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.

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.

Removal of anthracene and phenanthrene by filamentous fungi capable of cortexolone 11-hydroxylation.

PubMed

Lisowska, K; Długoński, J

1999-01-01

Nine fungal strains showing ability of cortexolone hydroxylation to epicortisol and/or cortisol were screened in this work for anthracene and phenanthrene elimination (250 mg/l). All of the strains (Cylindrocladium simplex IM 2358, C. simplex IM 2358/650, Monosporium olivaceum IM 484, Curvularia lunata IM 2901, C. lunata IM 2901/366, C. tuberculata IM 4417, Cunninghamella elegans IM 1785, C. elegans IM 1785/21Gp, C. elegans IM 1785/10Gi) significantly removed anthracene and phenanthrene. During incubation with anthracene formation of intermediate products was observed. The amount of the main intermediate product, identified as 9, 10-anthraquinone, was not greater than 22.2% of the anthracene introduced to the fungal cultures. C. elegans IM 1785/21Gp was the best degrader of both anthracene and phenanthrene, removing 81.6 and 99.4% of these compounds after 7 days, respectively. Phenanthrene removal by C. elegans IM 1785/21Gp was preceded by PAHs accumulation in mycelium and growth inhibition. Elimination of phenanthrene started after one day of incubation and was related to the fungus growth.

Microbial characterization and hydrocarbon biodegradation potential of natural bilge waste microflora.

PubMed

Olivera, N L; Commendatore, M G; Delgado, O; Esteves, J L

2003-09-01

Shipping operations produce oily wastes that must be managed properly to avoid environmental pollution. The aim of this study was to characterize microorganisms occurring in ship bilge wastes placed in open lagoons and, particularly, to assess their potential to degrade polycyclic aromatic hydrocarbons (PAHs). A first-order kinetic was suitable for describing hydrocarbon biodegradation after 17 days of treatment. The calculated rate constants were 0.0668 and 0.0513 day(-1) with a corresponding half-life of 10.3 and 13.5 days for the aliphatic and aromatic hydrocarbon fractions, respectively. At day 17, PAH removal percentages were: acenaphtylene 100, fluorene 95.2, phenanthrene 93.6, anthracene 70.3, and pyrene 71.5. Methyl phenanthrene removals were lower than that of their parent compound (3-methyl phenanthrene 83.6, 2-methyl phenanthrene 80.8, 1-methyl phenanthrene 77.3, 9-methyl phenanthrene 75.1, and 2,7-dimethyl phenanthrene 76.6). Neither pure cultures nor the microbial community from these wastes showed extracellular biosurfactant production suggesting that the addition of an exogenously produced biosurfactant may be important in enhancing hydrocarbon bioavailability and biodegradation. DNA analysis of bilge waste samples revealed a ubiquitous distribution of the nahAc genotype in the dump pools. Although almost all of the isolates grew on naphthalene as sole carbon source, only some of them yielded nahAc amplification under the experimental conditions used. The variety of PAHs in bilge wastes could support bacteria with multiple degradation pathways and a diversity of catabolic genes divergent from the classical nah-like type.

Application of solid-phase microextraction method to determine bioavailable fraction of PAH in hazardous waste.

PubMed

Jefimova, J; Irha, N; Mägi, R; Kirso, U

2012-10-01

The solid-phase microextraction (SPME) method was developed to determine PAH free dissolved concentration (C(free)) in field leachates from hazardous waste disposal. SPME technique, involving a 100-μm polydimethylsiloxane (PDMS) fiber coupled to GC-MS was optimized for determination of C(free). The following PAH were found in bioavailable form: acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, with C(free) varying between 2.38 and 62.35 ng/L. Conventional solvent extraction was used for measurement of total concentration (C(total)) in the same samples, and ranging from 1.26 to 77.56 μg/L. Determining C(free) of the hydrophobic toxic pollutants could give useful information for risk assessment of the hazardous waste.

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.

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.

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.

Phototoxic effects of PAH and UVA exposure on molecular responses and developmental success in coral larvae.

PubMed

Overmans, Sebastian; Nordborg, Mikaela; Díaz-Rúa, Rubén; Brinkman, Diane L; Negri, Andrew P; Agustí, Susana

2018-05-01

Exposure to polycyclic aromatic carbons (PAHs) poses a growing risk to coral reefs due to increasing shipping and petroleum extraction in tropical waters. Damaging effects of specific PAHs can be further enhanced by the presence of ultraviolet radiation, known as phototoxicity. We tested phototoxic effects of the PAHs anthracene and phenanthrene on larvae of the scleractinian coral Acropora tenuis in the presence and absence of UVA (320-400 nm). Activity of superoxide dismutase (SOD) enzyme was reduced by anthracene while phenanthrene and UVA exposure did not have any effect. Gene expression of MnSod remained constant across all treatments. The genes Catalase, Hsp70 and Hsp90 showed increased expression levels in larvae exposed to anthracene, but not phenanthrene. Gene expression of p53 was upregulated in the presence of UVA, but downregulated when exposed to PAHs. The influence on stress-related biochemical pathways and gene expresson in A. tenuis larvae was considerably greater for anthracene than phenanthrene, and UVA-induced phototoxicity was only evident for anthracene. The combined effects of UVA and PAH exposure on larval survival and metamorphosis paralleled the sub-lethal stress responses, clearly highlighting the interaction of UVA on anthracene toxicity and ultimately the coral's development. Copyright © 2018 The Authors. Published by Elsevier B.V. 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.

Arbuscular mycorrhizal fungal hyphae contribute to the uptake of polycyclic aromatic hydrocarbons by plant roots.

PubMed

Gao, Yanzheng; Cheng, Zhaoxia; Ling, Wanting; Huang, Jing

2010-09-01

The arbuscular mycorrhizal (AM) hyphae-mediated uptake of polycyclic aromatic hydrocarbons (PAHs) by the roots of ryegrass (Lolium multiflorum Lam.) was investigated using three-compartment systems. Glomus mosseae and Glomus etunicatum were chosen, and fluorene and phenanthrene were used as representative PAHs. When roots were grown in un-spiked soils, AM hyphae extended into PAH-spiked soil and clearly absorbed and transported PAHs to roots, resulting in high concentrations of fluorene and phenanthrene in roots. This was further confirmed by the batch equilibration experiment, which revealed that the partition coefficients (K(d)) of tested PAHs by mycorrhizal hyphae were 270-356% greater than those by roots, suggesting the great potential of hyphae to absorb PAHs. Because of fluorene's lower molecular weight and higher water solubility, its translocation by hyphae was greater than that of phenanthrene. These results provide new perspectives on the AM hyphae-mediated uptake by plants of organic contaminants from soil. Copyright 2010 Elsevier Ltd. All rights reserved.

Investigation of hydrophobic contaminants in an urban slough system using passive sampling - Insights from sampling rate calculations

USGS Publications Warehouse

McCarthy, K.

2008-01-01

Semipermeable membrane devices (SPMDs) were deployed in the Columbia Slough, near Portland, Oregon, on three separate occasions to measure the spatial and seasonal distribution of dissolved polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds (OCs) in the slough. Concentrations of PAHs and OCs in SPMDs showed spatial and seasonal differences among sites and indicated that unusually high flows in the spring of 2006 diluted the concentrations of many of the target contaminants. However, the same PAHs - pyrene, fluoranthene, and the alkylated homologues of phenanthrene, anthracene, and fluorene - and OCs - polychlorinated biphenyls, pentachloroanisole, chlorpyrifos, dieldrin, and the metabolites of dichlorodiphenyltrichloroethane (DDT) - predominated throughout the system during all three deployment periods. The data suggest that storm washoff may be a predominant source of PAHs in the slough but that OCs are ubiquitous, entering the slough by a variety of pathways. Comparison of SPMDs deployed on the stream bed with SPMDs deployed in the overlying water column suggests that even for the very hydrophobic compounds investigated, bed sediments may not be a predominant source in this system. Perdeuterated phenanthrene (phenanthrene-d10). spiked at a rate of 2 ??g per SPMD, was shown to be a reliable performance reference compound (PRC) under the conditions of these deployments. Post-deployment concentrations of the PRC revealed differences in sampling conditions among sites and between seasons, but indicate that for SPMDs deployed throughout the main slough channel, differences in sampling rates were small enough to make site-to-site comparisons of SPMD concentrations straightforward. ?? Springer Science+Business Media B.V. 2007.

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.

[Transport and differentiation of polycyclic aromatic hydrocarbons in air from Dashiwei karst Sinkholes in Guangxi, China].

PubMed

Kong, Xiang-Sheng; Qi, Shi-Hua; Sun, Qian; Huang, Bao-Jian

2012-12-01

The typical karst Dashiwei Sinkholes located in Leye County, Guangxi were chosen as the study object. The air samples from the opening of Dashiwei Sinkholes to the underground river profiles were collected by polyurethane foam passive samplers (PUF-PAS), and the meteorological parameters were observed. The 16 PAHs were analyzed using GC-MS. The results showed that the total PAHs concentration in air in Dashiwei Sinkholes ranged from 33.76 ng x d(-1) to 150.86 ng x d(-1), with an average of 80.36 ng x d(-1). The mean concentrations in the cliff, the bottom and the underground river profiles were 67.17, 85.36 and 101.67 ng x d(-1), respectively. The 2-3 rings PAHs (including phenanthrene, anthracene, napnthalene and fluorene) accounted for 87.97% of the total of PAHs. The transport and accumulation processes of PAHs in air in Dashiwei Sinkholes were: the ground to the cliff section to the bottom section and then to the underground river, and the total PAHs concentrations showed an obvious increasing tendency with the decrease in altitude or increase in the length of the underground river. Low molecular weight PAHs compounds (including phenanthrene, anthracene, flourene and fluoranthene) in air went through differentiation at the bottom of the west peak, the bottom of the sinkhole and the underground river. The primary sources of PAHs were pyrogenic sources with atmosphere transport. Ambient temperature was the predominating factor influencing the transport and accumulation of gas phase PAHs in Dashiwei Sinkholes, following by wind speed, wind direction and relative humidity. Relative humidity and the temperature were the predominating factors influencing the differentiation, following by wind speed and wind direction. As a whole, a "cold trapping effect" of POPs was showed obviously in Dashiwei Sinkholes.

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.

Biodegradation of polycyclic hydrocarbons by Phanerochaete chrysosporium.

PubMed

Bumpus, J A

1989-01-01

The ability of the white rot fungus Phanerochaete chrysosporium to degrade polycyclic aromatic hydrocarbons (PAHs) that are present in anthracene oil (a distillation product obtained from coal tar) was demonstrated. Analysis by capillary gas chromatography and high-performance liquid chromatography showed that at least 22 PAHs, including all of the most abundant PAH components present in anthracene oil, underwent 70 to 100% disappearance during 27 days of incubation with nutrient nitrogen-limited cultures of this fungus. Because phenanthrene is the most abundant PAH present in anthracene oil, this PAH was selected for further study. In experiments in which [14C]phenanthrene was incubated with cultures of P. chrysosporium containing anthracene oil for 27 days, it was shown that 7.7% of the recovered radiolabeled carbon originally present in [14C]phenanthrene was metabolized to 14CO2 and 25.2% was recovered from the aqueous fraction, while 56.1 and 11.0% were recovered from the methylene chloride and particulate fractions, respectively. High-performance liquid chromatography of the 14C-labeled material present in the methylene chloride fraction revealed that most (91.9%) of this material was composed of polar metabolites of [14C]phenanthrene. These results suggest that this microorganism may be useful for the decontamination of sites in the environment contaminated with PAHs.

Biodegradation of polycyclic hydrocarbons by Phanerochaete chrysosporium.

PubMed Central

Bumpus, J A

1989-01-01

The ability of the white rot fungus Phanerochaete chrysosporium to degrade polycyclic aromatic hydrocarbons (PAHs) that are present in anthracene oil (a distillation product obtained from coal tar) was demonstrated. Analysis by capillary gas chromatography and high-performance liquid chromatography showed that at least 22 PAHs, including all of the most abundant PAH components present in anthracene oil, underwent 70 to 100% disappearance during 27 days of incubation with nutrient nitrogen-limited cultures of this fungus. Because phenanthrene is the most abundant PAH present in anthracene oil, this PAH was selected for further study. In experiments in which [14C]phenanthrene was incubated with cultures of P. chrysosporium containing anthracene oil for 27 days, it was shown that 7.7% of the recovered radiolabeled carbon originally present in [14C]phenanthrene was metabolized to 14CO2 and 25.2% was recovered from the aqueous fraction, while 56.1 and 11.0% were recovered from the methylene chloride and particulate fractions, respectively. High-performance liquid chromatography of the 14C-labeled material present in the methylene chloride fraction revealed that most (91.9%) of this material was composed of polar metabolites of [14C]phenanthrene. These results suggest that this microorganism may be useful for the decontamination of sites in the environment contaminated with PAHs. PMID:2705768

Biomonitoring of polycyclic aromatic hydrocarbon exposure in pregnant women in Trujillo, Peru — Comparison of different fuel types used for cooking☆

PubMed Central

Adetona, Olorunfemi; Li, Zheng; Sjödin, Andreas; Romanoff, Lovisa C.; Aguilar-Villalobos, Manuel; Needham, Larry L.; Hall, Daniel B.; Cassidy, Brandon E.; Naeher, Luke P.

2016-01-01

Women and children in developing countries are often exposed to high levels of air pollution including polycyclic aromatic hydrocarbons (PAHs), which may negatively impact their health, due to household combustion of biomass fuel for cooking and heating. We compared creatinine adjusted hydroxy-PAH (OH-PAH) concentrations in pregnant women in Trujillo, Peru who cook with wood to levels measured in those who cook with kerosene, liquefied petroleum gas or a combination of fuels. Seventy-nine women were recruited for the study between May and July 2004 in the first trimester of their pregnancy. Urine samples were collected from the subjects in the first, second and third trimesters for OH-PAH analyses. The concentrations of the OH-PAHs were compared across the type of fuel used for cooking and pregnancy trimesters. The relationships between OH-PAHs levels in the first trimester and concurrently measured personal exposures to PM2.5, carbon monoxide and nitrogen dioxide together with their indoor and outdoor air concentrations were also investigated. Women cooking with wood or kerosene had the highest creatinine adjusted OH-PAH concentrations compared with those using gas, coal briquette or a combination of fuels. Concentrations of creatinine adjusted 2-hydroxy-fluorene, 3-hydroxy-fluorene, 1-hydroxy-fluorene, 2-hydroxy-phenanthrene and 4-hydroxy-phenanthrene were significantly higher (p<0.05) in women who used wood or kerosene alone compared with women who used liquefied petroleum gas (LPG), coal briquette or a combination of fuels. An increase in the concentrations of creatinine adjusted 9-hydroxy-fluorene, 1-hydroxy-phenanthrene, 2-hydroxy-phenanthrene, 4-hydroxy-phenanthrene and 1-hydroxy-pyrene in the third trimesters was also observed. Weak positive correlation (Spearman correlation coefficient, ρ<0.4; p<0.05) was observed between all first trimester creatinine adjusted OH-PAHs and indoor (kitchen and living room), and personal 48-h TWA PM2.5. Women who cooked exclusively with wood or kerosene had higher creatinine adjusted OH-PAH levels in their urine samples compared to women who cooked with LPG or coal briquette. PMID:23314038

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

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.

Evidence of polycyclic aromatic hydrocarbon biodegradation in a contaminated aquifer by combined application of in situ and laboratory microcosms using (13)C-labelled target compounds.

PubMed

Bahr, Arne; Fischer, Anko; Vogt, Carsten; Bombach, Petra

2015-02-01

The number of approaches to evaluate the biodegradation of polycyclic aromatic hydrocarbons (PAHs) within contaminated aquifers is limited. Here, we demonstrate the applicability of a novel method based on the combination of in situ and laboratory microcosms using (13)C-labelled PAHs as tracer compounds. The biodegradation of four PAHs (naphthalene, fluorene, phenanthrene, and acenaphthene) was investigated in an oxic aquifer at the site of a former gas plant. In situ biodegradation of naphthalene and fluorene was demonstrated using in situ microcosms (BACTRAP(®)s). BACTRAP(®)s amended with either [(13)C6]-naphthalene or [(13)C5/(13)C6]-fluorene (50:50) were incubated for a period of over two months in two groundwater wells located at the contaminant source and plume fringe, respectively. Amino acids extracted from BACTRAP(®)-grown cells showed significant (13)C-enrichments with (13)C-fractions of up to 30.4% for naphthalene and 3.8% for fluorene, thus providing evidence for the in situ biodegradation and assimilation of those PAHs at the field site. To quantify the mineralisation of PAHs, laboratory microcosms were set up with BACTRAP(®)-grown cells and groundwater. Naphthalene, fluorene, phenanthrene, or acenaphthene were added as (13)C-labelled substrates. (13)C-enrichment of the produced CO2 revealed mineralisation of between 5.9% and 19.7% for fluorene, between 11.1% and 35.1% for acenaphthene, between 14.2% and 33.1% for phenanthrene, and up to 37.0% for naphthalene over a period of 62 days. Observed PAH mineralisation rates ranged between 17 μg L(-1) d(-1) and 1639 μg L(-1) d(-1). The novel approach combining in situ and laboratory microcosms allowed a comprehensive evaluation of PAH biodegradation at the investigated field site, revealing the method's potential for the assessment of PAH degradation within contaminated aquifers. Copyright © 2014 Elsevier Ltd. All rights reserved.

Do nonbonded H--H interactions in phenanthrene stabilize it relative to anthracene? A possible resolution to this question and its implications for ligands such as 2,2'-bipyridyl.

PubMed

Hancock, Robert D; Nikolayenko, Igor V

2012-08-23

The problem of whether interactions between the hydrogen atoms at the 1,10-positions in the "cleft" of the "bent" phenanthrene stabilize the latter molecule thermodynamically relative to "linear" anthracene, or whether the higher stability of phenanthrene is due to a more energetically favorable π-system, is considered. DFT calculations at the X3LYP/cc-pVTZ(-f)++ level of the ground state energies (E) of anthracene, phenanthrene, and the set of five benzoquinolines are reported. In the gas phase, "bent" phenanthrene was computed to be thermodynamically more stable than "linear" anthracene by -28.5 kJ mol(-1). This fact was attributed predominantly to the phenomenon of higher aromatic stabilization of the π-system of phenanthrene relative to anthracene, and not to the stabilizing influence of the nonbonding H--H interactions in its cleft. In fact, these interactions in phenanthrene were shown to be destabilizing. Similar calculations for five benzoquinolines (bzq) indicate that ΔE values vary as: 6,7-bzq (linear) ≤ 2,3-bzq (linear) < 5,6-bzq (bent) ≤ 3,4-bzq (bent) < 7,8-bzq (bent, no H--H nonbonding interactions in cleft), supporting the idea that it is a more stable π-system that favors 7,8-bzq over 2,3-bzq and 6,7-bzq, and that the H--H interactions in the clefts of 3,4-bzq and 5,6-bzq are destabilizing. Intramolecular hydrogen bonding in the cleft of 7,8-bzq plays a secondary role in its stabilization relative 6,7-bzq. The question of whether H--H nonbonded interactions between H atoms at the 3 and 3' positions of 2,2'-bipyridyl (bpy) coordinated to metal ions are stabilizing or destabilizing is then considered. The energy of bpy is scanned as a function of N-C-C-N torsion angle (χ) in the gas-phase, and it is found that the trans form is 32.8 kJ mol(-1) more stable than the cis conformer. A relaxed coordinate scan of energy of bpy in aqueous solution as a function of χ is modeled using the PBF approach, and it is found that the trans conformer is still more stable than the cis, but now only by 5.34 kJ mol(-1). The effect that the latter energy has on the thermodynamic stability of complexes of metal ions with bpy in aqueous solution is discussed.

Polycyclic aromatic hydrocarbons bioaccessibility in seafood: Culinary practices effects on dietary exposure.

PubMed

Dos Santos Fogaça, Fabíola Helena; Soares, Cristina; Oliveira, Marta; Alves, Ricardo N; Maulvault, Ana L; Barbosa, Vera L; Anacleto, Patrícia; Magalhães, João Avelar; Bandarra, Narcisa M; Ramalhosa, Maria João; Morais, Simone; Marques, António

2018-07-01

This work aimed to determine the effect of culinary practices on the contamination level and bioaccessibility of polycyclic aromatic hydrocarbons (PAHs) in seafood. The selected farmed seafood species (marine shrimp, clams and seaweed) were commercially available in Portugal. The mean concentrations of PAHs varied between 0.23 and 51.8 µg kg -1 , with the lowest value being observed in raw shrimp and the highest in dried seaweed. The number of compounds detected in seaweed and clams (naphthalene, acenaphthene, fluorene, phenanthrene, benzo(b)fluoranthene and benzo(j)fluoranthene) were higher than in shrimp (fluorene and pyrene). Among the PAHs measured, fluorene was the predominant one. There was a significant interaction effect between species and culinary treatment (p < 0.05), thus boiled and dried seaweed samples presented the lowest and the highest levels of fluorene (0.13 and 1.8 µg kg -1 ), respectively. The daily intake of PAHs decreased with bioaccessibility, varying from 22% for benzo(k)fluoranthene (in raw clam) to 84% for phenanthrene (in steamed clam). According to the potency equivalent concentrations, screening values and bioaccessibility of PAHs, the consumption of marine shrimp, clam and seaweed is considered as safe for consumers. Copyright © 2018 Elsevier Inc. All rights reserved.

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.

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

Destruction of acenaphthene, fluorene, anthracene and pyrene by a dc gliding arc plasma reactor.

PubMed

Yu, Liang; Tu, Xin; Li, Xiaodong; Wang, Yu; Chi, Yong; Yan, Jianhua

2010-08-15

In this study, four kinds of PAHs (polycyclic aromatic hydrocarbons) i.e. acenaphthene, fluorene, anthracene and pyrene are used as targets for investigation of PAHs treatment process assisted by dc gliding arc discharge. The effects of carrier gas and external resistance on the PAHs decomposition process are discussed. The results indicate that the destruction rate can be achieved to the highest with the carrier gas of oxygen and the external resistance of 50 kOmega independent of type of PAHs. Furthermore, experimental results suggest that destruction energy efficiency of gliding arc plasma would be improved by treating higher concentration pollutants. Based on the analysis of experimental results, possible destruction mechanisms in different gas discharge are discussed. Copyright 2010 Elsevier B.V. All rights reserved.

Recyclable nanoscale zero-valent iron-based magnetic polydopamine coated nanomaterials for the adsorption and removal of phenanthrene and anthracene

NASA Astrophysics Data System (ADS)

Li, Jing; Zhou, Qingxiang; Liu, Yongli; Lei, Man

2017-12-01

In this study, nanoscale zero-valent iron nanoparticles (NZVIs) were coated with silica and polydopamine using a two-step process. The coated nanoparticles were applied as adsorbents for removal of two common polycyclic aromatic hydrocarbons pollutants, phenanthrene (PHE) and anthracene (ANT) from aqueous system. Adsorption kinetics followed a pseudo-second-order model. Isotherms and thermodynamics were investigated and the results indicated that the adsorption process fit best to the Freundlich model and exhibited the characteristics of an exothermal physical adsorption process. Owing to their superparamagnetic characteristics and stability, these adsorbents could be easily collected and recycled for reuse.

Degradation of some representative polycyclic aromatic hydrocarbons by the water-soluble protein extracts from Zea mays L. cv PR32-B10.

PubMed

Barone, Roberto; de Biasi, Margherita-Gabriella; Piccialli, Vincenzo; de Napoli, Lorenzo; Oliviero, Giorgia; Borbone, Nicola; Piccialli, Gennaro

2016-10-01

The ability of the water-soluble protein extracts from Zea mais L. cv. PR32-B10 to degrade some representative polycyclic aromatic hydrocarbons (PAHs), has been evaluated. Surface sterilized seeds of corn (Zea mais L. Pioneer cv. PR32-B10) were hydroponically cultivated in a growth chamber under no-stressful conditions. The water-soluble protein extracts isolated from maize tissues showed peroxidase, polyphenol oxidase and catalase activities. Incubation of the extracts with naphthalene, fluorene, phenanthrene and pyrene, led to formation of oxidized and/or degradation products. GC-MS and TLC monitoring of the processes showed that naphthalene, phenanthrene, fluorene and pyrene underwent 100%, 78%, 92% and 65% oxidative degradation, respectively, after 120 min. The chemical structure of the degradation products were determined by (1)H NMR and ESI-MS spectrometry. Copyright © 2016 Elsevier Ltd. All rights reserved.

CHEMISTRY OF OXIDATION OF POLYCYCLIC AROMATIC HYDROCARBONS BY SOIL PSEUDOMONADS

PubMed Central

Rogoff, Martin H.

1962-01-01

Rogoff, Martin H. (U.S. Bureau of Mines, Pittsburgh, Pa.). Oxidation of polycyclic aromatic hydrocarbons by soil pseudomonads. J. Bacteriol. 83:998–1004. 1962.—Substitution of phenanthrene by a methyl group at the 9-carbon blocks oxidation of the compound by a resting-cell suspension of a phenanthrene-grown soil pseudomonad. When 2-methylphenanthrene is provided, the oxidation rate is considerably higher; 3-methylphenanthrene is oxidized at a rate intermediate between the other two, even though the methyl group is attached to a carbon directly involved in ring splitting. Cells grown on naphthalene or anthracene oxidize phenanthrene at a much lower rate than cells grown with phenanthrene or 2-methylnaphthalene as the source of carbon. Naphthalene-grown cells also absorb less phenanthrene from aqueous solution than do their phenanthrene-grown counterparts. The data are in keeping with the hypothesis that polynuclear aromatic hydrocarbons attach to the relevant bacterial enzymes at carbon-carbon bonds of high electron density (K regions; localized double bonds), and that the ring-splitting reactions then occur at other bonds on the substrate molecule. The actual bond that undergoes fission is determined by the electronic and steric configurations of the enzyme-substrate complex. When linearly arranged aromatic compounds such as naphthalene or anthracene are attacked, attachment to an enzyme and ring splitting may take place on the same ring; angular aromatic compounds such as phenanthrene afford attachment to an enzyme at a bond in a ring other than the one containing the ring-splitting site. PMID:14493381

Hydrous pyrolysis of polycyclic aromatic hydrocarbons and implications for the origin of PAH in hydrothermal petroleum

NASA Technical Reports Server (NTRS)

McCollom, T. M.; Simoneit, B. R.; Shock, E. L.

1999-01-01

Polycyclic aromatic hydrocarbons (PAH) are found at high concentrations in thermally altered organic matter and hydrothermally generated petroleum from sediment-covered seafloor hydro-thermal systems. To better understand the factors controlling the occurrence of PAH in thermally altered environments, the reactivities of two PAH, phenanthrene and anthracene, were investigated in hydrothermal experiments. The compounds were heated with water at 330 degrees C in sealed reaction vessels for durations ranging from 1 to 17 days. Iron oxide and sulfide minerals, formic acid, or sodium for-mate were included in some experiments to vary conditions within the reaction vessel. Phenanthrene was unreactive both in water alone and in the presence of minerals for up to 17 days, while anthracene was partially hydrogenated (5-10%) to di- and tetrahydroanthracene. In the presence of 6-21 vol % formic acid, both phenanthrene and anthracene reacted extensively to form hydrogenated and minor methylated derivatives, with the degree of hydrogenation and methylation increasing with the amount of formic acid. Phenanthrene was slightly hydrogenated in sodium formate solutions. The hydrogenation reactions could be readily reversed; heating a mixture of polysaturated phenanthrenes resulted in extensive dehydrogenation (aromatization) after 3 days at 330 degrees C. While the experiments demonstrate that reaction pathways for the hydrogenation of PAH under hydrothermal conditions exist, the reactions apparently require higher concentrations of H2 than are typical of geologic settings. The experiments provide additional evidence that PAH may be generated in hydrothermal systems from progressive aromatization and dealkylation of biologically derived polycyclic precursors such as steroids and terpenoids. Furthermore, the results indicate that PAH initially present in sediments or formed within hydrothermal systems are resistant to further thermal degradation during hydrothermal alteration.

Benz[a]anthracene Biotransformation and Production of Ring Fission Products by Sphingobium sp. Strain KK22

PubMed Central

Kunihiro, Marie; Ozeki, Yasuhiro; Nogi, Yuichi; Hamamura, Natsuko

2013-01-01

A soil bacterium, designated strain KK22, was isolated from a phenanthrene enrichment culture of a bacterial consortium that grew on diesel fuel, and it was found to biotransform the persistent environmental pollutant and high-molecular-weight polycyclic aromatic hydrocarbon (PAH) benz[a]anthracene. Nearly complete sequencing of the 16S rRNA gene of strain KK22 and phylogenetic analysis revealed that this organism is a new member of the genus Sphingobium. An 8-day time course study that consisted of whole-culture extractions followed by high-performance liquid chromatography (HPLC) analyses with fluorescence detection showed that 80 to 90% biodegradation of 2.5 mg liter−1 benz[a]anthracene had occurred. Biodegradation assays where benz[a]anthracene was supplied in crystalline form (100 mg liter−1) confirmed biodegradation and showed that strain KK22 cells precultured on glucose were equally capable of benz[a]anthracene biotransformation when precultured on glucose plus phenanthrene. Analyses of organic extracts from benz[a]anthracene biodegradation by liquid chromatography negative electrospray ionization tandem mass spectrometry [LC/ESI(−)-MS/MS] revealed 10 products, including two o-hydroxypolyaromatic acids and two hydroxy-naphthoic acids. 1-Hydroxy-2- and 2-hydroxy-3-naphthoic acids were unambiguously identified, and this indicated that oxidation of the benz[a]anthracene molecule occurred via both the linear kata and angular kata ends of the molecule. Other two- and single-aromatic-ring metabolites were also documented, including 3-(2-carboxyvinyl)naphthalene-2-carboxylic acid and salicylic acid, and the proposed pathways for benz[a]anthracene biotransformation by a bacterium were extended. PMID:23686261

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

Recyclable nanoscale zero-valent iron-based magnetic polydopamine coated nanomaterials for the adsorption and removal of phenanthrene and anthracene

PubMed Central

Li, Jing; Zhou, Qingxiang; Liu, Yongli; Lei, Man

2017-01-01

Abstract In this study, nanoscale zero-valent iron nanoparticles (NZVIs) were coated with silica and polydopamine using a two-step process. The coated nanoparticles were applied as adsorbents for removal of two common polycyclic aromatic hydrocarbons pollutants, phenanthrene (PHE) and anthracene (ANT) from aqueous system. Adsorption kinetics followed a pseudo-second-order model. Isotherms and thermodynamics were investigated and the results indicated that the adsorption process fit best to the Freundlich model and exhibited the characteristics of an exothermal physical adsorption process. Owing to their superparamagnetic characteristics and stability, these adsorbents could be easily collected and recycled for reuse. PMID:28179954

JPRS Report, Science & Technology USSR: Physics & Mathematics.

DTIC Science & Technology

1991-01-17

Irregularities on Readings of Local Work Function by Scanning Tunneling Microscope [A.O. Golubok, N.A. Tarasov, et al; PISMA V ZHURNAL TEKHNICHESKOY...constant. The substances tested (anthracene, phenanthrene, naphthacene, triphenylene, p- terphenyl, pentacene , benzo(def)phenanthrene, benzo(ghl...in nucleus-nucleus collisions are analyzed, considering that local thermodynamic equilibrium establishes itself after two or three collisions to be

Microplastics Reduce Short-Term Effects of Environmental Contaminants. Part II: Polyethylene Particles Decrease the Effect of Polycyclic Aromatic Hydrocarbons on Microorganisms.

PubMed

Kleinteich, Julia; Seidensticker, Sven; Marggrander, Nikolaj; Zarfl, Christiane

2018-02-07

Microplastic particles in terrestrial and aquatic ecosystems are currently discussed as an emerging persistent organic pollutant and as acting as a vector for hydrophobic chemicals. Microplastic particles may ultimately deposit and accumulate in soil as well as marine and freshwater sediments where they can be harmful to organisms. In this study, we tested the sensitivity of natural freshwater sediment bacterial communities (by genetic fingerprint) to exposure to microplastics (polyethylene, 2 and 20 mg/g sediment) and microplastics loaded with polycyclic aromatic hydrocarbons (PAHs, phenanthrene and anthracene), using a laboratory-based approach. After two weeks of incubation, the bacterial community composition from an unpolluted river section was altered by high concentrations of microplastics, whereas the community downstream of a wastewater treatment plant remained unchanged. Low microplastic concentrations loaded with phenanthrene or anthracene induced a less pronounced response in the sediment communities compared to the same total amount of phenanthrene or anthracene alone. In addition, biodegradation of the PAHs was reduced. This study shows, that microplastic can affect bacterial community composition in unpolluted freshwater sediments. Moreover, the results indicate that microplastics can serve as a vehicle for hydrophobic pollutants but bioavailability of the latter is reduced by the sorption to microplastics.

Microplastics Reduce Short-Term Effects of Environmental Contaminants. Part II: Polyethylene Particles Decrease the Effect of Polycyclic Aromatic Hydrocarbons on Microorganisms

PubMed Central

Kleinteich, Julia; Marggrander, Nikolaj; Zarfl, Christiane

2018-01-01

Microplastic particles in terrestrial and aquatic ecosystems are currently discussed as an emerging persistent organic pollutant and as acting as a vector for hydrophobic chemicals. Microplastic particles may ultimately deposit and accumulate in soil as well as marine and freshwater sediments where they can be harmful to organisms. In this study, we tested the sensitivity of natural freshwater sediment bacterial communities (by genetic fingerprint) to exposure to microplastics (polyethylene, 2 and 20 mg/g sediment) and microplastics loaded with polycyclic aromatic hydrocarbons (PAHs, phenanthrene and anthracene), using a laboratory-based approach. After two weeks of incubation, the bacterial community composition from an unpolluted river section was altered by high concentrations of microplastics, whereas the community downstream of a wastewater treatment plant remained unchanged. Low microplastic concentrations loaded with phenanthrene or anthracene induced a less pronounced response in the sediment communities compared to the same total amount of phenanthrene or anthracene alone. In addition, biodegradation of the PAHs was reduced. This study shows, that microplastic can affect bacterial community composition in unpolluted freshwater sediments. Moreover, the results indicate that microplastics can serve as a vehicle for hydrophobic pollutants but bioavailability of the latter is reduced by the sorption to microplastics. PMID:29414906

Diversity of metabolic capacities among strains degrading polycyclic aromatic hydrocarbons

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

Bouchez, M.; Besnaienou, B.; Blanchet, D.

1995-12-31

Strains of Pseudomonas and Rhodococcus genera were isolated for their capacity to use, as a sole carbon and energy source, one of the following polycyclic aromatic hydrocarbons (PAHs): naphthalene (NAP), fluorene (FLU), phenanthrene (PHE), anthracene (ANT), fluoranthene (FLT), and pyrene (PYR). The range of PAHs supporting growth of these pure strains was usually restricted, but several other hydrocarbons were used by Rhodococcus sp. All strains could grow on simple organic acids. Maximal specific growth rates ({mu}{sub max}) of all strains on their PAH growth substrates were determined by respirometry. No clear relationships between {mu}{sub max} values and the molecular weightmore » or water solubility of PAHs were apparent, but Pseudomonas sp. exhibited the highest {mu}{sub max} values. Carbon balances for PAH biodegradation were established. Differences between strains were observed, but high mineralization rates and low production of soluble metabolites were obtained for all PAHs. Bacterial biomass represented 16% to 35% of the carbon consumed. Strain diversity was also apparent in the interactions observed in the degradation of a mixture of two PAHs by individual strains, which often involved inhibition of PAH substrate degradation, with or without cometabolization of the second PAH.« less

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

Biodegradation of low and high molecular weight hydrocarbons in petroleum refinery wastewater by a thermophilic bacterial consortium.

PubMed

Pugazhendi, Arulazhagan; Abbad Wazin, Hadeel; Qari, Huda; Basahi, Jalal Mohammad Al-Badry; Godon, Jean Jacques; Dhavamani, Jeyakumar

2017-10-01

Clean-up of contaminated wastewater remains to be a major challenge in petroleum refinery. Here, we describe the capacity of a bacterial consortium enriched from crude oil drilling site in Al-Khobar, Saudi Arabia, to utilize polycyclic aromatic hydrocarbons (PAHs) as sole carbon source at 60°C. The consortium reduced low molecular weight (LMW; naphthalene, phenanthrene, fluorene and anthracene) and high molecular weight (HMW; pyrene, benzo(e)pyrene and benzo(k)fluoranthene) PAH loads of up to 1.5 g/L with removal efficiencies of 90% and 80% within 10 days. PAH biodegradation was verified by the presence of PAH metabolites and evolution of carbon dioxide (90 ± 3%). Biodegradation led to a reduction of the surface tension to 34 ± 1 mN/m thus suggesting biosurfactant production by the consortium. Phylogenetic analysis of the consortium revealed the presence of the thermophilic PAH degrader Pseudomonas aeruginosa strain CEES1 (KU664514) and Bacillus thermosaudia (KU664515) strain CEES2. The consortium was further found to treat petroleum wastewater in continuous stirred tank reactor with 96 ± 2% chemical oxygen demand removal and complete PAH degradation in 24 days.

BIODEGRADATION OF POLYCYCLIC AROMATIC HYDROCARBONS (PAH) FROM CRUDE OIL IN SANDY-BEACH MICROCOSMS.

EPA Science Inventory

Though the lower n-alkanes are considered the most degradable components of crude oil, our experiments with microcosms simulating oiled beaches showed substantial depletion of fluorene, phenanthrene, dibenzothiophene, and other PAH in control treatments consisting of raw seawater...

The degradation of three-ringed polycyclic aromatic hydrocarbons by wood-inhabiting fungus Pleurotus ostreatus and soil-inhabiting fungus Agaricus bisporus.

PubMed

Pozdnyakova, Natalia; Dubrovskaya, Ekaterina; Chernyshova, Marina; Makarov, Oleg; Golubev, Sergey; Balandina, Svetlana; Turkovskaya, Olga

2018-05-01

The degradation of two isomeric three-ringed polycyclic aromatic hydrocarbons by the white rot fungus Pleurotus ostreatus D1 and the litter-decomposing fungus Agaricus bisporus F-8 was studied. Despite some differences, the degradation of phenanthrene and anthracene followed the same scheme, forming quinone metabolites at the first stage. The further fate of these metabolites was determined by the composition of the ligninolytic enzyme complexes of the fungi. The quinone metabolites of phenanthrene and anthracene produced in the presence of only laccase were observed to accumulate, whereas those formed in presence of laccase and versatile peroxidase were metabolized further to form products that were further included in basal metabolism (e.g. phthalic acid). Laccase can catalyze the initial attack on the PAH molecule, which leads to the formation of quinones, and that peroxidase ensures their further oxidation, which eventually leads to PAH mineralization. A. bisporus, which produced only laccase, metabolized phenanthrene and anthracene to give the corresponding quinones as the dominant metabolites. No products of further utilization of these compounds were detected. Thus, the fungi's affiliation with different ecophysiological groups and their cultivation conditions affect the composition and dynamics of production of the ligninolytic enzyme complex and the completeness of PAH utilization. Copyright © 2018 British Mycological Society. Published by Elsevier Ltd. All rights reserved.

A comparative study to evaluate natural attenuation, mycoaugmentation, phytoremediation, and microbial-assisted phytoremediation strategies for the bioremediation of an aged PAH-polluted soil.

PubMed

García-Sánchez, Mercedes; Košnář, Zdeněk; Mercl, Filip; Aranda, Elisabet; Tlustoš, Pavel

2018-01-01

Biological treatments are considered an environmentally option to clean-up polluted soil with polycyclic aromatic hydrocarbons (PAHs). A pot experiment was conducted to comparatively evaluate four different strategies, including natural attenuation (NA), mycoaugmentation (M) by using Crucibulum leave, phytoremediation (P) using maize plants, and microbial-assisted phytoremediation (MAP) for the bioremediation of an aged PAH-polluted soil at 180 days. The P treatment had higher affinity degrading 2-3 and 4 ring compounds than NA and M treatments, respectively. However, M and P treatments were more efficient in regards to naphthalene, indeno[l,2,3-c,d]pyrene and benzo[g,h,i]perylene degradation respect to NA. However, 4, 5-6 rings undergo a strong decline during the microbe-assisted phytoremediation, being the treatment which determined the highest rates of PAHs degradation. Sixteen PAH compounds, except fluorene and dibenzo[a,h]anthracene, were found in maize roots, whereas the naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene were accumulated in the shoots, in both P and MAP treatments. However, higher PAH content in maize biomass was achieved during the MAP treatment respect to P treatment. The bioconversion and translocation factors were less than 1, indicating that phystabilization/phytodegradation processes occurred rather than phytoextraction. The microbial biomass, activity and ergosterol content were significantly boosted in the MAP treatment respect to the other treatments at 180 days. Ours results demonstrated that maize-C. laeve association was the most profitable technique for the treatment of an aged PAH-polluted soil when compared to other bioremediation approaches. Copyright © 2017 Elsevier Inc. All rights reserved.

[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.

Description of Immundisolibacter cernigliae gen. nov., sp. nov., a high-molecular-weight polycyclic aromatic hydrocarbon-degrading bacterium within the class Gammaproteobacteria, and proposal of Immundisolibacterales ord. nov. and Immundisolibacteraceae fam. nov.

PubMed

Corteselli, Elizabeth M; Aitken, Michael D; Singleton, David R

2017-04-01

The bacterial strain TR3.2T was isolated from aerobic bioreactor-treated soil from a polycyclic aromatic hydrocarbon (PAH)-contaminated site in Salisbury, NC, USA. Strain TR3.2T was identified as a member of 'Pyrene Group 2' or 'PG2', a previously uncultivated cluster of organisms associated with the degradation of high-molecular-weight PAHs by stable-isotope probing. Based on its 16S rRNA gene sequence, the strain was classified as a member of the class Gammaproteobacteria but possessed only 90.5 % gene identity to its closest described relative, Methylococcus capsulatus strain Bath. Strain TR3.2T grew on the PAHs pyrene, phenanthrene, anthracene, benz[a]anthracene and fluorene, as well as the azaarene carbazole, and could additionally metabolize a limited number of organic acids. Optimal growth occurred aerobically under mesophilic temperature, neutral pH and low salinity conditions. Strain TR3.2T was catalase and oxidase positive. Predominant fatty acids were C17 : 0 cyclo and C16 : 0. Genomic G+C content of the single chromosome was 67.79 mol% as determined by complete genome sequencing. Due to the high sequence divergence from any cultivated species and its unique physiological properties compared to its closest relatives, strain TR3.2T is proposed as a representative of a novel order, family, genus and species within the class Gammaproteobacteria, for which the name Immundisolibacter cernigliae gen. nov., sp. nov. is proposed. The associated order and family are therefore proposed as Immundisolibacteralesord. nov. and Immundisolibacteraceaefam. nov. The type strain of the species is TR3.2T (=ATCC TSD-58T=DSM 103040T).

Acute photo-induced toxicity and toxicokinetics of single compounds and mixtures of polycyclic aromatic hydrocarbons in zebrafish.

PubMed

Willis, Alison M; Oris, James T

2014-09-01

The present study examined photo-induced toxicity and toxicokinetics for acute exposure to selected polycyclic aromatic hydrocarbons (PAHs) in zebrafish. Photo-enhanced toxicity from co-exposure to ultraviolet (UV) radiation and PAHs enhanced the toxicity and exhibited toxic effects at PAH concentrations orders of magnitude below effects observed in the absence of UV. Because environmental exposure to PAHs is usually in the form of complex mixtures, the present study examined the photo-induced toxicity of both single compounds and mixtures of PAHs. In a sensitive larval life stage of zebrafish, acute photo-induced median lethal concentrations (LC50s) were derived for 4 PAHs (anthracene, pyrene, carbazole, and phenanthrene) to examine the hypothesis that phototoxic (anthracene and pyrene) and nonphototoxic (carbazole and phenanthrene) pathways of mixtures could be predicted from single exposures. Anthracene and pyrene were phototoxic as predicted; however, carbazole exhibited moderate photo-induced toxicity and phenanthrene exhibited weak photo-induced toxicity. The toxicity of each chemical alone was used to compare the toxicity of mixtures in binary, tertiary, and quaternary combinations of these PAHs, and a predictive model for environmental mixtures was generated. The results indicated that the acute toxicity of PAH mixtures was additive in phototoxic scenarios, regardless of the magnitude of photo-enhancement. Based on PAH concentrations found in water and circumstances of high UV dose to aquatic systems, there exists potential risk of photo-induced toxicity to aquatic organisms. © 2014 SETAC.

Oxidative metabolism of phenanthrene and anthracene by soil pseudomonads. The ring-fission mechanism

PubMed Central

Evans, W. C.; Fernley, H. N.; Griffiths, E.

1965-01-01

1. Phenanthrene is oxidatively metabolized by soil pseudomonads through trans-3,4-dihydro-3,4-dihydroxyphenanthrene to 3,4-dihydroxyphenanthrene, which then undergoes cleavage. 2. Some properties of the ring-fission product, cis-4-(1-hydroxynaphth-2-yl)-2-oxobut-3-enoic acid, are described. The Fe2+-dependent oxygenase therefore disrupts the bond between C-4 and the angular C of the phenanthrene nucleus. 3. An enzyme of the aldolase type converts the fission product into 1-hydroxy-2-naphthaldehyde (2-formyl-1-hydroxynaphthalene). An NAD-specific dehydrogenase is also present in the cell-free extract, which oxidizes the aldehyde to 1-hydroxy-2-naphthoic acid. This is then oxidatively decarboxylated to 1,2-dihydroxynaphthalene, thus allowing continuation of metabolism via the naphthalene pathway. 4. Anthracene is similarly metabolized, through 1,2-dihydro-1,2-dihydroxyanthracene to 1,2-dihydroxyanthracene, in which ring-fission occurs to give cis-4-(2-hydroxynaphth-3-yl)-2-oxobut-3-enoic acid. The position of cleavage is again at the bond between the angular C and C-1 of the anthracene nucleus. 5. Enzymes that convert the fission product through 2-hydroxy-3-naphthaldehyde into 2-hydroxy-3-naphthoic acid were demonstrated. The further metabolism of this acid is discussed. 6. The Fe2+-dependent oxygenase responsible for cleavage of all the o-dihydroxyphenol derivatives appears to be catechol 2,3-oxygenase, and is a constitutive enzyme in the Pseudomonas strains used. PMID:14342521

Kinetics of hydrophobic organic contaminant extraction from sediment by granular activated carbon.

PubMed

Rakowska, M I; Kupryianchyk, D; Smit, M P J; Koelmans, A A; Grotenhuis, J T C; Rijnaarts, H H M

2014-03-15

Ex situ solid phase extraction with granular activated carbon (GAC) is a promising technique to remediate contaminated sediments. The methods' efficiency depends on the rate by which contaminants are transferred from the sediment to the surface of GAC. Here, we derive kinetic parameters for extraction of polycyclic aromatic hydrocarbons (PAH) from sediment by GAC, using a first-order multi-compartment kinetic model. The parameters were obtained by modeling sediment-GAC exchange kinetic data following a tiered model calibration approach. First, parameters for PAH desorption from sediment were calibrated using data from systems with 50% (by weight) GAC acting as an infinite sink. Second, the estimated parameters were used as fixed input to obtain GAC uptake kinetic parameters in sediment slurries with 4% GAC, representing the ex situ remediation scenario. PAH uptake rate constants (kGAC) by GAC ranged from 0.44 to 0.0005 d(-1), whereas GAC sorption coefficients (KGAC) ranged from 10(5.57) to 10(8.57) L kg(-1). These values are the first provided for GAC in the presence of sediment and show that ex situ extraction with GAC is sufficiently fast and effective to reduce the risks of the most available PAHs among those studied, such as fluorene, phenanthrene and anthracene. Copyright © 2013 Elsevier Ltd. 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.

Phytoremediation of polycyclic aromatic hydrocarbons (PAH) by cv. Crioula: A Brazilian alfalfa cultivar.

PubMed

Alves, Wilber S; Manoel, Evelin A; Santos, Noemi S; Nunes, Rosane O; Domiciano, Giselli C; Soares, Marcia R

2018-07-03

This work aimed to evaluate the phytoremediation capacity of the alfalfa cultivar Crioula in soils contaminated with polycyclic aromatic hydrocarbons (PAHs), primary pollutants with mutagenic and carcinogenic potential. Alfalfa was grown from seed for 40 days on soil amended with anthracene, pyrene, and phenanthrene. Soil and plant tissue was collected for biometric assay, dry mass analysis, and PAH analysis by liquid chromatography. Increased total PAH concentration was associated with decreases in plant biomass, height, and internode length. The Crioula cultivar had a satisfactory phytoremediation effect, reducing total PAH concentration (300 ppm) in the experimental soil by 85% in 20 days, and by more than 95% in 40 days. The PAH showed a tendency to be removed in the temporal order: phenanthrene before pyrene before anthracene, and the removal ratio was influenced by the initial soil concentration of each PAH.

Effect of Substrate Character on Heterogeneous Ozone Reaction Rate with Individual PAHs and Their Reaction Mixtures

NASA Astrophysics Data System (ADS)

Holmen, B. A.; Stevens, T.

2009-12-01

Vehicle exhaust contains many unregulated chemical compounds that are harmful to human health and the natural environment, including polycyclic aromatic hydrocarbons (PAH), a class of organic compounds derived from fuel combustion that can be carcinogenic and mutagenic. PAHs have been quantified in vehicle-derived ultrafine particles (Dp<100nm), which are more toxic than larger particles and are linked to adverse health problems, including respiratory and cardiac disease. Once emitted into the atmosphere, particle-bound PAHs can undergo “aging” reactions with oxidants, such as ozone, to form more polar species. These polar reaction products include species such as quinones that can be more toxic than the parent PAH compounds. Here, 0.4ppm ozone was reacted over a 24-hour period with the 16 EPA priority PAHs plus coronene adsorbed to (i) a quartz fiber filter and (ii) NIST diesel PM. The difference in the PAH/O3 heterogeneous reaction rate resulting from the two substrates will be discussed. The experiments were completed by spiking a known PAH mixture to the solid, reacting the samples with gas-phase ozone, and determining both PAH loss over time and products formed, using thermal-desorption gas chromatography / mass spectrometry (TD-GC/MS). The individual PAHs anthracene, phenanthrene, and fluorene, adsorbed to a QFF were also separately reacted with 0.4 ppm ozone. A volatilization control and the collection of volatilized PAHs using a Tenax-packed thermal desorption vial completed the mass balance and aided determination parent-product relationships. Heterogeneous reaction products analyzed directly without derivatization indicate the formation of 9,10-anthracenedione, 9H-fluoren-9-one, and (1,1’-biphenyl)-2,2’-dicarboxaldehyde from the reaction of ozone with the PAH mix on a QFF, but only 9,10-anthracenedione was detected for the diesel PM reaction. The implications of these results for aging of diesel particulate in urban environments will be discussed.

Determination of polycyclic aromatic hydrocarbons by four-way parallel factor analysis in presence of humic acid.

PubMed

Yang, Ruifang; Zhao, Nanjing; Xiao, Xue; Yu, Shaohui; Liu, Jianguo; Liu, Wenqing

2016-01-05

There is not effective method to solve the quenching effect of quencher in fluorescence spectra measurement and recognition of polycyclic aromatic hydrocarbons in aquatic environment. In this work, a four-way dataset combined with four-way parallel factor analysis is used to identify and quantify polycyclic aromatic hydrocarbons in the presence of humic acid, a fluorescent quencher and an ubiquitous substance in aquatic system, through modeling the quenching effect of humic acid by decomposing the four-way dataset into four loading matrices corresponding to relative concentration, excitation spectra, emission spectra and fluorescence quantum yield, respectively. It is found that Phenanthrene, pyrene, anthracene and fluorene can be recognized simultaneously with the similarities all above 0.980 between resolved spectra and reference spectra. Moreover, the concentrations of them ranging from 0 to 8μgL(-1) in the test samples prepared with river water could also be predicted successfully with recovery rate of each polycyclic aromatic hydrocarbon between 100% and 120%, which were higher than those of three-way PARAFAC. These results demonstrate that the combination of four-way dataset with four-way parallel factor analysis could be a promising method to recognize the fluorescence spectra of polycyclic aromatic hydrocarbons in the presence of fluorescent quencher from both qualitative and quantitative perspective. Copyright © 2015 Elsevier B.V. All rights reserved.

PAHs in leachates from thermal power plant wastes and ash-based construction materials.

PubMed

Irha, Natalya; Reinik, Janek; Jefimova, Jekaterina; Koroljova, Arina; Raado, Lembi-Merike; Hain, Tiina; Uibu, Mai; Kuusik, Rein

2015-08-01

The focus of the current study is to characterise the leaching behaviour of polycyclic aromatic hydrocarbons (PAHs) from oil shale ashes (OSAs) of pulverised firing (PF) and circulating fluidised-bed (CFB) boilers from Estonian Thermal Power Plant (Estonia) as well as from mortars and concrete based on OSAs. The target substances were 16 PAHs from the EPA priority pollutant list. OSA samples and OSA-based mortars were tested for leaching, according to European standard EN 12457-2 (2002). European standard CEN/TC 15862(2012) for monolithic matter was used for OSA-based concrete. Water extracts were analysed by GC-MS for the concentration of PAHs. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene were detected. Still, the release of PAHs was below the threshold limit value for inert waste. The amount of the finest fraction (particle size <0.045 mm), the content of the Al-Si glass phase and the surface characteristics were the main factors, which could affect the accessibility of PAHs for leaching. The mobility of PAHs from OSA of CFB and PF boilers was 20.2 and 9.9%, respectively. Hardening of OSA-based materials did not lead to the immobilisation of soluble PAHs. Release of PAHs from the monolith samples did not exceed 0.5 μg/m(2). In terms of leaching of PAHs, OSA is safe to be used for construction purposes.

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

Online investigations on ozonation products of pyrene and benz[ a]anthracene particles with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer

NASA Astrophysics Data System (ADS)

Gao, Shaokai; Zhang, Yang; Meng, Junwang; Shu, Jinian

The reaction products of ozone with pyrene and benz[ a]anthracene absorbed on azelaic acid particles under the pseudo-first-order reaction conditions have been investigated with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The pyrene and benz[ a]anthracene particles with the initial concentrations of ˜1 mg m -3 are respectively exposed to ˜22 ppm ozone in a reaction chamber with a volume of ˜180 L. The time-of-flight mass spectra of the particulate ozonides are obtained. The assignments of the mass spectra reveal that 4-carboxy-5-phenanthrene-carboxyaldehyde (71%) and hydroxypyrene (23%) are the main solid state ozonides of pyrene, while 2-(2-formyl)phenyl-3-naphthoic acid (35%), hydroxybenz[ a]anthrone (30%), and benz[ a]anthracene-7,12-dione (18%) are the main solid state ozonides of benz[ a]anthracene. The pathways of the ozonations are proposed in the paper.

Temperature-dependent vibrational spectroscopy to study order-disorder transitions in charge transfer complexes

NASA Astrophysics Data System (ADS)

Isaac, Rohan; Goetz, Katelyn P.; Roberts, Drew; Jurchescu, Oana D.; McNeil, L. E.

2018-02-01

Charge-transfer (CT) complexes are a promising class of materials for the semiconductor industry because of their versatile properties. This class of compounds shows a variety of phase transitions, which are of interest because of their potential impact on the electronic characteristics. Here temperature-dependent vibrational spectroscopy is used to study structural phase transitions in a set of organic CT complexes. Splitting and broadening of infrared-active phonons in the complex formed between pyrene and pyromellitic dianhydride (PMDA) confirm the structural transition is of the order-disorder type and complement previous x-ray diffraction (XRD) results. We show that this technique is a powerful tool to characterize transitions, and apply it to a range of binary CT complexes composed of polyaromatic hyrdocarbons (anthracene, perylene, phenanthrene, pyrene, and stilbene) and PMDA. We extend the understanding of transitions in perylene-PMDA and pyrene-PMDA, and show that there are no order-disorder transitions present in anthracene-PMDA, stilbene-PMDA and phenanthrene-PMDA in the temperature range investigated here.

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.

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.

40 CFR 464.21 - Specialized definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... § 464.21 Specialized definitions. For the purpose of this subpart: (a) Total Toxic Organics (TTO). TTO... comprised of a discrete list of toxic organic pollutants for each process segment where it is regulated, as.... chrysene 77. acenaphthylene 78. anthracene 81. phenanthrene 84. pyrene (5) Mold Cooling (§ 464.25(g) and...

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.

Exchangeable cations-mediated photodegradation of polycyclic aromatic hydrocarbons (PAHs) on smectite surface under visible light.

PubMed

Jia, Hanzhong; Li, Li; Chen, Hongxia; Zhao, Yue; Li, Xiyou; Wang, Chuanyi

2015-04-28

Clay minerals saturated with different exchangeable cations are expected to play various roles in photodegradation of polycyclic aromatic hydrocarbons (PAHs) via direct and/or indirect pathways on clay surfaces. In the present study, anthracene and phenanthrene were selected as molecule probes to investigate the roles of exchangeable cations on their photodegradation under visible light irradiation. For five types of cation-modified smectite clays, the photodegradation rate of anthracene and phenanthrene follows the order: Fe(3+)>Al(3+)>Cu(2+)>Ca(2+)>K(+)>Na(+), which is consistent with the binding energy of cation-π interactions between PAHs and exchangeable cations. The result suggests that PAHs photolysis rate depends on cation-π interactions on clay surfaces. Meanwhile, the deposition of anthracene at the Na(+)-smectite and K(+)-smectite surface favors solar light absorption, resulting in enhanced direct photodecomposition of PAHs. On the other hand, smectite clays saturated with Fe(3+), Al(3+), and Cu(2+) are highly photoreactive and can act as potential catalysts giving rise to oxidative radicals such as O2(-) , which initiate the transformation of PAHs. The present work provides valuable insights into understanding the transformation and fate of PAHs in the natural soil environment and sheds light on the development of technologies for contaminated land remediation. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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.

Biodegradation of polycyclic aromatic hydrocarbons (PAHs) by laccase from Trametes versicolor covalently immobilized on amino-functionalized SBA-15.

PubMed

Bautista, Luis Fernando; Morales, Gabriel; Sanz, Raquel

2015-10-01

A covalent immobilization method based on glutaraldehyde and amino-functionalized SBA-15 supports has been successfully applied to covalently and stably immobilize laccase from Trametes versicolor. The resultant biocatalysts displayed high incorporation yields of enzyme and led to excellent biodegradation rates of selected HPAs models, i.e. naphthalene, phenanthrene and anthracene, in water. The nature of the hydrocarbon chain accompanying the amino group has been shown as determinant for the immobilization as well as for the activity and reusability of the materials. Thus, alkyl moieties displayed higher enzyme loadings than phenyl moieties, being more adequate the larger n-butyl tethering residue likely due to its higher mobility. Using the aminobutyl-based laccase-SBA-15, 82%, 73%, and 55% conversion of naphthalene, phenanthrene and anthracene, respectively, were achieved after 48 h, very close to the values obtained with free laccase under the same reaction conditions. On the other hand, aminopropyl-based laccase-SBA-15 biocatalysts displayed the best reusability properties, retaining higher activity after four repeated uses than the corresponding aminobutyl-based materials. Copyright © 2015 Elsevier Ltd. All rights reserved.

Influence of processing in the prevalence of polycyclic aromatic hydrocarbons in a Portuguese traditional meat product.

PubMed

Roseiro, L C; Gomes, A; Santos, C

2011-06-01

The concentration of 16 polycyclic aromatic hydrocarbons (PAHs) was determined in traditional dry/fermented sausage along distinct stages of processing under two different technological procedures (traditional and modified processes). The influence of product's position in the smoking room, on the variation of contaminants and in their migration dynamics from the outer into the inner part, was also followed up. Raw material mixtures presented expressive total PAH values, 106.17 μg kg(-1) in wet samples and 244.34 μg kg(-1) in dry mater (DM), expressing the frequent fire woods occurred in the regions pigs were extensively reared. Traditional processing produced a higher (p<0.01) total PAH levels comparatively to modified/industrial procedures, with mean values reaching 3237.10 and 1702.85 μg kg(-1) DM, respectively. Both, raw materials and final products, showed PAH profiles with light compounds representing about 99.0% of the total PAHs, mostly accounted by those having two rings (naphthalene-27.5%) or three rings (acenaphtene-16.9%; fluorene-27.1%; phenanthrene-19.5% and anthracene-3.9%). The benzo[a]pyrene (BaP) accumulated in traditional and modified processed products never surpassed the limit of 5 μg kg(-1) established by the EU legislation. PAHs in products hanged in bars closer to heating/smoking source speed up their transfer from the surface/outer portion to the inner part of the product. Copyright © 2011 Elsevier Ltd. All rights reserved.

Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons.

PubMed

Topuz, Fuat; Uyar, Tamer

2017-07-01

Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitousenvironmental contaminants,and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13 C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon. Copyright © 2017 Elsevier Inc. All rights reserved.

Comparison of PAHs uptake by selected Monocotyledones and Dicotyledones from municipal and industrial sewage sludge.

PubMed

Gworek, Barbara; Klimczak, Katarzyna; Kijeńska, Marta; Gozdowski, Dariusz

2016-10-01

The study was focused on two goals: (i) the confirmation of the existence of a general relation between the content of polycyclic aromatic hydrocarbons (PAHs) in sewage sludge and in plants growing in it, regardless of the type and content of sewage sludge, and (ii) if so, the answer to the question whether the uptake of PAHs by plants depends on their type. To realize the set aims, the contents of PAHs in four differentiated plant species were measured, two belonging to the Monocotyledones and two belonging to Dicotyledones group, growing in municipal and industrial sewage sludge in two locations. All the investigations were carried out during the period of 3 years. The results clearly demonstrated that the uptake of PAHs by a plant depended on polyaromatic hydrocarbon concentration in the sewage sludge. The relation between accumulation coefficient of PAHs in plant material vs. the content of PAH in sewage sludge was of exponential character. The results indicate that in case of four- and five-ring PAHs, the root uptake mechanism from soil solution occurs, regardless of the type and origin of sewage sludge and the type of plant. For three-ring PAHs, we can assume for Monocotyledones that the root uptake mechanism occurs because we observe a significant correlation between the content of fluorene, phenanthrene, and anthracene in plant material and in the sewage sludge. For Dicotyledones, the correlation is insignificant, and in this case probably two mechanisms occur-the uptake by roots and by leaves.

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.

Identification of products formed during the heterogeneous nitration and ozonation of polycyclic aromatic hydrocarbons

NASA Astrophysics Data System (ADS)

Cochran, Richard E.; Jeong, Haewoo; Haddadi, Shokouh; Fisseha Derseh, Rebeka; Gowan, Alexandra; Beránek, Josef; Kubátová, Alena

2016-03-01

The 3- and 4-ring polycyclic aromatic hydrocarbons (PAHs) are the most abundant of PAHs in air particulate matter (PM). Thus we have investigated heterogeneous oxidation of 3- and 4-ring PAHs in a small-scale flow reactor using quartz filter as a support. Four representative PAHs, anthracene, phenanthrene, pyrene, and fluoranthene, were exposed to either NO2, O3 or NO2+O3 (NO3/N2O5) with a goal to identify and attempt quantification of major product distribution. A combination of gas chromatography with mass spectrometry (GC-MS) with/without derivatization and liquid chromatography with high resolution MS (LC-HRMS) was used for identification. For the first time, a comprehensive characterization of a broad range of products enabled identifying ketone/diketone, aldehyde, hydroxyl, and carboxylic acid PAH derivatives. Exposure to NO3/N2O5 (formed by reacting NO2 with O3, a more powerful reactant than either O3 or NO2) produced additional compounds not observed with either oxidant alone. Multiple isomers of nitrofluoranthene and, for the first time, nitrophenanthrene were identified. In addition hydroxy-nitro-PAH derivatives were observed for the reaction of anthracene with NO3/N2O5. Monitoring of specific common ions such as those of 176 and 205 m/z attributed to carbonyl phenanthrene and deprotonated phenanthrene ions respectively was shown to be a useful tool for identification of multiple pyrene oxidation products.

Endophytic Burkholderia fungorum DBT1 can improve phytoremediation efficiency of polycyclic aromatic hydrocarbons.

PubMed

Andreolli, Marco; Lampis, Silvia; Poli, Marika; Gullner, Gabor; Biró, Borbala; Vallini, Giovanni

2013-07-01

Burkholderia fungorum DBT1 is a bacterial strain isolated from an oil refinery discharge and capable of transforming dibenzothiophene, phenanthrene, naphthalene, and fluorene. In order to evaluate the influence of a policyclic aromatic hydrocarbon (PAH)-transforming bacterial strain on the phytoremediation of organic contaminants, B. fungorum DBT1 was inoculated into hybrid poplar (Populus deltoides×Populus nigra). The poplar plants were grown for 18-wk with or without naphthalene, phenanthrene, fluorene and dibenzothiophene (488mgkg(-1) soil each) in non-sterile sand-peat substrate. Evidences were gained that B. fungorum DBT1 was present in high concentration in poplar root tissues (2.9-9.5×10(3)CFUg(-1)), while the strain was not detected in stem, leaves and rhizosphere. When poplar was planted in uncontaminated substrate, the infection caused negative effects on biomass index, leaves and stem dry weight, without showing however any disease symptoms. On the other hand, plants inoculated with the strain DBT1 resulted in better tolerance against the toxic effects of PAHs, in terms of root dry weight. Although the presence of plants acted as the main effective treatment for PAH dissipation (82-87%), the inoculum with DBT1 strain lead to the highest PAH abatement (up to 99%). In the present study, an environmental isolate with proper metabolic features was demonstrated to be possibly suitable as a poplar endophyte for improving microbe-assisted phytoremediation in PAH contaminated matrices. Copyright © 2013 Elsevier Ltd. All rights reserved.

Could saponins be used to enhance bioremediation of polycyclic aromatic hydrocarbons in aged-contaminated soils?

PubMed

Davin, Marie; Starren, Amandine; Deleu, Magali; Lognay, Georges; Colinet, Gilles; Fauconnier, Marie-Laure

2018-03-01

Polycyclic aromatic hydrocarbons (PAH) are persistent organic compounds of major concern that tend to accumulate in the environment, threatening ecosystems and health. Brownfields represent an important tank for PAHs and require remediation. Researches to develop bioremediation and phytoremediation techniques are being conducted as alternatives to environmentally aggressive, expensive and often disruptive soil remediation strategies. The objectives of the present study were to investigate the potential of saponins (natural surfactants) as extracting agents and as bioremediation enhancers on an aged-contaminated soil. Two experiments were conducted on a brownfield soil containing 15 PAHs. In a first experiment, soil samples were extracted with saponins solutions (0; 1; 2; 4 and 8 g.L -1 ). In a second experiment conducted in microcosms (28 °C), soil samples were incubated for 14 or 28 days in presence of saponins (0; 2.5 and 5 mg g -1 ). CO 2 emissions were monitored throughout the experiment. After the incubation, dehydrogenase activity was measured as an indicator of microbiological activity and residual PAHs were determined. In both experiments PAHs were determined using High-Performance Liquid Chromatography and Fluorimetric Detection. The 4 g.L -1 saponins solution extracted significantly more acenaphtene, fluorene, phenanthrene, anthracene, and pyrene than water. PAHs remediation was not enhanced in presence of saponins compared to control samples after 28 days. However CO 2 emissions and dehydrogenase activities were significantly more important in presence of saponins, suggesting no toxic effect of these surfactants towards soil microbiota. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

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.

The diversity of PAH-degrading bacteria in a deep-sea water column above the Southwest Indian Ridge.

PubMed

Yuan, Jun; Lai, Qiliang; Sun, Fengqin; Zheng, Tianling; Shao, Zongze

2015-01-01

The bacteria involved in organic pollutant degradation in pelagic deep-sea environments are largely unknown. In this report, the diversity of polycyclic aromatic hydrocarbon (PAH)-degrading bacteria was analyzed in deep-sea water on the Southwest Indian Ridge (SWIR). After enrichment with a PAH mixture (phenanthrene, anthracene, fluoranthene, and pyrene), nine bacterial consortia were obtained from depths of 3946-4746 m. While the consortia degraded all four PAHs when supplied in a mixture, when PAHs were tested individually, only phenanthrene supported growth. Thus, degradation of the PAH mixture reflected a cometabolism of anthracene, fluoranthene, and pyrene with phenanthrene. Further, both culture-dependent and independent methods revealed many new bacteria involved in PAH degradation. Specifically, the alpha and gamma subclasses of Proteobacteria were confirmed as the major groups within the communities. Additionally, Actinobacteria, the CFB group and Firmicutes were detected. Denaturing Gradient Gel Electrophoresis (DGGE) analysis showed that bacteria closely affiliated with Alcanivorax, Novosphingobium, and Rhodovulum occurred most frequently in different PAH-degrading consortia. By using general heterotrophic media, 51 bacteria were isolated from the consortia and of these 34 grew with the PAH mixture as a sole carbon source. Of these, isolates most closely related to Alterierythrobacter, Citricella, Erythrobacter, Idiomarina, Lutibacterium, Maricaulis, Marinobacter, Martelella, Pseudidiomarina, Rhodobacter, Roseovarius, Salipiger, Sphingopyxis, and Stappia were found to be PAH degraders. To the best of our knowledge, this is the first time these bacteria have been identified in this context. In summary, this report revealed significant diversity among the PAH-degrading bacteria in the deep-sea water column. These bacteria may play a role in PAH removal in deep-sea environments.

The diversity of PAH-degrading bacteria in a deep-sea water column above the Southwest Indian Ridge

PubMed Central

Yuan, Jun; Lai, Qiliang; Sun, Fengqin; Zheng, Tianling; Shao, Zongze

2015-01-01

The bacteria involved in organic pollutant degradation in pelagic deep-sea environments are largely unknown. In this report, the diversity of polycyclic aromatic hydrocarbon (PAH)-degrading bacteria was analyzed in deep-sea water on the Southwest Indian Ridge (SWIR). After enrichment with a PAH mixture (phenanthrene, anthracene, fluoranthene, and pyrene), nine bacterial consortia were obtained from depths of 3946–4746 m. While the consortia degraded all four PAHs when supplied in a mixture, when PAHs were tested individually, only phenanthrene supported growth. Thus, degradation of the PAH mixture reflected a cometabolism of anthracene, fluoranthene, and pyrene with phenanthrene. Further, both culture-dependent and independent methods revealed many new bacteria involved in PAH degradation. Specifically, the alpha and gamma subclasses of Proteobacteria were confirmed as the major groups within the communities. Additionally, Actinobacteria, the CFB group and Firmicutes were detected. Denaturing Gradient Gel Electrophoresis (DGGE) analysis showed that bacteria closely affiliated with Alcanivorax, Novosphingobium, and Rhodovulum occurred most frequently in different PAH-degrading consortia. By using general heterotrophic media, 51 bacteria were isolated from the consortia and of these 34 grew with the PAH mixture as a sole carbon source. Of these, isolates most closely related to Alterierythrobacter, Citricella, Erythrobacter, Idiomarina, Lutibacterium, Maricaulis, Marinobacter, Martelella, Pseudidiomarina, Rhodobacter, Roseovarius, Salipiger, Sphingopyxis, and Stappia were found to be PAH degraders. To the best of our knowledge, this is the first time these bacteria have been identified in this context. In summary, this report revealed significant diversity among the PAH-degrading bacteria in the deep-sea water column. These bacteria may play a role in PAH removal in deep-sea environments. PMID:26379634

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 (

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.

Response of microbial activities and diversity to PAHs contamination at coal tar contaminated land

NASA Astrophysics Data System (ADS)

Zhao, Xiaohui; Sun, Yujiao; Ding, Aizhong; Zhang, Dan; Zhang, Dayi

2015-04-01

Coal tar is one of the most hazardous and concerned organic pollutants and the main hazards are polycyclic aromatic hydrocarbons (PAHs). The indigenous microorganisms in soils are capable to degrade PAHs, with essential roles in biochemical process for PAHs natural attenuation. This study investigated 48 soil samples (from 8 depths of 6 boreholes) in Beijing coking and chemistry plant (China) and revealed the correlation between PAHs contamination, soil enzyme activities and microbial community structure, by 16S rRNA denaturing gradient gel electrophoresis (DGGE). At the site, the key contaminants were identified as naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene and anthracene, and the total PAHs concentration ranged from 0.1 to 923.9 mg/kg dry soil. The total PAHs contamination level was positively correlated (p<0.05) with the bacteria count (0.9×107-14.2×107 CFU/mL), catalase activities (0.554-6.230 mL 0.02 M KMnO4/g•h) and dehydrogenase activities (1.9-30.4 TF μg/g•h soil), showing the significant response of microbial population and degrading functions to the organic contamination in soils. The PAHs contamination stimulated the PAHs degrading microbes and promoted their biochemical roles in situ. The positive relationship between bacteria count and dehydrogenase activities (p<0.05) suggested the dominancy of PAHs degrading bacteria in the microbial community. More interestingly, the microbial community deterioration was uncovered via the decline of microbial biodiversity (richness from 16S rRNA DGGE) against total PAHs concentration (p<0.05). Our research described the spatial profiles of PAHs contamination and soil microbial functions at the PAHs heavily contaminated sites, offering deeper understanding on the roles of indigenous microbial community in natural attenuation process.

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.

Laboratory studies to characterize the efficacy of sand capping a coal tar-contaminated sediment.

