respectively. Winter is most polluted for both PM2.5 and PAHs. Average PAH and PM2.5 concentrations during three episode events are 454 ng m-3 and 453 μg m-3, respectively, much higher than values during normal days (299 ng m-3 and 180 μg m-3, respectively). Ratios of Σ16PAH/PM2.5 varied with seasons and concentrations of PM2.5, but showed a negative correlation with PM2.5 concentrations during episode events. The dominant components of PAHs are Benzo[b]fluoranthene, Chrysene, Fluoranthene, and Benzo[k]fluoranthene, Benz[a]anthracene, Pyrene, Indeno(1,2,3-cd)pyrene and their total concentrations vary from 27 to 342 ng m-3, accounting for 58-82% (average = 73%) of 16 PAHs. The Benzo[a]pyrene (Bap) concentration obtained was 9.4 ng m-3 (3-year average), exceeding nearly one order of magnitude of ambient air BaP standard (annual average: 1.0 ng m-3) in China. Diagnose ratios and Positive Matrix Factorization results show that coal combustion, vehicles, coking plant, and biomass burning are main sources for PAHs in this area. The high concentrations of PM2.5 and PAHs, especially during episode events, reflected a potential health problem for nearby public and the necessity of air pollution control for both stationary and mobile sources.

Application of a fuzzy neural network model in predicting polycyclic aromatic hydrocarbon-mediated perturbations of the Cyp1b1 transcriptional regulatory network in mouse skin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larkin, Andrew; Department of Statistics, Oregon State University; Superfund Research Center, Oregon State University

2013-03-01

Polycyclic aromatic hydrocarbons (PAHs) are present in the environment as complex mixtures with components that have diverse carcinogenic potencies and mostly unknown interactive effects. Non-additive PAH interactions have been observed in regulation of cytochrome P450 (CYP) gene expression in the CYP1 family. To better understand and predict biological effects of complex mixtures, such as environmental PAHs, an 11 gene input-1 gene output fuzzy neural network (FNN) was developed for predicting PAH-mediated perturbations of dermal Cyp1b1 transcription in mice. Input values were generalized using fuzzy logic into low, medium, and high fuzzy subsets, and sorted using k-means clustering to create Mamdanimore » logic functions for predicting Cyp1b1 mRNA expression. Model testing was performed with data from microarray analysis of skin samples from FVB/N mice treated with toluene (vehicle control), dibenzo[def,p]chrysene (DBC), benzo[a]pyrene (BaP), or 1 of 3 combinations of diesel particulate extract (DPE), coal tar extract (CTE) and cigarette smoke condensate (CSC) using leave-one-out cross-validation. Predictions were within 1 log{sub 2} fold change unit of microarray data, with the exception of the DBC treatment group, where the unexpected down-regulation of Cyp1b1 expression was predicted but did not reach statistical significance on the microarrays. Adding CTE to DPE was predicted to increase Cyp1b1 expression, whereas adding CSC to CTE and DPE was predicted to have no effect, in agreement with microarray results. The aryl hydrocarbon receptor repressor (Ahrr) was determined to be the most significant input variable for model predictions using back-propagation and normalization of FNN weights. - Highlights: ► Tested a model to predict PAH mixture-mediated changes in Cyp1b1 expression ► Quantitative predictions in agreement with microarrays for Cyp1b1 induction ► Unexpected difference in expression between DBC and other treatments predicted ► Model predictions for combining PAH mixtures in agreement with microarrays ► Predictions highly dependent on aryl hydrocarbon receptor repressor expression.« less

Biomonitoring, status and source risk assessment of polycyclic aromatic hydrocarbons (PAHs) using honeybees, pine tree leaves, and propolis.

PubMed

Kargar, Navid; Matin, Golnar; Matin, Amir Abbas; Buyukisik, Hasan Baha

2017-11-01

In this study, to identify and quantify the sources of airborne polycyclic aromatic hydrocarbons (PAHs), we gathered honeybee, pine tree leaf, and propolis samples to serve as bioindicators from five stations in the village of "Bozkoy" in the Aliaga industrial district of Izmir (Turkey) during April-May 2014. The PAH concentrations which measured by gas chromatography (GC) varied from 261.18 to 553.33 μg kg -1 dry weight (dw) in honeybee samples, 138.57-853.67 μg kg -1 dw in pine leaf samples, and 798.61-2905.53 μg kg -1 dw in propolis samples. The total PAH concentrations can be ranked as follows: propolis > pine leaves > honeybees. The ring sequence pattern was 5 > 3 > 6 > 4 > 2 for honeybees, 5 > 3 > 4 > 6 > 2 for pine leaves, and 5 > 4 > 6 > 3 > 2 for propolis. The diagnostic ratios [fluoranthene/fluoranthene + pyrene], [indeno(1,2,3-c,d)pyrene/indeno(1,2,3-c,d)pyrene + benzo(g,h,i)perylene], and [benzo(a)anthracene/benzo(a)anthracene + chrysene] indicate coal and biomass combustion to be the dominant PAH source in the study area. In biomonitoring studies of airborne PAHs based on honeybees, fluoranthene is considered to be a characteristic PAH compound. Distribution maps with different numbers of PAH rings among the sampling sites show the advantages of honeybee samples as indicators due to the honeybee's provision of a broader range of information with respect to heavier pollutants that are typically not in the gas or suspended phase for long periods of time. Our correlation, factor analysis, and principal components analysis (PCA) results indicate potential sources of PAH pollution in pine leaves and honeybees from airborne emissions, but we found propolis to be contaminated by PAHs due to the replacement of herbal sources of resins with synthetic gummy substances from paving materials (e.g., asphalt and tar leaks). Copyright © 2017 Elsevier Ltd. All rights reserved.

Bioaccumulation and cancer risk of polycyclic aromatic hydrocarbons in leafy vegetables grown in soils within automobile repair complex and environ in Uyo, Nigeria.

PubMed

Inam, Edu; Ibanga, Felicia; Essien, Joseph

2016-12-01

Using gas chromatography-mass spectrometry and an incremental lifetime cancer risks (ILCRs) assessment model, the bioaccumulation and cancer risk of 16 USEPA priority polycyclic aromatic hydrocarbons (PAHs) in leafy vegetables (Vernonia amygdalina and Lasianthera africanum) grown in soils within an automobile repair complex environment in Uyo, Nigeria was studied. The total PAHs concentrations recorded for soils ranged from 0.02 to 1.77 mg/kg. The highest level of 1.77 mg/kg was recorded for soils from the main automobile repair complex (site 1). Low molecular weight (LMW) PAHs were predominant although some high molecular weight (HMW) PAHs suites (0.04 mg/kg of chrysene and 0.04 of benzo[k]fluoranthene) were also found in site 1. The leafy vegetables accumulated PAHs were mostly LMW. Accumulation levels were similar but the extent of PAH uptake in vegetables was species dependent as V. amygdalina accumulated more (0.81 mg/kg). The bioaccumulation factors (BaFs) calculated ranged from 0.22 to 0.63 for L. africanum, and 0.18 to 0.55 for V. amygdalina in site 1 where high PAH levels were recorded in soil. Pearson correlation coefficient analysis revealed a strong positive relation between the PAH content of soil and the amount accumulated by L. africanum (r = 0.5) and V. amygdalina (r = 0.8) at p = 0.05. The vegetable's potential to bioaccumulate PAHs is indicative of their use as good bioindicators for PAH contamination in soil. Only two of the USEPA possible human carcinogenic PAHs were detected, and carcinogenic risk assessment based on occupational exposures to soil particles by adults revealed that the total risk level (7.17 × 10 -5 ) contribution from incidental soil ingestion, dermal contact, and soil particle dust inhalation slightly exceed the USEPA acceptable limits (< 1.00 × 10 -5 ). There is a need for public education on consumption of vegetables grown in and around automobile repair complexes across Nigeria.

Polycyclic aromatic hydrocarbons associated with total suspended particles and surface soils in Kunming, China: distribution, possible sources, and cancer risks.

PubMed

Yang, Xiaoxia; Ren, Dong; Sun, Wenwen; Li, Xiaoman; Huang, Bin; Chen, Rong; Lin, Chan; Pan, Xuejun

2015-05-01

The concentrations, distribution, possible sources, and cancer risks of polycyclic aromatic hydrocarbons (PAHs) in total suspended particles (TSPs) and surface soils collected from the same sampling spots were compared in Kunming, China. The total PAH concentrations were 9.35-75.01 ng/m(3) and 101.64-693.30 ng/g dry weight (d.w.), respectively, in TSPs and surface soils. Fluoranthene (FLA), pyrene (PYR), chrysene (CHR), and phenanthrene (PHE) were the abundant compounds in TSP samples, and phenanthrene (PHE), fluorene (FLO), fluoranthene (FLA), benzo[b]fluoranthene (BbF), and benzo[g,h,i]perylene (BghiP) were the abundant compounds in surface soil samples. The spatial distribution of PAHs in TSPs is closely related to the surrounding environment, which varied significantly as a result of variations in source emission and changes in meteorology. However, the spatial distribution of PAHs in surface soils is supposed to correlate with a city's urbanization history, and high levels of PAHs were always observed in industry district, or central or old district of city. Based on the diagnostic ratios and principal component analysis (PCA), vehicle emissions (especially diesel-powered vehicles) and coal and wood combustion were the main sources of PAHs in TSPs, and the combustion of wood and coal, and spills of unburnt petroleum were the main sources of PAHs in the surface soils. The benzo[a]pyrene equivalent concentration (BaPeq) for the TSPs and surface soil samples were 0.16-2.57 ng/m(3) and 11.44-116.03 ng/g d.w., respectively. The incremental lifetime cancer risk (ILCR) exposed to particulate PAHs ranged from 10(-4) to 10(-3) indicating high potential of carcinogenic risk, and the ILCR exposed to soil PAHs was from 10(-7) to 10(-6) indicating virtual safety. These presented results showed that particle-bound PAHs had higher potential carcinogenic ability for human than soil PAHs. And, the values of cancer risk for children were always higher than for adults, which demonstrated that children were sensitive to carcinogenic effects of PAHs.

Significance of Cytochrome P450 System Responses and Levels of Bile Fluorescent Aromatic Compounds in Marine Wildlife Following Oil Spills

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Richard F.; Anderson, Jack W.

2005-07-01

The relationships among cytochrome P450 induction in marine wildlife species, levels of fluorescent aromatic compounds (FAC) in their bile, the chemical composition of the inducing compounds, the significance of the exposure pathway, and any resulting injury, as a consequence of exposure to crude oil following a spill, are reviewed. Fish collected after oil spills often show increases in cytochrome P450 system activity, cytochrome P4501A (CYP1A) and bile fluorescent aromatic compounds (FAC), that are correlated with exposure to polycyclic aromatic hydrocarbons (PAH) in the oil. There is also some evidence for increases in bile FAC and induction of cytochrome P450 inmore » marine birds and mammals after oil spills. However, when observed, increases in these exposure indicators are transitory and generally decrease to background levels within one year after the exposure. Laboratory studies have shown induction of cytochrome P450 systems occurs after exposure of fish to crude oil in water, sediment or food. Most of the PAH found in crude oil (dominantly 2- and 3-ring PAH) are not strong inducers of cytochrome P450. Exposure to the 4-ring chrysenes or the photooxidized products of the PAH may account for the cytochrome P450 responses in fish collected from oil-spill sites. The contribution of non-spill background PAH, particularly combustion-derived (pyrogenic) PAH, to bile FAC and cytochrome P450 system responses can be confounding and needs to be considered when evaluating oil spill effects. The ubiquity of pyrogenic PAH makes it important to fully characterize all sources of PAH, including PAH from natural resources, e.g. retene, in oil spill studies. In addition, such parameters as species, sex, age, ambient temperature and season need to be taken into account. While increases in fish bile FAC and cytochrome P450 system responses, can together, be sensitive general indicators of PAH exposure after an oil spill, there is little unequivocal evidence to suggest a linkage to higher order biological effects, e.g. toxicity, lesions, reproductive failure.« less

Polycyclic aromatic hydrocarbons and trace metals in mosque's carpet dust of Riyadh, Saudi Arabia, and their health risk implications.