PubMed

Hyun, Seunghun; Jafvert, Chad T; Lee, Linda S; Rao, P Suresh C

2006-06-01

Placement of a microbial active sand cap on a coal tar-contaminated river sediment has been suggested as a cost effective remediation strategy. This approach assumes that the flux of contaminants from the sediment is sufficiently balanced by oxygen and nutrient fluxes into the sand layer such that microbial activity will reduce contaminant concentrations within the new benthic zone and reduce the contaminant flux to the water column. The dynamics of such a system were evaluated using batch and column studies with microbial communities from tar-contaminated sediment under different aeration and nutrient inputs. In a 30-d batch degradation study on aqueous extracts of coal tar sediment, oxygen and nutrient concentrations were found to be key parameters controlling the degradation rates of polycyclic aromatic hydrocarbons (PAHs). For the five PAHs monitored (naphthalene, fluorene, phenanthrene, anthracene, and pyrene), degradation rates were inversely proportional to molecular size. For the column studies, where three columns were packed with a 20-cm sand layer on the top of a 5 cm of sediment layer, flow was established to sand layers with (1) aerated water, (2) N(2) sparged water, or (3) HgCl(2)-sterilized N(2) sparged water. After steady-state conditions, PAH concentrations in effluents were the lowest in the aerated column, except for pyrene, whose concentration was invariant with all effluents. These laboratory scale studies support that if sufficient aeration can be achieved in the field through either active and passive means, the resulting microbially active sand layer can improve the water quality of the benthic zone and reduce the flux of many, but not all, PAHs to the water column.

Biodegradation of polycyclic aromatic hydrocarbons by Sphingomonas strains isolated from the terrestrial subsurface

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

Shi, T; Fredrickson, Jim K.; Balkwill, David L.

Several strains of Sphingomonas isolated from deep Atlantic coastal plain aquifers at the US Department of Energy Savannah River Site (SRS) near Aiken, SC were shown to degrade a variety of aromatic hydrocarbons in a liquid culture medium. Sphingomonas aromaticivorans strain B0695 was the most versatile of the five strains examined. This strain was able to degrade acenaphthene, anthracene, phenanthrene, 2,3-benzofluorene, 2-methyl naphthalene, 2,3-dimethylnaphthalene, and fluoranthene in the presence of 400 mg l(-1) Tween 80. Studies involving microcosms composed of aquifer sediments showed that S. aromaticivorans B0695 could degrade phenanthrene effectively in sterile sediment and could enhance the rate atmore » which this compound was degraded in nonsterile sediment. These findings indicate that it may be feasible to carry out (or, at least, to enhance) in situ bioremediation of phenanthrene-contaminated soils and subsurface environments with S. aromaticivorans B0695. In contrast, stra in B0695 was unable to degrade fluoranthene in microcosms containing aquifer sediments, even though it readily degraded this polynuclear aromatic hydrocarbon (PAH) in a defined liquid growth medium.« less

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

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.

A Free-Radical Pathway to Hydrogenated Phenanthrene in Molecular Clouds-Low Temperature Growth of Polycyclic Aromatic Hydrocarbons.

PubMed

Thomas, Aaron M; Lucas, Michael; Yang, Tao; Kaiser, Ralf I; Fuentes, Luis; Belisario-Lara, Daniel; Mebel, Alexander M

2017-08-05

The hydrogen-abstraction/acetylene-addition mechanism has been fundamental to unravelling the synthesis of polycyclic aromatic hydrocarbons (PAHs) detected in combustion flames and carbonaceous meteorites like Orgueil and Murchison. However, the fundamental reaction pathways accounting for the synthesis of complex PAHs, such as the tricyclic anthracene and phenanthrene along with their dihydrogenated counterparts, remain elusive to date. By investigating the hitherto unknown chemistry of the 1-naphthyl radical with 1,3-butadiene, we reveal a facile barrierless synthesis of dihydrophenanthrene adaptable to low temperatures. These aryl-type radical additions to conjugated hydrocarbons via resonantly stabilized free-radical intermediates defy conventional wisdom that PAH growth is predominantly a high-temperature phenomenon and thus may represent an overlooked path to PAHs as complex as coronene and corannulene in cold regions of the interstellar medium like in the Taurus Molecular Cloud. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct observation of organic contaminant uptake, storage, and metabolism within plant roots.

PubMed

Wild, Edward; Dent, John; Thomas, Gareth O; Jones, Kevin C

2005-05-15

Two-photon excitation microscopy (TPEM) is used to visualize and track the uptake and movement of anthracene and phenanthrene from a contaminated growth medium into living unmodified roots of maize and wheat over a 56-day period. The degradation of anthracene was also directly observed within the cortex cells of both species. The power of this technique is that neither the plant nor the compound require altering (staining or sectioning) to visualize them, meaning they are in their natural form throughout the experiment. Initially both compounds bound to the epidermis along the zone of elongation, passing through the epidermal cells to reach the cortex within the root hair, and branching zones of the root. The PAHs entered the epidermis radially; however, once within the cortex cells this movement was dominated by slow lateral movement of both compounds toward the shoot. Highly focused "streams" of compound were observed to form over time; zones where phenanthrene concentrated extended up to 1500 microm in length over a 56-day period, for example, passing through several adjoining cells, and were detectable in cell walls and cell vacuoles. Radial movement was not observed to extend beyond the cortex cells to reach the vascular tissues of the plant. The longitudinal movement of both compounds was not observed to extend beyond the root base into the stem or vegetative parts of the plant. The lateral movement of both compounds within the cortex cells was dominated by movement within the cell walls, suggesting apoplastic flow through multiple cell walls, but with a low level of symplastic movement to transport compound into the cellular vacuoles. Degradation of anthracene to the partial breakdown products anthrone, anthraquinone, and hydroxyanthraquinone was observed directly in the zones of root elongation and branching. The technique and observations have important applications to the fields of agrochemistry and phytoremediation.

Syntheses and Chemosensory of Anthracene and Phenanthrene Bisimide Derivatives

NASA Technical Reports Server (NTRS)

Bogusz, Zachary A.

2004-01-01

As the present technology of biochemical weapons advances, it is essential for science to attempt to prepare our nation for such an occurrence. Various areas of current research are devoted to precautionary measures and potential antidotes for national security. A practical application of these precautions would be the development of a chemical capable of detecting harmful gas. The benefits of being capable to synthesis a chemical compound that would warn and identify potentially deadly gases would ensure a higher level of safety. The chemicals in question can be generalized as bisimide anthracene derivatives. The idea behind these compounds is that in the presence of certain nerve gases, the compound will actually fluoresce, giving an indication that there is a strong likelihood of the presence of a nerve gas and ensure the proper precautionary measures are taken. The fluorescence is due to the quenching of an electric proton transfer within the structure of the molecule. The system proves to be very unique on account of the fact that the fluorescence can be "turned off" by reducing the system. By utilizing the synthesis designed by Dr. Faysal Ilhan, four distinct compounds can be synthesized through photochemical reactions involving para- and ortho- diketones. The photochemistry involved is very modem and much research is being devoted to fully understanding the possibilities and alternative applications of such materials. and meta-nitro anthracene bisimide (ABI-NO2), the amine of each (ABI-NH2), a para- and meta-nitro phenanthrene bisimjde (PBI-NO2), and the amine of each (PBI-NH2). Upon synthesizing these distinct compounds, I must then purify and analyze them in order to obtain any relevant trends, behaviors, and characteristics. The chemical composition analyses that will be conducted are the procedures taken by Dr. Daniel Tyson on previous experiments. The results generated from the data will point further research in the correct direction and hopefully provide enough information to possibly create a stepping-stone for a brand new area in an unexplored frontier of chemistry.

A new liquid chromatography-tandem mass spectrometry method using atmospheric pressure photo ionization for the simultaneous determination of azaarenes and azaarones in Dutch river sediments.

PubMed

Brulik, Jan; Simek, Zdenek; de Voogt, Pim

2013-06-14

A new method for the analysis of azaarenes and their degradation products (azaarones) was developed, optimized and validated using liquid chromatography coupled with atmospheric pressure photo ionization tandem mass spectrometric detection (LC-APPI/MS/MS). Seventeen compounds including 4 PAHs (naphthalene, anthracene, phenanthrene, benz[a]anthracene), 7 azaarenes (quinoline, acridine, phenanthridine, 5,6-benzoquinoline and 7,8-benzoquinoline, benzo[a]acridine, benzo[c]acridine), and 6 azaarones (2-OH-quinoline, 4-OH-quinoline, 5-OH-quinoline, 6-OH-quinoline, 9(10H)-acridone, 6(5H)phenanthridinone) were analyzed in sediment samples from Dutch rivers. All compounds were analyzed simultaneously in multi reaction monitoring (MRM) mode. Soxhlet extraction was used for the extraction of analytes from sediments. The limits of quantification of azaarenes and azaarones varied from 0.21 to 1.12μg/l and from 0.23 to 1.58μg/l, respectively. The limits of quantification for PAHs varied from 32 to 769μg/l. Matrix-independent recoveries of sediment samples were in the range 85-110%; matrix-dependent recoveries were in the range 73-148%, respectively. The method was tested on real sediment samples and the results were compared with a previous study in which GC/MS/MS was used for the simultaneous measurement of azaarenes and azaarones. 4-, 5- and 6-OH-quinolines and naphthalene, anthracene and phenanthrene were not present or below detection limits in some samples. All other analytes were present in samples in the concentration range 0.2-1200ng/g (dw). To our knowledge, this is the first report showing the possibility of measurement non-polar polyaromatic hydrocarbons together with polar azaarenes and their degradation products azaarones simultaneously with sufficient sensitivity and accuracy using LC/MS/MS. Copyright © 2013 Elsevier B.V. All rights reserved.

Impacts of UV radiation and photomodification on the toxicity of PAHs to the higher plant Lemna gibba (duckweed)

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

Xiaodong Huang; Dixon, D.G.; Greenberg, B.M.

1993-06-01

The toxicity of polycyclic aromatic hydrocarbons (PAHs) can be enhanced by both biotic and abiotic processes. This is exemplified by light, which, by virtue of the extensive [pi]-orbital systems of PAHs, can be a major factor in PAH toxicity. Light activation of PAHs is known to occur via photosensitization reactions and potentially by photomodification of the chemicals to more toxic species. To examine the modes of PAH action in the light and determine if the photomodified compounds are hazardous, the authors investigated the photoinduced toxicity of anthracene, phenanthrene and benzo[a]pyrene to the aquatic higher plant Lemna gibba (a duckweed). Toxicitymore » end points were inhibition of growth and extent of chlorosis. Light did indeed activated the phytotoxicity of PAHs, with UV radiation more effective than visible light. Dose-response curves based on chemical concentration and light intensity revealed the order of phytotoxic strength to be anthracene > phenanthrene > benzo[a]pyrene. To explore whether photomodified PAHs were contributing to toxicity, the chemicals were irradiated before toxicity testing. The rates of photomodification of the three PAHs were rapid, and the relative velocities were coincident with the order of toxic strength. Furthermore, the photomodified PAHs were more hazardous to Lemna than the intact compounds. Because interpretations of the potential impacts of PAHs in the environment are based mostly on measurements of the structurally intact chemicals, the severity of PAH hazards is possibly underestimated.« less

Multiple stress effects on marine planktonic organisms: Influence of temperature on the toxicity of polycyclic aromatic hydrocarbons to Tetraselmis chuii

NASA Astrophysics Data System (ADS)

Vieira, L. R.; Guilhermino, L.

2012-08-01

In the present context of global warming and increasing long-range transport of oil and goods by sea potentially resulting in oil spills, more knowledge on the toxicological interactions between temperature and oil components on marine organisms is urgently needed. Therefore, the effects of temperature increase on the toxicity of three polycyclic aromatic hydrocarbons (PAH; anthracene, phenanthrene and naphthalene) to the marine planktonic algae Tetraselmis chuii were investigated under laboratory conditions. T. chuii cultures were exposed for 96 h to different concentrations of each of the test substances at both 20 and 25 °C. Effect criterion was the inhibition of culture growth assessed at 24 h intervals. All the PAHs significantly reduced T. chuii growth after 96 h of exposure with 20% inhibition concentrations between 0.052 and 1.124 mg L- 1 at 20 °C, and between 0.048 and 0.831 mg L- 1 at 25 °C. At both temperatures, the ranking, in order of decreasing toxicity based on the 50% inhibition concentration, was phenanthrene > naphthalene > anthracene. The increase of temperature by 5 °C significantly increased the toxicity of all the PAHs tested. These findings highlight the importance of considering temperature variation in the ecological risk assessment of oil and other chemical spills in the marine environment, and the need of more research on the toxic effects of multiple stressors on marine organisms.

Quantifying the equilibrium partitioning of substituted polycyclic aromatic hydrocarbons in aerosols and clouds using COSMOtherm.

PubMed

Awonaike, Boluwatife; Wang, Chen; Goss, Kai-Uwe; Wania, Frank

2017-03-22

Functional groups attached to polycyclic aromatic hydrocarbons (PAHs) can significantly modify the environmental fate of the parent compound. Equilibrium partition coefficients, which are essential for describing the environmental phase distribution of a compound, are largely unavailable for substituted PAHs (SPAHs). Here, COSMOtherm, a software based on quantum-chemical calculations is used to estimate the atmospherically relevant partition coefficients between the gas phase, the aqueous bulk phase, the water surface and the water insoluble organic matter phase, as well as the salting-out coefficients, for naphthalene, anthracene, phenanthrene, benz(a)anthracene, benzo(a)pyrene and dibenz(a,h)anthracene and 62 of their substituted counterparts. They serve as input parameters for the calculation of equilibrium phase distribution of these compounds in aerosols and clouds. Our results, which were compared with available experimental data, show that the effect of salts, the adsorption to the water surface and the dissolution in a bulk aqueous phase can be safely neglected when estimating the gas-particle partitioning of SPAHs in aerosols. However, for small PAHs with more than one polar functional group the aqueous phase can be the dominant reservoir in a cloud.

Polycyclic aromatic hydrocarbons profiles of spent drilling fluids deposited at Emu-Uno, Delta State, Nigeria.

PubMed

Iwegbue, Chukwujindu M A

2011-10-01

The concentrations and profiles of polycyclic aromatic hydrocarbons were determined in spent drilling fluid deposited at Emu-Uno, Delta State of Nigeria. The total concentrations of polycyclic aromatic hydrocarbons in the spent drilling fluid deposits ranged between 40 and 770 μg kg(-1). The PAHs profile were predominantly 2- and 3-rings with acenaphthalene, phenanthrene, fluorene being the predominant PAHs. The prevalence of 2- and 3-rings PAHs in the spent drilling fluid deposits indicate contamination of the drilling fluids with crude oil during drilling. Incorporation of spent drilling fluids into the soil has serious implication for soil, surface water and groundwater quality. © Springer Science+Business Media, LLC 2011

Polycyclic aromatic hydrocarbons in Italian preserved food products in oil.

PubMed

Sannino, Anna

2016-06-01

A method based on gas chromatography/ tandem mass spectrometry was used to assess levels of 16 EU priority polycyclic aromatic hydrocarbons (PAHs) in 48 preserved food products in oil including foods such as vegetables in oil, fish in oil and oil-based sauces obtained from the Italian market. The benzo[a]pyrene concentrations ranged from <0.04 to 0.40 µg kg(-1), and 72.9% of the samples showed detectable levels of this compound. The highest contamination level was observed for chrysene with three additional PAHs (benzo[a]anthracene, benzo[b]fluoranthene and benzo[c]fluorene) giving mean values higher than the mean value for benzo[a]pyrene. Chrysene was detected in all the samples at concentrations ranging from 0.07 to 1.80 µg kg(-1) (median 0.31 µg kg(-1)). The contamination expressed as PAH4 (sum of benzo(a)pyrene, chrysene, benzo(a)anthracene and benzo(b)fluoranthene), for which the maximum tolerable limit has been set by Commission Regulation (EU) No. 835/2011, varied between 0.10 and 2.94 µg kg(-1).

Evaluation of PAH contamination in soil treated with solid by-products from shale pyrolysis.

PubMed

Nicolini, Jaqueline; Khan, Muhammad Y; Matsui, M; Côcco, Lílian C; Yamamoto, Carlos I; Lopes, Wilson A; de Andrade, Jailson B; Pillon, Clenio N; Arizaga, Gregorio G Carbajal; Mangrich, Antonio S

2015-01-01

The aim of this work was to evaluate the concentrations of polycyclic aromatic hydrocarbons (PAHs) in soils to which solid shale materials (SSMs) were added as soil conditioners. The SSMs were derived from the Petrosix pyrolysis process developed by Petrobras (Brazil). An improved ultrasonic agitation method was used to extract the PAHs from the solid samples (soils amended with SSMs), and the concentrations of the compounds were determined by gas chromatography coupled to mass spectrometry (GC-MS). The procedure provided satisfactory recoveries, detection limits, and quantification limits. The two-, three-, and four-ring PAHs were most prevalent, and the highest concentration was obtained for phenanthrene (978 ± 19 μg kg(-1) in a pyrolyzed shale sample). The use of phenanthrene/anthracene and fluoranthene/pyrene ratios revealed that the PAHs were derived from petrogenic rather than pyrogenic sources. The measured PAH concentrations did not exceed national or international limit values, suggesting that the use of SSMs as soil conditioners should not cause environmental damage.

Uptake of polycyclic aromatic hydrocarbons and their cellular effects in the mangrove Bruguiera gymnorrhiza.

PubMed

Naidoo, Gonasageran; Naidoo, Krishnaveni

2016-12-15

The uptake of polycyclic aromatic hydrocarbons and their cellular effects were investigated in the mangrove Bruguiera gymnorrhiza. Seedlings were subjected to sediment oiling for three weeks. In the oiled treatment, the ƩPAHs was higher in roots (99%) than in leaves (1%). In roots, PAHs included phenanthrene (55%), acenaphthene (13%), fluorine (12%) and anthracene (8%). In leaves, PAHs possessed two to three rings and included acenaphthene (35%), naphthalene (33%), fluorine (18%) and phenanthrene (14%). In the roots, oil caused disorganization of cells in the root cap, meristem and conducting tissue. Oil contaminated cells were distorted and possessed large and irregularly shaped vacuoles. Ultrastructural changes included loss of cell contents and fragmentation of the nucleus and mitochondrion. In the leaves, oil caused dilation and distortion of chloroplasts and disintegration of grana and lamellae. Oil targets critical organelles such as nuclei, chloroplasts and mitochondria which are responsible for cell vitality and energy transformation. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

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

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

Generation and distribution of PAHs in the process of medical waste incineration

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

Chen, Ying, E-mail: echochen327@163.com; National Center of Solid Waste Management, Ministry of Environmental Protection, Beijing 100029; Zhao, Rongzhi

Highlights: ► PAHs generation and distribution features of medical waste incineration are studied. ► More PAHs were found in fly ash than that in bottom ash. ► The highest proportion of PAHs consisted of the seven most carcinogenic ones. ► Increase of free oxygen molecule and burning temperature promote PAHs degradation. ► There is a moderate positive correlation between total PCDD/Fs and total PAHs. - Abstract: After the deadly earthquake on May 12, 2008 in Wenchuan county of China, several different incineration approaches were used for medical waste disposal. This paper investigates the generation properties of polycyclic aromatic hydrocarbons (PAHs)more » during the incineration. Samples were collected from the bottom ash in an open burning slash site, surface soil at the open burning site, bottom ash from a simple incinerator, bottom ash generated from the municipal solid waste (MSW) incinerator used for medical waste disposal, and bottom ash and fly ash from an incinerator exclusively used for medical waste. The species of PAHs were analyzed, and the toxicity equivalency quantities (TEQs) of samples calculated. Analysis results indicate that the content of total PAHs in fly ash was 1.8 × 10{sup 3} times higher than that in bottom ash, and that the strongly carcinogenic PAHs with four or more rings accumulated sensitively in fly ash. The test results of samples gathered from open burning site demonstrate that Acenaphthylene (ACY), Acenaphthene (ACE), Fluorene (FLU), Phenanthrene (PHE), Anthracene (ANT) and other PAHs were inclined to migrate into surrounding environment along air and surface watershed corridors, while 4- to 6-ring PAHs accumulated more likely in soil. Being consistent with other studies, it has also been confirmed that increases in both free oxygen molecules and combustion temperatures could promote the decomposition of polycyclic PAHs. In addition, without the influence of combustion conditions, there is a positive correlation between total PCDD/Fs and total PAHs, although no such relationship has been found for TEQ.« less

Leaching of polycyclic aromatic hydrocarbons from oil shale processing waste deposit: a long-term field study.

PubMed

Jefimova, Jekaterina; Irha, Natalya; Reinik, Janek; Kirso, Uuve; Steinnes, Eiliv

2014-05-15

The leaching behavior of selected polycyclic aromatic hydrocarbons (PAHs) from an oil shale processing waste deposit was monitored during 2005-2009. Samples were collected from the deposit using a special device for leachate sampling at field conditions without disturbance of the upper layers. Contents of 16 priority PAHs in leachate samples collected from aged and fresh parts of the deposit were determined by GC-MS. The sum of the detected PAHs in leachates varied significantly throughout the study period: 19-315 μg/l from aged spent shale, and 36-151 μg/l from fresh spent shale. Among the studied PAHs the low-molecular weight compounds phenanthrene, naphthalene, acenaphthylene, and anthracene predominated. Among the high-molecular weight PAHs benzo[a]anthracene and pyrene leached in the highest concentrations. A spent shale deposit is a source of PAHs that could infiltrate into the surrounding environment for a long period of time. Copyright © 2014 Elsevier B.V. All rights reserved.

Solubilization, Solution Equilibria, and Biodegradation of PAH's under Thermophilic Conditions

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

Viamajala, S.; Peyton, B. M.; Richards, L. A.

Biodegradation rates of PAHs are typically low at mesophilic conditions and it is believed that the kinetics of degradation is controlled by PAH solubility and mass transfer rates. Solubility tests were performed on phenanthrene, fluorene and fluoranthene at 20 C, 40 C and 60 C and, as expected, a significant increase in the equilibrium solubility concentration and of the rate of dissolution of these polycyclic aromatic hydrocarbons (PAHs) was observed with increasing temperature. A first-order model was used to describe the PAH dissolution kinetics and the thermodynamic property changes associated with the dissolution process (enthalpy, entropy and Gibb's free energymore » of solution) were evaluated. Further, other relevant thermodynamic properties for these PAHs, including the activity coefficients at infinite dilution, Henry's law constants and octanol-water partition coefficients, were calculated in the temperature range 20-60 C. In parallel with the dissolution studies, three thermophilic Geobacilli were isolated from compost that grew on phenanthrene at 60 C and degraded the PAH more rapidly than other reported mesophiles. Our results show that while solubilization rates of PAHs are significantly enhanced at elevated temperatures, the biodegradation of PAHs under thermophilic conditions is likely mass transfer limited due to enhanced degradation rates.« less

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.

Bacterial Degradation of Aromatic Compounds

PubMed Central

Seo, Jong-Su; Keum, Young-Soo; Li, Qing X.

2009-01-01

Aromatic compounds are among the most prevalent and persistent pollutants in the environment. Petroleum-contaminated soil and sediment commonly contain a mixture of polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatics. Aromatics derived from industrial activities often have functional groups such as alkyls, halogens and nitro groups. Biodegradation is a major mechanism of removal of organic pollutants from a contaminated site. This review focuses on bacterial degradation pathways of selected aromatic compounds. Catabolic pathways of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene are described in detail. Bacterial catabolism of the heterocycles dibenzofuran, carbazole, dibenzothiophene, and dibenzodioxin is discussed. Bacterial catabolism of alkylated PAHs is summarized, followed by a brief discussion of proteomics and metabolomics as powerful tools for elucidation of biodegradation mechanisms. PMID:19440284

Preparation of Silver Nanoparticles from Synthetic and Natural Sources: Remediation Model for PAHs

NASA Astrophysics Data System (ADS)

Abbasi, Maryam; Saeed, Fatima; Rafique, Uzaira

2014-06-01

The emergence of nanoscience and technology is gaining popularity with an increasing demand for metal nanoparticles applicability in various areas such as electronics, catalysis, chemistry, energy and medicine. Metallic nanoparticles are traditionally synthesized by wet chemical techniques, where the chemicals used are quite often toxic and flammable. In this work, an attempt is made to compare the efficiency of two different synthesis methods and application of each for the remediation of poly aromatic hydrocarbons (PAHs). In this regard, silver nanoparticles are prepared by green and wet chemical method using plant extract of garlic (Allium sativum). The extract is known to reduce the metal during synthesis and acts as stabilizing ligand. These synthesized silver nanoparticles (Agp) and (AgW) were applied as adsorbents in synthetic batch mode experiments at varying parameters of pH and temperature. A concentration of 0.01mg/L of Phenanthrene, Anthracene, and Pyrene were induced at fixed dosage of 1mg/Kg of adsorbent. Residual concentration of each PAH was analyzed on UV-Visible spectrophotometer. The results indicated that both adsorbents follow the sequence of Phenanthrene>Pyrene>Anthracene with optimal removal of higher than 85% in each case. A distinguishing privilege is attained by Agp adsorbent showing 3, 3 and 11 orders of magnitude higher efficiency than Agw. It may be attributed to more functional groups in the plant extract participating in binding of PAH to the surface. Each synthesized adsorbents was characterized by FTIR, SEM and EDX. The average particle size was determined to be of the order of 13-26 nm. The study concludes the use of alternate economical and green adsorbents for control of poly aromatic hydrocarbons (PAHs).

Fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp in Hong Kong following an oil spill.

PubMed

Ke, L; Wong, Teresa W Y; Wong, Y S; Tam, Nora F Y

2002-01-01

The fate of polycyclic aromatic hydrocarbon (PAH) contamination in a mangrove swamp (Yi O) in Hong Kong after an oil spill accident was investigated. The concentrations and profiles of PAHs in surface sediments collected from five quadrats (each of 10 m x 10 m) covering different degrees of oil contamination and the most contaminated mangrove leaves were examined in December 2000 (30 days after the accident) and March 2001 (126 days later). The concentrations of total PAHs in surface sediments ranged from 138 to 2,135 ng g(-1), and PAHs concentrations decreased with time. In the most contaminated sediments, total PAHs dropped from 2,135 (30 days) to 1,196 ng g(-1) (120 days), and the decrease was smaller in less contaminated sediments. The percentage reduction in sediment PAHs over three months (44%) was less significant than that in contaminated leaves (85%), indicating PAH in or on leaves disappeared more rapidly. The PAH profiles were very similar in sediments collected from quadrats Q1 and Q2 with benzo[a]anthracene and pyrene being the most abundant PAH compounds, but were different in the other three quadrats. The proportion of the light molecular weight PAHs to total PAHs increased after three months, especially phenanthrene. Results suggest that physical and photo-chemical weathering (tidal washing and photo-oxidation) of crude oil in surface sediments and on plant leaves were important processes in the first few months after the oil spill. The PAH contamination in Yi O swamp came from both petrogenic and pyrolytic sources. The petrogenic characteristic in the most contaminated sediment was confirmed with high values of phenanthrene to anthracene ratio (>10) and low values of fluoranthene to pyrene ratio (0.3-0.4).

Cancer risk assessment, indicators, and guidelines for polycyclic aromatic hydrocarbons in the ambient air.

PubMed Central

Boström, Carl-Elis; Gerde, Per; Hanberg, Annika; Jernström, Bengt; Johansson, Christer; Kyrklund, Titus; Rannug, Agneta; Törnqvist, Margareta; Victorin, Katarina; Westerholm, Roger

2002-01-01

Polycyclic aromatic hydrocarbons (PAHs) are formed during incomplete combustion. Domestic wood burning and road traffic are the major sources of PAHs in Sweden. In Stockholm, the sum of 14 different PAHs is 100-200 ng/m(3) at the street-level site, the most abundant being phenanthrene. Benzo[a]pyrene (B[a]P) varies between 1 and 2 ng/m(3). Exposure to PAH-containing substances increases the risk of cancer in humans. The carcinogenicity of PAHs is associated with the complexity of the molecule, i.e., increasing number of benzenoid rings, and with metabolic activation to reactive diol epoxide intermediates and their subsequent covalent binding to critical targets in DNA. B[a]P is the main indicator of carcinogenic PAHs. Fluoranthene is an important volatile PAH because it occurs at high concentrations in ambient air and because it is an experimental carcinogen in certain test systems. Thus, fluoranthene is suggested as a complementary indicator to B[a]P. The most carcinogenic PAH identified, dibenzo[a,l]pyrene, is also suggested as an indicator, although it occurs at very low concentrations. Quantitative cancer risk estimates of PAHs as air pollutants are very uncertain because of the lack of useful, good-quality data. According to the World Health Organization Air Quality Guidelines for Europe, the unit risk is 9 X 10(-5) per ng/m(3) of B[a]P as indicator of the total PAH content, namely, lifetime exposure to 0.1 ng/m(3) would theoretically lead to one extra cancer case in 100,000 exposed individuals. This concentration of 0.1 ng/m(3) of B[a]P is suggested as a health-based guideline. Because the carcinogenic potency of fluoranthene has been estimated to be approximately 20 times less than that of B[a]P, a tentative guideline value of 2 ng/m(3) is suggested for fluoranthene. Other significant PAHs are phenanthrene, methylated phenanthrenes/anthracenes and pyrene (high air concentrations), and large-molecule PAHs such as dibenz[a,h]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, and indeno[1,2,3-cd]pyrene (high carcinogenicity). Additional source-specific indicators are benzo[ghi]perylene for gasoline vehicles, retene for wood combustion, and dibenzothiophene and benzonaphthothiophene for sulfur-containing fuels. PMID:12060843

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.

Magnetic micro-solid-phase-extraction of polycyclic aromatic hydrocarbons in water.

PubMed

Naing, Nyi Nyi; Yau Li, Sam Fong; Lee, Hian Kee

2016-04-01

A novel sorbent, magnetic chitosan functionalized graphene oxide (MCFG) was synthesized and used in the micro-solid-phase-extraction (μ-SPE) and gas chromatography-mass spectrometric (GC-MS) analysis of polycyclic aromatic hydrocarbons (PAHs) from water. Through the use of the magnetic sorbent, the μ-SPE device also functioned as a stir bar during extraction. Three types of MCFG were prepared using glutaraldehyde cross-linked chitosan and graphene oxide with different amounts of magnetic nanoparticles (Fe3O4) (0.05g, 0.07g and 0.1g). The material was characterized using Fourier transform infrared spectroscopy and field emission scanning electron microscopy. Parameters affecting the extraction such as the type of sorbent, extraction and desorption times, volume of sample solution and type of desorption solvent were optimized. Under the most favourable conditions, the highest extraction was obtained by using the composite prepared with 0.1g of Fe3O4. For the latter material as sorbent, the linearity of the analytes was in the range of 0.01 and 100μgL(-1) for naphthalene, fluoranthene and pyrene while acenaphthylene and phenanthrene exhibited linearity in the range of 0.05 and 100μgL(-1). For fluorene and anthracene, the linearity range was from 0.01 to 50μgL(-1). The coefficients of determination (r(2)) associated with the above linear ranges were higher than 0.987. The limits of detection from GC-MS analysis of the seven PAHs were in the range 0.2-1.8ngL(-1); limits of quantification were between 0.8 and 5.9ngL(-1) while the relative standard deviations (RSDs) varied from 2.1 to 8.2%. The recoveries of the method for the compounds at spiking levels of 1 and 5μgL(-1) were in the range 67.5-106.9% with RSDs below 15%. The enrichment factors were found to be in between 67 and 302. The developed method afforded an interesting and innovative approach using MCFG as an efficient and promising sorbent. Copyright © 2016 Elsevier B.V. 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.

Gradient distribution of persistent organic contaminants along northern slope of central-Himalayas, China.

PubMed

Wang, Xiao-Ping; Yao, Tan-Dong; Cong, Zhi-Yuan; Yan, Xing-Liang; Kang, Shi-Chang; Zhang, Yong

2006-12-15

High mountains may serve as condenser for persistent organic pollutants (POPs) and the vegetation in remote areas has been used as a means to characterized atmospheric concentrations of air pollutants. In this study, organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) in Himalayan spruce needle samples from Zhangmu-Nyalam region (central-Himalayas) were analyzed and the altitudinal gradient of these pollutants was investigated. Total HCHs and DDTs concentration in needles were in the range of 1.3-2.9 ng g(-1) dry weight and 1.7-11 ng g(-1) dry weight, which were lower than concentrations reported in spruce needles from Alps, however higher than concentrations in conifer needles from mountain areas of Alberta. Total Himalayan spruce needle PAHs was below 600 ng g(-1) and fluorene, phenanthrene and acenaphthene were abundant individual compounds measured. The ratios of alpha-HCH/gamma-HCH in pine needles were similar with the usual values for technical HCH, implying technical HCHs might be used in this region. The high ratios of o-p'-DDT/p-p'-DDT and no p-p'-DDE measured in this study led to the suspicion that a new source of o-p'-DDT and/or p-p'-DDT existed in this region. In addition, higher ratios of low molecular weight-/high molecular weight-PAHs in this region indicated that petroleum combustion, vehicle emission and low-temperature combustion might be the major contributions of PAH source. To examine the POPs distillation, the analyte concentrations were correlated with altitude. The more volatile OCPs, alpha-HCH, gamma-HCH, aldrin and alpha-endosulfan positively correlated with altitude, however, less volatile OCPs (DDT and DDD) inversely related with elevation. Almost all PAHs detected in this area showed positive correlations with altitude. It is worthy to note that heavy PAHs (Benzo[k] fluoranthene and Benzo[a]anthracene) displayed positive correlation, which implied the sources of PAHs were near the sampling sites. The distillation of POPs was strongly affected by the proximity between sampling sites and contaminant sources. If the contaminant sources are close to the mountains, it may be the dominant factor that controls the concentration gradient.

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.

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.

Analysis of particle and vapour phase PAHs from the personal air samples of bus garage workers exposed to diesel exhaust.

PubMed

Kuusimaki, Leea; Peltonen, Kimmo; Mutanen, Pertti; Savela, Kirsti

2003-07-01

The levels of particle and vapour phase polycyclic aromatic hydrocarbons (PAHs) derived from the diesel exhaust compounds in bus garage work were measured in winter and in summer. Five personal air samples were collected from the breathing zones of 22 garage workers every other day of consecutive weeks. Control samples (n = 22) were collected from office workers in Helsinki. Fifteen PAHs in the air samples were analysed by HPLC using a fluorescence detector. Statistically significant differences were observed between total PAH levels of the exposed workers (2241 and 1245 ng/m(3)) and the control group (254 and 275 ng/m(3)) in both winter (P < 0.001) and summer (P < 0.001). Phenanthrene, pyrene, benzo[ghi]perylene and fluoranthene were the major compounds in the particle phase, and naphthalene, phenanthrene and fluorene in the vapour phase. About 98% of PAHs measured were related to the vapour phase compounds, whereas the high molecular weight PAH compounds were detected only in the particle phase. The PAH levels in the garages were twice as high (P < 0.001) in winter as in summer. Even though the exposure levels were low in the bus garages, the low level does not allow conclusions to be drawn about the possible adverse health effects due to exposure to diesel exhaust.

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.

Gene cloning and in vivo characterization of a dibenzothiophene dioxygenase from Xanthobacter polyaromaticivorans.

PubMed

Hirano, Shin-Ichi; Haruki, Mitsuru; Takano, Kazufumi; Imanaka, Tadayuki; Morikawa, Masaaki; Kanaya, Shigenori

2006-02-01

Xanthobacter polyaromaticivorans sp. nov. 127W is a bacterial strain that is capable of degrading a wide range of cyclic aromatic compounds such as dibenzothiophene, biphenyl, naphthalene, anthracene, and phenanthrene even under extremely low oxygen [dissolved oxygen (DO)< or = 0.2 ppm] conditions (Hirano et al., Biosci Biotechnol Biochem 68:557-564, 2004). A major protein fraction carrying dibenzothiophene degradation activity was purified. Based on its partial amino acid sequences, dbdCa gene encoding alpha subunit terminal oxygenase (DbdCa) and its flanking region were cloned and sequenced. A phylogenetic analysis based on the amino acid sequence demonstrates that DbdCa is a member of a terminal oxygenase component of group IV ring-hydroxylating dioxygenases for biphenyls and monocyclic aromatic hydrocarbons, rather than group III dioxygenases for polycyclic aromatic hydrocarbons. Gene disruption in dbdCa abolished almost of the degradation activity against biphenyl, dibenzothiophene, and anthracene. The gene disruption also impaired degradation activity of the strain under extremely low oxygen conditions (DO< or = 0.2 ppm). These results indicate that Dbd from 127W represents a group IV dioxygenase that is functional even under extremely low oxygen conditions.

Natural Mediators in the Oxidation of Polycyclic Aromatic Hydrocarbons by Laccase Mediator Systems

PubMed Central

Johannes, Christian; Majcherczyk, Andrzej

2000-01-01

The oxidation of polycyclic aromatic compounds was studied in systems consisting of laccase from Trametes versicolor and so-called mediator compounds. The enzymatic oxidation of acenaphthene, acenaphthylene, anthracene, and fluorene was mediated by various laccase substrates (phenols and aromatic amines) or compounds produced and secreted by white rot fungi. The best natural mediators, such as phenol, aniline, 4-hydroxybenzoic acid, and 4-hydroxybenzyl alcohol were as efficient as the previously described synthetic compounds ABTS [2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid)] and 1-hydroxybenzotriazole. The oxidation efficiency increased proportionally with the redox potentials of the phenolic mediators up to a maximum value of 0.9 V and decreased thereafter with redox potentials exceeding this value. Natural compounds such as methionine, cysteine, and reduced glutathione, containing sulfhydryl groups, were also active as mediator compounds. PMID:10653713

Photolysis of polycyclic aromatic hydrocarbons (PAHs) on Fe3+-montmorillonite surface under visible light: Degradation kinetics, mechanism, and toxicity assessments.

PubMed

Zhao, Song; Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Wang, Chuanyi

2017-10-01

Photochemical behavior of various polycyclic aromatic hydrocarbons (PAHs) on Fe 3+ -modified montmorillonite was explored to determine their potential kinetics, pathways, and mechanism under visible light. Depending on the type of PAH molecules, the transformation rate follows the order of benzo[a]pyrene ≈ anthracene > benzo[a]anthracene > phenanthrene. Quantum simulation results confirm the crucial role of "cation-π" interaction between Fe 3+ and PAHs on their transformation kinetics. Primary intermediates, including quinones, ring-opening products and benzene derivatives, were identified by gas chromatography-mass spectrometer (GC-MS), and the possible photodegradation pathway of benzo[a]pyrene was proposed. Meanwhile, radical intermediates, such as reactive oxygen species (ROS) and free organic radicals, were detected by electron paramagnetic resonance (EPR) technique. The photolysis of selected PAHs, such as anthracene and benzo[a]pyrene, on clay surface firstly occurs by electron transfer from PAHs to Fe 3+ -montmorillonite, followed by degradation involving photo-induced ROS such as ·OH and ·O 2 - . To investigate the acute toxicity of photolysis products, the Microtox ® toxicity test was performed during the photodegradation processes of various PAHs. As a result, the photo-irradiation initially induces increased toxicity by generating reactive intermediates, such as free organic radicals, and then the toxicity gradually decreases with increasing of reaction time. Overall, the present study provides useful information to understand the fate and photo-transformation of PAHs in contaminated soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fe3O4@ionic liquid@methyl orange nanoparticles as a novel nano-adsorbent for magnetic solid-phase extraction of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Liu, Xiaofei; Lu, Xin; Huang, Yong; Liu, Chengwei; Zhao, Shulin

2014-02-01

A novel nano-adsorbent, Fe3O4@ionic liquid@methyl orange nanoparticles (Fe3O4@IL@MO NPs), was prepared for magnetic solid-phase extraction (MSPE) of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. The Fe3O4@IL@MO NPs were synthesized by self-assembly of the ionic liquid 1-octadecyl-3-methylimidazolium bromide (C18mimBr) and methyl orange (MO) onto the surface of Fe3O4 silica magnetic nanoparticles, as confirmed by infrared spectroscopy, ultraviolet-visible spectroscopy and superconducting quantum interface device magnetometer. The extraction performance of Fe3O4@IL@MO NPs as a nano-adsorbent was evaluated by using five PAHs, fluorene (FLu), anthracene (AnT), pyrene (Pyr), benzo(a)anthracene (BaA) and benzo(a)pyrene (BaP) as model analytes. Under the optimum conditions, detection limits in the range of 0.1-2 ng/L were obtained by high performance liquid chromatography-fluorescence detection (HPLC-FLD). This method has been successfully applied for the determination of PAHs in environmental water samples by using the MSPE-HPLC-FLD. The recoveries for the five PAHs tested in spiked real water samples were in the range of 80.4-104.0% with relative standard deviations ranging from 2.3 to 4.9%. © 2013 Published by Elsevier B.V.

Natural mediators in the oxidation of polycyclic aromatic hydrocarbons by laccase mediator systems

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

Johannes, C.; Majcherczyk, A.

2000-02-01

The oxidation of polycyclic aromatic compounds was studied in systems consisting of laccase from Trametes versicolor and so-called mediator compounds. The enzymatic oxidation of acenaphthene, acenaphthylene, anthracene, and fluorene was mediated by various laccase substrates (phenols and aromatic amines) or compounds produced and secreted by white rot fungi. The best natural mediators, such as phenol, aniline, 4-hydroxybenzoic acid, and 4-hydroxybenzyl alcohol were as efficient as the previously described synthetic compounds ABTS [2,2{prime}-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid)] and 1-hydroxybenzotriazole. The oxidation efficiency increased proportionally with the redox potentials of the phenolic mediators up to a maximum value of 0.9 V and decreased thereafter withmore » redox potentials exceeding this value. Natural compounds such as methionine, cysteine, and reduced glutathione, containing sulfhydryl groups, were also active as mediator compounds.« less

Hydrocarbons identified in extracts from estuarine water accommodated no. 2 fuel oil by gas chromatography-mass spectrometry

NASA Technical Reports Server (NTRS)

Lewis, B. W.; Walker, A. L.; Bieri, R. H.

1974-01-01

Results are presented on a computerized gas chromatograph-mass spectrometer analysis of methylene chloride and n-heptane extracts of a No. 2 fuel oil accommodated estuarine water sample. The analytical method is briefly described, and the limitations on the identifications are categorized. Some attempt was made to determine major and trace constituents in the water accommodate. Altogether 66 hydrocarbon compounds were identified specifically, and 75 compounds were partially identified. Seven compounds could be recognized as major constituents of the water accommodated oil and ten were present only as traces. The aromatic compounds found were alkyl benzenes, naphthalene, tetralin, indane, biphenyl, fluorene, anthracene, and some of their alkyl substituted isomers in the range of carbon numbers C7 to C15. Four n-alkanes, C10 to C13, were found along with four other assorted hydrocarbons.

Peroxidases from root exudates of Medicago sativa and Sorghum bicolor: Catalytic properties and involvement in PAH degradation.

PubMed

Dubrovskaya, Ekaterina; Pozdnyakova, Natalia; Golubev, Sergey; Muratova, Anna; Grinev, Vyacheslav; Bondarenkova, Anastasiya; Turkovskaya, Olga

2017-02-01

Peroxidases from root exudates of sorghum (Sorghum bicolor L. Moench) and alfalfa (Medicago sativa L.) were purified and characterized, and their ability to oxidize native PAHs and PAH-derivatives was evaluated. The obtained data confirm that peroxidases are involved in the rhizosphere degradation of PAHs. Nondenaturing PAGE showed that the peroxidases of both plants were represented by a range of isoforms/isoenzymes (five to eight). Minor forms were lost during further purification, and as a result, the major anionic form from alfalfa root exudates and the major cationic form from those of sorghum were obtained. Both electrophoretically homogeneous peroxidases were monomeric proteins with a molecular weight of about 46-48 kDa. The pH optima and the main catalytic constants for the test substrates were determined. On the basis of their molecular and catalytic properties, the obtained enzymes were found to be typical plant peroxidases. Derivatives of PAHs and potential products of their microbial degradation (9-phenanthrol and 9,10-phenanthrenequinone), unlike the parent PAH (phenanthrene), inhibited the catalytic activity of the peroxidases, possibly indicating greater availability of the enzymes' active centers to these substances. Peroxidase-catalyzed decreases in the concentrations of a number of PAHs and their derivatives were observed. Sorghum peroxidase oxidized anthracene and phenanthrene, while alfalfa peroxidase oxidized only phenanthrene. 1-Hydroxy-2-naphthoic acid was best oxidized by peroxidase of alfalfa. However, quinone derivatives of PAHs were unavailable to sorghum peroxidase, but were oxidized by alfalfa peroxidase. These results indicate that the major peroxidases from root exudates of alfalfa and sorghum can have a role in the rhizosphere degradation of PAHs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Degradation of petroleum hydrocarbons and treatment of refinery wastewater under saline condition by a halophilic bacterial consortium enriched from marine environment (Red Sea), Jeddah, Saudi Arabia.

PubMed

Jamal, Mamdoh T; Pugazhendi, Arulazhagan

2018-06-01

A halophilic bacterial consortium was enriched from Red Sea saline water and sediment samples collected from Abhor, Jeddah, Saudi Arabia. The consortium potentially degraded different low (above 90% for phenanthrene and fluorene) and high (69 ± 1.4 and 56 ± 1.8% at 50 and 100 mg/L of pyrene) molecular weight polycyclic aromatic hydrocarbons (PAHs) at different concentrations under saline condition (40 g/L NaCl concentration). The cell hydrophobicity (91° ± 1°) and biosurfactant production (30 mN/m) confirmed potential bacterial cell interaction with PAHs to facilitate biodegradation process. Co-metabolic study with phenanthrene as co-substrate during pyrene degradation recorded 90% degradation in 12 days. The consortium in continuous stirred tank reactor with petroleum refinery wastewater showed complete and 90% degradation of low and high molecular weight PAHs, respectively. The reactor study also revealed 94 ± 1.8% chemical oxygen demand removal by the halophilic consortium under saline condition (40 g/L NaCl concentration). The halophilic bacterial strains present in the consortium were identified as Ochrobactrum halosaudis strain CEES1 (KX377976), Stenotrophomonas maltophilia strain CEES2 (KX377977), Achromobacter xylosoxidans strain CEES3 (KX377978) and Mesorhizobium halosaudis strain CEES4 (KX377979). Thus, the promising halophilic consortium was highly recommended to be employed in petroleum saline wastewater treatment process.

Isolation and characterization of bacteria capable of degrading polycyclic aromatic hydrocarbons (PAHs) and organophosphorus pesticides from PAH-contaminated soil in Hilo, Hawaii.

PubMed

Seo, Jong-Su; Keum, Young-Soo; Harada, Renee M; Li, Qing X

2007-07-11

Nineteen bacterial strains were isolated from petroleum-contaminated soil in Hilo, HI, and characterized by two different spray-plated methods, turbidity test in liquid medium, and 16S rRNA gene sequence analysis. Analysis of the soil showed 13 polycyclic aromatic hydrocarbons (PAHs) in a range from 0.6 to 30 mg/kg of dry weight each and 12 PAH metabolites. Five distinct bacterial strains (C3, C4, P1-1, JS14, and JS19b1) selected from preliminary plating and turbidity tests were further tested for PAH degradation through single PAH degradation assay. Strains C3, C4, and P1-1 degraded phenanthrene (40 mg/L) completely during 7 days of incubation. Strain JS14 degraded fluoranthene (40 mg/L) completely during 10 days of incubation. Strain JS19b1 degraded 100% of phenanthrene (40 mg/L) in 7 days, 77% of fluorene (40 mg/L) in 14 days, 97% of fluoranthene (40 mg/L) in 10 days, and 100% of pyrene (40 mg/L) in 14 days. Turbidity tests showed that strains P1-1, JS14, and JS19b1 utilized several organophosphorus pesticides as growth substrate. P1-1 can degrade carbofenothion, chlorfenvinphos, diazinon, fonofos, and pirimiphos-methyl. JS14 can transform chlorfenvinphos and diazinon. JS19b1 can break down diazinon, pirimiphos-methyl, and temephos.

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.

Selective removal of organic contaminants from sediments: A methodology for toxicity identification evaluations (TIEs)

USGS Publications Warehouse

Lebo, J.A.; Huckins, J.N.; Petty, J.D.; Ho, K.T.; Stern, E.A.

2000-01-01

Aqueous slurries of a test sediment spiked with dibenz[a,h]anthracene, 2,4,5,2′,4′,5′-hexachlorobiphenyl, p,p′-DDE, or phenanthrene were subjected to decontamination experimentation. The spiked sediments were agitated at elevated temperatures for at least 96 h in the presence of either of the two contaminant-absorbing media: clusters of polyethylene membrane or lipid-containing semipermeable membrane devices (SPMDs). The effects of treatment temperature and surface area of media on the removal of contaminants were explored. This work is part of a larger methodology for whole-sediment toxicity identification evaluation (TIE). A method is being sought that is capable of detoxifying sediments with respect to organic contaminants while leaving toxicity attributable to inorganic contaminants unaffected.

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

Characterization of parent and oxygenated-polycyclic aromatic hydrocarbons (PAHs) in Xi'an, China during heating period: An investigation of spatial distribution and transformation.

PubMed

Wang, Jingzhi; Hang Ho, Steven Sai; Huang, Rujin; Gao, Meiling; Liu, Suixin; Zhao, Shuyu; Cao, Junji; Wang, Gehui; Shen, Zhenxing; Han, Yongming

2016-09-01

Polycyclic aromatic hydrocarbons (PAHs) and its oxygenated derivatives (OPAHs) are toxins in PM2.5. Little information has been known for their transformation in the ambient airs. In this study, PM2.5 samples were collected at 19 sampling sites in Xi'an, China during the heating period, which is classified into: urban residential, university, commercial area, suburban region, and industry. Organic compounds including PAHs, OPAHs, hopanes and cholestanes were quantified. The average of total quantified PAHs and OPAHs concentrations were 196.5 ng/m(3) and 29.4 ng/m(3), respectively, which were consistent with other northern cities in China. Statistical analyses showed that there were significant differences on the distributions of PAHs between urban and suburban regions. The industry also had distinguishable profiles compared with urban residential and commercial area for OPAHs. The greater diversity of OPAHs than PAHs might be due to different primary emission sources and transformation and degradation pathways. The ratios of OPAHs to the corresponding parent PAHs, including 9-fluorenone/fluorene, anthraquinone/anthracene, benz[a]anthracene-7,12-dione/benzo[a]anthracene were 6.2, 12.7, and 1.4, respectively, which were much higher than those for the fresh emissions from coal combustion and biomass burning. These prove the importance of secondary formation and transformation of OPAHs in the ambient airs. Biomarkers such as retene, cyclopenta[CD]pyrene and αα-homohopane were characterized for the source apportionment. With Positive Matrix Factorization (PMF) model analysis, biomass burning was recognized as the most dominant pollution sources for PAHs during the heading period, which accounted for a contribution of 37.1%. Vehicle emission (22.8%) and coal combustion (22.6%) were also contributors in Xi'an. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

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.

Polycyclic aromatic hydrocarbons in soil and surface marine sediment near Jubany Station (Antarctica). Role of permafrost as a low-permeability barrier.

PubMed

Curtosi, Antonio; Pelletier, Emilien; Vodopivez, Cristian L; Mac Cormack, Walter P

2007-09-20

Although Antarctica is still considered as one of the most pristine areas of the world, the growing tourist and fisheries activities as well as scientific operations and their related logistic support are responsible for an increasing level of pollutants in this fragile environment. Soils and coastal sediments are significantly affected near scientific stations particularly by polycyclic aromatic hydrocarbons (PAHs). In this work sediment and soil were sampled in two consecutive summer Antarctic expeditions at Potter Cove and peninsula, in the vicinity of Jubany Station (South Shetland Islands). Two- and 3-ring PAHs (methylnaphthalene, fluorene, phenanthrene and anthracene) were the main compounds found in most sites, although total PAH concentrations showed relatively low levels compared with other human-impacted areas in Antarctica. Pattern distribution of PAHs observed in samples suggested that low-temperature combustion processes such as diesel motor combustion and open-field garbage burning are the main sources of these compounds. An increase in PAH concentrations was observed from surface to depth into the active soil layer except for a unique sampling site where a fuel spill had been recently reported and where an inverted PAH concentration gradient was observed. The highest level was detected in the upper layer of permafrost followed by a sharp decrease in depth, showing this layer is acting as a barrier for downward PAH migration. When PAH levels in soil from both sampling programs were compared a significant decrease (p<0.01) was observed in summer 2005 (range at 75-cm depth: 12+/-1-153+/-22 ng/g) compared to summer 2004 (range at 75-cm depth: 162+/-15-1182+/-113 ng/g) whereas concentrations in surface sediment collected nearby the station PAHs increased drastically in 2005 (range: 36+/-3-1908+/-114 ng/g) compared to 2004 (range: 28+/-3-312+/-24 ng/g). Precipitation regime and water run off suggest that an important wash out of soil-PAHs occurred during the interval time between samplings. Results showed that the present PAH contamination level of Jubany Station is relatively low compared to other reported cases in Antarctica but also suggests that an increase in rain and in thawing processes caused by the global warming could result in an important soil-associated PAH mobilization with unpredictable consequences for the biota of Potter Cove.

Airborne Measurements of atmospheric PAH's across Europe

NASA Astrophysics Data System (ADS)

Davison, B.; Jaward, F.; Jones, K.; Lee, R.

2003-04-01

Atmospheric measurements of PAHs were taken aboard the DRL Falcon 20 during May 2001. A sampling system was designed to work aboard this aircraft platform. Particulate PAHs were collected on a glass fiber filter (GFF) with their gaseous component concentrated on a polyurethane foam sheets located behind the filter. Typically sampling volumes of between 20-50m^3 were collected which equated to a collection time of about 30minutes. In this way the distance travelled was kept within an acceptable level, about 60 nautical miles. The average concentrations of the data set for phenanthrene was 450 pg m-3 while values for many of the heavier PAH marker compounds used in the UK such as benzo(a)pyrene, diben(ah)anthracene were below the detection limits on all flights. The results will be discussed with consideration of location, altitude and airmass trajectory.

Polycyclic aromatic hydrocarbons in sediments and mussels of Corral Bay, south central Chile.

PubMed

Palma-Fleming, Hernan; P, Adalberto J Asencio; Gutierrez, Elena

2004-03-01

PAHs were measured in sediments and mussels (Mytilus chilensis) from Carboneros and Puerto Claro, located in Corral Bay, Valdivia. According to the ratio of phenanthrene/anthracene and fluoranthene/pyrene concentrations, these sites are medium polluted with PAHs originating mainly from pyrolytic sources. Fluoranthene was the major component measured in mussels (3.1-390 ng g(-1) dry weight) and sediments (6.9-74.1 ng g(-1) dry weight). In general, mussels were mainly exposed to the dissolved fraction of the lower molecular weight PAHs (tri- and tetra-aromatics) while the higher molecular ring systems (penta- and hexa-aromatics) were more bioavailable to sediments. Mussel PAHs content was relatively constant, with the exception of the 1999 summer season (March), when higher concentration values were found in both sites; however, PAHs residues in sediments showed a temporal variation.

Distribution and Source of Polycyclic Aromatic Hydrocarbons (PAHs) in Water Dissolved Phase, Suspended Particulate Matter and Sediment from Weihe River in Northwest China

PubMed Central

Chen, Yuyun; Jia, Rui; Yang, Shengke

2015-01-01

Weihe River is a typical river located in the arid and semi-arid regions of Northwest China. In this study, the distribution and sources of 16 polycyclic aromatic hydrocarbons (PAHs) in Weihe River were investigated. The concentrations of ∑PAHs ranged from 351 to 4427 ng/L with a mean value of 835.4 ng/L in water dissolved phase (WDP), from 3557 ng/L to 147,907 ng/L with a mean value of 20,780 ng /L in suspended particulate matter (SPM), and from 362 to 15,667 ng/g dry weight (dw) with a mean value of 2000 ng/g dw in sediment, respectively. The concentrations of PAHs in Weihe River were higher compared with other rivers in the world. In both WDP and sediment, the highest concentrations of ∑PAHs were observed in the middle reach, while the lowest concentrations of ∑PAHs were found in the lower reach. For SPM, however, the PAHs concentrations in the lower reach were highest and the PAHs concentrations in the upper reach were lowest. The ratios of anthracene/(anthracene + phenanthrene) and fluoranthene/(fluoranthene + pyrene) reflected a pattern of both pyrolytic and petrogenic input of PAHs in Weihe River. The potential ecosystem risk assessment indicated that harmful biological impairments occur frequently in Weihe River. PMID:26561824

Photo-assisted intersystem crossing: The predominant triplet formation mechanism in some isolated polycyclic aromatic molecules excited with pulsed lasers

DOE PAGES

Johnson, Philip M.; Sears, Trevor J.

2015-07-28

Naphthalene, anthracene, and phenanthrene are shown to have very long-lived triplet lifetimes when the isolated molecules are excited with nanosecond pulsed lasers resonant with the lowest singlet state. For naphthalene, triplet state populations are created only during the laser pulse, excluding the possibility of normal intersystem crossing at the one photon level, and all molecules have triplet lifetimes greater than hundreds of microseconds, similar to the behavior previously reported for phenylacetylene. Although containing 7–12 thousand cm⁻¹ of vibrational energy, the triplet molecules have ionization thresholds appropriate to vibrationless T₁ states. The laser power dependences (slopes of log-log power plots) ofmore » the excited singlet and triplet populations are about 0.7 for naphthalene and about 0.5 for anthracene. Kinetic modeling of the power dependences successfully reproduces the experimental results and suggests that the triplet formation mechanism involves an enhanced spin orbit coupling caused by sigma character in states at the 2-photon level. Symmetry Adapted Cluster-Configuration Interaction calculations produced excited state absorption spectra to provide guidance for estimating kinetic rates and the sigma character present in higher electronic states. It is concluded that higher excited state populations are significant when larger molecules are excited with pulsed lasers and need to be taken into account whenever discussing the molecular photodynamics.« less

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.

Development and certification of a coal fly ash certified reference material for selected polycyclic aromatic hydrocarbons.

PubMed

Cao, X; Xu, X; Cui, W; Xi, Z

2001-08-01

The development and certification of a coal fly ash certified reference material (CRM) for polycyclic aromatic hydrocarbons (PAH) is described; this is the first natural matrix CRM for organic environmental analysis in China. The homogeneity and stability of this material have been tested by HPLC. The concentrations of several PAH were determined by use of two independent, different methods--solvent extraction-HPLC analysis with UV detection coupled with fluorescence detection (FLD) and solvent extraction, isolation with a silica column, and GC analysis with flame ionization detection (FID). Five certified values were determined: phenanthrene 7.1 +/- 2.6 microg g(-1), anthracene 2.0 +/- 0.8 microg g(-1), fluoranthene 7.4 +/- 1.9 microg g(-1), pyrene 7 +/- 2 microg g(-1), and benzo[a]pyrene 1.3 +/- 0.3 microg g(-1). Reference values for several other PAH are also suggested.

Polycyclic aromatic hydrocarbons (PAHs) in yogurt samples.

PubMed

Battisti, Chiara; Girelli, Anna Maria; Tarola, Anna Maria

2015-01-01

The concentrations and distributions of major polycyclic aromatic hydrocarbons (PAHs) were determined in 20 kinds of yogurt specimens collected from Italian supermarkets using reversed phase high-performance liquid chromatography equipped with fluorescence detection. The method was validated by determination of recovery percentages, precision (repeatability) and sensitivity (limits of detection) with yogurt samples fortified at 0.25, 0.5 and 1 µg/kg concentration levels. The recovery of 13 PAHs, with the exception of naphthalene and acenaphthene, ranged from 61% to 130% and from 60% to 97% at all the levels for yogurts with low (0.1%) and high (3.9%) fat content, respectively. The method is repeatable with relative standard deviation values <20% for all analytes. The results obtained demonstrate that acenaphthene, fluorantene, phenanthrene, anthracene, fluoranthene and pyrene were found in all samples with a similar distribution, but different content when yogurts with low and high fats were compared.

Solid-state surface luminescence of polycyclic aromatic hydrocarbons adsorbed on cellulose diacetate matrices

NASA Astrophysics Data System (ADS)

Rogacheva, Svetlana M.; Shipovskaya, Anna B.; Volkova, Elena V.; Khurshudyan, Grachia N.; Suska-Malawska, Malgorzata; Gubina, Tamara I.

2018-04-01

The spectral-kinetic characteristics of luminescence of 17 polycyclic aromatic hydrocarbons (PAH) sorbed from a "water-organic solvent" medium on cellulose diacetate (CDA) matrices were studied. A significant increase in the fluorescence signal on the CDA matrix was observed for 13 PAHs in comparison with aqueous solutions. The highest detection sensitivity was found for pyrene, benzo(a)pyrene, and benzo(k)fluoranthene. The fluorescence spectra of two PAH indicator pairs (anthracene-phenanthrene and pyrene-fluoranthene) used to control toxicant emission sources were studied with the simultaneous presence of isomers in the analyte, depending on the excitation wavelength. For both isomer pairs, it has been found that the spectra of their solid-state luminescence overlap insignificantly, the characteristic peaks do not coincide and do not overlap, the sensitivities of detection are close to each other, which makes it possible to consider this technique as promising to control PAH contamination sources.

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

Does Switching to Reduced Ignition Propensity Cigarettes Alter Smoking Behavior or Exposure to Tobacco Smoke Constituents?

PubMed Central

Rees, Vaughan W.; Norton, Kaila J.; Cummings, K. Michael; Connolly, Gregory N.; Alpert, Hillel R.; Sjödin, Andreas; Romanoff, Lovisa; Li, Zheng; June, Kristie M.; Giovino, Gary A.

2010-01-01

Introduction: Since 2004, several jurisdictions have mandated that cigarettes show reduced ignition propensity (RIP) in laboratory testing. RIP cigarettes may limit fires caused by smoldering cigarettes, reducing fire-related deaths and injury. However, some evidence suggests that RIP cigarettes emit more carbon monoxide and polycyclic aromatic hydrocarbons, and smokers may alter their smoking patterns in response to RIP cigarettes. Both of these could increase smokers’ exposures to harmful constituents in cigarettes. Methods: An 18-day switching study with a comparison group was conducted in Boston, MA (N = 77), and Buffalo, NY (N = 83), in 2006–2007. Current daily smokers completed 4 laboratory visits and two 48-hr field data collections. After a 4-day baseline, Boston participants switched to RIP cigarettes for 14 days, whereas Buffalo participants smoked RIP cigarettes throughout. Outcome measures included cigarettes smoked per day; smoking topography; salivary cotinine; breath CO; and hydroxylated metabolites of pyrene, naphthalene, phenanthrene, and fluorene. Because the groups differed demographically, analyses adjusted for race, age, and sex. Results: We observed no significant changes in smoking topography or CO exposure among participants who switched to RIP cigarettes. Cigarette use decreased significantly in the switched group (37.7 cigarettes/48 hr vs. 32.6 cigarettes/48 hr, p = .031), while hydroxyphenanthrenes increased significantly (555 ng/g creatinine vs. 669 ng/g creatinine, p = .007). No other biomarkers were significantly affected. Discussion: Small increases in exposure to phenanthrene among smokers who switched to RIP versions were observed, while other exposures and smoking topography were not significantly affected. Toxicological implications of these findings are unclear. These findings should be weighed against the potential public health benefits of adopting RIP design standards for cigarette products. PMID:20805292

Joint approximate diagonalization of eigenmatrices as a high-throughput approach for analysis of hyphenated and comprehensive two-dimensional gas chromatographic data.

PubMed

Zarghani, Maryam; Parastar, Hadi

2017-11-17

The objective of the present work is development of joint approximate diagonalization of eigenmatrices (JADE) as a member of independent component analysis (ICA) family, for the analysis of gas chromatography-mass spectrometry (GC-MS) and comprehensive two-dimensional gas chromatography-mass spectrometry (GC×GC-MS) data to address incomplete separation problem occurred during the analysis of complex sample matrices. In this regard, simulated GC-MS and GC×GC-MS data sets with different number of components, different degree of overlap and noise were evaluated. In the case of simultaneous analysis of multiple samples, column-wise augmentation for GC-MS and column-wise super-augmentation for GC×GC-MS was used before JADE analysis. The performance of JADE was evaluated in terms of statistical parameters of lack of fit (LOF), mutual information (MI) and Amari index as well as analytical figures of merit (AFOMs) obtained from calibration curves. In addition, the area of feasible solutions (AFSs) was calculated by two different approaches of MCR-BANDs and polygon inflation algorithm (FACPACK). Furthermore, JADE performance was compared with multivariate curve resolution-alternating least squares (MCR-ALS) and other ICA algorithms of mean-field ICA (MFICA) and mutual information least dependent component analysis (MILCA). In all cases, JADE could successfully resolve the elution and spectral profiles in GC-MS and GC×GC-MS data with acceptable statistical and calibration parameters and their solutions were in AFSs. To check the applicability of JADE in real cases, JADE was used for resolution and quantification of phenanthrene and anthracene in aromatic fraction of heavy fuel oil (HFO) analyzed by GC×GC-MS. Surprisingly, pure elution and spectral profiles of target compounds were properly resolved in the presence of baseline and interferences using JADE. Once more, the performance of JADE was compared with MCR-ALS in real case. On this matter, the mutual information (MI) values were 1.01 and 1.13 for resolved profiles by JADE and MCR-ALS, respectively. In addition, LOD values (μg/mL) were respectively 1.36 and 1.24 for phenanthrene and 1.26 and 1.09 for anthracene using MCR-ALS and JADE which showed outperformance of JADE over MCR-ALS. Copyright © 2017 Elsevier B.V. All rights reserved.

The Triplet State

NASA Astrophysics Data System (ADS)

Zahlan, A. B.

2010-01-01

Preface; List of participants; Part I. Spin-orbit Coupling and Intersystem Crossing: 1. Spin-orbit interactions in organic molecules; 2. Singlet-triplet transitions in organic molecules; 3. Triplet decay and intersystem crossing in aromatic hydrocarbons; 4. Statistical aspects of resonance energy transfer; Discussion; Part II. Magnetic Resonance and Magnetic Interactions: 5. Magnetic resonance spectra of organic molecules in triplet states in single crystals; 6. Magnetic interactions related to phosphorescence; 7. ESR investigations of naphthalene-d8:Naphthalene-h8 mixed crystals; 8. Biradicals and polyradicals in the nitroxide series; 9. Changes induced in the phosphorescent radiation of aromatic molecules by paramagnetic resonance in their metastable triplet states; 10. Paramagnetic resonance of the triplet state of tetramethylpyrazine; 11. On magnetic dipole contributions to the intrinsic S0 = T1 transition in simple aromatics; Discussion; Part III. Photochemistry: 12. The kinetics of energy transfer from the triplet state in rigid solutions; 13. Triplet states in gas-phase photochemistry; 14. Biphotonic photochemistry, involving the triplet state: polarisation of the effective T-T transition and solvent effects; 15. Direct and sensitised photo-oxidation of aromatic hydrocarbons in boric acid glass; Discussion; Part IV. Radiationless Transitions: 16. Radiationless transitions in gaseous benzene; 17. Low-lying excited triplet states and intersystem crossing in aromatic hydrocarbons; 18. De-excitation rates of triplet states in condensed media; 19. Lifetimes of the triplet state of aromatic hydrocarbons in the vapour phase; Discussion; Part V. Triplet Excitons: 20. Some comments on the properties of triplet excitons in molecular crystals; 21. Exact treatment of coherent and incoherent triplet exciton migration; 22. Magnetic susceptibility of a system of triplet excitons: Würster's Blue Perchlorate; 23. A study of triplet excitons in anthracene crystals under laser excitation; 24. The electronic states in crystaline anthracene; Discussion; Part VI. Delayed Fluorescent and Phosphorescence: 25. Delayed fluorescence of solutions; 26. The kinetics of the excited states of anthracene and phenanthrene vapor; 27. Optical investigations of the triplet states of naphthalene in different crystalline environments; 28. Excitation of the triplet states of organic molecules; 29. The delayed luminescence and triplet quantum yields of pyrene solutions; 30. Triplet state studies of some polyphenyls in rigid glasses; 31. Decay time of delayed fluorescence of anthracene as a function of temperature (2-30ºK); 32. Energy transfer between benzene and biacetyl and the lifetime of triplet benzene in the gas phase; 33. Charge transfer triplet state of molecular complexes. 34. Flash-photolytic detection of triplet acridine formed by energy transfer from biacetyl; 35. Extinction coefficients of triplet-triplet transitions between 3000 and 8800 A in anthracene; 36. Anthracene triplet-triplet annihilation rate constant; Discussion; Part VII. Triplet State Related to Biology: 37. ESR and optical studies of some triplet states of biological interest; 38. The triplet state of DNA; 39. Some characteristics of the triplet states of the nucleic bases; Discussion; Indexes.

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.

Reports of investigations on: Derivation of an infinite-dilution activity coefficient model and application to two-component vapor/liquid equilibria data: Final report

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

Roper, V.P.; Kobayashi, R.

1988-02-01

Infinite-dilution fugacity coefficients were obtained for the system fluorene/phenanthrene at thirteen temperatures by fitting total pressure across the entire mole fraction range by a computer routine. A thermodynamically consistent routine, that allowed for both positive and negative pressure deviations from the ideal values, was used to correlate data over the full mole fraction range from 0 to 1. The four-suffix Margules activity coefficient model without modification essentially served this purpose since total pressures and total pressure derivatives with respect to mole fraction were negligible compared to pressure measurement precision. The water/ethanol system and binary systems comprised of aniline, chlorobenzene, acetonitrilemore » and other polar compounds were fit for total pressure across the entire mole fraction range for binary Vapor-Liquid-Equilbria (VLE) using the rigorous, thermodynamically consistent Gibbs-Duhem Relation derived by Ibl and Dodge. Data correlation was performed using a computer least squares procedure. Infinite-dilution fugacity coefficients were obtained using a modified Margules activity coefficient model.« less

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.

Determination of polycyclic aromatic hydrocarbons in drinking water samples by solid-phase nanoextraction and high-performance liquid chromatography.

PubMed

Wang, Huiyong; Campiglia, Andres D

2008-11-01

A novel alternative is presented for the extraction and preconcentration of polycyclic aromatic hydrocarbons (PAH) from water samples. The new approachwhich we have named solid-phase nanoextraction (SPNE)takes advantage of the strong affinity that exists between PAH and gold nanoparticles. Carefully optimization of experimental parameters has led to a high-performance liquid chromatography method with excellent analytical figures of merit. Its most striking feature correlates to the small volume of water sample (500 microL) for complete PAH analyses. The limits of detection ranged from 0.9 (anthracene) to 58 ng.L (-1) (fluorene). The relative standard deviations at medium calibration concentrations vary from 3.2 (acenaphthene) to 9.1% (naphthalene). The analytical recoveries from tap water samples of the six regulated PAH varied from 83.3 +/- 2.4 (benzo[ k]fluoranthene) to 95.7 +/- 4.1% (benzo[ g,h,i]perylene). The entire extraction procedure consumes less than 100 microL of organic solvents per sample, which makes it environmentally friendly. The small volume of extracting solution makes SPNE a relatively inexpensive extraction approach.

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.

Evidence for a novel pathway in the degradation of fluorene by Pseudomonas sp. strain F274.

PubMed Central

Grifoll, M; Selifonov, S A; Chapman, P J

1994-01-01

A fluorene-utilizing microorganism, identified as a species of Pseudomonas, was isolated from soil severely contaminated from creosote use and was shown to accumulate six major metabolites from fluorene in washed-cell incubations. Five of these products were identified as 9-fluorenol, 9-fluorenone, (+)-1,1a-dihydroxy-1-hydro-9-fluorenone, 8-hydroxy-3,4-benzocoumarin, and phthalic acid. This last compound was also identified in growing cultures supported by fluorene. Fluorene assimilation into cell biomass was estimated to be approximately 50%. The structures of accumulated products indicate that a previously undescribed pathway of fluorene catabolism is employed by Pseudomonas sp. strain F274. This pathway involves oxygenation of fluorene at C-9 to give 9-fluorenol, which is then dehydrogenated to the corresponding ketone, 9-fluorenone. Dioxygenase attack on 9-fluorenone adjacent to the carbonyl group gives an angular diol, 1,1a-dihydroxy-1-hydro-9-fluorenone. Identification of 8-hydroxy-3,4-benzocoumarin and phthalic acid suggests that the five-membered ring of the angular diol is opened first and that the resulting 2'-carboxy derivative of 2,3-dihydroxy-biphenyl is catabolized by reactions analogous to those of biphenyl degradation, leading to the formation of phthalic acid. Cell extracts of fluorene-grown cells possessed high levels of an enzyme characteristic of phthalate catabolism, 4,5-dihydroxyphthalate decarboxylase, together with protocatechuate 4,5-dioxygenase. On the basis of these findings, a pathway of fluorene degradation is proposed to account for its conversion to intermediary metabolites. A range of compounds with structures similar to that of fluorene was acted on by fluorene-grown cells to give products consistent with the initial reactions proposed. PMID:8074523

Seasonal variation of polycyclic aromatic hydrocarbons concentrations in urban streams at Niterói City, RJ, Brazil.

PubMed

Ribeiro, Angelo Morgado; da Rocha, Camila Coimbra Martins; Franco, Caroline Fernandes Jaegger; Fontana, Luiz Francisco; Pereira Netto, Annibal D

2012-12-01

Polycyclic aromatic hydrocarbons (PAHs) were determined in water samples collected in two streams and a lake located at Niteroi City, Rio de Janeiro State, Brazil between October 2008 and September 2009. Samples were extracted using liquid-liquid extraction and analyzed using high performance liquid chromatography with fluorescence detection. The limits of quantification were sufficiently low to accomplish PAH determination below the maximum concentration levels established by the Brazilian (50 ng/L) and USEPA legislations, with recoveries larger than 81.6%. Phenanthrene, fluoranthene, pyrene and benz[a]anthracene predominated among PAHs. Total concentrations of PAHs were well correlated with rainfall indicating a possible role of runoff to local pollution of water by PAHs and showed a seasonal variation in wet and dry seasons. Our results highlight the contribution of the widespread streams located around Guanabara Bay to the PAH burden found in its waters. Copyright © 2012 Elsevier Ltd. All rights reserved.

Does the concept of Clar's aromatic sextet work for dicationic forms of polycyclic aromatic hydrocarbons?--testing the model against charged systems in singlet and triplet states.

PubMed

Dominikowska, Justyna; Palusiak, Marcin

2011-07-07

The concept of Clar's π-electron aromatic sextet was tested against a set of polycyclic aromatic hydrocarbons in neutral and doubly charged forms. Systems containing different types of rings (in the context of Clar's concept) were chosen, including benzene, naphthalene, anthracene, phenanthrene and triphenylene. In the case of dicationic structures both singlet and triplet states were considered. It was found that for singlet state dicationic structures the concept of aromatic sextet could be applied and the local aromaticity could be discussed in the context of that model, whereas in the case of triplet state dicationic structures Clar's model rather failed. Different aromaticity indices based on various properties of molecular systems were applied for the purpose of the studies. The discussion about the interdependence between the values of different aromaticity indices applied to neutral and charged systems in singlet and triplet states is also included. This journal is © the Owner Societies 2011

Identification and quantification of phencyclidine pyrolysis products formed during smoking.

PubMed

Lue, L P; Scimeca, J A; Thomas, B F; Martin, B R

1986-01-01

As a result of frequent phencyclidine (PCP) abuse, pyrolysis studies were conducted to further investigate its fate during smoking. Marijuana placebo cigarettes were impregnated with 3H-PCP X HCI and burned under conditions simulating smoking. Mainstream smoke was passed through glass wool filters as well as acidic and basic traps. Approximately 90% of the starting material could be accounted for in the first glass wool trap and cigarette holder. HPLC and GC/MS analysis of methanol extracts of these glass wool traps revealed the presence of 1-phenyl-1-cyclohexene (47% of the starting material) greater than PCP (40%) greater than piperidine (15%) greater than N-acetylpiperidine (9%). It was not possible to fully account for the remainder of the piperidine moiety. It has been reported that at high temperatures PCP is converted to numerous polynuclear aromatic compounds which include styrene, alpha-methylstyrene, naphthalene, 2-methylnaphthalene, 1-methylnaphthalene, biphenyl, cyclohexylbenzene, acenaphthene, phenanthrene, and anthracene. These compounds were not formed from PCP under smoking conditions.

Predicting the equilibrium solubility of solid polycyclic aromatic hydrocarbons and dibenzothiophene using a combination of MOSCED plus molecular simulation or electronic structure calculations

NASA Astrophysics Data System (ADS)

Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.

2017-06-01

Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.

Identification and quantification of phencyclidine pyrolysis products formed during smoking

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

Lue, L.P.; Scimeca, J.A.; Thomas, B.F.

As a result of frequent phencyclidine (PCP) abuse, pyrolysis studies were conducted to further investigate its fate during smoking. Marijuana placebo cigarettes were impregnated with /sup 3/H-PCP HCl and burned under conditions simulating smoking. Mainstream smoke was passed through glass wool filters as well as acidic and basic traps. Approximately 90% of the starting material could be accounted for in the first glass wool trap and cigarette holder. HPLC and GC/MS analysis of methanol extracts of these glass wool traps revealed the presence of 1-phenyl-1-cyclohexene (47% of the starting material) > PCP (40%) > piperidine (15%) > N-acetylpiperidine (9%). Itmore » was not possible to fully account for the remainder of the piperidine moiety. It has been reported that at high temperatures PCP is converted to numerous polynuclear aromatic compounds which include styrene, ..cap alpha..-methylstyrene, naphthalene, 2-methyl-naphthalene, 1-methylnaphthalene, biphenyl, cyclohexylbenzene, acenaphthene, phenanthrene, and anthracene. These compounds were not formed from PCP under smoking conditions.« 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.

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.

Investigating the Effects of Environmental Solutes on the Reaction Environment in Ice and at Ice Surfaces

NASA Astrophysics Data System (ADS)

Malley, Philip Patrick Anthony

The reaction environments present in water, ice, and at ice surfaces are physically distinct from one another and studies have shown that photolytic reactions can take place at different rates in the different media. Kinetics of reactions in frozen media are measured in snow and ice prepared from deionized water. This reduces experimental artifacts, but is not relevant to snow in the environment, which contains solutes. We have monitored the effect of nonchromophoric (will not absorb sunlight) organic matter on the photolytic fate of the polycyclic aromatic hydrocarbons (PAHs) phenanthrene, pyrene, and anthracene in ice and at ice surfaces. Nonchromophoric organic matter reduced photolysis rates to below our detection limit in bulk ice, and reduced rates at ice surfaces to a lesser extent due to the PAHs partially partitioning to the organics present. In addition, we have monitored the effect of chromophoric (will absorb sunlight) dissolved organic matter (cDOM) on the fate of anthracene in water, ice, and ice surfaces. cDOM reduced rates in all three media. Suppression in liquid water was due to physical interactions between anthracene and the cDOM, rather than to competitive photon absorbance. More suppression was observed in ice cubes and ice granules than in liquid water due to a freeze concentrating effect. Sodium Chloride (NaCl) is another ubiquitous environmental solute that can influence reaction kinetics in water, ice, and at ice surfaces. Using Raman microscopy, we have mapped the surface of ice of frozen NaCl solutions at 0.02M and 0.6M, as well as the surface of frozen samples of Sargasso Sea Water. At temperatures above and below the eutectic temperature (-21.1°C). Above the eutectic, regions of ice and liquid water were observed in all samples. Liquid regions generally took the form of channels. Channel widths and fractional liquid surface coverage increased with NaCl concentration and temperature. Volume maps of the three samples at temperatures above the eutectic point, showed that liquid channels were distributed throughout the ice sample. Liquid fractions were similar at ice surfaces and in the bulk at depths of at least 80 microm.

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.

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.

2,2′-Bi(9,9-di­ethyl­fluorene)

PubMed Central

Park, Ki-Min; Oh, Hankook; Kang, Youngjin

2014-01-01

The title compound, C34H34, systematic name 9,9,9′,9′-tetra­ethyl-2,2′-bi(9H-fluorene), crystallized with two crystallographically independent mol­ecules (A and B) in the asymmetric unit. These differ mainly in the orientation of the lateral ethyl chains: in mol­ecule A, they are both on the same side of the mol­ecule whereas in mol­ecule B, one di­ethyl­fluorene moiety has undergone a 180° rotation such that the two pairs of ethyl residues appear on opposite sides of the mol­ecule. The fluorene ring systems subtend dihedral angles of 31.37 (4) and 43.18 (3)° in mol­ecules A and B, respectively. Hence the two fluorene moieties are tilted slightly toward one another. This may be due to the presence of inter­molecular C—H⋯π inter­actions between neighboring mol­ecules. The lateral ethyl chains (excluding H atoms) are also almost planar, with each pair almost perpendicular to the plane of the fluorene system to which they are attached with dihedral angles between the ethyl and fluorene planes in the range 86.04 (8)–89.5 (1)°. PMID:24764898

Degradation of phenanthrene by Trametes versicolor and its laccase.

PubMed

Han, Mun-Jung; Choi, Hyoung-Tae; Song, Hong-Gyu

2004-06-01

Phenanthrene is a three-ring polycyclic aromatic hydrocarbon and commonly found as a pollutant in various environments. Degradation of phenanthrene by white rot fungus Trametes versicolor 951022 and its laccase, isolated in Korea, was investigated. After 36 h of incubation, about 46% and 65% of 100 mg/l of phenanthrene added in shaken and static fungal cultures were removed, respectively. Phenanthrene degradation was maximal at pH 6 and the optimal temperature for phenanthrene removal was 30 degrees C. Although the removal percentage of phenanthrene was highest (76.7%) at 10 mg/l of phenanthrene concentration, the transformation rate was maximal (0.82 mg/h) at 100 mg/L of phenanthrene concentration in the fungal culture. When the purified laccase of T versicolor 951022 reacted with phenanthrene, phenanthrene was not transformed. The addition of redox mediator, 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) or 1-hydroxybenzotriazole (HBT) to the reaction mixture increased oxidation of phenanthrene by laccase about 40% and 30%, respectively.

Ascorbic Acid Enhances the Accumulation of Polycyclic Aromatic Hydrocarbons (PAHs) in Roots of Tall Fescue (Festuca arundinacea Schreb.)

PubMed Central

Gao, Yanzheng; Li, Hui; Gong, Shuaishuai

2012-01-01

Plant contamination by polycyclic aromatic hydrocarbons (PAHs) is crucial to food safety and human health. Enzyme inhibitors are commonly utilized in agriculture to control plant metabolism of organic components. This study revealed that the enzyme inhibitor ascorbic acid (AA) significantly reduced the activities of peroxidase (POD) and polyphenol oxidase (PPO), thus enhancing the potential risks of PAH contamination in tall fescue (Festuca arundinacea Schreb.). POD and PPO enzymes in vitro effectively decomposed naphthalene (NAP), phenanthrene (PHE) and anthracene (ANT). The presence of AA reduced POD and PPO activities in plants, and thus was likely responsible for enhanced PAH accumulation in tall fescue. This conclusion is supported by the significantly enhanced uptake of PHE in plants in the presence of AA, and the positive correlation between enzyme inhibition efficiencies and the rates of metabolism of PHE in tall fescue roots. This study provides a new perspective, that the common application of enzyme inhibitors in agricultural production could increase the accumulation of organic contaminants in plants, hence enhancing risks to food safety and quality. PMID:23185628

Spatial and temporal variation of freely dissolved PAHs in an urban river undergoing Superfund remediation

PubMed Central

Sower, GJ; Anderson, K.A.

2014-01-01

Urban rivers with a history of industrial use can exhibit spatial and temporal variations in contaminant concentrations that may significantly affect risk evaluations and even the assessment of remediation efforts. Concentrations of 15 biologically available priority pollutant polycyclic aromatic hydrocarbons (PAHs) were measured over five years along 18.5 miles of the lower Willamette River using passive sampling devices and HPLC. The study area includes the Portland Harbor Superfund megasite with several PAH sources including remediation operations for coal tar at RM 6.3 west and an additional Superfund site, McCormick and Baxter, at RM 7 east consisting largely of creosote contamination. Study results show that organoclay capping at the McCormick and Baxter Superfund Site reduced PAHs from a pre-cap average of 440 ± 422 ng/L to 8 ± 3 ng/L post-capping. Results also reveal that dredging of submerged coal tar nearly tripled nearby freely dissolved PAH concentrations. For apportioning sources, fluoranthene/ pyrene and phenanthrene/anthracene diagnostic ratios from passive sampling devices were established for creosote and coal tar contamination and compared to published sediment values. PMID:19174872

Spatial and temporal variation of freely dissolved polycyclic aromatic hydrocarbons in an urban river undergoing Superfund remediation.

PubMed

Sower, Gregory James; Anderson, Kim A

2008-12-15

Urban rivers with a history of industrial use can exhibit spatial and temporal variations in contaminant concentrations that may significantly affect risk evaluations and even the assessment of remediation efforts. Concentrations of 15 biologically available priority pollutant polycyclic aromatic hydrocarbons (PAHs) were measured over five years along 18.5 miles of the lower Willamette River using passive sampling devices and HPLC. The study area includes the Portland Harbor Superfund megasite with several PAH sources including remediation operations for coal tar at RM 6.3 west and an additional Superfund site, McCormick and Baxter, at RM 7 east consisting largely of creosote contamination. Study results show that organoclay capping at the McCormick and Baxter Superfund Site reduced PAHs from a precap average of 440 +/- 422 ng/L to 8 +/- 3 ng/L postcapping. Results also reveal that dredging of submerged coal tar nearly tripled nearby freely dissolved PAH concentrations. For apportioning sources, fluoranthene/pyrene and phenanthrene/anthracene diagnostic ratios from passive sampling devices were established for creosote and coal tar contamination and compared to published sediment values.

Ultrafast optical excitations in supramolecular metallacycles with charge transfer properties.

PubMed

Flynn, Daniel C; Ramakrishna, Guda; Yang, Hai-Bo; Northrop, Brian H; Stang, Peter J; Goodson, Theodore

2010-02-03

New organometallic materials such as two-dimensional metallacycles and three-dimensional metallacages are important for the development of novel optical, electronic, and energy related applications. In this article, the ultrafast dynamics of two different platinum-containing metallacycles have been investigated by femtosecond fluorescence upconversion and transient absorption. These measurements were carried out in an effort to probe the charge transfer dynamics and the rate of intersystem crossing in metallacycles of different geometries and dimensions. The processes of ultrafast intersystem crossing and charge transfer vary between the two different classes of metallacyclic systems studied. For rectangular anthracene-containing metallacycles, the electronic coupling between adjacent ligands was relatively weak, whereas for the triangular phenanthrene-containing structures, there was a clear interaction between the conjugated ligand and the metal complex center. The transient lifetimes increased with increasing conjugation in that case. The results show that differences in the dimensionality and structure of metallacycles result in different optical properties, which may be utilized in the design of nonlinear optical materials and potential new, longer-lived excited state materials for further electronic applications.

RECOIL LABELING OF ORGANIC COMPOUNDS (in Japanese)

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

Oae, S.; Hamada, M.; Otsuji, Y.

1963-01-01

The results of C/sup 14/-labeling under neutron irradiation of two groups of compounds are reported: (1) naphthalene, phenanthrene, and anthracene in an attempt to determine whether or not high energy C/sup 14/ fragments formed by nuclear recoil would favor or discriminate against any particular position in product formations; (2) pseudoephedrine, 2-amino-pyrimidine, and 3,6- dihydroxypyridazine as complex nitrogen-containing compounds. These samples were irradiated with thermal neutrons obtained from a pile. To determine the radiochemical yields and the relative ratios of the C/sup 14/ distributions in the respective compounds, the samples were purified radlochemically and were degraded chemically. The results deduced frommore » the experimental data are the following: (1) higher distribution of C/sup 14/ was found in the positions where the localizations of electrons are known to be higher; (2) the re-entry of C/sup 14/ into angular positions was very small; (3) the difference of phase affected the yield but not the distribution of C/sup 14/ in the products; (4) the relatively complex compounds could be labeled directly by this method. (A.G.W.)« less

Contamination of polycyclic aromatic hydrocarbons (PAHs) in surface sediments and plants of mangrove swamps in Shenzhen, China.

PubMed

Li, Fenglan; Zeng, Xiaokang; Yang, Junda; Zhou, Kai; Zan, Qijie; Lei, Anping; Tam, Nora F Y

2014-08-30

The concentrations of 16 individual and total polycyclic aromatic hydrocarbons (∑PAHs) in sediments, roots and leaves of three mangrove swamps in Shenzhen, China, namely Futian, Baguang and Waterlands, were determined. The mean concentration of ∑PAHs in Futian (4480 ng g(-1)) was significantly higher than that in Baguang (1262 ng g(-1)) and Waterlands (2711 ng g(-1)). Among the 16 PAHs, the concentration of naphthalene was the highest. Based on the ratios of phenanthrene/anthracene and fluoranthene/pyrene, PAHs in Futian and Waterlands came from petrogenic and pyrolytic sources, while Baguang was mainly from pyrolytic. More PAHs were accumulated in leaves, as reflected by its higher mean concentration of ∑PAHs (3697 ng g(-1)) and bioconcentration factor of PAHs (BCF) (>1.5) than that in roots. The BCF values in plants collected from Futian were significantly higher than that from Waterlands. These results indicated that more attention should be paid to the PAH contamination in Futian. Copyright © 2014 Elsevier Ltd. All rights reserved.

New metabolites in the degradation of fluorene by Arthrobacter sp. strain F101.

PubMed

Casellas, M; Grifoll, M; Bayona, J M; Solanas, A M

1997-03-01

Identification of new metabolites and demonstration of key enzyme activities support and extend the pathways previously reported for fluorene metabolism by Arthrobacter sp. strain F101. Washed-cell suspensions of strain F101 with fluorene accumulated 9-fluorenone, 4-hydroxy-9-fluorenone, 3-hydroxy-1-indanone, 1-indanone, 2-indanone, 3-(2-hydroxyphenyl) propionate, and a compound tentatively identified as a formyl indanone. Incubations with 2-indanone produced 3-isochromanone. The growth yield with fluorene as a sole source of carbon and energy corresponded to an assimilation of about 34% of fluorene carbon. About 7.4% was transformed into 9-fluorenol, 9-fluorenone, and 4-hydroxy-9-fluorenone. Crude extracts from fluorene-induced cells showed 3,4-dihydrocoumarin hydrolase and catechol 2,3-dioxygenase activities. These results and biodegradation experiments with the identified metabolites indicate that metabolism of fluorene by Arthrobacter sp. strain F101 proceeds through three independent pathways. Two productive routes are initiated by dioxygenation at positions 1,2 and 3,4, respectively. meta cleavage followed by an aldolase reaction and loss of C-1 yield the detected indanones. Subsequent biological Baeyer-Villiger reactions produce the aromatic lactones 3,4-dihydrocoumarin and 3-isochromanone. Enzymatic hydrolysis of the former gives 3-(2-hydroxyphenyl) propionate, which could be a substrate for a beta oxidation cycle, to give salicylate. Further oxidation of the latter via catechol and 2-hydroxymuconic semialdehyde connects with the central metabolism, allowing the utilization of all fluorene carbons. Identification of 4-hydroxy-9-fluorenone is consistent with an alternative pathway initiated by monooxygenation at C-9 to give 9-fluorenol and then 9-fluorenone. Although dioxygenation at 3,4 positions of the ketone apparently occurs, this reaction fails to furnish a subsequent productive oxidation of this compound.

New metabolites in the degradation of fluorene by Arthrobacter sp. strain F101.

PubMed Central

Casellas, M; Grifoll, M; Bayona, J M; Solanas, A M

1997-01-01

Identification of new metabolites and demonstration of key enzyme activities support and extend the pathways previously reported for fluorene metabolism by Arthrobacter sp. strain F101. Washed-cell suspensions of strain F101 with fluorene accumulated 9-fluorenone, 4-hydroxy-9-fluorenone, 3-hydroxy-1-indanone, 1-indanone, 2-indanone, 3-(2-hydroxyphenyl) propionate, and a compound tentatively identified as a formyl indanone. Incubations with 2-indanone produced 3-isochromanone. The growth yield with fluorene as a sole source of carbon and energy corresponded to an assimilation of about 34% of fluorene carbon. About 7.4% was transformed into 9-fluorenol, 9-fluorenone, and 4-hydroxy-9-fluorenone. Crude extracts from fluorene-induced cells showed 3,4-dihydrocoumarin hydrolase and catechol 2,3-dioxygenase activities. These results and biodegradation experiments with the identified metabolites indicate that metabolism of fluorene by Arthrobacter sp. strain F101 proceeds through three independent pathways. Two productive routes are initiated by dioxygenation at positions 1,2 and 3,4, respectively. meta cleavage followed by an aldolase reaction and loss of C-1 yield the detected indanones. Subsequent biological Baeyer-Villiger reactions produce the aromatic lactones 3,4-dihydrocoumarin and 3-isochromanone. Enzymatic hydrolysis of the former gives 3-(2-hydroxyphenyl) propionate, which could be a substrate for a beta oxidation cycle, to give salicylate. Further oxidation of the latter via catechol and 2-hydroxymuconic semialdehyde connects with the central metabolism, allowing the utilization of all fluorene carbons. Identification of 4-hydroxy-9-fluorenone is consistent with an alternative pathway initiated by monooxygenation at C-9 to give 9-fluorenol and then 9-fluorenone. Although dioxygenation at 3,4 positions of the ketone apparently occurs, this reaction fails to furnish a subsequent productive oxidation of this compound. PMID:9055403

New Findings on Aromatic Compounds' Degradation and Their Metabolic Pathways, the Biosurfactant Production and Motility of the Halophilic Bacterium Halomonas sp. KHS3.

PubMed

Corti Monzón, Georgina; Nisenbaum, Melina; Herrera Seitz, M Karina; Murialdo, Silvia E

2018-04-24

The study of the aromatic compounds' degrading ability by halophilic bacteria became an interesting research topic, because of the increasing use of halophiles in bioremediation of saline habitats and effluents. In this work, we focused on the study of aromatic compounds' degradation potential of Halomonas sp. KHS3, a moderately halophilic bacterium isolated from hydrocarbon-contaminated seawater of the Mar del Plata harbour. We demonstrated that H. sp. KHS3 is able to grow using different monoaromatic (salicylic acid, benzoic acid, 4-hydroxybenzoic acid, phthalate) and polyaromatic (naphthalene, fluorene, and phenanthrene) substrates. The ability to degrade benzoic acid and 4-hydroxybenzoic acid was analytically corroborated, and Monod kinetic parameters and yield coefficients for degradation were estimated. Strategies that may enhance substrate bioavailability such as surfactant production and chemotactic responses toward aromatic compounds were confirmed. Genomic sequence analysis of this strain allowed us to identify several genes putatively related to the metabolism of aromatic compounds, being the catechol and protocatechuate branches of β-ketoadipate pathway completely represented. These features suggest that the broad-spectrum xenobiotic degrader H. sp. KHS3 could be employed as a useful biotechnological tool for the cleanup of aromatic compounds-polluted saline habitats or effluents.

Different profiles of carcinogen exposure in Chinese compared with US cigarette smokers.

PubMed

Benowitz, Neal L; Gan, Quan; Goniewicz, Maciej L; Lu, Wei; Xu, Jiying; Li, Xinjian; Jacob, Peyton; Glantz, Stanton

2015-12-01

Differences in carcinogen exposure from different cigarette products could contribute to differences in smoking-associated cancer incidence among Chinese compared with US smokers. Urine concentrations of metabolites of nicotine, the tobacco-specific nitrosamine (TSNA) 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), and polycyclic aromatic hydrocarbon metabolites (PAHs) were compared in 238 Chinese and 203 US daily smokers. Comparing Chinese versus US smokers, daily nicotine intake and nicotine intake per cigarette smoked were found to be similar. When normalised for cigarettes per day, urine NNAL excretion was fourfold higher in US smokers, while the excretion of urine metabolites of the PAHs fluorene, phenanthrene and pyrene metabolites was 50% to fourfold higher in Chinese smokers (all, p<0.0001). Similar results were seen when NNAL and PAHs excretion was normalised for daily nicotine intake. Patterns of carcinogen exposure differ, with lower exposure to TSNA and higher exposure to PAHs in Chinese compared with US smokers. These results most likely reflect country differences in cigarette tobacco blends and manufacturing processes, as well as different environmental exposures. NCT00264342. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/

Removing polycyclic aromatic hydrocarbons from water using granular activated carbon: kinetic and equilibrium adsorption studies.

PubMed

Eeshwarasinghe, Dinushika; Loganathan, Paripurnanda; Kalaruban, Mahatheva; Sounthararajah, Danious Pratheep; Kandasamy, Jaya; Vigneswaran, Saravanamuthu

2018-05-01

Polycyclic aromatic hydrocarbons (PAHs) constitute a group of highly persistent, toxic and widespread environmental micropollutants that are increasingly found in water. A study was conducted in removing five PAHs, specifically naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene, from water by adsorption onto granular activated carbon (GAC). The pseudo-first-order (PFO) model satisfactorily described the kinetics of adsorption of the PAHs. The Weber and Morris diffusion model's fit to the data showed that there were faster and slower rates of intra-particle diffusion probably into the mesopores and micropores of the GAC, respectively. These rates were negatively related to the molar volumes of the PAHs. Batch equilibrium adsorption data fitted well to the Langmuir, Freundlich and Dubinin-Radushkevich models, of which the Freundlich model exhibited the best fit. The adsorption affinities were related to the hydrophobicity of the PAHs as determined by the log K ow values. Free energies of adsorption calculated from the Dubinin-Radushkevich model and the satisfactory kinetic data fitting to the PFO model suggested physical adsorption of the PAHs. Adsorption of naphthalene, acenaphthylene and acenaphthene in fixed-bed columns containing a mixture of GAC (0.5 g) + sand (24.5 g) was satisfactorily simulated by the Thomas model.

Health-hazard evaluation report HETA 82-309-1630, Inland Steel, East Chicago, Indiana

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

Almaguer, D.; Orris, P.

1985-10-01

Environmental and breathing-zone samples were analyzed for polynuclear aromatic hydrocarbons (PAHs) and coal-tar-pitch volatiles at the Inland Steel Company, East Chicago, Indiana in November, 1982 and September, 1984. The evaluation was requested because of concern about employee exposures during maintenance of the coke battery precipitator at the number 2 facility. Four former employees were interviewed. The cyclohexane soluble fraction of coal-tar-pitch volatiles ranged from 0.232 to 0.668 mg/m/sup 3/. The OSHA standard is 0.15mg/m/sup 3/. Naphthalene concentrations up to 0.107mg/m/sup 3/ were detected. The OSHA standard for naphthalene is 50mg/m/sup 3/. Other PAHs detected included phenanthrene, fluorene and acenaphthene. Themore » employees reported experiencing local skin, eye, ear, nose, and throat irritation while working on the coke battery precipitator in the past. Personal protective measures such as wearing safety boots, barrier creams on exposed skin surfaces, and showering and changing clothes before leaving the facility were implemented. The authors conclude that a potential health hazard from PAHs and coal-tar-pitch volatiles is being adequately addressed by the facility. Recommendations include continuing the present personal protective measures and providing emergency rescue training.« less

Diversity of organotrophic bacteria, activity of dehydrogenases and urease as well as seed germination and root growth Lepidium sativum, Sorghum saccharatum and Sinapis alba under the influence of polycyclic aromatic hydrocarbons.

PubMed

Lipińska, Aneta; Wyszkowska, Jadwiga; Kucharski, Jan

2015-12-01

Polycyclic aromatic hydrocarbons are organic compounds with highly toxic, carcinogenic, and mutagenic properties, which adversely affect the basic biological parameters of the soil, including the count of microorganisms, and the enzymatic activity. In addition to disturbances to the biological activity of the soil, PAHs may also exhibit toxic effects on plants. In view of the above, the study involved testing aimed at the determination of the effects of polycyclic aromatic hydrocarbons in a form of naphthalene, phenanthrene, anthracene and pyrene on the count, colony development (CD) index, ecophysiological (EP) diversity index of organotrophic bacteria, and the activity of soil dehydrogenases and soil urease. Moreover, an attempt was made to determine the soil's resistance based on the activity of the above-listed enzymes, and the effect of polycyclic aromatic hydrocarbons on seed germination and root growth was assessed by Lepidium sativum, Sorghum saccharatum, and Sinapis alba. In addition, the species of bacteria found in a soil subjected to strong pressure of polycyclic aromatic hydrocarbons were isolated. The experiment was performed in a laboratory on samples of loamy sand. Polycyclic aromatic hydrocarbons were introduced into the soil in an amount of 0, 1000, 2000, and 4000 mg kg(-1) of soil dry matter. Germination and growth of cress (L. sativum), white mustard (S. alba), and sweet sorghum (S. saccharatum) were determined using Phytotoxkit tests. It was found that the tested PAHs increased the average colony counts of organotrophic soil bacteria; pyrene did so to the greatest extent (2.2-fold relative to non-contaminated soil), phenanthrene to the smallest extent (1.4-fold relative to non-contaminated soil). None of the PAHs changed the value of the bacterial colony development (CD) index, while anthracene and pyrene increased the value of the eco-physiological (EP) diversity indicator. PAHs lowered the activity of the tested enzymes. The activity of dehydrogenases was dependent on a greater extent by the type of hydrocarbon (54.56%) rather than by the dose (10.64%), while for the activity of urease, it was the opposite. The greater extent was dependent on dose (95.42%) rather than by type (0.21%). Dehydrogenases are characterised by greater resistance to the action of PAHs than urease. Based on seed germination and root growth, it has shown that S. alba is best suited, being the most vulnerable plant, while S. saccharatum is the least suited. Subjecting a soil to strong pressure of PAHs leads to disturbances to the biological parameters of the soil, seed germination, and root growth L. sativum, S. saccharatum, and S. alba.

Interactions among buffelgrass, phenanthrene and phenanthrene-degrading bacteria in gnotobiotic microcosms.

PubMed

Robert, Francoise M; Sun, Wenhao H; Toma, Marisa; Jones, Ryan K; Tang, Chung-Shih

2008-07-15

An experiment was undertaken in gnotobiotic microcosms to determine the role of buffelgrass (Cenchrus ciliaris) and a phenanthrene-degrading bacterium (strain PM600) in the degradation of phenanthrene. The Gram-negative bacterium was identified as a Sphingomonas sp. by 16S rRNA gene sequence analysis and as S. paucimobilis by biochemical tests (API 20 NE strips). Its yellow pigment corresponded to nostoxanthin and its cellular fatty acids were typical of the genus Sphingomonas. Moreover, it was devoid of lipopolysaccharides. Strain PM600 was tested for growth on mineral medium supplemented with No. 2 diesel, hexadecane, mineral oil, pristane, phenanthrene, and pyrene as single carbon sources. It was capable of utilizing phenanthrene only. In the gnotobiotic microcosms silica sand was either or not supplemented with 150 mg of phenanthrene kg(-1) sand, inoculated with strain PM600, and planted to sterile young seedlings of buffelgrass. After 28 days, 67% of the reduction of the phenanthrene concentration was assigned to degradation by the bacterium and ca. 20% to abiotic factors. No statistically significant effect of the young buffelgrass was found. In the absence of phenanthrene, the bacterial population significantly increased in the rhizosphere of buffelgrass. However, in the presence of buffelgrass and phenanthrene, the bacterial population preferentially responded to phenanthrene. The growth of buffelgrass was severely curtailed by phenanthrene in the absence of the bacterium. However, strain PM600 effectively protected buffelgrass against the phytotoxicity of phenanthrene.

Effect of Cosolutes on the Sorption of Phenanthrene onto Mineral Surface of River Sediments and Kaolinite

PubMed Central

2014-01-01

Sorption of phenanthrene onto the natural sediment with low organic carbon content (OC%), organic-free sediment, and kaolinite was investigated through isotherm experiments. Effects of cosolutes (pyrene, 4-n-nonyphenol (NP), and humic acid (HA)) on phenanthrene sorption were also studied by comparing apparent solid-water distribution coefficients (K d app) of phenanthrene. Two addition sequences, including “cosolute added prior to phenanthrene” and “cosolute and phenanthrene added simultaneously,” were adopted. The Freundlich model fits phenanthrene sorption on all 3 sorbents well. The sorption coefficients on these sorbents were similar, suggesting that mineral surface plays an important role in the sorption of hydrophobic organic contaminants on low OC% sediments. Cosolutes could affect phenanthrene sorption on the sorbents, which depended on their properties, concentrations, and addition sequences. Pyrene inhibited phenanthrene sorption. Sorbed NP inhibited phenanthrene sorption at low levels and promoted sorption at high levels. Similar to NP, effect of HA on phenanthrene sorption onto the natural sediment depended on its concentrations, whereas, for the organic-free sediment and kaolinite, preloading of HA at high levels led to an enhancement in phenanthrene K d app while no obvious effect was observed at low HA levels; dissolved HA could inhibit phenanthrene sorption on the two sorbents. PMID:25147865

Synthesis, spectral studies, antimicrobial, antioxidant and insect antifeedant activities of some 9 H-fluorene-2-yl keto-oxiranes

NASA Astrophysics Data System (ADS)

Thirunarayanan, G.; Vanangamudi, G.

2011-10-01

Thirteen ee (α S, β R) 9 H-fluorene-2-yl keto-oxiranes (2-(9 H)-fluorene-4-yl[3-(substituted phenyl)oxiran-2-yl]methanones) have been synthesized by phase transfer catalysed epoxidation of 9 H-fluorene-2-yl chalcones. The yields of oxiranes are more than 95%. The synthesized oxiranes have been characterized by IR, 1H, 13C and GC-MS spectral data. The spectral data are correlated with Hammett substituent constants and Swain-Lupton parameters. From the regression analysis, the effect of substituents on the group frequencies has been predicted. The antimicrobial, antioxidant and insect antifeedant activities of all the synthesized oxiranes have been studied.

Photodegradation of fluorene in aqueous solution: Identification and biological activity testing of degradation products.

PubMed

Kinani, Said; Souissi, Yasmine; Kinani, Aziz; Vujović, Svetlana; Aït-Aïssa, Sélim; Bouchonnet, Stéphane

2016-04-15

Degradation of fluorene under UV-vis irradiation in water was investigated and structural elucidation of the main photoproducts was achieved using gas chromatography coupled with mass spectrometry. Twenty-six photoproducts were structurally identified, mainly on the basis of electron ionization mass spectra interpretation. The main generated transformation products are hydroxy derivatives. Some secondary photoproducts including fluorenone, hydroxy fluorenone, 2-biphenyl carboxylic acid, biphenylene, methanol fluorene congeners and hydroxy fluorene dimers were also observed. A photodegradation pathway was suggested on the basis of the chemical structures of photoproducts. Fluorene as well as its main photoproducts for which chemical standards were commercially available were tested for their ability to elicit cytotoxic, estrogenic and dioxin-like activity by using in vitro cell-based bioassays. None of the tested compounds was cytotoxic at concentrations up to 100 μM. However, 2-hydroxyfluorene and 3-hydroxyfluorene exerted significant estrogenic and dioxin-like activity on a concentration range of 3-30 μM, while fluorene and 9-hydroxyfluorene were weakly or not active, respectively, in our assays. This supports the view that photodegradation processes can generate by-products of higher toxicological concern than the parent compound and strengthens the need to further identify transformation products in the aquatic environment. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of phenanthrene bioavailability by using a self-dying reporter bacterium: test with model solids and soil.

PubMed

Shin, Doyun; Nam, Kyoungphile

2012-02-20

The present study was conducted to investigate the performance and feasibility of a self-dying reporter bacterium to visualize and quantify phenanthrene bioavailability in soil. The self-dying reporter bacterium was designed to die on the initiation of phenanthrene biodegradation. The viability of the reporter bacterium was determined by a fluorescence live/dead cell staining method and visualized by confocal laser scanning microscopic observation. Phenanthrene was spiked into four types of model solids and a sandy loam. The bioavailability of phenanthrene to the reporter bacterium was remarkably declined with the hydrophobicity of the model solids: essentially no phenanthrene was biodegraded in the presence of 9-nm pores and about 35.8% of initial phenanthrene was biodegraded without pores. Decrease in bioavailability was not evident in the nonporous hydrophilic bead, but a small decrease was observed in the porous hydrophilic bead at 1000 mg/kg of phenanthrene. The fluorescence intensity was commensurate with the extent of phenanthrene biodegradation by the reporter bacterium at the concentration range from 50 to 500 mg/kg. Such a quantitative relationship was also confirmed with a sandy loam spiked up to 1000 mg/kg of phenanthrene. This reporter bacterium may be a useful means to determine phenanthrene bioavailability in soil. Copyright © 2011 Elsevier B.V. All rights reserved.

The mechanisms by which phenanthrene affects the photosynthetic apparatus of cucumber leaves.

PubMed

Jin, Liqiao; Che, Xingkai; Zhang, Zishan; Li, Yuting; Gao, Huiyuan; Zhao, Shijie

2017-02-01

Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) that is widely distributed in the environment and seriously affects the growth and development of plants. To clarify the mechanisms of the direct effects of phenanthrene on the plant photosynthetic apparatus, we measured short-term phenanthrene-treated cucumber leaves. Phenanthrene inhibited Rubisco carboxylation activity, decreasing photosynthesis rates (Pn). And phenanthrene inhibited photosystem II (PSII) activity, thereby blocking photosynthetic electron transport. The inhibition of the light and dark reactions decreased the photosynthetic electron transport rate (ETR) and increased the excitation pressure (1-qP). Under high light, the maximum photochemical efficiency of photosystem II (F v /F m ) in phenanthrene-treated cucumber leaves decreased significantly, but photosystem I (PSI) activity (Δ I/I o ) did not. Phenanthrene also caused a J-point rise in the OJIP curve under high light, which indicated that the acceptor side of PSII Q A to Q B electron transfer was restricted. This was primarily due to the net degradation of D1 protein, which is caused by the accumulation of reactive oxygen species (ROS) in phenanthrene-treated cucumber leaves under high light. This study demonstrated that phenanthrene could directly inhibit photosynthetic electron transport and Rubisco carboxylation activity to decrease net Pn. Under high light, phenanthrene caused the accumulation of ROS, resulting in net increases in D1 protein degradation and consequently causing PSII photoinhibition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Thermodynamics of phenanthrene partition into solid organic matter from water.

PubMed

Chen, Bao-liang; Zhu, Li-zhong; Tao, Shu

2005-01-01

The thermodynamic behavior of organic contaminants in soils is essential to develop remediation technologies and assess risk from alternative technologies. Thermodynamics of phenanthrene partition into four solids(three soils and a bentonite) from water were investigated. The thermodynamics parameters (deltaH, deltaG degrees, deltaS degrees) were calculated according to experimental data. The total sorption heats of phenanthrene to solids from water ranged from -7.93 to -17.1 kJ/mol, which were less exothermic than the condensation heat of phenanthrene-solid (i.e., -18.6 kJ/mol). The partition heats of phenanthrene dissolved into solid organic matter ranged from 23.1 to 32.2 kJ/mol, which were less endothermic than the aqueous dissolved heat of phenanthrene (i.e., 40.2 kJ/mol), and were more endothermic than the fusion heat of phenanthrene-solid (i.e., 18.6 kJ/mol). The standard free energy changes, deltaG degrees, are all negative which suggested that phenanthrene sorption into solid was a spontaneous process. The positive values of standard entropy changes, deltaS degrees, show a gain in entropy for the transfer of phenanthrene at the stated standard state. Due to solubility-enhancement of phenanthrene, the partition coefficients normalized by organic carbon contents decrease with increasing system temperature (i.e., ln Koc = -0.284 ln S + 9.82 (n = 4, r2 = 0.992)). The solubility of phenanthrene in solid organic matter increased with increasing temperatures. Transports of phenanthrene in different latitude locations and seasons would be predicted according to its sorption thermodynamics behavior.

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.

Impact of methylene chloride on microorganisms and phenanthrene mineralization in soil.

PubMed

Schwartz, Egbert; Trinh, Sinh V; Scow, Kate M

2002-01-01

This study investigated the effects of the quantity of methylene chloride, used as a carrier solvent for phenanthrene when added to soil, on phenanthrene mineralization kinetics, soil phospholipid fatty add profiles (PLFA), and phenanthrene distribution. Methylene chloride dosages of 25 microL/g soil or more resulted in an enrichment of saturated PLFAs, suggesting soil microorganisms had adjusted their cell membranes in response to the solvent. A greater fraction of phenanthrene mineralized when spiked in 5 microL/g than in 25 microL/g methylene chloride suggesting that the methylene chloride became toxic to phenanthrene-degrading organisms in soil. Phenanthrene was more equally distributed among 0.1 g soil subsamples if spiked in 25 than 5 or 1 microL methylene chloride per gram soil. Thus the amount of methylene chloride used to spike phenanthrene in soil strongly impacted the mineralization kinetics, phenanthrene distribution, and microbial community in soil. Because a variety of spiking methods are used in biodegradation research, scientists should consider the quantity of solvents used when comparing results among different studies.

Characterization of the Upper Pathway Genes for Fluorene Metabolism in Terrabacter sp. Strain DBF63

PubMed Central

Habe, Hiroshi; Chung, Jin-Sung; Kato, Hiroyuki; Ayabe, Yuko; Kasuga, Kano; Yoshida, Takako; Nojiri, Hideaki; Yamane, Hisakazu; Omori, Toshio

2004-01-01

Genes involved in the degradation of fluorene to phthalate were characterized in the fluorene degrader Terrabacter sp. strain DBF63. The initial attack on both fluorene and 9-fluorenone was catalyzed by DbfA to yield 9-fluorenol and 1,1a-dihydroxy-1-hydro-9-fluorenone, respectively. The FlnB protein exhibited activities against both 9-fluorenol and 1,1a-dihydroxy-1-hydro-9-fluorenone to produce 9-fluorenone and 2′-carboxy-2,3-dihydroxybiphenyl, respectively. FlnD is a heteromeric protein encoded by flnD1 and ORF16, being a member of the class III two-subunit extradiol dioxygenase. FlnE was identified as a serine hydrolase for the meta-cleavage products that yield phthalate. PMID:15317800

Impacts of Pantoea agglomerans strain and cation-modified clay minerals on the adsorption and biodegradation of phenanthrene.

PubMed

Tao, Kelin; Zhao, Song; Gao, Pin; Wang, Lijin; Jia, Hanzhong

2018-06-06

Interactions between microorganisms and minerals have the potential contribution to remove polycyclic aromatic hydrocarbons (PAHs) in model systems. In this study, phenanthrene (PHE) was used as a probe molecule to explore the potential adsorption and biotransformation processes in the presence of microorganisms and various reference clays, such as montmorillonite (M), kaolinite (K), and pyrophyllite (P). Equilibrium adsorption experiments and scanning electron microscopy (SEM) technique were used to investigate the sorption of Pantoea agglomerans strains on clay minerals saturated with cations (Na + and Fe 3+ ). The adsorption isotherms of PHE and Pantoea agglomerans strains on cation-modified clay minerals fitted to Langmuir equation, and their adsorbed amounts both followed the sequence: montmorillonite > kaolinite > pyrophyllite. For six types of cation-modified minerals, the behavior of PHE adsorbed and Pantoea agglomerans adhered onto mentioned minerals was in the order of Na(I)-M > Fe(Ⅲ)-M, Na(I)-K > Fe(Ⅲ)-K and Fe(Ⅲ)-P > Na(I)-P, respectively. The biodegradation results showed that cation-modified clay minerals could enhance the biodegradation of PHE, ascribing to their large specific surface area, and cation exchange capability, as well as the difference in zeta potential between minerals and Pantoea agglomerans strains. Comparison of biodegradation rates displayed that PHE was degraded the highest in the presence of Na-M (93.285%). In addition, the obtained results suggested that the adhesion of bacteria onto cation-exchanged clay minerals was beneficial to the biodegradation of PHE. Anthracen-9-ylmethanol and 3,4-dimethyl-2-(3-methylbutanoyl)benzoic acid were detected as the main intermediate compounds, which can be further biodegraded into small molecules. The overall results obtained in this study are of valuable significance for the understanding of the behavior of PHE in soil and associated environment. Copyright © 2018 Elsevier Inc. All rights reserved.

Spatial distribution and temporal trends of polycyclic aromatic hydrocarbons (PAHs) in water and sediment from Songhua River, China.

PubMed

Zhao, Xuesong; Ding, Jing; You, Hong

2014-02-01

The spatial and temporal distributions of polycyclic aromatic hydrocarbons (PAHs) in the Songhua River, Harbin, China, were investigated. Seventy-seven samples, 42 water and 35 sediment samples, were collected in April and October of 2007 and January of 2008. The concentrations of total PAHs in water ranged from 163.54 to 2,746.25 ng/L with the average value of 934.62 ng/L, which were predominated by 2- and 3-ring PAHs. The concentrations of total 16 PAHs in sediment ranged from 68.25 to 654.15 ng/g dw with the average value of 234.15 ng/g dw, which were predominated by 4-, 5- and 6-ring PAHs. Statistical analysis of the PAH concentrations shown that the highest concentrations of the total PAHs were found during rainy season (October of 2007) and the lowest during snowy season (January of 2008). Ratios of specific PAH compounds, including fluoranthene/(fluoranthene + pyrene) (Flu/(Flu + Pyr)) and phenanthrene/(phenanthrene + anthracene) (An/(Ant + PhA)), were calculated to evaluate the possible sources of PAH contaminations. These ratios reflected pyrolytic inputs of PAHs in Songhua River water and a mixed pattern of pyrolytic and petrogenic inputs of PAHs in the Songhua River sediments. Ecotoxicological risk levels calculated for PAHs suggested that there were individual PAHs, which can less frequently cause biological impairment in some samples, but no samples had constituents that may frequently cause biological impairment. Total toxic benzo[a]pyrene equivalent of ΣcPAHs varied from 10.03 to 29.7 ng/g dw and from 0.36 to 1.92 ng/g dw for total toxic tetrachlorodibenzo-p-dioxin equivalent. The level of PAHs indicated a low toxicological risk to this area.

Spatial and temporal variation of freely dissolved polycyclic aromatic hydrocarbons in an urban river undergoing Superfund remediation

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

Aregory James Sower; Kim A. Anderson

2008-12-15

Urban rivers with a history of industrial use can exhibit spatial and temporal variations in contaminant concentrations that may significantly affect risk evaluations and even the assessment of remediation efforts. Concentrations of 15 biologically available priority pollutant polycyclic aromatic hydrocarbons (PAHs) were measured over five years along 18.5 miles of the lower Willamette River using passive sampling devices and HPLC. The study area includes the Portland Harbor Superfund megasite with several PAH sources including remediation operations for coal tar at RM 6.3 west and an additional Superfund site, McCormick and Baxter, at RM 7 east consisting largely of creosote contamination.more » Study results show that organoclay capping at the McCormick and Baxter Superfund Site reduced PAHs from a precap average of 440 {+-} 422 ng/L to 8 {+-} 3 ng/L postcapping. Results also reveal that dredging of submerged coal tar nearly tripled nearby freely dissolved PAH concentrations. For apportioning sources, fluoranthene/pyrene and phenanthrene/anthracene diagnostic ratios from passive sampling devices were established for creosote and coal tar contamination and compared to published sediment values. 29 refs., 3 figs., 3 tabs.« less

Detection of polycyclic aromatic hydrocarbons (PAHs) in Medicago sativa L. by fluorescence microscopy.

PubMed

Alves, Wilber S; Manoel, Evelin A; Santos, Noemi S; Nunes, Rosane O; Domiciano, Giselli C; Soares, Marcia R

2017-04-01

Green technologies, such as phytoremediation, are effective for removing organic pollutants derived from oil and oil products, including polycyclic aromatic hydrocarbons (PAHs). Given the increasing popularity of these sustainable remediation techniques, methods based on fluorescence microscopy and multiphoton microscopy for the environmental monitoring of such pollutants have emerged in recent decades as effective tools for phytoremediation studies aimed at understanding the fate of these contaminants in plants. However, little is known about the cellular and molecular mechanisms involved in PAH uptake, responses and degradation by plants. Thus, the present study aimed to detect the location of pyrene, anthracene and phenanthrene using fluorescence microscopy techniques in shoots and roots of Medicago sativa L. (alfalfa) plants grown in artificially contaminated soil (150ppm PAHs) for 40days. Leaflet and root samples were then collected and observed under a fluorescence microscope to detect the presence of PAHs in various tissues. One important finding of the present study was intense fluorescence in the glandular secreting trichomes (GSTs) of plants grown in contaminated soil. These trichomes, with a previously unknown function, may be sites of PAH conjugation and degradation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Selectivity of hexaphenylbenzene-based hydrocarbon stationary phase with propeller-like conformation for aromatic and aliphatic isomers.

PubMed

Yang, Yinhui; Chang, Zhengfeng; Yang, Xiaohong; Qi, Meiling; Wang, Jinliang

2018-08-03

Herein we report a propeller-like hexaphenylbenzene-based hydrocarbon material (denoted as BT) as the stationary phase for capillary gas chromatography (GC). The statically-coated BT capillary column showed a high column efficiency of 4340 plates m -1 and weak polarity. Owing to its unique conformation, π-electron toroidal delocalization and intrinsic microporosity, the BT stationary phase exhibited interesting selectivity for aromatic compounds over alkanes. Compared with the graphene (G) column, the BT column showed much prolonged retention and high selectivity for aromatic isomers, especially methylnaphthalenes, dimethylnaphthalenes and phenanthrene/anthracene, mainly because of its propeller-like conformation with rich intercalation effects. Moreover, it exhibited good column repeatability (intra-day, inter-day) and reproducibility (between-column) with RSD values on the retention times less than 0.08% for intra-day, 0.32% for inter-day and 3.8% for between-column, respectively. Also, it showed good potential for determination of minor isomer impurities in real samples. To the best of our knowledge, this work presents the first example of employing an neat aromatic hydrocarbon material as the GC stationary phase with high selectivity for analytes of a wide ranging polarity. Copyright © 2018 Elsevier B.V. All rights reserved.

Removal efficiency of polycyclic aromatic hydrocarbons and phthalate esters by surface flow wetland in Shunyi district, Beijing

NASA Astrophysics Data System (ADS)

Li, Binghua; Liu, Licai; Han, Li; Yang, Yong

2017-03-01

The surface flow wetland (SFW) system was located on Shunyi district, Beijing. It was built to treat industrial wastewater and domestic sewage, which were looked as its influent. Here sixteen polycyclic aromatic hydrocarbons (PAHs) and six phthalate esters (PAEs) were detected by gas chromatography-mass spectrometry (GC-MS).To determine treatment effect of SFW system, concentrations of targeted compounds in the influent were compared with those in the effluent. Results showed typical compounds of industrial wastewater were naphthalene (NAP), phenanthrene (PHE), dibutyl phthalate (DBP), di-(2-ethylhexyl) phthalate (DEHP), and their concentrations were ranged from 122.6 ng.L-1 to 760.6 ng.L-1. However typical compounds of domestic sewage were NAP, anthracene (ANT), PHE, DBP, diethyl phthalate (DEP), DEHP, and their concentrations were ranged from 280 ng.L-1 to 7998.1 ng.L-1. Typical compounds of effluent were NAP, PHE, DBP, DEHP, and their concentrations changed between 4.2 ng.L-1 and 1430.74 ng.L-1. The removal rate of those compounds were 10% ~ 99%, and nineteen compounds removal rate reached above 70%.Therefore, it can be concluded that SFW system had a strong effect on the removal of these compounds.

Remediation of soil-bound polynuclear aromatic hydrocarbons using nonionic surfactants

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

Yeom, IckTae; Ghosh, Mriganka; Cox, C.

1996-12-31

The solubilization and biodegradation of soil-bound PAHs from a manufactured gas plant (MGP) site soil was investigated using surfactants. Three nonionic polyoxyethylene (POE) surfactants, Triton X-100, Tween 80, and Brij 35, were used. The fate of four PAHs, phenanthrene, anthracene, pyrene, and benzo(a)pyrene were monitored during the remediation process. The measured concentrations of solubilized PAHs agreed well with those estimated using micelle-water partitioning coefficient, K{sub m}, and Raoult`s law. The solubilization of soil-bound PAHs by surfactants is a slow, nonequilibrium process. Diffusion of PAH molecules within the weathered soil-tar matrix is proposed as the rate-limiting step in solubilizing PAHs frommore » such soils. A radial diffusion model is used to describe solubilization of PAHs by surfactant washing. The model predicts experimental results fairly well at low surfactant dosages while at high dosages it somewhat overestimates the extent of solubilization. Biodegradation studies were performed using a natural consortium of microorganisms enriched from PAH-contaminated soils. Surfactants enhanced biodegradation of PAHs except for Tween 80. However, biodegradation of surfactants themselves appear to attenuate the beneficial effects of surfactant-mediated bioremediation.« less

First-Principles DFT Studies of the Vibrational Properties of Germanene Nanoflakes

NASA Astrophysics Data System (ADS)

Richardson, Steven; Peroparde, Borja; Andrade, Xavier; Aspuru-Guzik, AláN.

The germanium analogue of graphene, germanene, is a potentially new atomically thin quantum material which theory predicts will possess unique transport and optoelectronic properties. Recently, there have been a number of experimental efforts to successfully grow two-dimensional films of germanene on noble metal substrates using molecular beam epitaxy. In addition to this top-down approach of synthesizing large scale films of germanene, we would like to focus on a bottom-up approach where nanoflakes of germanene could be used as molecular seeds or precursors to grow large films of two-dimensional germanene. A knowledge of their infrared and Raman spectra will be critical for characterizing these germanene nanoflakes in future experiments. In this work we used density-functional theory (DFT) to compute the vibrational spectra of a selected number of lower order germanene nanoflakes (e.g. hexagermabenzene, germa-naphthalene, germa-anthracene, germa-phenanthrene, germa-pyrene, germa-tetracene, and germa-pentacene). Our DFT studies also reveal that these germanene nanoflakes are vibrationally stable with buckling of these molecules from their normal two-dimensional planar forms which exist in graphene nanoflakes. This research is supported by NSF Grant No. DMR-1231319.

PAH dissipation in spiked soil: impacts of bioavailability, microbial activity, and trees.

PubMed

Mueller, Kevin E; Shann, Jodi R

2006-08-01

While trees have demonstrated potential in phytoremediation of several organic contaminants, little is known regarding their ability to impact the common soil contaminant PAHs. Several species of native North American trees were planted in soil artificially contaminated with three PAHs. Plant biomass, PAH dissipation, and microbial mineralization were monitored over the course of one year and environmental conditions were allowed to follow typical seasonal patterns. PAH dissipation and mineralization were not affected by planting. Extensive and rapid loss of PAHs was observed and attributed to high bioavailability and microbial activity in all treatments. The rate of this loss may have masked any significant planting effects. Anthracene was found to be more recalcitrant than pyrene or phenanthrene. Parallel soil aging studies indicated that sequestration to soil components was minimal. Contrary to common inferences in literature, amendment with decaying fine roots inhibited PAH degradation by the soil microbial community. Seasonal variation in environmental factors and rhizosphere dynamics may have also reduced or negated the effect of planting and should be taken into account in future phytoremediation trials. The unique root traits of trees may pose a challenge to traditional thought regarding PAH dissipation in the rhizosphere of plants.

Oil-bioremediation potential of two hydrocarbonoclastic, diazotrophic Marinobacter strains from hypersaline areas along the Arabian Gulf coasts.

PubMed

Al-Mailem, D M; Eliyas, M; Radwan, S S

2013-05-01

Two halophilic, hydrocarbonoclastics bacteria, Marinobacter sedimentarum and M. flavimaris, with diazotrophic potential occured in hypersaline waters and soils in southern and northern coasts of Kuwait. Their numbers were in the magnitude of 10(3) colony forming units g(-1). The ambient salinity in the hypersaline environments was between 3.2 and 3.5 M NaCl. The partial 16S rRNA gene sequences of the two strains showed, respectively, 99 and 100% similarities to the sequences in the GenBank. The two strains failed to grow in the absence of NaCl, exhibited best growth and hydrocarbon biodegradation in the presence of 1 to 1.5 M NaCl, and still grew and maintained their hydrocarbonoclastic activity at salinities up to 5 M NaCl. Both species utilized Tween 80, a wide range of individual aliphatic hydrocarbons (C9-C40) and the aromatics benzene, biphenyl, phenanthrene, anthracene and naphthalene as sole sources of carbon and energy. Experimental evidence was provided for their nitrogen-fixation potential. The two halophilic Marinobacter strains successfully mineralized crude oil in nutrient media as well as in hypersaline soil and water microcosms without the use of any nitrogen fertilizers.

Heavy metal effects on the biodegradation of fluorene by Sphingobacterium sp. KM-02 isolated from PAHs-contaminated mine soil

NASA Astrophysics Data System (ADS)

Nam, I.; Chon, C.; Jung, K.; Kim, J.

2012-12-01

Polycyclic aromatic hydrocarbon compounds (PAHs) are widely distributed in the environment and occur ubiquitously in fossil fuels as well as in products of incomplete combustion and are known to be strongly toxic, often with carcinogenic and mutagenic properties. Fluorene is one of the 16 PAHs included in the list of priority pollutants of the Environmental Protection Agency. The fluorene-degrading bacterial strain Sphingobacterium sp. KM-02 was isolated from PAHs-contaminated soil near an abandoned mine impacted area by selective enrichment techniques. Fluorene added to the Sphingobacterium sp. KM-02 culture as sole carbon and energy source was 78.4% removed within 120 h. A fluorene degradation pathway is tentatively proposed based on mass spectrometric identification of the metabolic intermediates 9-fluorenone, 4-hydroxy-9-fluorenone, and 8-hydroxy-3,4-benzocoumarin. Further the ability of Sphingobacterium sp. KM-02 to bioremediate 100 mg/kg fluorene in mine soil was examined by composting under laboratory conditions. Treatment of microcosm soil with the strain KM-02 for 20 days resulted in a 65.6% reduction in total amounts. These results demonstrate that Sphingobacterium sp. KM-02 could potentially be used in the bioremediation of fluorene from contaminated soil. Mine impacted area comprises considerable amounts of heavy metals such as cadmium, lead, mercury, arsenic, and copper. Although some of these metals are necessary for biological life, excessive quantities often result in the inhibition of essential biological reactions via numerous pathways. A number of reports collectively show that various metals, such as Al, Co, Ni, Cu, Zn, Pb, and Hg at a range of concentrations have adverse effects on the degradation of organic compounds. However, at present there is only limited information on the effect of individual heavy metals on the biological degradation of polyaromatic hydrocarbons (PAHs) including fluorene. Moreover, heavy metal effects were not considered during biodegradation in mine impacted areas. The heavy metal effects on the degradation of fluorene by Sphingobacterium sp. KM-02 was determined in liquid cultures. The results showed that 10 mg/L cadmium, mercury and copper not only affected the growth of KM-02 with fluorene but also the ability of resting cells to degrade this compound. Growth and degradation were strongly inhibited by mercury, even at 1 mg/L, while the inhibitory effect of cadmium and copper at the same concentration or at 5 mg/L were negligible. In contrast, arsenic and lead did not affect degradation or growth, even at very high concentrations of 100 mg/L. Subsequent analyses additionally revealed that concentrations of arsenic and lead remained unchanged following incubation, while those of cadmium, mercury and copper decreased significantly. These data suggest the potential inhibition of fluorene degradation in mine soil, the major source of PAHs degradation, but which also would limit the applicability of a slurry-based fermentation reactor for PAHs degradation. Therefore, further study should be performed to elucidate whether these conditions are effectively imitating those of contaminated mine impacted soil, which are very complicated chemical and physical phenomena.

Numerical taxonomy of phenanthrene-degrading bacteria isolated from the Chesapeake Bay

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

West, P.A.; Okpokwasili, G.C.; Brayton, P.R.

1984-11-01

Phenanthrene-degrading bacteria were isolated from Chesapeake Bay samples by the use of a solid medium which had been overlaid with an ethanol solution of phenanthrene before inoculation. Eighteen representative strains of phenanthrene-degrading bacteria with 21 type and reference bacteria were examined for 123 characteristics representing physiological, biochemical, and nutritional properties. Relationships between strains were computed with several similarity coefficients. The phenogram constructed by unweighted-pair-group arithmetic average linkage and use of the simple Jaccard (S/sub J/) coefficient was used to identify seven phena. Phenanthrene-degrading bacteria were identified as Vibrio parahaemolyticus and Vibrio fluvialis by their clustering with type and reference strains.more » Several phenanthrene-degrading bacteria resembled Enterobacteriaceae family members, although some Vibrio-like phenanthrene degraders could not be identified. 22 references, 1 figure, 2 tables.« less

Reinforced microextraction of polycyclic aromatic hydrocarbons from polluted soil samples using an in-needle coated fiber with polypyrrole/graphene oxide nanocomposite.

PubMed

Behfar, Mina; Ghiasvand, Ali Reza; Yazdankhah, Fatemeh

2017-07-01

The surface of a stainless-steel wire was platinized using electrophoretic deposition method to create a high-surface-area with porous and cohesive substrate. The platinized fiber was coated by the polypyrrole/graphene oxide nanocomposite by electropolymerization and accommodated into a stainless-steel needle to fabricate an in-needle coated fiber. The developed setup was coupled to gas chromatography with flame ionization detection and applied to extract and determine polycyclic aromatic hydrocarbons (naphthalene, fluorene, phenanthrene, fluoranthene, and pyrene) in complicated solid matrices, along with reinforcement of the extraction by cooling the sorbent, using liquid carbon dioxide. To obtain the best extraction efficiency, the important experimental variables including extraction temperature and time, temperature of cooled sorbent, sampling flow rate, and desorption condition were studied. Under the optimal condition, limits of detection for five studied analytes were in the range of 0.2-0.8 pg/g. Linear dynamic ranges for the calibration curves were found to be in the range of 0.001-1000 ng/g. Relative standard deviations obtained for six replicated analyses of 1 ng/g of analytes were 4.9-13.5%. The reinforced in-needle coated fiber method was successfully applied for the analysis of polycyclic aromatic hydrocarbons in contaminated soil samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Polycyclic aromatic hydrocarbons (PAHs) biodegradation potential and diversity of microbial consortia enriched from tsunami sediments in Miyagi, Japan.

PubMed

Bacosa, Hernando Pactao; Inoue, Chihiro

2015-01-01

The Great East Japan Earthquake caused tsunamis and resulted in widespread damage to human life and infrastructure. The disaster also resulted in contamination of the environment by chemicals such as polycyclic aromatic hydrocarbons (PAHs). This study was conducted to investigate the degradation potential and describe the PAH-degrading microbial communities from tsunami sediments in Miyagi, Japan. PAH-degrading bacteria were cultured by enrichment using PAH mixture or pyrene alone as carbon and energy sources. Among the ten consortia tested for PAH mixture, seven completely degraded fluorene and more than 95% of phenanthrene in 10 days, while only four consortia partially degraded pyrene. Six consortia partially degraded pyrene as a single substrate. Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) revealed that each sample was dominated by unique microbial populations, regardless of sampling location. The consortia were dominated by known PAHs degraders including Sphingomonas, Pseudomonas, and Sphingobium; and previously unknown degraders such as Dokdonella and Luteimonas. A potentially novel and PAH-degrading Dokdonella was detected for the first time. PAH-ring hydroxylating dioxygenase (PAH-RHDα) gene was shown to be more effective than nidA in estimating pyrene-degrading bacteria in the enriched consortia. The consortia obtained in this study are potential candidates for remediation of PAHs contaminated soils. Copyright © 2014 Elsevier B.V. All rights reserved.

Occupational PAH exposures during prescribed pile burns.

PubMed

Robinson, M S; Anthony, T R; Littau, S R; Herckes, P; Nelson, X; Poplin, G S; Burgess, J L

2008-08-01

Wildland firefighters are exposed to particulate matter and gases containing polycyclic aromatic hydrocarbons (PAHs), many of which are known carcinogens. Our objective was to evaluate the extent of firefighter exposure to particulate and PAHs during prescribed pile burns of mainly ponderosa pine slash and determine whether these exposures were correlated with changes in urinary 1-hydroxypyrene (1-HP), a PAH metabolite. Personal and area sampling for particulate and PAH exposures were conducted on the White Mountain Apache Tribe reservation, working with 21 Bureau of Indian Affairs/Fort Apache Agency wildland firefighters during the fall of 2006. Urine samples were collected pre- and post-exposure and pulmonary function was measured. Personal PAH exposures were detectable for only 3 of 16 PAHs analyzed: naphthalene, phenanthrene, and fluorene, all of which were identified only in vapor-phase samples. Condensed-phase PAHs were detected in PM2.5 area samples (20 of 21 PAHs analyzed were detected, all but naphthalene) at concentrations below 1 microg m(-3). The total PAH/PM2.5 mass fractions were roughly a factor of two higher during smoldering (1.06 +/- 0.15) than ignition (0.55 +/- 0.04 microg mg(-1)). There were no significant changes in urinary 1-HP or pulmonary function following exposure to pile burning. In summary, PAH exposures were low in pile burns, and urinary testing for a PAH metabolite failed to show a significant difference between baseline and post-exposure measurements.

Initial environmental impacts of the Obed Mountain coal mine process water spill into the Athabasca River (Alberta, Canada).

PubMed

Cooke, Colin A; Schwindt, Colin; Davies, Martin; Donahue, William F; Azim, Ekram

2016-07-01

On October 31, 2013, a catastrophic release of approximately 670,000m(3) of coal process water occurred as the result of the failure of the wall of a post-processing settling pond at the Obed Mountain Mine near Hinton, Alberta. A highly turbid plume entered the Athabasca River approximately 20km from the mine, markedly altering the chemical composition of the Athabasca River as it flowed downstream. The released plume traveled approximately 1100km downstream to the Peace-Athabasca Delta in approximately four weeks, and was tracked both visually and using real-time measures of river water turbidity within the Athabasca River. The plume initially contained high concentrations of nutrients (nitrogen and phosphorus), metals, and polycyclic aromatic hydrocarbons (PAHs); some Canadian Council of Ministers of the Environmental (CCME) Guidelines were exceeded in the initial days after the spill. Subsequent characterization of the source material revealed elevated concentrations of both metals (arsenic, lead, mercury, selenium, and zinc) and PAHs (acenaphthene, fluorene, naphthalene, phenanthrene, and pyrene). While toxicity testing using the released material indicated a relatively low or short-lived acute risk to the aquatic environment, some of the water quality and sediment quality variables are known carcinogens and have the potential to exert negative long-term impacts. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Extractive biodegradation and bioavailability assessment of phenanthrene in the cloud point system by Sphingomonas polyaromaticivorans.

PubMed

Pan, Tao; Deng, Tao; Zeng, Xinying; Dong, Wei; Yu, Shuijing

2016-01-01

The biological treatment of polycyclic aromatic hydrocarbons is an important issue. Most microbes have limited practical applications because of the poor bioavailability of polycyclic aromatic hydrocarbons. In this study, the extractive biodegradation of phenanthrene by Sphingomonas polyaromaticivorans was conducted by introducing the cloud point system. The cloud point system is composed of a mixture of (40 g/L) Brij 30 and Tergitol TMN-3, which are nonionic surfactants, in equal proportions. After phenanthrene degradation, a higher wet cell weight and lower phenanthrene residue were obtained in the cloud point system than that in the control system. According to the results of high-performance liquid chromatography, the residual phenanthrene preferred to partition from the dilute phase into the coacervate phase. The concentration of residual phenanthrene in the dilute phase (below 0.001 mg/L) is lower than its solubility in water (1.18 mg/L) after extractive biodegradation. Therefore, dilute phase detoxification was achieved, thus indicating that the dilute phase could be discharged without causing phenanthrene pollution. Bioavailability was assessed by introducing the apparent logP in the cloud point system. Apparent logP decreased significantly, thus indicating that the bioavailability of phenanthrene increased remarkably in the system. This study provides a potential application of biological treatment in water and soil contaminated by phenanthrene.

Metabolism of a Representative Oxygenated Polycyclic Aromatic Hydrocarbon (PAH) Phenanthrene-9,10-quinone in Human Hepatoma (HepG2) Cells

PubMed Central

2014-01-01

Exposure to polycyclic aromatic hydrocarbons (PAHs) in the food chain is the major human health hazard associated with the Deepwater Horizon oil spill. Phenanthrene is a representative PAH present in crude oil, and it undergoes biological transformation, photooxidation, and chemical oxidation to produce its signature oxygenated derivative, phenanthrene-9,10-quinone. We report the downstream metabolic fate of phenanthrene-9,10-quinone in HepG2 cells. The structures of the metabolites were identified by HPLC–UV–fluorescence detection and LC–MS/MS. O-mono-Glucuronosyl-phenanthrene-9,10-catechol was identified, as reported previously. A novel bis-conjugate, O-mono-methyl-O-mono-sulfonated-phenanthrene-9,10-catechol, was discovered for the first time, and evidence for both of its precursor mono conjugates was obtained. The identities of these four metabolites were unequivocally validated by comparison to authentic enzymatically synthesized standards. Evidence was also obtained for a minor metabolic pathway of phenanthrene-9,10-quinone involving bis-hydroxylation followed by O-mono-sulfonation. The identification of 9,10-catechol conjugates supports metabolic detoxification of phenanthrene-9,10-quinone through interception of redox cycling by UGT, COMT, and SULT isozymes and indicates the possible use of phenanthrene-9,10-catechol conjugates as biomarkers of human exposure to oxygenated PAH. PMID:24646012

Isolation of Soil Bacteria Adapted To Degrade Humic Acid-Sorbed Phenanthrene

PubMed Central

Vacca, D. J.; Bleam, W. F.; Hickey, W. J.

2005-01-01

The goal of these studies was to determine how sorption by humic acids affected the bioavailability of polynuclear aromatic hydrocarbons (PAHs) to PAH-degrading microbes. Micellar solutions of humic acid were used as sorbents, and phenanthrene was used as a model PAH. Enrichments from PAH-contaminated soils established with nonsorbed phenanthrene yielded a total of 25 different isolates representing a diversity of bacterial phylotypes. In contrast, only three strains of Burkholderia spp. and one strain each of Delftia sp. and Sphingomonas sp. were isolated from enrichments with humic acid-sorbed phenanthrene (HASP). Using [14C]phenanthrene as a radiotracer, we verified that only HASP isolates were capable of mineralizing HASP, a phenotype hence termed “competence.” Competence was an all-or-nothing phenotype: noncompetent strains showed no detectable phenanthrene mineralization in HASP cultures, but levels of phenanthrene mineralization effected by competent strains in HASP and NSP cultures were not significantly different. Levels and rates of phenanthrene mineralization exceeded those predicted to be supported solely by the metabolism of phenanthrene in the aqueous phase of HASP cultures. Thus, competent strains were able to directly access phenanthrene sorbed by the humic acids and did not rely on desorption for substrate uptake. To the best of our knowledge, this is the first report of (i) a selective interaction between aerobic bacteria and humic acid molecules and (ii) differential bioavailability to bacteria of PAHs sorbed to a natural biogeopolymer. PMID:16000791

2,5-linked polyfluorenes for optoelectronic devices

DOEpatents

Cella, James Anthony; Shiang, Joseph John; Shanklin, Elliott West; Smigelski, Paul Michael

2010-06-08

Polyfluorene polymers and copolymers having substantial amounts (10-100%) of fluorenes coupled at the 2 and 5 positions of fluorene are useful as active layers in OLED devices where triplet energies >2.10 eV are required.

2,5-linked polyfluorenes for optoelectronic devices

DOEpatents

Cella, James Anthony [Clifton Park, NY; Shiang, Joseph John [Niskayuna, NY; Shanklin, Elliott West [Altamont, NY; Smigelski, Jr, Paul Michael

2011-06-28

Polyfluorene polymers and copolymers having substantial amounts (10-100%) of fluorenes coupled at the 2 and 5 positions of fluorene are useful as active layers in OLED devices where triplet energies >2.10 eV are required.

2,5-linked polyfluorenes for optoelectronic devices

DOEpatents

Cella, James Anthony [Clifton Park, NY; Shiang, Joseph John [Niskayuna, NY; Shanklin, Elliott West [Altamont, NY; Smigelski, Paul Michael [Scotia, NY

2009-12-22

Polyfluorene polymers and copolymers having substantial amounts (10-100%) of fluorenes coupled at the 2 and 5 positions of fluorene are useful as active layers in OLED devices where triplet energies >2.10 eV are required.

Fluorene

Integrated Risk Information System (IRIS)

Fluorene ; CASRN 86 - 73 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effects )

2,5-linked polyfluorenes for optoelectronic devices

DOEpatents

Cella, James Anthony [Clifton Park, NY; Shiang, Joseph John [Niskayuna, NY; Shanklin, Elliott West [Altamont, NY; Smigelski, Jr., Paul Michael

2011-11-08

Polyfluorene polymers and copolymers having substantial amounts (10-100%) of fluorenes coupled at the 2 and 5 positions of fluorene are useful as active layers in OLED devices where triplet energies >2.10 eV are required.

Free-volume characteristics of epoxies

NASA Technical Reports Server (NTRS)

Singh, Jag J.; Eftekhari, Abe; Shultz, William J.; St.clair, Terry L.

1992-01-01

Positron annihilation spectroscopy was used to measure free-volume characteristics of selected epoxies. Fluorene resins, a new family of high-temperature thermosetting resins, were selected as the test medium. Experimental results indicate that the free-volume cell size V sub f varies with the molecular weight between the cross-links M sub c according to an equation of the form V sub f = AM sub c sup B, where A and B are structural constants. In two of the samples, the concentration of bulky fluorene groups was increased in the network backbone by replacement of some of the conventional bisphenol A epoxy resin with fluorene-derived epoxy resin. This resulted in an increase in their glass transition temperature for a given level of cross-linking. It was found that in these samples, the Doppler broadening of the annihilation peak decreases with the increasing fluorene content, presumably due to enhanced damping of the chain motions.

Uptake of aromatic hydrocarbon vapors (benzene and phenanthrene) at the air-water interface of micron-size water droplets.

PubMed

Raja, Suresh; Valsaraj, Kalliat T

2004-12-01

Uptake of aromatic hydrocarbon vapors (benzene and phenanthrene) by typical micrometer-sized fog-water droplets was studied using a falling droplet reactor at temperatures between 296 and 316 K. Uptake of phenanthrene vapor greater than that predicted by bulk (air-water)-phase equilibrium was observed for diameters less than 200 microm, and this was attributed to surface adsorption. The experimental values of the droplet-vapor partition constant were used to obtain the overall mass transfer coefficient and the mass accommodation coefficient for both benzene and phenanthrene. Mass transfer of phenanthrene was dependent only on gas-phase diffusion and mass accommodation at the interface. However, for benzene, the mass transfer was limited by liquid-phase diffusion and mass accommodation. A large value of the mass accommodation coefficient, alpha = (1.4 +/- 0.4) x 10(-2) was observed for the highly surface-active (hydrophobic) phenanthrene, whereas a small alpha = (9.7 +/- 1.8) x 10(-5) was observed for the less hydrophobic benzene. Critical cluster numbers ranging from 2 for benzene to 5.7 for phenanthrene were deduced using the critical cluster nucleation theory for mass accommodation. The enthalpy of mass accommodation was more negative for phenanthrene than it was for benzene. Consequently, the temperature effect was more pronounced for phenanthrene. A linear correlation was observed for the enthalpy of accommodation with the excess enthalpy of solution. A natural organic carbon surrogate (Suwannee Fulvic acid) in the water droplet increased the uptake for phenanthrene and benzene, the effect being more marked for phenanthrene. A characteristic time constant analysis showed that uptake and droplet scavenging would compete for the fog deposition of phenanthrene, whereas deposition would be unimpeded by the uptake rate for benzene vapor. For both compounds, the characteristic atmospheric reaction times were much larger and would not impact fog deposition.