PubMed

El-Mubarak, Aarif H; Rushdi, Ahmed I; Al-Mutlaq, Khalid F; Al Mdawi, Falah Z; Al-Hazmi, Khalid; Dumenden, Ramil S; Pascua, Rex A

2016-11-01

The main objectives of this work were to identify and determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and trace metals in carpet dust samples from various mosques of the city of Riyadh and to assess the health risks associated with the exposure to these pollutants. Therefore, 31 samples of mosque's carpet dust from Riyadh were collected. The results showed that 14 PAHs were present in the dust samples with concentrations ranged from 90 to 22,146 ng g -1 (mean = 4096 ± 4277 ng g -1 ) where low molecular weight compounds were dominant. The presence of PAHs were in the order of naphthalene > chrysene and benzo(b)fluoranthene > benzo(a)pyrene > acenaphthene and benzo(k)fluoranthene > pyrene and the absence of indeno(1,2,3-cd)pyrene and dibenz(a,h)anthracene. The diagnostic ratio coupled with principle component analysis (PCA) revealed mix sources of petrogenic from traffic, stack emission, and pyrogenic inputs from essence and perfumed wood burning. Trace metals were significant in the dust samples, and their concentrations decrease in the order of Zn, Mn, Cu, Cr, Pb, Ni, and V where Zn being the highest (94.4 ± 91.5 μg g -1 ) and indium was the lowest (1.9 ± 9.3 μg g -1 ). The trace metals were major in southern and central parts of Riyadh and followed the order of central Riyadh > southern Riyadh > western Riyadh > eastern Riyadh > northern Riyadh. Estimated risk based on the total PAHs was found to be 4.30 × 10 -11 for adult and 1.56 × 10 -11 for children. Elemental non-cancer risk for adults ranged from 7.9 × 10 -4 for Co to 7.58 × 10 -1 for Li and for children ranged from 3.70 × 10 -3 for Co to 3.54 for Li. Policy implication and mitigations of PAHs in Riyadh and Saudi Arabia were highlighted.

Carbon nanotube-based benzyl polymethacrylate composite monolith as a solid phase extraction adsorbent and a stationary phase material for simultaneous extraction and analysis of polycyclic aromatic hydrocarbon in water.

PubMed

Al-Rifai, Asma'a; Aqel, Ahmad; Wahibi, Lamya Al; ALOthman, Zeid A; Badjah-Hadj-Ahmed, Ahmed-Yacine

2018-02-02

A composite of multi-walled carbon nanotubes incorporated into a benzyl methacrylate-co-ethylene dimethacrylate porous monolith was prepared, characterized and used as solid phase adsorbent and as stationary phase for simultaneous extraction and separation of ten polycyclic aromatic hydrocarbons, followed by nano-liquid chromatography analysis. The extraction and chromatographic parameters were optimized with regard to the extraction efficiency and the quality of chromatographic analytes separation. Under the optimized conditions, all PAHs were separated in 13 min with suitable resolution values (Rs = 1.74-3.98). Addition of a small amount of carbon nanotubes (0.1% with respect to monomers) to the polymerization mixture increased the efficiency for the separation column to over 41,700 plates m -1 for chrysene at flow rate of 0.5 μL min -1 . The method showed a wide linear range (1-500 μg L -1 with R 2 more than 0.9938), acceptable extraction repeatability (RSDs < 6.4%, n = 3) and reproducibility (RSDs < 12.6%, five parallel-made solid phase extraction cartridges) and satisfactory detection limits (0.02-0.22 μg L -1 ). Finally, the proposed method was successfully applied to the detection of polycyclic aromatic hydrocarbons in environmental water samples. After a simple extraction procedure with preconcentration factor equal to 100, the average recovery values in ultra-pure, tap and sea water samples were found to be in the range 81.3-95.4% with %RSD less than 6.4. Again, the presence of carbon nanotubes (0.3% relatively to monomers) in native polymer enhanced the extraction performance for the solid phase adsorbent up to 78.4%. The application of the monoliths modified with CNTs in extraction and nano-scale liquid chromatography for analysis of environmental samples offered several advantages; it demonstrated an acceptable precision, low detection limits, good reproducibility, satisfying recoveries and wide dynamic linear ranges. Copyright © 2018. Published by Elsevier B.V.

Structural Investigations of the Ferredoxin and Terminal Oxygenase Components of the biphenyl 2,3-dioxygenase from Sphingobium yanoikuyae B1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ferraro,D.; Brown, E.; Yu, C.

The initial step involved in oxidative hydroxylation of monoaromatic and polyaromatic compounds by the microorganism Sphingobium yanoikuyae strain B1 (B1), previously known as Sphingomonas yanoikuyae strain B1 and Beijerinckia sp. strain B1, is performed by a set of multiple terminal Rieske non-heme iron oxygenases. These enzymes share a single electron donor system consisting of a reductase and a ferredoxin (BPDO-F{sub B1}). One of the terminal Rieske oxygenases, biphenyl 2,3-dioxygenase (BPDO-O{sub B1}), is responsible for B1's ability to dihydroxylate large aromatic compounds, such as chrysene and benzo(a)pyrene. Results: In this study, crystal structures of BPDO-O{sub B1} in both native and biphenylmore » bound forms are described. Sequence and structural comparisons to other Rieske oxygenases show this enzyme to be most similar, with 43.5 % sequence identity, to naphthalene dioxygenase from Pseudomonas sp. strain NCIB 9816-4. While structurally similar to naphthalene 1,2-dioxygenase, the active site entrance is significantly larger than the entrance for naphthalene 1,2-dioxygenase. Differences in active site residues also allow the binding of large aromatic substrates. There are no major structural changes observed upon binding of the substrate. BPDO-F{sub B1} has large sequence identity to other bacterial Rieske ferredoxins whose structures are known and demonstrates a high structural homology; however, differences in side chain composition and conformation around the Rieske cluster binding site are noted. Conclusion: This is the first structure of a Rieske oxygenase that oxidizes substrates with five aromatic rings to be reported. This ability to catalyze the oxidation of larger substrates is a result of both a larger entrance to the active site as well as the ability of the active site to accommodate larger substrates. While the biphenyl ferredoxin is structurally similar to other Rieske ferredoxins, there are distinct changes in the amino acids near the iron-sulfur cluster. Because this ferredoxin is used by multiple oxygenases present in the B1 organism, this ferredoxin-oxygenase system provides the structural platform to dissect the balance between promiscuity and selectivity in protein-protein electron transport systems.« less

Monitoring of environmental exposure to polycyclic aromatic hydrocarbons: a review.

PubMed

Srogi, K

2007-01-01

Polycyclic aromatic hydrocarbons (PAHs) are a large group of organic compounds with two or more fused aromatic rings. They have a relatively low solubility in water, but are highly lipophilic. Most of the PAHs with low vapour pressure in the air are adsorbed on particles. When dissolved in water or adsorbed on particulate matter, PAHs can undergo photodecomposition when exposed to ultraviolet light from solar radiation. In the atmosphere, PAHs can react with pollutants such as ozone, nitrogen oxides and sulfur dioxide, yielding diones, nitro- and dinitro-PAHs, and sulfonic acids, respectively. PAHs may also be degraded by some microorganisms in the soil. PAHs are widespread environmental contaminants resulting from incomplete combustion of organic materials. The occurrence is largely a result of anthropogenic emissions such as fossil fuel-burning, motor vehicle, waste incinerator, oil refining, coke and asphalt production, and aluminum production, etc. PAHs have received increased attention in recent years in air pollution studies because some of these compounds are highly carcinogenic or mutagenic. Eight PAHs (Car-PAHs) typically considered as possible carcinogens are: benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene (B(a)P), dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene and benzo(g,h,i)perylene. In particular, benzo(a)pyrene has been identified as being highly carcinogenic. The US Environmental Protection Agency (EPA) has promulgated 16 unsubstituted PAHs (EPA-PAH) as priority pollutants. Thus, exposure assessments of PAHs in the developing world are important. The scope of this review will be to give an overview of PAH concentrations in various environmental samples and to discuss the advantages and limitations of applying these parameters in the assessment of environmental risks in ecosystems and human health. As it well known, there is an increasing trend to use the behavior of pollutants (i.e. bioaccumulation) as well as pollution-induced biological and biochemical effects on human organisms to evaluate or predict the impact of chemicals on ecosystems. Emphasis in this review will, therefore, be placed on the use of bioaccumulation and biomarker responses in air, soil, water and food, as monitoring tools for the assessment of the risks and hazards of PAH concentrations for the ecosystem, as well as on its limitations.

Characteristics of polycyclic aromatic hydrocarbons in PM2.5 emitted from different cooking activities in China.

PubMed

Li, Yun-Chun; Qiu, Jia-Qian; Shu, Man; Ho, Steven Sai Hang; Cao, Jun-Ji; Wang, Ge-Hui; Wang, Xian-Xiang; Zhao, Xiao-Qing

2018-02-01

Nineteen polycyclic aromatic hydrocarbons (PAHs) in PM 2.5 emitted from five different cooking activities were characterized, and their influencing factors were determined. The total quantified particle-bounded PAH concentrations (ΣPAHs) in the airs from the cooking activities were 4.2-36.5-fold higher than those in corresponding backgrounds. The highest ΣPAHs were seen in cafeteria frying (783 ± 499 ng/m 3 ), followed by meat roasting (420 ± 191 ng/m 3 ), fish roasting (210 ± 105 ng/m 3 ), snack-street boiling (202 ± 230 ng/m 3 ), and cafeteria boiling (150 ± 65 ng/m 3 ). The main influencing factors on the PAH emissions were cooking methods, fat contents in raw materials, and oil consumptions. Four- to six-ringed PAHs had the highest contributions to the ΣPAHs (avg. 87.5%). Diagnostic ratios of individual PAH were similar between the two charbroiling and other three conventional Chinese cooking methods, respectively, demonstrating the dominance of cooking methods in the PAH emissions. Remarkably high benzo(b)fluoranthene/benzo(k)fluoranthene (BbF/BkF) ratio (8.31) was seen in the snack-street boiling, attributed to the coal combustion as cooking fuel. Both fluoranthene/(fluoranthene + pyrene) [FLT/(FLT + PYR)] and benzo(a)anthracene/(benzo(a)anthracene + chrysene) [BaA/(BaA + CHR)] ratios were higher for the oil-based cooking than those from the water-based ones. In addition, two ratios of indeno(1,2,3-cd)pyrene/(indeno(1,2,3-cd)pyrene + benzo(g,h,i)perylene) [IPY/(IPY + BPE)] and benzo(a)pyrene/(benzo(a)pyrene + benzo(g,h,i)perylene) [BaP/(BaP + BPE)] were higher for two charbroiling than the three conventional Chinese cooking methods. The characterization work in this study is particularly important since cooking is a potential contributor of atmospheric PAHs in urban China. Carcinogenic potencies of PAHs were assessed by comparison with the air quality guideline and health risk estimation. The BaP and BaP equivalent were higher for the oil-based than the water-based cooking activities.

Characterization and health risk assessment of airborne pollutants in commercial restaurants in northwestern China: Under a low ventilation condition in wintertime.

PubMed

Dai, Wenting; Zhong, Haobin; Li, Lijuan; Cao, Junji; Huang, Yu; Shen, Minxia; Wang, Liqin; Dong, Jungang; Tie, Xuexi; Ho, Steven Sai Hang; Ho, Kin Fai

2018-08-15

Impacts on indoor air quality of dining areas from cooking activities were investigated in eight categories of commercial restaurants including Szechwan Hotpot, Hunan, Shaanxi Noodle, Chinese Barbecue, Chinese Vegetarian, Korean Barbecue, Italian, and Indian, in Northwestern China during December 2011 to January 2012. Chemical characterization and health risk assessment for airborne carbonyls, and particulate-bound polycyclic aromatic hydrocarbons (PAHs) and heavy metals were conducted under low ventilation conditions in wintertime. The highest total quantified carbonyls (Σ carbonyls ) concentration of 313.6μgm -3 was found in the Chinese Barbecue, followed by the Szechwan Hotpot (222.6μgm -3 ) and Indian (221.9μgm -3 ) restaurants. However, the highest Σ carbonyls per capita was found at the Indian restaurant (4500μgcapita -1 ), suggesting that cooking methods such as stir-fly and bake for spices ingredients released more carbonyls from thermal cooking processes. Formaldehyde, acetaldehyde, and acetone were the three most abundant species, totally accounting for >60% of mass concentrations of the Σ carbonyls . Phenanthrene, chrysene, and benzo[a]anthracene were the three most abundant PAHs. Low molecular weight fraction (ΣPAHs ≤178 ) had the highest contributions accounting for 40.6%-65.7%, much greater than their heaver counterparts. Diagnostic PAHs ratios suggest that cooking fuel and environmental tobacco smoke (ETS) contribute to the indoor PAHs profiles. Lead was the most abundant heavy metal in all sampled restaurants. High quantity of nickel was also found in samples due to the emissions from stainless-steel made kitchen utensils and cookware and ETS. Cancer risk assessments on the toxic substances demonstrate that the working environment of dining areas were hazard to health. Formation of reactive organic species (ROS) from the cooking activities was evidenced by measurement of hydroxyl radical (OH) formed from simulating particulate matter (PM) react with surrogate lung fluid. The highest OH concentration of 294.4ngm -3 was detected in Chinese Barbecue. In addition, the elevation of the concentrations of PM and OH after non-dining periods implies that the significance of formation of oxidizing-active species indoor at poor ventilation environments. Copyright © 2018 Elsevier B.V. All rights reserved.