Biodegradation and adsorption of C1- and C2-phenanthrenes and C1- and C2-dibenzothiophenes in the presence of clay minerals: effect on forensic diagnostic ratios.

PubMed

Ugochukwu, Uzochukwu C; Head, Ian M; Manning, David A C

2014-07-01

The impact of modified montmorillonites on adsorption and biodegradation of crude oil C1-phenanthrenes, C1-dibenzothiophenes, C2-phenanthrenes and C2-dibenzothiophenes was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. Consequently, the effect on C1-dibenzothiophenes/C1-phenanthrenes, C2-dibenzothiophenes/C2-phenanthrenes, 2+3-methyldibenzothiophene/4-methyldibenzothiophene and 1-methyldibenzothiophene/4-methyldibenzothiophene ratios commonly used as diagnostic ratios for oil forensic studies was evaluated. The clay mineral samples were treated to produce acid activated montmorillonite, organomontmorillonite and homoionic montmorillonite which were used in this study. The different clay minerals (modified and unmodified) showed varied degrees of biodegradation and adsorption of the C1-phenanthrenes, C1-dibenzothiophenes, C2-phenanthrenes and C2-dibenzothiophenes. The study indicated that as opposed to biodegradation, adsorption has no effect on the diagnostic ratios. Among the diagnostic ratios reviewed, only C2-dibenzothiophenes/C2-phenanthrenes ratio was neither affected by adsorption nor biodegradation making this ratio very useful in forensic studies of oil spills and oil-oil correlation.

Effect of aging of chemicals in soil on their biodegradability and extractability

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

Hatzinger, P.B.; Alexander, M.

1995-11-01

A study was conducted to determine whether the time that a compound remains in a soil affects its biodegradability and the ease of its extraction. Phenanthrene and 4-nitrophenol were aged in sterilized loam and muck, and bacteria able to degrade the compounds were then added to the soils. increasingly smaller amounts of phenanthrene in the muck and 4-nitrophenol in both soils were mineralized with increasing duration of aging. Aging also increased the resistance of phenanthrene to biodegradation in nutrient-amended aquifer sand. The rate of miner- alization of the two compounds in both soils declined with increasing periods of aging. Themore » amount of phenanthrene and 4-nitrophenol added to sterile soils that was recovered by butanol extraction declined with duration of aging, but subsequent Soxhlet extraction recovered phenanthrene from the loam but not the muck. The extents of mineralization of phenanthrene previously incubated for up to 27 days with soluble or insoluble organic matter from the muck were similar. Less aged than freshly added phenanthrene was biodegraded if aggregates in the muck were sonically disrupted. The data show that phenanthrene and 4-nitrophenol added to soil become increasingly more resistant with time to biodegradation and extraction.« less

Effects of the inoculant strain Sphingomonas paucimobilis 20006FA on soil bacterial community and biodegradation in phenanthrene-contaminated soil.

PubMed

Coppotelli, B M; Ibarrolaza, A; Del Panno, M T; Morelli, I S

2008-02-01

The effects of the inoculant strain Sphingomonas paucimobilis 20006FA (isolated from a phenanthrene-contaminated soil) on the dynamics and structure of microbial communities and phenanthrene elimination rate were studied in soil microcosms artificially contaminated with phenanthrene. The inoculant managed to be established from the first inoculation as it was evidenced by denaturing gradient gel electrophoresis analysis, increasing the number of cultivable heterotrophic and PAH-degrading cells and enhancing phenanthrene degradation. These effects were observed only during the inoculation period. Nevertheless, the soil biological activity (dehydrogenase activity and CO(2) production) showed a late increase. Whereas gradual and successive changes in bacterial community structures were caused by phenanthrene contamination, the inoculation provoked immediate, significant, and stable changes on soil bacterial community. In spite of the long-term establishment of the inoculated strain, at the end of the experiment, the bioaugmentation did not produce significant changes in the residual soil phenanthrene concentration and did not improve the residual effects on the microbial soil community.

Biodegradation of PAHs in Soil: Influence of Initial PAHs Concentration

NASA Astrophysics Data System (ADS)

Kamil, N. A. F. M.; Talib, S. A.

2016-07-01

Most studies on biodegradation of Polycyclic Aromatic Hydrocarbons (PAHs) evaluate the effect of initial PAHs concentration in liquid medium. There are limited studies on evaluation in solid medium such as contaminated soil. This study investigated the potential of the bacteria, Corynebacterium urealyticum isolated from municipal sludge in degrading phenanthrene contaminated soil in different phenanthrene concentration. Batch experiments were conducted over 20 days in reactors containing artificially contaminated phenanthrene soil at different concentration inoculated with a bacterial culture. This study established the optimum condition for phenanthrene degradation by the bacteria under nonindigenous condition at 500 mg/kg of initial phenanthrene concentration. High initial concentration required longer duration for biodegradation process compared to low initial concentration. The bacteria can survive for three days for all initial phenanthrene concentrations.

Polycyclic aromatic hydrocarbons in Haliotis tuberculata (Linnaeus, 1758) (Mollusca, Gastropoda): Considerations on food safety and source investigation.

PubMed

Conte, Francesca; Copat, Chiara; Longo, Sabrina; Conti, Gea Oliveri; Grasso, Alfina; Arena, Giovanni; Dimartino, Angela; Brundo, Maria Violetta; Ferrante, Margherita

2016-08-01

Polycyclic aromatic hydrocarbons were analyzed in wild specimens of Haliotis tuberculata from three sites of the Sothern Ionian Sea. The species Ht is commonly found at these sites and has significant commercial value. Main results revealed mean values of benzo(a)pyrene higher than the threshold set by Regulation No. 835/2011/EU in all sampling sites and the sum of selected PAHs, expressed as ΣPAH4 by EC Regulation, were below the limit set by the same Regulation in ME and VSG. We found generally higher concentrations than literature finding, especially for low molecular weight PAHs, and results of diagnostic ratios highlighted both pyrolytic and petrogenic sources. The potential human health risks due consumption of Ht by local inhabitants have been assessed by exposure daily intake (EDI), target hazard quotient (THQ) and lifetime cancer risk (CR). EDI values were below the intake range reviewed by EFSA for each class of contaminant. BaP daily intake was below the value of 10 ng/Kg/day, suggested by JFCFA, and CRBaP was slightly higher than the acceptable risk level (ARL) of 1×10(-5). Conversely, target hazard quotient (THQ) resulted always below 1, thus the risk to develop chronic systemic effects due naphthalene, acenaphthene, fluorene, anthracene, fluoranthene and pyrene was low. Copyright © 2016 Elsevier Ltd. All rights reserved.

Linking of Microorganisms to Phenanthrene Metabolism in Soil by Analysis of 13C-Labeled Cell Lipids

PubMed Central

Johnsen, Anders R.; Winding, Anne; Karlson, Ulrich; Roslev, Peter

2002-01-01

Phenanthrene-metabolizing soil microbial communities were characterized by examining mineralization of [14C]phenanthrene, by most-probable-number (MPN) counting, by 16S-23S spacer DNA analysis of the numerically dominant, culturable phenanthrene-degrading isolates, and by examining incorporation of [13C]phenanthrene-derived carbon into sterols and polar lipid fatty acids (PLFAs). An unpolluted agricultural soil, a roadside soil diffusely polluted with polycyclic aromatic hydrocarbons (PAHs), and two highly PAH-polluted soils from industrial sites were analyzed. Microbial phenanthrene degraders were not detected by MPN counting in the agricultural soil and the roadside soil. In the industrial soils, phenanthrene degraders constituted 0.04 and 3.6% of the total number of CFU. 16S-23S spacer DNA analysis followed by partial 16S DNA sequencing of representative isolates from one of the industrial soils showed that one-half of the isolates belonged to the genus Sphingomonas and the other half were closely related to an unclassified beta-proteobacterium. The 13C-PLFA profiles of the two industrial soils were relatively similar and resembled the profiles of phenanthrene-degrading Sphingomonas reference strains and unclassified beta-proteobacterium isolates but did not match the profiles of Pseudomonas, Mycobacterium, or Nocardia reference strains. The 13C-PLFA profiles of phenanthrene degraders in the agricultural soil and the roadside soil were different from each other and different from the profiles of the highly polluted industrial soils. Only in the roadside soil were 10me/12me18:0 PLFAs enriched in 13C, suggesting that actinomycetes metabolized phenanthrene in this soil. The 13C-PLFA profiles of the unpolluted agricultural soil did not resemble the profiles of any of the reference strains. In all of the soils investigated, no excess 13C was recovered in the 18:2ω6,9 PLFA, suggesting that fungi did not contribute significantly to assimilation of [13C]phenanthrene. PMID:12450834

Different effects of copper (II), cadmium (II) and phosphate on the sorption of phenanthrene on the biomass of cyanobacteria.

PubMed

Tao, Yuqiang; Li, Wei; Xue, Bin; Zhong, Jicheng; Yao, Shuchun; Wu, Qinglong

2013-10-15

Due to the large surface area and high organic carbon content of cyanobacteria, organic contaminants can be readily sorbed on cyanobacteria during algal blooms, and then be transferred to the food web. This process is likely to be affected by the coexisting metals and nutrients, however, the possible impacts remain unclear. Effects of Cu(2+), Cd(2+), and phosphate on the sorption of phenanthrene on cyanobacterial biomass collected from an algal bloom were therefore studied. Continuous decrease in phenanthrene sorption was observed in the presence of low concentrations of Cu(2+), and Cd(2+) (<0.04 mmol L(-1)), because Cu(2+) and Cd(2+) were coadsorbed with phenanthrene on the surface of cyanobacteria as suggested by scanning electron microscopy-energy dispersive X-ray (SEM-EDX) and Fourier transform infrared (FTIR) analyses. Phenanthrene sorption began to increase with the further increase in Cu(2+) concentration, but remained lower than that in the absence of Cu(2+). This increase in sorption was ascribed to the cation-π interaction between Cu(2+) and phenanthrene, as suggested by the enhanced ultraviolet absorbance at 251 nm. In contrast, sorption rebounding of phenanthrene did not occur in the presence of higher concentrations of Cd(2+). The different effects of Cu(2+) and Cd(2+) on phenanthrene sorption were attributed to that Cd(2+) required much more energy than Cu(2+) to form cation-π complexes with phenanthrene in the solutions. Phenanthrene sorption decreased continuously with the increase in phosphate concentration. Phosphate blocked the binding sites, modified the cell morphology, and increased the negative charge as well as the hydrophilicity of the cyanobacterial surface, thereby suppressing phenanthrene sorption. This study indicates that sorption of aromatic organic compounds by cyanobacteria could be significantly alerted by concentrations and properties of the coexisting transition metals and phosphates, which may subsequently affect their transfer to the food web in eutrophic waters. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

The efficacy of an oxidation pond in mineralizing some industrial waste products with special reference to fluorene degradation: A case study

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

Ahmed, M.T.; Dewedar, A.; Mekki, L.

1999-07-01

The efficacy of the oxidation pond on the outskirts of the 10th of Ramadan, the main industrial city in Egypt, was examined. Samples of wastewater collected from the inlet and the outlet were screened for some priority pollutants. Acenaphethene and fluorene were the most frequently detected polycyclic aromatic hydrocarbons, while dimethyl phthalate was the most frequently detected phthalate ester. The spectrum of pollutants, their concentrations and frequencies were similar in the inlet and the outlet, indicating an inferior mineralization capability of the pond. Several degradative bacterial strains were isolated from the pond and grown on M56 minimal media supplemented withmore » different pollutants as the carbon source. The efficacy of pure and mixed cultures to break down fluorene, the most frequently detected pollutant was examined. Fluorene degradation was fast in the first 10 days, the followed by a slow phase. Mixed culture had a higher rate of fluorene degradation in comparison to pure cultures. High performance liquid chromatography analysis of fluorene degradation showed three degradative metabolites. But GC/MS analysis detected one compound, identified as acetamide. The present work has indicated the poor efficacy of the pond. Lack of primary treatment of industrial effluent at factory level, coupled with shock loads of toxicants that may damage the microorganisms and their degradative capabilities are presumably main factors behind such inferior performance. Moreover, the type of pollutants discharged into the pond tend to fluctuate and change depending on the rate from the factories discharge and work shifts. Such irregular feeding of persistent pollutants may have led to a wash out of specialized strains of bacteria capable to degrade such persistent pollutants.« less

Bioremediation of polycyclic aromatic hydrocarbon (PAH) compounds: (acenaphthene and fluorene) in water using indigenous bacterial species isolated from the Diep and Plankenburg rivers, Western Cape, South Africa.

PubMed

Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Olutoyin; Jackson, Vanessa

This study was conducted to investigate the occurrence of PAH degrading microorganisms in two river systems in the Western Cape, South Africa and their ability to degrade two PAH compounds: acenaphthene and fluorene. A total of 19 bacterial isolates were obtained from the Diep and Plankenburg rivers among which four were identified as acenaphthene and fluorene degrading isolates. In simulated batch scale experiments, the optimum temperature for efficient degradation of both compounds was determined in a shaking incubator after 14 days, testing at 25°C, 30°C, 35°C, 37°C, 38°C, 40°C and 45°C followed by experiments in a Stirred Tank Bioreactor using optimum temperature profiles from the batch experiment results. All experiments were run without the addition of supplements, bulking agents, biosurfactants or any other form of biostimulants. Results showed that Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila efficiently degraded both compounds at 37°C, 37°C, 30°C and 35°C respectively. The degradation of fluorene was more efficient and rapid compared to that of acenaphthene and degradation at Stirred Tank Bioreactor scale was more efficient for all treatments. Raoultella ornithinolytica, Serratia marcescens, Bacillus megaterium and Aeromonas hydrophila degraded a mean total of 98.60%, 95.70%, 90.20% and 99.90% acenaphthene, respectively and 99.90%, 97.90%, 98.40% and 99.50% fluorene, respectively. The PAH degrading microorganisms isolated during this study significantly reduced the concentrations of acenaphthene and fluorene and may be used on a larger, commercial scale to bioremediate PAH contaminated river systems. Copyright © 2016 Sociedade Brasileira de Microbiologia. Published by Elsevier Editora Ltda. All rights reserved.

The first-principles investigations on magnetic ground-state in Sm-doped phenanthrene

NASA Astrophysics Data System (ADS)

Han, Jia-Xing; Zhong, Guo-Hua; Wang, Xiao-Hui; Chen, Xiao-Jia; Lin, Hai-Qing

2017-05-01

Based on the density functional theory plus the effective Coulomb repulsion U, we have investigated the crystal structure, electronic properties and magnetic characteristics in Sm-doped phenanthrene, recently characterized as a superconductor with Tc˜5 -6 Kelvin. Calculated total energies of different magnetic states indicate that Sm-doped phenanthrene is stable at the ferromagnetic ground-state. Considered the strong electronic correlations effect due to the intercalation of Sm-4f electrons, we found that the Sm-4f contributes to the Fermi surface together with C-2p, which is different from K-doped phenanthrene. Compared with alkali-metal-doped phenanthrene, Sm atom has larger local magnetic moment, which suppresses the superconductivity in conventional superconductors. Our results indicate that the electron-electron correlations play an important role in superconductivity of Sm-doped phenanthrene.

[Degradation of fluorene and fluoranthene by the basidiomycete Pleurotus ostreatus].

PubMed

Pozdnyakova, N N; Chernyshova, M P; Grinev, V S; Landesman, E O; Koroleva, O V; Turkovskaya, O V

2016-01-01

The dependence of the degree of fluorene and fluoranthene degradation by the fungus Pleurotus ostreatus D1 on the culture medium composition has been studied. Polycyclic aromatic hydrocarbons (PAHs) have been transformed in Kirk’s medium (under conditions of laccase production) with the formation of a quinone metabolite and 9-fluorenone upon the use of fluoranthene and fluorene as substrates, respectively. More complete degradation with the formation of an intermediate metabolite, phthalic acid that has undergone subsequent utilization, has occurred in basidiomycete-rich medium (under the production of both laccase and versatile peroxidase). The formation of phthalic acid as a metabolite of fluoranthene degradation by lignolytic fungi has been revealed for the first time. The data allow the supposition that both extracellular laccase and laccase on the mycelium surface can participate in the initial stages of PAH metabolism, while versatile peroxidase is necessary for the oxidation of the formed metabolites. A scheme of fluorene metabolism by Pleurotus ostreatus D1 is suggested.

Use of bromodeoxyuridine immunocapture to identify psychrotolerant phenanthrene-degrading bacteria in phenanthrene-enriched polluted Baltic Sea sediments

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

Edlund, A.; Jansson, J.

The aim of this study was to enrich and identify psychrotolerant phenanthrenedegrading bacteria from polluted Baltic Sea sediments. Polyaromatic hydrocarbon (PAH)-contaminated sediments were spiked with phenanthrene and incubated for 2 months in the presence of bromodeoxyuridine that is incorporated into the DNA of replicating cells. The bromodeoxyuridine-incorporated DNA was extracted by immunocapture and analyzed by terminal-restriction fragment length polymorphism and 16S rRNA gene cloning and sequencing to identify bacterial populations that were growing. In addition, degradation genes were quantified in the bromodeoxyuridine-incorporated DNA by real-time PCR. Phenanthrene concentrations decreased after 2 months of incubation in the phenanthrene-enriched sediments and thismore » reduction correlated to increases in copy numbers of xylE and phnAc dioxygenase genes. Representatives of Exiguobacterium, Schewanella,Methylomonas, Pseudomonas, Bacteroides and an uncultured Deltaproteobacterium and a Gammaproteobacterium dominated the growing community in the phenanthrene spiked sediments. Isolates that were closely related to three of these bacteria (two pseudomonads and an Exiguobacterium sp.) could reduce phenanthrene concentrations in pure cultures and they all harbored phnAc dioxygenase genes. These results confirm that this combination of culture-based and molecular approaches was useful for identification of actively growing bacterial species with a high potential for phenanthrene degradation.« less

Distribution of phenanthrene between soil and an aqueous phase in the presence of anionic micelle-like amphiphilic polyurethane particles.

PubMed

Lee, Kangtaek; Choi, Heon-Sik; Kim, Ju-Young; Ahn, Ik-Sung

2003-12-12

Sorption of micelle-like amphiphilic polyurethane (APU) particles to soil was studied and compared to that of a model anionic surfactant, sodium dodecyl sulfate (SDS). Three types of APU particles with different hydrophobicity were synthesized from urethane acrylate anionomers (UAA) and used in this study. Due to the chemically cross-linked structure, APU exhibited less sorption to the soil than SDS and a greater reduction in the sorption of phenanthrene, a model soil contaminant, to the soil was observed in the presence of APU than SDS even though the solubility of phenanthrene was higher in the presence of SDS than APU. A mathematical model was developed to describe the phenanthrene distribution between soil and an aqueous phase containing APU particles. The sorption of phenanthrene to the test soil could be well described by Linear isotherm. APU sorption to the soil was successfully described by Langmuir and Freundlich isotherms. The partition of phenanthrene between water and APU were successfully explained with a single partition coefficient. The model, which accounts for the limited solubilization of phenanthrene in sorbed APU particles, successfully described the experimental data for the distribution of phenanthrene between the soil and the aqueous phase in the presence of APU.

Use of nutrient supplements to increase the microbial degradation of PAH in contaminated soils

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

Carmichael, L.M.; Pfaender, F.K.

1994-12-31

The microbial degradation of polycyclic aromatic hydrocarbons (PAH) is often low in soils due to unavailability of PAH and/or to conditions in the soil that are not favorable to microbial activity. As a result, successful bioremediation of PAH contaminated soils may require the addition of supplements to impact PAH availability or soil conditions. This paper reports on the addition of supplements (Triton X-100, Inopol, nutrient buffer, an organic nutrient solution, salicylic acid) on the fate of (9-{sup 14}C) phenanthrene, a model PAH, in creosote contaminated soils. Phenanthrene metabolism was assessed using a mass balance approach that accounts for metabolism ofmore » phenanthrene to CO{sub 2}, relative metabolite production, and uptake of phenanthrene into cells. Most of the supplements did not drastically alter the fate of phenanthrene in the contaminated soils. Additions of Inopol, however, increased phenanthrene mineralization, while salicylic acid decreased phenanthrene mineralization but greatly increased the production of polar and water soluble metabolites. All supplements (excluding salicylic acid and the organic nutrient solution) increased populations of heterotrophic microorganisms, as measured by plate counts. Phenanthrene degrader populations, however, were only slightly increased by additions of the nutrient buffer, as measured by the Most Probable Number assay.« less

Biodegradation of phenanthrene in bioaugmented microcosm by consortium ASP developed from coastal sediment of Alang-Sosiya ship breaking yard.

PubMed

Patel, Vilas; Patel, Janki; Madamwar, Datta

2013-09-15

A phenanthrene-degrading bacterial consortium (ASP) was developed using sediment from the Alang-Sosiya shipbreaking yard at Gujarat, India. 16S rRNA gene-based molecular analyses revealed that the bacterial consortium consisted of six bacterial strains: Bacillus sp. ASP1, Pseudomonas sp. ASP2, Stenotrophomonas maltophilia strain ASP3, Staphylococcus sp. ASP4, Geobacillus sp. ASP5 and Alcaligenes sp. ASP6. The consortium was able to degrade 300 ppm of phenanthrene and 1000 ppm of naphthalene within 120 h and 48 h, respectively. Tween 80 showed a positive effect on phenanthrene degradation. The consortium was able to consume maximum phenanthrene at the rate of 46 mg/h/l and degrade phenanthrene in the presence of other petroleum hydrocarbons. A microcosm study was conducted to test the consortium's bioremediation potential. Phenanthrene degradation increased from 61% to 94% in sediment bioaugmented with the consortium. Simultaneously, bacterial counts and dehydrogenase activities also increased in the bioaugmented sediment. These results suggest that microbial consortium bioaugmentation may be a promising technology for bioremediation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Indigenous 14C-phenanthrene biodegradation in "pristine" woodland and grassland soils from Norway and the United Kingdom.

PubMed

Okere, Uchechukwu V; Schuster, Jasmin K; Ogbonnaya, Uchenna O; Jones, Kevin C; Semple, Kirk T

2017-11-15

In this study, the indigenous microbial mineralisation of 14 C-phenanthrene in seven background soils (four from Norwegian woodland and three from the UK (two grasslands and one woodland)) was investigated. ∑PAHs ranged from 16.39 to 285.54 ng g -1 dw soil. Lag phases (time before 14 C-phenanthrene mineralisation reached 5%) were longer in all of the Norwegian soils and correlated positively with TOC, but negatively with ∑PAHs and phenanthrene degraders for all soils. 14 C-phenanthrene mineralisation in the soils varied due to physicochemical properties. The results show that indigenous microorganisms can adapt to 14 C-phenanthrene mineralisation following diffuse PAH contamination. Considering the potential of soil as a secondary PAH source, these findings highlight the important role of indigenous microflora in the processing of PAHs in the environment.

Trichoderma longibrachiatum Evx1 is a fungal biocatalyst suitable for the remediation of soils contaminated with diesel fuel and polycyclic aromatic hydrocarbons.

PubMed

Andreolli, Marco; Lampis, Silvia; Brignoli, Pierlorenzo; Vallini, Giovanni

2016-05-01

Trichoderma sp. strain Evx1 was isolated from a semi-deciduous forest soil in Southern Italy. It decolorizes polynuclear organic dyes and tolerates high concentrations of phenanthrene, anthracene, fluoranthene, and pyrene. The ability of this ascomycete fungus to degrade polycyclic aromatic hydrocarbons was verified in vitro and confirmed by its strong phenoloxidase activity in the presence of gallic acid. Phylogenetic characterization of Trichoderma sp. Evx1 positioned this strain within the species Trichoderma longibrachiatum. The potential use of this species for the bioremediation of contaminated environmental matrices was tested by inoculating diesel-spiked soil with a dense mycelial suspension. The biodegradation percentage of the C12-40 hydrocarbon fraction in the inoculated soil rose to 54.2 ± 1.6 %, much higher than that in non-inoculated soil or soil managed solely by a combination of watering and aeration. The survival and persistence of T. longibrachiatum Evx1 throughout the bioremediation trial was monitored by PCR-DGGE analysis. The fungal strain was still present in the soil 30 days after bioaugmentation. These findings indicate that T. longibrachiatum Evx1 may be a suitable inoculum in bioremediation protocols for the reclamation of soils contaminated by complex mixtures of hydrocarbons.

High-Sensitivity Surface-Enhanced Raman Scattering (SERS) Substrate Based on a Gold Colloid Solution with a pH Change for Detection of Trace-Level Polycyclic Aromatic Hydrocarbons in Aqueous Solution.

PubMed

Shi, Xiaofeng; Liu, Shu; Han, Xiaohong; Ma, Jun; Jiang, Yongchao; Yu, Guifeng

2015-05-01

In this study, a gold colloid solution whose parameters were optimized, and without any surfactants, was developed as a surface-enhanced Raman scattering (SERS) substrate for the detection of trace-level polycyclic aromatic hydrocarbons (PAHs). A gold colloid solution with 57 nm gold particles and pH 13 was prepared to be the SERS substrate. It had impressive enhancement that was two orders of magnitude higher than that of a gold colloid solution with 57 nm gold particles and without pH change (pH 6). Even with a compact field-based Raman spectrometer, naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene were detected, with limits of detection at 6.8 nM, 3.4 nM, 1.8 nM, 0.68 nM (680 pM), and 0.44 nM (440 pM), respectively. The significant enhancement was ascribed to an electromagnetic mechanism and a charge-transfer mechanism. Quantitative analyses for these five PAHs in water were also performed. The SERS intensities of PAHs were found to have good linear dependence relations with the concentrations in low concentration. This high-sensitivity, easily prepared substrate offers a promising technology for the quantitative detection of trace-level PAHs.

Levels, composition profiles and risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sludge from ten textile dyeing plants.

PubMed

Ning, Xun-An; Lin, Mei-Qing; Shen, Ling-Zhi; Zhang, Jian-Hao; Wang, Jing-Yu; Wang, Yu-Jie; Yang, Zuo-Yi; Liu, Jing-Yong

2014-07-01

As components of synthetic dyes, polycyclic aromatic hydrocarbons (PAHs) are present as contaminants in textile dyeing sludge due to the recalcitrance in wastewater treatment process, which may pose a threat to environment in the process of sludge disposal. In order to evaluate PAHs in textile dyeing sludge, comprehensive investigation comprising 10 textile dyeing plants was undertaken. Levels, composition profiles and risk assessment of 16 EPA-priority PAHs were analyzed in this study. The total concentrations of 16 PAHs (∑16 PAHs) varied from 1463 ± 177 ng g(-1) to 16,714 ± 1,507 ng g(-1) with a mean value of 6386 ng g(-1). The composition profiles of PAHs were characterized by 3- and 4-ring PAHs, among which phenanthrene, anthracene and fluoranthene were the most dominant components. The mean benzo[a]pyrene equivalent (BaPeq) concentration of ∑16 PAHs in textile dyeing sludge was 423 ng g(-1), which was 2-3 times higher than concentrations reported for urban soil. According to ecological risk assessment, the levels of PAHs in the textile dyeing sludge may cause a significant risk to soil ecosystem after landfill or dumping on soil. Copyright © 2014 Elsevier Inc. All rights reserved.

Gas chromatographic retention behavior of polycyclic aromatic hydrocarbons (PAHs) and alkyl-substituted PAHs on two stationary phases of different selectivity.

PubMed

Nalin, Federica; Sander, Lane C; Wilson, Walter B; Wise, Stephen A

2018-01-01

Retention indices (I) for 45 polycyclic aromatic hydrocarbons (PAHs) and 63 methyl-substituted PAHs were determined by gas chromatography - mass spectrometry (GC-MS) using two different stationary phases: a Rxi-PAH phase (a "higher phenyl-content stationary phase") and a 50% (mole fraction) liquid crystalline dimethylpolysiloxane phase. Retention data were obtained for parent PAHs from molecular mass (MM) 128 g/mol (naphthalene) to 328 g/mol (benzo[c]picene) and for 12 sets of methyl-PAHs (methylfluorenes, methylanthracenes, methylphenanthrenes, methylfluoranthenes, methylpyrenes, methylbenz[a]anthracenes, methylbenzo[c]phenanthrenes, methylchrysenes, methyltriphenylenes, methylbenzo[a]pyrenes, methylperylenes, and methylpicenes). Molecular shape descriptors such as length-to-breath ratio (L/B) and thickness (T) were determined for all the PAHs studied. Correlation between I and L/B ratio was evaluated for both stationary phases with a better correlation observed for the 50% liquid crystalline phase (correlation coefficients ranging from 0.22 to 1.00). Graphical Abstract GC separation of six methylchrysene isomers (m/z 242) on two different stationary phases: 50 % phenyl-like methylpolysiloxane phase and 50 % liquid crystalline phase. Retention indices (I) are plotted as a function of L/B for both phases. The data marker numbers identify each isomer based on methyl-substitution position.

Effect of short-chain organic acids on the enhanced desorption of phenanthrene by rhamnolipid biosurfactant in soil-water environment.

PubMed

An, Chun-jiang; Huang, Guo-he; Wei, Jia; Yu, Hui

2011-11-01

This study investigated the effect of short-chain organic acids on biosurfactant-enhanced mobilization of phenanthrene in soil-water system. The desorption characteristics of phenanthrene by soils were assessed in the presence of rhamnolipid and four SCOAs, including acetic acid, oxalic acid, tartaric acid and citric acid. The tests with rhamnolipid and different organic acids could attain the higher desorption of phenanthrene compared to those with only rhamnolipid. Among the different combinations, the series with rhamnolipid and citric acid exhibited more significant effect on the desorption performance. The removal of phenanthrene using rhamnolipid and SCOAs gradually increased as the SCOA concentration increased up to a concentration of 300 mmol/L. The effects of pH, soil dissolved organic matter and ionic strength were further evaluated in the presence of both biosurfactant and SCOAs. The results showed that the extent of phenanthrene desorption was more significant at pH 6 and 9. Desorption of phenanthrene was relatively lower in the DOM-removed soils with the addition of biosurfactant and SCOAs. The presence of more salt ions made phenanthrene more persistent on the solid phase and adversely affected its desorption from contaminated soil. The results from this study may have important implications for soil washing technologies used to treat PAH-contaminated soil and groundwater. Copyright © 2011 Elsevier Ltd. All rights reserved.

Mobile bacteria and transport of polynuclear aromatic hydrocarbons in porous media.

PubMed Central

Jenkins, M B; Lion, L W

1993-01-01

Sorption of hydrophobic pollutants such as polynuclear aromatic hydrocarbons (PAHs) to soil and aquifer materials can severely retard their mobility and the time course of their removal. Because mobile colloids may enhance the mobility of hydrophobic pollutants in porous media and indigenous bacteria are generally colloidal in size, bacterial isolates from soil and subsurface environments were tested for their ability to enhance the transport of phenanthrene, a model PAH, in aquifer sand. Batch isotherm experiments were performed to measure the ability of selected bacteria, including 14 isolates from a manufactured gas plant waste site, to sorb 14C-phenanthrene and to determine whether the presence of the suspended cells would reduce the distribution coefficient (Kd) for phenanthrene with the sand. Column experiments were then used to test the mobility of isolates that reduced the Kd for phenanthrene and to test the most mobile isolate for its ability to enhance the transport of phenanthrene. All of the isolates tested passively sorbed phenanthrene, and most but not all of the isolates reduced the Kd for phenanthrene. Some, but not all, of those isolates were mobile in column experiments. The most mobile isolate significantly enhanced the transport of phenanthrene in aquifer sand, reducing its retardation coefficient by 25% at a cell concentration of approximately 5 x 10(7) ml-1. The experimental results demonstrated that mobile bacteria may enhance the transport of PAHs in the subsurface. PMID:8250555

Effects of nanoplastics and microplastics on toxicity, bioaccumulation, and environmental fate of phenanthrene in fresh water.

PubMed

Ma, Yini; Huang, Anna; Cao, Siqi; Sun, Feifei; Wang, Lianhong; Guo, Hongyan; Ji, Rong

2016-12-01

Contamination of fine plastic particles (FPs), including micrometer to millimeter plastics (MPs) and nanometer plastics (NPs), in the environment has caught great concerns. FPs are strong adsorbents for hydrophobic toxic pollutants and may affect their fate and toxicity in the environment; however, such information is still rare. We studied joint toxicity of FPs with phenanthrene to Daphnia magna and effects of FPs on the environmental fate and bioaccumulation of 14 C-phenanthrene in fresh water. Within the five sizes particles we tested (from 50 nm to 10 μm), 50-nm NPs showed significant toxicity and physical damage to D. magna. The joint toxicity of 50-nm NPs and phenanthrene to D. magna showed an additive effect. During a 14-days incubation, the presence of NPs significantly enhanced bioaccumulation of phenanthrene-derived residues in daphnid body and inhibited the dissipation and transformation of phenanthrene in the medium, while 10-μm MPs did not show significant effects on the bioaccumulation, dissipation, and transformation of phenanthrene. The differences may be attributed to higher adsorption of phenanthrene on 50-nm NPs than 10-μm MPs. Our findings underlined the high potential ecological risks of FPs, and suggested that NPs should be given more concerns, in terms of their interaction with hydrophobic pollutants in the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Visible light photodegradation of phenanthrene catalyzed by Fe(III)-smectite: role of soil organic matter.

PubMed

Jia, Hanzhong; Li, Li; Fan, Xiaoyun; Liu, Mingdeng; Deng, Wenye; Wang, Chuanyi

2013-07-15

In the present study, phenanthrene is employed as a model to explore the roles played by three soil organic matter (SOM) fractions, i.e., dissolved organic matter (DOM), humic acid (HA), and fulvic acid (FA), in its photodegradation with assistance of Fe(III)-smectite under visible-light. Slight decrease in phenanthrene photodegradation rate was observed in the presence of DOM, which is explained in terms of oxidative-radical competition between DOM and target phenanthrene molecules due to the high electron-donor capacity of phenolic moieties in DOM. On the other hand, a critic content is observed with FA (0.70mg/g) and HA (0.65mg/g). Before reaching the critic content, the removal of phenanthrene is accelerated; while after that, the photodegradation rate is suppressed. The acceleration of phenanthrene degradation can be attributed to the photosensitization of FA and HA. Due to the strong interaction between phenanthrene and the phenyl rings, however, the retention of phenanthrene on SOM-Fe(III)-smectite in the presence of high content of HA or FA is enhanced, thus slowing down its photodegradation. Those observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and open a window for using clay-humic substances complexes for remediation of contaminated soil. Copyright © 2013 Elsevier B.V. All rights reserved.

Studies on organic semiconductors. 15: Effects of the substituents on the photoconductivities of substituted anthracenes

NASA Technical Reports Server (NTRS)

Sugimoto, A.; Kato, S.; Inoue, H.; Imoto, E.

1985-01-01

The photocurrents of the substituted anthracenes, 1,5-diacetylanthracene (2), 1-acetylanthracene (3), 9-acetylanthracene (4), 1,5-dichloroanthracene (5), 1,5-diethylanthracene (6), 1,5-dimethoxyanthracene (7), 9-cyanoanthracene (8), and anthracene (1) were measured by using their surface type cells in nitrogen. The compounds of (1), (5), (6), (7), and (8) showed the photocurrent spectra which corresponded to the absorption spectra of their evaporated films. In the cases of (2) and (3), however, the anomalous photocurrent appeared in the threshold region of their absorption spectra. The appearance of the anomalous photocurrent was characteristic of anthracenes having the acetyl group at 1- and/or 5-position. The magnitude of the photocurrents of the 1,5-disubstituted anthracenes was similar to that of (1). The photocurrents of the monosubstituted anthracenes were smaller than that of (1). Among the monosubstituted anthracenes, the compound (4) showed no photocurrent under the same conditions. Contrary to the results obtained in the cases of phenazines, the photoconductivities of the anthracene derivatives became better in air.

Occupational PAH Exposures during Prescribed Pile Burns

PubMed Central

Robinson, M. S.; Anthony, T. R.; Littau, S. R.; Herckes, P.; Nelson, X.; Poplin, G. S.; Burgess, J. L.

2008-01-01

Wildland firefighters are exposed to particulate matter and gases containing polycyclic aromatic hydrocarbons (PAHs), many of which are known carcinogens. Our objective was to evaluate the extent of firefighter exposure to particulate and PAHs during prescribed pile burns of mainly ponderosa pine slash and determine whether these exposures were correlated with changes in urinary 1-hydroxypyrene (1-HP), a PAH metabolite. Personal and area sampling for particulate and PAH exposures were conducted on the White Mountain Apache Tribe reservation, working with 21 Bureau of Indian Affairs/Fort Apache Agency wildland firefighters during the fall of 2006. Urine samples were collected pre- and post-exposure and pulmonary function was measured. Personal PAH exposures were detectable for only 3 of 16 PAHs analyzed: naphthalene, phenanthrene, and fluorene, all of which were identified only in vapor-phase samples. Condensed-phase PAHs were detected in PM2.5 area samples (20 of 21 PAHs analyzed were detected, all but naphthalene) at concentrations below 1 μg m−3. The total PAH/PM2.5 mass fractions were roughly a factor of two higher during smoldering (1.06 ± 0.15) than ignition (0.55 ± 0.04 μg mg−1). There were no significant changes in urinary 1-HP or pulmonary function following exposure to pile burning. In summary, PAH exposures were low in pile burns, and urinary testing for a PAH metabolite failed to show a significant difference between baseline and post-exposure measurements. PMID:18515848

Anaerobic biodegradation of PAHs in mangrove sediment with amendment of NaHCO3.

PubMed

Li, Chun-Hua; Wong, Yuk-Shan; Wang, Hong-Yuan; Tam, Nora Fung-Yee

2015-04-01

Mangrove sediment is unique in chemical and biological properties. Many of them suffer polycyclic aromatic hydrocarbon (PAH) contamination. However, the study on PAH biological remediation for mangrove sediment is deficient. Enriched PAH-degrading microbial consortium and electron acceptor amendment are considered as two effective measures. Compared to other electron acceptors, the study on CO2, which is used by methanogens, is still seldom. This study investigated the effect of NaHCO3 amendment on the anaerobic biodegradation of four mixed PAHs, namely fluorene (Fl), phenanthrene (Phe), fluoranthene (Flua) and pyrene (Pyr), with or without enriched PAH-degrading microbial consortium in mangrove sediment slurry. The trends of various parameters, including PAH concentrations, microbial population size, electron-transport system activities, electron acceptor and anaerobic gas production were monitored. The results revealed that the inoculation of enriched PAH-degrading consortium had a significant effect with half lives shortened by 7-13 days for 3-ring PAHs and 11-24 days for 4-ring PAHs. While NaHCO3 amendment did not have a significant effect on the biodegradation of PAHs and other parameters, except that CO2 gas in the headspace of experimental flasks was increased. One of the possible reasons is that mangrove sediment contains high concentrations of other electron acceptors which are easier to be utilized by anaerobic bacteria, the other one is that the anaerobes in mangrove sediment can produce enough CO2 gas even without adding NaHCO3. Copyright © 2015. Published by Elsevier B.V.

Oxidation of anthracene using waste Mn oxide minerals: the importance of wetting and drying sequences.

PubMed

Clarke, Catherine; Tourney, Janette; Johnson, Karen

2012-02-29

PAHs are a common problem in contaminated urban soils due to their recalcitrance. This study presents results on the oxidation of anthracene on synthetic and natural Mn oxide surfaces. Evaporation of anthracene spiked Mn oxide slurries in air results in the oxidation of 30% of the anthracene to anthraquinone. Control minerals, quartz and calcite, also oxidised a small but significant proportion of the anthracene (4.5% and 14% conversion, respectively) when spiked mineral slurries were evaporated in air. However, only Mn oxide minerals showed significant anthracene oxidation (5-10%) when evaporation took place in the absence of oxygen (N2 atmosphere). In the fully hydrated systems where no drying took place, natural Mn oxides showed an increase in anthracene oxidation with decreasing pH, with a conversion of 75% anthracene at pH 4. These results show both acidification and drying favor the oxidation of anthracene on Mn oxide mineral surfaces. It has also been demonstrated that non-redox active mineral surfaces, such as calcite, may play a role in contaminant breakdown during wetting and drying sequences. Given that climate changes suggest that wetting and drying sequences are likely to become more significant these results have important implications for contaminated land remediation technologies. Copyright © 2012 Elsevier B.V. All rights reserved.

Unimolecular reaction energies for polycyclic aromatic hydrocarbon ions.

PubMed

West, Brandi; Rodriguez Castillo, Sarah; Sit, Alicia; Mohamad, Sabria; Lowe, Bethany; Joblin, Christine; Bodi, Andras; Mayer, Paul M

2018-03-07

Imaging photoelectron photoion coincidence spectroscopy was employed to explore the unimolecular dissociation of the ionized polycyclic aromatic hydrocarbons (PAHs) acenaphthylene, fluorene, cyclopenta[d,e,f]phenanthrene, pyrene, perylene, fluoranthene, dibenzo[a,e]pyrene, dibenzo[a,l]pyrene, coronene and corannulene. The primary reaction is always hydrogen atom loss, with the smaller species also exhibiting loss of C 2 H 2 to varying extents. Combined with previous work on smaller PAH ions, trends in the reaction energies (E 0 ) for loss of H from sp 2 -C and sp 3 -C centres, along with hydrocarbon molecule loss were found as a function of the number of carbon atoms in the ionized PAHs ranging in size from naphthalene to coronene. In the case of molecules which possessed at least one sp 3 -C centre, the activation energy for the loss of an H atom from this site was 2.34 eV, with the exception of cyclopenta[d,e,f]phenanthrene (CPP) ions, for which the E 0 was 3.44 ± 0.86 eV due to steric constraints. The hydrogen loss from PAH cations and from their H-loss fragments exhibits two trends, depending on the number of unpaired electrons. For the loss of the first hydrogen atom, the energy is consistently ca. 4.40 eV, while the threshold to lose the second hydrogen atom is much lower at ca. 3.16 eV. The only exception was for the dibenzo[a,l]pyrene cation, which has a unique structure due to steric constraints, resulting in a low H loss reaction energy of 2.85 eV. If C 2 H 2 is lost directly from the precursor cation, the energy required for this dissociation is 4.16 eV. No other fragmentation channels were observed over a large enough sample set for trends to be extrapolated, though data on CH 3 and C 4 H 2 loss obtained in previous studies is included for completeness. The dissociation reactions were also studied by collision induced dissociation after ionization by atmospheric pressure chemical ionization. When modeled with a simple temperature-based theory for the post-collision internal energy distribution, there was reasonable agreement between the two sets of data.

Effect of bioaugmentation to enhance phytoremediation for removal of phenanthrene and pyrene from soil with Sorghum and Onobrychis sativa

PubMed Central

2014-01-01

The use of plants to remove Poly-aromatic-hydrocarbons (PAHs) from soil (phytoremediation) is emerging as a cost-effective method. Phytoremediation of contaminated soils can be promoted by the use of adding microorganisms with the potential of pollution biodegradation (bioaugmentation). In the present work, the effect of bacterial consortium was studied on the capability of Sorghum and Onobrychis sativa for the phytoremediation of soils contaminated with phenanthrene and pyrene. 1.5 kg of the contaminated soil in the ratio of 100 and 300 mg phenanthrene and/or pyrene per kg of dry soil was then transferred into each pot (nine modes). The removal efficiency of natural, phytoremediation and bioaugmentation, separately and combined, were evaluated. The samples were kept under field conditions, and the remaining concentrations of pyrene and phenanthrene were determined after 120 days. The rhizosphere as well as the microbial population of the soil was also determined. Results indicated that both plants were able to significantly remove pyrene and phenanthrene from the contaminated soil samples. Phytoremediation alone had the removal efficiency of about 63% and 74.5% for pyrene and phenanthrene respectively. In the combined mode, the removal efficiency dramatically increased, leading to pyrene and phenanthrene removal efficiencies of 74.1% and 85.02% for Onobrychis sativa and 73.84% and 85.2% for sorghum, respectively. According to the results from the present work, it can be concluded that Onobrychis sativa and sorghum are both efficient in removing pyrene and phenanthrene from contamination and bioaugmentation can significantly enhance the phytoremediation of soils contaminated with pyrene and phenanthrene by 22% and 16% respectively. PMID:24406158

Fire-Resistant Composites

NASA Technical Reports Server (NTRS)

Kourtides, D. A.; Parker, J. A.

1983-01-01

Resin blend produces high-char-yield, low-smoke composites. Diglycidyl Ether of Bis-(4-Hydroxyphenyl)-Fluorene is prepared by reacting epichlorohydrin and sodium hydroxide with 9,9-bis(hydroxyphenyl) fluorene. End of reaction determined by gas or liquid chromatography, mass spectroscopy or infrared techniques. Used to manufacture printed circuit boards and panels for buildings, ships and aircraft.

Specific adsorption of cadmium on surface-engineered biocompatible organoclay under metal-phenanthrene mixed-contamination.

PubMed

Biswas, Bhabananda; Sarkar, Binoy; Mandal, Asit; Naidu, Ravi

2016-11-01

Bioremediation of polycyclic aromatic hydrocarbons (PAHs) is extremely challenging when they coexist with heavy metals. This constrain has led to adsorption-based techniques that help immobilize the metals and reduce toxicity. However, the adsorbents can also non-selectively bind the organic compounds, which reduces their bioavailability. In this study we developed a surface-engineered organoclay (Arquad ® 2HT-75-bentonite-palmitic acid) which enhanced bacterial proliferation and adsorbed cadmium, but elevated phenanthrene bioavailability. Adsorption models of single and binary solutes revealed that the raw bentonite adsorbed cadmium and phenanthrene non-selectively at the same binding sites and sequestrated phenanthrene. In contrast, cadmium selectively bound to the deprotonated state of carboxyl groups in the organoclay and phenanthrene on the outer surface of the adsorbent led to a microbially congenial microenvironment with a higher phenanthrene bioavailability. This study provided valuable information which would be highly important for developing a novel clay-modulated bioremediation technology for cleaning up PAHs under mixed-contaminated situations. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of amphiphilic polyurethane nanoparticles on sorption-desorption of phenanthrene in aquifer material.

PubMed

Kim, Ju-Young; Shim, Sun-Bo; Shim, Jin-Kie

2003-03-17

Micelle-like amphiphilic nano-sized polyurethane (APU) nanoparticles were synthesized via chemical cross-linking reaction of nano-aggregates of urethane acrylate nonionomer (UAN) chain and were tested for extraction efficiency of sorbed phenanthrene from aquifer material. Even though the solubilizing performance and interfacial activity of APU nanoparticles were inferior to that of Triton X-100, in the low concentration region, APU nanoparticles could effectively reduce phenanthrene sorption on the aquifer material and extracted sorbed phenanthrene from the aquifer material, whereas Triton X-100 could not extract sorbed phenanthrene and rather increased phenanthrene sorption onto the aquifer materials. At higher concentrations, APU nanoparticles and Triton X-100 had almost the same soil washing effectiveness. This interesting result is mainly due to a lower degree of sorption of APU nanoparticles onto the aquifer material. The sorption of APU nanoparticles onto aquifer sand is largely hindered by their chemically cross-linked nature, resulting in better soil-washing performance of APU nanoparticles than Triton X-100. Copyright 2003 Elsevier Science B.V.

Solubilization of phenanthrene above cloud point of Brij 30: a new application in biodegradation.

PubMed

Pantsyrnaya, T; Delaunay, S; Goergen, J L; Guseva, E; Boudrant, J

2013-06-01

In the present study a new application of solubilization of phenanthrene above cloud point of Brij 30 in biodegradation was developed. It was shown that a temporal solubilization of phenanthrene above cloud point of Brij 30 (5wt%) permitted to obtain a stable increase of the solubility of phenanthrene even when the temperature was decreased to culture conditions of used microorganism Pseudomonas putida (28°C). A higher initial concentration of soluble phenanthrene was obtained after the cloud point treatment: 200 against 120μM without treatment. All soluble phenanthrene was metabolized and a higher final concentration of its major metabolite - 1-hydroxy-2-naphthoic acid - (160 against 85μM) was measured in the culture medium in the case of a preliminary cloud point treatment. Therefore a temporary solubilization at cloud point might have a perspective application in the enhancement of biodegradation of polycyclic aromatic hydrocarbons. Copyright © 2013 Elsevier Ltd. All rights reserved.

Fluorene biodegradation and identification of transformation products by white-rot fungus Armillaria sp. F022.

PubMed

Hadibarata, Tony; Kristanti, Risky Ayu

2014-06-01

A diverse surfactant, including the nonionic Tween 80 and Brij 30, the anionic sodium dodecyl sulphate, the cationic surfactant Tetradecyltrimethylammonium bromide, and biosurfactant Rhamnolipid were investigated under fluorine-enriched medium by Armilaria sp. F022. The cultures were performed at 25 °C in malt extract medium containing 1 % of surfactant and 5 mg/L of fluorene. The results showed among the tested surfactants, Tween-80 harvested the highest cell density and obtained the maximum specific growth rate. This due Tween-80 provide a suitable carbon source for fungi. Fluorane was also successfully eliminated (>95 %) from the cultures within 30 days in all flasks. During the experiment, laccase production was the highest among other enzymes and Armillaria sp. F022-enriched culture containing Non-ionic Tween 80 showed a significant result for laccase activity (1,945 U/L). The increased enzyme activity was resulted by the increased biodegradation activity as results of the addition of suitable surfactants. The biotransformation of fluorene was accelerated by Tween 80 at the concentration level of 10 mg/L. Fluorene was initially oxidized at C-2,3 positions resulting 9-fluorenone. Through oxidative decarboxylation, 9-fluorenone subjected to meta-cleavage to form salicylic acid. One metabolite detected in the end of experiment, was identified as catechol. Armillaria sp. F022 evidently posses efficient, high effective degrader and potential for further application on the enhanced bioremediation technologies for treating fluorene-contaminated soil.

Barium alginate caged Fe3O4@C18 magnetic nanoparticles for the pre-concentration of polycyclic aromatic hydrocarbons and phthalate esters from environmental water samples.

PubMed

Zhang, Shengxiao; Niu, Hongyun; Cai, Yaqi; Shi, Yali

2010-04-30

The hydrophobic octadecyl (C(18)) functionalized Fe(3)O(4) magnetic nanoparticles (Fe(3)O(4)@C(18)) were caged into hydrophilic barium alginate (Ba(2+)-ALG) polymers to obtain a novel type of solid-phase extraction (SPE) sorbents, and the sorbents were applied to the pre-concentration of polycyclic aromatic hydrocarbons (PAHs) and phthalate esters (PAEs) pollutants from environmental water samples. The hydrophilicity of the Ba(2+)-ALG cage enhances the dispersibility of sorbents in water samples, and the superparamagnetism of the Fe(3)O(4) core facilitates magnetic separation. With the magnetic SPE technique based on the Fe(3)O(4)@C(18)@Ba(2+)-ALG sorbents, it requires only 30 min to extract trace levels of analytes from 500 mL water samples. After the eluate is condensed to 0.5 mL, concentration factors for both phenanthrene and di-n-propyl-phthalate are over 500, while for other analytes are about 1000. The recoveries of target compounds are independent of salinity and solution pH under testing conditions. Under optimized conditions, the detection limits for phenanthrene, pyrene, benzo[a]anthracene, and benzo[a]pyrene are 5, 5, 3, and 2 ng L(-1), and for di-n-propyl-phthalate, di-n-butyl-phthalate, di-cyclohexyl-phthalate, and di-n-octyl-phthalate are 36, 59, 19, and 36 ng L(-1), respectively. The spiked recoveries of several real water samples for PAHs and PAEs are in the range of 72-108% with relative standard deviations varying from 1% to 9%, showing good accuracy of the method. The advantages of the new SPE method include high extraction efficiency, short analysis time and convenient extraction procedure. To the best of our knowledge, it is unprecedented that hydrophilic Ba(2+)-ALG polymer caged Fe(3)O(4)@C(18) magnetic nanomaterial is used to extract organic pollutants from large volumes of water samples. Copyright 2010 Elsevier B.V. All rights reserved.

Long-term reproductive and behavioral toxicity of anthracene to fish in the presence of solar ultraviolet radiation

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

Hall, A.T.; Oris, J.T.

1994-12-31

The long-term, low-level effects of anthracene in the presence of solar ultraviolet radiation (SUVR) were examined in the fathead minnow (Pimephales promelas). Adult fish exposed to anthracene exhibited reduced egg laying capacity, with altered oocyte maturation as a potential mechanism of action. Eggs and larvae maternally exposed to anthracene exhibited reduced hatching success and severe developmental abnormalities when incubated under SUVR. The combination of reduced egg output and developmental effects resulted in an inhibition in reproductive capacity in the range of 70--100%. Maternal transfer of anthracene to eggs was efficient; the BCF was 717 for maternally exposed eggs. However, anthracenemore » deputation from eggs after oviposition with only maternal PAH exposure was rapid; anthracene half-life from eggs equaled 1.3 days. Exposure to anthracene under SUVR altered locomotor activity patterns in fathead minnows by inducing hyperactivity or hypoactivity during the light or dark phases of the photoperiod, respectively. Altered activity patterns indicated potential effects of anthracene on the nervous system and/or pineal gland. These alterations disrupted normal activity patterns and reproductive behaviors, and thus have major implications on a fish`s ability to survive and reproduce. Anthracene, a model phototoxic PAH, has many potential sites of toxic action, and any organism exposed to such contaminants will be an considerable SUVR-enhanced risk in the environment.« less

Characterization of a photoproduct of 7,12-dimethylbenz[alpha]anthracene and its effects on chick-embryo cells in culture.

PubMed Central

Warshawsky, D; Kerns, E; Bissell, M J; Calvin, M

1977-01-01

A common impurity of 7,12-dimethylbenz[alpha]anthracene was more effective than 7,12-dimethylbenz[alpha]anthracene in inducing morphological alterations, and in causing an increase in glucose uptake, DNA synthesis and cell number in chick-embryo fibroblasts. Gradual morphological transformation follows the increase in DNA synthesis after 2 days when either primary or secondary cultures are treated with 3 microgram of the compound/ml. The compound, isolated from 7,12-dimethylbenz[alpha]anthracene by alumina column chromatography, was characterized by t.l.c., mass spectroscopy, carbon-hydrogen analysis, u.v. and nuclear-magnetic-resonance spectroscopy and thermal decomposition. It was the photo-oxidation product of 7,12-dimethylbenz[alpha]anthracene, 7,12-epidioxy-7,12-dimethylbenz[alpha]anthracene. It is suggested that some of the biological effects observed after treatment of cultures with 7,12-dimethylbenz[alpha]anthracene may be due in part to the presence of the photo-oxidation product. PMID:407902

Turbulent Coagulation of Particles Smaller Than the Length Scales of Turbulence and Equilibrium Sorption of Phenanthrene to Clay: Implications for Pollutant Transport in the Estuarine Water Column

DTIC Science & Technology

1997-05-01

estuaries was modeled using phenanthrene, bacterial extracellular polymer and kaolinite clay as surrogates for a hydrophobic organic pollutant...coefficients obtained for phenanthrene sorption to kaolinite and bentonite in the presence of varying amounts of DOM represented by alginic acid and tannic...acid. 333 Table B.3: Literature values for sorption between phenanthrene, humic acid and kaolinite for [DOM]a = 10 mg/L 334 Table E.1: Sample output data

Combined remediation of Cd-phenanthrene co-contaminated soil by Pleurotus cornucopiae and Bacillus thuringiensis FQ1 and the antioxidant responses in Pleurotus cornucopiae.

PubMed

Jiang, Juan; Liu, Hongying; Li, Qiao; Gao, Ni; Yao, Yuan; Xu, Heng

2015-10-01

Remediation of soil co-contaminated with heavy metals and PAHs by mushroom and bacteria is a novel technique. In this study, the combined remediation effect of mushroom (Pleurotus cornucopiae) and bacteria (FQ1, Bacillus thuringiensis) on Cd and phenanthrene co-contaminated soil was investigated. The effect of bacteria (B. thuringiensis) on mushroom growth, Cd accumulation, phenanthrene degradation by P. cornucopiae and antioxidative responses of P. cornucopiae were studied. P. cornucopiae could adapt easily and grow well in Cd-phenanthrene co-contaminated soil. It was found that inoculation of FQ1 enhanced mushroom growth (biomass) and Cd accumulation with the increment of 26.68-43.58% and 14.29-97.67% respectively. Up to 100% and 95.07% of phenanthrene were removed in the bacteria-mushroom (B+M) treatment respectively spiked with 200mg/kg and 500mg/kg phenanthrene. In addition, bacterial inoculation alleviated oxidative stress caused by co-contamination with relative decreases in lipid peroxidation and enzyme activity, including malondialdehyde (MDA), superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD). This study demonstrated that the integrated remediation strategy of bacteria and mushroom is an effective and promising method for Cd-phenanthrene co-contaminated soil bioremediation. Copyright © 2015 Elsevier Inc. All rights reserved.

Comparative transcriptomic evidence for Tween80-enhanced biodegradation of phenanthrene by Sphingomonas sp. GY2B.

PubMed

Liu, Shasha; Guo, Chuling; Lin, Weijia; Wu, Fengji; Lu, Guining; Lu, Jing; Dang, Zhi

2017-12-31

Previous study of the effects of surfactants on the biodegradation of phenanthrene focused on investigating alterations of the cell characteristics of Sphingomonas sp. GY2B. However, genes regulation associated with biodegradation and biological processes in response to the presence of surfactants, remains unclear. In this study, comparative transcriptome analysis was conducted to observe the gene expression of GY2B during phenanthrene biodegradation in the presence and absence of Tween80. A diverse set of genes was regulated by Tween80, leading to increased biodegradation of phenanthrene by GY2B: (i) Tween80 increased expression of genes related to H + transport in the plasma membrane to provide a driving force (i.e., ATP) for accelerating transmembrane transport of phenanthrene with increasing Tween80 concentrations, thereby enhancing the uptake and degradation of phenanthrene by GY2B; (ii) Tween80 (1 and 8 CMC) promoted intracellular biodegradation of phenanthrene by stimulating expression of genes encoding dioxygenases and monooxygenase, increasing expression of genes involved in intracellular metabolic processes (e.g., TCA cycle); and (iii) Tween80 likely increased GY2B vitality and growth by inducing expression of genes associated with ABC transporters and protein transport, regulating genes involved in other biological processes (e.g., transcription, translation). Copyright © 2017. Published by Elsevier B.V.

Inoculation of a phenanthrene-degrading endophytic bacterium reduces the phenanthrene level and alters the bacterial community structure in wheat.

PubMed

Liu, Juan; Xiang, Yanbing; Zhang, Zhiming; Ling, Wanting; Gao, Yanzheng

2017-06-01

Colonization by polycyclic aromatic hydrocarbon (PAH)-degrading endophytic bacteria (PAHDEB) can reduce the PAH contamination risk in plant. However, little information is available on the impact of PAHDEB colonization on the endophytic bacterial community of inner plant tissues. A phenanthrene-degrading endophytic bacterium (PDEB), Massilia sp. Pn2, was inoculated onto the roots of wheat and subjected to greenhouse container experiments. The endophytic bacterial community structure in wheat was investigated using high-throughput sequencing technology. The majority of endophytic bacteria in wheat were Proteobacteria, and the dominant genus was Pseudomonas. Phenanthrene contamination clearly increased the diversity of endophytic bacteria in wheat. The cultivable endophytic bacteria counts in wheat decreased with increasing the level of phenanthrene contamination; the endophytic bacterial community structure changed correspondingly, and the bacterial richness first increased and then decreased. Inoculation of strain Pn2 reduced the phenanthrene contamination in wheat, enlarged the biomass of wheat roots, changed the bacterial community structure and enhanced the cell counts, diversity and richness of endophytic bacteria in phenanthrene-contaminated wheat in a contamination level-dependent manner. The findings of this investigation provide insight into the responses of endophytic bacterial community in plant to external PAH contamination and PAHDEB colonization.

Electro Optical Properties of Copolymer Blends: Lasing, Electroluminescence and Photophysics

DTIC Science & Technology

2006-04-15

conjugated main chain structures with high photoluminescent and electroluminescent quantum yields. The structures incorporated fluorene containing moieties...The systems studied focused on novel conjugated main chain structures with high photoluminescent and electroluminescent quantum yields. The structures...the quantum efficient fluorine group. The properties of segmented copolymers that incorporate fluorenes were compared to the homo-PPV type systems

Solar-energy production and energy-efficient lighting: photovoltaic devices and white-light-emitting diodes using poly(2,7-fluorene), poly(2,7-carbazole), and poly(2,7-dibenzosilole) derivatives.

PubMed

Beaupré, Serge; Boudreault, Pierre-Luc T; Leclerc, Mario

2010-02-23

World energy needs grow each year. To address global warming and climate changes the search for renewable energy sources with limited greenhouse gas emissions and the development of energy-efficient lighting devices are underway. This Review reports recent progress made in the synthesis and characterization of conjugated polymers based on bridged phenylenes, namely, poly(2,7-fluorene)s, poly(2,7-carbazole)s, and poly(2,7-dibenzosilole)s, for applications in solar cells and white-light-emitting diodes. The main strategies and remaining challenges in the development of reliable and low-cost renewable sources of energy and energy-saving lighting devices are discussed.

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.

Sediment contamination of residential streams in the metropolitan kansas city area, USA: Part I. distribution of polycyclic aromatic hydrocarbon and pesticide-related compounds

USGS Publications Warehouse

Tao, J.; Huggins, D.; Welker, G.; Dias, J.R.; Ingersoll, C.G.; Murowchick, J.B.

2010-01-01

This is the first part of a study that evaluates the influence of nonpoint-source contaminants on the sediment quality of five streams within the metropolitan Kansas City area, central United States. Surficial sediment was collected in 2003 from 29 sites along five streams with watersheds that extend from the core of the metropolitan area to its development fringe. Sediment was analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), 3 common polychlorinated biphenyl mixtures (Aroclors), and 25 pesticide-related compounds of eight chemical classes. Multiple PAHs were detected at more than 50% of the sites, and concentrations of total PAHs ranged from 290 to 82,150 ??g/kg (dry weight). The concentration and frequency of detection of PAHs increased with increasing urbanization of the residential watersheds. Four- and five-ring PAH compounds predominated the PAH composition (73-100%), especially fluoranthene and pyrene. The PAH composition profiles along with the diagnostic isomer ratios [e.g., anthracene/(anthracene + phenanthrene), 0.16 ?? 0.03; fluoranthene/(fluoranthene + pyrene), 0.55 ?? 0.01)] indicate that pyrogenic sources (i.e., coal-tar-related operations or materials and traffic-related particles) may be common PAH contributors to these residential streams. Historical-use organochlorine insecticides and their degradates dominated the occurrences of pesticide-related compounds, with chlordane and dieldrin detected in over or nearly 50% of the samples. The occurrence of these historical organic compounds was associated with past urban applications, which may continue to be nonpoint sources replenishing local streams. Concentrations of low molecular weight (LMW; two or three rings) and high molecular weight (HMW; four to six rings) PAHs covaried along individual streams but showed dissimilar distribution patterns between the streams, while the historical pesticide-related compounds generally increased in concentration downstream. Correlations were noted between LMW and HMW PAHs for most of the streams and between historical-use organochlorine compounds and total organic carbon and clay content of sediments for one of the streams (Brush Creek). Stormwater runoff transport modes are proposed to describe how the two groups of contaminants migrated and distributed in the streambed. ?? 2010 Springer Science+Business Media, LLC.

SYNTHESIS OF p-TRIFLUOROMETHYL-TOLUENE AND 3,6-BIS(TRIFLUOROMETHYL) PHENANTHRENE USING SULFUR TETRAFLUORIDE

DTIC Science & Technology

studies on the soxhlet extractors showed promise that separation and isolation is possible. Corrosion data gathered during the course of the p-toluic...production of 3, 6-bis(trifluoromethyl) phenanthrene based on a 20% conversion to 3,6- bis(trifluoromethyl) phenanthrene plus an additional 30% yield of

Fate of phenanthrene and mineralization of its non-extractable residues in an oxic soil.

PubMed

Wang, Yongfeng; Xu, Jun; Shan, Jun; Ma, Yini; Ji, Rong

2017-05-01

The fate of organic pollutants in the environment, especially the formation and stability of non-extractable (i.e., bound) residues (NERs) determines their environmental risk. Using 14 C-tracers, we studied the fate of the carcinogen phenanthrene in active or sterilized oxic loamy soil in the absence and presence of the geophagous earthworm Metaphire guillelmi and characterized the NERs derived from phenanthrene. After incubation of 14 C-phenanthrene in active soil for 28 days, 40 ± 3.1% of the initial amount was mineralized and 70.1 ± 1.9% was converted to NERs. Most of the NERs (>92%) were bound to soil humin. Silylation of the humin-bound residues released 45.3 ± 5.3% of these residues, which indicated that they were physically entrapped, whereas the remainder of the residues were chemically bound or biogenic. By contrast, in sterilized soil, only 43.4 ± 12.6% of the phenanthrene was converted to NERs and all of these residues were completely released upon silylation, which underlines the essential role of microbial activity in NER formation. The presence of M. guillelmi in active soil significantly inhibited phenanthrene mineralization (24.4 ± 2.6% mineralized), but NER formation was not significantly affected. Only a small amount of phenanthrene-derived residues (1.9-5.3% of the initial amount) accumulated in the earthworm body. When humin-bound residues were mixed with fresh soil, 33.9% (humin recovered from active soils) and 12.4% (humin recovered from sterilized soils) of the residues were mineralized after 75 days of incubation, respectively, which indicated a high bioavailability of NERs, albeit lower than the initial addition of phenanthrene. Our results indicated that many phenanthrene-derived NERs, especially those physically entrapped, are still bioavailable and may pose a toxic threat to soil organisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

The onset of anthracene phototoxicity to Lemna gibba and the protective effects of humic acid

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

Gensemer, R.W.; Dixon, D.G.; Greenberg, B.M.

1994-12-31

The toxicity of anthracene to the freshwater duckweed Lemna gibba is strongly photo-induced in the presence of light containing natural levels of ultraviolet (UV) radiation. This was demonstrated using 8-day static renewal bioassays at an anthracene concentration of 2 mg-L{sup {minus}1}. Plants were incubated under simulated solar radiation (SSR) which mimics UV levels found in natural sunlight at a visible:UV-A:UV-B ratio of 100:10:1. Anthracene phototoxicity was expressed as inhibition of population growth and fluorescence induction decreases in chlorophyll content, and changes in low-temperature chlorophyll fluorescence emission scans. Furthermore, adding 6.2 mg-L-1 of an artificial humic acid ameliorated anthracene phototoxicity evenmore » though HA is also photo modified by UV light. However, anthracene inhibited photosynthesis days before the endpoint assays were performed. Therefore, the authors repeated these experiments at short time intervals following exposure to both light and chemical. Anthracene phototoxicity occurred after only 1 hour as detected by chlorophyll fluorescence induction, whereas chlorophyll contents and low-temperature fluorescence emission scans were not affected until 24--48 hours, respectively. Humic acid again ameliorated anthracene toxicity by delaying the negative physiological events by approximately 24 hours.« less

Degradation of anthracene by laccase of Trametes versicolor in the presence of different mediator compounds.

PubMed

Johannes, C; Majcherczyk, A; Hüttermann, A

1996-10-01

Laccase of Trametes versicolor was generally able to oxidize anthracene in vitro. After 72 h incubation about 35% of the anthracene was transformed stoichiometrically to 9,10-anthraquinone. Transformation of anthracene increased rapidly in the presence of different mediators that readily generate stable radicals: 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and 1-hydroxybenzotriazole. For the reaction, the presence of both the laccase and the mediator was necessary. In the presence of 0.005 mM 1-hydroxybenzotriazole this conversion had removed 47% of the anthracene after 72 h; 75% of the substrate was oxidized during this period when ABTS (1 mM) was used as mediator. In contrast to reactions without or with only low concentrations of a mediator, there was a discrepancy between the disappearance of anthracene and the formation of 9,10-anthraquinone in mediator-forced reactions. Coupling-products of mediators with anthracene degradation products were found. Anthracene disappeared nearly completely after incubation for 72 h with laccase in a 0.1 mM solution of 1-hydroxybenzotriazole and was transformed to 9,10-anthraquinone in about 80% yield; 90% of the substrate was transformed in the presence of ABTS (2.0 mM) resulting again in 80% quinone. Phenothiazine was not effective in this system.

Vectorial photoinduced energy transfer between boron-dipyrromethene (Bodipy) chromophores across a fluorene bridge.

PubMed

Puntoriero, Fausto; Nastasi, Francesco; Campagna, Sebastiano; Bura, Thomas; Ziessel, Raymond

2010-08-02

A series of novel multichromophoric, luminescent compounds has been prepared, and their absorption spectra, luminescence properties (both at 77 K in rigid matrix and at 298 K in fluid solution), and photoinduced intercomponent energy-transfer processes have been studied. The series contains two new multichromophoric systems 1 and 2, each one containing two different boron-dipyrromethene (Bodipy) subunits and one bridging fluorene species, and two fluorene-Bodipy bichromophoric species, 6 and 7. Three monochromophoric compounds, 3, 4, and 5, used as precursors in the synthetic process, were also fully characterized. The absorption spectra of the multichromophoric compounds are roughly the summation of the absorption spectra of their individual components, thus demonstrating the supramolecular nature of the assemblies. Luminescence studies show that quantitative energy transfer occurs in 6 and 7 from the fluorene chromophore to the Bodipy dyes. Luminescence studies, complemented by transient-absorption spectroscopy studies, also indicate that efficient inter-Bodipy energy transfer across the rigid fluorene spacer takes place in 1 and 2, with rate constants, evaluated by several experimental methods, between 2.0 and 7.0 x 10(9) s(-1). Such an inter-Bodipy energy transfer appears to be governed by the Förster mechanism. By taking advantage of the presence of various protonable sites in the substituents of the lower-energy Bodipy subunit of 1 and 2, the effect of protonation on the energy-transfer rates has also been investigated. The results suggest that control of energy-transfer rate and efficiency of inter-Bodipy energy transfer in this type of systems can be achieved by an external, reversible input.

Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character

PubMed Central

Rice, James W.; Fu, Jinxia; Suuberg, Eric M.

2010-01-01

To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474

MEASURING GROWTH OF A PHENANTHRENE DEGRADING BACTERIAL INOCULUM IN SOIL WITH A QUANTITATIVE COMPETITIVE POLYMERASE CHAIN REACTION METHOD. (R825433)

EPA Science Inventory

We measured growth of a phenanthrene-degrading bacterium, Arthrobacter, strain RP17, in Forbes soil, amended with 500 g g⁻¹ phenanthrene using a quantitati...

Fluorene-Based Two-Dimensional Covalent Organic Framework with Thermoelectric Properties through Doping.

PubMed

Wang, Liangying; Dong, Bin; Ge, Rile; Jiang, Fengxing; Xu, Jingkun

2017-03-01

Organic semiconductors have great potential as flexible thermoelectric materials. A fluorene-based covalent organic framework (FL-COF-1) was designed with the aim of creating an enhanced π-π interaction among the crystalline backbones. By the introduction of fluorene units into the frameworks, the FL-COF-1 had high thermal stability with a BET surface area over 1300 m 2 g -1 . The open frameworks were favorable for doping with iodine and followed with the improved charge carrier mobility. The compressed pellet of I 2 @FL-COF-1 exhibited a high Seebeck coefficient of 2450 μV K -1 and power factor of 0.063 μW m -1 K -2 at room temperature, giving the first example of COFs' potential application as thermoelectric materials.

Proteomic analysis of plasma membrane proteins in wheat roots exposed to phenanthrene.

PubMed

Shen, Yu; Du, Jiangxue; Yue, Le; Zhan, Xinhua

2016-06-01

Polycyclic aromatic hydrocarbons (PAHs) are potentially carcinogenic and toxic to humans through ingestion of contaminated food crops. PAHs can enter crop roots through proton/PAH symporters; however, to date, the symporter remains unclear. Here we reveal, for the first time, the plasma membrane proteome of Triticum aestivum seedling roots in response to phenanthrene (a model PAH) exposure. Two-dimensional gel electrophoresis (2-DE) coupled with MALDI-TOF/TOF-MS and protein database search engines were employed to analyze and identify phenanthrene-responsive proteins. Over 192 protein spots are reproducibly detected in each gel, while 8 spots are differentially expressed under phenanthrene treatment. Phenanthrene induces five up-regulated proteins distinguished as 5-methyltetrahydropteroyltriglutamate-homocysteine methyltransferase 2, enolase, heat shock protein 80-2, probable mediator of RNA polymerase II transcription subunit 37e (heat shock 70-kDa protein 1), and lactoylglutathione lyase. Three proteins identified as adenosine kinase 2, 4-hydroxy-7-methoxy-3-oxo-3,4-dihydro-2H-1,4-benzoxazin-2-yl glucoside beta-D-glucosidase 1c, and glyceraldehyde-3-phosphate dehydrogenase 3 are down-regulated under exposure to phenanthrene. The up-regulated proteins are related to plant defense response, antioxidant system, and glycolysis. The down-regulated proteins involve the metabolism of high-energy compounds and plant growth. Magnesium, which is able to bind to enolase, can enhance the transport of phenanthrene into wheat roots. Therefore, it is concluded that phenanthrene can induce differential expression of proteins in relation to carbohydrate metabolism, self-defense, and plant growth on wheat root plasma membrane. This study not only provides novel insights into PAH uptake by plant roots and PAH stress responses, but is also a good starting point for further determination and analyses of their functions using genetic and other approaches.