Laboratory insights into the chemical and kinetic evolution of several organic molecules under simulated Mars surface UV radiation conditions

NASA Astrophysics Data System (ADS)

Poch, O.; Kaci, S.; Stalport, F.; Szopa, C.; Coll, P.

2014-11-01

The search for organic carbon at the surface of Mars, as clues of past habitability or remnants of life, is a major science goal of Mars' exploration. Understanding the chemical evolution of organic molecules under current martian environmental conditions is essential to support the analyses performed in situ. What molecule can be preserved? What is the timescale of organic evolution at the surface? This paper presents the results of laboratory investigations dedicated to monitor the evolution of organic molecules when submitted to simulated Mars surface ultraviolet radiation (190-400 nm), mean temperature (218 ± 2 K) and pressure (6 ± 1 mbar) conditions. Experiments are done with the MOMIE simulation setup (for Mars Organic Molecules Irradiation and Evolution) allowing both a qualitative and quantitative characterization of the evolution the tested molecules undergo (Poch, O. et al. [2013]. Planet. Space Sci. 85, 188-197). The chemical structures of the solid products and the kinetic parameters of the photoreaction (photolysis rate, half-life and quantum efficiency of photodecomposition) are determined for glycine, urea, adenine and chrysene. Mellitic trianhydride is also studied in order to complete a previous study done with mellitic acid (Stalport, F., Coll, P., Szopa, C., Raulin, F. [2009]. Astrobiology 9, 543-549), by studying the evolution of mellitic trianhydride. The results show that solid layers of the studied molecules have half-lives of 10-103 h at the surface of Mars, when exposed directly to martian UV radiation. However, organic layers having aromatic moieties and reactive chemical groups, as adenine and mellitic acid, lead to the formation of photoresistant solid residues, probably of macromolecular nature, which could exhibit a longer photostability. Such solid organic layers are found in micrometeorites or could have been formed endogenously on Mars. Finally, the quantum efficiencies of photodecomposition at wavelengths from 200 to 250 nm, determined for each of the studied molecules, range from 10-2 to 10-6 molecule photon-1 and apply for isolated molecules exposed at the surface of Mars. These kinetic parameters provide essential inputs for numerical modeling of the evolution of Mars' current reservoir of organic molecules. Organic molecules adsorbed on martian minerals may have different kinetic parameters and lead to different endproducts. The present study paves the way for the interpretation of more complex simulation experiments where organics will be mixed with martian mineral analogs.

8,9-dihydroxy-8,9-dihydrodibenzo[a,l]pyrene is a potent morphological cell-transforming agent in C3H10T(1)/(2)Cl8 mouse embryo fibroblasts in the absence of detectable stable covalent DNA adducts.

PubMed

Nesnow, S; Davis, C; Padgett, W T; Adams, L; Yacopucci, M; King, L C

2000-06-01

The comparative genotoxic effects of racemic trans-8,9-dihydroxy-8, 9-dihydrodibenzo[a,l]pyrene (trans-DB[a,l]P-8,9-diol), the metabolic K-region dihydrodiol of dibenzo[a,l] pyrene (DB[a,l]P) (dibenzo[def, p]chrysene) and DB[a,l]P in transformable mouse embryo C3H10T(1)/(2)Cl8 (C3H10T(1)/(2)) fibroblasts was investigated. The C3H10T(1)/(2) mouse embryo morphological cell-transforming activities of these polycyclic aromatic hydrocarbons (PAHs) were assayed using concentration-response studies. At concentrations of 33 nM and above both trans-DB[a,l]P-8,9-diol and DB[a,l]P produced significant (and similar) numbers of type II and III foci per dish and numbers of dishes with type II and II foci. Concomitant cytotoxicity studies revealed a reduction in colony survival of approximately 25% up to 198 nM for both PAHs. DNA adducts of trans-DB[a,l]P-8,9-diol and DB[a,l]P in C3H10T(1)/(2) cells were analyzed by a (32)P-post-labeling TLC/HPLC method. No adducts were observed in the DNA of C3H10T(1)/(2) cells treated with trans-DB[a, l]P-8,9-diol at concentrations that induced morphological cell transformation. Under the same exposure and chromatographic conditions, DNA adducts of deoxyadenosine and deoxyguanosine derived from the fjord region anti-DB[a,l]P-11,12-diol-13,14-epoxide and syn-DB[a,l]P-11,12-diol-13,14-epoxide were observed in the DNA of DB[a,l]P-treated cells. These results indicate that trans-DB[a,l]P-8, 9-diol has intrinsic genotoxic activity equal to that of DB[a,l]P, based on morphological cell transformation of mouse embryo fibroblasts. The activity of trans-DB[a,l]P-8,9-diol is apparently not associated with the formation of observable stable covalent DNA adducts. These results suggest that under appropriate conditions, trans-DB[a,l]P-8,9-diol may serve as an intermediate in the genotoxicity of DB[a,l]P.

Occupational exposure to aromatic hydrocarbons and polycyclic aromatic hydrocarbons at a coke plant.

PubMed

Bieniek, Grażyna; Łusiak, Agnieszka

2012-08-01

The objective of this study was to assess the external exposure to aromatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) of coke-oven workers and by-product workers at a coke plant in Poland. The content of benzene, toluene, xylene, and naphthalene in a gaseous phase and the content of dibenzo[a,h]anthracene, benz[a]anthracene, anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, benz[ghi]perylene, chrysene, and indeno[1,2,3-c,d]pyrene in a particulate phase of coke plant workers were measured in the workers mentioned above. A toxic equivalency factor BaP(eq) was used to estimate human health risk associated with respiratory exposure to PAHs. Time-weighted values of the exposure to AHs in the coke plant were as follows: benzene (range 0.01-2.71 mg m(-3)), toluene (0.01-1.73 mg m(-3)), xylene (0.01-0.78 mg m(-3)), naphthalene (6.0-6079 μg m(-3)), and the concentrations of hydrocarbons did not exceed the exposure limits. The results for particle-bound PAHs were equal to 1.96 μg m(-3) for B(a)P, 0.73 μg m(-3) for DBA, 3.23 μg m(-3) for BaA, 4.35 μg m(-3) for BbF, 3.02 μg m(-3) for BkF, 4.54 μg m(-3) for IND, 4.32 μg m(-3) for CHR, and 0.73 μg m(-3) for Ant. The results of personal air measurements (median values of the sum of nine carcinogenic PAHs) were 2.115 μg m(-3) (coke-oven workers, n = 207), 0.326 μg m(-3) (coke by-product workers, n = 33), and 0.653 μg m(-3) (total area workers, n = 38). The benzo[a]pyrene equivalent concentrations (BaP(eq)) of 10 PAHs were 1.33, 0.183, and 0.284 μg m(-3), respectively. We found out that coke plant workers are simultaneously exposed to a mixture of aromatic and polycyclic hydrocarbons present in the breathing zone air. Exposure levels are significantly influenced by job categories. Coke by-product workers are significantly more exposed to benzene, toluene, and xylene and less to PAHs. Coke-oven workers are mainly exposed to PAHs. Coke-oven workplaces (top side, coke side, and push side) are characterized by higher carcinogenic risk than other coke plant workplaces.

Urinary carcinogenic 4-6 ring polycyclic aromatic hydrocarbons in coke oven workers and in subjects belonging to the general population: role of occupational and environmental exposure.

PubMed

Campo, Laura; Fustinoni, Silvia; Consonni, Dario; Pavanello, Sofia; Kapka, Lucyna; Siwinska, Ewa; Mielzyňska, Danuta; Bertazzi, PierAlberto

2014-03-01

A new solid phase microextraction-gas chromatography-mass spectrometry method (SPME-GC-MS) to detect urinary unmetabolized 3-, 6-ring polycyclic aromatic hydrocarbons (PAHs) was applied to coke oven workers and general population subjects with the aim to assess exposure to carcinogenic PAHs, to evaluate the role of occupational and environmental variables on PAHs levels, and to compare present results with those previously obtained with a less sensitive method. A total of 104 coke oven workers (CW) from Poland [recruited in 2000 (CW-2000; n=55) and 2006 (CW-2006; n=49)], and 45 control subjects from the same area, provided urine spot samples for measurement of 10 PAHs (from phenanthrene to benzo[g,h,i]perylene). The comparison between the two methods was performed only on CW-2000 subjects. Information regarding personal characteristics and job variables was collected by a questionnaire. The new method enables the quantification of 5-, 6-ring PAHs; precision and accuracy were in the 7.3-20.8% and 89.4-110% range, respectively; in CW-2000 samples results obtained with the new and the old method were highly correlated (Lin's concordance correlation coefficients: from 0.790 to 0.965); the mean difference between measured PAHS increased with the molecular weight of the analytes (from +5 to +27%). Urinary PAHs were above or equal to the quantification limit, depending on the compound, in 67-100% (min-max), 26-100% and 6-100% of samples from CW-2000, CW-2006 and controls, respectively. Chrysene and benz[a]anthracene were the most abundant carcinogenic PAHs with median levels of 43.4, 13.4, and 2.3 ng/L and 45.9, 14.9, and 0.7 ng/L in CW-2000, CW-2006, and controls, respectively, while benzo[a]pyrene levels were 6.5, 0.7 and <0.5 ng/L. The multiple linear regression model showed that the determinants of exposure were the use of wood and/or coke for house heating for controls, and job title or the plant for CW-2006. Urinary benzo[a]pyrene and other carcinogenic PAHs were, for the first time, quantified in urine samples from both occupationally and environmentally exposed subjects. These results show that urinary PAHs can discriminate exposure at different levels. Moreover, the simultaneous determination of several PAHs allows for the development of excretion profiles to assess exposure to specific compounds. Copyright © 2013 Elsevier GmbH. All rights reserved.

Ideal versus real automated twin column recycling chromatography process.

PubMed

Gritti, Fabrice; Leal, Mike; McDonald, Thomas; Gilar, Martin

2017-07-28

The full baseline separation of two compounds (selectivity factors α<1.03) is either impractical (too long analysis times) or even impossible when using a single column of any length given the pressure limitations of current LC instruments. The maximum efficiency is that of an infinitely long column operated at infinitely small flow rates. It is determined by the maximum allowable system pressure, the column permeability (particle size), the viscosity of the eluent, and the intensity of the effective diffusivity of the analytes along the column. Alternatively, the twin-column recycling separation process (TCRSP) can overcome the efficiency limit of the single-column approach. In the TCRSP, the sample mixture may be transferred from one to a second (twin) column until its band has spread over one column length. Basic theory of chromatography is used to confirm that the speed-resolution performance of the TCRSP is intrinsically superior to that of the single-column process. This advantage is illustrated in this work by developing an automated TCRSP for the challenging separation of two polycyclic aromatic hydrocarbon (PAH) isomers (benzo[a]anthracene and chrysene) in the reversed-phase retention mode at pressure smaller than 5000psi. The columns used are the 3.0mm×150mm column packed with 3.5μm XBridge BEH-C 18 material (α=1.010) and the 3.0mm or 4.6mm×150mm columns packed with the same 3.5μm XSelect HSST 3 material (α=1.025). The isocratic mobile phase is an acetonitrile-water mixture (80/20, v/v). Remarkably, significant differences are observed between the predicted retention times and efficiencies of the ideal TCRSP (given by the number of cycles multiplied by the retention time and efficiency of one column) and those of the real TCRSP. The fundamental explanation lies in the pressure-dependent retention of these PAHs or in the change of their partial molar volume as they are transferred from the mobile to the stationary phase. A revisited retention and efficiency model is then built to predict the actual performance of real TCRSPs. The experimental and calculated resolution data are found in very good agreement for a change, Δv m =-10cm 3 /mol, of the partial molar volume of the two PAH isomers upon transfer from the acetonitrile-water eluent mixture to the silica-C 18 stationary phase. Copyright © 2017 Elsevier B.V. All rights reserved.