Reduced biodegradability of desorption-resistant fractions of polycyclic aromatic hydrocarbons in soil and aquifer solids

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

White, J.C.; Alexander, M.

1996-11-01

Less of the desorption-resistant fractions of phenanthrene and naphthalene than freshly added phenanthrene and naphthalene was mineralized in columns of aquifer solids, loam, or muck. Slurrying columns of hydrocarbon-amended aquifer solids, loam, or muck enhanced the rate and extent of mineralization of desorption-resistant phenanthrene and naphthalene, but degradation was still less than in slurries amended with fresh compound. A substantial portion of the desorption-resistant compound remained undergraded in the slurry. A surfactant and methanol increased the mineralization of resistant phenanthrene in slurries of loam. A mixed culture of microorganisms enriched on desorption-resistant phenanthrene degraded twice as much of this fractionmore » of compound as a pseudomonad. The authors suggest that predictions of the environment fate of toxic chemicals require information on the biodegradability of the fraction of a compound that is resistant to desorption.« less

Synthesis and solar-cell applications of novel furanyl-substituted anthracene derivatives

NASA Astrophysics Data System (ADS)

Kivrak, Arif; Er, Ömer Faruk; Kivrak, Hilal; Topal, Yasemin; Kuş, Mahmut; Çamlısoy, Yesim

2017-11-01

At present, novel furanyl-substituted anthracene derivatives; namely 9,10-di(furan-2-yl)anthracene (DFA), 5,5‧-(anthracene-9,10-diyl)bis(furan-2-carbaldehyde) (DAFA) and 2,2‧-((5,5‧-(anthracene-9,10-diyl)bis(furan-5,2-diyl))bis(methanylylidene))dimalononitrile (DCNFA) were designed and synthesized successfully by employing Stille Cross-Coupling, Vilsmeier-Haack and Knoevenagel condensation reactions, respectively. This methodology provides a practical new route for the synthesis of furanyl-substituted anthracene derivatives bearing strong electron-withdrawing groups. The electrochemical and electro-optical properties of these novel furanyl-substituted anthracene derivatives were also examined with strong acceptor-π-donor-π-acceptor interactions. Furthermore, Highest occupied molecular orbital (HOMO), Lowest Unoccupied molecular orbital (LUMO), and band gap (Eg) values were investigated by using spectroscopic methods. Electrochemical and electro-optical properties were calculated and compared to DFA, DAFA and DCNFA. Eg was found as 2.85, 2.71, and 2.33 eV, respectively. Consequently, Organic Solar Cells (OSC) were fabricated to investigate their solar cell performances. The strong electron withdrawing groups did not increase the solar cell performance of furanyl-anthracenes. Surprisingly, DFA was found to exhibit the best OSCs performance (Efficiency = 3.36). As a result, one could note that these novel furanyl-substituted anthracene derivatives are good candidate for the applications of the OSCs. Our results might help in the development of new materials with important electrochemical functions by giving the advantage of designing and further derivatization of new generation small organic molecules for photovoltaic device applications.

Isolation, plant colonization potential, and phenanthrene degradation performance of the endophytic bacterium Pseudomonas sp. Ph6-gfp

PubMed Central

Sun, Kai; Liu, Juan; Gao, Yanzheng; Jin, Li; Gu, Yujun; Wang, Wanqing

2014-01-01

This investigation provides a novel method of endophyte-aided removal of polycyclic aromatic hydrocarbons (PAHs) from plant bodies. A phenanthrene-degrading endophytic bacterium Pseudomonas sp. Ph6 was isolated from clover (Trifolium pratense L.) grown in a PAH-contaminated site. After being marked with the GFP gene, the colonization and distribution of strain Ph6-gfp was directly visualized in plant roots, stems, and leaves for the first time. After ryegrass (Lolium multiflorum Lam.) roots inoculation, strain Ph6-gfp actively and internally colonized plant roots and transferred vertically to the shoots. Ph6-gfp had a natural capacity to cope with phenanthrene in vitro and in planta. Ph6-gfp degraded 81.1% of phenanthrene (50 mg·L−1) in a culture solution within 15 days. The inoculation of plants with Ph6-gfp reduced the risks associated with plant phenanthrene contamination based on observations of decreased concentration, accumulation, and translocation factors of phenanthrene in ryegrass. Our results will have important ramifications in the assessment of the environmental risks of PAHs and in finding ways to circumvent plant PAH contamination. PMID:24964867

Quantifying the biodegradation of phenanthrene by Pseudomonas stutzeri P16 in the presence of a nonionic surfactant.

PubMed Central

Grimberg, S J; Stringfellow, W T; Aitken, M D

1996-01-01

The low water solubility of polycyclic aromatic hydrocarbons is believed to limit their availability to microorganisms, which is a potential problem for bioremediation of polycyclic aromatic hydrocarbon-contaminated sites. Surfactants have been suggested to enhance the bioavailability of hydrophobic compounds, but both negative and positive effects of surfactants on biodegradation have been reported in the literature. Earlier, we presented mechanistic models of the effects of surfactants on phenanthrene dissolution and on the biodegradation kinetics of phenanthrene solubilized in surfactant micelles. In this study, we combined the biodegradation and dissolution models to quantify the influence of the surfactant Tergitol NP-10 on biodegradation of solid-phase phenanthrene by Pseudomonas stutzeri P16. Although micellized phenanthrene does not appear to be available directly to the bacterium, the ability of the surfactant to increase the phenanthrene dissolution rate resulted in an overall increase in bacterial growth rate in the presence of the surfactant. Experimental observations could be predicted well by the derived model with measured biokinetic and dissolution parameters. The proposed model therefore can serve as a base case for understanding the physical-chemical effects of surfactants on nonaqueous hydrocarbon bioavailability. PMID:8779577

Assessing the environmental impact of phenanthrene in different types of land use based on the binding characteristics with dissolved organic matter.

PubMed

Chen, Xiao-Meng; Zhao, Yue; Ma, Ying-Ying; Zhu, Long-Ji; Yang, Tian-Xue; Wei, Zi-Min; Dong, Ying-Li; Wei, Qing-Bin

2018-01-01

The binding characteristics of phenanthrene with dissolved organic matter (DOM) were studied by the excitation emission matrix fluorescence spectroscopy with parallel factor analysis in four types of land use which derived from forest (F), meadow (M), cropland (C), and greenhouse (G). The results showed that the humification degree and binding characteristics of phenanthrene with DOM were distinct differences in the four soils. The binding capacities of humic-like components with phenanthrene were stronger than those of protein-like components. The log K derived from the Stern-Volmer equation significantly correlated with the humification degree of DOM (p < 0.05) in different types of land use. Besides, correlation analysis demonstrated that the potential binding index (Fk) obtained from the modified Stern-Volmer model was a more accurate parameter to describe the combination degree of DOM with phenanthrene than log K, which presented a decrease order of C > F > M > G. Therefore, the environmental impact of phenanthrene in different types of land use could be assessed deeply based on the Fk and DOM concentration. Copyright © 2017 Elsevier Inc. All rights reserved.

Effect of linear alkyl benzene sulfonates (LAS) on the fate of phenanthrene in a model ecosystem (water-lava-plant-air).

PubMed

Jiang, Xia; Jin, Xiang-can; Yan, Chang-zhou; Yediler, Ayfer; Ou, Zi-qing; Kettrup, Antonius

2004-01-01

Advanced closed chamber system was used to study the fate of phenanthrene (3-rings PAHs) in the presence of linear alkylbenzene sulphonates (LAS). The results showed mineralization and metabolism of phenanthrene are fast in the "culture solution-lava-plant-air" model ecological system. The distribution proportions of applied 14C-activity in this simulative ecological system were 41%-45%, 14% to 10% and 1% in plant, lava and culture solution respectively, and 18% to 29%, 11% to 8% recovered in the forms of VOCs and CO2. Main parts of the applied 14C-activity exist in two forms, one is polar metabolites (25%) which mainly distribute in the root (23%), the other is unextractable part (23%) which have been constructed into plant root (8.98%), shoot (0.53%) or bonded to lava (13.2%). The main metabolites of phenanthrene were polar compounds (25% of applied 14C-activity), and small portion of 14C-activity was identified as non-polar metabolites (6% of applied 14C-activity) and apparent phenanthrene (1.91% of applied 14C-activity). Phenanthrene and its metabolites can be taken up through plant roots and translocated to plant shoots. The presence of LAS significantly increased the the concentration of 14C-activity in the plant and production of VOCs, at the same time it decreased the phenanthrene level in the plant and the production of CO2 at the concentration of 200 mg/L.

Biodegradation of naphthalene and phenanthren by Bacillus subtilis 3KP

NASA Astrophysics Data System (ADS)

Ni'matuzahroh, Trikurniadewi, N.; Pramadita, A. R. A.; Pratiwi, I. A.; Salamun, Fatimah, Sumarsih, Sri

2017-06-01

The purposes of this research were to know growth response, degradation ability, and uptake mechanism of naphthalene and phenanthrene by Bacillus subtilis 3KP. Bacillus subtilis 3KP was grown on Mineral Synthetic (MS) medium with addition of 1% yeast extract and naphthalene and phenanthrene respectively 200 ppm in different cultures. Bacillus subtilis 3KP growth response was monitored by Total Plate Count (TPC) method, the degradation ability was monitored by UV-Vis spectrophotometer, and the uptake mechanism of hydrocarbon was monitored by emulsification activity, decrease of surface tension, and activity of Bacterial Adherence to Hydrocarbon (BATH). Bacillus subtilis 3KP was able to grow and show biphasic growth pattern on both of substrates. Naphthalene and phenanthrene were used as a carbon source for Bacillus subtilis 3KP growth that indicated by the reduction of substrate concomitant with the growth. At room temperature conditions (± 30°C) and 90 rpm of agitation for 7 days, Bacillus subtilis 3KP could degrade naphthalene in the amount of 70.5% and phenanthrene in the amount of 24.8%. Based on the analysis of UV-Vis spectrophotometer, three metabolites, 1-hydroxy-2-naphthoic acid, salicylic acid, and pyrocatechol were found in both cultures. The metabolite identification became basis of propose degradation pathway of naphthalene and phenanthrene by Bacillus subtilis 3KP. The results of hydrocarbon uptake mechanism test show that Bacillus subtilis 3KP used all of the mechanism to degrade naphthalene and phenanthrene.

Spatial Distribution of Bacterial Communities and Phenanthrene Degradation in the Rhizosphere of Lolium perenne L.

PubMed Central

Corgié, S. C.; Beguiristain, T.; Leyval, C.

2004-01-01

Rhizodegradation of organic pollutants, such as polycyclic aromatic hydrocarbons, is based on the effect of root-produced compounds, known as exudates. These exudates constitute an important and constant carbon source that selects microbial populations in the plant rhizosphere, modifying global as well as specific microbial activities. We conducted an experiment in two-compartment devices to show the selection of bacterial communities by root exudates and phenanthrene as a function of distance to roots. Using direct DNA extraction, PCR amplification, and thermal gradient gel electrophoresis screening, bacterial population profiles were analyzed in parallel to bacterial counts and quantification of phenanthrene biodegradation in three layers (0 to 3, 3 to 6, and 6 to 9 mm from root mat) of unplanted-polluted (phenanthrene), planted-polluted, and planted-unpolluted treatments. Bacterial community differed as a function of the distance to roots, in both the presence and the absence of phenanthrene. In the planted and polluted treatment, biodegradation rates showed a strong gradient with higher values near the roots. In the nonplanted treatment, bacterial communities were comparable in the three layers and phenanthrene biodegradation was high. Surprisingly, no biodegradation was detected in the section of planted polluted treatment farthest from the roots, where the bacterial community structure was similar to those of the nonplanted treatment. We conclude that root exudates and phenanthrene induce modifications of bacterial communities in polluted environments and spatially modify the activity of degrading bacteria. PMID:15184156

Different conical intersections control nonadiabatic photochemistry of fluorene light-driven molecular rotary motor: A CASSCF and spin-flip DFT study

NASA Astrophysics Data System (ADS)

Li, Yuanying; Liu, Fengyi; Wang, Bin; Su, Qingqing; Wang, Wenliang; Morokuma, Keiji

2016-12-01

We report the light-driven isomerization mechanism of a fluorene-based light-driven rotary motor (corresponding to Feringa's 2nd generation rotary motor, [M. M. Pollard et al., Org. Biomol. Chem. 6, 507-512 (2008)]) at the complete active space self-consistent field (CASSCF) and spin-flip time-dependent density functional theory (TDDFT) (SFDFT) levels, combined with the complete active space second-order perturbation theory (CASPT2) single-point energy corrections. The good consistence between the SFDFT and CASSCF results confirms the capability of SFDFT in investigating the photoisomerization step of the light-driven molecular rotary motor, and proposes the CASPT2//SFDFT as a promising and effective approach in exploring photochemical processes. At the mechanistic aspect, for the fluorene-based motor, the S1/S0 minimum-energy conical intersection (MECIs) caused by pyramidalization of a fluorene carbon have relatively low energies and are easily accessible by the reactive molecule evolution along the rotary reaction path; therefore, the fluorene-type MECIs play the dominant role in nonadiabatic decay, as supported by previous experimental and theoretical works. Comparably, the other type of MECIs that results from pyramidalization of an indene carbon, which has been acting as the dominant nonadiabatic decay channel in the stilbene motor, is energetically inaccessible, thus the indene-type MECIs are "missing" in previous mechanistic studies including molecular dynamic simulations. A correlation between the geometric and electronic factors of MECIs and that of the S1 energy profile along the C═C rotary coordinate was found. The findings in current study are expected to deepen the understanding of nonadiabatic transition in the light-driven molecular rotary motor and provide insights into mechanistic tuning of their performance.

Occurrence and Risk Assessment of PAHs in Surface Sediments from Western Arctic and Subarctic Oceans

PubMed Central

Lin, Yan; Cai, Minggang; Zhang, Jingjing; Zhang, Yuanbiao; Kuang, Weiming; Liu, Lin; Huang, Peng; Ke, Hongwei

2018-01-01

In the fourth Chinese National Arctic Research Expedition (from July to September, 2010), 14 surface sediment samples were collected from the Bering Sea, Chukchi Sea, and Canadian Basin to examine the spatial distributions, potential sources, as well as ecological and health risk assessment of polycyclic aromatic hydrocarbons (PAHs). The ∑PAH (refers to the sum of 16 priority PAHs) concentration range from 27.66 ng/g to 167.48 ng/g (dry weight, d.w.). Additionally, the concentrations of ∑PAH were highest in the margin edges of the Canadian Basin, which may originate from coal combustion with an accumulation of Canadian point sources and river runoff due to the surface ocean currents. The lowest levels occurred in the northern of Canadian Basin, and the levels of ∑PAH in the Chukchi Sea were slightly higher than those in the Being Sea. Three isomer ratios of PAHs (Phenanthrene/Anthracene, BaA/(BaA+Chy), and LMW/HMW) were used to investigate the potential sources of PAHs, which showed the main source of combustion combined with weaker petroleum contribution. Compared with four sediment quality guidelines, the concentrations of PAH are much lower, indicating a low potential ecological risk. All TEQPAH also showed a low risk to human health. Our study revealed the important role of the ocean current on the redistribution of PAHs in the Arctic. PMID:29649142

Numerical evaluation of bioaccumulation and depuration kinetics of PAHs in Mytilus galloprovincialis.

PubMed

Yakan, S D; Focks, A; Klasmeier, J; Okay, O S

2017-01-01

Polycyclic aromatic hydrocarbons (PAHs) are important organic pollutants in the aquatic environment due to their persistence and bioaccumulation potential both in organisms and in sediments. Benzo(a)anthracene (BaA) and phenanthrene (PHE), which are in the priority pollutant list of the U.S. EPA (Environmental Protection Agency), are selected as model compounds of the present study. Bioaccumulation and depuration experiments with local Mediterranean mussel species, Mytilus galloprovincialis were used as the basis of the study. Mussels were selected as bioindicator organisms due to their broad geographic distribution, immobility and low enzyme activity. Bioaccumulation and depuration kinetics of selected PAHs in Mytilus galloprovincialis were described using first order kinetic equations in a three compartment model. The compartments were defined as: (1) biota (mussel), (2) surrounding environment (seawater), and (3) algae (Phaeodactylum tricornutum) as food source of the mussels. Experimental study had been performed for three different concentrations. Middle concentration of the experimental data was used as the model input in order to represent other high and low concentrations of selected PAHs. Correlations of the experiment and model data revealed that they are in good agreement. Accumulation and depuration trend of PAHs in mussels regarding also the durations can be estimated effectively with the present study. Thus, this study can be evaluated as a supportive tool for risk assessment in addition to monitoring studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

A Novel Phenanthrene Dioxygenase from Nocardioides sp. Strain KP7: Expression in Escherichia coli

PubMed Central

Saito, Atsushi; Iwabuchi, Tokuro; Harayama, Shigeaki

2000-01-01

Nocardioides sp. strain KP7 grows on phenanthrene but not on naphthalene. This organism degrades phenanthrene via 1-hydroxy-2-naphthoate, o-phthalate, and protocatechuate. The genes responsible for the degradation of phenanthrene to o-phthalate (phd) were found by Southern hybridization to reside on the chromosome. A 10.6-kb DNA fragment containing eight phd genes was cloned and sequenced. The phdA, phdB, phdC, and phdD genes, which encode the α and β subunits of the oxygenase component, a ferredoxin, and a ferredoxin reductase, respectively, of phenanthrene dioxygenase were identified. The gene cluster, phdAB, was located 8.3 kb downstream of the previously characterized phdK gene, which encodes 2-carboxybenzaldehyde dehydrogenase. The phdCD gene cluster was located 2.9 kb downstream of the phdB gene. PhdA and PhdB exhibited moderate (less than 60%) sequence identity to the α and β subunits of other ring-hydroxylating dioxygenases. The PhdC sequence showed features of a [3Fe-4S] or [4Fe-4S] type of ferredoxin, not of the [2Fe-2S] type of ferredoxin that has been found in most of the reported ring-hydroxylating dioxygenases. PhdD also showed moderate (less than 40%) sequence identity to known reductases. The phdABCD genes were expressed poorly in Escherichia coli, even when placed under the control of strong promoters. The introduction of a Shine-Dalgarno sequence upstream of each initiation codon of the phdABCD genes improved their expression in E. coli. E. coli cells carrying phdBCD or phdACD exhibited no phenanthrene-degrading activity, and those carrying phdABD or phdABC exhibited phenanthrene-degrading activity which was significantly less than that in cells carrying the phdABCD genes. It was thus concluded that all of the phdABCD genes are necessary for the efficient expression of phenanthrene-degrading activity. The genetic organization of the phd genes, the phylogenetically diverged positions of these genes, and an unusual type of ferredoxin component suggest phenanthrene dioxygenase in Nocardioides sp. strain KP7 to be a new class of aromatic ring-hydroxylating dioxygenases. PMID:10735855

Preferential glutathione conjugation of a reverse diol epoxide compared to a bay region diol epoxide of phenanthrene in human hepatocytes: relevance to molecular epidemiology studies of glutathione-s-transferase polymorphisms and cancer.

PubMed

Hecht, Stephen S; Berg, Jeannette Zinggeler; Hochalter, J Bradley

2009-03-16

Bay region diol epoxides are recognized ultimate carcinogens of polycyclic aromatic hydrocarbons (PAH), and in vitro studies have demonstrated that they can be detoxified by conjugation with glutathione, leading to the widely investigated hypothesis that individuals with low activity forms of glutathione-S-transferases are at higher risk of PAH induced cancer, a hypothesis that has found at most weak support in molecular epidemiology studies. A weakness in this hypothesis was that the mercapturic acids resulting from the conjugation of PAH bay region diol epoxides had never been identified in human urine. We recently analyzed smokers' urine for mercapturic acids derived from phenanthrene, the simplest PAH with a bay region. The only phenanthrene diol epoxide-derived mercapturic acid in smokers' urine was produced from the reverse diol epoxide, anti-phenanthrene-3,4-diol-1,2-epoxide (11), not the bay region diol epoxide, anti-phenanthrene-1,2-diol-3,4-epoxide (10), which does not support the hypothesis noted above. In this study, we extended these results by examining the conjugation of phenanthrene metabolites with glutathione in human hepatocytes. We identified the mercapturic acid N-acetyl-S-(r-4,t-2,3-trihydroxy-1,2,3,4-tetrahydro-c-1-phenanthryl)-L-cysteine (14a), (0.33-35.9 pmol/mL at 10 microM 8, 24 h incubation, N = 10) in all incubations with phenanthrene-3,4-diol (8) and the corresponding diol epoxide 11, but no mercapturic acids were detected in incubations with phenanthrene-1,2-diol (7), and only trace amounts were observed in incubations with the corresponding bay region diol epoxide 10. Taken together with our previous results, these studies clearly demonstrate that glutathione conjugation of a reverse diol epoxide of phenanthrene is favored over conjugation of a bay region diol epoxide. Since reverse diol epoxides of PAH are generally weakly or nonmutagenic/carcinogenic, these results, if generalizable to other PAH, do not support the widely held assumption that glutathione-S-transferases are important in the detoxification of PAH in humans.

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

Analysis of a PAH-degrading bacterial population in subsurface sediments on the Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Shao, Zongze; Cui, Zhisong; Dong, Chunming; Lai, Qiliang; Chen, Liang

2010-05-01

Little is known about the types and concentrations of polycyclic aromatic hydrocarbons (PAHs) existing in the deep-sea subsurface environment, which is believed to be cold, oligothrophic and of high static pressure. PAHs in the upper layers of the water column are unavoidably subjected to degradation while they are deposited to the sea floor and become embedded in the deep-sea sediment. In this report, a high concentration of PAHs was discovered in the sediment 2.7 m beneath the bottom surface at a water depth of 3962 m on the Mid-Atlantic Ridge (MAR). The total concentration of PAHs was 445 ng (g dry wt sediment) -1. Among the seven detected PAHs, the concentrations of phenanthrene (222 ng g -1) and fluorene (79 ng g -1) were relatively high. In addition, PAH-degrading bacteria were found within the sediments. As in a previously detected site on the MAR, in the PAH-enriched region of this site, a bacterium of the genus Cycloclasticus was found to be the predominant isolate detected by PCR-DGGE analysis. In addition, bacteria of the Halomonas, Marinobacter, Alcanivorax, Thalassospira and Maricaulis genera, were also included in the PAH-degrading community. In summary, a high concentration of PAHs was detected in the subsurface of the deep-sea sediment, and once again, the Cycloclasticus bacterium was confirmed to be a ubiquitous marine PAH degrader even in the subsurface marine environment. Considering the abundance of PAHs therein, biodegradation is thus thought to be inactive, probably because of the low temperature, limited oxygen and/or limited nutrients.

Calcium Alginate-Caged Multiwalled Carbon Nanotubes Dispersive Microsolid Phase Extraction Combined With Gas Chromatography-Flame Ionization Detection for the Determination of Polycyclic Aromatic Hydrocarbons in Water Samples.

PubMed

Abboud, Ayad Sami; Sanagi, Mohd Marsin; Ibrahim, Wan Aini Wan; Keyon, Aemi S Abdul; Aboul-Enein, Hassan Y

2018-02-01

In this study, caged calcium alginate-caged multiwalled carbon nanotubes dispersive microsolid phase extraction was described for the first time for the extraction of polycyclic aromatic hydrocarbons (PAHs) from water samples prior to gas chromatographic analysis. Fluorene, phenanthrene and fluoranthene were selected as model compounds. The caged calcium alginate-caged multiwalled carbon nanotubes was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and thermal gravimetry analyses. The effective parameters namely desorption solvent, solvent volume, extraction time, desorption time, the mass of adsorbent and sample volume were optimized. Under the optimum extraction conditions, the developed method showed good linearity in the range of 0.5-50 ng mL-1 (R2 ≥ 0.996), low limits of detection and quantification (0.42-0.22 ng mL-1) (0.73-1.38 ng mL-1) respectively, good relative recoveries (71.2-104.2%) and reproducibility (RSD 1.8-12.4%, n = 3) for the studied PAHs in water sample. With high enrichment factor (1,000), short extraction time (<30 min), low amounts of adsorbent (100 mg) and low amounts of solvent (0.1 mol) have proven that the microsolid phase extraction method based on calcium alginate-caged multiwalled carbon nanotubes are environmentally friendly and convenient extraction method to use as an alternative adsorbent in the simultaneous preconcentration of PAHs from environmental water samples. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Development of a short path thermal desorption-gas chromatography/mass spectrometry method for the determination of polycyclic aromatic hydrocarbons in indoor air.

PubMed

Li, Yingjie; Xian, Qiming; Li, Li

2017-05-12

Polycyclic aromatic hydrocarbons (PAHs) are present in petroleum based products and are combustion by-products of organic matters. Determination of levels of PAHs in the indoor environment is important for assessing human exposure to these chemicals. A new short path thermal desorption (SPTD) gas chromatography/mass spectrometry (GC/MS) method for determining levels of PAHs in indoor air was developed. Thermal desorption (TD) tubes packed with glass beads, Carbopack C, and Carbopack B in sequence, were used for sample collection. Indoor air was sampled using a small portable pump over 7 days at 100ml/min. Target PAHs were thermally released and introduced into the GC/MS for analysis through the SPTD unit. During tube desorption, PAHs were cold trapped (-20°C) at the front end of the GC column. Thermal desorption efficiencies were 100% for PAHs with 2 and 3 rings, and 99-97% for PAHs with 4-6 rings. Relative standard deviation (RSD) values among replicate samples spiked at three different levels were around 10-20%. The detection limit of this method was at or below 0.1μg/m 3 except for naphthalene (0.61μg/m 3 ), fluorene (0.28μg/m 3 ) and phenanthrene (0.35μg/m 3 ). This method was applied to measure PAHs in indoor air in nine residential homes. The levels of PAHs in indoor air found in these nine homes are similar to indoor air values reported by others. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultra-Deep Adsorptive Desulfurization of Light-Irradiated Diesel Fuel over Supported TiO 2-CeO 2 Adsorbents

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

Xiao, Jing; Wang, Xiaoxing; Chen, Yongsheng

2014-02-13

This study investigates ultra-deep adsorptive desulfurization (ADS) from light-irradiated diesel fuel over supported TiO 2–CeO 2 adsorbents. A 30-fold higher desulfurization capacity of 95 mL of fuel per gram of adsorbent (mL-F/g-sorb) or 1.143 mg of sulfur per gram of adsorbent (mg-S/g-sorb) was achieved from light-irradiated fuel over the original low-sulfur fuel containing about 15 ppm by weight (ppmw) of sulfur. The sulfur species on spent TiO 2–CeO 2/MCM-48 adsorbent was identified by sulfur K-edge XANES as sulfones and the adsorption selectivity to different compounds tested in a model fuel decreases in the order of indole > dibenzothiophenesulfone → dibenzothiophenemore » > 4-methyldibenzothiophene > benzothiophene > 4,6-dimethyldibenzothiophene > phenanthrene > 2-methylnaphthalene ~ fluorene > naphthalene. The results suggest that during ADS of light-irradiated fuel, the original sulfur species were chemically transformed to sulfones, resulting in the significant increase in desulfurization capacity. For different supports for TiO2–CeO2 oxides, the ADS capacity increases with a decrease in the point of zero charge (PZC) value; for silica-supported TiO 2–CeO 2 oxides (the lowest PZC value of 2–4) with different surface areas, the ADS capacity increases monotonically with increasing surface area. The supported TiO 2–CeO 2/MCM-48 adsorbent can be regenerated using oxidative air treatment. The present study provides an attractive new path to achieve ultraclean fuel more effectively.« less

Towards field detection of polycyclic aromatic hydrocarbons (PAHs) in environment water using a self-assembled SERS sensor

NASA Astrophysics Data System (ADS)

Yan, Xia; Shi, Xiaofeng; Yang, Jie; Zhang, Xu; Jia, Wenjie; Ma, Jun

2017-10-01

A self-assembled surface enhanced Raman scattering (SERS) sensor is reported in this paper. To achieve high sensitivity, a high sensitive SERS substrate and a high efficient self-constructed light path were made. The SERS substrate was composed by gold nanoparticles (AuNPs, pH=13), glycidyl methacrylate-ethylene dimethacrylate (GMA-EDMA) porous material and syringe filter. The substrate had a good repeatability, and the relative standard deviation (RSD) of the same substrate was less than 5%. The efficiency of the self-constructed light path is about two times better than RPB Y type reflection fiber when the energy density was roughly equal on samples. The size of the SERS sensor is 350×300×180 mm and the weight is 15 kg. Its miniaturization and portable can comply with the requirements of field detection. Besides, it has good sensitivity, stability and selectivity. For lab experiments, strong enhancements of Raman scattering from organic pollutant polycyclic aromatic hydrocarbons (PAHs) molecules were exhibited. The dependences of SERS intensities on concentrations of PAHs were investigated, and the results indicated that they revealed a satisfactory linear relationship in low concentrations. The limits of detection (LODs) of PAHs phenanthrene and fluorene are 8.3×10-10 mol/L and 7.1×10-10 mol/L respectively [signal to noise ratio (S/N) =3]. Based on this SERS sensor, signals of benzo (a) pyrene and pyrene were found in environmental water and the sensor would be an ideal candidate for field detection of PAHs.

Mass transfer of hydrophobic organic chemicals between silicone sheets and through plant leaves and low-density polyethylene.

PubMed

Ahmadi, Hamid; Bolinius, Damien Johann; Jahnke, Annika; MacLeod, Matthew

2016-12-01

Plant leaves play an important role in the fate of hydrophobic organic contaminants (HOCs) in the environment. Yet much remains unknown about the permeability of leaves by HOCs. In this pilot study we measured (i) the kinetics of mass transfer of three polycyclic aromatic hydrocarbons (PAHs) and six polychlorinated biphenyls between a spiked and an unspiked sheet of polydimethylsiloxane (PDMS) in direct contact with each other for 24 h and (ii) kinetics of mass transfer of two PAHs through leaves and low-density polyethylene (LDPE) in a passive dosing experiment by inserting these matrices between the two sheets of PDMS for 48 h. The kinetics of mass transfer of fluoranthene between PDMS sheets in direct contact were a factor of 12 slower than those reported in the literature. The kinetics of mass transfer of fluorene and phenanthrene through leaves were within the range of those previously reported for 2,4-dichlorophenoxyacetic acid through isolated cuticles. Our results provide a proof-of-concept demonstration that the passive dosing method applied in this study can be used to measure the mass transfer coefficients of organic chemicals through leaves. Key recommendations for future experiments are to load the PDMS at the highest feasible concentrations to avoid working at analyte levels close to the limit of detection, to keep the leaves moist and to minimize potential pathways for contamination of the PDMS sheets by exposure to laboratory air. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

Effects of profession on urinary PAH metabolite levels in the US population.

PubMed

Liu, Bian; Jia, Chunrong

2016-01-01

Although exposure to polycyclic aromatic hydrocarbons (PAHs) is common in both environmental and occupational settings, few studies have compared PAH exposure among people with different professions. The purpose of this study was to investigate the variations in recent PAH exposure among different occupational groups over time using national representative samples. The study population consisted of 4162 participants from the 2001 to 2008 National Health and Nutrition Examination Survey, who had both urinary PAH metabolites and occupational information. Four corresponding monohydroxy-PAH urine metabolites: naphthalene (NAP), fluorene (FLUO), phenanthrene (PHEN), and pyrene (PYR) among seven broad occupational groups were analyzed using weighted linear regression models, adjusting for creatinine levels, sociodemographic factors, smoking status, and sampling season. The overall geometric mean concentrations of NAP, FLUO, PHEN, and PYR were 6927, 477, 335, and 87 ng/L, respectively. All four PAH metabolites were elevated in the "extractive, construction, and repair (ECR)" group, with 21-42 % higher concentrations than those in the reference group of "management." Similar trends were seen in the "operators, fabricators, and laborers (OFL)" group for FLUO, PHEN, and PYR. In addition, both "service" and "support" groups had elevated FLUO. Significant (p < 0.001) upward temporal trends were seen in NAP and PYR, with an approximately 6-17 % annual increase, and FLUO and PHEN remained relatively stable. Race and socioeconomic status show independent effects on PAH exposure. Heterogeneous distributions of urinary PAH metabolites among people with different job categories exist at the population level. The upward temporal trends in NAP and PYR warrant reduction in PAH exposure, especially among those with OFL and ECR occupations.

[Feasibility of using laser-induced fluorescence to detect directly polycyclic aromatic hydrocarbons in soil].

PubMed

Yang, Ren-Jie; Shang, Li-Ping; Bao, Zhen-Bo; He, Jun; Deng, Hu; Liu, Yu-Le

2011-08-01

Abstract In the present paper, a technique of laser-induced fluorescence(LIF)for direct assay of polycyclic aromatic hydrocarbons(PAH) in soil was put forward. The research objective of this article is anthracene. The possibility of using LIF spectra to detect directly anthracene in soil was studied. Anthracene was detected in soil by AvaSpec-3648 Fiber Optic Spectrometer of thermoelectric refrigeration. The authors drew a conclusion that in the range of certain anthracene concentration(0.000 005-0.001 g x g(-1)), the intensity of LIF fluorescence is linear with anthracene concentration in soil, with a regression coefficient of 0. 929. This showed that direct assay of anthracene in soil was feasible by laser-induced fluorescence. The study is important to developing a new analytical technique of quantitative fluorescence detector which can be applied to the analysis of PAH in soil without pretreatment, and is significant to realization of real-time, in-line, in-situ measurement of PAH in soil.

Single-layer electroluminescent devices based on fluorene-1H-pyrazolo[3,4-b]quinoxaline co-polymers

NASA Astrophysics Data System (ADS)

Pokladko-Kowar, Monika; Danel, Andrzej; Chacaga, Łukasz

2013-11-01

A fluorene based copolymer was synthesized for electroluminescent application. To the main chain of polymer the nitrogen heterocyclic, 1H-pyrazolo[3,4-b]quinoxaline, unit was introduced. The incorporation of this derivative tuned the emission from the blue to yellow-green one. A simple, single layered device was fabricated with the configuration ITO/PEDOT/co-poly-FLU-PQX/Ca/Mg.

Fluorene- and benzofluorene-cored oligomers as low threshold and high gain amplifying media

NASA Astrophysics Data System (ADS)

Kazlauskas, Karolis; Kreiza, Gediminas; Bobrovas, Olegas; AdomÄ--nienÄ--, Ona; AdomÄ--nas, Povilas; Jankauskas, Vygintas; JuršÄ--nas, Saulius

2015-07-01

Deliberate control of intermolecular interactions in fluorene- and benzofluorene-cored oligomers was attempted via introduction of different-length alkyl moieties to attain high emission amplification and low amplified spontaneous emission (ASE) threshold at high oligomer concentrations. Containing fluorenyl peripheral groups decorated with different-length alkyl moieties, the oligomers were found to express weak concentration quenching of emission, yet excellent carrier drift mobilities (close to 10-2 cm2/V/s) in the amorphous films. Owing to the larger radiative decay rates (>1.0 × 109 s-1) and smaller concentration quenching, fluorene-cored oligomers exhibited down to one order of magnitude lower ASE thresholds at higher concentrations as compared to those of benzofluorene counterparts. The lowest threshold (300 W/cm2) obtained for the fluorene-cored oligomers at the concentration of 50 wt % in polymer matrix is among the lowest reported for solution-processed amorphous films in ambient conditions, what makes the oligomers promising for lasing application. Great potential in emission amplification was confirmed by high maximum net gain (77 cm-1) revealed for these compounds. Although the photostability of the oligomers was affected by photo-oxidation, it was found to be comparable to that of various organic lasing materials including some commercial laser dyes evaluated under similar excitation conditions.

Preparation and characterization of a novel graphene/biochar composite for aqueous phenanthrene and mercury removal.

PubMed

Tang, Jingchun; Lv, Honghong; Gong, Yanyan; Huang, Yao

2015-11-01

A graphene/biochar composite (G/BC) was synthesized via slow pyrolysis of graphene (G) pretreated wheat straw, and tested for the sorption characteristics and mechanisms of representative aqueous contaminants (phenanthrene and mercury). Structure and morphology analysis showed that G was coated on the surface of biochar (BC) mainly through π-π interactions, resulting in a larger surface area, more functional groups, greater thermal stability, and higher removal efficiency of phenanthrene and mercury compared to BC. Pseudo second-order model adequately simulated sorption kinetics, and sorption isotherms of phenanthrene and mercury were simulated well by dual-mode and BET models, respectively. FTIR and SEM analysis suggested that partitioning and surface sorption were dominant mechanisms for phenanthrene sorption, and that surface complexation between mercury and C-O, CC, -OH, and OC-O functional groups was responsible for mercury removal. The results suggested that the G/BC composite is an efficient, economic, and environmentally friendly multifunctional adsorbent for environmental remediation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sorption of phenanthrene and benzene on differently structural kerogen: important role of micropore-filling.

PubMed

Zhang, Yulong; Ma, Xiaoxuan; Ran, Yong

2014-02-01

Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (Vo,d) initially increase and then decrease. The Vo,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The Vo,d of phenanthrene and benzene on the kerogen samples accounts for 23-46% and 36-65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling. Copyright © 2013 Elsevier Ltd. All rights reserved.

Phenanthrene binding by humic acid-protein complexes as studied by passive dosing technique.

PubMed

Zhao, Jian; Wang, Zhenyu; Ghosh, Saikat; Xing, Baoshan

2014-01-01

This work investigated the binding behavior of phenanthrene by humic acids (HA-2 and HA-5), proteins (bovine serum albumin (BSA)), lysozyme and pepsin), and their complexes using a passive dosing technique. All sorption isotherms were fitted well with Freundlich model and the binding capability followed an order of HA-5 > HA-2 > BSA > pepsin > lysozyme. In NaCl solution, phenanthrene binding to HA-BSA complexes was much higher than the sum of binding to individual HA and BSA, while there was no enhancement for HA-pepsin. Positively charged lysozyme slightly lowered phenanthrene binding on both HAs due to strong aggregation of HA-lysozyme complexes, leading to reduction in the number of binding sites. The binding enhancement by HA-BSA was observed under all tested ion species and ionic strengths. This enhancement can be explained by unfolding of protein, reduction of aggregate size and formation of HA-BSA complexes with favorable conformations for binding phenanthrene. Copyright © 2013 Elsevier Ltd. All rights reserved.

Comparative proteomics reveal the mechanism of Tween80 enhanced phenanthrene biodegradation by Sphingomonas sp. GY2B.

PubMed

Liu, Shasha; Guo, Chuling; Dang, Zhi; Liang, Xujun

2017-03-01

Previous study concerning the effects of surfactants on phenanthrene biodegradation focused on observing the changes of cell characteristics of Sphingomonas sp. GY2B. However, the impact of surfactants on the expression of bacterial proteins, controlling phenanthrene transport and catabolism, remains obscure. To overcome the knowledge gap, comparative proteomic approaches were used to investigate protein expressions of Sphingomonas sp. GY2B during phenanthrene biodegradation in the presence and absence of a nonionic surfactant, Tween80. A total of 23 up-regulated and 19 down-regulated proteins were detected upon Tween80 treatment. Tween80 could regulate ion transport (e.g. H + ) in cell membrane to provide driving force (ATP) for the transmembrane transport of phenanthrene thus increasing its uptake and biodegradation by GY2B. Moreover, Tween80 probably increased GY2B vitality and growth by inducing the expression of peptidylprolyl isomerase to stabilize cell membrane, increasing the abundances of proteins involved in intracellular metabolic pathways (e.g. TCA cycle), as well as decreasing the abundances of translation/transcription-related proteins and cysteine desulfurase, thereby facilitating phenanthrene biodegradation. This study may facilitate a better understanding of the mechanisms that regulate surfactants-enhanced biodegradation of PAHs at the proteomic level. Copyright © 2016 Elsevier Inc. All rights reserved.

Theoretical investigation on the mechanism of NO3 radical-initiated atmospheric reactions of phenanthrene

NASA Astrophysics Data System (ADS)

Zhao, Nan; Shi, Xiangli; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing

2017-07-01

Phenanthrene is a polycyclic aromatic hydrocarbon from fossil fuel combustion with toxic properties. The products arising from atmospheric reaction can be more mutagenic and carcinogenic compared to unmodified phenanthrene, and are therefore important to be studied. The products of the specific NO3-radical reactions with phenanthrene where therefore investigated in this study by means of Density Functional Theory (DFT). The results show that the main products are proposed to be 10-(nitrooxy)-10-hydro-phenanthrene-9-one, 2,2‧-diformylbiphenyl, 9,10-phenanthrenequinone, 9-fluorenone and dibenzopyranone. 10-(nitrooxy)-10-hydro-phenanthrene-9-one and 2,2‧-diformylbiphenyl are classified as first-generation products which are subject to secondary reactions to produce 9,10-phenanthrenequinone, 9-fluorenone and dibenzopyranone. The rate constants of elementary reactions were assessed by Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The atmospheric lifetime of Phe determined by the gas-phase reaction with NO3 is estimated to be 1.8 h, based on the calculated overall rate constant of 3.04 × 10-13 cm3 molecule-1 s-1 at 298 K and 1 atm. Combined with available experimental observation, this work should help to clarify the transformation and potential health risk of Phe in the atmosphere.

Bioventing remediation and ecotoxicity evaluation of phenanthrene-contaminated soil.

PubMed

García Frutos, F Javier; Escolano, Olga; García, Susana; Babín, Mar; Fernández, M Dolores

2010-11-15

The objectives of soil remediation processes are usually based on threshold levels of soil contaminants. However, during remediation processes, changes in bioavailability and metabolite production can occur, making it necessary to incorporate an ecotoxicity assessment to estimate the risk to ecological receptors. The evolution of contaminants and soil ecotoxicity of artificially phenanthrene-contaminated soil (1000 mg/kg soil) during soil treatment through bioventing was studied in this work. Bioventing was performed in glass columns containing 5.5 kg of phenanthrene-contaminated soil and uncontaminated natural soil over a period of 7 months. Optimum conditions of mineralisation (humidity=60% WHC; C/N/P=100:20:1) were determined in a previous work. The evolution of oxygen consumption, carbon dioxide production, phenanthrene concentration and soil toxicity were studied on sacrificed columns at periods of 0, 3 and 7 months. Toxicity to soil and aquatic organisms was determined using a multispecies system in the soil columns (MS-3). In the optimal bioventing treatability test, we obtained a reduction rate in phenanthrene concentration higher that 93% after 7 months of treatment. The residual toxicity obtained at the end of the treatment was not attributed to the low phenanthrene concentration, but to the ammonia used to restore the optimal C/N ratio. Copyright © 2010 Elsevier B.V. All rights reserved.

Isolation and Characterization of Phenanthrene Degrading Bacteria from Diesel Fuel-Contaminated Antarctic Soils

PubMed Central

Gran-Scheuch, Alejandro; Fuentes, Edwar; Bravo, Denisse M.; Jiménez, Juan Cristobal; Pérez-Donoso, José M.

2017-01-01

Antarctica is an attractive target for human exploration and scientific investigation, however the negative effects of human activity on this continent are long lasting and can have serious consequences on the native ecosystem. Various areas of Antarctica have been contaminated with diesel fuel, which contains harmful compounds such as heavy metals and polycyclic aromatic hydrocarbons (PAH). Bioremediation of PAHs by the activity of microorganisms is an ecological, economical, and safe decontamination approach. Since the introduction of foreign organisms into the Antarctica is prohibited, it is key to discover native bacteria that can be used for diesel bioremediation. By following the degradation of the PAH phenanthrene, we isolated 53 PAH metabolizing bacteria from diesel contaminated Antarctic soil samples, with three of these isolates exhibiting a high phenanthrene degrading capacity. In particular, the Sphingobium xenophagum D43FB isolate showed the highest phenanthrene degradation ability, generating up to 95% degradation of initial phenanthrene. D43FB can also degrade phenanthrene in the presence of its usual co-pollutant, the heavy metal cadmium, and showed the ability to grow using diesel-fuel as a sole carbon source. Microtiter plate assays and SEM analysis revealed that S. xenophagum D43FB exhibits the ability to form biofilms and can directly adhere to phenanthrene crystals. Genome sequencing analysis also revealed the presence of several genes involved in PAH degradation and heavy metal resistance in the D43FB genome. Altogether, these results demonstrate that S. xenophagum D43FB shows promising potential for its application in the bioremediation of diesel fuel contaminated-Antarctic ecosystems. PMID:28894442

Fungal biodegradation of anthracene-polluted cork: A comparative study.

PubMed

Jové, Patrícia; Olivella, Maria À; Camarero, Susana; Caixach, Josep; Planas, Carles; Cano, Laura; De Las Heras, Francesc X

2016-01-01

The efficiency of cork waste in adsorbing aqueous polycyclic aromatic hydrocarbons (PAHs) has been previously reported. Biodegradation of contaminated cork using filamentous fungi could be a good alternative for detoxifying cork to facilitate its final processing. For this purpose, the degradation efficiency of anthracene by three ligninolytic white-rot fungi (Phanerochaete chrysosporium, Irpex lacteus and Pleurotus ostreatus) and three non-ligninolytic fungi which are found in the cork itself (Aspergillus niger, Penicillium simplicissimum and Mucor racemosus) are compared. Anthracene degradation by all fungi was examined in solid-phase cultures after 0, 16, 30 and 61 days. The degradation products of anthracene by P. simplicissimum and I. lacteus were also identified by GC-MS and a metabolic pathway was proposed for P. simplicissimum. Results show that all the fungi tested degraded anthracene. After 61 days of incubation, approximately 86%, 40%, and 38% of the initial concentration of anthracene (i.e., 100 µM) was degraded by P. simplicissimum, P. chrysosporium and I. lacteus, respectively. The rest of the fungi degraded anthracene to a lesser extent (<30%). As a final remark, the results obtained in this study indicate that P. simplicissimum, a non-ligninolytic fungi characteristic of cork itself, could be used as an efficient degrader of PAH-contaminated cork.

Soil mineral composition matters: response of microbial communities to phenanthrene and plant litter addition in long-term matured artificial soils.

PubMed

Babin, Doreen; Vogel, Cordula; Zühlke, Sebastian; Schloter, Michael; Pronk, Geertje Johanna; Heister, Katja; Spiteller, Michael; Kögel-Knabner, Ingrid; Smalla, Kornelia

2014-01-01

The fate of polycyclic aromatic hydrocarbons (PAHs) in soil is determined by a suite of biotic and abiotic factors, and disentangling their role in the complex soil interaction network remains challenging. Here, we investigate the influence of soil composition on the microbial community structure and its response to the spiked model PAH compound phenanthrene and plant litter. We used long-term matured artificial soils differing in type of clay mineral (illite, montmorillonite) and presence of charcoal or ferrihydrite. The soils received an identical soil microbial fraction and were incubated for more than two years with two sterile manure additions. The matured artificial soils and a natural soil were subjected to the following spiking treatments: (I) phenanthrene, (II) litter, (III) litter + phenanthrene, (IV) unspiked control. Total community DNA was extracted from soil sampled on the day of spiking, 7, 21, and 63 days after spiking. Bacterial 16S rRNA gene and fungal internal transcribed spacer amplicons were quantified by qPCR and subjected to denaturing gradient gel electrophoresis (DGGE). DGGE analysis revealed that the bacterial community composition, which was strongly shaped by clay minerals after more than two years of incubation, changed in response to spiked phenanthrene and added litter. DGGE and qPCR showed that soil composition significantly influenced the microbial response to spiking. While fungal communities responded only in presence of litter to phenanthrene spiking, the response of the bacterial communities to phenanthrene was less pronounced when litter was present. Interestingly, microbial communities in all artificial soils were more strongly affected by spiking than in the natural soil, which might indicate the importance of higher microbial diversity to compensate perturbations. This study showed the influence of soil composition on the microbiota and their response to phenanthrene and litter, which may increase our understanding of complex interactions in soils for bioremediation applications.

Soil Mineral Composition Matters: Response of Microbial Communities to Phenanthrene and Plant Litter Addition in Long-Term Matured Artificial Soils

PubMed Central

Babin, Doreen; Vogel, Cordula; Zühlke, Sebastian; Schloter, Michael; Pronk, Geertje Johanna; Heister, Katja; Spiteller, Michael; Kögel-Knabner, Ingrid; Smalla, Kornelia

2014-01-01

The fate of polycyclic aromatic hydrocarbons (PAHs) in soil is determined by a suite of biotic and abiotic factors, and disentangling their role in the complex soil interaction network remains challenging. Here, we investigate the influence of soil composition on the microbial community structure and its response to the spiked model PAH compound phenanthrene and plant litter. We used long-term matured artificial soils differing in type of clay mineral (illite, montmorillonite) and presence of charcoal or ferrihydrite. The soils received an identical soil microbial fraction and were incubated for more than two years with two sterile manure additions. The matured artificial soils and a natural soil were subjected to the following spiking treatments: (I) phenanthrene, (II) litter, (III) litter + phenanthrene, (IV) unspiked control. Total community DNA was extracted from soil sampled on the day of spiking, 7, 21, and 63 days after spiking. Bacterial 16S rRNA gene and fungal internal transcribed spacer amplicons were quantified by qPCR and subjected to denaturing gradient gel electrophoresis (DGGE). DGGE analysis revealed that the bacterial community composition, which was strongly shaped by clay minerals after more than two years of incubation, changed in response to spiked phenanthrene and added litter. DGGE and qPCR showed that soil composition significantly influenced the microbial response to spiking. While fungal communities responded only in presence of litter to phenanthrene spiking, the response of the bacterial communities to phenanthrene was less pronounced when litter was present. Interestingly, microbial communities in all artificial soils were more strongly affected by spiking than in the natural soil, which might indicate the importance of higher microbial diversity to compensate perturbations. This study showed the influence of soil composition on the microbiota and their response to phenanthrene and litter, which may increase our understanding of complex interactions in soils for bioremediation applications. PMID:25222697

Unexpected DNA affinity and sequence selectivity through core rigidity in guanidinium-based minor groove binders.

PubMed

Nagle, Padraic S; McKeever, Caitriona; Rodriguez, Fernando; Nguyen, Binh; Wilson, W David; Rozas, Isabel

2014-09-25

In this paper we report the design and biophysical evaluation of novel rigid-core symmetric and asymmetric dicationic DNA binders containing 9H-fluorene and 9,10-dihydroanthracene cores as well as the synthesis of one of these fluorene derivatives. First, the affinity toward particular DNA sequences of these compounds and flexible core derivatives was evaluated by means of surface plasmon resonance and thermal denaturation experiments finding that the position of the cations significantly influence the binding strength. Then their affinity and mode of binding were further studied by performing circular dichroism and UV studies and the results obtained were rationalized by means of DFT calculations. We found that the fluorene derivatives prepared have the ability to bind to the minor groove of certain DNA sequences and intercalate to others, whereas the dihydroanthracene compounds bind via intercalation to all the DNA sequences studied here.

Self-assembly behavior of poly(fluorenyl styrene)-block-poly(2-vinyl pyridine) and their blends with single wall carbon nanotubes (SWCNT)

NASA Astrophysics Data System (ADS)

Mezzenga, Raffaele; Li, Chaoxu; Hsu, Jung-Ching; Chen, Wen-Chang; Sugiyama, Kenji; Hirao, Akira

2010-03-01

We describe a supramolecular strategy to disperse carbon nanotubes in block copolymer matrices. To achieve the desired functions and morphologies, comb-type architectures in which one and two fluorene units attached on the styrene ring of polystyrene-block-poly(2-vinyl pyridine) were studied. Depending on the pendant fluorene units, the block ratio, the casting solvent and thermal annealing history, multiple morphologies were found. The phase diagram, compared to PS-b-P2VP, was interpreted in terms of the conformational asymmetry arising from grafting of fluorene units of variable lengths. Hydrogen bonds between COOH-SWCNT and P2VP favor miscibility of SWCNT within P2VP domains and the blending of these two components is reflected both on the final morphologies and on the electron conductivity of the blends.

Single-photon and two-photon excited fluorescence behavior of a novel fluorene-based compound

NASA Astrophysics Data System (ADS)

Ma, Wenbo; Wu, Yiquan; Gu, Donghong; Gan, Fuxi

2005-09-01

A D-π-D type compound, 2,7-bis(4-methoxystyryl)-9,9-bis(2-ethylhexyl)-9H-fluorene (abbreviated as MO-Flu-MO), where electron-donor D is methoxy group andπis fluorene unit, has been synthesized. The molecular structures of the compound were characterized by elemental analyses, EI-MS and FT-IR spectra. UV-Vis spectra in the region 230--1000 nm and single-photon excited fluorescence in tetrahydrofuran (THF) of the compound were measured. It is found that the new compound exhibits strong two-photon excited fluorescence in the region 380--500 nm and moderate two-photon absorption (TPA) value in the femtoseconds regime (TPA cross-section as high as 55×10-50 cm4 s photon-1 with 13fs laser pulses). The results demonstrate that the compound is a promising candidate for two-photon three-dimensional (3D) optical data storage.

A new boronic acid fluorescent sensor based on fluorene for monosaccharides at physiological pH

NASA Astrophysics Data System (ADS)

Hosseinzadeh, Rahman; Mohadjerani, Maryam; Pooryousef, Mona; Eslami, Abbas; Emami, Saeed

2015-06-01

Fluorescent boronic acids are very useful fluorescent sensor for detection of biologically important saccharides. Herein we synthesized a new fluorene-based fluorescent boronic acid that shows significant fluorescence changes upon addition of saccharides at physiological pH. Upon addition of fructose, sorbitol, glucose, galactose, ribose, and maltose at different concentration to the solution of 7-(dimethylamino)-9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (7-DMAFBA, 1), significant decreases in fluorescent intensity were observed. It was found that this boronic acid has high affinity (Ka = 3582.88 M-1) and selectivity for fructose over glucose at pH = 7.4. The sensor 1 showed a linear response toward D-fructose in the concentrations ranging from 2.5 × 10-5 to 4 × 10-4 mol L-1 with the detection limit of 1.3 × 10-5 mol L-1.

The influence of mechanochemical modification on prevention of toxic ability of humic acids towards phenanthrene in aquatic environment

NASA Astrophysics Data System (ADS)

Shekhovtsova, N. S.; Maltseva, E. V.; Glyzina, T. S.; Ovchinnikova, I. S.

2015-11-01

The aim of the research work is to quantify interaction between phenanthrene with modified humic acids in aquatic environment. The changes in the structure and properties of humic acids after modifications were studied with 1H NMR spectroscopy and potentiometric titration methods. Our research demonstrates that the application of thiourea as a modified agent increases the binding capacity of humic acids towards phenanthrene.

Constraint on the potassium content for the superconductivity of potassium-intercalated phenanthrene.

PubMed

Huang, Qiao-Wei; Zhong, Guo-Hua; Zhang, Jiang; Zhao, Xiao-Miao; Zhang, Chao; Lin, Hai-Qing; Chen, Xiao-Jia

2014-03-21

Raman-scattering measurements were performed on K(x)phenanthrene (0 ⩽ x ⩽ 6.0) at room temperature. Three phases (x = 3.0, 3.5, and 4.0) are identified based on the obtained Raman spectra. Only the K3phenanthrene phase is found to exhibit the superconducting transition at 5 K. The C-C stretching modes are observed to broaden and become disordered in K(x)phenanthrene with x = 2.0, 2.5, 6.0, indicating some molecular disorder in the metal intercalation process. This disorder is expected to influence the nonmetallic nature of these materials. The absence of metallic character in these nonsuperconducting phases is found from the calculated electronic structures based on the local density approximation.

Raman and surface enhanced Raman scattering study of the orientation of cruciform 9,10-anthracene thiophene and furan derivatives deposited on a gold colloidal surface

NASA Astrophysics Data System (ADS)

Muñoz-Pérez, J.; Leyton, P.; Paipa, C.; Soto, J. P.; Brunet, J.; Gómez-Jeria, J. S.; Campos-Vallette, M. M.

2016-10-01

The 9,10-di(thiophen-2-yl)anthracene (TAT), 9,10-di(furan-2-yl)anthracene (FAF) and 2-[(10-(thiophen-2-yl)anthracen-9-yl)]furan (TAF) cruciform molecular systems were synthesized using one-step coupling reactions and structurally characterized via Raman, infrared, 1H NMR, 13C NMR and mass spectroscopies. The orientation of the analytes on a gold colloidal surface was inferred from a surface-enhanced Raman scattering (SERS) study. The metal surface interaction was driven by the S and O atoms of the thiophene and furan α-substituents, and the plane of the anthracene fragment remained parallel to the surface. Theoretical calculations based on a simplified molecular model for the analyte-surface interaction provide a good representation of the experimental data.

Presence of PAHs in water and sediments of the Colombian Cauca River during heavy rain episodes, and implications for risk assessment.

PubMed

Sarria-Villa, Rodrigo; Ocampo-Duque, William; Páez, Martha; Schuhmacher, Marta

2016-01-01

In Colombia little attention has been paid to river pollution with Polycyclic Aromatic Hydrocarbons (PAHs). Low environmental control and legislation in such emerging region could significantly contribute to high PAHs releases. In this study, we report the presence of PAHs in water and sediments of the Cauca River (Colombia). Three sampling campaigns were carried out between May 2010 and June 2011, and the samples were collected at eight relevant sites. The sampling time included measuring before, during, and after a season of heavy rains, which were influenced by the global coupled ocean-atmospheric phenomenon, which affected tropical countries with huge flooding, commonly called "La Niña", and/or "El Niño" Southern Oscillation (ENSO). The highest mean ∑PAH concentrations were 4476.5 ng/l and 1582.7 ng/g in water and sediments, respectively. The PAHs most detected were Benzo[b]fluoranthene, Benzo[k]fluoranthene, and Pyrene in sediments; and Fluorene, Acenaphtylene, and Anthracene in water. After the season of rains statistically significant higher PAH concentrations were detected. The results of the study were compared to other rivers worldwide at both environmental compartments, and did not show concentrations of special concern. In some sites, concentrations detected of PAHs were higher than screening benchmarks for ecological protection. Estimation of human health risks was carried out, and the results suggested some likely carcinogenic effects due to PAHs especially in children exposed during current recreational swimming and adults working in low technology sand extraction. Copyright © 2015 Elsevier B.V. All rights reserved.

Biodegradability of nonaqueous-phase liquids affects the mineralization of phenanthrene in soil because of microbial competition

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

Morrison, D.E.; Alexander, M.

1997-08-01

A study was conducted to determine the effects of biodegradability of nonaqueous-phase liquids (NAPLs) and microbial competition on the biodegradation in soil of a constituent of the NAPLs. The rates of mineralization of phenanthrene dissolved in 8 mg of 2,2,4,4,6,8,8-heptamethylnonane (HMN), di(2-ethylhexyl) phthalate (DEHP), or pristane per g of soil were faster than the rates when the compound was dissolved in hexadecane or dodecane. Addition of inorganic N and P to the soil increased the mineralization rate in the first two but not the last two NAPLs. N and P addition did not enhance mineralization of phenanthrene when added inmore » 500 {micro}g of hexadecane, pristane, or HMN per g of soil. Hexadecane was rapidly degraded, pristane was slowly metabolized, DEHP was still slower, and HMN was not mineralized in the test period. Mixing the soil stimulated mineralization of phenanthrene dissolved in HMN but not in hexadecane. Mineralization of phenanthrene dissolved in HMN was the same if the gas phase contained 21%, 2.1%, or traces of O{sub 2}. In contrast, the biodegradation of phenanthrene dissolved in hexadecane, although the same at 21 and 2.1% O{sub 2}, was not observed if traces of O{sub 2} were present. The mineralization was slower in unshaken soil-water mixtures if phenanthrene was added in hexadecane than in HMN or pristane, but the rates with the 3 NAPLs were increased by shaking the suspensions. The authors suggest that the biodegradability of major components of NAPLs and microbial competition for N, P, or O{sub 2} will have a major impact on the rate of transformation of minor constituents of NAPLs.« less

Molecular modelling investigations on the possibility of phenanthrene dimers to be the primary nuclei of soot

NASA Astrophysics Data System (ADS)

Wei, Mingrui; Wu, Sheng; Li, Fan; Zhang, Dongju; Zhang, Tingting; Guo, Guanlun

2017-11-01

Pyrene dimerisation was successfully used to model the beginning of soot nucleation in some simulation models. However, the quantum mechanics (QM) calculations proved that the binding energy of a PAH dimer with three six-member rings was similar to that of a pyrene dimer. Meanwhile, the high concentration of phenanthrene at flame conditions indicated high probability of collisions among them. The small difference of the binding energy and high concentration indicated that PAHs structurally smaller than pyrene also could be involved in soot inception. Hence, binary collisions of phenanthrene were simulated to find out whether phenanthrene dimers can serve as soot primary nuclei or not by using non-equilibrium molecular dynamics (MD). Three temperatures, six collision orientations and 155 initial translational velocities (ITVs) were considered. The results indicated that the number of dimers with lifetime over 10 ps which can serve as soot nuclei decreased from 52 at 1000 K to 17 at 1600 K, and further to 6 at 2400 K, which means that low temperature was more favourable for phenanthrene to form soot nuclei. Meanwhile, no soot nuclei were formed at the high velocity region (HVR), compared to 43 and 9 at low and middle velocity regions (LVR and MVR), respectively, when temperature was 1000 K. Also, no soot nuclei were formed at HVR when the temperature was raised to 1600 K and 2400 K. This indicated that HVR was unfavourable for phenanthrene to form soot nuclei. The results computationally further illustrated that small PAHs such as phenanthrene could serve as soot primary nuclei, since they have similar mole fractions in some flames. This may be useful for future soot simulation models.

Metal oxides, clay minerals and charcoal determine the composition of microbial communities in matured artificial soils and their response to phenanthrene.

PubMed

Babin, Doreen; Ding, Guo-Chun; Pronk, Geertje Johanna; Heister, Katja; Kögel-Knabner, Ingrid; Smalla, Kornelia

2013-10-01

Microbial communities in soil reside in a highly heterogeneous habitat where diverse mineral surfaces, complex organic matter and microorganisms interact with each other. This study aimed to elucidate the long-term effect of the soil mineral composition and charcoal on the microbial community composition established in matured artificial soils and their response to phenanthrene. One year after adding sterile manure to different artificial soils and inoculating microorganisms from a Cambisol, the matured soils were spiked with phenanthrene or not and incubated for another 70 days. 16S rRNA gene and internal transcribed spacer fragments amplified from total community DNA were analyzed by denaturing gradient gel electrophoresis. Metal oxides and clay minerals and to a lesser extent charcoal influenced the microbial community composition. Changes in the bacterial community composition in response to phenanthrene differed depending on the mineral composition and presence of charcoal, while no shifts in the fungal community composition were observed. The abundance of ring-hydroxylating dioxygenase genes was increased in phenanthrene-spiked soils except for charcoal-containing soils. Here we show that the formation of biogeochemical interfaces in soil is an ongoing process and that different properties present in artificial soils influenced the bacterial response to the phenanthrene spike. © 2012 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Effect of low-molecular-weight organic acids on photo-degradation of phenanthrene catalyzed by Fe(III)-smectite under visible light.

PubMed

Jia, Hanzhong; Chen, Hongxia; Nulaji, Gulimire; Li, Xiyou; Wang, Chuanyi

2015-11-01

The photolysis of polycyclic aromatic hydrocarbons (PAHs) is potentially an important process for its transformation and fate on contaminated soil surfaces. In this study, phenanthrene is employed as a model to explore PAH photodegradation with the assistance of Fe(III)-smectite under visible-light while focusing on roles played by five low-molecular-weight organic acids (LMWOAs), i.e., malic acid, oxalic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), and nitrilotriacetic acid. Our results show that oxalic acid is most effective in promoting the photodegradation of phenanthrene, while only a slight increase in the rate of phenanthrene photodegradation is observed in the presence of malic acid. Electron paramagnetic resonance experiments confirm the formation of CO2(-) radicals in the presence of malic and oxalic acid, which provides strong evidence for generating OH and subsequent photoreaction pathways. The presence of EDTA or nitrilotriacetic acid significantly inhibits both Fe(II) formation and phenanthrene photodegradation because these organic anions tend to chelate with Fe(III), leading to decreases in the electron-accepting potential of Fe(III)-smectite and a weakened interaction between phenanthrene and Fe(III)-smectite. These observations provide valuable insights into the transformation and fate of PAHs in the natural soil environment and demonstrate the potential for using some LMWOAs as additives for the remediation of contaminated soil. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electronic absorption spectroscopy of matrix-isolated polycyclic aromatic hydrocarbon cations. II. The phenanthrene cation (C14H10+) and its 1-methyl derivative

NASA Technical Reports Server (NTRS)

Salama, F.; Joblin, C.; Allamandola, L. J.

1994-01-01

The ultraviolet, visible, and near infrared absorption spectra of phenanthrene (C14H10), 1-methylphenanthrene [(CH3)C14H9], and their radical ions [C14H10+; (CH3)C14H9+], formed by vacuum-ultraviolet irradiation, were measured in neon matrices at 4.2 K. The associated vibronic band systems and their spectroscopic assignments are discussed. The oscillator strengths were calculated for the phenanthrene ion and found lower than the theoretical predictions. This study presents the first spectroscopic data for phenanthrene and its methyl derivative trapped in a neon matrix where the perturbation of the isolated species by its environment is minimum; a condition crucial to astrophysical applications.

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.

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

High levels of PAH-metabolites in urine of e-waste recycling workers from Agbogbloshie, Ghana.

PubMed

Feldt, Torsten; Fobil, Julius N; Wittsiepe, Jürgen; Wilhelm, Michael; Till, Holger; Zoufaly, Alexander; Burchard, Gerd; Göen, Thomas

2014-01-01

The informal recycling of electronic waste (e-waste) is an emerging source of environmental pollution in Africa. Among other toxins, polycyclic aromatic hydrocarbons (PAHs) are a major health concern for exposed individuals. In a cross-sectional study, the levels of PAH metabolites in the urine of individuals working on one of the largest e-waste recycling sites of Africa, and in controls from a suburb of Accra without direct exposure to e-waste recycling activities, were investigated. Socioeconomic data, basic health data and urine samples were collected from 72 exposed individuals and 40 controls. In the urine samples, concentrations of the hydroxylate PAH metabolites (OH-PAH) 1-hydroxyphenanthrene (1-OH-phenanthrene), the sum of 2- and 9-hydroxyphenanthrene (2-/9-OH-phenanthrene), 3-hydroxyphenanthrene (3-OH-phenanthrene), 4-hydroxyphenanthrene (4-OH-phenanthrene) and 1-hydroxypyrene (1-OH-pyrene), as well as cotinine and creatinine, were determined. In the exposed group, median urinary concentrations were 0.85 μg/g creatinine for 1-OH-phenanthrene, 0.54 μg/g creatinine for 2-/9-OH-phenanthrene, 0.99 μg/g creatinine for 3-OH-phenanthrene, 0.22 μg/g creatinine for 4-OH-phenanthrene, and 1.33 μg/g creatinine for 1-OH-pyrene, all being significantly higher compared to the control group (0.55, 0.37, 0.63, 0.11 and 0.54 μg/g creatinine, respectively). Using a multivariate linear regression analysis including sex, cotinine and tobacco smoking as covariates, exposure to e-waste recycling activities was the most important determinant for PAH exposure. On physical examination, pathological findings were rare, but about two thirds of exposed individuals complained about cough, and one quarter about chest pain. In conclusion, we observed significantly higher urinary PAH metabolite concentrations in individuals who were exposed to e-waste recycling compared to controls who were not exposed to e-waste recycling activities. The impact of e-waste recycling on exposure to environmental toxins and health of individuals living in the surroundings of e-waste recycling sites warrant further investigation. © 2013 Elsevier B.V. All rights reserved.

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

Schachtl, Eva; Yoo, Jong Suk; Gutiérrez, Oliver Y.

The reaction network and elementary steps of the hydrogenation of phenanthrene are explored on parent and Ni-promoted MoS2/c-Al2O3. Two pathways were identified, i.e., Path 1: Phenanthrene _ 9,10-dihydrophenanthrene (DiHPhe)?1,2,3,4,4a,9,10,10a-octahydro-phenanthrene (asymOHPhe), and Path 2: Phenanthrene ?1,2,3,4-tetrahydrophenanthrene (TetHPhe)?1,2,3,4,5,6,7,8-octahydrophenan threne. The steps TetHPhe?asymOHPhe (hydrogenation), and DiHPhe?TetHPhe (hydrogenationisomerization) become notable at phenanthrene conversions above 20%. The reaction preferentially proceeds via Path 1 (90% selectivity) on MoS2/Al2O3. Ni promotion (Ni/(Ni + Mo) molar ratio of 0.3 at the edges on MoS2) increases the hydrogenation activity per active edge twofold and leads to 50% selectivity to both pathways. The reaction orders in H2 vary from _0.8more » on MoS2/Al2O3 to _1.2 on Ni-MoS2/Al2O3, whereas the reaction orders in phenanthrene (_0.6) hardly depend on Ni promotion. The reaction orders in H2S are zero on MoS2/Al2O3 and slightly negative on Ni-MoS2/Al2O3. DFT calculations indicate that phenanthrene is preferentially adsorbed parallel to the basal planes, while H is located at the edges perpendicular to the basal planes. Theory also suggests that Ni atoms, incorporated preferentially on the S-edges, increase the stability of hydrogenated intermediates. Hydrogenation of phenanthrene proceeds through quasi-equilibrated adsorption of the reactants followed by consecutive addition of hydrogen pairs to the adsorbed hydrocarbon. The rate determining steps for the formation of DiHPhe and TetHPhe are the addition of the first and second hydrogen pair, respectively. The concentration of SH groups (activated H at the edges) increases with Ni promotion linearly correlating the rates of Path 1 and Path 2, albeit with different functions. The enhancing effect of Ni on Path 2 is attributed to accelerated hydrogen addition to adsorbed hydrocarbons without important changes in their coverages.« less

Modeling the preferred shapes of polyamine transporter ligands and dihydromotuporamine-C mimics: shovel versus hoe.

PubMed

Breitbeil, Fred; Kaur, Navneet; Delcros, Jean-Guy; Martin, Bénédicte; Abboud, Khalil A; Phanstiel, Otto

2006-04-20

Preferred conformers generated from motuporamine and anthracene-polyamine derivatives provided insight into the shapes associated with polyamine transporter (PAT) recognition and potentially dihydromotuporamine C (4a) bioactivity. Molecular modeling revealed that N(1)-(anthracen-9-ylmethyl)-3,3-triamine (6a), N(1)-(anthracen-9-ylmethyl)-4,4-triamine (6b), N(1)-(anthracen-9-ylmethyl)-N(1)-ethyl-3,3-triamine (7a), N(1)-(anthracen-9-ylmethyl)-N(1)-ethyl-4,4-triamine (7b), and 4a all preferred a hoe motif. This hoe shape was defined by the all-anti polyamine shaft extending above the relatively flat, appended ring system. The hoe geometry was also inferred by the (1)H NMR spectrum of the free amine of 7a (CDCl(3)), which showed a strong shielding effect of the anthracene ring on the chemical shifts associated with the appended polyamine chain. This shielding effect was found to be independent over a broad concentration range of 7a, which also supported an intramolecular phenomenon. The degree of substitution at the N(1)-position seems to be an important determinant of both the molecular shape preferences and biological activity of anthracenylmethyl-polyamine conjugates.

Fabrication and characterization of anthracene thin films for wide-scale organic optoelectronic applications based on linear/nonlinear analyzed optical dispersion parameters

NASA Astrophysics Data System (ADS)

Nawar, Ahmed M.; Yahia, I. S.

2017-08-01

This research work is devoted to studying the linear and nonlinear optical properties of anthracene thin films. For the first time, the fabrication of nanocrystalline anthracene films is presented by using the thermal evaporation conventional technique. All the studied anthracene films exhibit monoclinic crystal structure with dominant preferred orientation along the (001) plane in accordance with X-ray diffraction analysis. The average crystalline size and the strain parameter were calculated and found to be ≈ 14 nm and 42 lines2. nm, respectively. The transparency of the fabricated anthracene films is high (>80%) from the end of the visible to the near-infrared region at 1500 nm, after that; it reaches to 87%. The characteristic behavior, analysis of refractive index and absorption coefficient based on the measured spectrophotometric data of the transmittance and reflectance spectra. The transition is allowed one and the evaluated optical band gap ∼3.1 eV with energy tail ∼105 meV. The dispersion curves of the refractive index were found to follow the Wemple-DiDomenico model. The static optical dielectric constant was found to be 2.592. The molecular polarizability of anthracene thin films presented and its value ∼56.58 (Å)3. A simple spectroscopic method is used to characterize and estimate the nonlinear optical susceptibilities. Thermal evaporation technology could be useful to fabricate blue OLED and window film in photodetector devices based-anthracene films.

Construction of energy transfer pathways self-assembled from DNA-templated stacks of anthracene.

PubMed

Iwaura, Rika; Yui, Hiroharu; Someya, Yuu; Ohnishi-Kameyama, Mayumi

2014-01-05

We describe optical properties of anthracene stacks formed from single-component self-assembly of thymidylic acid-appended anthracene 2,6-bis[5-(3'-thymidylic acid)pentyloxy] anthracene (TACT) and the binary self-assembly of TACT and complementary 20-meric oligoadenylic acid (TACT/dA20) in an aqueous buffer. UV-Vis and emission spectra for the single-component self-assembly of TACT and the binary self-assembly of TACT/dA20 were very consistent with stacked acene moieties in both self-assemblies. Interestingly, time-resolved fluorescence spectra from anthracene stacks exhibited very different features of the single-component and binary self-assemblies. In the single-component self-assembly of TACT, a dynamic Stokes shift (DSS) and relatively short fluorescence lifetime (τ=0.35ns) observed at around 450nm suggested that the anthracene moieties were flexible. Moreover, a broad emission at 530nm suggested the formation of an excited dimer (excimer). In the binary self-assembly of TACT/dA20, we detected a broad, red-shifted emission component at 534nm with a lifetime (τ=0.4ns) shorter than that observed in the TACT single-component self-assembly. Combining these results with the emission spectrum of the binary self-assembly of TACT/5'-HEX dA20, we concluded that the energy transfer pathway was constructed by columnar anthracene stacks formed from the DNA-templated self-assembly of TACT. Copyright © 2013 Elsevier B.V. All rights reserved.

Biochemical response of anthracene and benzo [a] pyrene in milkfish Chanos chanos.

PubMed

Palanikumar, L; Kumaraguru, A K; Ramakritinan, C M; Anand, M

2012-01-01

Polycyclic aromatic hydrocarbons (PAHs) are common toxic pollutants found in the aquatic environment, and the assessment of their impact on biota is of considerable concern. The aim of the present research was to study the acute toxicity, bioaccumulation and biochemical response of milkfish Chanos chanos (Forsskal) to two selected PAHs: anthracene and benzo [a] pyrene. Acute toxicity test results were evaluated by the Probit analysis method and 96h LC(50) values for C. chanos exposed to anthracene was 0.030mgl(-1) and 0.014mgl(-1) for benzo [a] pyrene. Bioaccumulation concentration of anthracene was high when compared to benzo [a] pyrene. Biomarkers indicative of neurotoxicity (acetylcholinesterase, AchE), oxidative stress (lipid peroxidation, LPO and catalase, CAT) and phase II biotransformation of xenobiotics (glutathione S transferase, GST and reduced glutathione, GSH) were measured to assess effects of selected PAHs. Anthracene and benzo [a] pyrene increase LPO and CAT level of C. chanos suggesting that these PAHs may induce oxidative stress. Both the PAHs inhibited AchE indicating that they have at least one mechanism of neurotoxicity in common: the disruption of cholinergic transmission by inhibition of AChE. An induction of C. chanos glutathione S-transferase (GST) activity was found in fish exposed to benzo [a] pyrene, while an inhibition was observed after exposure to anthracene. These results suggest that GST is involved in the detoxification of benzo [a] pyrene, but not of anthracene. Copyright © 2011 Elsevier Inc. All rights reserved.

Removal of phenanthrene from soil by co-cultures of bacteria and fungi pregrown on sugarcane bagasse pith.

PubMed

Chávez-Gómez, B; Quintero, R; Esparza-García, F; Mesta-Howard, A M; Zavala Díaz de la Serna, F J; Hernández-Rodríguez, C H; Gillén, T; Poggi-Varaldo, H M; Barrera-Cortés, J; Rodríguez-Vázquez, R

2003-09-01

Sixteen co-cultures composed of four bacteria and four fungi grown on sugarcane bagasse pith were tested for phenanthrene degradation in soil. The four bacteria were identified as Pseudomonas aeruginose, Ralstonia pickettii, Pseudomonas sp. and Pseudomonas cepacea. The four fungi were identified as: Penicillium sp., Trichoderma viride, Alternaria tenuis and Aspergillus terrus that were previously isolated from different hydrocarbon-contaminated soils. Fungi had a statistically significant positive (0.0001

Microbial Degradation of Phenanthrene in Pristine and Contaminated Sandy Soils.

PubMed

Schwarz, Alexandra; Adetutu, Eric M; Juhasz, Albert L; Aburto-Medina, Arturo; Ball, Andrew S; Shahsavari, Esmaeil

2018-05-01

Phenanthrene mineralisation studies in both pristine and contaminated sandy soils were undertaken through detailed assessment of the activity and diversity of the microbial community. Stable isotope probing (SIP) was used to assess and identify active 13 C-labelled phenanthrene degraders. Baseline profiling indicated that there was little difference in fungal diversity but a significant difference in bacterial diversity dependent on contamination history. Identification of dominant fungal and bacterial species highlighted the presence of organisms capable of degrading various petroleum-based compounds together with other anthropogenic compounds, regardless of contamination history. Community response following a simulated contamination event ( 14 C-phenanthrene) showed that the microbial community in deep pristine and shallow contaminated soils adapted most to the presence of phenanthrene. The similarity in microbial community structure of well-adapted soils demonstrated that a highly adaptable fungal community in these soils enabled a rapid response to the introduction of a contaminant. Ten fungal and 15 bacterial species were identified as active degraders of phenanthrene. The fungal degraders were dominated by the phylum Basidiomycota including the genus Crypotococcus, Cladosporium and Tremellales. Bacterial degraders included the genera Alcanivorax, Marinobacter and Enterococcus. There was little synergy between dominant baseline microbes, predicted degraders and those that were determined to be actually degrading the contaminant. Overall, assessment of baseline microbial community in contaminated soils provides useful information; however, additional laboratory assessment of the microbial community's ability to degrade pollutants allows for better prediction of the bioremediation potential of a soil.

Potential of Endophytic Bacterium Paenibacillus sp. PHE-3 Isolated from Plantago asiatica L. for Reduction of PAH Contamination in Plant Tissues

PubMed Central

Zhu, Xuezhu; Jin, Li; Sun, Kai; Li, Shuang; Ling, Wanting; Li, Xuelin

2016-01-01

Endophytes are ubiquitous in plants, and they may have a natural capacity to biodegrade polycyclic aromatic hydrocarbons (PAHs). In our study, a phenanthrene-degrading endophytic Paenibacillus sp. PHE-3 was isolated from P. asiatica L. grown in a PAH-contaminated site. The effects of environmental variables on phenanthrene biodegradation by strain PHE-3 were studied, and the ability of strain PHE-3 to use high molecular weight PAH (HMW-PAH) as a sole carbon source was also evaluated. Our results indicated that pH value of 4.0–8.0, temperature of 30 °C–42 °C, initial phenanthrene concentration less than 100 mg·L−1, and some additional nutrients are favorable for the biodegradation of phenanthrene by strain PHE-3. The maximum biodegradation efficiency of phenanthrene was achieved at 99.9% after 84 h cultivation with additional glutamate. Moreover, the phenanthrene biodegradation by strain PHE-3 was positively correlated with the catechol 2,3-dioxygenase activity (ρ = 0.981, p < 0.05), suggesting that strain PHE-3 had the capability of degrading HMW-PAHs. In the presence of other 2-, 3-ringed PAHs, strain PHE-3 effectively degraded HMW-PAHs through co-metabolism. The results of this study are beneficial in that the re-colonization potential and PAH degradation performance of endophytic Paenibacillus sp. PHE-3 may be applied towards reducing PAH contamination in plants. PMID:27347988

Changes in the Bacterial Community Structure of Remediated Anthracene-Contaminated Soils

PubMed Central

Delgado-Balbuena, Laura; Bello-López, Juan M.; Navarro-Noya, Yendi E.; Rodríguez-Valentín, Analine; Luna-Guido, Marco L.; Dendooven, Luc

2016-01-01

Mixing soil or adding earthworms (Eisenia fetida (Savigny, 1826)) accelerated the removal of anthracene, a polycyclic aromatic hydrocarbon, from a pasture and an arable soil, while a non-ionic surfactant (Surfynol® 485) inhibited the removal of the contaminant compared to the untreated soil. It was unclear if the treatments affected the soil bacterial community and consequently the removal of anthracene. Therefore, the bacterial community structure was monitored by means of 454 pyrosequencing of the 16S rRNA gene in the pasture and arable soil mixed weekly, amended with Surfynol® 485, E. fetida or organic material that served as food for the earthworms for 56 days. In both soils, the removal of anthracene was in the order: mixing soil weekly (100%) > earthworms applied (92%) > organic material applied (77%) > untreated soil (57%) > surfactant applied (34%) after 56 days. There was no clear link between removal of anthracene from soil and changes in the bacterial community structure. On the one hand, application of earthworms removed most of the contaminant from the arable soil and had a strong effect on the bacterial community structure, i.e. a decrease in the relative abundance of the Acidobacteria, Chloroflexi and Gemmatimonadetes, and an increase in that of the Proteobacteria compared to the unamended soil. Mixing the soil weekly removed all anthracene from the arable soil, but had little or no effect on the bacterial community structure. On the other hand, application of the surfactant inhibited the removal of anthracene from the arable soil compared to the untreated soil, but had a strong effect on the bacterial community structure, i.e. a decrease in the relative abundance of Cytophagia (Bacteroidetes), Chloroflexi, Gemmatimonadetes and Planctomycetes and an increase in that of the Flavobacteria (Bacteroidetes) and Proteobacteria. Additionally, the removal of anthracene was similar in the different treatments of both the arable and pasture soil, but the effect of application of carrot residue, earthworms or the surfactant on the bacterial community structure was more accentuated in the arable soil than in the pasture soil. It was found that removal of anthracene was not linked to changes in the bacterial community structure. PMID:27727277

A new boronic acid fluorescent sensor based on fluorene for monosaccharides at physiological pH.

PubMed

Hosseinzadeh, Rahman; Mohadjerani, Maryam; Pooryousef, Mona; Eslami, Abbas; Emami, Saeed

2015-06-05

Fluorescent boronic acids are very useful fluorescent sensor for detection of biologically important saccharides. Herein we synthesized a new fluorene-based fluorescent boronic acid that shows significant fluorescence changes upon addition of saccharides at physiological pH. Upon addition of fructose, sorbitol, glucose, galactose, ribose, and maltose at different concentration to the solution of 7-(dimethylamino)-9,9-dimethyl-9H-fluoren-2-yl-2-boronic acid (7-DMAFBA, 1), significant decreases in fluorescent intensity were observed. It was found that this boronic acid has high affinity (K(a)=3582.88 M(-1)) and selectivity for fructose over glucose at pH=7.4. The sensor 1 showed a linear response toward d-fructose in the concentrations ranging from 2.5×10(-5) to 4×10(-4) mol L(-1) with the detection limit of 1.3×10(-5) mol L(-1). Copyright © 2015 Elsevier B.V. All rights reserved.

16S metagenomic analysis reveals adaptability of a mixed-PAH-degrading consortium isolated from crude oil-contaminated seawater to changing environmental conditions.

PubMed

Muangchinda, Chanokporn; Rungsihiranrut, Adisan; Prombutara, Pinidphon; Soonglerdsongpha, Suwat; Pinyakong, Onruthai

2018-05-29

A bacterial consortium, named SWO, was enriched from crude oil-contaminated seawater from Phrao Bay in Rayong Province, Thailand, after a large oil spill in 2013. The bacterial consortium degraded a polycyclic aromatic hydrocarbon (PAH) mixture consisting of phenanthrene, anthracene, fluoranthene, and pyrene (50 mg L -1 each) by approximately 73%, 69%, 52%, and 48%, respectively, within 21 days. This consortium exhibited excellent adaptation to a wide range of environmental conditions. It could degrade a mixture of four PAHs under a range of pH values (4.0-9.0), temperatures (25 °C-37 °C), and salinities (0-10 g L -1 with NaCl). In addition, this consortium degraded 20-30% of benzo[a]pyrene and perylene (10 mg L -1 each), high molecular weight PAHs, in the presence of other PAHs within 35 days, and degraded 40% of 2% (v/v) crude oil within 20 days. The 16S rRNA gene amplicon sequencing analysis demonstrated that Pseudomonas and Methylophaga were the dominant genera of consortium SWO in almost all treatments, while Pseudidiomarina, Thalassospira and Alcanivorax were predominant under higher salt concentrations. Moreover, Pseudomonas and Alcanivorax were dominant in the crude oil-degradation treatment. Our results suggest that the consortium SWO maintained its biodegradation ability by altering the bacterial community profile upon encountering changes in the environmental conditions. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

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

Phytoremediation of Polycyclic Aromatic Hydrocarbons in Soils Artificially Polluted Using Plant-Associated-Endophytic Bacteria and Dactylis glomerata as the Bioremediation Plant.

PubMed

Gałązka, Ann; Gałązka, Rafał

2015-01-01

The reaction of soil microorganisms to the contamination of soil artificially polluted with polycyclic aromatic hydrocarbons (PAHs) was evaluated in pot experiments. The plant used in the tests was cock's foot (Dactylis glomerata). Three different soils artificially contaminated with PAHs were applied in the studies. Three selected PAHs (anthracene, phenanthrene, and pyrene) were used at the doses of 100, 500, and 1000 mg/kg d.m. of soil and diesel fuel at the doses of 100, 500, and 1000 mg/kg d.m. of soil. For evaluation of the synergistic effect of nitrogen fixing bacteria, the following strains were selected: associative Azospirillum spp. and Pseudomonas stutzerii. Additionally, in the bioremediation process, the inoculation of plants with a mixture of the bacterial strains in the amount of 1 ml suspension per 500 g of soil was used. Chamber pot-tests were carried out in controlled conditions during four weeks of plant growth period. The basic physical, microbiological and biochemical properties in contaminated soils were determined. The obtained results showed a statistically important increase in the physical properties of soils polluted with PAHs and diesel fuel compared with the control and also an important decrease in the content of PAHs and heavy metals in soils inoculated with Azospirillum spp. and P. stutzeri after cock's foot grass growth. The bioremediation processes were especially intensive in calcareous rendzina soil artificially polluted with PAHs.

Polycyclic aromatic hydrocarbons (PAHs) in soils and vegetation near an e-waste recycling site in South China: concentration, distribution, source, and risk assessment.

PubMed

Wang, Yan; Tian, Zhongjing; Zhu, Haolin; Cheng, Zhineng; Kang, Meiling; Luo, Chunling; Li, Jun; Zhang, Gan

2012-11-15

This study determined the concentrations of PAHs generated from e-waste recycling activities and their potential impacts on soil, vegetation, and human health. The total PAH concentrations in soils and plants ranged from 127 to 10,600 and 199 to 2420 ng/g, respectively. Samples from an e-waste burning site had higher PAH concentrations than samples from adjacent locations. The PAHs in plants varied with plant species and tissue, and Lactuca sativa L. contained the highest PAHs of all the vegetable species. Various land use types showed different PAH concentrations in soils, with vegetable fields showing higher concentrations than paddy fields. Low molecular weight PAHs, such as phenanthrene, were the predominant congeners in soils, whereas high molecular weight PAHs, such as fluoranthene, pyrene, and benzo[a]anthracene, were enriched in plants relative to soils. Dissimilar PAH profiles in soil and the corresponding vegetation indicated that the uptake of PAHs by plants was selective. A source analysis showed that the contamination by PAHs originated primarily from the open burning of e-waste. The total daily intakes of PAHs and carcinogenic PAHs through vegetables at the e-waste dismantling site were estimated to be 279 and 108 ng/kg/d, respectively, indicating that the consumption of vegetables grown near e-waste recycling sites is risky and should be completely avoided. Copyright © 2012 Elsevier B.V. All rights reserved.

Two-liquid-phase system: A promising technique for predicting bioavailability of polycyclic aromatic hydrocarbons in long-term contaminated soils.

PubMed

Wang, Congying; Wang, Ziyu; Li, Zengbo; Ahmad, Riaz

2017-02-01

A two-liquid-phase system (TLPS), which consisted of soil slurry and silicone oil, was employed to extract polycyclic aromatic hydrocarbons (PAHs) in four long-term contaminated soils in order to assess the bioavailability of PAHs. Extraction kinetics of six PAHs viz. phenanthrene, fluoranthene, pyrene, benzo(a)anthracene, benzo(a)pyrene, dibenzo(a,h)anthrancene were selected to investigate as they covered the susceptible and recalcitrant PAHs in soil. A parallel experiments were also carried out on the microbial degradation of these PAHs in soil with and without biostimulation (by adding (NH 4 ) 2 HPO 4 ). The rapidly desorbed fraction of fluoranthene, as indicated by the two-fraction model, was found the highest, ranging from 21.4% to 37.4%, whereas dibenzo(a,h)anthrancene was the lowest, ranging from 8.9% to 20.5%. The rapid desorption of selected PAHs was found to be finished within 24 h. The rapidly desorbed fraction of PAHs investigated using TLPS, was significantly correlated (R 2  = 0.95) with that degraded by microorganisms in biostimulation treatment. This suggested that the TLPS-assisted extraction could be a promising technique in determining the bioavailability of aged PAHs in contaminated soils. It also suggested that applying sufficient nutrients in bioremediation of field contaminated soils is crucial. Further work is required to test its application to more hydrophobic organic pollutants in long-term contaminated soils. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biotechnological procedures to select white rot fungi for the degradation of PAHs.

PubMed

Lee, Hwanhwi; Jang, Yeongseon; Choi, Yong-Seok; Kim, Min-Ji; Lee, Jaejung; Lee, Hanbyul; Hong, Joo-Hyun; Lee, Young Min; Kim, Gyu-Hyeok; Kim, Jae-Jin

2014-02-01

White rot fungi are essential in forest ecology and are deeply involved in wood decomposition and the biodegradation of various xenobiotics. The fungal ligninolytic enzymes involved in these processes have recently become the focus of much attention for their possible biotechnological applications. Successful bioremediation requires the selection of species with desirable characteristics. In this study, 150 taxonomically and physiologically diverse white rot fungi, including 55 species, were investigated for their performance in a variety of biotechnological procedures, such as dye decolorization, gallic acid reaction, ligninolytic enzymes, and tolerance to four PAHs, phenanthrene, anthracene, fluoranthene, and pyrene. Among these fungi, six isolates showed the highest (>90%) tolerance to both individual PAH and mixed PAHs. And six isolates oxidized gallic acid with dark brown color and they rapidly decolorized RBBR within ten days. These fungi revealed various profiles when evaluated for their biotechnological performance to compare the capability of degradation of PAHs between two groups selected. As the results demonstrated the six best species selected from gallic acid more greatly degraded four PAHs than the other isolates selected via tolerance test. It provided that gallic acid reaction test can be performed to rank the fungi by their ability to degrade the PAHs. Most of all, Peniophora incarnata KUC8836 and Phlebia brevispora KUC9033 significantly degraded the four PAHs and can be considered prime candidates for the degradation of xenobiotic compounds in environmental settings. Copyright © 2013 Elsevier B.V. All rights reserved.

Biodegradation Ability and Catabolic Genes of Petroleum-Degrading Sphingomonas koreensis Strain ASU-06 Isolated from Egyptian Oily Soil

PubMed Central

Mostafa, Yasser M.; Shoreit, Ahmed

2014-01-01

Polycyclic aromatic hydrocarbons (PAHs) are serious pollutants and health hazards. In this study, 15 PAHs-degrading bacteria were isolated from Egyptian oily soil. Among them, one Gram-negative strain (ASU-06) was selected and biodegradation ability and initial catabolic genes of petroleum compounds were investigated. Comparison of 16S rRNA gene sequence of strain ASU-06 to published sequences in GenBank database as well as phylogenetic analysis identified ASU-06 as Sphingomonas koreensis. Strain ASU-06 degraded 100, 99, 98, and 92.7% of 100 mg/L naphthalene, phenanthrene, anthracene, and pyrene within 15 days, respectively. When these PAHs present in a mixed form, the enhancement phenomenon appeared, particularly in the degradation of pyrene, whereas the degradation rate was 98.6% within the period. This is the first report showing the degradation of different PAHs by this species. PCR experiments with specific primers for catabolic genes alkB, alkB1, nahAc, C12O, and C23O suggested that ASU-06 might possess genes for aliphatic and PAHs degradation, while PAH-RHDαGP gene was not detected. Production of biosurfactants and increasing cell-surface hydrophobicity were investigated. GC/MS analysis of intermediate metabolites of studied PAHs concluded that this strain utilized these compounds via two main pathways, and phthalate was the major constant product that appeared in each day of the degradation period. PMID:25177681

L-cysteine-capped core/shell/shell quantum dot-graphene oxide nanocomposite fluorescence probe for polycyclic aromatic hydrocarbon detection.

PubMed

Adegoke, Oluwasesan; Forbes, Patricia B C

2016-01-01

Environmental pollutants, such as the polycyclic aromatic hydrocarbons (PAHs), become widely distributed in the environment after emission from a range of sources, and they have potential biological effects, including toxicity and carcinogenity. In this work, we have demonstrated the analytical potential of a covalently linked L-cysteine-capped CdSeTe/ZnSe/ZnS core/shell/shell quantum dot (QD)-graphene oxide (GO) nanocomposite fluorescence probe to detect PAH compounds in aqueous solution. Water-soluble L-cysteine-capped CdSeTe/ZnSe/ZnS QDs were synthesized for the first time and were covalently bonded to GO. The fluorescence of the QD-GO nanocomposite was enhanced relative to the unconjugated QDs. Various techniques including TEM, SEM, HRSEM, XRD, Raman, FT-IR, UV/vis and fluorescence spectrophotometry were employed to characterize both the QDs and the QD-GO nanocomposite. Four commonly found priority PAH analytes namely; phenanthrene (Phe), anthracene (Ant), pyrene (Py) and naphthalene (Naph), were tested and it was found that each of the PAH analytes enhanced the fluorescence of the QD-GO probe. Phe was selected for further studies as the PL enhancement was significantly greater for this PAH. A limit of detection (LOD) of 0.19 µg/L was obtained for Phe under optimum conditions, whilst the LOD of Ant, Py and Naph were estimated to be ~0.26 µg/L. The fluorescence detection mechanism is proposed. Copyright © 2015 Elsevier B.V. All rights reserved.

Examining spatial patterns in polycyclic aromatic compounds measured in stream macroinvertebrates near a small subarctic oil and gas operation.

PubMed

Korosi, J B; Eickmeyer, D C; Chin, K S; Palmer, M J; Kimpe, L E; Blais, J M

2016-03-01

The Cameron River runs through a small, remote petrochemical development in the Cameron Hills (Northwest Territories, Canada). In order to evaluate the exposure of aquatic biota to contaminants from oil and gas activities, we measured polycyclic aromatic compounds (PACs) in macroinvertebrates collected from sites and tributaries along the Cameron River, including upstream and downstream of the development, and sites located near drilled wells (developed). Macroinvertebrate tissue PAC burdens ranged from 0.2-2.8 μg g(-1) lipid for unsubstituted compounds, and from 4.2-63.2 μg g(-1) lipid for alkylated compounds, relatively low compared to similar studies from more industrialized regions in North America. There was no significant difference in tissue PAC burdens between upstream, downstream, or developed sites (p = 0.12), although alkyl PACs in five out of seven developed sites were higher than the regional average. Petrogenic PACs were dominant in most samples, including alkyl fluorines, alkyl phenanthrene/anthracenes, and alkyl dibenzothiophenes. Minimal changes in PAC composition in macroinvertebrate tissues were detected along the Cameron River, with the exception of the two sites furthest downstream that had high concentrations of C3-C4 naphthalene. Overall, our results suggest that oil and gas development in the Cameron Hills has not resulted in substantial increases in PAC bioaccumulation in stream macroinvertebrates, although the potential that alkyl naphthalenes are being transported downstream from the development warrants further attention.

Distribution and sources of polycyclic aromatic hydrocarbon (PAH) in marine environment of China

NASA Astrophysics Data System (ADS)

Zheng, Jinshu; Richardson, Bruce J.; Shouming, O.; Zheng, Jianhua

2004-06-01

Polycyclic aromatic hydrocarbons (PAHs) are potentially carcinogenic and mutagenic compounds that have raised considerable environmental concern. The highest concentrations of PAHs in the coastal sediment samples in China was 5.8 11.0μg/g (dry weight) in the core from the Huangpu River, Shanghai. The second highest concentration of PAHs was 4.42μg/g (dry weight) in surface sediment of Victoria Harbour in Hong Kong, and 5.73μg/g (dry weight) in sediment of Jiaozhou Bay, Qingdao City. The low concentrations of PAHs were always in the sediments far away from industrial zones and cities, and ranged from 0.10 to 0.30μg/g (dry weight). Several environmental parameters are considered for the identification of sources of PAHs in marine environment. High proportion of naphthalene, low molecular weight PAHs and alkylated PAHs, plus high ratio of phenanthrene to anthracene (>15) and low ratio of fluoranthene to pyrene (<1) suggested a petrogenic source. According to these parameters, the Changjiang (Yangtze) River estuary of Shanghai, Jiaozhou Bay of Qingdao City, Zhujiang (Pearl) River mouth, Jiulong River mouth and most of Hong Kong coastal waters were heavily contaminated by PAHs from petrogenic sources. However, PAHs in rural coastal areas were dominated by pyrolytic origin PAHs. This review clearly showed that oil pollution and incomplete combustion of oil, coal and biomass are the main reason for PAHs anormalies in the study areas.

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

Comparison of Biomarkers of Tobacco Exposure between Premium and Discount Brand Cigarette Smokers in the NHANES 2011-2012 Special Sample.

PubMed

Wasserman, Emily J; Reilly, Samantha M; Goel, Reema; Foulds, Jonathan; Richie, John P; Muscat, Joshua E

2018-05-01

Background: Increased cigarette costs have inadvertently strengthened the appeal of discounted brands to price-sensitive smokers. Although smokers perceive discounted brands as having poorer quality, little is known about their delivery of toxic tobacco smoke constituents compared with premium-branded tobacco products. Methods: We investigated the differences between discount and premium brand smokers using the National Health and Nutrition Examination Survey 2011-2012 Special Smoker Sample. Our analyses focused on demographic differences and 27 biomarkers of harmful and potentially harmful constituents (HPHC) listed by the FDA, including volatile organic compounds, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol and its glucuronide [4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol glucuronide; reported as total NNAL (tNNAL)], metals, and polycyclic aromatic hydrocarbons (PAHs). Data were analyzed using linear regression models adjusting for potential confounders. Results: A total of 976 non-tobacco users and 578 recent cigarette smokers were eligible for analysis, of which 141 (26.0% weighted) smoked discount brand cigarettes and 437 (74.0% weighted) smoked premium. Discount brand smokers were older, predominantly non-Hispanic white, and had higher serum cotinine. Discount brand smokers had significantly higher levels of 13 smoking-related biomarkers, including tNNAL, uranium, styrene, xylene, and biomarkers of exposure to PAHs (naphthalene, fluorene, and phenanthrene), compared with premium brand smokers. Conclusions: These findings suggest that discount cigarette use is associated with higher exposure to several carcinogenic and toxic HPHCs. Impact: These results may have important regulatory implications for product standards, as higher exposures could lead to a greater degree of harm. Cancer Epidemiol Biomarkers Prev; 27(5); 601-9. ©2018 AACR . ©2018 American Association for Cancer Research.

A comparison of physicochemical methods for the remediation of porous medium systems contaminated with tar

NASA Astrophysics Data System (ADS)

Hauswirth, Scott C.; Miller, Cass T.

2014-10-01

The remediation of former manufactured gas plant (FMGP) sites contaminated with tar DNAPLs (dense non-aqueous phase liquids) presents a significant challenge. The tars are viscous mixtures of thousands of individual compounds, including known and suspected carcinogens. This work investigates the use of combinations of mobilization, solubilization, and chemical oxidation approaches to remove and degrade tars and tar components in porous medium systems. Column experiments were conducted using several flushing solutions, including an alkaline-polymer (AP) solution containing NaOH and xanthan gum (XG), a surfactant-polymer (SP) solution containing Triton X-100 surfactant (TX100) and XG, an alkaline-surfactant-polymer (ASP) solution containing NaOH, TX100, and XG, and base-activated sodium persulfate both with and without added TX100. The effectiveness of the flushing solutions was assessed based on both removal of polycyclic aromatic hydrocarbon (PAH) mass and on the reduction of dissolved-phase PAH concentrations. SP flushes of 6.6 to 20.9 PV removed over 99% of residual PAH mass and reduced dissolved-phase concentrations by up to two orders of magnitude. ASP flushing efficiently removed 95-96% of residual PAH mass within about 2 PV, and significantly reduced dissolved-phase concentrations of several low molar mass compounds, including naphthalene, acenaphthene, fluorene, and phenanthrene. AP flushing removed a large portion of the residual tar (77%), but was considerably less effective than SP and ASP in terms of the effect on dissolved PAH concentrations. Persulfate was shown to oxidize tar components, primarily those with low molar mass, however, the overall degradation was relatively low (30-50% in columns with low initial tar saturations), and the impact on dissolved-phase concentrations was minimal.

Evaluating environmental modeling and sampling data with biomarker data to identify sources and routes of exposure

NASA Astrophysics Data System (ADS)

Shin, Hyeong-Moo; McKone, Thomas E.; Bennett, Deborah H.

2013-04-01

Exposure to environmental chemicals results from multiple sources, environmental media, and exposure routes. Ideally, modeled exposures should be compared to biomonitoring data. This study compares the magnitude and variation of modeled polycyclic aromatic hydrocarbons (PAHs) exposures resulting from emissions to outdoor and indoor air and estimated exposure inferred from biomarker levels. Outdoor emissions result in both inhalation and food-based exposures. We modeled PAH intake doses using U.S. EPA's 2002 National Air Toxics Assessment (NATA) county-level emissions data for outdoor inhalation, the CalTOX model for food ingestion (based on NATA emissions), and indoor air concentrations from field studies for indoor inhalation. We then compared the modeled intake with the measured urine levels of hydroxy-PAH metabolites from the 2001-2002 National Health and Nutrition Examination Survey (NHANES) survey as quantifiable human intake of PAH parent-compounds. Lognormal probability plots of modeled intakes and estimated intakes inferred from biomarkers suggest that a primary route of exposure to naphthalene, fluorene, and phenanthrene for the U.S. population is likely inhalation from indoor sources. For benzo(a)pyrene, the predominant exposure route is likely from food ingestion resulting from multi-pathway transport and bioaccumulation due to outdoor emissions. Multiple routes of exposure are important for pyrene. We also considered the sensitivity of the predicted exposure to the proportion of the total naphthalene production volume emitted to the indoor environment. The comparison of PAH biomarkers with exposure variability estimated from models and sample data for various exposure pathways supports that both indoor and outdoor models are needed to capture the sources and routes of exposure to environmental contaminants.

An enhanced procedure for measuring organic acids and methyl esters in PM2.5

NASA Astrophysics Data System (ADS)

Liu, F.; Duan, F. K.; He, K. B.; Ma, Y. L.; Rahn, K. A.; Zhang, Q.

2015-11-01

A solid-phase extraction (SPE) pretreatment procedure allowing organic acids to be separated from methyl esters in fine aerosol has been developed. The procedure first separates the organic acids from fatty acid methyl esters (FAMEs) and other nonacid organic compounds by aminopropyl-based SPE cartridge and then quantifies them by gas chromatography/mass spectrometry. The procedure prevents the fatty acids and dimethyl phthalate from being overestimated, and so allows us to accurately quantify the C4-C11 dicarboxylic acids (DCAs) and the C8-C30 monocarboxylic acids (MCAs). Results for the extraction of DCAs, MCAs, and AMAs in eluate and FAMEs in effluate by SAX and NH2 SPE cartridges exhibited that the NH2 SPE cartridge gave higher extraction efficiency than the SAX cartridge. The recoveries of analytes ranged from 67.5 to 111.3 %, and the RSD ranged from 0.7 to 10.9 %. The resulting correlations between the aliphatic acids and FAMEs suggest that the FAMEs had sources similar to those of the carboxylic acids, or were formed by esterifying carboxylic acids, or that aliphatic acids were formed by hydrolyzing FAMEs. Through extraction and cleanup using this procedure, 17 aromatic acids in eluate were identified and quantified by gas chromatography/tandem mass spectrometry, including five polycyclic aromatic hydrocarbon (PAH): acids 2-naphthoic, biphenyl-4-carboxylic, 9-oxo-9H-fluorene-1-carboxylic, biphenyl-4,4´-dicarboxylic, and phenanthrene-1-carboxylic acid, plus 1,8-naphthalic anhydride. Correlations between the PAH acids and the dicarboxylic and aromatic acids suggested that the first three acids and 1,8-naphthalic anhydride were secondary atmospheric photochemistry products and the last two mainly primary.

Long-Term Oil Pollution and In Situ Microbial Response of Groundwater in Northwest China.

PubMed

Sun, Yujiao; Lu, Sidan; Zhao, Xiaohui; Ding, Aizhong; Wang, Lei

2017-05-01

Potential threats exist where groundwater is polluted by high concentrations of oil compounds (980.20 mg L -1 the highest TPHs). An abandoned petrochemical plant in Lanzhou City, where long-term petrochemical products leakage contaminated the groundwater, was used as a field site in this study. To determine the extent of pollution and find an effective solution, chemical techniques combined with molecular biological techniques were used to survey the migration and decomposition of pollutants. Moreover, Illumina Sequencing was employed to reveal the microbial changes of different sites. Light-chain alkanes (mostly C6-C9), most benzene compounds, and some polycyclic aromatic hydrocarbons (naphthalene, 2-methylnaphthalene) mainly polluted the source. C29 to C36 and chlorobenzenes (hexachlorocyclohexane) polluted the secondary polluted sites. Moreover, chloralkane (trichloroethane and dichloroethane), benzene derivatives (trimethylbenzene and butylbenzene), and PAHs (fluorene and phenanthrene) were present in the other longtime-contaminated water. The bacterial genera are closely related with the chemical matters, and different groups of microorganisms gather in the sample sites that are polluted with different kinds of oil. The biodiversity and abundance of observed species change with pollution conditions. The dominant phyla (81%) of the bacterial community structure are Proteobacteria (62.2% of the total microbes), Bacteroidetes (8.85%), Actinobacteria (6.70%), and Choloroflexi (3.03%). Pseudomonadaceae is significant in the oil-polluted source and Comamonadaceae is significant in the secondary polluted (migrated oil) sample; these two genera are natural decomposers of refractory matters. Amycolatopsis, Rhodocyclaceae, Sulfurimonas, and Sulfuricurvum are the dominant genera in the long-migrated oil-polluted samples. Bioavailability of the oil-contaminated place differs with levels of pollution and cleaning the worse-polluted sites by microbes is more difficult.

Urinary polycyclic aromatic hydrocarbons as a biomarker of exposure to PAHs in air: a pilot study among pregnant women.

PubMed

Nethery, Elizabeth; Wheeler, Amanda J; Fisher, Mandy; Sjödin, Andreas; Li, Zheng; Romanoff, Lovisa C; Foster, Warren; Arbuckle, Tye E

2012-01-01

Recent studies have linked increased polycyclic aromatic hydrocarbons (PAHs) in air and adverse fetal health outcomes. Urinary PAH metabolites are of interest for exposure assessment if they can predict PAHs in air. We investigated exposure to PAHs by collecting air and urine samples among pregnant women pre-selected as living in "high" (downtown and close to steel mills, n=9) and "low" (suburban, n=10) exposure areas. We analyzed first-morning urine voids from all 3 trimesters of pregnancy for urinary PAH metabolites and compared these to personal air PAH/PM(2.5)/NO(2)/NO(X) samples collected in the 3rd trimester. We also evaluated activities and home characteristics, geographic indicators and outdoor central site PM(2.5)/NO(2)/NO(X) (all trimesters). Personal air exposures to the lighter molecular weight (MW) PAHs were linked to indoor sources (candles and incense), whereas the heavier PAHs were related to outdoor sources. Geometric means of all personal air measurements were higher in the "high" exposure group. We suggest that centrally monitored heavier MW PAHs could be used to predict personal exposures for heavier PAHs only. Urine metabolites were only directly correlated with their parent air PAHs for phenanthrene (Pearson's r=0.31-0.45) and fluorene (r=0.37-0.58). Predictive models suggest that specific metabolites (3-hydroyxyfluorene and 3-hydroxyphenanthrene) may be related to their parent air PAH exposures. The metabolite 2-hydroxynaphthalene was linked to smoking and the metabolite 1-hydroxypyrene was linked to dietary exposures. For researchers interested in predicting exposure to airborne lighter MW PAHs using urinary PAH metabolites, we propose that hydroxyfluorene and hydroxyphenanthrene metabolites be considered.

A chemical extraction method for mimicking bioavailability of polycyclic aromatic hydrocarbons to wheat grown in soils containing various amounts of organic matter

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

Shu Tao; Fuliu Xu; Wenxin Liu

Severe contamination of agricultural soils by polycyclic aromatic hydrocarbons (PAHs) occurs in many places in China mainly as a result of coal and biomass combustion. Because ingestion is the main source of human exposure to PAHs and vegetables are basic ingredients for the Chinese diet, it is important to know how and to what extent PAHs are accumulated in vegetables produced in contaminated soils. This study, evaluated the extent to which organic matter contents in soils influence the accumulation of PAHs by the roots of wheat plants and have developed a rapid chemical method for determining the bioavailability of PAH.more » Four PAHs, naphthalene, acenaphthylene, fluorene, and phenanthrene, were added to natural soil samples with different amounts of organic matter for pot experiments to evaluate apparent bioavailability of PAHs to wheat roots (Triticum aestivum L.). The extractabilities of PAHs in the soil were tested by a sequential extraction scheme using accelerated solvent extraction with water, n-hexane, and a mixture of dichloromethane and acetone as solvents. The water or n-hexane-extractable PAHs were positively correlated to dissolved organic matter (DOM) and negatively correlated to total organic matter (TOM), indicating mobilization and immobilization effects of DOM and TOM on soil PAHs, respectively. The apparent accumulation of PAHs by wheat roots was also positively and negatively correlated to DOM and TOM, respectively. As a result, there are positive correlations between the amounts of PAHs extracted by water or n-hexane and the quantities accumulated in plant roots, suggesting the feasibility of using water- or n-hexanes-extractable fractions as indicators of PAH availability to plants. 19 refs., 8 figs., 1 tab.« less

Biodegradation of Mixed PAHs by PAH-Degrading Endophytic Bacteria.

PubMed

Zhu, Xuezhu; Ni, Xue; Waigi, Michael Gatheru; Liu, Juan; Sun, Kai; Gao, Yanzheng

2016-08-09

Endophytic bacteria can promote plant growth, induce plant defence mechanisms, and increase plant resistance to organic contaminants. The aims of the present study were to isolate highly PAH-degrading endophytic bacteria from plants growing at PAH-contaminated sites and to evaluate the capabilities of these bacteria to degrade polycyclic aromatic hydrocarbons (PAHs) in vitro, which will be beneficial for re-colonizing target plants and reducing plant PAH residues through the inoculation of plants with endophytic bacteria. Two endophytic bacterial strains P₁ (Stenotrophomonas sp.) and P₃ (Pseudomonas sp.), which degraded more than 90% of phenanthrene (PHE) within 7 days, were isolated from Conyza canadensis and Trifolium pretense L., respectively. Both strains could use naphthalene (NAP), PHE, fluorene (FLR), pyrene (PYR), and benzo(a)pyrene (B(a)P) as the sole sources of carbon and energy. Moreover, these bacteria reduced the contamination of mixed PAHs at high levels after inoculation for 7 days; strain P₁ degraded 98.0% NAP, 83.1% FLR, 87.8% PHE, 14.4% PYR, and 1.6% B(a)P, and strain P₃ degraded 95.3% NAP, 87.9% FLR, 90.4% PHE, 6.9% PYR, and negligible B(a)P. Notably, the biodegradation of PAHs could be promoted through additional carbon and nitrogen nutrients; therein, beef extract was suggested as the optimal co-substrate for the degradation of PAHs by these two strains (99.1% PHE was degraded within 7 days). Compared with strain P₁, strain P₃ has more potential for the use in the removal of PAHs from plant tissues. These results provide a novel perspective in the reduction of plant PAH residues in PAH-contaminated sites through inoculating plants with highly PAH-degrading endophytic bacteria.

Highly Soluble p-Terphenyl and Fluorene Derivatives as Efficient Dopants in Plastic Scintillators for Sensitive Nuclear Material Detection.

PubMed

Yemam, Henok A; Mahl, Adam; Tinkham, Jonathan S; Koubek, Joshua T; Greife, Uwe; Sellinger, Alan

2017-07-03

Plastic scintillators are commonly used as first-line detectors for special nuclear materials. Current state-of-the-art plastic scintillators based on poly(vinyltoluene) (PVT) matrices containing high loadings (>15.0 wt %) of 2,5-diphenyloxazole (PPO) offer neutron signal discrimination in gamma radiation background (termed pulse shape discrimination, PSD), however, they suffer from poor mechanical properties. In this work, a series of p-terphenyl and fluorene derivatives were synthesized and tested as dopants in PVT based plastic scintillators as possible alternatives to PPO to address the mechanical property issue and to study the PSD mechanism. The derivatives were synthesized from low cost starting materials in high yields using simple chemistry. The photophysical and thermal properties were investigated for their influence on radiation sensitivity/detection performance, and mechanical stability. A direct correlation was found between the melting point of the dopants and the subsequent mechanical properties of the PVT based plastic scintillators. For example, select fluorene derivatives used as dopants produced scintillator samples with mechanical properties exceeding those of the commercial PPO-based scintillators while producing acceptable PSD capabilities. The physical properties of the synthesized dopants were also investigated to examine their effect on the final scintillator samples. Planar derivatives of fluorene were found to be highly soluble in PVT matrices with little to no aggregation induced effects. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toxic effects of combined effects of anthracene and UV radiation on Brachionus plicatilis

NASA Astrophysics Data System (ADS)

Gao, Ceng; Zhang, Xinxin; Xu, Ningning; Tang, Xuexi

2017-05-01

Anthracene is a typical polycyclic aromatic hydrocarbon, with photo activity, can absorb ultraviolet light a series of chemical reactions, aquatic organisms in the ecosystem has a potential light induced toxicity. In this paper, the effects of anthracene and UV radiation on the light-induced toxicity of Brachionus plicatilis were studied. The main methods and experimental results were as follows: (1) The semi-lethal concentration of anthracene in UV light was much lower than that in normal light, The rotifers have significant light-induced acute toxicity. (2) Under UV irradiation, anthracene could induce the increase of ROS and MDA content in B. plicatilis, and the activity of antioxidant enzymes in B. plicatilis significantly changed, Where SOD, GPx activity was induced within 24 hours of the beginning of the experiment. And the content of GPX and CAT was inhibited after 48 hours. Therefore, the anthracite stress induced by UV radiation could more strongly interfere with the ant oxidative metabolism of B. plicatilis, and more seriously cause oxidative damage, significant light-induced toxicity.

Assigning ecological roles to the populations belonging to a phenanthrene-degrading bacterial consortium using omic approaches

PubMed Central

Coppotelli, Bibiana Marina; Madueño, Laura; Loviso, Claudia Lorena; Macchi, Marianela; Neme Tauil, Ricardo Martin; Valacco, María Pía; Morelli, Irma Susana

2017-01-01

The present study describes the behavior of a natural phenanthrene-degrading consortium (CON), a synthetic consortium (constructed with isolated strains from CON) and an isolated strain form CON (Sphingobium sp. AM) in phenanthrene cultures to understand the interactions among the microorganisms present in the natural consortium during phenanthrene degradation as a sole carbon and energy source in liquid cultures. In the contaminant degradation assay, the defined consortium not only achieved a major phenanthrene degradation percentage (> 95%) but also showed a more efficient elimination of the intermediate metabolite. The opposite behavior occurred in the CON culture where the lowest phenanthrene degradation and the highest HNA accumulation were observed, which suggests the presence of positive and also negative interaction in CON. To consider the uncultured bacteria present in CON, a metagenomic library was constructed with total CON DNA. One of the resulting scaffolds (S1P3) was affiliated with the Betaproteobacteria class and resulted in a significant similarity with a genome fragment from Burkholderia sp. HB1 chromosome 1. A complete gene cluster, which is related to one of the lower pathways (meta-cleavage of catechol) involved in PAH degradation (ORF 31–43), mobile genetic elements and associated proteins, was found. These results suggest the presence of at least one other microorganism in CON besides Sphingobium sp. AM, which is capable of degrading PAH through the meta-cleavage pathway. Burkholderiales order was further found, along with Sphingomonadales order, by a metaproteomic approach, which indicated that both orders were metabolically active in CON. Our results show the presence of negative interactions between bacterial populations found in a natural consortium selected by enrichment techniques; moreover, the synthetic syntrophic processing chain with only one microorganism with the capability of degrading phenanthrene was more efficient in contaminant and intermediate metabolite degradation than a generalist strain (Sphingobium sp. AM). PMID:28886166

POLYMERIZATION AND COPOLYMERIZATION OF TETRACYANOETHYLENE UNDER THE EFFECT OF POLYMERS WITH A CONJUGATED SYSTEM,

DTIC Science & Technology

reactivity monomers such as tetracyanoethylene (I), anthracene, naphthacene and pentacene . I was polymerized alone or copolymerized with anthracene...naphthacene, or pentacene . Soluble fractions of polyphenylene or polyanthryl were used as the catalyst in various concentrations so as to vary the...magnitude as high as that of anthracene, and had an activation energy of 8-11 kcal/mol. Naphthacene, pentacene , and polyphenylene also copolymerized

Data on synthesis and thermo-mechanical properties of stimuli-responsive rubber materials bearing pendant anthracene groups.

PubMed

Manhart, Jakob; Ayalur-Karunakaran, Santhosh; Radl, Simone; Oesterreicher, Andreas; Moser, Andreas; Ganser, Christian; Teichert, Christian; Pinter, Gerald; Kern, Wolfgang; Griesser, Thomas; Schlögl, Sandra

2016-12-01

The photo-reversible [4πs+4πs] cycloaddition reaction of pendant anthracene moieties represents a convenient strategy to impart wavelength dependent properties into hydrogenated carboxylated nitrile butadiene rubber (HXNBR) networks. The present article provides the 1 H NMR data on the reaction kinetics of the side chain functionalization of HXNBR. 2-(Anthracene-9-yl)oxirane with reactive epoxy groups is covalently attached to the polymer side chain of HXNBR via ring opening reaction between the epoxy and the carboxylic groups. Along with the identification, 1 H NMR data on the quantification of the attached functional groups are shown in dependence on reaction time and concentration of 2-(anthracene-9-yl)oxirane. Changes in the modification yield are reflected in the mechanical properties and DMA data of photo-responsive elastomers are illustrated in dependence on the number of attached anthracene groups. DMA curves over repeated cycles of UV induced crosslinking ( λ >300 nm) and UV induced cleavage ( λ =254 nm) are further depicted, demonstrating the photo-reversibility of the thermo-mechanical properties. Interpretation and discussion of the data are provided in "Design and application of photo-reversible elastomer networks by using the [4πs+4πs] cycloaddition reaction of pendant anthracene groups" (Manhart et al., 2016) [1].

An integrated biomarker response index for the mussel Mytilus edulis based on laboratory exposure to anthracene and field transplantation experiments

NASA Astrophysics Data System (ADS)

Yuan, Mengqi; Wang, You; Zhou, Bin; Jian, Xiaoyang; Dong, Wenlong; Tang, Xuexi

2017-09-01

Organic pollution is a serious environmental problem in coastal areas and it is important to establish quantitative methods for monitoring this pollution. This study screened a series of sensitive biomarkers to construct an integrated biomarker response (IBR) index using Mytilus edulis. Mussels were exposed to the polycyclic aromatic hydrocarbon anthracene under controlled laboratory conditions and the activities of components of the glutathione antioxidant system, and the concentrations of oxidative-damage markers, were measured in the gills and digestive glands. Anthracene exposure resulted in increased levels of malondialdehyde (MDA) and superoxide radicals (O 2 • ), indicating that oxidative damage had occurred. Correspondingly, anthracene exposure induced increased activities of glutathione S-transferase (GST), glutathione peroxidase (GPx) and reduced glutathione (GSH) in digestive glands, and GPx and glutathione reductase (GR) in gills, consistent with stimulation of the antioxidant system. A field experiment was set up, in which mussels from a relatively clean area were transplanted to a contaminated site. One month later, the activities of GST, GPx and GR had increased in several tissues, particularly in the digestive glands. Based on the laboratory experiment, an IBR, which showed a positive relationship with anthracene exposure, was constructed. The IBR is suggested to be a potentially useful tool for assessing anthracene pollution.

Phenanthrene

Integrated Risk Information System (IRIS)

Phenanthrene ; CASRN 85 - 01 - 8 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effec

Effect of rhamnolipid biosurfactant on solubilization of polycyclic aromatic hydrocarbons.

PubMed

Li, Shudong; Pi, Yongrui; Bao, Mutai; Zhang, Cong; Zhao, Dongwei; Li, Yiming; Sun, Peiyan; Lu, Jinren

2015-12-15

Rhamnolipid biosurfactant-producing bacteria, Bacillus Lz-2, was isolated from oil polluted water collected from Dongying Shengli oilfield, China. The factors that influence PAH solubilization such as biosurfactant concentration, pH, ionic strength and temperature were discussed. The results showed that the solubilities of naphthalene, phenanthrene and pyrene increased linearly with the rise of rhamnolipid biosurfactant dose above the biosurfactant critical micelle concentration (CMC). Furthermore, the molar solubilization ratio (MSR) values decreased in the following order: naphthalene>phenanthrene>pyrene. However, the solubility percentage increased and followed the opposite order: pyrene>phenanthrene>naphthalene. The solubilities of PAHs in rhamnolipid biosurfactant solution increased with the rise of pH and ionic strength, and reached the maximum values under the conditions of pH11 and NaCl concentration 8 g · L(-1). The solubility of phenanthrene and pyrene increased with the rise of temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Longitudinal Study of [D10]Phenanthrene Metabolism by the Diol Epoxide Pathway in Smokers

PubMed Central

Hecht, Stephen S.; Hochalter, J. Bradley; Carmella, Steven G.; Zhang, Yan; Rauch, Diane M.; Fujioka, Naomi; Jensen, Joni; Hatsukami, Dorothy K.

2013-01-01

The extent of metabolism of [D10]phenanthrene to [D10]r-1,t-2,3,c-4-tetrahydroxy-1,2,3,4-tetradeuterophenanthrene ([D10]PheT) could be a biomarker of human metabolic activation of carcinogenic polycyclic aromatic hydrocarbons, leading to identification of smokers particularly susceptible to lung cancer. The longitudinal stability of [D10]PheT was evaluated in 24 cigarette smokers given 7 – 8 oral doses of [D10]phenanthrene (10 μg) over 5.5 months. [D10]PheT in 6 h urine was quantified after each dose. The overall coefficient of variation for 24 subjects was (mean ± S.D.) 27.4 ± 8.83%. Thus, a single administration of [D10]phenanthrene is likely sufficient to determine a smoker’s ability to metabolize it to [D10]PheT. PMID:23336104

Analyses of polycyclic aromatic hydrocarbon (PAH) and chiral-PAH analogues-methyl-β-cyclodextrin guest-host inclusion complexes by fluorescence spectrophotometry and multivariate regression analysis.

PubMed

Greene, LaVana; Elzey, Brianda; Franklin, Mariah; Fakayode, Sayo O

2017-03-05

The negative health impact of polycyclic aromatic hydrocarbons (PAHs) and differences in pharmacological activity of enantiomers of chiral molecules in humans highlights the need for analysis of PAHs and their chiral analogue molecules in humans. Herein, the first use of cyclodextrin guest-host inclusion complexation, fluorescence spectrophotometry, and chemometric approach to PAH (anthracene) and chiral-PAH analogue derivatives (1-(9-anthryl)-2,2,2-triflouroethanol (TFE)) analyses are reported. The binding constants (K b ), stoichiometry (n), and thermodynamic properties (Gibbs free energy (ΔG), enthalpy (ΔH), and entropy (ΔS)) of anthracene and enantiomers of TFE-methyl-β-cyclodextrin (Me-β-CD) guest-host complexes were also determined. Chemometric partial-least-square (PLS) regression analysis of emission spectra data of Me-β-CD-guest-host inclusion complexes was used for the determination of anthracene and TFE enantiomer concentrations in Me-β-CD-guest-host inclusion complex samples. The values of calculated K b and negative ΔG suggest the thermodynamic favorability of anthracene-Me-β-CD and enantiomeric of TFE-Me-β-CD inclusion complexation reactions. However, anthracene-Me-β-CD and enantiomer TFE-Me-β-CD inclusion complexations showed notable differences in the binding affinity behaviors and thermodynamic properties. The PLS regression analysis resulted in square-correlation-coefficients of 0.997530 or better and a low LOD of 3.81×10 -7 M for anthracene and 3.48×10 -8 M for TFE enantiomers at physiological conditions. Most importantly, PLS regression accurately determined the anthracene and TFE enantiomer concentrations with an average low error of 2.31% for anthracene, 4.44% for R-TFE and 3.60% for S-TFE. The results of the study are highly significant because of its high sensitivity and accuracy for analysis of PAH and chiral PAH analogue derivatives without the need of an expensive chiral column, enantiomeric resolution, or use of a polarized light. Published by Elsevier B.V.

Effects of oil dispersants on photodegradation of parent and alkylated anthracene in seawater.

PubMed

Cai, Zhengqing; Liu, Wen; Fu, Jie; O'Reilly, S E; Zhao, Dongye

2017-10-01

This study investigated effects of three model oil dispersants on photodegradation of two model PAHs (anthracene and 9,10-dimethyanthracene (9,10-DMA)) under simulated sunlight. All three dispersants, i.e. Corexit EC9500A, Corexit EC9527A and SPC 1000, promoted the photolysis rate of 9,10-DMA, following the order of Corexit EC9500A > Corexit EC9527A > SPC 1000. The photodegradation rate was well interpreted by a two-stage, first-order kinetic law with a faster initial photolysis rate in the presence of the dispersants. Span 80, Tween 85 and kerosene were found as the key dispersant components, of which Span 80 and Tween 85 promoted the photodegradation by boosting absorbance of solar irradiation while kerosene by dispersing more PAHs in the upper layer of the water column. Dissolved oxygen (DO) inhibited photolysis of anthracene regardless of dispersant resulting from quenching the excited states of the PAH, while DO facilitated photolysis of 9,10-DMA due to the formation singlet oxygen ( 1 O 2 ) radicals in the presence of oil dispersants. The other ROS, i.e. •O 2 - and •OH, played a negligible role on the photodegradation of anthracene and 9,10-DMA. Fluorescence analysis showed that more anthracene was associated with dispersant than 9,10-DMA, which favored the direct transfer of energy to anthracene, while energy is more likely transferred to oxygen to form 1 O 2 in the case of 9,10-DMA. Direct photolysis dominated the photodegradation of anthracene and 9,10-DMA. Both direct ionization of anthracene and the electron transfer from excited 9,10-DMA to oxygen can lead to formation of the corresponding PAH radical cations. Overall, the oil dispersants accelerated the photolysis rates of the PAHs without altering the degradation pathway. The findings are useful for understanding photochemical weathering of dispersed oil components in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of nano bamboo charcoal on PAHs-degrading strain Sphingomonas sp. GY2B.

PubMed

She, Bojia; Tao, Xueqin; Huang, Ting; Lu, Guining; Zhou, Zhili; Guo, Chuling; Dang, Zhi

2016-03-01

Nano bamboo charcoal (NBC) has been commonly used in the production of textiles, plastics, paint, etc. However, little is known regarding their effects towards the microorganisms. The effects of NBC on phenanthrene degrading strain Sphingomonas sp. GY2B were investigated in the present study. Results showed that the addition of NBC could improve the phenanthrene removal by Sphingomonas sp. GY2B, with removal efficiencies increased by 10.29-18.56% in comparison to the control at 24h, and phenanthrene was almost completely removed at 48h. With the presence of low dose of NBC (20 and 50mgL(-1)), strain GY2B displayed a better growth at 6h, suggesting that NBC was beneficial to the growth of GY2B and thus resulting in the quick removal of phenanthrene from water. However, the growth of strain GY2B in high dose of NBC (200mgL(-1)) was inhibited at 6h, and the inhibition could be attenuated and eliminated after 12h. NBC-effected phenanthrene solubility experiment suggested that NBC makes a negligible contribution to the solubilization of phenanthrene in water. Results of electronic microscopy analysis (SEM and TEM) indicated NBC may interact with the cell membrane, causing the enhanced membrane permeability and then NBC adsorbed on the membrane would enter into the cells. The findings of this work would provide important information for the future usage and long-term environmental risk assessment of NBC. Copyright © 2015 Elsevier Inc. All rights reserved.

(4,5-Diaza­fluoren-9-one-κ2 N,N′)bis­(thio­cyanato-κS)mercury(II)

PubMed Central

Notash, Behrouz; Safari, Nasser; Amani, Vahid

2011-01-01

In the title compound, [Hg(NCS)2(C11H6N2O)], the HgII atom, lying on a twofold rotation axis, is four-coordinated in a distorted tetra­hedral geometry by an N,N′-bidentate diaza­fluoren-9-one ligand and two thio­cyanate anions. In the crystal, inter­molecular C—H⋯N and C—H⋯O hydrogen bonds are effective in the stabilization of the structure. PMID:21753948

Use of antioxidant enzymes of clam Ruditapes philippinarum as biomarker to polycyclic aromatic hydrocarbon pollution

NASA Astrophysics Data System (ADS)

Zhu, Lin; Tang, Xuexi; Wang, Ying; Sui, Yadong; Xiao, Hui

2016-03-01

The typical organic pollutant polycyclic aromatic hydrocarbon (PAH) anthracene was selected as a contaminant to investigate its effects on the activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GSH-Px) in the clam Ruditapes philippinarum. The results show that SOD, CAT and GSH-Px had diff erent induction and inhibition reactions to anthracene stress, and that three diff erent organs in R. philippinarum (visceral mass, muscle tissue and mantle) had diff erent sensitivities to anthracene stress. This study suggest that SOD activities of the visceral mass, CAT activitities of the mantle and the visceral mass, and GSH-Px activity of the muscle tissue could be used as sensitive indicators of anthracene stress in R. philippinarum.

Changes in bacterial community of anthracene bioremediation in municipal solid waste composting soil*

PubMed Central

Zhang, Shu-ying; Wang, Qing-feng; Wan, Rui; Xie, Shu-guang

2011-01-01

Polycyclic aromatic hydrocarbons (PAHs) are common contaminants in a municipal solid waste (MSW) composting site. Knowledge of changes in microbial structure is useful to identify particular PAH degraders. However, the microbial community in the MSW composting soil and its change associated with prolonged exposure to PAHs and subsequent biodegradation remain largely unknown. In this study, anthracene was selected as a model compound. The bacterial community structure was investigated using terminal restriction fragment length polymorphism (TRFLP) and 16S rRNA gene clone library analysis. The two bimolecular tools revealed a large shift of bacterial community structure after anthracene amendment and subsequent biodegradation. Genera Methylophilus, Mesorhizobium, and Terrimonas had potential links to anthracene biodegradation, suggesting a consortium playing an active role. PMID:21887852

Comparison between Soil- and Biochar-Derived Humic Acids: Composition, Conformation, and Phenanthrene Sorption.

PubMed

Jin, Jie; Sun, Ke; Yang, Yan; Wang, Ziying; Han, Lanfang; Wang, Xiangke; Wu, Fengchang; Xing, Baoshan

2018-02-20

Biochar-derived organic matter (BDOM) plays an important role in determining biochar's application potential in soil remediation. However, little is known about the physicochemical properties of BDOM and its sorption of hydrophobic organic compounds (HOCs). Humic acids (HAs) were extracted from oxidized biochars produced from plant straws and animal manures at 450 °C, and their sorption of phenanthrene, a representative of HOCs, was investigated. The organic carbon recovery of biochar-derived HAs (BDHAs) was 13.9-69.3%. The 13 C NMR spectra of BDHAs mainly consisted of aromatic and carboxylic C, while those of soil-derived HAs (SDHAs) contained abundant signals in aliphatic region. BDHAs and SDHAs had comparable CO 2 cumulative surface areas. BDHAs were found to exhibit higher phenanthrene sorption than SDHAs. After the removal of amorphous aromatic components, the logK oc values of BDHAs were significantly decreased, implying that amorphous aromatic C regulated phenanthrene sorption by BDHAs. In contrast, aliphatic moieties dominated phenanthrene sorption by SDHAs, as evidenced by the enhanced sorption after the removal of amorphous aromatics. This study clearly demonstrated the contrasting characteristics and sorption behaviors of BDHA and SDHA, indicating that biochar addition and subsequent weathering could greatly affect native organic matter properties and the fate of HOCs in biochar-amended soils.

Novel Phenanthrene-Degrading Bacteria Identified by DNA-Stable Isotope Probing

PubMed Central

Luo, Chunling; Zhang, Dayi; Zhang, Gan

2015-01-01

Microorganisms responsible for the degradation of phenanthrene in a clean forest soil sample were identified by DNA-based stable isotope probing (SIP). The soil was artificially amended with either 12C- or 13C-labeled phenanthrene, and soil DNA was extracted on days 3, 6 and 9. Terminal restriction fragment length polymorphism (TRFLP) results revealed that the fragments of 219- and 241-bp in HaeIII digests were distributed throughout the gradient profile at three different sampling time points, and both fragments were more dominant in the heavy fractions of the samples exposed to the 13C-labeled contaminant. 16S rRNA sequencing of the 13C-enriched fraction suggested that Acidobacterium spp. within the class Acidobacteria, and Collimonas spp. within the class Betaproteobacteria, were directly involved in the uptake and degradation of phenanthrene at different times. To our knowledge, this is the first report that the genus Collimonas has the ability to degrade PAHs. Two PAH-RHDα genes were identified in 13C-labeled DNA. However, isolation of pure cultures indicated that strains of Staphylococcus sp. PHE-3, Pseudomonas sp. PHE-1, and Pseudomonas sp. PHE-2 in the soil had high phenanthrene-degrading ability. This emphasizes the role of a culture-independent method in the functional understanding of microbial communities in situ. PMID:26098417

A New Fiber-Optic-Based Phase-Resolved Phosphorescence Spectrometer.

DTIC Science & Technology

1988-02-15

microcomputer employing least-squares programs described elsewhere (24). Reagents and Materials. Anthracene, acridine, phenazine , 7,8-benzoquinoline, and...Resolution. In an effort to more thoroughly evaluate the new fiber-optic-based spectrometer, ternary mixtures of anthracene, phenazine , and acridine were...eq. 2) Value Anthracene 0.094(0.013) 0.096(0.008) 0.09 NO Phenazine 0.321(0.007) 0.317(0.002) - NO Acridine 0.012(0.006) 0.013(0.004) - NO p

Influence of heavy metals on the formation and the distribution behavior of PAH and PCDD/F during simulated fires.

PubMed

Wobst, M; Wichmann, H; Bahadir, M

2003-04-01

Combustion experiments were performed with an artificial fire load (polystyrene and quartz powder) in a laboratory scale incinerator in the presence of gaseous HCl to simulate accidental fire conditions. The aim of this investigation was to trace back the alterations of the formation and the distribution behavior of PAH and PCDD/PCDF to the presence of CuO or a mixture of metal oxides (CdO, CuO, Fe(2)O(3), PbO, MoO(3), ZnO). The total amount of the 16 PAH target compounds was reduced by the factor of 5-9 when the mixture of metal oxides was present rather than merely CuO. PAH patterns as well as their distribution behavior were significantly influenced by these oxides. In general, transportation inside the installation was enhanced for most of the 16 analyzed PAH. Only fluorene and dibenzo[a,h]anthracene were transported to a smaller extent. In contrast to PAH, total concentrations of PCDD were increased by factor 9 and of PCDF by factor 10, respectively, when CuO was present. Adding the mixture of metal oxides resulted in an increase of PCDD by factor 14 and of PCDF by factor 7. CuO and the mixture of metal oxides had a different influence on the PCDD/F homologue patterns. For instance, the HxCDF to OCDF ratio after incineration without any metal oxide was 1 to 6, whereas addition of CuO or the mixture of the metal oxides shifted the HxCDF to OCDF ratios towards 1 to 40 or 1 to 17, respectively. Combustion along with CuO increased transportation of higher chlorinated PCDF congeners, whereas the mixture of the metal oxides caused a strong decrease of PCDF distribution throughout the system.

Ice growth from supercooled aqueous solutions of benzene, naphthalene, and phenanthrene.

PubMed

Liyana-Arachchi, Thilanga P; Valsaraj, Kalliat T; Hung, Francisco R

2012-08-23

Classical molecular dynamics (MD) were performed to investigate the growth of ice from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene. The main objective of this study is to explore the fate of those aromatic molecules after freezing of the supercooled aqueous solutions, i.e., if these molecules become trapped inside the ice lattice or if they are displaced to the QLL or to the interface with air. Ice growth from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene result in the formation of quasi-liquid layers (QLLs) at the air/ice interface that are thicker than those observed when pure supercooled water freezes. Naphthalene and phenanthrene molecules in the supercooled aqueous solutions are displaced to the air/ice interface during the freezing process at both 270 and 260 K; no incorporation of these aromatics into the ice lattice is observed throughout the freezing process. Similar trends were observed during freezing of supercooled aqueous solutions of benzene at 270 K. In contrast, a fraction of the benzene molecules become trapped inside the ice lattice during the freezing process at 260 K, with the rest of the benzene molecules being displaced to the air/ice interface. These results suggest that the size of the aromatic molecule in the supercooled aqueous solution is an important parameter in determining whether these molecules become trapped inside the ice crystals. Finally, we also report potential of mean force (PMF) calculations aimed at studying the adsorption of gas-phase benzene and phenanthrene on atmospheric air/ice interfaces. Our PMF calculations indicate the presence of deep free energy minima for both benzene and phenanthrene at the air/ice interface, with these molecules adopting a flat orientation at the air/ice interface.

The coupling of the plant and microbial catabolisms of phenanthrene in the rhizosphere of Medicago sativa.

PubMed

Muratova, Anna; Dubrovskaya, Ekaterina; Golubev, Sergey; Grinev, Vyacheslav; Chernyshova, Marina; Turkovskaya, Olga

2015-09-01

We studied the catabolism of the polycyclic aromatic hydrocarbon phenanthrene by four rhizobacterial strains and the possibility of enzymatic oxidation of this compound and its microbial metabolites by the root exudates of alfalfa (Medicago sativa L.) in order to detect the possible coupling of the plant and microbial metabolisms under the rhizospheric degradation of the organic pollutant. A comparative study of phenanthrene degradation pathways in the PAH-degrading rhizobacteria Ensifer meliloti, Pseudomonas kunmingensis, Rhizobium petrolearium, and Stenotrophomonas sp. allowed us to identify the key metabolites from the microbial transformation of phenanthrene, including 9,10-phenanthrenequinone, 2-carboxybenzaldehyde, and 1-hydroxy-2-naphthoic, salicylic, and o-phthalic acids. Sterile alfalfa plants were grown in the presence and absence of phenanthrene (0.03 g kg(-1)) in quartz sand under controlled environmental conditions to obtain plant root exudates. The root exudates were collected, concentrated by ultrafiltration, and the activity of oxidoreductases was detected spectrophotometrically by the oxidation rate for various substrates. The most marked activity was that of peroxidase, whereas the presence of oxidase and tyrosinase was detected on the verge of the assay sensitivity. Using alfalfa root exudates as a crude enzyme preparation, we found that in the presence of the synthetic mediator, the plant peroxidase could oxidize phenanthrene and its microbial metabolites. The results indicate the possibility of active participation of plants in the rhizospheric degradation of polycyclic aromatic hydrocarbons and their microbial metabolites, which makes it possible to speak about the coupling of the plant and microbial catabolisms of these contaminants in the rhizosphere. Copyright © 2015 Elsevier GmbH. All rights reserved.

Rhizoremediation of phenanthrene and pyrene contaminated soil using wheat.

PubMed

Shahsavari, Esmaeil; Adetutu, Eric M; Taha, Mohamed; Ball, Andrew S

2015-05-15

Rhizoremediation, the use of the plant rhizosphere and associated microorganisms represents a promising method for the clean up of soils contaminated with polycyclic aromatic hydrocarbons (PAHs) including phenanthrene and pyrene, two model PAHs. Although numerous studies have been published reporting the degradation of phenanthrene and pyrene, very few evaluate the microbial basis of the rhizoremediation process through the application of molecular tools. The aim of this study was to investigate the effect of wheat on the degradation of two model PAHs (alone or in combination) and also on soil bacterial, fungal and nidA gene (i.e. a key gene in the degradation of pyrene) communities. The addition of wheat plants led to a significant enhancement in the degradation of both phenanthrene and pyrene. In pyrene-contaminated soils, the degradation rate increased from 15% (65 mg/kg) and 18% (90 mg/kg) in unplanted soils to 65% (280 mg/kg) and 70% (350 mg/kg) in planted treatments while phenanthrene reduction was enhanced from 97% (394 mg/kg) and 87% (392 mg/kg) for unplanted soils to 100% (406 mg/kg) and 98% (441 mg/kg) in the presence of wheat. PCR-DGGE results showed that the plant root let to some changes in the bacterial and fungal communities; these variations did not reflect any change in hydrocarbon-degrading communities. However, plate counting, traditional MPN and MPN-qPCR of nidA gene revealed that the wheat rhizosphere led to an increase in the total microbial abundance including PAH degrading organisms and these increased activities resulted in enhanced degradation of phenanthrene and pyrene. This clearer insight into the mechanisms underpinning PAH degradation will enable better application of this environmentally friendly technique. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interactions of rice (Oryza sativa L.) and PAH-degrading bacteria (Acinetobacter sp.) on enhanced dissipation of spiked phenanthrene and pyrene in waterlogged soil.

PubMed

Gao, Y; Yu, X Z; Wu, S C; Cheung, K C; Tam, N F Y; Qian, P Y; Wong, M H

2006-12-15

The effects of cultivation of rice (Oryza sativa L.) and PAH-degrading bacteria (Acinetobacter sp.) separately, and in combination, on the dissipation of spiked phenanthrene and pyrene (0, 50+50, 100+100, 200+200 mg kg(-1)) in waterlogged soil were studied using pot trials. The population of introduced PAH-degrading bacteria remained at 10(5) CFU g(-1) dry soil after 20 days of treatment with Acinetobacter sp. only, but increased to 10(6) when planted with rice simultaneously. Shoot and root biomass of rice when grown alone was adversely affected by spiked PAHs, but significantly increased by 2-55% and 8-409%, respectively, when inoculated with Acinetobacter sp.. Phenanthrene and pyrene concentrations in roots ranged from 1-27 and 20-98 mg kg(-1), respectively, while their concentrations in shoots were generally lower than 0.2 mg kg(-1). The dissipation of phenanthrene was mainly due to abiotic loss as 70-78% phenanthrene was lost from the control soil at the end of 80 days, while removal of 86-87% phenanthrene had been achieved after 40 days in the treatment co-cultivated with Acinetobacter sp. and rice. Compared with the control where only 6-15% of pyrene was removed from soil, a much higher dissipation of pyrene (43-62%) was attained for the treatments co-cultivated with Acinetobacter sp. and rice at the end of 80 days. The results demonstrated that co-cultivation of rice and PAH-degrading bacteria may have a great potential to accelerate the bioremediation process of PAH-contaminated soil under waterlogged conditions.

DNA single strand breakage, DNA adducts, and sister chromatid exchange in lymphocytes and phenanthrene and pyrene metabolites in urine of coke oven workers.

PubMed Central

Popp, W; Vahrenholz, C; Schell, C; Grimmer, G; Dettbarn, G; Kraus, R; Brauksiepe, A; Schmeling, B; Gutzeit, T; von Bülow, J; Norpoth, K

1997-01-01

OBJECTIVES: To investigate the specificity of biological monitoring variables (excretion of phenanthrene and pyrene metabolites in urine) and the usefulness of some biomarkers of effect (alkaline filter elution, 32P postlabelling assay, measurement of sister chromatid exchange) in workers exposed to polycyclic aromatic hydrocarbons (PAHs). METHODS: 29 coke oven workers and a standardised control group were investigated for frequencies of DNA single strand breakage, DNA protein cross links (alkaline filter elution assay), sister chromatid exchange, and DNA adducts (32P postlabelling assay) in lymphocytes. Phenanthrene and pyrene metabolites were measured in 24 hour urine samples. 19 different PAHs (including benzo(a)pyrene, pyrene, and phenanthrene) were measured at the workplace by personal air monitoring. The GSTT1 activity in erythrocytes and lymphocyte subpopulations in blood was also measured. RESULTS: Concentrations of phenanthrene, pyrene, and benzo(a)pyrene in air correlated well with the concentration of total PAHs in air; they could be used for comparisons of different workplaces if the emission compositions were known. The measurement of phenanthrene metabolites in urine proved to be a better biological monitoring variable than the measurement of 1-hydroxypyrene. Significantly more DNA strand breaks in lymphocytes of coke oven workers were found (alkaline filter elution assay); the DNA adduct rate was not significantly increased in workers, but correlated with exposure to PAHs in a semiquantitative manner. The number of sister chromatid exchanges was lower in coke oven workers but this was not significant; thus counting sister chromatid exchanges was not a good variable for biomonitoring of coke oven workers. Also, indications for immunotoxic influences (changes in lymphocyte subpopulations) were found. CONCLUSIONS: The measurement of phenanthrene metabolites in urine seems to be a better biological monitoring variable for exposure to PAHs than measurement of hydroxypyrene. The alkaline filter elution assay proved to be the most sensitive biomarker for genotoxic damage, whereas the postlabelling assay was the only one with some specificity for DNA alterations caused by known compounds. PMID:9155778

Vasorelaxant and Hypotensive Effects of an Ethanolic Extract of Eulophia macrobulbon and Its Main Compound 1-(4′-Hydroxybenzyl)-4,8-Dimethoxyphenanthrene-2,7-Diol

PubMed Central

Wisutthathum, Sutthinee; Chootip, Krongkarn; Martin, Hélène; Ingkaninan, Kornkanok; Temkitthawon, Prapapan; Totoson, Perle; Demougeot, Céline

2018-01-01

Background: Ethnopharmacological studies demonstrated the potential for Eulophia species to treat inflammation, cancer, and cardio-metabolic diseases. The aim of the study was to investigate the vasorelaxant effect of ethanolic Eulophia macrobulbon (EM) extract and its main phenanthrene on rat isolated mesenteric artery and to investigate the hypotensive effect of EM. Methods: The vasorelaxant effects of EM extract or phenanthrene and the underlying mechanisms were evaluated on second-order mesenteric arteries from Sprague Dawley rats. In addition, the acute hypotensive effect was evaluated in anesthetized rats infused with cumulative concentrations of the EM extract. Results: Both EM extract (10-4–1 mg/ml) and phenanthrene (10-7–10-4 M) relaxed endothelium-intact arteries, an effect that was partly reduced by endothelium removal (p < 0.001). A significant decrease in the relaxant effect of the extract and the phenanthrene was observed with L-NAME and apamin/charybdotoxin in endothelium-intact vessels, and with iberiotoxin in denuded vessels. SNP (sodium nitroprusside)-induced relaxation was significantly enhanced by EM extract and phenanthrene. By contrast, ODQ (1H-[1,2,4]oxadiazolo[4,3-a]quinoxaline-1-one), 4-aminopyridine and glibenclamide (endothelium-denuded vessels) and indomethacin (endothelium-intact vessels) had no effect. In calcium-free solution, both the EM extract and phenanthrene inhibited extracellular Ca2+-induced contraction in high KCl and phenylephrine (PE) pre-contracted rings. They also inhibited the intracellular Ca2+ release sensitive to PE. The acute infusion of EM extract (20 and 70 mg/kg) induced an immediate and transient dose-dependent hypotensive effect. Conclusion: The ethanolic extract of EM tubers and its main active compound, 1-(4′-hydroxybenzyl)-4,8-dimethoxyphenanthrene-2,7-diol (phenanthrene) induced vasorelaxant effects on rat resistance vessels, through pleiotropic effects including endothelium-dependent effects (NOS activation, enhanced EDH production) and endothelium-independent effects (opening of KCa channels, inhibition of Ca2+ channels, inhibition of intracellular Ca2+ release and PDE inhibition). PMID:29872393

1H NMR Metabolomics: A New Molecular Level Tool for Assessment of Organic Contaminant Bioavailability to Earthworms in Soil

NASA Astrophysics Data System (ADS)

McKelvie, J. R.; Wolfe, D. M.; Celejewski, M. A.; Simpson, A. J.; Simpson, M. J.