Comparative oesophageal cancer risk assessment of hot beverage consumption (coffee, mate and tea): the margin of exposure of PAH vs very hot temperatures.

PubMed

Okaru, Alex O; Rullmann, Anke; Farah, Adriana; Gonzalez de Mejia, Elvira; Stern, Mariana C; Lachenmeier, Dirk W

2018-03-01

Consumption of very hot (> 65 °C) beverages is probably associated with increased risk of oesophageal cancer. First associations were reported for yerba mate and it was initially believed that high content of polycyclic aromatic hydrocarbons (PAH) might explain the risk. Later research on other beverage groups such as tea and coffee, which are also consumed very hot, found associations with increased risk of oesophageal cancer as well. The risk may therefore not be inherent in any compound contained in mate, but due to temperature. The aim of this study was to quantitatively assess the risk of PAH in comparison with the risk of the temperature effect using the margin of exposure (MOE) methodology. The human dietary benzo[a]pyrene (BaP) and PAH4 (sum of benzo[a]pyrene, benzo[a]anthracene, chrysene, and benzo[b]fluoranthene) exposure through consumption of coffee, mate, and tea was estimated. The oesophageal cancer risk assessment for both PAH and temperature was conducted using the MOE approach. Considering differences in the transfer of the PAH from the leaves of mate and tea or from the ground coffee to the infusion, and considering the different preparation methods, exposures may vary considerably. The average individual exposure in μg/kg bw/day arising from consumption of 1 cup (0.2 L) of infusion was highest for mate (2.85E-04 BaP and 7.22E-04 PAH4). The average per capita exposure in μg/kg bw/day was as follows: coffee (4.21E-04 BaP, 4.15E-03 PAH4), mate (4.26E-03 BaP, 2.45E-02 PAH4), and tea (8.03E-04 BaP, 4.98E-03 PAH4). For all individual and population-based exposure scenarios, the average MOE for BaP and PAH4 was > 100,000 independent of beverage type. MOE values in this magnitude are considered as a very low risk. On the contrary, the MOE for the temperature effect was estimated as < 1 for very hot drinking temperatures, corroborating epidemiological observations about a probable oesophageal cancer risk caused by this behaviour. The temperature effect but not PAH exposure may pose an oesophageal cancer risk. Consumer education on risks associated with consumption of 'very hot' beverages and policy measures to threshold serving temperatures should be discussed.

Size distribution of particle-phase molecular markers during a severe winter pollution episode.

PubMed

Kleeman, Michael J; Riddle, Sarah G; Jakober, Chris A

2008-09-01

Airborne particulate matter was collected using filter samplers and cascade impactors in six size fractions below 1.8 microm during a severe winter air pollution event at three sites in the Central Valley of California. The smallest size fraction analyzed was 0.056 < Dp <0.1 microm particle diameter, which accounts for the majority of the mass in the ultrafine (PM0.1) size range. Separate samples were collected during the daytime (10 a.m. to 6 p.m. PST) and nighttime (8 p.m. to 8 a.m. PST) to characterize diurnal patterns. Each sample was extracted with organic solvents and analyzed using gas chromatography mass spectrometry for molecular markers that can be used for size-resolved source apportionment calculations. Colocated impactor and filter measurements were highly correlated (R8 > 0.8) for retene, benzo[ghi]flouranthene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[e]pyrene, benzo[a]pyrene, perylene, indeno[1,2,3-cd]pyrene, benzo[ghi]perylene, coronene, MW302 polycyclic aromatic hydrocarbon (PAHs), 17beta(H)-21alpha(H)-30-norhopane, 17alpha(H)-21beta(H)-hopane, alphabetabeta-20R-C29-ethylcholestane, levoglucosan, and cholesterol. Of these compounds, levoglucosan was present in the highest concentration (60-2080 ng m(-3)) followed by cholesterol (6-35 ng m(-3)), PAHs (2-38 ng m(-3)), and hopanes and steranes (0-2 ng m(-3)). Nighttime concentrations were higher than daytime concentrations in all cases. Organic compound size distributions were generally similar to the total carbon size distributions during the nighttime but showed greater variability during the daytime. This may reflect the dominance of fresh emission in the stagnant surface layer during the evening hours and the presence of aged organic aerosol at the surface during the daytime when the atmosphere is better mixed. All of the measured organic compound particle size distributions had a single mode that peaked somewhere between 0.18 and 0.56 microm, but the width of each distribution varied by compound. Cholesterol generally had the broadest particle size distribution, while benzo[ghi]perylene and 17alpha(H)-21beta(H)-29-norhopane generally had sharper peaks. The difference between the size distributions of the various particle-phase organic compounds reflects the fact that these compounds exist in particles emitted from different sources. The results of the current study will prove useful for size-resolved source apportionment exercises.

[Laser Induced Fluorescence Spectroscopic Analysis of Aromatics from One Ring to Four Rings].

PubMed

Zhang, Peng; Liu, Hai-feng; Yue, Zong-yu; Chen, Bei-ling; Yao, Ming-fa

2015-06-01

In order to distinguish small aromatics preferably, a Nd : YAG Laser was used to supply an excitation laser, which was adjusted to 0.085 J x cm(-2) at 266 nm. Benzene, toluene, naphthalene, phenanthrene, anthracene, pyrene and chrysene were used as the representative of different rings aromatics. The fluorescence emission spectra were researched for each aromatic hydrocarbon and mixtures by Laser induced fluorescence (LIF). Results showed that the rings number determined the fluorescence emission spectra, and the structure with same rings number did not affect the emission fluorescence spectrum ranges. This was due to the fact that the absorption efficiency difference at 266 nm resulted in that the fluorescence intensities of each aromatic hydrocarbon with same rings number were different and the fluorescence intensities difference were more apparently with aromatic ring number increasing. When the absorption efficiency was similar at 266 nm and the concentrations of each aromatic hydrocarbon were same, the fluorescence intensities were increased with aromatic ring number increasing. With aromatic ring number increasing, the fluorescence spectrum and emission peak wavelength were all red-shifted from ultraviolet to visible and the fluorescence spectrum range was also wider as the absorption efficiency was similar. The fluorescence emission spectra from one to four rings could be discriminated in the following wavelengths, 275 to 320 nm, 320 to 375 nm, 375 to 425 nm, 425 to 556 nm, respectively. It can be used for distinguish the type of the polycyclic aromatic hydrocarbons (PAHs) as it exists in single type. As PAHs are usually exist in a variety of different rings number at the same time, the results for each aromatic hydrocarbon may not apply to the aromatic hydrocarbon mixtures. For the aromatic hydrocarbon mixtures, results showed that the one- or two-ring PAHs in mixtures could not be detected by fluorescence as three- or four-ring PAHs existed in mixture. This was caused by radiation energy transfer mechanism, in which the ultraviolet light was lost in mixtures but the fluorescence intensities were increased with the one- or two-ring PAHs adding. When the mixture only contained three- and four-ring PAHs, the fluorescence emission spectrum showed the both characteristics of three- and four-ring PAHs fluorescence. When three- and four-ring PAHs existed in mixtures at the same time, the fluorescence emission spectra were related to each concentration, so the rings number could be discriminated to a certain extent.

Role of snow in the fate of gaseous and particulate exhaust pollutants from gasoline-powered vehicles.

PubMed

Nazarenko, Yevgen; Fournier, Sébastien; Kurien, Uday; Rangel-Alvarado, Rodrigo Benjamin; Nepotchatykh, Oleg; Seers, Patrice; Ariya, Parisa A

2017-04-01

Little is known about pollution in urban snow and how aerosol and gaseous air pollutants interact with the urban snowpack. Here we investigate interactions of exhaust pollution with snow at low ambient temperature using fresh snow in a temperature-controlled chamber. A gasoline-powered engine from a modern light duty vehicle generated the exhaust and was operated in homogeneous and stratified engine regimes. We determined that, within a timescale of 30 min, snow takes up from the exhaust a large mass of organic pollutants and aerosol particles, which were observed by electron microscopy, mass spectrometry and aerosol sizers. Specifically, the concentration of total organic carbon in the exposed snow increased from 0.948 ± 0.009 to 1.828 ± 0.001 mg/L (homogeneous engine regime) and from 0.275 ± 0.005 to 0.514 ± 0.008 mg/L (stratified engine regime). The concentrations of benzene, toluene and 13 out of 16 measured polycyclic aromatic hydrocarbons (PAHs), particularly naphthalene, benz[a]anthracene, chrysene and benzo[a]pyrene in snow increased upon exposure from near the detection limit to 0.529 ± 0.058, 1.840 ± 0.200, 0.176 ± 0.020, 0.020 ± 0.005, 0.025 ± 0.005 and 0.028 ± 0.005 ng/kg, respectively, for the homogeneous regime. After contact with snow, 50-400 nm particles were present with higher relative abundance compared to the smaller nanoparticles (<50 nm), for the homogeneous regime. The lowering of temperature from 25 ± 1 °C to (-8) - (-10) ± 1 °C decreased the median mode diameter of the exhaust aerosol particles from 69 nm to 57 nm (p < 0.1) and addition of snow to 51 nm (p < 0.1) for the stratified regime, but increased it from 20 nm to 27 nm (p < 0.1) for the homogeneous regime. Future studies should focus on cycling of exhaust-derived pollutants between the atmosphere and cryosphere. The role of the effects we discovered should be evaluated as part of assessment of pollutant loads and exposures in regions with a defined winter season. Copyright © 2017 Elsevier Ltd. All rights reserved.

Scavenging ratio of polycyclic aromatic compounds in rain and snow at the Athabasca oil sands region

NASA Astrophysics Data System (ADS)

Zhang, L.; Cheng, I.; Muir, D.; Charland, J.-P.

2014-07-01

Athabasca oil sands industry in northern Alberta, Canada is a possible source of polycyclic aromatic compounds (PACs). Monitored PACs, including polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes, in precipitation and in air at three near-source sites in the Fort MacKay and Fort McMurray area during May 2011 to August 2012 were analyzed to generate a database of scavenging (or washout) ratios (Wt) for PACs scavenged by both snow and rain. Median precipitation and air concentrations of parent PAHs over the May 2011 to August 2012 period ranged from 0.3-184.9 (chrysene) ng L-1 and 0.01-3.9 (naphthalene) ng m-3, respectively, which were comparable to literature values. Higher concentrations in precipitation and air were observed for alkylated PAHs and dibenzothiophenes. The median precipitation and air concentrations were 11.3-646.7 (C3-fluoranthene/pyrene) ng L-1 and 0.21-16.9 (C3-naphthalene) ng m-3, respectively, for alkylated PAHs, and 8.5-530.5 (C4-dibenzothiophene) ng L-1 and 0.13-6.6 (C2-dibenzothiophene) ng m-3 for dibenzothiophenes and their alkylated derivatives. Median Wt over the measurement period were 6100-1.1 × 106 from snow scavenging and 350-2.3 × 105 from rain scavenging depending on the PAC species. Median Wt for parent PAHs were within the range of those observed at other urban and suburban locations. But Wt for acenaphthylene in snow samples was 2-7 times higher. Some individual snow and rain samples exceeded literature values by a factor of 10. Wt for benzo(a)pyrene, dibenz(a,h)anthracene, and benzo(g,h,i)perylene in snow samples had reached 107, which is the maximum for PAH snow scavenging ratios reported in literature. From the analysis of data subsets, Wt for particulate-phase dominant PACs were 14-20 times greater than gas-phase dominant PACs in snow samples and 7-20 times greater than gas-phase dominant PACs in rain samples. Wt from snow scavenging was ∼9 times greater than rain scavenging for particulate-phase dominant PACs and 4-9.6 times greater than rain scavenging for gas-phase dominant PACs. Gas-particle fractions of each PAC, particle size distributions of particulate-phase dominant PACs, and Henry's Law constant of gas-phase dominant PACs explained, to a large extent, the different Wt values among the different PACs and precipitation types. This study verified findings from a previous study of Wang et al. (2014) which suggested that snow scavenging is more efficient than rain scavenging of particles for equivalent precipitation amount, and also provided new knowledge on the scavenging of gas-phase PACs by snow and rain.