2009-05-01

At contaminated field sites, the complete removal of polycyclic aromatic hydrocarbons (PAHs) is rarely achieved since a portion of these compounds remain tightly bound to the soil matrix. The concentration of PAHs in soil typically decreases until a plateau is reached, at which point the remaining contaminant is considered non- bioavailable. Numerous soil extraction techniques, including cyclodextrin extraction, have been developed to estimate contaminant bioavailability. However, these are indirect methods that do not directly measure the response of organisms to chemical exposure in soil. Earthworm metabolomics offers a promising new way to directly evaluate the bioavailability and toxicity of contaminants in soil. Metabolomics involves the measurement of changes in small-molecule metabolites, including sugars and amino acids, in living organisms due to an external stress, such as contaminant exposure. The objective of this study was to compare cyclodextrin extraction of soil (a bioavailability proxy) and 1H NMR metabolomic analysis of aqueous earthworm tissue extracts as indicators of contaminant bioavailability. A 30 day laboratory experiment was conducted using phenanthrene-spiked sphagnum peat soil and the OECD recommended earthworm species for toxicity testing, Eisenia fetida. The initial phenanthrene concentration in the soil was 320 mg/kg. Rapid biodegradation of phenanthrene occurred and concentrations decreased to 16 mg/kg within 15 days. After 15 days, phenanthrene biodegradation slowed and cyclodextrin extraction of the soil suggested that phenanthrene was no longer bioavailable. Multivariate statistical analysis of the 1H NMR spectra for E. fetida tissue extracts indicated that the metabolic profile of phenanthrene exposed earthworms differed from control earthworms throughout the 30 day experiment. This suggests that the residual phenanthrene remaining in the soil after 15 days continued to elicit a metabolic response, even though it was not extractable using cyclodextrin. Hence, while cyclodextrin extraction may serve as a good proxy for microbial bioavailability, our results suggest that it may not serve as a good proxy for earthworm bioavailability. 1H NMR metabolomics therefore offers considerable promise as a novel, molecular-level method to directly monitor earthworm bioavailability of potentially toxic and persistent compounds in the environment.

COSOLVENT EFFECTS ON PHENANTHRENE SORPTION-DESORPTION ON A FRESH-WATER SEDIMENT

EPA Science Inventory

This study evaluated the effects of the water-miscible cosolvent methanol on the sorption-desorption of phenanthrene by the natural organic matter (NOM) of a fresh-water sediment. A biphasic pattern was observed in the relationship between the log of the carbon-normalized sorpti...

Remediation of phenanthrene from contaminated kaolinite by electroremediation-Fenton technology.

PubMed

Alcantara, T; Pazos, M; Gouveia, S; Cameselle, C; Sanroman, M A

2008-07-01

Polycyclic aromatic hydrocarbons (PAHs) cause a high environmental impact when released into the environment. The objective of this study was to evaluate the capacity to decontaminate polluted soils with phenanthrene as a model PAH using a combination of two technologies: electrokinetic remediation and Fenton process. Kaolinite was used as a model sample that was artificially polluted at the laboratory at an initial concentration of phenanthrene of 500 mg kg(-1) of dried kaolinite. The standard electrokinetic process resulted in negligible removal of phenanthrene from the kaolinite sample. Faster and more efficient degradation of this compound can be promoted by introduction of a strong oxidant into the soil such as hydroxyl radicals. For this reason, the Fenton reactions have been induced in several experiments in which H(2)O(2) (10%) was used as flushing solution, and kaolinite polluted with iron was used. When anode and cathode chambers were filled with H(2)O(2) (10%), the kaolinite pH is maintained at an acid value around 3.5 without pH control and an overall removal and destruction efficiency of phenanthrene of 99% was obtained in 14 days by applying a voltage gradient of 3 V cm(-1). Therefore, it is evident that a combined technology of electrokinetic remediation and Fenton reaction is capable of simultaneously removing and degrading of PAHs in polluted model samples with kaolinite.

CeO2 nanoparticles induce no changes in phenanthrene toxicity to the soil organisms Porcellionides pruinosus and Folsomia candida.

PubMed

Tourinho, Paula S; Waalewijn-Kool, Pauline L; Zantkuijl, Irene; Jurkschat, Kerstin; Svendsen, Claus; Soares, Amadeu M V M; Loureiro, Susana; van Gestel, Cornelis A M

2015-03-01

Cerium oxide nanoparticles (CeO2 NPs) are used as diesel fuel additives to catalyze oxidation. Phenanthrene is a major component of diesel exhaust particles and one of the most common pollutants in the environment. This study aimed at determining the effect of CeO2 NPs on the toxicity of phenanthrene in Lufa 2.2 standard soil for the isopod Porcellionides pruinosus and the springtail Folsomia candida. Toxicity tests were performed in the presence of CeO2 concentrations of 10, 100 or 1000mg Ce/kg dry soil and compared with results in the absence of CeO2 NPs. CeO2 NPs had no adverse effects on isopod survival and growth or springtail survival and reproduction. For the isopods, LC50s for the effect of phenanthrene ranged from 110 to 143mg/kg dry soil, and EC50s from 17.6 to 31.6mg/kg dry soil. For the springtails, LC50s ranged between 61.5 and 88.3mg/kg dry soil and EC50s from 52.2 to 76.7mg/kg dry soil. From this study it may be concluded that CeO2 NPs have a low toxicity and do not affect toxicity of phenanthrene to isopods and springtails. Copyright © 2014 Elsevier Inc. All rights reserved.

Dynamic behavior of semivolatile organic compounds in indoor air. 2. Nicotine and phenanthrene with carpet and wallboard.

PubMed

Van Loy, M D; Riley, W J; Daisey, J M; Nazaroff, W W

2001-02-01

The surface interactions of nicotine and phenanthrene with carpet, painted wallboard, and stainless steel were investigated in a room-sized environmental test chamber. Adsorption kinetics were tested by flash evaporating a known mass of each compound into a sealed 20 m3 chamber containing one or more of the tested sorbents. In each experiment, one or more emissions were performed after the gas-phase concentration had reached an apparent plateau. At the end of each experiment, the chamber was ventilated and resealed to monitor reemission of the compound from the sorbents. Kinetic sorption parameters were determined by fitting a mass-balance model to the experimental results. The sorption capacity of stainless steel was of similar magnitude for nicotine and phenanthrene. Sorption of nicotine on carpet and wallboard was much stronger, with equilibrium partitioning values 2-3 orders of magnitude higher. The sorption capacities of phenanthrene on carpet and wallboard were smaller, approximately 10-20% of the stainless steel values. The rates of uptake are of similar magnitude for all sorbate--sorbent pairs and are consistent with the limit imposed by gas-phase boundary-layer mass transport. The rates of desorption are much faster for phenanthrene than for nicotine. Model simulations predict average nicotine levels in a typical smoking residence that are consistent with published data.

Unraveling the early molecular and physiological mechanisms involved in response to phenanthrene exposure.

PubMed

Dumas, Anne-Sophie; Taconnat, Ludivine; Barbas, Evangelos; Rigaill, Guillem; Catrice, Olivier; Bernard, Delphine; Benamar, Abdelilah; Macherel, David; El Amrani, Abdelhak; Berthomé, Richard

2016-10-21

Higher plants have to cope with increasing concentrations of pollutants of both natural and anthropogenic origin. Given their capacity to concentrate and metabolize various compounds including pollutants, plants can be used to treat environmental problems - a process called phytoremediation. However, the molecular mechanisms underlying the stabilization, the extraction, the accumulation and partial or complete degradation of pollutants by plants remain poorly understood. Here, we determined the molecular events involved in the early plant response to phenanthrene, used as a model of polycyclic aromatic hydrocarbons. A transcriptomic and a metabolic analysis strongly suggest that energy availability is the crucial limiting factor leading to high and rapid transcriptional reprogramming that can ultimately lead to death. We show that the accumulation of phenanthrene in leaves inhibits electron transfer and photosynthesis within a few minutes, probably disrupting energy transformation. This kinetic analysis improved the resolution of the transcriptome in the initial plant response to phenanthrene, identifying genes that are involved in primary processes set up to sense and detoxify this pollutant but also in molecular mechanisms used by the plant to cope with such harmful stress. The identification of first events involved in plant response to phenanthrene is a key step in the selection of candidates for further functional characterization, with the prospect of engineering efficient ecological detoxification systems for polycyclic aromatic hydrocarbons.

Pulsed Laser Annealing of Carbon

NASA Astrophysics Data System (ADS)

Abrahamson, Joseph P.

This dissertation investigates laser heating of carbon materials. The carbon industry has been annealing carbon via traditional furnace heating since at least 1800, when Sir Humphry Davy produced an electric arc with carbon electrodes made from carbonized wood. Much knowledge has been accumulated about carbon since then and carbon materials have become instrumental both scientifically and technologically. However, to this day the kinetics of annealing are not known due to the slow heating and cooling rates of furnaces. Additionally, consensus has yet to be reached on the cause of nongraphitizability. Annealing trajectories with respect to time at temperature are observed from a commercial carbon black (R250), model graphitizable carbon (anthracene coke) and a model nongraphitizable carbon (sucrose char) via rapid laser heating. Materials were heated with 1064 nm and 10.6 im laser radiation from a Q-switched Nd:YAG laser and a continuous wave CO2 laser, respectively. A pulse generator was used reduce the CO2 laser pulse width and provide high temporal control. Time-temperature-histories with nanosecond temporal resolution and temperature reproducibility within tens of degrees Celsius were determined by spectrally resolving the laser induced incandescence signal and applying multiwavelength pyrometry. The Nd:YAG laser fluences include: 25, 50, 100, 200, 300, and 550 mJ/cm2. The maximum observed temperature ranged from 2,400 °C to the C2 sublimation temperature of 4,180 °C. The CO2 laser was used to collect a series of isothermal (1,200 and 2,600 °C) heat treatments versus time (100 milliseconds to 30 seconds). Laser heated samples are compared to furnace annealing at 1,200 and 2,600 °C for 1 hour. The material transformation trajectory of Nd:YAG laser heated carbon is different than traditional furnace heating. The traditional furnace annealing pathway is followed for CO2 laser heating as based upon equivalent end structures. The nanostructure of sucrose char after 5 seconds of isothermal annealing at 2,600 °C is comprised almost entirely of quasi-spherical closed shell particles that are free of sp3 and oxygen content. With additional time at temperature the particles unravel and propagative particle opening occurs throughout the material. The irregular pore structure found in the end product is a result of particle unraveling. The structures found in heat treated sucrose char believed to contain odd membered rings are not manufactured during the annealing process due to impinging growth of stacks. Thus, odd membered rings are likely present in the starting non-graphitizable char. Furnace annealing of cokes and chars produced from: oxygen containing compounds (polyfurfuryl alcohol and anthanthrone), from a five membered ring containing polyaromatic hydrocarbon (fluorene), and from sulfur containing decant oil and a blend of anthracene-dibenzothiophene were compared to furnace annealed anthracene coke and sucrose char. The majority of initial oxygen content evolved out during low temperature carbonization. The intermediate species formed after oxygen evolution dictated the resulting carbon skeleton and thus the graphitizability. Carbonization of anthanthrone resulted in a graphitizable coke. It is proposed that carbon monoxide loss from anthanthrone results in the formation of perylene. An obvious resemblance was observed in structure between heat treated sucrose and polyfurfuryl alcohol char as compared to heated treated char embedded with 5 membered rings via carbonization of fluorene. Thus, providing evidence that 5 membered rings are present in the virgin chars and are the cause of non-graphitizability. The heteroatom sulfur effects carbon structure in a different way as compared to oxygen. Sulfur is thermally stable in carbon up to ˜ 1,000 °C and thus plays little role in the initial low temperature (500 °C) carbonization. As such it imparts a relatively unobservable impact on nanostructure, but rather acts to cause micro-cracks upon rapid evolution in the form of H2S and CS2, upon subsequent heat treatment. Laboratory generated synthetic soot from benzene and benzene-thiophene were Nd:YAG laser and furnace annealed. Furnace annealing of sulfur doped synthetic soot results in cracks and rupturing due to the high pressures caused by explosive sulfur evolution at elevated temperature. Whereas Nd:YAG laser heating of the sulfur doped sample acted to induce curvature. The observed curvature is owed to annealing occurring simultaneously with sulfur evolution. The unset lamellae are strongly influenced by the defect formed upon sulfur evolution. Coke and char samples were prepared via carbonization in sealed tubing reactors. The extent of mesophase development was assessed by measuring the materials optical anisotropy with a polarized light microscope. Physical and chemical transformations from annealing were measured with electron microscopy, energy dispersive X-ray spectroscopy, selected area electron diffraction, and electron energy loss spectroscopy. Virgin samples and traditional furnace annealed samples available in bulk were analyzed with X-ray diffraction. The potential technological importance of laser annealing carbon is demonstrated as annealing can be performed continuously and rapidly. Examples of material processing and synthesis not possible via traditional furnace annealing are provided.

Effects of 7,8-benzoflavone of skin tumor-initiating activities of various 7- and 12-substituted derivatives of 7,12-dimenthylbenz(a)anthracene in mice

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

DiGiovanni, J.; Slaga, T.J.; Viaje, A.

1978-07-01

The skin tumor-initiating activities of various 7- and 12-substituted derivatives of 7,12-dimethylbenz(a)anthracene (DMBA) were investigated in female outbred Charles River CD-1 mice. 7-Formyl-12-methylbenz(a)anthracene (7-CHO-12-MBA) at 740 nmoles/mouse was an effective tumor initiator, at a dose 74-fold greater than that of DMBA. 7,8-Benzoflavone (7,8-BF) inhibited the tumor-initiating activity of 7-CHO-12-MBA by 51%. 12-Formyl-7-methylbenz(a)anthranene and 7,12-diformylbenz(a)anthracene, applied at initiating doses of 740 nmoles and 704 nmoles/mouse, respectively, were much less active than 7-CHO-12-MBA. 7-Bromomethyl-12-methylbenz(a)anthracene (7-BRME-12-MBA) and 7-bromomethylbenz(a)anthracene (7-BRMEBA) were also investigated. 7-BRME-12-MBA was a more effective tumor initiator than 7-BRMEBA, but both were less active than DMBA. 7,8-BF inhibited the tumor-initiating activitymore » of 7-BRME- 12-MBA and 7-BRMEBA by 34 and 54%, respectively. 12-Bromomethyl-7-methylbenz(a)anthracene (12-BRME-7-MBA) was as active an initiator as 7-BRME-12-MBA. 7,8-BF inhibited tumor initiation with 12-BRME-7-MBA by 29%. Three naturally occurring flavones, quercetin, myricetin, and 4',5,7-trihydroxyflavonone, and the cytochrome P/sub 450/, inhibitor 1-benzylimidazole were investigated after topical application(100 ..mu..g) for their effects on tumor initiation with DMBA. Quercetin inhibited tumor initiation with DMBA. Quercetin inhibited tumor initiation with DMBA by 22%, whereas myricetin and 4',5,7-trihydroxyflavanone enhanced tumor initiation with DMBA by 54 and 29%, respectively. 1-Benzylimidazole had no effect. The abilities of the flavones and 1-benzylimidazole to inhibit aryl hydrocarbon hydroxylase in vitro did not correlate with their effects on tumor initiation with DMBA.« less

Formation of bound residues during microbial degradation of [{sup 14}C]anthracene in soil

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

Kaestner, M.; Streibich, S.; Beyrer, M.

1999-05-01

Carbon partitioning and residue formation during microbial degradation of polycyclic aromatic hydrocarbons (PAH) in soil and soil-compost mixtures were examined by using [{sup 14}C]anthracenes labeled at different positions. In native soil 43.8% of [9-{sup 14}C]anthracene was mineralized by the autochthonous microflora and 45.4% was transformed into bound residues within 176 days. Addition of compost increased the metabolism and decreased the residue formation (20.7% of the anthracene was transformed). Thus, the higher organic carbon content after compost was added did not increase the level of residue formation. [{sup 14}C]anthracene labeled at position 1,2,3,4,4a,5a was metabolized more rapidly and resulted in formationmore » of higher levels of residues (28.5%) by the soil-compost mixture than [{sup 14}C]anthracene radiolabeled at position C-9 (20.7%). Two phases of residue formation were observed in the experiments. In the first phase the original compound was sequestered in the soil, as indicated by its limited extractability. In the second phase metabolites were incorporated into humic substances after microbial degradation of the PAH (biogenic residue formation). PAH metabolites undergo oxidative coupling to phenolic compounds to form nonhydrolyzable humic substance-like macromolecules. The authors found indications that monomeric educts are coupled by C-C- or either bonds. Hydrolyzable ester bonds or sorption of the parent compounds plays a minor role in residue formation. Moreover, experiments performed with {sup 14}CO{sub 2} revealed that residues may arise from CO{sub 2} in the soil in amounts typical for anthracene biodegradation. The extent of residue formation depends on the metabolic capacity of the soil microflora and the characteristics of the soil. The position of the {sup 14}C label is another important factor which controls mineralization and residue formation from metabolized compounds.« less

Exposure chamber measurements of mass transfer and partitioning at the plant/air interface.

PubMed

Maddalena, Randy L; McKone, Thomas E; Kado, Norman Y

2002-08-15

Dynamic measures of air and vegetation concentrations in an exposure chamber and a two-box mass balance model are used to quantify factors that control the rate and extent of chemical partitioning between vegetation and the atmosphere. A continuous stirred flow-through exposure chamber was used to investigate the gas-phase transfer of pollutants between air and plants. A probabilistic two-compartment mass balance model of plant/air exchange within the exposure chamber was developed and used with measured concentrations from the chamber to simultaneously evaluate partitioning (Kpa), overall mass transfer across the plant/air interface (Upa), and loss rates in the atmosphere (Ra) and aboveground vegetation (Rp). The approach is demonstrated using mature Capsicum annuum (bell pepper) plants exposed to phenanthrene (PH), anthracene (AN), fluoranthene (FL) and pyrene (PY). Measured values of log Kpa (V[air]/V[fresh plant]) were 5.7, 5.7, 6.0, and 6.2 for PH, AN, FL, and PY, respectively. Values of Upa (m d(-1)) under the conditions of this study ranged from 42 for PH to 119 for FL. After correcting for wall effects, the estimated reaction half-lives in air were 3, 9, and 25 h for AN, FL and PY. Reaction half-lives in the plant compartment were 17, 6, 17, and 5 d for PH, AN, FL, and PY, respectively. The combined use of exposure chamber measurements and models provides a robust tool for simultaneously measuring several different transfer factors that are important for modeling the uptake of pollutants into vegetation.

The use of cork waste as a biosorbent for persistent organic pollutants-Study of adsorption/desorption of polycyclic aromatic hydrocarbons.

PubMed

Olivella, Maria À; Jové, Patrícia; Oliveras, Anna

2011-01-01

The aim of this study is to determine the sorption-desorption behavior of a mixture of thirteen aqueous PAHs on cork waste at a particle of size 0.25-0.42 mm obtained from the remains of cork strips. The final purpose is to use this natural adsorbent as an alternative to activated carbon in an innovative approach for the removal of this class of toxic compounds, and significantly reduce the regeneration costs of the process. The chemical composition of the selected cork revealed that suberin (38.5 %) and lignin (31.6 %) were the main structural components of the cell wall. The high efficiency of cork as a biosorbent of PAHs is shown by the fact that just over 80 % of adsorption occurred during the first two minutes of contact time. Both Freundlich's and Langmuir's isotherms gave good fits to the sorption process. The highest adsorption affinities were exhibited for pyrene, anthracene, and phenanthrene. Desorption studies indicate a high degree of irreversibility for all PAHs, and especially so in the case of high molecular PAHs. The correlation with K(F) and low molecular weight PAHs was the most significant. The quantity of cork required to reduce water pollution was estimated to be between 3 and 15 times less than the quantities required in the case of other materials (i.e. aspen wood and leonardite). This study demonstrates for the first time that cork is a potential biosorbent for PAHs and may have relevance in the future treatment of PAH-contaminated waters.

Microwave-assisted extraction and ultrasonic extraction to determine polycyclic aromatic hydrocarbons in needles and bark of Pinus pinaster Ait. and Pinus pinea L. by GC-MS.

PubMed

Ratola, Nuno; Lacorte, Sílvia; Barceló, Damià; Alves, Arminda

2009-01-15

Two different extraction strategies (microwave-assisted extraction (MAE) and ultrasonic extraction (USE)) were tested in the extraction of the 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from pine trees. Extraction of needles and bark from two pine species common in the Iberian Peninsula (Pinus pinaster Ait. and Pinus pinea L.) was optimized using two amounts of sample (1g and 5 g) and two PAHs spiking levels (20 ng/g and 100 ng/g). In all cases, the clean-up procedure following extraction consisted in solid-phase extraction (SPE) with alumina cartridges. Quantification was done by gas chromatography (GC) with mass spectrometry (MS), using five deuterated PAH surrogate standards as internal standards. Limits of detection were globally below 0.2 ng/g. The method was robust for the matrices studied regardless of the extraction procedures. Recovery values between 70 and 130% were reached in most cases, except for high molecular weight PAHs (indeno[1,2,3-cd]pyrene, dibenzo[a,h]anthracene and benzo[ghi]perylene). A field study with naturally contaminated samples from eight sites (four in Portugal and four in Catalonia, Spain) showed that needles are more suitable biomonitors for PAHs, yielding concentrations from 2 to 17 times higher than those found in bark. The levels varied according to the sampling site, with the sum of the individual PAH concentrations between 213 and 1773 ng/g (dry weight). Phenanthrene was the most abundant PAH, followed by fluoranthene, naphthalene and pyrene.

New naphthalene whole-cell bioreporter for measuring and assessing naphthalene in polycyclic aromatic hydrocarbons contaminated site.

PubMed

Sun, Yujiao; Zhao, Xiaohui; Zhang, Dayi; Ding, Aizhong; Chen, Cheng; Huang, Wei E; Zhang, Huichun

2017-11-01

A new naphthalene bioreporter was designed and constructed in this work. A new vector, pWH1274_Nah, was constructed by the Gibson isothermal assembly fused with a 9 kb naphthalene-degrading gene nahAD (nahAa nahAb nahAc nahAd nahB nahF nahC nahQ nahE nahD) and cloned into Acinetobacter ADPWH_lux as the host, capable of responding to salicylate (the central metabolite of naphthalene). The ADPWH_Nah bioreporter could effectively metabolize naphthalene and evaluate the naphthalene in natural water and soil samples. This whole-cell bioreporter did not respond to other polycyclic aromatic hydrocarbons (PAHs; pyrene, anthracene, and phenanthrene) and demonstrated a positive response in the presence of 0.01 μM naphthalene, showing high specificity and sensitivity. The bioluminescent response was quantitatively measured after a 4 h exposure to naphthalene, and the model simulation further proved the naphthalene metabolism dynamics and the salicylate-activation mechanisms. The ADPWH_Nah bioreporter also achieved a rapid evaluation of the naphthalene in the PAH-contaminated site after chemical spill accidents, showing high consistency with chemical analysis. The engineered Acinetobacter variant had significant advantages in rapid naphthalene detection in the laboratory and potential in situ detection. The state-of-the-art concept of cloning PAHs-degrading pathway in salicylate bioreporter hosts led to the construction and assembly of high-throughput PAH bioreporter array, capable of crude oil contamination assessment and risk management. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of red clover on the microbial transformation of phenanthrene and octadecane in the soil

NASA Astrophysics Data System (ADS)

Nazarov, A. V.; Shestakova, E. A.; Anan'yina, L. N.

2017-08-01

The influence of red clover ( Trifolium pratense L.) plants on the decomposition of phenanthrene and octadecane in the soil has been studied. Effect of plant root mass on the abundance of hydrocarbondegrading bacteria, the composition of their communities, and the degradation of hydrocarbons in the soil has been revealed. Changes in the taxonomic composition of hydrocarbon-degrading bacteria under the effect of red clover are characterized by an increase in the abundance of species from the genera Acinetobacter, Kaistia, Novosphingobium, Pseudomonas, and Xanthomonas. A positive effect of the studied microbial-plant association on the degradation of octadecane and especially phenanthrene in the soil has been revealed.

Anthracene

Integrated Risk Information System (IRIS)

Anthracene ; CASRN 120 - 12 - 7 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

Downscaling the in vitro test of fungal bioremediation of polycyclic aromatic hydrocarbons: methodological approach.

PubMed

Drevinskas, Tomas; Mickienė, Rūta; Maruška, Audrius; Stankevičius, Mantas; Tiso, Nicola; Mikašauskaitė, Jurgita; Ragažinskienė, Ona; Levišauskas, Donatas; Bartkuvienė, Violeta; Snieškienė, Vilija; Stankevičienė, Antanina; Polcaro, Chiara; Galli, Emanuela; Donati, Enrica; Tekorius, Tomas; Kornyšova, Olga; Kaškonienė, Vilma

2016-02-01

The miniaturization and optimization of a white rot fungal bioremediation experiment is described in this paper. The optimized procedure allows determination of the degradation kinetics of anthracene. The miniaturized procedure requires only 2.5 ml of culture medium. The experiment is more precise, robust, and better controlled comparing it to classical tests in flasks. Using this technique, different parts, i.e., the culture medium, the fungi, and the cotton seal, can be analyzed. A simple sample preparation speeds up the analytical process. Experiments performed show degradation of anthracene up to approximately 60% by Irpex lacteus and up to approximately 40% by Pleurotus ostreatus in 25 days. Bioremediation of anthracene by the consortium of I. lacteus and P. ostreatus shows the biodegradation of anthracene up to approximately 56% in 23 days. At the end of the experiment, the surface tension of culture medium decreased comparing it to the blank, indicating generation of surfactant compounds.

Metabolism of 7-nitrogenz[a]anthracene by intestinal microflora

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

Morehead, M.C.; Franklin, W.; Fu, P.P.

1994-12-31

Pure cultures of anaerobic intestinal bacteria and mixed fecal microflora from human, rat, mouse, and pig were screened for the ability to metabolize 7-nitrobenz[a]anthracene. Based on analysis by high-performance liquid chromatography (HPLC) and by ultraviolent (UV), mass, and nuclear magnetic resonance (NMR) spectral techniques, the compounds were identified as 7-aminobenz[a]anthracene and benz[a]anthracene 7,12-dione. Identification of 7-NH{sub 2}BA as a metabolite of 7-NO{sub 2}BA indicates that the anaerobic intestinal bacteria are capable of reducing 7-NO{sub 2}BA to potentially bioactive intermediates. The reductive capacities of the mixed intestinal microflora were generally greater than those of pure cultures. Thus, metabolism of 7-NO{sub 2}BAmore » in the intestinal tract may be underestimated if pure cultures are used as the sole method for evaluating the potential hazard.« less

Toxicity, feeding rate and growth rate response to sub-lethal concentrations of anthracene and benzo [a] pyrene in milkfish Chanos chanos (Forskkal).

PubMed

Palanikumar, L; Kumaraguru, A K; Ramakritinan, C M; Anand, M

2013-01-01

The feeding rate, growth rate and gross conversion efficiency were studied in milkfish Chanos chanos for 28 days of exposure to sub-lethal concentrations of anthracene (1.00, 2.00, 3.00, 6.00 and 12.0 μg l(-1)) and benzo [a] pyrene (0.30, 0.70, 1.40, 2.80 and 5.60 μg l(-1)) under continuous flow through bioassays. Based on survival and growth data, No Observed Effect Concentration; Lowest Observed Effect Concentration were estimated after 28 days, the values for anthracene were 2.03 and 3.09 μg l(-1), and the values for benzo [a] pyrene were 0.82 and 1.46 μg l(-1), respectively. Anthracene and benzo [a] pyrene exposure caused reduction in feeding and growth rate.

A molecular-sized tunnel-porous crystal with a ratchet gear structure and its one-way guest-molecule transportation property

NASA Astrophysics Data System (ADS)

Kataoka, Keisuke; Yasumoto, Tetsuaki; Manabe, Yousuke; Sato, Hiroyasu; Yamano, Akihito; Katagiri, Toshimasa

2013-01-01

An anisotropic tunnel microporous crystal was prepared. Active transportation of anthracene as a guest molecule in the anisotropic tunnels was observed. The direction of anthracene movement implies that the anisotropic tunnel did not work as a flap-check valve. The direction of the movement was consistent with that caused by a Brownian ratchet.An anisotropic tunnel microporous crystal was prepared. Active transportation of anthracene as a guest molecule in the anisotropic tunnels was observed. The direction of anthracene movement implies that the anisotropic tunnel did not work as a flap-check valve. The direction of the movement was consistent with that caused by a Brownian ratchet. Electronic supplementary information (ESI) available. CCDC reference numbers 837539 and 837540. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2nr30880k

A new selective fluorene-based fluorescent internal charge transfer (ICT) sensor for sugar alcohols in aqueous solution.

PubMed

Hosseinzadeh, Rahman; Mohadjerani, Maryam; Pooryousef, Mona

2016-03-01

Sugar alcohols, such as sorbitol, are commonly used as a replacement for sucrose in the food industry, applied as starting material for vitamin C synthesis, and involved as one of the causative factors in diabetic complications. Therefore, their detection and quantification in aqueous solution are necessary. The reversible covalent interactions between boronic acids and diols are the basis of efficient methods for the detection of saccharides. Herein, we report a new internal charge transfer (ICT) fluorene-based fluorescent boronic acid sensor (1) 2-[(9,9-dimethyl-9H-fluoren-2-yl-amino)methyl] phenyl boronic acid that shows significant fluorescence changes upon addition of saccharides. The boronic acid has high affinity (K a = 1107.9 M(-1)) and selectivity for sorbitol at pH = 8.31. It showed a linear response toward sorbitol in the concentration range from 1.0 × 10(-5) to 6.0 × 10(-4) mol L(-1) with the detection limit of 7.04 × 10(-6) mol L(-1). Sensor 1 was used to detect sorbitol in real samples with good recovery.

Quantifying the atomic-level mechanics of single long physisorbed molecular chains.

PubMed

Kawai, Shigeki; Koch, Matthias; Gnecco, Enrico; Sadeghi, Ali; Pawlak, Rémy; Glatzel, Thilo; Schwarz, Jutta; Goedecker, Stefan; Hecht, Stefan; Baratoff, Alexis; Grill, Leonhard; Meyer, Ernst

2014-03-18

Individual in situ polymerized fluorene chains 10-100 nm long linked by C-C bonds are pulled vertically from an Au(111) substrate by the tip of a low-temperature atomic force microscope. The conformation of the selected chains is imaged before and after manipulation using scanning tunneling microscopy. The measured force gradient shows strong and periodic variations that correspond to the step-by-step detachment of individual fluorene repeat units. These variations persist at constant intensity until the entire polymer is completely removed from the surface. Calculations based on an extended Frenkel-Kontorova model reproduce the periodicity and magnitude of these features and allow us to relate them to the detachment force and desorption energy of the repeat units. The adsorbed part of the polymer slides easily along the surface during the pulling process, leading to only small oscillations as a result of the high stiffness of the fluorenes and of their length mismatch with respect to the substrate surface structure. A significant lateral force also is caused by the sequential detachment of individual units. The gained insight into the molecule-surface interactions during sliding and pulling should aid the design of mechanoresponsive nanosystems and devices.

Analysis and toxicity of 59 PAH in petrogenic and pyrogenic environmental samples including dibenzopyrenes, 7H-benzo[c]fluorene, 5-methylchrysene and 1-methylpyrene.

PubMed

Richter-Brockmann, Sigrid; Achten, Christine

2018-06-01

In this study 59 PAH were analyzed in samples of petrogenic and pyrogenic sources as well as mixed environmental matrices. Among the analytes, PAH of molecular weights from 128 Da to 302 Da in alkylated and in native form were included. Results show that non-EPA PAH make up 69.3–95.1% of the overall toxic equivalents (TEQ) as based on the toxic equivalent factors (TEF) of 24 PAH. Particularly 7H-benzo[c]fluorene, dibenzopyrene isomers and alkylated PAH (in particular 5-methylchrysene and 1-methylpyrene) turned out to have a huge impact on the toxicity and must not be neglected in future risk assessment. In detail, dibenzopyrenes have a high impact on toxicity predominantly in pyrogenic materials (21% to 84%; mean: 59%) whereas 7H-benzo[c]fluorene dominates toxicity of petrogenic materials (up to 80%; mean: 26%). However, in the studied mixed environmental samples the toxic impact of both groups together is as high as about 80%. Many non-EPA PAH are not considered in risk assessment and amongst them there are some very toxic ones. This needs to be carefully evaluated in future studies.

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

Biswas, Shubhadeep; Champion, Christophe; Weck, P. F.

Interaction between polycyclic aromatic hydrocarbon (PAH) molecule and energetic ion is a subject of interest in different areas of modern physics. Here, we present measurements of energy and angular distributions of absolute double differential electron emission cross section for coronene (C 24H 12) and fluorene (C 13H 10) molecules under fast bare oxygen ion impact. For coronene, the angular distributions of the low energy electrons are quite different from that of simpler targets like Ne or CH 4, which is not the case for fluorene. The behaviour of the higher electron energy distributions for both the targets are similar tomore » that for simple targets. In case of coronene, a clear signature of plasmon resonance is observed in the analysis of forward-backward angular asymmetry of low energy electron emission. For fluorene, such signature is not identified probably due to lower oscillator strength of plasmon compared to the coronene. The theoretical calculation based on the first-order Born approximation with correct boundary conditions (CB1), in general, reproduced the experimental observations qualitatively, for both the molecules, except in the low energy region for coronene, which again indicates the role of collective excitation. Single differential and total cross sections are also deduced. An overall comparative study is presented.« less

Benz[a]anthracene

Integrated Risk Information System (IRIS)

Benz [ a ] anthracene ; CASRN 56 - 55 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinoge

Polycyclic Aromatic Hydrocarbon Affects Acetic Acid Production during Anaerobic Fermentation of Waste Activated Sludge by Altering Activity and Viability of Acetogen.

PubMed

Luo, Jingyang; Chen, Yinguang; Feng, Leiyu

2016-07-05

Till now, almost all the studies on anaerobic fermentation of waste activated sludge (WAS) for bioproducts generation focused on the influences of operating conditions, pretreatment methods and sludge characteristics, and few considered those of widespread persistent organic pollutants (POPs) in sludge, for example, polycyclic aromatic hydrocarbons (PAHs). Herein, phenanthrene, which was a typical PAH and widespread in WAS, was selected as a model compound to investigate its effect on WAS anaerobic fermentation for short-chain fatty acids (SCFAs) accumulation. Experimental results showed that the concentration of SCFAs derived from WAS was increased in the presence of phenanthrene during anaerobic fermentation. The yield of acetic acid which was the predominant SCFA in the fermentation reactor with the concentration of 100 mg/kg dry sludge was 1.8 fold of that in the control. Mechanism exploration revealed that the present phenanthrene mainly affected the acidification process of anaerobic fermentation and caused the shift of the microbial community to benefit the accumulation of acetic acid. Further investigation showed that both the activities of key enzymes (phosphotransacetylase and acetate kinase) involved in acetic acid production and the quantities of their corresponding encoding genes were enhanced in the presence of phenanthrene. Viability tests by determining the adenosine 5'-triphosphate content and membrane potential confirmed that the acetogens were more viable in anaerobic fermentation systems with phenanthrene, which resulted in the increased production of acetic acid.

Homoleptic 2,2'-bipyridine metalates(-I) of iron and cobalt, one cocrystallized with an anthracene radical anion and the other with neutral anthracene.

PubMed

Brennessel, William W; Ellis, John E

2014-08-01

Homoleptic 2,2'-bipyridine (bipy) metalates of iron and cobalt have been synthesized directly from the corresponding homoleptic anthracene metalates. In the iron structure, bis[([2.2.2]cryptand)potassium(I)] tris(2,2'-bipyridine)ferrate(-I) anthracene(-I), [K(C18H36N2O6)]2[Fe(C10H8N2)3](C14H10), the asymmetric unit contains one potassium complex cation in a general position, the Fe center and one and a half bipy ligands of the ferrate complex on a crystallographic twofold axis that includes the Fe atom, and one half of an anthracene radical anion whose other half is generated by a crystallographic inversion center. The cations and anions are well separated and the geometry about the Fe center is essentially octahedral. In the cobalt structure, ([2.2.2]cryptand)potassium(I) bis(2,2'-bipyridine)cobaltate(-I) anthracene hemisolvate tetrahydrofuran (THF) disolvate, [K(C18H36N2O6)][Co(C10H8N2)2]·0.5C14H10·2C4H8O, the asymmetric unit contains the cation, anion, and both cocrystallized THF solvent molecules in general positions, and one half of a cocrystallized anthracene molecule whose other half is generated by a crystallographic inversion center. The cation and anion are well separated and the ligand planes in the cobaltate anion are periplanar. Each anthracene molecule is midway between and is oriented perpendicular to a pair of symmetry-related bipy ligands such that aromatic donor-acceptor interactions may play a role in the packing arrangement. The lengths of the bonds that connect the bipy rings support the assertion that the ligands are bipy radical anions in the iron structure. However, in the case of cobalt, these lengths are between the known ranges for a bipy radical anion and a bipy dianion, and therefore no conclusion can be made from the crystallography alone. One cocrystallized THF solvent molecule in the cobalt structure was modeled as disordered over three positions with appropriate geometric and thermal restraints, which resulted in a refined component mass ratio of 0.412 (4):0.387 (3):0.201 (3).

The variability of standard artificial soils: cadmium and phenanthrene sorption measured by a batch equilibrium method.

PubMed

Bielská, Lucie; Hovorková, Ivana; Kuta, Jan; Machát, Jiří; Hofman, Jakub

2017-01-01

Artificial soil (AS) is used in soil ecotoxicology as a test medium or reference matrix. AS is prepared according to standard OECD/ISO protocols and components of local sources are usually used by laboratories. This may result in significant inter-laboratory variations in AS properties and, consequently, in the fate and bioavailability of tested chemicals. In order to reveal the extent and sources of variations, the batch equilibrium method was applied to measure the sorption of 2 model compounds (phenanthrene and cadmium) to 21 artificial soils from different laboratories. The distribution coefficients (K d ) of phenanthrene and cadmium varied over one order of magnitude: from 5.3 to 61.5L/kg for phenanthrene and from 17.9 to 190L/kg for cadmium. Variations in phenanthrene sorption could not be reliably explained by measured soil properties; not even by the total organic carbon (TOC) content which was expected. Cadmium logK d values significantly correlated with cation exchange capacity (CEC), pH H2O and pH KCl , with Pearson correlation coefficients of 0.62, 0.80, and 0.79, respectively. CEC and pH H2O together were able to explain 72% of cadmium logK d variability in the following model: logK d =0.29pH H2O +0.0032 CEC -0.53. Similarly, 66% of cadmium logK d variability could be explained by CEC and pH KCl in the model: logKd=0.27pH KCl +0.0028 CEC -0.23. Variable cadmium sorption in differing ASs could be partially treated with these models. However, considering the unpredictable variability of phenanthrene sorption, a more reliable solution for reducing the variability of ASs from different laboratories would be better harmonization of AS preparation and composition. Copyright © 2016 Elsevier Inc. All rights reserved.

Dibenz[a,h]anthracene

Integrated Risk Information System (IRIS)

Dibenz [ a , h ] anthracene ; CASRN 53 - 70 - 3 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncar

Aggregation-induced emission enhancement of anthracene-derived Schiff base compounds and their application as a sensor for bovine serum albumin and optical cell imaging.

PubMed

Densil, Simon; Chang, Chien-Huei; Chen, Chia-Ling; Mathavan, Alagarsamy; Ramdass, Arumugam; Sathish, Veerasamy; Thanasekaran, Pounraj; Li, Wen-Shan; Rajagopal, Seenivasan

2018-06-01

Three anthracene-based Schiff base complexes, R1-R3 (R1 = (E)-N´-((anthracen-10-yl)methylene)benzohydrazide; R2 = (E)-1-((anthracen-10-yl)methylene)-4-phenylsemicarbazide; and R3 = (E)-1-((anthracen-10-yl)methylene)-4-phenylthiosemicarbazide) were synthesized from 9-anthracenecarboxaldehyde, benzohydrazide, 4-phenylsemicarbazide and 4-phenylthiosemi-carbazide respectively, and characterized by various spectral techniques. The absorption spectral characteristics of R1-R3 were bathochromically tuned to the visible region by extending the π conjugation. These target compounds were weakly fluorescent in tetrahydrofuran (THF) solution because of rapid isomerization of the C=N double bond in the excited state. However, the aqueous dispersion of R1-R3 in the THF/water mixture by the gradual addition of water up to 90% resulted in an increase in the fluorescence intensity mainly due to aggregation-induced emission enhancement (AIEE) properties. The formation of nanoaggregates of R1-R3 were confirmed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The compounds R1-R3 are ideal probes for the fluorescence sensing of bovine serum albumin (BSA) and breast cancer cells by optical cell imaging. Copyright © 2018 John Wiley & Sons, Ltd.

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface

NASA Astrophysics Data System (ADS)

Morbec, Juliana M.; Kratzer, Peter

2017-01-01

Using first-principles calculations based on density-functional theory (DFT), we investigated the effects of the van der Waals (vdW) interactions on the structural and electronic properties of anthracene and pentacene adsorbed on the Ag(111) surface. We found that the inclusion of vdW corrections strongly affects the binding of both anthracene/Ag(111) and pentacene/Ag(111), yielding adsorption heights and energies more consistent with the experimental results than standard DFT calculations with generalized gradient approximation (GGA). For anthracene/Ag(111) the effect of the vdW interactions is even more dramatic: we found that "pure" DFT-GGA calculations (without including vdW corrections) result in preference for a tilted configuration, in contrast to the experimental observations of flat-lying adsorption; including vdW corrections, on the other hand, alters the binding geometry of anthracene/Ag(111), favoring the flat configuration. The electronic structure obtained using a self-consistent vdW scheme was found to be nearly indistinguishable from the conventional DFT electronic structure once the correct vdW geometry is employed for these physisorbed systems. Moreover, we show that a vdW correction scheme based on a hybrid functional DFT calculation (HSE) results in an improved description of the highest occupied molecular level of the adsorbed molecules.

Effects of weathering on biological marker and aromatic hydrocarbon composition of organic matter in Phosphoria shale outcrop

USGS Publications Warehouse

Clayton, J.L.; King, J.D.

1987-01-01

GC-MS analyses were performed on core samples collected from a shale outcrop of the Permian Phosphoria Formation in Utah, U.S.A., to study effects of weathering on selected biological marker and aromatic (phenanthrene) hydrocarbon compounds. Among the biological markers, the most important weathering effects are a decrease in the 20S 20R diastereomer ratio of the C29 steranes and loss of low molecular weight triaromatic steroids. A decrease in the C19 through C22 tricylcic terpanes occurs relative to the total C19-C26 tricyclic fraction. Pronounced loss of methyl-substituted phenanthrenes occurs relative to phenanthrene. No major effect on the overall distribution of pentacyclic terpanes is evident. ?? 1987.

PEG and mPEG-anthracene induce DNA condensation and particle formation.

PubMed

Froehlich, E; Mandeville, J S; Arnold, D; Kreplak, L; Tajmir-Riahi, H A

2011-08-18

In this study, we investigated the binding of DNA with poly(ethylene glycol) (PEG) of different sizes and compositions such as PEG 3350, PEG 6000, and mPEG-anthracene in aqueous solution at physiological conditions. The effects of size and composition on DNA aggregation and condensation as well as conformation were determined using Fourier transform infrared (FTIR), UV-visible, CD, fluorescence spectroscopic methods and atomic force microscopy (AFM). Structural analysis showed moderate complex formation for PEG 3350 and PEG 6000 and weaker interaction for mPE-anthracene-DNA adducts with both hydrophilic and hydrophobic contacts. The order of ± stability of the complexes formed is K(PEG 6000) = 1.5 (±0.4) × 10(4) M(-1) > K(PEG 3350) = 7.9 (±1) × 10(3) M(-1) > K(m(PEG-anthracene))= 3.6 (±0.8) × 10(3) M(-1) with nearly 1 bound PEG molecule per DNA. No B-DNA conformational changes were observed, while DNA condensation and particle formation occurred at high PEG concentration.

Anti-inflammatory phenanthrene derivatives from stems of Dendrobium denneanum.

PubMed

Lin, Yuan; Wang, Fei; Yang, Li-Juan; Chun, Ze; Bao, Jin-Ku; Zhang, Guo-Lin

2013-11-01

Cultivated Dendrobium denneanum has been substituted for other endangered Dendrobium species in recent years, but there have been few studies regarding either its chemical constituents or pharmacological effects. In this study, three phenanthrene glycosides, three 9,10-dihydrophenanthrenes, two 9,10-dihydrophenanthrenes glycosides, and four known phenanthrene derivatives, were isolated from the stems of D. denneanum. Their structures were elucidated on the basis of MS and NMR spectroscopic data. Ten compounds were found to inhibit nitric oxide (NO) production in lipopolysaccharide (LPS)-activated mouse macrophage RAW264.7 cells with IC50 values of 0.7-41.5 μM, and exhibited no cytotoxicity in RAW264.7, HeLa, or HepG2 cells. Additionally, it was found that 2,5-dihydroxy-4-methoxy-phenanthrene 2-O-β-d-glucopyranoside, and 5-methoxy-2,4,7,9S-tetrahydroxy-9,10-dihydrophenanthrene suppressed LPS-induced expression of inducible NO synthase (iNOS) inhibited phosphorylation of p38, JNK as well as mitogen-activated protein kinase (MAPK), and inhibitory kappa B-α (IκBα). This indicated that both compounds exert anti-inflammatory effects by inhibiting MAPKs and nuclear factor κB (NF-κB) pathways. Copyright © 2013 Elsevier Ltd. All rights reserved.

Isolation, Characterization, and Polyaromatic Hydrocarbon Degradation Potential of Aerobic Bacteria from Marine Macrofaunal Burrow Sediments and Description of Lutibacterium anuloederans gen. nov., sp. nov., and Cycloclasticus spirillensus sp. nov.†

PubMed Central

Chung, W. K.; King, G. M.

2001-01-01

Two new polyaromatic hydrocarbon-degrading marine bacteria have been isolated from burrow wall sediments of benthic macrofauna by using enrichments on phenanthrene. Strain LC8 (from a polychaete) and strain M4-6 (from a mollusc) are aerobic and gram negative and require sodium chloride (>1%) for growth. Both strains can use 2- and 3-ring polycyclic aromatic hydrocarbons as their sole carbon and energy sources, but they are nutritionally versatile. Physiological and phylogenetic analyses based on 16S ribosomal DNA sequences suggest that strain M4-6 belongs to the genus Cycloclasticus and represents a new species, Cycloclasticus spirillensus sp. nov. Strain LC8 appears to represent a new genus and species, Lutibacterium anuloederans gen. nov., sp. nov., within the Sphingomonadaceae. However, when inoculated into sediment slurries with or without exogenous phenanthrene, only L. anuloederans appeared to sustain a significant phenanthrene uptake potential throughout a 35-day incubation. In addition, only L. anuloederans appeared to enhance phenanthrene degradation in heavily contaminated sediment from Little Mystic Cove, Boston Harbor, Boston, Mass. PMID:11722910

Focused ion beam and field-emission microscopy of metallic filaments in memory devices based on thin films of an ambipolar organic compound consisting of oxadiazole, carbazole, and fluorene units

USGS Publications Warehouse

Pearson, Christopher; Bowen, Leon; Lee, Myung Won; Fisher, Alison L.; Linton, Katherine E.; Bryce, Martin R.; Petty, Michael C.

2013-01-01

We report on the mechanism of operation of organic thin film resistive memory architectures based on an ambipolar compound consisting of oxadiazole, carbazole, and fluorene units. Cross-sections of the devices have been imaged by electron microscopy both before and after applying a voltage. The micrographs reveal the growth of filaments, with diameters of 50 nm–100 nm, on the metal cathode. We suggest that these are formed by the drift of aluminium ions from the anode and are responsible for the observed switching and negative differential resistance phenomena in the memory devices.

Chemical insight from density functional modeling of molecular adsorption: Tracking the bonding and diffusion of anthracene derivatives on Cu(111) with molecular orbitals

NASA Astrophysics Data System (ADS)

Wyrick, Jonathan; Einstein, T. L.; Bartels, Ludwig

2015-03-01

We present a method of analyzing the results of density functional modeling of molecular adsorption in terms of an analogue of molecular orbitals. This approach permits intuitive chemical insight into the adsorption process. Applied to a set of anthracene derivates (anthracene, 9,10-anthraquinone, 9,10-dithioanthracene, and 9,10-diselenonanthracene), we follow the electronic states of the molecules that are involved in the bonding process and correlate them to both the molecular adsorption geometry and the species' diffusive behavior. We additionally provide computational code to easily repeat this analysis on any system.

Functionalised polyurethane for efficient laser micromachining

NASA Astrophysics Data System (ADS)

Brodie, G. W. J.; Kang, H.; MacMillan, F. J.; Jin, J.; Simpson, M. C.

2017-02-01

Pulsed laser ablation is a valuable tool that offers a much cleaner and more flexible etching process than conventional lithographic techniques. Although much research has been undertaken on commercially available polymers, many challenges still remain, including contamination by debris on the surface, a rough etched appearance and high ablation thresholds. Functionalizing polymers with a photosensitive group is a novel way and effective way to improve the efficiency of laser micromachining. In this study, several polyurethane films grafted with different concentrations of the chromophore anthracene have been synthesized which are specifically designed for 248 nm KrF excimer laser ablation. A series of lines etched with a changing number of pulses and fluences by the nanosecond laser were applied to each polyurethane film. The resultant ablation behaviours were studied through optical interference tomography and Scanning Electron Microscopy. The anthracene grafted polyurethanes showed a vast improvement in both edge quality and the presence of debris compared with the unmodified polyurethane. Under the same laser fluence and number of pulses the spots etched in the anthracene contained polyurethane show sharp depth profiles and smooth surfaces, whereas the spots etched in polyurethane without anthracene group grafted present rough cavities with debris according to the SEM images. The addition of a small amount of anthracene (1.47%) shows a reduction in ablation threshold from unmodified polyurethane showing that the desired effect can be achieved with very little modification to the polymer.

Formation and Stabilization of Environmentally Persistent Free Radicals Induced by the Interaction of Anthracene with Fe(III)-Modified Clays.

PubMed

Jia, Hanzhong; Nulaji, Gulimire; Gao, Hongwei; Wang, Fu; Zhu, Yunqing; Wang, Chuanyi

2016-06-21

Environmentally persistent free radicals (EPFRs) are occasionally detected in Superfund sites but the formation of EPFRs induced by polycyclic aromatic hydrocarbons (PAHs) is not well understood. In the present work, the formation of EPFRs on anthracene-contaminated clay minerals was quantitatively monitored via electron paramagnetic resonance (EPR) spectroscopy, and surface/interface-related environmental influential factors were systematically explored. The obtained results suggest that EPFRs are more readily formed on anthracene-contaminated Fe(III)-montmorillonite than in other tested systems. Depending on the reaction condition, more than one type of organic radicals including anthracene-based radical cations with g-factors of 2.0028-2.0030 and oxygenic carbon-centered radicals featured by g-factors of 2.0032-2.0038 were identified. The formed EPFRs are stabilized by their interaction with interlayer surfaces, and such surface-bound EPFRs exhibit slow decay with 1/e-lifetime of 38.46 days. Transformation pathway and possible mechanism are proposed on the basis of experimental results and quantum mechanical simulations. Overall, the formation of EPFRs involves single-electron-transfer from anthracene to Fe(III) initially, followed by H2O addition on formed aromatic radical cation. Because of their potential exposure in soil and atmosphere, such clay surface-associated EPFRs might induce more serious toxicity than PAHs and exerts significant impacts on human health.

Differential electron emission from polycyclic aromatic hydrocarbon molecules under fast ion impact

DOE PAGES

Biswas, Shubhadeep; Champion, Christophe; Weck, P. F.; ...

2017-07-17

Interaction between polycyclic aromatic hydrocarbon (PAH) molecule and energetic ion is a subject of interest in different areas of modern physics. Here, we present measurements of energy and angular distributions of absolute double differential electron emission cross section for coronene (C 24H 12) and fluorene (C 13H 10) molecules under fast bare oxygen ion impact. For coronene, the angular distributions of the low energy electrons are quite different from that of simpler targets like Ne or CH 4, which is not the case for fluorene. The behaviour of the higher electron energy distributions for both the targets are similar tomore » that for simple targets. In case of coronene, a clear signature of plasmon resonance is observed in the analysis of forward-backward angular asymmetry of low energy electron emission. For fluorene, such signature is not identified probably due to lower oscillator strength of plasmon compared to the coronene. The theoretical calculation based on the first-order Born approximation with correct boundary conditions (CB1), in general, reproduced the experimental observations qualitatively, for both the molecules, except in the low energy region for coronene, which again indicates the role of collective excitation. Single differential and total cross sections are also deduced. An overall comparative study is presented.« less

40 CFR 464.31 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (dichloromethane) 55. naphthalene 64. pentachlorophenol 65. phenol 66. bis(2-ethylhexyl)phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 70. diethyl phthalate 71. dimethyl phthalate 72. benzo (a)anthracene (1,2...-ethylhexyl) phthalate 67. butyl benzyl phthalate 68. di-n-butyl phthalate 72. benzo (a)anthracene (1,2...

77 FR 10450 - Designation of Hazardous Substances; Designation, Reportable Quantities, and Notification

Federal Register 2010, 2011, 2012, 2013, 2014

2012-02-22

... K169 Benzene 220.0 K170 Benzene 1.2 Benzo (a) pyrene 230.0 Dibenz (a,h) anthracene... 49.0 Benzo (a......... 27.0 7, 12-Dimethylbenz (a) 1,200.0 anthracene. K171 Benzene 500.0 Arsenic 1,600.0 K172 Benzene 100.0...

A convenient synthesis of tetrabenzo[de,hi,mn,qr]naphthacene from readily available 1,2-di(phenanthren-4-yl)ethyne.

PubMed

Mukherjee, Anupam; Pati, Kamalkishore; Liu, Rai-Shung

2009-08-21

We report here a convenient synthesis of tetrabenzo[de,hi,mn,qr]naphthacenes from 1,2-di(phenanthren-4-yl)ethynes through initial Brønsted acid-catalyzed hydroarylation, followed by FeCl(3)-oxidative coupling reactions. This new method is applicable to tetrabenzo[de,hi,mn,qr]naphthacenes bearing various alkyl substituents.

Toxicity of combined chromium(VI) and phenanthrene pollution on the seed germination, stem lengths, and fresh weights of higher plants.

PubMed

Hu, Shuangqing; Gu, Hairong; Cui, Chunyan; Ji, Rong

2016-08-01

Studies of the interaction and toxicity of pollutant combinations such as heavy metals and PAHs are of practical importance in the remediation and monitoring of the industrial soil environment. This study investigated the single and combined toxicity of chromium(VI) and phenanthrene on three important higher plants: mung beans (Phaseolus aureus), pakchoi cabbage (Brassica chinensis), and rice (Oryza sativa). In experiments using artificial soil matrix, the EC10 and EC20 of the two pollutants, alone and in combination, were analyzed with respect to seed germination, stem length, and above-ground fresh weight of these higher plants. The additive index method was used to evaluate the combined biological toxicity of chromium(VI) and phenanthrene. The results showed that the EC20 of chromium(VI) on the stem lengths of mung beans, pakchoi cabbage, and rice was 289, 248, and 550 mg kg(-1), respectively. The corresponding EC20 values for the fresh weights of the three plants were 334, 307, and 551 mg kg(-1). The EC20 of phenanthrene on the stem lengths of mung beans, pakchoi cabbage, and rice was 528, 426, and 628 mg kg(-1), respectively. The corresponding EC20 values for the fresh weights of the three plants were 696, 585, and 768 mg kg(-1). The EC20 of a combination of chromium(VI) and phenanthrene on the stem lengths of mung beans, pakchoi cabbage, and rice was 192, 173, and 279 mg kg(-1), respectively, and 200, 205, and 271 mg kg(-1) for the fresh weights of the three plants. The single and combined exposure of soil to chromium(VI) and phenanthrene had deleterious effects on plants in the early stage of growth. Overall, pakchoi cabbage was more sensitive than mung beans and rice. The two pollutants exerted synergistic effects on the stem lengths and above-ground fresh weights of both mung beans and rice but antagonistic effects on pakchoi cabbage. The results of this study also suggested pakchoi cabbage as a sensitive indicator of soil pollution.

Biomass burning influences determination based on PM2.5 chemical composition combined with fire counts at southeastern Tibetan Plateau during pre-monsoon period

NASA Astrophysics Data System (ADS)

Zhang, Ningning; Cao, Junji; Wang, Qiyuan; Huang, Rujin; Zhu, Chongshu; Xiao, Shun; Wang, Linlin

2018-07-01

Influences of biomass burning (BB) on a high altitude site were investigated by collecting fine particulate matter (PM2.5) samples from 29 March to 27 April of 2012 at Mt. Yulong (4500 m above sea level), and analyzing them for selected chemical species including water soluble ions (WSIs), organic carbon (OC), elemental carbon (EC), polycyclic aromatic hydrocarbons (PAHs) and n-alkanes. The mean PM2.5 mass loading for the study was 6.30 ± 4.90 μg m-3, and 15.48 ± 2.82 μg m-3 and 1.75 ± 0.41 μg m-3 for a high and a low PM episode, respectively. WSIs accounted for 62% of the total mass, and SO42- was the dominant anion and NH4+ was the main cation. PAHs were mainly 3 ring compounds, fluorene (Flo) and phenanthrene (Phe) together accounted for 54% of the total PAHs. For n-alkanes, n-Nonacosane (C29) concentration was the highest with the value of 1.09 ± 1.18 ng m-3, following is n-Hentriacontane (C31) and n-Heptacosane (C27) suggested that n-alkane in our samples were mainly contributed by biogenic sources. BB emission was confirmed by the diagnostic ratios, and it also had a significant influence on aerosol optical depth (AOD) distribution and enhances the concentration of most species, especially for OC, K+ and EC. Significant relationships were found between daily fire counts and BB species, and correlation coefficients (r) for mass, K+, OC, and EC were 0.58, 0.57, 0.53 and 0.60 (n = 29, P < 0.01), respectively. It indicated that daily fire counts can advance our understanding of how biomass burning affect aerosols and air quality at a high-altitude site.

Effect of linear alkylbenzene sulphonate (LAS) on the mineralization, metabolism and uptake of 14C-phenanthrene in a model ecosystem (water-lava-plant-air).

PubMed

Jiang, Xia; Yediler, Ayfer; Yufang, Song; Sun, Tieheng; Kettrup, Antonius

2005-11-01

The aim of this work was to evaluate the effect of linear alkylbenzene sulfonate (LAS, 200 mg l(-1)) on the fate of phenanthrene in a model ecosystem "water-lava-hydrophytes-air". The experiments were conducted using two closed cultivation chamber systems. Rushes (Juncus effesus) were selected as a representative hydrophyte. Five hundred micrograms per liter of phenanthrene in a culture solution containing a 14C-activity of 75 microCi per chamber was applied (i) to investigate the degradation of the labeled test substance and the transfer processes within the system; (ii) to determine the mass-balance possible and (iii) to detect the occurrence of volatile test substances, their volatile metabolites and the degradation end-product CO2 in the gas phase. Most of the applied 14C-activity was found in the plant (41-45%), in which approximately 95% was associated with plant roots and approximately 5% with shoots. The 14C-activity recovered in the form of VOCs and CO2 was measured in lava (18-29%, 8-11%), and in the culture solution (10-14% and 1%), respectively. Majority of the applied 14C-activity existed in two forms, i.e. (1) polar metabolites (26%), of which 91% were found in plant roots, and (2) un-extractable residues (23%), most of which were in plant roots (40%) and bounded to lava (58%). The presence of LAS significantly increased the volatilization of phenanthrene and its metabolites, inhibited its mineralization and decreased the level of 14C-activity in lava. Moreover, LAS reduced the phenanthrene level in plant roots.

Stable-Isotope Probing of Bacteria Capable of Degrading Salicylate, Naphthalene, or Phenanthrene in a Bioreactor Treating Contaminated Soil

PubMed Central

Singleton, David R.; Powell, Sabrina N.; Sangaiah, Ramiah; Gold, Avram; Ball, Louise M.; Aitken, Michael D.

2005-01-01

[13C6]salicylate, [U-13C]naphthalene, and [U-13C]phenanthrene were synthesized and separately added to slurry from a bench-scale, aerobic bioreactor used to treat soil contaminated with polycyclic aromatic hydrocarbons. Incubations were performed for either 2 days (salicylate, naphthalene) or 7 days (naphthalene, phenanthrene). Total DNA was extracted from the incubations, the “heavy” and “light” DNA were separated, and the bacterial populations associated with the heavy fractions were examined by denaturing gradient gel electrophoresis (DGGE) and 16S rRNA gene clone libraries. Unlabeled DNA from Escherichia coli K-12 was added to each sample as an internal indicator of separation efficiency. While E. coli was not detected in most analyses of heavy DNA, a low number of E. coli sequences was recovered in the clone libraries associated with the heavy DNA fraction of [13C]phenanthrene incubations. The number of E. coli clones recovered proved useful in determining the relative amount of light DNA contamination of the heavy fraction in that sample. Salicylate- and naphthalene-degrading communities displayed similar DGGE profiles and their clone libraries were composed primarily of sequences belonging to the Pseudomonas and Ralstonia genera. In contrast, heavy DNA from the phenanthrene incubations displayed a markedly different DGGE profile and was composed primarily of sequences related to the Acidovorax genus. There was little difference in the DGGE profiles and types of sequences recovered from 2- and 7-day incubations with naphthalene, so secondary utilization of the 13C during the incubation did not appear to be an issue in this experiment. PMID:15746319

Cell and microsome mediated binding of 7,12-dimethylbenz(a)anthracene to DNA studied by fluorescence spectroscopy.

PubMed

Ivanovic, V; Geacintov, N E; Jeffrey, A M; Fu, P P; Harvey, R G; Weinstein, I B

1978-03-01

Fluorescence spectra of DNA isolated from hamster embryo cells incubated with 7,12-dimethylbenz(a)anthracene, or DNA modified in a microsomal system by reaction with this carcinogen or its 7-hydroxymethyl derivative, were compared to various model compounds. The spectra indicate that the DMBA derivative bound to DNA, in all 3 cases, has a 9,10-dimethylanthracene-like chromophore. They also provide the first evidence of the similarity in structure of the DNA-bound products between 7,12-dimethylbenz(a)anthracene and its 7-hydroxymethyl derivative. Our results are consistent with an activation mechanism that involves saturation of the 1,2,3,4-ring positions.

The 2.5-diacyl-1,4-dimethylbenzenes: Examples of bisphotoenol equivalents

NASA Technical Reports Server (NTRS)

Meador, Michael A.

1987-01-01

The photochemistry of 2,5-dibenzoyl(DBX)-and 2,5-diacetyl-1,4-dimethylbenzene (DAX) has been investigated. Both compounds readily undergo photoenolization similar to 0-alkylphenyl ketones. However, unlike 0-alkylphenyl ketones DAX and DBX are each capable of undergoing two tandem photoenolizations. Photoenols derived from o-alkylphenyl ketones have been successfully trapped with Diels-Alder dienophiles to provide a convenient synthesis of substituted tetralins. Similarly, Diels-Alder trapping of DBX photoenils afforded substituted tetra- and octahydro anthracenes. Further mainpulation of these photadducts provided the corresponding anthracenes in good yield. The photochemistry of DAX and DBX will be discussed, in particular their use in the synthesis of substituted anthracenes.

Effects of simulated solar radiation on the bioaccumulation of polycyclic aromatic hydrocarbons by the duckweed, Lemna gibba

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

Duxbury, C.L.; Dixon, D.G.; Greenberg, B.M.

1997-08-01

Light (particularly ultraviolet B) results in photomodification of polycyclic aromatic hydrocarbons (PAHs) to products with increased polarity and water solubility and enhanced toxicity relative to the parent compounds. The uptake and depuration kinetics of three representative PAHs, anthracene (ANT), phenanthrene (PHE), and benzo[a]pyrene (BAP), and their photomodified products were determined for Lemna gibba. The {sup 14}C-labeled PAHs were delivered to the plants in their aqueous growth medium either via a dimethylsulfoxide (DMSO) carrier or adsorbed directly to sand placed in the medium. Assimilation was carried out under simulated solar radiation (SSR) and in darkness. The potential sites of PAH actionmore » within the plants were defined by identifying the subcellular location of both intact and photomodified PAHs following assimilation. Lemna gibba had a high capacity for intact ANT, PHE, and BAP in the dark regardless of the two routes of delivery. Depuration was also rapid. Net assimilation of all three PAHs in the dark was always higher when the chemicals were delivered with DMSO than from sand, although first-order kinetics were apparent with both delivery systems. The relative levels of assimilation were PHE > ANT > BAP. Polycyclic aromatic hydrocarbons were rapidly assimilated under SSR, albeit net assimilation for both the intact and photomodified forms was generally lower under SSR compared with darkness. This was also reflected in the bioconcentration factors, which were highest in darkness for each PAH and dropped significantly under SSR and after photomodification. Both intact and photooxidized PAHs accumulated preferentially in the thylakoids and microsomes of L. gibba, suggesting these to be the subcellular compartments most at risk from PAH damage.« less

Presence, distribution and risk assessment of polycyclic aromatic hydrocarbons in rice-wheat continuous cropping soils close to five industrial parks of Suzhou, China.

PubMed

Li, Yong; Long, Ling; Ge, Jing; Yang, Li-Xuan; Cheng, Jin-Jin; Sun, Ling-Xiang; Lu, Changying; Yu, Xiang-Yang

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) accumulated in agricultural soils are likely to threaten human health and ecosystem though the food chain, therefore, it is worth to pay more attention to soil contamination by PAHs. In this study, the presence, distribution and risk assessment of 16 priority PAHs in rice-wheat continuous cropping soils close to industrial parks of Suzhou were firstly investigated. The concentrations of the total PAHs ranged from 125.99 ng/g to 796.65 ng/g with an average of 352.94 ng/g. Phenanthrene (PHE), fluoranthene (FLT), benzo [a] anthracene (BaA) and pyrene (PYR) were the major PAHs in those soil samples. The highest level of PAHs was detected in the soils around Chemical plant and Steelworks, followed by Printed wire board, Electroplate Factory and Paper mill. The composition of PAHs in the soils around Chemical plant was dominated by 3-ring PAHs, however, the predominant compounds were 4, 5-ring PAHs in the soils around other four factories. Meanwhile, the concentration of the total PAHs in the soils close to the factories showed a higher level of PAHs in November (during rice harvest) than that in June (during wheat harvest). Different with other rings of PAHs, 3-ring PAHs in the soils around Chemical plant and Steelworks had a higher concentration in June. The results of principal component analysis and isomeric ratio analysis suggested that PAHs in the studied areas mainly originated from biomass, coal and petroleum combustion. The risk assessment indicated that higher carcinogenic risk was found in those sites closer to the industrial park. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

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.

Photodegradation of polycyclic aromatic hydrocarbons in soils under a climate change base scenario.

PubMed

Marquès, Montse; Mari, Montse; Audí-Miró, Carme; Sierra, Jordi; Soler, Albert; Nadal, Martí; Domingo, José L

2016-04-01

The photodegradation of polycyclic aromatic hydrocarbons (PAHs) in two typical Mediterranean soils, either coarse- or fine-textured, was here investigated. Soil samples, spiked with the 16 US EPA priority PAHs, were incubated in a climate chamber at stable conditions of temperature (20 °C) and light (9.6 W m(-2)) for 28 days, simulating a climate change base scenario. PAH concentrations in soils were analyzed throughout the experiment, and correlated with data obtained by means of Microtox(®) ecotoxicity test. Photodegradation was found to be dependent on exposure time, molecular weight of each hydrocarbon, and soil texture. Fine-textured soil was able to enhance sorption, being PAHs more photodegraded than in coarse-textured soil. According to the EC50 values reported by Microtox(®), a higher detoxification was observed in fine-textured soil, being correlated with the outcomes of the analytical study. Significant photodegradation rates were detected for a number of PAHs, namely phenanthrene, anthracene, benzo(a)pyrene, and indeno(123-cd)pyrene. Benzo(a)pyrene, commonly used as an indicator for PAH pollution, was completely removed after 7 days of light exposure. In addition to the PAH chemical analysis and the ecotoxicity tests, a hydrogen isotope analysis of benzo(a)pyrene was also carried out. The degradation of this specific compound was associated to a high enrichment in (2)H, obtaining a maximum δ(2)H isotopic shift of +232‰. This strong isotopic effect observed in benzo(a)pyrene suggests that compound-specific isotope analysis (CSIA) may be a powerful tool to monitor in situ degradation of PAHs. Moreover, hydrogen isotopes of benzo(a)pyrene evidenced a degradation process of unknown origin occurring in the darkness. Copyright © 2016 Elsevier Ltd. All rights reserved.

Enrichment and identification of polycyclic aromatic compound-degrading bacteria enriched from sediment samples.

PubMed

Long, Rachel M; Lappin-Scott, Hilary M; Stevens, Jamie R

2009-07-01

The degradation of polycyclic aromatic compounds (PACs) has been widely studied. Knowledge of the degradation of PACs by microbial populations can be utilized in the remediation of contaminated sites. To isolate and identify PAC-degrading bacteria for potential use in future bioremediation programmes, we established a series of PAC enrichments under the same experimental conditions from a single sediment sample taken from a highly polluted estuarine site. Enrichment cultures were established using the pollutants: anthracene, phenanthrene and dibenzothiophene as a sole carbon source. The shift in microbial community structure on each of these carbon sources was monitored by analysis of a time series of samples from each culture using 16S rRNA polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE). Significantly, our findings demonstrate that shifts in the constituent species within each degradative community are directly attributable to enrichment with different PACs. Subsequently, we characterized the microorganisms comprising the degradative communities within each enrichment using 16S rRNA sequence data. Our findings demonstrate that the ability to degrade PACs is present in five divisions of the Proteobacteria and Actinobacteria. By determining the precise identity of the PAC-degrading bacterial species isolated from a single sediment sample, and by comparing our findings with previously published research, we demonstrate how bacteria with similar PAC degrading capabilities and 16S rRNA signatures are found in similarly polluted environments in geographically very distant locations, e.g., China, Italy, Japan and Hawaii. Such a finding suggests that geographical barriers do not limit the distribution of key PAC-degrading bacteria; this finding is in accordance with the Baas-Becking hypothesis "everything is everywhere; the environment selects" and may have significant consequences for the global distribution of PAC-degrading bacteria and their use in bioremediation.