Peat fires as source of polycyclic aromatic hydrocarbons in soils

NASA Astrophysics Data System (ADS)

Tsibart, Anna

2013-04-01

Polycyclic aromatic hydrocarbons (PAHs) arrive from pyrogenic sources including volcanism and the combustion of oil products and plant materials. The production of PAHs during the combustion of plant materials was considered in a number of publications, but their results were mainly obtained in laboratory experiments. Insufficient data are available on the hightemperature production of PAHs in environmental objects. For example, natural fires are frequently related to the PAH sources in landscapes, but very little factual data are available on this topic. On Polistovskii reserve (Russia, Pskov region) the soil series were separated depending on the damage to the plants; these series included soils of plots subjected to fires of different intensities, as well as soils of the background plots. The series of organic and organomineral soils significantly differed in their PAH distributions. In this series, the concentration of PAHs in the upper horizons of the peat soils little varied or slightly decreased, but their accumulation occurred at a depth of 5-10 or 10-20 cm in the soils after the fires. For example, in the series of high moor soils, the content of PAHs in the upper horizons remained almost constant; significant differences were observed in the subsurface horizons: from 2 ng/g in the background soil to 70 ng/g after the fire. In the upper horizons of the oligotrophic peat soils under pine forests, the total PAH content also varied only slightly. At the same time, the content of PAHs in the soil series increased from 15 to 90 ng/g with the increasing pyrogenic damage to the plot. No clear trends of the PAH accumulation were recorded in the organomineral soils. The content of PAHs in the soddy-podzolic soil subjected to fire slightly decreased (from 20 to 10 ng/g) compared to the less damaged soil. In peat fires, the access of oxygen to the fire zone is lower than in forest fires. The oxygen deficit acts as a factor of the organic fragments recombination and PAH production; therefore, larger amounts of PAHs are formed in peat fires. In addition, the peat fires occur directly in the soil layer; therefore, larger amounts of the resulting polyarenes remain in the soils of the fire sites. PAHs also can be formed at the heating of organic matter on the areas adjacent to the fire sites. After the combustion of peat in fires, phenanthrene, chrysene, benz[a]pyrene, and tetraphene accumulate in soils. This is mainly the group of 4-nuclear compounds with the participation of 3-nuclear phenanthrene and 5-nuclear benz[a]pyrene. The formation of high-molecular weight compounds like benz[a]pyrene and, in some places, benzo[ghi]perylene is possible during smoldering under a low oxygen supply.

PM10-bound polycyclic aromatic hydrocarbons in Chiang Mai (Thailand): Seasonal variations, source identification, health risk assessment and their relationship to air-mass movement

NASA Astrophysics Data System (ADS)

Wiriya, Wan; Prapamontol, Tippawan; Chantara, Somporn

2013-04-01

This study aims to analyze the seasonal variations of PM10-bound polycyclic aromatic hydrocarbons (PAHs) for an estimation of the human health risk and identification of their possible sources. Ninety four PM10 samples were collected during the dry and wet seasons of 2010 and the dry season of 2011 in Chiang Mai, Thailand, and analyzed for 16 PAHs by gas chromatography-mass spectrometry. The average PM10 concentrations were 104.91 ± 32.70, 13.28 ± 11.34 and 36.24 ± 19.16 μg/m3 in dry season of 2010, wet season of 2010 and dry season of 2011, respectively, while the average 16-PAHs concentrations were 25.87 ± 10.13, 3.12 ± 2.18 and 4.58 ± 2.18 ng/m3, respectively. Correlations of PM10 and total PAHs concentrations were relatively high during all seasons (r > 0.796). In addition, PM10 concentrations were highly correlated with carcinogenic PAHs (r = 0.927) during the dry season of 2010, indicating that carcinogenic compounds were dominant in the particulate PAHs and could be generated from open burning, usually conducted in the dry season. The average PM10 concentration in the dry season of 2011 was much lower than that in 2010 and lower than the annual average of the past 12 years (48.17 μg/m3) because of the unusually high amount of rain precipitation and low open burning activity in this year. According to the accumulated number of hot spots occurring in northern part of Thailand, approximately 19,000 spots were found in the dry season of 2010, while only 6,600 spots were found in the dry season of 2011. It can be seen that larger scale open burning activities were performed in the dry season of 2010 than in the dry season of 2011. The value of toxicity equivalent concentration from PAHs in the dry season of 2010 was higher than that of the wet season of 2010 and the dry season of 2011. This is obviously related to concentrations of PM10 and PAHs. Diagnostic ratio and principal component analysis were used to find out the sources of PM10-bound PAHs. It was found that vehicle emission and biomass burning were the main sources of PM10 and PAHs in this area. The high ratio value of benzo(a)anthracene/chrysene (BaA/CHR) in the dry season of 2010 indicated possible photochemical processes and long distance emissions. Findings on source identification of PM10 and PAHs were found to be relevant to the direction and speed of air mass movement run by backward trajectory.

Chemical (polycyclic aromatic hydrocarbon and heavy metal) levels in contaminated stormwater and sediments from a motorway dry detention pond drainage system.

PubMed

Kamalakkannan, Ragunathan; Zettel, Vic; Goubatchev, Alex; Stead-Dexter, Karen; Ward, Neil I

2004-03-01

Chemical (polycyclic aromatic hydrocarbon - PAH and heavy metal) levels in stormwater and sediment samples collected from the London Orbital (M25) motorway drainage dry detention pond at Oxted, Surrey, UK were determined. Such chemicals are derived from vehicular combustion products and the wear and tear materials deposited onto the motorway surface. Gas chromatography-mass spectrometry (GC-MS) was used for the qualitative and quantitative determination of 16 USEPA priority PAHs in motorway drainage sediments. The GC-MS method, incorporating a solid phase extraction step, provides detection limits ranging from 0.17 to 0.41 mg kg(-1)(dry weight). Almost all of the 16 USEPA listed PAHs were detected. Phenanthrene, fluoranthene, pyrene, benzo(a)anthracene, chrysene, benzo(b)fluoranthene, benzo(a)pyrene and benzo(g,h,i)perylene (PAH numbers 5, 7, 8, 9, 10, 11, 13 and 16) were among the PAHs found at "higher" levels (ranging from 0.3-10.2 mg kg(-1), dry weight) in the sediment samples. PAH levels show little change along the motorway drainage silt trap (facility for reducing the levels of suspended particulate matter in the stormwater). PAH concentrations are considerably higher in the dry detention pond outflow interceptor. Statistical analysis showed that significant correlation coefficients (based on a t-test at the 95% confidence interval) were obtained between those PAHs found at high concentrations over all of the sampling sites. Several PAHs were dispersed beyond the treatment facility and accumulation in the sediment of the deer park resulted in levels ranging from 0.3-1.6 mg kg(-1), dry weight. These PAHs found beyond the treatment facility (in the local farm deer park) may contribute a serious health threat to farm animals or even fish in the aquatic environment. Heavy metal levels (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Cd, Sb and Pb) of the drainage stormwater and sediments were determined by inductively coupled plasma mass spectrometry (ICP-MS), with quality control evaluation using two certified reference materials. Typical detection limits were found to be below 0.1 [micro sign]g l(-1) for stormwater and 0.005 mg kg(-1) for acid digested sediments. Raised heavy metal levels were found throughout the dry detention pond facility and only decrease when the stormwater is diluted following discharge into the river Eden. Statistical analysis also confirms that some significant correlations exist between various heavy metals and PAHs. However, no overall conclusive trend is found indicating that a particular PAH is deposited in sediment relative to a specific heavy metal/s. These results raise some serious concerns about the dispersion and accumulation of chemicals in the sediments of motorway stormwater drainage systems and the need for maintenance and clean-up of contaminated material from such systems.

In vivo formation of mutagens by intraperitoneal administration of polycyclic aromatic hydrocarbons in animals during exposure to nitrogen dioxide.

PubMed

Miyanishi, K; Kinouchi, T; Kataoka, K; Kanoh, T; Ohnishi, Y

1996-07-01

Consumption of fossil fuels has increased indoor and outdoor concentrations of polycyclic aromatic hydrocarbons (PAHs) and nitrogen dioxide (NO2). To study the combined effect of PAH administration and NO2 exposure on mutagenicity of urine from animals we injected 400 mg/kg body wt i.p. one of five kinds of PAH (pyrene, fluoranthene, fluorene, anthracene and chrysene) into ICR mice, Wistar rats, Syrian golden hamsters or Hartley guinea pigs after exposure to 20 p.p.m. NO2 gas for 24 h and then exposed the animals to NO2 gas for an additional 24 h. During the latter 24 h we collected the urine and assayed its mutagenicity with the Ames Salmonella strains after treatment with beta-glucuronidase and arylsulfatase and extraction with dichloromethane. The urine from mice treated with both PAH and NO2 showed high mutagenicity for Salmonella typhimurium strains TA98 and TA100, whereas the urine from mice treated with PAH and air showed almost no mutagenic activity. The mutagenicity was decreased in nitroreductase- and acetyltransferase-deficient strains TA98NR and TA98/1,8-DNP6 respectively. Treatment with a mixture of 20% of each of the five kinds of PAH and NO2 augmented the urinary mutagenicity of mice 1.5-fold. The urine from hamsters treated with pyrene or fluoranthene and NO2 was also highly mutagenic, but that from rats or guinea pigs was not very mutagenic. The mutagenicity was also decreased in strains TA98NR and TA98/1,8-DNP6. These results suggest that the urine contains nitro compounds and that the nitration of PAHs occurs in the body of animals under exposure to NO2 gas. Actually, the nitrated metabolites of pyrene, 1-nitro-6/8-hydroxypyrene and 1-nitro-3-hydroxypyrene, were detected in the urine from mice treated with pyrene under exposure to NO2 gas. To elucidate the mechanism of in vivo nitration, NO2 (20 p.p.m.) was bubbled through 50 mM Tris-HCl buffer (pH 7.4) or dichloromethane solution containing pyrene or 1-hydroxypyrene (10 microg/ml). Pyrene was not nitrated by NO2 in either aqueous or organic solutions. However, 1-hydroxypyrene was changed to nitrohydroxypyrenes by NO2 in the Tris-HCl buffer, but not in the organic solution. Ascorbic acid, alpha-tocopherol, glutathione oleic acid and hemoglobin were found to inhibit the nitration of 1-hydroxypyrene in aqueous solution. The urinary mutagenicity of mice treated with both pyrene and NO2 was also decreased by oral administration of ascorbic acid and alpha-tocopherol. These results suggest that 1-hydroxypyrene is nitrated by an ionic reaction in the animal body after hydroxylation of pyrene in the liver.

Characterization of trace organic compounds associated with aged and diluted sidestream tobacco smoke in a controlled atmosphere—volatile organic compounds and polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Baek, Sung-Ok; Jenkins, Roger A.

In this study, a wide range of volatile organic constituents of aged and diluted sidestream tobacco smoke (ADSS) were determined in a controlled atmosphere, where ADSS is the sole source of target compounds. The ADSS was generated in a 30 m 3 environmental test chamber using a variety of cigarettes, including the Kentucky 1R4F reference cigarette and eight commercial brands, and a total of 24 experimental runs were conducted. Target analytes were divided into three groups, i.e. vapor and particulate phase markers for environmental tobacco smoke (ETS), volatile organic compounds (VOC) including carbonyls, and polycyclic aromatic hydrocarbons (PAH). The VOC samples were collected on triple sorbent traps, and then analyzed by thermal desorption coupled with gas chromatography/mass spectrometry (GC/MS), while the carbonyl compounds were sampled on DNPH cartridges, being analyzed by HPLC. ETS particles in the chamber were collected by high volume sampling, and then used for the determination of PAHs by GC/MS. Among more than 30 target VOCs, acetaldehyde appeared to be the most abundant compound, followed by 2-methyl-1,3-butadiene, and formaldehyde. The results from the chamber study were further used to generate characterized ratios of selected VOCs to 3-ethenyl pyridine (3-EP), a vapor phase ETS marker. The ratios appeared to be in generally good agreement with published values in the literature. This suggests that the characteristic ratios may be useful for quantifying the impact of ETS on the VOC concentrations in 'real world' indoor environments, which are affected by a complex mixture of components from multiple sources. The yields of ETS markers from this study are all slightly lower than those estimated by other studies, while VOC yields are in reasonable agreement in many cases with values in the literature. Among 16 target PAHs, chrysene appeared to be most abundant, followed by benzo(a)anthracene (BaA) and benzo(a)pyrene (BaP). The average contents of BaP and BaA in ADSS particles for the commercial brands were 12.8 and 21.5 μg g -1, respectively. These values are all approximately 1.5-3 times higher than those determined previously by other studies. The average yields of BaP per cigarette were estimated to be 209 and 215 ng for the reference and commercial cigarettes, respectively. Comparison of the PAH data from this study with literature values was complicated by a lack of consistency in cigarette smoke generating methodology among other studies. These data on the cigarette yields of ETS components may provide useful information to studies on the mathematical modeling of indoor air quality regarding tobacco smoke as a source of interest, or to studies on the assessment of human exposure to ETS.

Amelioration of soil PAH and heavy metals by combined application of fly ash and biochar

NASA Astrophysics Data System (ADS)

Masto, Reginald; George, Joshy; Ansari, Md; Ram, Lal

2016-04-01

Generation of electricity through coal combustion produces huge quantities of fly ash. Sustainable disposal and utilization of these fly ash is a major challenge. Fly ash along with other amendments like biochar could be used for amelioration of soil. In this study, fly ash and biochar were used together for amelioration of polycyclic aromatic hydrocarbon (PAH) contaminated soil. Field experiment was conducted to investigate the effects of fly ash and biochar on the amelioration of soil PAH, and the yield of Zea mays. The treatments were control, biochar (4 t/ha), fly ash (4 t/ha), ash + biochar ( 2 + 2 t/ha). Soil samples were collected after the harvest of maize crop and analysed for chemical and biological parameters. Thirteen PAHs were analysed in the postharvest soil samples. Soil PAHs were extracted in a microwave oven at 120 °C using hexane : acetone (1:1) mixture. The extracted solutions were concentrated, cleaned and the 13 PAHs [Acenaphthene (Ace), fluorene (Flr), phenanthrene (Phn), anthracene(Ant), pyrene(Pyr), benz(a)anthracene (BaA), chrysene (Chy), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene, benzo(g,h,i)perylene (BghiP), dibenzo(a,h)anthracene, and indeno(1,2,3-cd)pyrene)(Inp)] were analysed using GC-MS. The mean pH increased from 6.09 in control to 6.64 and 6.58 at biochar and fly ash treated soils, respectively. N content was not affected, whereas addition of biochar alone and in combination with fly ash, has significantly increased the soil organic carbon content. P content was almost double in combined (9.06 mg/kg) treatment as compared to control (4.32 mg/kg). The increase in K due to biochar was 118%, whereas char + ash increased soil K by 64%. Soil heavy metals were decreased: Zn (-48.4%), Ni (-41.4%), Co (-36.9%), Cu (-35.7%), Mn (-34.3%), Cd (-33.2%), and Pb (-30.4%). Soil dehydrogenase activity was significantly increased by ash and biochar treatments and the maximum activity was observed for the combined treatment. Peroxidase, phenol oxidase, and catalase activities were not affected by these treatments. Acid phosphatase activity decreased, whereas alkaline phosphatase activity increased due to biochar and fly ash treatment. Microbial biomass carbon increased significantly (P < 0.05) with biochar (+27.9%), fly ash (19.8%), and char + ash (+27.9%) applications. Maize grain yield was increased by biochar (+11.4%) and char + ash (+28.1%) treatments. The total PAH concentration decreased from 4191 μg/kg in control to 1930 μg/kg in fly ash; 1509 μg/kg in biochar and 1011 μg/kg in ash + char treatments. Among the different PAHs the concentration was higher for BkF, which decreased from 713 μg/kg in control to 139 - 315 μg/kg under different treatments. Overall, combined application of fly ash and biochar was found to be effective in amelioration of soil quality parameters and improving crop yield.

Decline of the Macquarie Marshes ecosystem, Australia, since European arrival recorded by organic geochemical proxies in sediments

NASA Astrophysics Data System (ADS)

Yu, L.; Chivas, A. R.; Garcia, A.; Hu, J.

2011-12-01

The Macquarie Marshes are floodplain wetlands in semi-arid NSW, Australia, and a Ramsar site experiencing accelerated deterioration in the last 50 years due to anthropogenic activities. We investigated environmental changes occurring in the northern and southern marshes using organic geochemical proxies from short cores and surface samples as modern analogues. Some proxies of modern plants (ferns, charophyte, reeds, Eucalyptus) and biota (black swan guano) samples, which are abundant in the Macquarie Marshes, were also analysed for comparison. The proxies analysed include bulk organic carbon and nitrogen (TOC, TN, C/N ratio), carbon and nitrogen isotopes (δ13C, δ15N) and some organic biomarkers (focusing on n-alkanes, sterols and polycylic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs)). TOC values in surface samples range between 2 to 5% depending on the organic input. The TOC and TN curves exhibit similar trends along time, decreasing to only one tenth at the depth of 70 cm (~ 565-752 years old) than those at the surface. The bulk δ13C values of modern samples (less than 50 years old) vary from -23% to -26%, falling within the range of values found in black swan guano(-21.6%) and plants (-27.0 to -31.5%). The calculated C/N ratios range from 10 to 25, and together with δ13C values suggest that the organic matter is mainly derived from terrestrial C3 plants. The contribution of aquatic plants is shown by shifts to higher δ13C values and lower C/N values in the core sections below the 40 cm depth (older than 130 years). Changes in vegetation type are also reflected by n-alkane and sterol biomarkers. In one core from the northern marshes, the temporal variation of (n-C27+C29)/n-C31 ratio indicates that the dominance of grasses has gradually been replaced by higher plants about 130 years ago. Sediments from the floodplain and dry lagoons show a dominant peak in long-chain n-alkanes with strong odd-to-even preference, contributed by emergent aquatic macrophytes and more drought-tolerant plants; while the sediments from permanently inundated watercourses show an additional peak in short-chain n-alkanes contributed by aquatic algae and bacteria. It is also indicated by the sterols that the most abundant sterol is C29 sterol (sitosterol), and the composition of C27 and C28 sterols varies slightly depending on the relative contributions of higher terrestrial plants and microalgae. Particularly, in areas where water-bird colonies were established, a fecal biomarker - coprostanol, is detected. The OCPs (e.g. DDT, DDD, endosulfans) used in cotton farming around the Marshes, and PAHs (e.g. chrysene, benzo[e]pyrene) from fires during drought years, were not found above the detection limit of 0.01 μg/g. The results indicate that the presence of colonial birds and various terrestrial/aquatic plants are registered in the sediments and that the Macquarie Marshes are still pristine regarding pesticides. However, the deterioration of the wetlands since Europeans arrival (~130 years agao) is indicated by increasing terrestrial vegetation and diminishing aquatic biota.

Effects of urbanization and long-term rainfall on the occurrence of organic compounds and trace elements in reservoir sediment cores, streambed sediment, and fish tissue from the Santa Ana River basin, California, 1998

USGS Publications Warehouse

Burton, Carmen A.

2002-01-01

Organcochlorine compounds, semivolatile-organic compounds (SVOC), and trace elements were analyzed in reservoir sediment cores, streambed sediment, and fish tissue in the Santa Ana River Basin as part of the U.S. Geological Survey's National Water-Quality Assessment Program. Three reservoirs were sampled in areas that have different degrees of urbanization. Streambed sediment and fish tissue collected at 12 sites were divided into two groups, urban and nonurban. More organochlorine compounds were detected in reservoir sediment cores, streambed sediment and fish tissue, and at higher concentrations at urban sites than at nonurban sites. At all sites, except West Street Basin, concentrations of organochlorine compounds were lower than the probable-effect concentration (PEC). At the highly urbanized West Street Basin, chlordane and p,p'-DDE exceeded the PEC throughout the historical record. The less stringent threshold-effect concentration (TEC) was exceeded for six compounds at eight sites. Most of the organochlorine compounds detected in streambed sediment and fish tissue were at urban sites on the Santa Ana River as opposed to its tributaries, suggesting accumulation and persistence in the river. More SVOCs were detected in reservoir sediment cores and streambed sediment, and at higher concentrations, at urban sites than at nonurban sites. At all the sites, except West Street Basin, concentrations of SVOCs were lower than the PEC. At West Street Basin, chrysene, pyrene, and total polycyclic-aromatic hydrocarbons exceeded the PEC throughout the historical record. The TEC was exceeded for 10 compounds at 3 sites. Most of the SVOCs were detected in streambed sediment at urban sites on tributaries to the Santa Ana River rather than the mainstem itself. The less frequent occurrence and lower concentrations in the Santa Ana River suggest that SVOCs are less persistent than organochlorine compounds, possibly as a result of volatization, gradation, or dilution. Most trace-element detections in reservoir sediment cores and streambed sediment were at urban sites, and the concentrations were generally higher than at nonurban sites. Lead and zinc exceeded their PECs at West Street Basin throughout the historical record; copper exceeded its PEC at Canyon Lake, an area of urban growth. The TEC was exceeded for 10 compounds at 11 sites. Frequency of detection and concentration did not differ between tributary and Santa Ana River sites, which may be attributed to the fact that trace elements occur naturally. Four trace elements (arsenic, copper, mercury, and selenium) had higher concentrations in fish tissue at nonurban sites than at urban sites. Concentrations decreased over time for organochlorine compounds at all three reservoirs, probably a result of the discontinued use of many of the compounds. Decreasing trends in SVOCs and trace elements were observed at West Street Basin, but increasing trends were observed at Canyon Lake. Concentrations of organochlorine compounds, SVOCs, and trace elements were higher during periods of above average rainfall at both West Street Basin and Canyon Lake.

Water- and Bed-Sediment Quality of Seguchie Creek and Selected Wetlands Tributary to Mille Lacs Lake in Crow Wing County, Minnesota, October 2003 to October 2006

USGS Publications Warehouse

Fallon, James D.; Yaeger, Christine S.

2009-01-01

Mille Lacs Lake and its tributaries, located in east-central Minnesota, are important resources to the public. In addition, many wetlands and lakes that feed Mille Lacs Lake are of high resource quality and vulnerable to degradation. Construction of a new four-lane expansion of U.S. Highway 169 has been planned along the western part of the drainage area of Mille Lacs Lake in Crow Wing County. Concerns exist that the proposed highway could affect the resource quality of surface waters tributary to Mille Lacs Lake. Baseline water- and bed-sediment quality characteristics of surface waters tributary to Mille Lacs Lake were needed prior to the proposed highway construction. The U.S. Geological Survey, in cooperation with the Minnesota Department of Transportation, characterized the water- and bed-sediment quality at selected locations that the proposed route intersects from October 2003 to October 2006. Locations included Seguchie Creek upstream and downstream from the proposed route and three wetlands draining to Mille Lacs Lake. The mean streamflow of Seguchie Creek increased between the two sites: flow at the downstream streamflow-gaging station of 0.22 cubic meter per second was 5.6 percent greater than the mean streamflow at the upstream streamflow-gaging station of 0.21 cubic meter per second. Because of the large amount of storage immediately upstream from both gaging stations, increases in flow were gradual even during intense precipitation. The ranges of most constituent concentrations in water were nearly identical between the two sampling sites on Seguchie Creek. No concentrations exceeded applicable water-quality standards set by the State of Minnesota. Dissolved-oxygen concentrations at the downstream gaging station were less than the daily minimum standard of 4.0 milligrams per liter for 6 of 26 measurements. Constituent loads in Seguchie Creek were greater at the downstream site than the upstream site for all measured, including dissolved chloride (1.7 percent), ammonia plus organic nitrogen (13 percent), total phosphorus (62 percent), and suspended sediment (11 percent) during the study. All constituents had seasonal peaks in spring and fall. The large loads during the fall resulted from unusually large precipitation and streamflow patterns. This caused the two greatest streamflow peaks at both sites to occur during October (2004 and 2005). In Seguchie Creek, bed-sediment concentrations of five metals and trace elements (arsenic, cadmium, chromium, lead, and zinc) exceeded the Interim Sediment Quality Guidelines (ISQG) set by the Canadian Council of Ministers of the Environment. Bed-sediment samples from the upstream site had more exceedances of ISQGs for metals and trace elements than did samples from the downstream site (seven and two exceedances, respectively). Bed-sediment samples from the downstream site had more exceedances of ISQGs (20 exceedances) for semivolatile organic compounds than did samples from the upstream site (8 exceedances), indicating different sources for organic compounds than for metals and trace elements. Concentrations of 11 semivolatile organic compounds exceeded ISQGs: ancenaphthene, acenaphthylene, anthracene, benzo[a]anthracene, benzo[a]pyrene, chrysene, fluoranthene, fluorene, naphthalene, phenanthrene, and pyrene. In bed-sediment samples collected from three wetlands, concentrations of all six metals exceeded ISQGs: arsenic, cadmium, chromium, copper, lead, and zinc. Concentrations of three semivolatile organic compounds exceeded ISQGs: flouranthene, phenanthrene, and pyrene. Results indicate that areas appearing relatively undisturbed and of high resource value can have degraded quality from previous unknown land use.

Heterogeneous ozonation reactions of PAHs and fatty acid methyl esters in biodiesel particulate matter

NASA Astrophysics Data System (ADS)

Kasumba, John; Holmén, Britt A.

2018-02-01

Numerous studies have examined the oxidation of PAHs found in diesel particulate matter (PM) by ozone, but no studies have investigated the ozone oxidation of biodiesel exhaust PM. Fatty acid methyl esters (FAMEs), found in high abundance in biodiesel PM, can potentially alter the kinetics of the reactions between atmospheric oxidants such as ozone and particle-phase PAHs. In this study, the heterogeneous reactivity of 16 EPA PAHs upon 24 h exposure to 0.4 ppm ozone in the presence (PAH + FAMES) and absence (PAH-only) of FAMEs was investigated at room temperature and 50% relative humidity. The ozone-reactivity of the PAHs detected in 20% biodiesel (B20) exhaust PM was also investigated. In the absence of FAMEs, the pseudo-first order ozone reaction rate constant, kO 3 , of PAHs varied from 0.086 ± 0.030 hr-1 (chrysene) to 0.184 ± 0.078 hr-1 (anthracene). In the presence of FAMEs, kO 3 of the PAHs varied between 0.013 ± 0.012 hr-1 (benzo[b]fluoranthene) and 0.168 ± 0.028 hr-1 (benzo[a]pyrene), and with the exception of benzo[a]pyrene, the kO 3 of PAHs were 1.2-8 times lower compared to those obtained during the PAH-only ozone exposure. Only one PAH, benzo[a]pyrene (BaP), did not show a significant change in kO3 with addition of FAMEs. Phenanthrene, fluoranthene, and pyrene, the only PAHs detected in the B20 PM, had kO 3 values about 4 times lower in B20 PM than those obtained when spiked PAHs-only were exposed to ozone. The kO 3 values of phenanthrene and fluoranthene in the B20 PM were 2 times higher than rates obtained when the PAH mix was exposed to ozone in the presence of the FAMEs. In contrast, pyrene's kO 3 in the B20 PM was about 2 times lower than that obtained for the PAH + FAMEs exposure. Observed differences in PAH behavior demonstrate individual PAH heterogeneous reactivity with gas-phase ozone is sensitive to PAH (vapor pressure, solubility/sorption to matrix components, chemical reactivity) as well as substrate properties (PAH and O3 diffusivity in the matrix that may evolve with reaction progress). Saturated FAMEs were not reactive with ozone (kO 3 range = 0.004 ± 0.003 to 0.012 ± 0.026 hr-1), but compared to PAHs, up to two times higher kO 3 was measured for the unsaturated FAMEs (range 0.087 ± 0.015 to 0.329 ± 0.023 hr-1) during PAH + FAMEs exposures. These changes in substrate composition during atmospheric aging would be expected to affect PAH diffusivity and therefore heterogeneous reactivity over time. The factor of 1.2-8 decreased heterogeneous reactivity of PAHs in the presence of the FAMEs mix and the B20 PM matrix suggests that the presence of FAMEs in the diesel fuel supply may lead to increased PAH atmospheric lifetimes and longer range PAH transport. Predictive methods to quantify changes in PAH reactivity with gas-phase oxidants as a function of substrate composition and characteristics (viscosity, polarity, degree of unsaturation) are needed as biodiesel is increasingly present in our diesel engine fuel supply from a variety of feedstocks at different blend ratios.

Measurement of PM and its chemical composition in real-world emissions from non-road and on-road diesel vehicles

NASA Astrophysics Data System (ADS)

Cui, Min; Chen, Yingjun; Feng, Yanli; Li, Cheng; Zheng, Junyu; Tian, Chongguo; Yan, Caiqing; Zheng, Mei

2017-06-01

With the rapid growth in the number of both non-road and on-road diesel vehicles, the adverse effects of particulate matter (PM) and its constituents on air quality and human health have attracted increasing attentions. However, studies on the characteristics of PM and its composition emitted from diesel vehicles are still scarce, especially under real-world driving conditions. In this study, six excavators and five trucks that provided a wide range of emission standards and operation modes were tested, and PM emissions and their constituents - including organic carbon (OC), elemental carbon (EC), water-soluble ions (WSIs), elements, and organic species like polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and hopanes - as well as steranes were analyzed and characterized. The average emission factors for PM (EFPM) from excavator and truck emissions were 829 ± 806 and 498 ± 234 mg kg-1 fuel, respectively. EFPM and PM constituents were significantly affected by fuel quality, operational mode, and emission standards. A significant correlation (R2 = 0. 79, p < 0. 01) was found between EFPM for excavators and the sulfur contents in fuel. The highest average EFPM for working excavators was 904 ± 979 mg kg-1 fuel as a higher engine load required in this mode. From pre-stage 1 to stage 2, the average EFPM for excavators decreased by 58 %. For trucks, the average non-highway EFPM at 548 ± 311 mg kg-1 fuel was higher than the highway EFPM at 497 ± 231 mg kg-1 fuel. Moreover, the reduction rates were 63.5 and 65.6 % when switched from China II and III to China IV standards, respectively. Generally, the PM composition emitted from excavators was dominated by OC (39. 2 ± 21. 0 %) and EC (33. 3 ± 25. 9 %); PM from trucks was dominated by EC (26. 9 ± 20. 8 %), OC (9. 89 ± 12 %), and WSIs (4. 67 ± 5. 74 %). The average OC / EC ratios for idling and working excavators were 3 to 4 times higher than those for moving excavators. Although the EFPM for excavators and trucks was reduced with the constraint of regulations, the element fractions for excavators increased from 0.49 % in pre-stage 1 to 3.03 % in stage 2, and the fraction of WSIs for the China IV truck was 5 times higher than the average value of all other-level trucks. Furthermore, as compared with other diesel vehicles, wide ranges were found for excavators of the ratios of benzo[a]anthracene / (benzo[a]anthracene + chrysene) (0.26-0.86), indeno[1,2,3-cd]pyrene / (indeno[1,2,3-cd]pyrene + benzo[ghi]perylene) (0.20-1.0), and fluoranthene / (fluoranthene + pyrene) (0.24-0.87), which might be a result of the complex characteristics of the excavator operation modes. A comparison of our results with those in the literature revealed that on-board measurement data more accurately reflect actual conditions. Although the fractions of the 16 priority PAHs in PM from the excavator and truck emissions were similar, the equivalent concentrations of total benzo[a]pyrene of excavators were 31 times than that for trucks, implying that more attention should be paid to non-road vehicle emissions.

Concentrations and distribution of manmade organic compounds in the Lake Tahoe Basin, Nevada and California, 1997-99

USGS Publications Warehouse

Lico, Michael S.; Pennington, Nyle

1999-01-01

The U.S. Geological Survey, in cooperation with the Tahoe Regional Planning Agency and the Lahontan Regional Water-Quality Control Board, sampled Lake Tahoe, major tributary streams to Lake Tahoe, and several other lakes in the Lake Tahoe Basin for manmade organic compounds during 1997-99. Gasoline components were found in all samples collected from Lake Tahoe during the summer boating season. Methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene, and xylenes (BTEX) were the commonly detected compounds in these samples. Most samples from tributary streams and lakes with no motorized boating had no detectable concentrations of gasoline components. Motorized boating activity appears to be directly linked in space and time to the occurrence of these gasoline components. Other sources of gasoline components to Lake Tahoe, such as the atmosphere, surface runoff, and subsurface flow, are minor compared to the input by motorized boating. Water sampled from Lake Tahoe during mid-winter, when motorized boating activity is low, had no MTBE and only one sample had any detectable BTEX compounds. Soluble pesticides rarely were detected in water samples from the Lake Tahoe Basin. The only detectable concentrations of these compounds were in samples from Blackwood and Taylor Creeks collected during spring runoff. Concentrations found in these samples were low, in the 1 to 4 nanograms per liter range. Organochlorine compounds were detected in samples collected from semipermeable membrane devices (SPMD's) collected from Lake Tahoe, tributary streams, and Upper Angora Lake. In Lake Tahoe, SPMD samples collected offshore from urbanized areas contained the largest number and highest concentrations of organochlorine compounds. The most commonly detected organochlorine compounds were cis- and trans-chlordane, p, p'-DDE, and hexachlorobenzene. In tributary streams, SPMD samples collected during spring runoff generally had higher combined concentrations of organochlorine compounds than those collected during baseflow conditions. Upper Angora Lake had the fewest number of organochlorine compounds detected of all lake samples. Dioxins and furans were not detected in SPMD samples from two sites in Lake Tahoe or from two tributary streams. The number of polycyclic aromatic hydrocarbon (PAH) compounds and their combined concentrations generally were higher in samples from Lake Tahoe than those from tributary streams. Areas of high-motorized boating activity at Lake Tahoe had the largest number and highest concentrations of PAH's. PAH compounds were detected in samples from SPMD's in four of six tributary streams during spring runoff, all tributary streams during baseflow conditions, and at all lake sites. The most commonly detected PAH's in tributary streams during spring runoff were phenanthrene, fluoranthene, pyrene, and chrysene, and during baseflow conditions were phenanthrene, 1-methylphenanthrene, diethylnaphthalene, and pyrene. Upper Truckee River, which has an urban area in its drainage basin, had the largest number and highest combined concentration of PAH's of all stream samples. Bottom-sediment from Lake Tahoe had detectable concentrations of p-cresol, a phenol, in all but one sample. A sample collected near Chambers Lodge contained phenol at an estimated concentration of 4 micrograms per kilogram (?g/kg). Bottom-sediment samples from tributary streams had no detectable concentrations of organochlorine or PAH compounds. Several compounds were detected in bottom sediment from Upper Angora Lake at high concentrations. These compounds and their concentrations were p, p'-DDD (10 ?g/kg), p, p'-DDE (7.4 ?g/kg), 2,6-dimethylnaphthalene (estimated at 190 ?g/kg), pentachlorophenol (3,000 ?g/kg), and p-cresol (4,400 ?g/kg).

Concentrations of polynuclear aromatic hydrocarbons and inorganic constituents in ambient surface soils, Chicago, Illinois, 2001-02

USGS Publications Warehouse

Kay, Robert T.; Arnold, Terri L.; Cannon, William F.; Graham, David; Morton, Eric; Bienert, Raymond

2003-01-01

Polynuclear aromatic hydrocarbon (PAH) compounds are ubiquitous in ambient surface soils in the city of Chicago, Illinois. PAH concentrations in samples collected in June 2001 and January 2002 were typically in the following order from highest to lowest: fluoranthene, pyrene, benzo(b)fluoranthene, phenanthrene, benzo(a)pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene, dibenzo(a,h)anthracene, and anthracene. Naphthalene, acenaphthene, acenaphthylene, and fluorene were consistently at the lowest concentrations in each sample. Concentrations of the PAH compounds showed variable correlation. Concentrations of PAH compounds with higher molecular weights typically show a higher degree of correlation with other PAH compounds of higher molecular weight, whereas PAH compounds with lower molecular weights tended to show a lower degree of correlation with all other PAH compounds. These differences indicate that high and low molecular-weight PAHs behave differentl y once released into the environment. Concentrations of individual PAH compounds in soils typically varied by at least three orders of magnitude across the city and varied by more than an order of magnitude over a distance of about 1,000 feet. Concentrations of a given PAH in ambient surface soils are affected by a variety of site-specific factors, and may be affected by proximity to industrial areas. Concentrations of a given PAH in ambient surface soils did not appear to be affected the organic carbon content of the soil, proximity to non-industrial land use, or proximity to a roadway. The concentration of the different PAH compounds in ambient surface soils appears to be affected by the propensity for the PAH compound to be in the vapor or particulate phase in the atmosphere. Lower molecular-weight PAH compounds, which are primarily in the vapor phase in the atmosphere, were detected in lower concentrations in the surface soils. Higher molecular-weight PAH compounds, which are present primarily in the particulate phase in the atmosphere, tended to be in higher concentrations in the surface soils. The apparent effect of the PAH phase in the atmosphere on the concentration of a PAH in ambient surface soils indicates that atmospheric settling of particulate matter is an important source of the PAH compounds in ambient surface soils in Chicago. The distribution of PAH compounds within the city was complex. Comparatively high concentrations were detected near Lake Michigan in the northern part of the city, in much of the western part of the city, and in isolated areas in the southern part of the city. Concentrations were lower in much of the northwestern, south-central, southwestern, and far southern parts of the city. The arithmetic mean concentration of arsenic, mercury, calcium, magnesium, phosphorus, copper, molybdenum, zinc, and selenium was from 2 to 6 times higher in ambient surface soils in the city of Chicago than in soils from surrounding agricultural areas. The arithmetic mean concentration of lead in Chicago soils was about 20 times higher. Concentrations of calcium and magnesium above those of surrounding agricultural areas appear to be related to the effects of dolomite bedrock on the chemical composition of the soil. Elevated concentrations of the remaining elements listed above indicate a potential anthropogenic source(s) of these elements in Chicago soils.

Areal distribution and concentration of contaminants of concern in surficial streambed and lakebed sediments, Lake St. Clair and tributaries, Michigan, 1990-2003

USGS Publications Warehouse

Rachol, Cynthia M.; Button, Daniel T.

2006-01-01

As part of the Lake St. Clair Regional Monitoring Project, the U.S. Geological Survey evaluated data collected from surficial streambed and lakebed sediments in the Lake Erie-Lake St. Clair drainages. This study incorporates data collected from 1990 through 2003 and focuses primarily on the U.S. part of the Lake St. Clair Basin, including Lake St. Clair, the St. Clair River, and tributaries to Lake St. Clair. Comparable data from the Canadian part of the study area are included where available. The data are compiled into 4 chemical classes and consist of 21 compounds. The data are compared to effects-based sediment-quality guidelines, where the Threshold Effect Level and Lowest Effect Level represent concentrations below which adverse effects on biota are not expected and the Probable Effect Level and Severe Effect Level represent concentrations above which adverse effects on biota are expected to be frequent.Maps in the report show the spatial distribution of the sampling locations and illustrate the concentrations relative to the selected sediment-quality guidelines. These maps indicate that sediment samples from certain areas routinely had contaminant concentrations greater than the Threshold Effect Concentration or Lowest Effect Level. These locations are the upper reach of the St. Clair River, the main stem and mouth of the Clinton River, Big Beaver Creek, Red Run, and Paint Creek. Maps also indicated areas that routinely contained sediment contaminant concentrations that were greater than the Probable Effect Concentration or Severe Effect Level. These locations include the upper reach of the St. Clair River, the main stem and mouth of the Clinton River, Red Run, within direct tributaries along Lake St. Clair and in marinas within the lake, and within the Clinton River headwaters in Oakland County.Although most samples collected within Lake St. Clair were from sites adjacent to the mouths of its tributaries, samples analyzed for trace-element concentrations were collected throughout the lake. The distribution of trace-element concentrations corresponded well with the results of a two-dimensional hydrodynamic model of flow patterns from the Clinton River into Lake St. Clair. The model was developed independent from the bed sediment analysis described in this report; yet it showed a zone of deposition for outflow from the Clinton River into Lake St. Clair that corresponded well with the spatial distribution of trace-element concentrations. This zone runs along the western shoreline of Lake St. Clair from L'Anse Creuse Bay to St. Clair Shores, Michigan and is reflected in the samples analyzed for mercury and cadmium.Statistical summaries of the concentration data are presented for most contaminants, and selected statistics are compared to effects-based sediment-quality guidelines. Summaries were not computed for dieldrin, chlordane, hexachlorocyclohexane, lindane, and mirex because insufficient data are available for these contaminants. A statistical comparison showed that the median concentration for hexachlorobenzene, anthracene, benz[a]anthracene, chrysene, and pyrene are greater than the Threshold Effect Concentration or Lowest Effect Level.Probable Effect Concentration Quotients provide a mechanism for comparing the concentrations of contaminant mixtures against effects-based biota data. Probable Effect Concentration Quotients were calculated for individual samples and compared to effects-based toxicity ranges. The toxicity-range categories used in this study were nontoxic (quotients < 0.5) and toxic (quotients > 0.5). Of the 546 individual samples for which Probable Effect Concentration Quotients were calculated, 469 (86 percent) were categorized as being nontoxic and 77 (14 percent) were categorized as being toxic. Bed-sediment samples with toxic Probable Effect Concentration Quotients were collected from Paint Creek, Galloway Creek, the main stem of the Clinton River, Big Beaver Creek, Red Run, Clinton River towards the mouth, Lake St. Clair along the western shore, and the St. Clair River near Sarnia.

Laboratory and Ambient Studies of the Products of Gas-Phase Hydroxyl and Nitrate Ion Radical-Initiated Reactions with Selected PAHs

NASA Astrophysics Data System (ADS)

Zimmermann, Kathryn Jean

Nitrated polycyclic aromatic hydrocarbon (nitro-PAH) product distributions from the gas-phase hydroxyl (OH) and nitrate (NO3) radical-initiated reactions with selected PAHs, as well as the heterogeneous reactions of surface-bound PAHs with N2O5 and HNO3, were investigated. Chapter 2 presents formation yields of nitro-PAHs from the gas-phase OH radical-initiated reactions of 1,7- and 2,7-dimethylnaphthalene (DMN) as a function of NO 2 concentration over the range 0.04-0.14 ppmv. The measured formation yields of dimethylnitronaphthalenes (DMNNs) under conditions that the OH-DMN adducts reacted solely with NO2 were 0.252 ± 0.094% for Σ1,7-DMNNs and 0.010 ± 0.005% for Σ2,7-DMNNs. 1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) was the major nitro-isomer formed, with a limiting high-NO 2 concentration yield of 0.212 ± 0.080% and with equal reactions of the 1,7-DMN-OH adduct with NO2 and O2 occurring in air at 60 ± 39 ppbv of NO2, indicating that the OH-DMN adduct reaction with NO2 can be important at NO2 concentrations commonly found in urban atmospheres. Although the yields of the DMNNs are low, ≤0.3%, the DMNN (and ethylnitronaphthalene) profiles from chamber experiments match well with those observed in polluted urban areas under conditions where OH radical-initiated chemistry is dominant, such as Mexico City, Mexico. Chapter 3 examines the nitro-PAH products of gas-phase OH and NO 3 radicals and heterogeneous N2O5 reactions with fluoranthene, pyrene, benz[a]anthracene, chrysene, and triphenylene. Analysis of nitro-PAHs in the NIST diesel particulate SRM (1975) and selected ambient samples are also presented. 2-Nitrofluoranthene (2-NFL) was the most abundant nitro-PAH in Riverside, CA and Mexico City, and the mw 273 nitro-PAHs were observed in lower concentrations. However, in Tokyo, Japan, concentrations of 1- + 2-nitrotriphenylene (NTP) were more similar to those of 2-NFL. Comparing specific nitro-PAH ratios in ambient particulate samples from Tokyo, Mexico City, and Riverside, and in diesel particles with those from chamber experiments confirms the atmospheric formation of 2-NFL and 2-nitropyrene (2-NPY) via gas-phase radical-initiated reactions. Heterogeneous nitration of ambient particle-bound PAHs is investigated in Chapter 4. Ambient particulate samples collected in Beijing, China, and from four sites within the Los Angeles air basin (Los Angeles, Azusa, Riverside, and Banning), along with filter-bound deuterated PAHs, were exposed to a gas-phase equilibrium mixture of N2O5, NO3 radicals, and NO2 in an environmental chamber at ambient pressure and temperature. For the majority of these reactions 1-nitropyrene was the nitro-PAH formed in the greatest amount and was determined to occur heterogeneously (and not in the gas-phase) by using isomer distribution patterns of deuterated nitro-PAHs either formed on filter surfaces or collected from the chamber in the gas-phase. Chapter 5 investigates the contributions of atmospheric formation (OH versus NO3 chemistry) and direct emissions (electrophilic nitration products) to ambient gas-phase and particulate nitro-PAHs sampled in the Los Angeles air basin and Mexico City, Mexico, over several sampling campaigns using a combination of several marker ratios of volatile and semi-volatile nitro-PAHs. Ratios of 2-nitrofluoranthene (2-NFL)/2-nitropyrene (2-NPY), 2-methyl-4-nitronaphthalene (2M4NN)/1-methyl-5-nitronaphthalene (1M5NN), and 2,7-dimethyl-4-nitronaphthalene (2,7DM4NN)/1,7-dimethyl-5-nitronaphthalene (1,7DM5NN) were used to assess the contribution of OH radical chemistry versus NO3 radical chemistry to ambient nitro-PAHs from 50 particle-phase and gas-phase samples. (Abstract shortened by UMI.).

Polycyclic Aromatic Hydrocarbon (pah) In The Bulk Precipitation of The Seine Estuary, France

NASA Astrophysics Data System (ADS)

Motelay-Massei, A.; Ollivon, D.; Garban, B.; Chevreuil, M.

The evolution of industry and the rising of population have resulted in deep changes in the quality of the environment. Nowadays much more often the attention of analysts is focused on the presence of organic pollutants in precipitation, such as polycyclic aromatic hydrocarbons or pesticides. Atmospheric inputs play a significant role in semivolatile chemicals cycling and alter so the hydrological cycle. PAHs are semi- volatile organic contaminants of great environmental concern because of their car- cinogenic properties. PAHs are produced primarily during incomplete combustion of fossil fuels and wood. Major sources of PAHs to urban atmosphere include au- tomobile traffic, home heating, municipal incinerators and industrial emissions. De- spite their production in urban and industrial sites, PAHs occur at high concentra- tions in rural areas due to their persistence and ability to be transported over long distances. The aim of this investigation was to obtain information about occurrence of organic trace components in precipitation in the Seine Estuary. It was also of in- terest to investigate the spatial and temporal variability of PAHs in the bulk (wet and dry) deposition occurring in the estuary region and to estimate PAH deposition flux on watershed (urban, industrial or rural). Precipitation samples were collected at four locations in the Seine Estuary: the first is an industrial site (Le Havre), two are urban sites (Rouen, representative of urban area influenced by heavy traffic and Notre-Dame de Gravenchon, near from an industrial center) and the last one is ru- ral (Evreux). Each of the sites is located close to a meteorological station. Sam- pling is performed weekly since March 2001. In our analytical conditions, "total PAH" includes 15 compounds: naphthalene (NAP), acenaphtene (ACE), phenanthrene (PHE), anthracene (ANT), fluoranthene (FTH), pyrene (PYR), benzo(a)anthracene (BaA), chrysene (CHR), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), dibenz(a,h)anthracene (DahA), benzo(g,h,i)perylene (BghiP) and indeno(1,2,3-cd)pyrene (IcdP). 130 precipitation samples were analyzed from March to October 2001. Analytical results indicated that PAHs were present in pre- cipitation in frequent basis. In spring the concentration of the PAHs varied between 4 ng.L-1 (Rouen, 14-21 May 2001) and 493 ng.L-1 (Le Havre, 14-21 May 2001) and were normally distributed. These values show good agreement with those measured in other sites in Europe. In addition the profile of the compounds was also similar. PHE 1 (18 to 24 %), FTH (18 to 22 %), PYR (10 to 13 %) were find in the highest concen- tration again. NAP contributed as much as 8 % to the total deposition at Le Havre, Rouen and Evreux and as 15 % at Notre-Dame de Gravenchon. This is probably due to relatively high solubility in water of NAP. Clouds arriving at our sites may contain NAP from distant as well as from local sources. The PAHs considered as carcinogenic (BaA, BbF, BkF, BaP, DahA, IcdP) by the International Association for Research on Cancer represent 14 to 25% of total PAHs. Wet deposition rates are also estimated: total fluxes ranged from 11 (Notre-Dame de Gravenchon) to 40 µg.m-2 (Le Havre) quarterly. This study assesses the seasonal and spatial variability in atmospheric de- position fluxes of these contaminants in the Seine Estuary. Spatial influences were observed and indicate both localized and long-range atmospheric source inputs and, indirectly, influence of direction and speed of winds. In addition, fluxes of PAHs seem to follow seasonal patterns, with increasing concentrations during the colder months of the year. These results highlighted the non-negligible contribution of atmospheric deposition to micropollutants supply to the watershed and consequently groundwater. Moreover, these chemical compounds, due to their high stability and residence times, could be used as tracers in the environment. 2