A lifestyle-based scenario for U.S. buildings: Implications for energy use

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

Diamond, Rick

Dynamic measures of air and vegetation concentrations in an exposure chamber and a two-box mass balance model are used to quantify factors that control the rate and extent of chemical partitioning between vegetation and the atmosphere. A continuous stirred flow-through exposure chamber was used to investigate the gas-phase transfer of pollutants between air and plants. A probabilistic two-compartment mass-balance model of plant/air exchange within the exposure chamber was developed and used with measured concentrations from the chamber to simultaneously evaluate partitioning (K{sub pa}), overall mass transfer across the plant/air interface (U{sub pa}) and loss rates in the atmosphere (R{sub a})more » and aboveground vegetation (R{sub p}). The approach is demonstrated using mature Capsicum annuum (bell pepper) plants exposed to phenanthrene (PH), anthracene (AN), fluoranthene (FL) and pyrene (PY). Measured values of log K{sub pa} (V{sub [air]}/V{sub [fresh plant]}) were 5.7, 5.7, 6.0 and 6.2 for PH, AN, FL and PY, respectively. Values of U{sub pa} (m d{sup -1}) under the conditions of this study ranged from 42 for PH to 119 for FL. After correcting for wall effects, the estimated reaction half-lives in air were 3, 9 and 25 hours for AN, FL and PY. Reaction half-lives in the plant compartment were 17, 6, 17 and 5 days for PH, AN, FL and PY. The combined use of exposure chamber measurements and models provides a robust tool for simultaneously measuring several different transfer factors that are important for modeling the uptake of pollutants into vegetation.« less

Biochemical studies on a versatile esterase that is most catalytically active with polyaromatic esters

PubMed Central

Martínez-Martínez, Mónica; Lores, Iván; Peña-García, Carlina; Bargiela, Rafael; Reyes-Duarte, Dolores; Guazzaroni, María-Eugenia; Peláez, Ana Isabel; Sánchez, Jesús; Ferrer, Manuel

2014-01-01

Herein, we applied a community genomic approach using a naphthalene-enriched community (CN1) to isolate a versatile esterase (CN1E1) from the α/β-hydrolase family. The protein shares low-to-medium identity (≤ 57%) with known esterase/lipase-like proteins. The enzyme is most active at 25–30°C and pH 8.5; it retains approximately 55% of its activity at 4°C and less than 8% at ≥ 55°C, which indicates that it is a cold-adapted enzyme. CN1E1 has a distinct substrate preference compared with other α/β-hydrolases because it is catalytically most active for hydrolysing polyaromatic hydrocarbon (phenanthrene, anthracene, naphthalene, benzoyl, protocatechuate and phthalate) esters (7200–21 000 units g−1 protein at 40°C and pH 8.0). The enzyme also accepts 44 structurally different common esters with different levels of enantio-selectivity (1.0–55 000 units g−1 protein), including (±)-menthyl-acetate, (±)-neomenthyl acetate, (±)-pantolactone, (±)-methyl-mandelate, (±)-methyl-lactate and (±)-glycidyl 4-nitrobenzoate (in that order). The results provide the first biochemical evidence suggesting that such broad-spectrum esterases may be an ecological advantage for bacteria that mineralize recalcitrant pollutants (including oil refinery products, plasticizers and pesticides) as carbon sources under pollution pressure. They also offer a new tool for the stereo-assembly (i.e. through ester bonds) of multi-aromatic molecules with benzene rings that are useful for biology, chemistry and materials sciences for cases in which enzyme methods are not yet available. PMID:24418210

Pleiotropic effect of fluoranthene on anthocyanin synthesis and nodulation of Medicago sativa is reversed by the plant flavone luteolin

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

Wetzel, A.; Parniske, M.; Werner, D.

1995-05-01

The symbiosis between leguminous plants and soil bacteria of the genus Rhizobium is of considerable agronominal importance. Recently it has been found, that polycyclic aromatic hydrocarbons (PAHs; e.g. anthracene, phenanthrene, fluoranthene), occurring as ubiquitous environmental contaminants can inhibit nodulation of Medicago sativa. Fluoranthene is one of the dominant PAHs found in urban particulate matter, sewage sludge or beside motorways. Several organisms have been shown to be able to metabolize and mineralize fluoranthene but the uptake of fluoranthene is limited due to low solubility of fluoranthene in water and strong adsorption to humic substances in soil. Rhizobium meliloti cannot degrade fluoranthene.more » Toxic effects of fluoranthene on bacterial growth have never been observed. In contrast to their rhizobial symbiotic partners, alfalfa plants grown on a solidified fluoranthene-containing medium, exhibited symptoms of toxicity. They showed a dose-responsive decrease in shoot length and, if inoculated with R. meliloti, inhibition of nodule formation. Growth retardation is accompanied by a decrease in anthocyanin pigmentation of shoots, and an atypical accumulation of anthocyanins in roots. Plant flavonoids are known to play a central role in the signal exchange of the Legume-Rhizobium symbiosis. Phenylpropane derived compounds and flavonoids have been implicated in nodule development. Since fluoranthene impairs nodulation and induces the production of anthocyanins, it is possible that these events are causally linked via phenylpropanoid metabolism. These experiments attempt to overcome the inhibitory effects of fluoranthene by exogeneous application of the flavonoid luteolin. This paper demonstrates that luteolin antagonizes the fluoranthene mediated inhibition of nodule formation and prevents the accumulation of anthocyanins in roots. 29 refs., 4 figs., 1 tab.« less

How does predation affect the bioaccumulation of hydrophobic organic compounds in aquatic organisms?

PubMed

Xia, Xinghui; Li, Husheng; Yang, Zhifeng; Zhang, Xiaotian; Wang, Haotian

2015-04-21

It is well-known that the body burden of hydrophobic organic compounds (HOCs) increases with the trophic level of aquatic organisms. However, the mechanism of HOC biomagnification is not fully understood. To fill this gap, this study investigated the effect of predation on the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs), one type of HOC, in low-to-high aquatic trophic levels under constant freely dissolved PAH concentrations (1, 5, or 10 μg L(-1)) maintained by passive dosing systems. The tested PAHs included phenanthrene, anthracene, fluoranthene, and pyrene. The test organisms included zebrafish, which prey on Daphnia magna, and cichlids, which prey on zebrafish. The results revealed that for both zebrafish and cichlids, predation elevated the uptake and elimination rates of PAHs. The increase of uptake rate constant ranged from 20.8% to 39.4% in zebrafish with the amount of predation of 5 daphnids per fish per day, and the PAH uptake rate constant increased with the amount of predation. However, predation did not change the final bioaccumulation equilibrium; the equilibrium concentrations of PAHs in fish only depended on the freely dissolved concentration in water. Furthermore, the lipid-normalized water-based bioaccumulation factor of each PAH was constant for fish at different trophic levels. These findings infer that the final bioaccumulation equilibrium of PAHs is related to a partition between water and lipids in aquatic organisms, and predation between trophic levels does not change bioaccumulation equilibrium but bioaccumulation kinetics at stable freely dissolved PAH concentrations. This study suggests that if HOCs have not reached bioaccumulation equilibrium, biomagnification occurs due to enhanced uptake rates caused by predation in addition to higher lipid contents in higher trophic organisms. Otherwise, it is only due to the higher lipid contents in higher trophic organisms.

[Transportation and transformation of 14C-phenanthrene in closed chamber (nutrient solution-lava-plant-air) system].

PubMed

Jiang, X; Ou, Z; Ying, P; Yediler, A; Ketrrup, A

2001-06-01

The transportation and transformation of 14C-phenanthrene in a closed 'plant-lava-nutrient solution-air' chamber system was studied by using radioactivity technology. The results showed that in this closed chamber system, phenanthrene was degraded fast. The radioactivity of 14C left at 23d in the nutrient solution was only 25% of applied. At the end of experiment (46d), the distribution sequence of 14C activity in the components of closed chamber system was root (38.55%) > volatile organic compounds (VOCs, 17.68%) > lava (14.35%) > CO2 (11.42%) > stem (2%). 14C-activities in plant tissue were combined with the tissue, and existed in the forms of lava-bound(root 4.68%; stem and leaves 0.68%) and polar metabolites (root 23.14%; stem 0.78%).

Bioactive Phenanthrene and Bibenzyl Derivatives from the Stems of Dendrobium nobile.

PubMed

Zhou, Xue-Ming; Zheng, Cai-Juan; Gan, Li-She; Chen, Guang-Ying; Zhang, Xiao-Peng; Song, Xiao-Ping; Li, Gao-Nan; Sun, Chong-Ge

2016-07-22

A new enantiomeric pair of spirodiketones, (+)- and (-)-denobilone A (1 and 2), three new phenanthrene derivatives (3-5), and three new biphenanthrenes (22-24), along with 11 known phenanthrene derivatives (6-16), five known bibenzyl derivatives (17-21), and four known biphenanthrenes (25-28), were isolated from Dendrobium nobile. The structures of 1-5 and 22-24 were elucidated using comprehensive spectroscopic methods. (+)-Denobilone and (-)-denobilone A (1 and 2) were isolated as a pair of enantiomers by chiral HPLC. The absolute configurations of (+)- and (-)-denobilone A (1 and 2) were determined by comparing their experimental and calculated electronic circular dichroism spectra. The absolute configuration of denobilone B (3) was determined by X-ray crystallographic analysis. The inhibitory activities of all compounds against nine phytopathogenic fungi and three cancer cell lines were evaluated.

New phenanthrene and 9, 10-dihydrophenanthrene derivatives from the stems of Dendrobium officinale with their cytotoxic activities.

PubMed

Zhao, Gui-Yun; Deng, Bo-Wen; Zhang, Chong-Yu; Cui, Yi-Da; Bi, Jia-Yi; Zhang, Guo-Gang

2018-01-01

Two new phenanthrene and 9, 10-dihydrophenanthrene derivatives (1-2) with six known congeners (3-8) were isolated from the extraction of stems of Dendrobium officinale. Compounds 1 and 2 were based on carbon skeleton in which phenanthrene and 9, 10-dihydrophenanthrene moiety were linked with a phenylpropane unit through a dioxane bridge, respectively. Their structures were determined by comprehensive NMR spectroscopic data, the absolute configuration of new compounds were determined by comparing their experimental and calculated ECD for the first time. All the compounds were investigated contains two cancer cell lines (HI-60, THP-1). All the isolates showed cytotoxicity, especially compound 4 showed markedly cytotoxic activities against HI-60 and THP-1 cell lines with IC 50 values of 11.96 and 8.92 μM.

ATRAZINE INCREASES DIMETHYLBENZ[A]ANTHRACENE-INDUCED MAMMARY TUMOR INCIDENCE IN LONG EVANS OFFSPRING EXPOSED IN UTERO

EPA Science Inventory

ATRAZINE INCREASES DIMETHYLBENZ[A]ANTHRACENE-INDUCED MAMMARY TUMOR INCIDENCE IN LONG EVANS OFFSPRING EXPOSED IN UTERO.

SE Fenton and CC Davis

Reproductive Toxicology Division, NHEERL, ORD, USEPA, Durham, NC, USA

Recently, we found that ATR exposure during ma...

Chloride channel blockers activate an endogenous cationic current in oocytes of Bufo arenarum.

PubMed

Cavarra, M S; del Mónaco, S M; Kotsias, B A

2004-07-01

A two-electrode, voltage-clamp technique was used to measure the effect of the Cl(-) channel blockers, 9-anthracene carboxylic acid and niflumic acid, upon the ionic currents of oocytes of the South American toad Bufo arenarum. The main results were: (1) both blockers produced a reversible increase of the outward currents on a dose-dependent manner; (2) the activated outward current was voltage dependent; (3) the 9-anthracene carboxylic acid-sensitive current was blocked with barium; and (4) the effect of 9-anthracene carboxylic acid was more pronounced in a zero-K(+) solution than in standard (2 mmol l(-1)) or high (20 mmol l(-1)) K(+) solutions, indicating that a K(+) conductance is activated. The effect of the Cl(-) channel blockers could be due to a direct interaction with endogenous cationic channels. Another possible explanation is that Cl(-) that enter the cell during depolarizing steps in control solution inhibit this cationic conductance; thus, the blockade of Cl(-) channels by 9-anthracene carboxylic acid and niflumic acid would remove this inhibition, allowing the cationic current to flow freely.

Ozonation of mutagenic and carcinogenic polyaromatic amines and polyaromatic hydrocarbons in water

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

Burleson, G.R.; Caulfield, M.J.; Pollard, M.

1979-06-01

The Salmonella-microsome assay for mutagenesis was used to determine the effect of ozone on the mutagenesis of selected carcinogens and mutagens in water. Short periods of ozonation were shown to completely inactivate the mutagenicity of several polyaromatic amine mutagens including acriflavine, proflavine, and beta-naphthylamine. Selected polyaromatic hydrocarbons were also sensitive to ozonation. Kinetic studies revealed that the mutagenicity of benzo(a)pyrene, 3-methylcholanthrene, and 7,12-dimethylbenz(a)anthracene was destroyed after short periods of ozonation. To correlate loss of mutagenicity with loss of carcinogenicity, two polyaromatic hydrocarbons were treated with ozone, extracted from water with hexane, and tested for carcinogenicity in mice. When 7,12-dimethyl-benz(a)anthracene andmore » 3-methyl-cholanthrene were treated with ozone, there was a substantial reduction in carcinogenicity compared to control groups treated with oxygen alone. However, a small number of tumors developed in the group of animals receiving a hexane extract of ozonated 7,12-dimethylbenz(a)anthracene. This activity may be due to breakdown products of 7,12-dimethylbenz(a)anthracene that are not mutagenic.« less

Hydrogen rearrangements in the fragmentation of anthracene by low-energy electron impact

NASA Astrophysics Data System (ADS)

van der Burgt, Peter J. M.; Dunne, Melissa; Gradziel, Marcin L.

2018-02-01

We have measured mass spectra for positive ions produced by low-energy electron impact on anthracene using a reflectron time-of-flight mass spectrometer. The electron impact energy has been varied from 0 to 100 eV in steps of 0.5 eV. Ion yield curves of most of the fragment ions have been determined by fitting groups of adjacent peaks in the mass spectra with sequences of normalized Gaussians. Appearance energies for all these ions have been determined, and we report the first direct measurement of the triple ionization energy of anthracene at 45.5±0.5 eV. The groups of fragments containing 8-13 carbon atoms provide evidence for hydrogen rearrangements during the fragmentation, involving retention or loss of one or two additional hydrogen atoms. Groups of fragments with 6 and 7 carbon atoms clearly show the presence of doubly-charged fragments. The smaller fragments with 1-4 carbon atoms all show broadened peaks, and these fragments may be partly or mostly due to energetic charge-separation fragmentations of doubly-charged anthracene.

Charge-Transfer-Induced Fluorescence Quenching of Anthracene Derivatives and Selective Detection of Picric Acid.

PubMed

Santra, Dines Chandra; Bera, Manas Kumar; Sukul, Pradip Kumar; Malik, Sudip

2016-02-01

2,6-Divinylpyridine-appended anthracene derivatives flanked by two alkyl chains at the 9,10-position of the core have been designed, synthesized, and characterized by NMR, MALDI-TOF, FTIR, and single-crystal XRD. These anthracene derivatives are able to recognize picric acid (2,4,6-trinitrophenol, PA) selectively down to parts per billion (ppb) level in aqueous as well as nonaqueous medium. Fluorescence emission of these derivatives in solution is significantly quenched by adding trace amounts of PA, even in the presence of other competing analogues, such as 2,4-dinitrophenol (2,4-DNP), 4-nitrophenol (NP), nitrobenzene (NB), benzoic acid (BA), and phenol (PH). The high sensitivity of these derivatives toward PA is considered as a combined effect of the proton-induced intramolecular charge transfer (ICT) as well as electron transfer from the electron-rich anthracene to the electron-deficient PA. Moreover, visual detection of PA has been successfully demonstrated in the solid state by using different substrates. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toward clean suspended CVD graphene

DOE PAGES

Yulaev, Alexander; Univ. of Maryland, College Park, MD; Cheng, Guangjun; ...

2016-08-26

The application of suspended graphene as electron transparent supporting media in electron microscopy, vacuum electronics, and micromechanical devices requires the least destructive and maximally clean transfer from their original growth substrate to the target of interest. Here, we use thermally evaporated anthracene films as the sacrificial layer for graphene transfer onto an arbitrary substrate. We show that clean suspended graphene can be achieved via desorbing the anthracene layer at temperatures in the 100 °C to 150 °C range, followed by two sequential annealing steps for the final cleaning, using a Pt catalyst and activated carbon. The cleanliness of the suspendedmore » graphene membranes was analyzed employing the high surface sensitivity of low energy scanning electron microscopy and X-ray photoelectron spectroscopy. A quantitative comparison with two other commonly used transfer methods revealed the superiority of the anthracene approach to obtain a larger area of clean, suspended CVD graphene. Lastly, our graphene transfer method based on anthracene paves the way for integrating cleaner graphene in various types of complex devices, including the ones that are heat and humidity sensitive.« less

Development of New Laser Protective Dyes. Phase 2.

DTIC Science & Technology

DYE LASERS, PROTECTION, LASERS, DYES , HAZARDS, SYNTHESIS, EYE SAFETY, OPTICAL MATERIALS, PLASTICS, LENSES, THERMAL STABILITY, CYANINE DYES , POLYCARBONATES, INJECTION MOLDING, NEAR INFRARED RADIATION, FLUORENES.

Development of miniaturized submersible fluorometers for the detection of aromatic hydrocarbons in marine waters

NASA Astrophysics Data System (ADS)

Tedetti, Marc; Bachet, Caroline; Joffre, Pascal; Ferretto, Nicolas; Guigue, Catherine; Goutx, Madeleine

2014-05-01

Polycyclic aromatic hydrocarbons (PAHs) are among the most widespread organic contaminants in aquatic environments. Due to their physico-chemical properties, PAHs are persistent and mobile, can strongly bioaccumulate in food chains and are harmful to living organisms. They are thus recognized by various international organizations as priority contaminants and are included in the list of 45 priority regulated substances by the European Union. Because of their aromatic structure, PAHs are "optically active" and have inherent fluorescence properties in the ultraviolet (UV) spectral domain (200-400 nm). Therefore, UV fluorescence spectroscopy has been successfully used to develop PAH sensors (i.e. UV fluorometers). Currently, five UV submersible fluorometers are commercially available for in situ measurements of PAHs: EnviroFlu-HC (TriOS Optical Sensors, Germany), Hydrocarbon Fluorometer (Sea & Sun Technology, Germany), HydroC ™ / PAH (CONTROS, Germany), UviLux AquaTracka (Chelsea Technology Group, UK) and Cyclops-7 (Turner Designs, US). These UV fluorometers are all dedicated to the measurement of phenanthrene (λEx /λEm: 255/360 nm), one of the most abundant and fluorescent PAHs found in the aquatic environment. In this study, we developed original, miniaturized submersible fluorometers based on deep UV light-emitting diodes (LEDs) for simultaneous measurements of two PAHs of interest: the MiniFluo-UV 1 for the detection of phenanthrene (PHE, at λEx /λEm: 255/360 nm) and naphthalene (NAP, at λEx /λEm: 270/340 nm), and the MiniFluo-UV 2 for the detection of fluorene (FLU, at λEx /λEm: 255/315 nm) and pyrene (PYR, at λEx /λEm: 270/380 nm). The MiniFluo-UV sensors have several features: measurements of two PAHs at the same time, small size (puck format, 80 x 60 mm), very low energy consumption (500 mW at 12V), LED monitoring, analog and numerical communication modes. The two MiniFluo-UV sensors were first tested in the laboratory: 1) on standard solutions of PHE, NAP, FLU and PYR in the range 0.1-100 µg l-1 and 2) on a water soluble fraction (WSF) of crude oil diluted in 0.2 µm filtered seawater (0 to 50% of WSF in seawater). Then, the MiniFluo-UV sensors were mounted onto a conductivity temperature depth (CTD) vertical profiler and tested at sea. Several profiles were performed in the Bay of Marseilles, in different harbours and hydrocarbon-impacted sites. The MiniFluo-UV measurements performed in the laboratory and in the field were associated with spectrofluorometric (EEM/PARAFAC) and/or chromatographic (GC-MS) analyses. The result obtained show that the MiniFluo-UV are pertinent and efficient tool for monitoring hydrocarbon pollutions in the marine environment. This work is a contribution of three projects labelled by the Competitivity Cluster Mer PACA: FUI SEA EXPLORER, DGCIS - Eco industries VASQUE (PI: ACSA-ALCEN, Meyreuil, France) and ANR - ECOTECH IBISCUS (PI: M. Goutx, MIO, Marseille, France).

Hierarchical structure and dynamics of oligocarbonate-functionalized PEG block copolymer gels

NASA Astrophysics Data System (ADS)

Prabhu, Vivek; Wei, Guangmin; Ali, Samim; Venkataraman, Shrinivas; Yang, Yi Yan; Hedrick, James

Hierarchical, self-assembled block copolymers in aqueous solutions provide advanced materials for biomaterial applications. Recent advancements in the synthesis of aliphatic polycarbonates have shown nontraditional micellar and hierarchical structures driven by the supramolecular assembly of the carbonate block functionality that includes cholesterol, vitamin D, and fluorene. This presentation shall describe the supramolecular assembly structure and dynamics observed by static and dynamic light scattering, small-angle neutron scattering and transmission electron microscopy in a model pi-pi stacking driven fluorene system. The combination of real-space and reciprocal space methods to develop appropriate models that quantify the structure from the micelle to transient gel network will be discussed. 1) Biomedical Research Council, Agency for Science, Technology and Research, Singapore, 2) NIST Materials Genome Initiative.

Development of acute and chronic sediment bioassays with the harpacticoid copepod Quinquelaophonte sp.

PubMed

Stringer, Tristan J; Glover, Chris N; Keesing, Vaughan; Northcott, Grant L; Gaw, Sally; Tremblay, Louis A

2014-01-01

Reliable environmentally realistic bioassay methodologies are increasingly needed to assess the effects of environmental pollution. This study describes two estuarine sediment bioassays, one acute (96 h) and one chronic (14 d), with the New Zealand harpacticoid copepod Quinquelaophonte sp. utilising behavioural and reproductive endpoints. Spiked sediments were used to expose Quinquelaophonte sp. to three reference compounds representing important categories of estuarine chemical stressors: zinc (a metal), atrazine (a pesticide), and phenanthrene (a polycyclic aromatic hydrocarbon). Acute-to-chronic ratios (ACR) were used to further characterise species responses. Acute sediment (sandy and low total organic content) 96 h EC50 values for the sublethal inhibition of mobility for zinc, atrazine and phenanthrene were 137, 5.4, and 2.6 µg/g, respectively. The chronic EC50 values for inhibition of reproduction (total offspring) were 54.5, 0.0083, and 0.067 µg/g for zinc, atrazine, and phenanthrene, respectively. For phenanthrene, a potentially novel mode of action was identified on reproduction. Quinquelaophonte sp. was found to be more sensitive than several other estuarine species indicating choice of test organism is important to characterising the effects of environmentally relevant levels of contamination. The bioassay sediment results demonstrate the sensitivity and suitability of Quinquelaophonte sp. as a tool for the assessment use of estuarine health. © 2013 Published by Elsevier Inc.

Insights into the sorption properties of cutin and cutan biopolymers.

PubMed

Shechter, Michal; Chefetz, Benny

2008-02-15

Plant cuticles have been reported as highly efficient sorbents for organic compounds. The objective of this study was to elucidate the sorption and desorption behavior of polar and nonpolar organic compounds with the major structural components of the plant cuticle: the biopolymers cutin and cutan. The sorption affinity values of the studied compounds followed the order: phenanthrene > atrazine > chlorotoluron > carbamazepine. A higher sorption affinity of phenanthrene and atrazine to cutin was probably due to the higher level of amorphous paraffinic carbon in this biopolymer. Phenanthrene exhibited reversible sorption behavior and a high ratio of organic-carbon-normalized distribution coefficient (Koc) to carbon-normalized octanol-water partitioning coefficients (Kowc) with both biopolymers. This suggests that both biopolymers provide phenanthrene with a partition medium for hydrophobic interactions with the flexible long alkyl-chain moieties of the biopolymers. The low Koc/Kowc ratios obtained for the polar sorbates suggest that the polar sites in the biopolymers are not accessible for sorption interactions. Atrazine and carbamazepine exhibited sorption-desorption hysteresis with both sorbents, indicating that both sorbates interact with cutin and cutan via both hydrophobic and specific interactions. In general, the sorptive properties of the studied biopolymers were similar, signifying that the active sorption sites are similar even though the biopolymers exhibit different properties.

Study on the structures and anti-hepatic fibrosis activity of stilbenoids from Arundina graminifolia (D. Don) Hochr.

NASA Astrophysics Data System (ADS)

Liu, Qingqing; Wang, Huiting; Lin, Fankai; Dai, Rongji; Yu, Deng lin; Lv, Fang

2017-12-01

A phytochemical study was performed on Arundina graminifolia (D.Don) Hochr. by silica gel column and semi-preparative HPLC, and ten stilbenoids were obtained. Their structures were elucidated by NMR and MS spectra and identified as 7-hydroxy-2,4-dimethoxy-9,10-dihydrophenanthrene (1), 4,7-dihydroxy-2-methoxy-9,10-dihydrophenanthrene (2), 2,7-dihydroxy-4-methoxy-9,10-dihydrophenanthrene (3), 3,3’-dihydroxy-5-methoxy-bibenzyl (4), 7-hydroxy-2,8-dimethoxy-phenanthrene-1,4-dione (5), 7-hydroxy-2,10-dimethoxy-phenanthre-ne-1,4-dione (6), 7-dihydroxy-2-methoxy-9,10-dihydrophenanthrene-1,4-dione (7), 7-hydroxy-2-methoxy-phenanthrene-1,4-dione (8), 7-hydroxy-1-(p-hydroxybenzyl)-2,4-dimethoxy-9,10-dihydroxy-phenanthrene (9), 2,7-dihydroxy-1-(p-hydroxybenzyl)-4-methoxy-9,10-dihydroxy-phenanthrene (10). Compounds 5 and 6 were isolated from this plant for the first time. The isolated compounds were examined for their anti-hepatic fibrosis activity against HSC-T6 cells in vitro. The results showed that compounds 4 and 5 exhibited moderate growth inhibitory effects with IC50 61.9 μg/mL and 52.7 μg/mL, respectively.

Bioavailable cadmium during the bioremediation of phenanthrene-contaminated soils using the diffusive gradients in thin-film technique.

PubMed

Amezcua-Allieri, M A; Rodríguez-Vázquez, R

2006-03-01

To study the impact of fungal bioremediation of phenanthrene on trace cadmium solid-solution fluxes and solution phase concentration. The bioremediation of phenanthrene in soils was performed using the fungus Penicillium frequentans. Metal behaviour was evaluated by the techniques of diffusive gradient in thin-films (DGT) and filtration. Fluxes of cadmium (Cd) show a significant (P < 0.002) increase after the start of bioremediation, indicating that the bioremediation process itself releases significant amount of Cd into solution from the soil solid-phase. Unlike DGT devices, the solution concentration from filtration shows a clear bimodal distribution. We postulate that the initial action of the fungi is most likely to breakdown the surface of the solid phase to smaller, 'solution-phase' material (<0.45 microm) leading to a peak in Cd concentration in solution. Phenanthrene removal from soils by bioremediation ironically results in the mobilization of another toxic pollutant (Cd). Bioremediation of organic pollutants in contaminated soil will likely lead to large increases in the mobilization of toxic metals, increasing metal bio-uptake and incorporation into the wider food chain. Bioremediation strategies need to account for this behaviour and further research is required both to understand the generality of this behaviour and the operative mechanisms.

High-Capacity and Photoregenerable Composite Material for Efficient Adsorption and Degradation of Phenanthrene in Water.

PubMed

Liu, Wen; Cai, Zhengqing; Zhao, Xiao; Wang, Ting; Li, Fan; Zhao, Dongye

2016-10-18

We report a novel composite material, referred to as activated charcoal supported titanate nanotubes (TNTs@AC), for highly efficient adsorption and photodegradation of a representative polycyclic aromatic hydrocarbon (PAH), phenanthrene. TNTs@AC was prepared through a one-step hydrothermal method, and is composed of an activated charcoal core and a shell of carbon-coated titanate nanotubes. TNTs@AC offered a maximum Langmuir adsorption capacity of 12.1 mg/g for phenanthrene (a model PAH), which is ∼11 times higher than the parent activated charcoal. Phenanthrene was rapidly concentrated onto TNTs@AC, and subsequently completely photodegraded under UV light within 2 h. The photoregenerated TNTs@AC can then be reused for another adsorption-photodegradation cycle without significant capacity or activity loss. TNTs@AC performed well over a wide range of pH, ionic strength, and dissolved organic matter. Mechanistically, the enhanced adsorption capacity is attributed to the formation of carbon-coated ink-bottle pores of the titanate nanotubes, which are conducive to capillary condensation; in addition, the modified microcarbon facilitates transfer of excited electrons, thereby inhibiting recombination of the electron-hole pairs, resulting in high photocatalytic activity. The combined high adsorption capacity, photocatalytic activity, and regenerability/reusability merit TNTs@AC a very attractive material for concentrating and degrading a host of micropollutants in the environment.

Effect of PEG and mPEG-anthracene on tRNA aggregation and particle formation.

PubMed

Froehlich, E; Mandeville, J S; Arnold, D; Kreplak, L; Tajmir-Riahi, H A

2012-01-09

Poly(ethylene glycol) (PEG) and its derivatives are synthetic polymers with major applications in gene and drug delivery systems. Synthetic polymers are also used to transport miRNA and siRNA in vitro. We studied the interaction of tRNA with several PEGs of different compositions, such as PEG 3350, PEG 6000, and mPEG-anthracene under physiological conditions. FTIR, UV-visible, CD, and fluorescence spectroscopic methods as well as atomic force microscopy (AFM) were used to analyze the PEG binding mode, the binding constant, and the effects of polymer complexation on tRNA stability, aggregation, and particle formation. Structural analysis showed that PEG-tRNA interaction occurs via RNA bases and the backbone phosphate group with both hydrophilic and hydrophobic contacts. The overall binding constants of K(PEG 3350-tRNA)= 1.9 (±0.5) × 10(4) M(-1), K(PEG 6000-tRNA) = 8.9 (±1) × 10(4) M(-1), and K(mPEG-anthracene)= 1.2 (±0.40) × 10(3) M(-1) show stronger polymer-RNA complexation by PEG 6000 and by PEG 3350 than the mPEG-anthracene. AFM imaging showed that PEG complexes contain on average one tRNA with PEG 3350, five tRNA with PEG 6000, and ten tRNA molecules with mPEG-anthracene. tRNA aggregation and particle formation occurred at high polymer concentrations, whereas it remains in A-family structure.

Annihilation limit of a visible-to-UV photon upconversion composition ascertained from transient absorption kinetics.

PubMed

Deng, Fan; Blumhoff, Jörg; Castellano, Felix N

2013-05-30

Noncoherent sensitized green-to-near-visible upconversion has been achieved utilizing palladium(II) octaethylporphyrin (PdOEP) as the triplet sensitizer and anthracene as the energy acceptor/annihilator in vacuum degassed toluene. Selective 547 nm excitation of PdOEP with incident irradiance as low as 600 μW/cm(2) results in the observation of anthryl fluorescence at higher energy. Stern-Volmer analysis of the dynamic phosphorescence quenching of PdOEP by anthracene possesses an extremely large K(SV) of 810,000 M(-1), yielding a triplet-triplet energy transfer quenching constant of 3.3 × 10(9) M(-1) s(-1). Clear evidence for the subsequent triplet-triplet annihilation (TTA) of anthracene was afforded by numerous experiments, one of the most compelling was an excitation scan illustrating that the Q-band absorption features of PdOEP are solely responsible for sensitizing the anti-Stokes fluorescence. The upconverted emission intensity with respect to the excitation power was shown to vary between quadratic and linear using either coherent or noncoherent light sources, illustrating the expected kinetic limits for the light producing photochemistry under continuous wave illumination. Time-resolved experiments directly comparing the total integrated anthracene intensity/time fluorescence data produced through upconversion (λ(ex) = 547 nm, delayed signal) and with direct excitation (λ(ex) = 355 nm, prompt signal) under conditions where the laser pulse is completely absorbed by the sample reveal annihilation efficiencies of approximately 40%. Similarly, the delayed fluorescence kinetic analysis reported by Schmidt and co-workers (J. Phys. Chem. Lett. 2010, 1, 1795-1799) was used to reveal the maximum possible efficiency from a model red-to-yellow upconverting composition and this treatment was applied to the anthryl triplet absorption decay transients of anthracene measured for the PdOEP/anthracene composition at 430 nm. From this analysis approximately 50% of the anthryl triplets that decay by TTA produce singlet fluorescence, consistent with the notion that annihilation spin statistics does not impose efficiency limits on upconversion photochemistry.

Effective elastic properties of a van der Waals molecular monolayer at a metal surface

NASA Astrophysics Data System (ADS)

Sun, Dezheng; Kim, Dae-Ho; Le, Duy; Borck, Øyvind; Berland, Kristian; Kim, Kwangmoo; Lu, Wenhao; Zhu, Yeming; Luo, Miaomiao; Wyrick, Jonathan; Cheng, Zhihai; Einstein, T. L.; Rahman, Talat S.; Hyldgaard, Per; Bartels, Ludwig

2010-11-01

Adsorbing anthracene on a Cu(111) surface results in a wide range of complex and intriguing superstructures spanning a coverage range from 1 per 17 to 1 per 15 substrate atoms. In accompanying first-principles density-functional theory calculations we show the essential role of van der Waals interactions in estimating the variation in anthracene adsorption energy and height across the sample. We can thereby evaluate the compression of the anthracene film in terms of continuum elastic properties, which results in an effective Young’s modulus of 1.5 GPa and a Poisson ratio ≈0.1 . These values suggest interpretation of the molecular monolayer as a porous material—in marked congruence with our microscopic observations.

Diffusion of anthracene derivatives on Cu(111) studied by STM and DFT

NASA Astrophysics Data System (ADS)

Wyrick, Jonathan; Bartels, Ludwig; Einstein, Theodore

2014-03-01

Substituted anthracenes have drawn attention due to their ability to diffuse uniaxially on a Cu(111) surface. We compare anthracene to three of its derivatives whose 9,10 hydrogens are replaced by elements of the chalcogen group that act as linkers binding the molecules to a Cu(111) substrate. DFT calculations shed light on STM imaging and diffusion studies on the three substituted species. We present an analysis of the DFT results in which energetic contributions to the diffusion barriers are partitioned among the Kohn-Sham orbitals, allowing us to make assignments as to how each orbital affects diffusion for each species and draw comparisons between them. Present address: Center for Nanoscale Science and Technology, NIST, Gaithersburg, MD.

A Novel Cardiotoxic Mechanism for a Pervasive Global Pollutant

NASA Astrophysics Data System (ADS)

Brette, Fabien; Shiels, Holly A.; Galli, Gina L. J.; Cros, Caroline; Incardona, John P.; Scholz, Nathaniel L.; Block, Barbara A.

2017-01-01

The Deepwater Horizon disaster drew global attention to the toxicity of crude oil and the potential for adverse health effects amongst marine life and spill responders in the northern Gulf of Mexico. The blowout released complex mixtures of polycyclic aromatic hydrocarbons (PAHs) into critical pelagic spawning habitats for tunas, billfishes, and other ecologically important top predators. Crude oil disrupts cardiac function and has been associated with heart malformations in developing fish. However, the precise identity of cardiotoxic PAHs, and the mechanisms underlying contractile dysfunction are not known. Here we show that phenanthrene, a PAH with a benzene 3-ring structure, is the key moiety disrupting the physiology of heart muscle cells. Phenanthrene is a ubiquitous pollutant in water and air, and the cellular targets for this compound are highly conserved across vertebrates. Our findings therefore suggest that phenanthrene may be a major worldwide cause of vertebrate cardiac dysfunction.

Energy transfer of highly vibrationally excited phenanthrene and diphenylacetylene.

PubMed

Hsu, Hsu Chen; Tsai, Ming-Tsang; Dyakov, Yuri; Ni, Chi-Kung

2011-05-14

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold phenanthrene and diphenylacetylene in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer between naphthalene and Kr, energy transfer between phenanthrene and Kr shows a larger cross-section for vibrational to translational (V → T) energy transfer, a smaller cross-section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation. These differences are further enlarged in the comparison between naphthalene and diphenylacetylene. In addition, less complex formation and significant increases in the large V → T energy transfer probabilities, termed supercollisions in diphenylacetylene and Kr collisions were observed. The differences in the energy transfer between these highly vibrationally excited molecules are attributed to the low-frequency vibrational modes, especially those vibrations with rotation-like wide-angle motions.

Assessment of bile fluorescence patterns in a tropical fish, Nile tilapia (Oreochromis niloticus) exposed to naphthalene, phenanthrene, pyrene and chrysene using fixed wavelength fluorescence and synchronous fluorescence spectrometry.

PubMed

Pathiratne, A; Hemachandra, C K; Pathiratne, K A S

2010-05-01

Bile fluorescence patterns in Nile tilapia, a potential fish for biomonitoring tropical water pollution were assessed following exposure to selected polycyclic aromatic hydrocarbons (PAHs): naphthalene, phenanthrene, pyrene and chrysene. Non-normalized fixed wavelength fluorescence signals in the fish exposed to these PAHs reflected dose and/or time response relationships of their metabolism. Normalizing signals to biliverdin introduced deviations to these response patterns. The optimal wavelength pairs (excitation/emission) for synchronous fluorescence scanning measurements of bile metabolites of naphthalene, phenanthrene, pyrene and chrysene were identified as 284/326, 252/357, 340/382 and 273/382 respectively. This study supports the use of bile fluorescence in Nile tilapia by fixed wavelength fluorescence and synchronous fluorescence spectrometry with non-normalized data as a simple method for screening bioavailability of these PAHs.

Flame-retardant EPDM compounds containing phenanthrene to enhance radiation resistance

NASA Astrophysics Data System (ADS)

Chen, Jian; Huang, Wei; Jiang, Shu-Bin; Li, Xiao-Yan; An, You; Li, Chuang; Gao, Xiao-Ling; Chen, Hong-Bing

2017-01-01

Ethylene propylene diene monomer (EPDM) compounds with good flame-retardant and γ-ray radiation resistant properties were prepared by adding complex flame retardants and phenathrene. The resultant EPDM formulations have a long time to ignition (TTI >46 s), a low peak heat release rate (PHRR 341 kW/m2) and a high limited oxygen index (LOI >30). Effects of γ-ray radiation on the resultant flame-retardant EPDM was investigated. The formulated EPDM is a crosslinking dominated polymer under γ-ray radiation. The γ-ray radiation resistant property of EPDM was enhanced by adding phenanthrene. Elongation at break of EPDM formulated with phenanthrene could retain 91% after being irradiated to 0.3 MGy and still retains 40% elongation even after being irradiated to 0.9 MGy, which is much better the control. It is expected that the formulated flame-retardant and radiation resistant EPDM materials could meet the requirements for use in radiation environments.

Digestive determinants of benzo[a]pyrene and phenanthrene bioaccumulation by a deposit-feeding polychaete

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

Penry, D.L.; Weston, D.P.

1998-11-01

The uptake of hydrophobic contaminants from ingested sediment can contribute significantly to body burdens of deposit feeders, and feeding behavior and digestive physiology can play important roles in bioaccumulation. The authors examined the uptake of polycyclic aromatic hydrocarbons (PAHs) by the deposit-feeding polychaete Abarenicola pacifica in experiments in which worms were first acclimated to low or high organic carbon sediments with 0.08 or 0.45% total organic carbon, respectively and then transferred to low or high organic carbon test sediments contaminated with radiolabeled phenanthrene or benzo[a]pyrene. Ingestion rate was measurements are essential in many types of bioaccumulation studies because differences inmore » ingestion rates between sediment types may confound some traditional measures of bioavailability. Physiological acclimation to the low or high organic carbon sediments did not appear to affect PAH uptake from the test sediments, but acclimation did affect biotransformation capabilities, particularly for phenanthrene.« less

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

PubMed

Martorell, Isabel; Nieto, Antonio; Nadal, Martí; Perelló, Gemma; Marcé, Rosa M; Domingo, José L

2012-11-01

In this study, the dietary intake of 16 polycyclic aromatic hydrocarbons (PAHs) by the population of Tarragona County (Catalonia, Spain) was assessed using the duplicate diet approach. Duplicate diet samples, prepared as per consumption, were collected during September 2010 in various restaurants offering a variety of daily menus (breakfast, lunch, and dinner). For analysis of PAHs, a total of 90 composite samples were prepared. Analytical procedure of PAHs was performed by means of gas chromatography/mass spectrometry. Intake calculations were made for the standard male adult population. The highest intakes corresponded to acenaphthylene (12.7 μg/day), acenaphthene (12.4 μg/day), and fluorene (11.9 μg/day), while the lowest intake corresponded to dibenz[a,h]anthracene (0.12 μg/day), being also comparatively low those of pyrene, benzo[b]fluoranthene+benzo[j]fluoranthene, benzo[a]pyrene and benzo[ghi]perylene (0.13 μg/day in all cases). The results were compared with data from previous total diet studies (TDS) recently performed in the same geographical area. In the present study, the estimated mean dietary intake for a standard male adult living in Catalonia was 59.2 μg/day, a value notably higher than that found in our recent TDS (6.72 μg/day). However, it is essential to remark that important methodological differences exist between both surveys, reflecting that calculation methods should be similar when the purpose is to compare results from different surveys. In general terms, we conclude that for PAHs, duplicate diet studies may be a good alternative to total diet studies, especially when there are important economical limitations to perform a suitable TDS. The costs associated to the former may be notably lower, as they do not require such an extensive number of samples for chemical analysis. Moreover, a duplicate diet approach may even be more realistic, as cooked foodstuffs are used for dietary exposure assessment. Copyright © 2012 Elsevier Ltd. All rights reserved.

Kinetics of sorption of polyaromatic hydrocarbons onto granular activated carbon and Macronet hyper-cross-linked polymers (MN200).

PubMed

Valderrama, C; Cortina, J L; Farran, A; Gamisans, X; Lao, C

2007-06-01

Polymeric supports are presented as an alternative to granular activated carbon (GAC) for organic contaminant removal from groundwater using permeable reactive barriers (PRB). The search for suitable polymeric sorbents for hydrocarbon extraction from aqueous streams has prompted the synthesis of new resins incorporating new functionalities or modifying the polymer network properties that solve many of the existing problems. Between them, the new type of polymeric sorbents Macronet Hypersol containing a styrene-divinylbenzene macroporous hyperreticulated network has been evaluated. Because of their potential sorptive properties, tests were conducted to determine the feasibility of using them as a low-cost reactive material for groundwater applications. The present work describes the sorption of six polycyclic hydrocarbons (PAHs) from aqueous solution onto both Macronet polymeric sorbent MN200 and granular activated carbon. Batch experiments were performed to determine loading rates of a family of PAHs (naphthalene, fluorene, anthracene, acenaphthene, pyrene, and fluoranthene), from a simple two-rings PAH (naphthalene) up to a four-ring PAH (pyrene). The behavior of a non-functionalized Macronet support (MN200) was compared with the behavior of a recognized material, granular activated carbon (GAC). Analyses of the respective rate data with three theoretical models (pseudo-first- and pseudo-second-order reaction models and the Elovich model) were used to describe the PAH sorption kinetics. Sorption rate constants were determined by graphical analysis of the proposed models. The study showed that sorption systems followed a pseudo-first-order reaction model, although the pseudo-second-order reaction model provides an acceptable description of the sorption process. Graphical analysis showed that the sorption process with activated carbon is a more complex process than the one observed for hyper-cross-linked polymers (MN200). A simulation of the barrier thickness needed to treat a PAH-polluted plume showed that 0.1-1 m of sorption media is enough even for high water fluxes such as 0.1-2 m(3)/m(2)/day for both sorbents.

Synthesis and fluorescence emission properties of 1,3,6,8-tetraarylpyrenes

NASA Astrophysics Data System (ADS)

Hu, Jian-Yong; Feng, Xing; Tomiyasu, Hirotsugu; Seto, Nobuyuki; Rayhan, Ummey; Elsegood, Mark R. J.; Redshaw, Carl; Yamato, Takehiko

2013-09-01

Three types of stable pyrene-based highly fluorescence (blue) compounds, 1-, 1,6-bis, 1,8-bis and 1,3,6,8-tetrakis(7-tert-butylpyrenyl)pyrenes and 1,3,6,8-tetrakis[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]pyrene, were successfully synthesized via a Pd/Cu-catalysed Suzuki cross-coupling reaction of the corresponding bromopyrenes with 7-tert-butyl-1-pyrenylboronic ester or 2-[9,9-bis(3-methylbutyl)-9H-fluoren-2-yl]-4,4,5,5-tetramethyl[1,3,2]dioxaborolane, respectively. All compounds have good solubility in common organic solvents and high thermal stability with melting points up to 270 °C; the exceptions are the isomeric 1,6-bis-, and 1,8-bispyrenyl-substituted pyrenes. All products show high extinction coefficients of absorption (λmax ≈ 349-396 nm) and high quantum yields (λmax ≈ 432-465 nm; Φf ≈ 0.75-0.99) in dichloromethane solution, and emit strong fluorescence in the visible region ranging from deep-blue to pure-blue on increasing the number of substituents. This data suggests that such systems have promise as blue emitters in organic light-emitting device (OLED) applications (OLED = organic light emitting diode). Crystal structures were determined for 1,3,6,8-tetrakis [9,9-bis(3-methylbutyl)-9H-fluoren-2-yl] pyrene and 1,3,6,8-tetrakis(4-methoxyphenyl)pyrene.

Synthesis and properties of functionalized 4 nm scale molecular wires with thiolated termini for self-assembly onto metal surfaces.

PubMed

Wang, Changsheng; Bryce, Martin R; Gigon, Joanna; Ashwell, Geoffrey J; Grace, Iain; Lambert, Colin J

2008-07-04

We report the synthesis of new oligo(aryleneethynylene) molecular wires of ca. 4 nm length scale by palladium-catalyzed Sonogashira cross-coupling methodology. Key structural features are the presence of electron donor 9-(1,3-dithiol-2-ylidene)fluorene (compounds 13 and 14) and electron acceptor 9-[di(4-pyridyl)methylene]fluorene units (compound 16) at the core of the molecules. Terminal thiolate substituents are protected as cyanoethylsulfanyl (13 and 16) or thioacetate derivatives (14). The molecules display well-defined redox processes in solution electrochemical studies. The optical properties in solution are similar to those of the fluorenone analog 6: the strongest absorptions for 6, 13 and 16 are in the region lambda(max) = 387-393 nm, with 13 showing an additional shoulder at 415 nm which is not present for 6 and 16; this shoulder is assigned to a HOMO-LUMO transition from the dithiole to the fluorene unit. Molecules 6, 13, 14 and 16 form self-assembled monolayers on gold substrates which exhibit essentially symmetrical current-voltage (I-V) characteristics when contacted by a gold scanning tunelling microscope (STM) tip. The effects of the chemical modifications at the central unit of 6, 14 and 16 on the HOMO-LUMO levels and electron transport through the molecules in vacuum have been computed by an ab initio approach.

Determination of total and available fractions of PAHs by SPME in oily wastewaters: overcoming interference from NAPL and NOM.

PubMed

Gomes, Rui B; Nogueira, Regina; Oliveira, José M; Peixoto, João; Brito, António G

2009-09-01

Polycyclic aromatic hydrocarbons (PAHs) are often found in oily wastewaters. Their presence is usually the result of human activities and has a negative effect on the environment. One important step in addressing this problem is to evaluate the effectiveness of PAH removal by biological processes since these are the most cost-effective treatments known today. Many techniques are presently available for PAH determination in wastewaters. Solid phase microextracion (SPME) is known to be one of the most effective techniques for this purpose. When analyzing complex matrices with substances such as natural organic matter (NOM) and non-aqueous phase liquids (NAPL), it is important to differentiate the free dissolved PAH from matrix-bonded PAH. PAHs associated with the bonded fraction are less susceptible to biological treatment. The present study concerns the development of a simple and suitable methodology for the determination of the freely dissolved and the total fraction of PAHs present in oily wastewaters. The methodology was then applied to an oily wastewater from a fuel station retention basin. Headspace SPME was used for analyzing PAH since the presence of a complex or dirty matrix in direct contact with the fiber may damage it. Four model PAHs-anthracene, fluorene, phenanthrene, and pyrene-were analyzed by GC-MS. Negligible depletion SPME technique was used to determine the free fraction. Total PAH was determined by enhancing the mass transfer from the bonded phase to the freely dissolved phase by temperature optimization and the use of the method of standard additions. The PAH absorption kinetics were determined in order to define the optimal sampling conditions for this method. The fitting of the experimental data to a mathematical model was accomplished using Berkeley Madonna software. Humic acid and silicon oil were used as model NOM and NAPL, respectively, to study the effect of these compounds on the decrease of SPME response. Then, the method was evaluated with wastewater from a fuel station spill retention basin. The SPME kinetic parameters-k (1) (uptake rate), k (2) (desorption rate), and K (SPME) (partition coefficient)-were determined from experimental data modeling. The determination of the free fraction required 15-min sampling to ensure that PAH depletion from sample was below 1%. For total PAH, a 30-min extraction at 100 degrees C ensured the maximum signal response in the GC-MS. For the determination of free and total PAHs, extractions were performed before reaching the SPME equilibrium. The wastewater used in this study had no free fraction of the analyzed PAHs. However, the four studied PAHs were found when the method for total PAH was used. The addition of NOM and NAPL dramatically decreased the efficiency of the SPME. This decrease was the result of a greater partition of the PAHs to the NAPL and NOM phases. This fact was also observed in the analysis of the fuel station spill retention basin, where no free PAH was measured. However, using the method of standard addition for the determination of total PAH, it was possible to quantify all four PAHs. The method developed in the present study was found to be adequate to differentiate between free and total PAH present in oily wastewater. It was determined that the presence of NOM and NAPL had a negative effect on SPME efficiency. The presence of binding substances had a great influence on SPME kinetics. Therefore, it is of extreme importance to determine their degree of interference when analyzing oily wastewaters or results can otherwise be erroneous. Other factors influencing the total PAH determinations should be considered in further studies.

Cement-based stabilization/solidification of oil refinery sludge: Leaching behavior of alkanes and PAHs.

PubMed

Karamalidis, Athanasios K; Voudrias, Evangelos A

2007-09-05

Stabilization/solidification is a process widely applied for the immobilization of inorganic constituents of hazardous wastes, especially for metals. Cement is usually one of the most common binders for that purpose. However, limited results have been presented on immobilization of hydrocarbons in cement-based stabilized/solidified petroleum solid waste. In this study, real oil refinery sludge samples were stabilized and solidified with various additions of I42.5 and II42.5 cement (Portland and blended cement, respectively) and subject to leaching. The target analytes were total petroleum hydrocarbons, alkanes and 16 polycyclic aromatic hydrocarbons of the EPA priority pollutant list. The experiments showed that the waste was confined in the cement matrix by macroencapsulation. The rapture of the cement structure led to the increase of leachability for most of the hydrocarbons. Leaching of n-alkanes from II42.5 cement-solidified samples was lower than that from I42.5 solidified samples. Leaching of alkanes in the range of n-C(10) to n-C(27) was lower than that of long chain alkanes (>n-C(27)), regardless the amount of cement addition. Generally, increasing the cement content in the solidified waste samples, increased individual alkane leachability. This indicated that cement addition resulted in destabilization of the waste. Addition of I42.5 cement favored immobilization of anthracene, benzo[a]anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene, benzo[a]pyrene and dibenzo[a,h]anthracene. However, addition of II42.5 favored 5 out of 16, i.e., naphthalene, anthracene, benzo[b]fluoroanthene, benzo[k]fluoroanthene and dibenzo[a,h]anthracene.

Estrogenic status modulates the effect of soy on hepatic responses to 7,12-dimethylbenz(a)anthracene (DMBA)

USDA-ARS?s Scientific Manuscript database

We examined the influence of estradiol (E2) status and soy protein isolate (SPI) intake on the hepatic responses altered by 7,12-dimethylbenz(a)anthracene (DMBA, a polycyclic aromatic hydrocarbon [PAH]). Sprague–Dawley rats were ovariectomized (OVX) at PND50 and infused with E2 or vehicle for 14 d a...

Estrogenic status modulates the effect of soy on hepatic responses to 7,12- dimethylbenz(a)anthracene

USDA-ARS?s Scientific Manuscript database

We examined the influence of estradiol (E2) status and soy protein isolate (SPI) intake on the hepatic responses altered by 7,12-dimethylbenz(a)anthracene (DMBA, a polycyclic aromatic hydrocarbon [PAH]). Sprague-Dawley rats were ovariectomized (OVX) at PND50 and infused with E2 or vehicle for 14d an...

Coordination Complexes as Catalysts: The Oxidation of Anthracene by Hydrogen Peroxide in the Presence of VO(acac)[subscript 2

ERIC Educational Resources Information Center

Charleton, Kimberly D. M.; Prokopchuk, Ernest M.

2011-01-01

A laboratory experiment aimed at students who are studying coordination chemistry of transition-metal complexes is described. A simple vanadyl acetylacetonate complex can be used as a catalyst in the hydrogen peroxide oxidation of anthracene to produce anthraquinone. The reaction can be performed under a variety of reaction conditions, ideally by…

INDUCTION OF DNA ADDUCTS, TUMORS, AND KI-RAS ONCOGENE MUTATIONS IN STRAIN A/J MOUSE LUNG BY IP. ADMINISTRATION OF DIBENZ[A,H]ANTHRACENE

EPA Science Inventory

Induction of DNA adducts, tumors, and Ki-ras oncogene mutations in strain AlJ mouse lung by ip. administration of dibenz[a,h]anthracene

Previous studies of polycyclic aromatic hydrocarbon (P AH) induced lung tumors in the strain NJ mouse model system have demonstrated qua...

A SYSTEM FOR CONTINUOUS MEASUREMENT OF RADIOACTIVITY IN FLOWING STREAMS

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

Rapkin, E.; Gibbs, J.A.

1962-10-31

An apparatus for the determination of alpha or BETA radioactivity in either circulating liquid or gas streams was developed. Solid anthracene crystals are used. The detector consists of a Lucite light pipe coated with titanium dioxide and coupled to two photomultipliers which are in turn fed to appropriate coincidence type circuitry. The detection cell, which consists of a 9-mm OD glass tube with appropriate fittings on either end, was packed with anthracene crystals. A glass frit, or glass wool, was incorporated in the cell on the downstream side to contain the anthracene and a pledget of glass wool was placedmore » above the anthracene on the upstream side. Carbon-14 counting efficiency was found to be of the order of 50% with a coincident background from 100 divisions to infinity of less than 40 cpm at 900 v. Tritium counting efficiency was in the range of 7% and the integral background from 100 divisions to infinity was about 90 cpm at 1130 v. Discussion is also given on the electronics of the detector and the performance in closed flowing systems and gas analysis. (P.C.H.)« less

Effect of multi-walled carbon nanotubes on phytotoxicity of sediments contaminated by phenanthrene and cadmium.

PubMed

Song, Biao; Zeng, Guangming; Gong, Jilai; Zhang, Peng; Deng, Jiaqin; Deng, Canhui; Yan, Jin; Xu, Piao; Lai, Cui; Zhang, Chen; Cheng, Min

2017-04-01

To implement effective control and abatement programs for contaminants accumulating in sediments, strategies are needed for evaluating the quality of amended sediments. In this study, phytotoxicity of the sediments contaminated by cadmium and phenanthrene was evaluated after in situ remediation with multi-walled carbon nanotubes (MWCNTs) as adsorbents. Adsorption experiments and measurement of aqueous concentrations of the contaminants in overlying water were used to investigate the remediation effectiveness from physical and chemical aspects. The results indicated that MWCNTs showed a much better adsorption performance towards phenanthrene and Cd(II) compared with the sediments. The in situ remediation with MWCNTs could distinctly decrease the aqueous concentrations of phenanthrene and Cd(II) released from the sediments, reducing environmental risk towards overlying water. Influences of MWCNTs dose, MWCNTs diameter, and contact time on phtotoxicity of the contaminated sediments were studied. No significant inhibition of the amended sediments on germination of the test species was observed in the experiments, while the root growth was more sensitive than biomass production to the changes of contaminant concentrations. The analysis of Pearson correlation coefficients between evaluation indicators and associated remediation parameters suggested that phytotoxicity of sediments might inaccurately indicate the changes of pollutant content, but it was significant in reflecting the ecotoxicity of sediments after remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

[Influence of Three Low-Molecular-Weight Organic Acids on the Adsorption of Phenanthrene in Purple Soil].

PubMed

Xie, Li; Chen, Ben-shou; Zhang, Jin-zhong; Lu, Song; Jiang, Tao

2016-03-15

The effects of three low-molecular-weight organic acids (citric acid, malic acid and oxalic acid) on the adsorption of phenanthrene in purple soil were studied by static adsorption experiment. The results showed that the adsorption kinetic process of phenanthrene in purple soil could be described by the second-order kinetic model, and the adsorption rate constant would significantly decrease in the presence of the three low-molecular-weight organic acids ( LMWOAs). The adsorption thermodynamic process could be well described by linear adsorption model, which was dominated by distribution role. The three LMWOAs could promote the adsorption of phenantherene in purple soil when their concentrations were less than 5 mmol · L⁻¹, whereas inhibit the adsorption when their concentrations were more than 10 mmol · L⁻¹, and the inhibition would increase with increasing concentrations. Moreover, the inhibitory ability displayed a decreasing order of citric acid, oxalic acid, and malic acid when their concentrations were 20 mmol · L⁻¹, which is related to the molecular structure and acidity of the three LMWOAs. Compared with the control, the content of dissolved organic matter (DOM) released from purple soil showed a trend of first decrease and then increase with increasing LMWOAs concentration, and the adsorption capacity of phenanthrene in purple soil was negatively related to DOM content.

Impact of nitrogen-polycyclic aromatic hydrocarbons on phenanthrene and benzo[a]pyrene mineralisation in soil.

PubMed

Anyanwu, Ihuoma N; Ikpikpini, Ojerime C; Semple, Kirk T

2018-01-01

When aromatic hydrocarbons are present in contaminated soils, they often occur in mixtures. The impact of four different (3-ring) nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs) on 12/14 C-phenanthrene and 12/14 C-benzo[a]pyrene (B[a]P) mineralisation in soil was investigated over a 90 d incubation period. The results revealed that both 12/14 C-phenanthrene and 12/14 C-benzo[a]pyrene showed no significant mineralisation in soils amended with 10mgkg -1 and 100mgkg -1 N-PAHs (p>0.05). However, increases in lag-phases and decreases in the rates and extents of mineralisation were observed, over time. Among the N-PAHs, benzo[h]quinoline impacted 14 C-phenanthrene mineralisation with extended and diauxic lag phases. Furthermore, 12/14 C-B[a]P and 14 C-benzo[a]pyrene-nitrogen-containing polycyclic aromatic hydrocarbons ( 14 C-B[a]P-N-PAHs) amended soils showed extensive lag phases (> 21 d); with some 14 C-B[a]P-N-PAH mineralisation recording <1% in both concentrations (10mgkg -1 and 100mgkg -1 ), over time. This study suggests that the presence of N-PAHs in contaminated soil may impact the microbial degradation of polycyclic aromatic hydrocarbons (PAHs) and the impact was most likely the result of limited success in achieving absolute biodegradation of some PAHs in soil. Copyright © 2017 Elsevier Inc. All rights reserved.

Dynamics of Bacterial Communities in Two Unpolluted Soils after Spiking with Phenanthrene: Soil Type Specific and Common Responders

PubMed Central

Ding, Guo-Chun; Heuer, Holger; Smalla, Kornelia

2012-01-01

Considering their key role for ecosystem processes, it is important to understand the response of microbial communities in unpolluted soils to pollution with polycyclic aromatic hydrocarbons (PAH). Phenanthrene, a model compound for PAH, was spiked to a Cambisol and a Luvisol soil. Total community DNA from phenanthrene-spiked and control soils collected on days 0, 21, and 63 were analyzed based on PCR-amplified 16S rRNA gene fragments. Denaturing gradient gel electrophoresis (DGGE) fingerprints of bacterial communities increasingly deviated with time between spiked and control soils. In taxon specific DGGE, significant responses of Alphaproteobacteria and Actinobacteria became only detectable after 63 days, while significant effects on Betaproteobacteria were detectable in both soils after 21 days. Comparison of the taxonomic distribution of bacteria in spiked and control soils on day 63 as revealed by pyrosequencing indicated soil type specific negative effects of phenanthrene on several taxa, many of them belonging to the Gamma-, Beta-, or Deltaproteobacteria. Bacterial richness and evenness decreased in spiked soils. Despite the significant differences in the bacterial community structure between both soils on day 0, similar genera increased in relative abundance after PAH spiking, especially Sphingomonas and Polaromonas. However, this did not result in an increased overall similarity of the bacterial communities in both soils. PMID:22934091

Short-Term Rhizosphere Effect on Available Carbon Sources, Phenanthrene Degradation, and Active Microbiome in an Aged-Contaminated Industrial Soil

PubMed Central

Thomas, François; Cébron, Aurélie

2016-01-01

Over the last decades, understanding of the effects of plants on soil microbiomes has greatly advanced. However, knowledge on the assembly of rhizospheric communities in aged-contaminated industrial soils is still limited, especially with regard to transcriptionally active microbiomes and their link to the quality or quantity of carbon sources. We compared the short-term (2–10 days) dynamics of bacterial communities and potential PAH-degrading bacteria in bare or ryegrass-planted aged-contaminated soil spiked with phenanthrene, put in relation with dissolved organic carbon (DOC) sources and polycyclic aromatic hydrocarbon (PAH) pollution. Both resident and active bacterial communities (analyzed from DNA and RNA, respectively) showed higher species richness and smaller dispersion between replicates in planted soils. Root development strongly favored the activity of Pseudomonadales within the first 2 days, and of members of Actinobacteria, Caulobacterales, Rhizobiales, and Xanthomonadales within 6–10 days. Plants slowed down the dissipation of phenanthrene, while root exudation provided a cocktail of labile substrates that might preferentially fuel microbial growth. Although the abundance of PAH-degrading genes increased in planted soil, their transcription level stayed similar to bare soil. In addition, network analysis revealed that plants induced an early shift in the identity of potential phenanthrene degraders, which might influence PAH dissipation on the long-term. PMID:26903971

Hybrid metal-organic conductive network with plasmonic nanoparticles and fluorene (Conference Presentation)

NASA Astrophysics Data System (ADS)

Fontana, Laura; Fratoddi, Ilaria; Matassa, Roberto; Familiari, Giuseppe; Venditti, Iole; Batocchio, Chiara; Magnano, Elena; Nappini, Silvia; Leahu, Grigore; Belardini, Alessandro; Li Voti, Roberto; Sibilia, Concita

2017-05-01

For the development of new generation portable electronic devices, the realization of thin and flexible electrodes have a crucial role. Conductive organic systems can address this issue in different ways. Indeed, conductance in organic molecules were studied in different papers starting from seminal papers in last 70's [1] up to recent ones [2]. Among organic species, conduction and electronic characteristics of Fluorene derivatives were studied in different configurations [3,4]. Unfortunately, the conductance of organic materials is limited by charge transport mechanism [5]. Hybrid system with organic conductive compounds covalently linked with metal centres can lead to enhanced conductivity [6]. Here we synthesized gold and silver nanoparticles (AuNPs and AgNPs) stabilized with a fluorene thiolate derivative, namely 9,9-Didodecyl-2,7-bis(acetylthio)fluorene (FL). In the synthesis process the metal nanoparticles (MNPs) size results to be around 5 nm in diameter [7]. When deposited on a planar substrate, the hybrid compound form a regular network of MNPs separated each other by fluorene spacers covalently linked by thiol groups [8]. We deposited the network on substrate with two interdigitated electrodes in order to measure conductive properties (I-V characteristics). In I-V measurements it results to be that AgNPs based network is 200 times more conductive than AuNPs one. Selective oxidation of AgNPs network close to positive electrodes gives rise to a Schottky diode behavior in the I-V characteristic that could find potential applications in nano-electronics devices. The fluorescence and extinction spectra of FL-AgNPs and FL-AuNPs where characterised. References [1] C. K. Chiang, C. R. Fincher, Jr., Y. W. Park, A. J. Heeger, H. Shirakawa, E. J. Louis, S. C. Gau, and Alan G. MacDiarmid, Phys. Rev. Lett. 39, 1098 (1977). [2] Hylke B. Akkerman, Paul W. M. Blom, Dago M. de Leeuw and Bert de Boer, Nature 441, 69 (2006). [3] Rajendra Prasad Kalakodimi, Aletha M. Nowak, and Richard L. McCreery, Chem. Mater. 17, 4939 (2005). [4] J. Wu, K. Mobley, and R. L. Mc Creery, J. Chem. Phys. 126, 024704 (2007). [5] Cristina Hermosa, Jose Vicente Álvarez, Mohammad-Reza Azani, Carlos J. Gómez-García, Michelle Fritz, Jose M. Soler, Julio Gómez-Herrero, Cristina Gómez-Navarro and Félix Zamora, Nature Commun. 4, 1709 (2013). DOI: 10.1038/ncomms2696. [6] Nunzio Tuccitto, Violetta Ferri, Marco Cavazzini, Silvio Quici, Genady Zhavnerko, Antonino Licciardello and Maria Anita Rampi, Nature Mater. 8, 41 (2009). [7] Quintiliani, M., Bassetti, M., Pasquini, C., et al. J. Mater. Chem. C, 2014, (2), pp. 2517-2527. [8] R. Matassa, G. Familiari, E. Battaglione, Concita Sibilia et al., Nanoscale, 2016,8, 18161-18169.

Structure-property relationships: asymmetric alkylphenyl-substituted anthracene molecules for use in small-molecule solar cells.

PubMed

Kim, Yu Jin; Ahn, Eun Soo; Jang, Sang Hun; An, Tae Kyu; Kwon, Soon-Ki; Chung, Dae Sung; Kim, Yun-Hi; Park, Chan Eon

2015-05-11

Two asymmetric anthracene-based organic molecules, NDHPEA and TNDHPEA, were prepared without or with a thiophene spacer between the anthracene and naphthalene units. These asymmetric oligomers displayed different degrees of coplanarity, as evidenced by differences in the dihedral angles calculated by using DFT. Differential scanning calorimetry and XRD studies were used to probe the crystallization characteristics and molecular packing structures in the active layers. The coplanarity of the molecules in the asymmetric structure significantly affected the crystallization behavior and the formation of crystalline domains in the solid state. The small-molecule crystalline properties were correlated with the device physics by determining the J-V characteristics and hole mobilities of the devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorescent mixed ligand copper(II) complexes of anthracene-appended Schiff bases: studies on DNA binding, nuclease activity and cytotoxicity.

PubMed

Jaividhya, Paramasivam; Ganeshpandian, Mani; Dhivya, Rajkumar; Akbarsha, Mohammad Abdulkadher; Palaniandavar, Mallayan

2015-07-14

A series of mixed ligand copper(ii) complexes of the type [Cu(L)(phen)(ACN)](ClO4)21-5, where L is a bidentate Schiff base ligand (N(1)-(anthracen-10-ylmethylene)-N(2)-methylethane-1,2-diamine (L1), N(1)-(anthracen-10-ylmethylene)-N(2),N(2)-dimethylethane-1,2-diamine (L2), N(1)-(anthracen-10-yl-methylene)-N(2)-ethylethane-1,2-diamine (L3), N(1)-(anthracen-10-ylmethylene)-N(2),N(2)-diethylethane-1,2-diamine (L4) and N(1)-(anthracen-10-ylmethylene)-N(3)-methylpropane-1,3-diamine (L5)) and phen is 1,10-phenanthroline, have been synthesized and characterized by spectral and analytical methods. The X-ray crystal structure of 5 reveals that the coordination geometry around Cu(ii) is square pyramidal distorted trigonal bipyramidal (τ, 0.76). The corners of the trigonal plane of the geometry are occupied by the N2 nitrogen atom of phen, the N4 nitrogen atom of L5 and the N5 nitrogen of acetonitrile while the N1 nitrogen of phen and the N3 nitrogen of L5 occupy the axial positions with an N1-Cu1-N3 bond angle of 176.0(3)°. All the complexes display a ligand field band (600-705 nm) and three less intense anthracene-based bands (345-395 nm) in solution. The Kb values calculated from absorption spectral titration of the complexes (π→π*, 250-265 nm) with Calf Thymus (CT) DNA vary in the order 5 > 4 > 3 > 2 > 1. The fluorescence intensity of the complexes (520-525 nm) decreases upon incremental addition of CT DNA, which reveals the involvement of phen rather than the appended anthracene ring in partial DNA intercalation with the DNA base stack. The extent of quenching is in agreement with the DNA binding affinities and the relative increase in the viscosity of DNA upon binding to the complexes as well. Thus 5 interacts with DNA more strongly than 4 on account of the stronger involvement in hydrophobic DNA interaction of the anthracenyl moiety, which is facilitated by the propylene ligand backbone with chair conformation. The ability of complexes (100 μM) to cleave DNA (pUC19 DNA) in 5 mM Tris-HCl/50 mM NaCl buffer at pH 7.1 in the absence of a reducing agent or light varies in the order 5 > 4 > 3 > 2 > 1, which is in conformity with their DNA binding affinities. Interestingly, cytotoxicity studies on the MCF-7 human breast cancer cell line show that the IC50 value of 5 is less than that of cisplatin for the same cell line, revealing that it can act as an effective cytotoxic drug in a time-dependent manner.

Phenanthrene and 2,2',5,5'-PCB sorption by several soils from methanol-water solutions: the effect of weathering and solute structure.

PubMed

Hyun, Seunghun; Kim, Minhee; Baek, Kitae; Lee, Linda S

2010-01-01

The effect of the sorption of phenanthrene and 2,2',5,5'-polychlorinated biphenyl (PCB52) by five differently weathered soils were measured in water and low methanol volume fraction (f(c)0.5) as a function of the apparent solution pH (pH(app)). Two weathered oxisols (A2 and DRC), and moderately weathered alfisols (Toronto) and two young soils (K5 and Webster) were used. The K(m) (linear sorption coefficient) values, which log-linearly decreases with f(c), were interpreted using a cosolvency sorption model. For phenanthrene sorption at the natural pH, the empirical constant (alpha) ranged between 0.95 and 1.14, and was in the order of oxisols (A2 and DRC)

Decomposition and transformation of cutin and cutan biopolymers in soils: effect on their sorptive capabilities

NASA Astrophysics Data System (ADS)

Shechter, M.; Chefetz, B.

2009-04-01

Plant cuticle materials, especially the highly aliphatic biopolymers cutin and cutan, have been reported as highly efficient natural sorbents. The objective of this study was to examine the effects of decomposition on their sorption behavior with naphthol and phenanthrene. The level of cutin and cutan was reduced by 15 and 27% respectively during the first 3 mo of incubation. From that point, the level of the cutan did not change, while the level of the cutin continued to decrease up to 32% after 20 mo. 13C NMR analysis suggested transformation of cutan mainly within its alkyl-C structure which are assigned as crystalline moieties. Cutin, however, did not exhibit significant structure changes with time. The level of humic-like substances increased due to cutin decomposition but was not influenced in the cutan system after 20 mo of incubation. This indicates that the cutin biopolymer has been decomposed and transformed into humic-like substances, whereas the cutan was less subject to transformation. Decomposition affected sorption properties in similar trends for both cutin and cutan. The Freundlich capacity coefficients (KFOC) of naphthol were much lower than phenanthrene and were less influenced by the decomposition, whereas with phenanthrene KFOC values increased significantly with time. Naphthol exhibited non-linear isotherms; and nonlinearity was decreased with incubation time. In contrast, phenanthrene isotherms were more linear and showed only moderate change with time. The decrease in the linearity of naphthol isotherms might relate to the transformation of the sorption sites due to structural changes in the biopolymers. However, with phenanthrene, these changes did not affect sorption linearity but increased sorption affinities mainly for cutan. This is probably due to decomposition of the rigid alkyl-C moieties in the cutan biopolymer. Our data suggest that both biopolymers were relatively stable in the soil for 20 mo. Cutan is less degradable than cutin and therefore is more likely to accumulate in soils and contribute to the refractory aliphatic components of soil organic matter.

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

Walton, B.T.

In the present study, acute and chronic toxicities of five PAHs (naphthalene, anthracene, benz(a)anthracene, pyrene, and benzo(a)pyrene) and an oxygenated PAH derivative (anthrone) were determined in a terrestrial insect, Acheta domesticus (L.), with emphasis on the influence of route of entry on toxicity. Hexamethylphosphoric triamide (hempa) was included in the chronic tests since this chemosterilant is a useful reference compound for investigations of reproductive effects of chemicals in insects.

DIELDRIN INDUCES CYTOSOLIC 7,12-[3H-]DIMETHYLBENZ[A]ANTHRACENE BINDING BUT NOT MULTIDRUG RESISTANCE PROTEINS IN RAINBOW TROUT LIVER.

EPA Science Inventory

Previously it was demonstrated that biliary excretion of a single dose of [14C]dieldrin or [3H]7,12-dimethylbenz[a]anthracene (DMBA) was stimulated up to 700% and 300%, respectively, in rainbow trout fed 0.3-0.4 mg dieldrin/kg/d for 9-12 wk. This was not explained by increased ac...

Comparative DNA binding of 7,12-dimethylbenz[a]anthracene and some of its metabolites in mouse epidermis in vivo as revealed by the 32P-postlabeling technique.

PubMed

Schoepe, K B; Friesel, H; Schurdak, M E; Randerath, K; Hecker, E

1986-04-01

The binding of some mouse skin metabolites and related derivatives of the tumor initiator 7,12-dimethylbenz[a]anthracene (DMBA) was investigated by 32P-postlabeling analysis after its topical administration. DMBA and trans-3,4-dihydro-3,4-dihydroxy-DMBA (DMBA-3,4-dihydrodiol) both led to the formation of four DNA adducts, which showed a very similar pattern of spots on thin-layer chromatograms. With trans-8,9-dihydro-8,9-dihydroxy-7,12-dimethylbenz[a]anthracene (DMBA-8,9-dihydrodiol) one major adduct was obtained which was chromatographically indistinguishable from one of the DMBA adducts. In contrast, 7-hydroxymethyl-12-methylbenz[a]anthracene (7-OHM-12-MBA) gave rise to two major adducts which were separable from DMBA adducts. 3-hydroxy-7,12-dimethylbenz[a]anthracene (3-OH-DMBA) and 7,12-dimethylbenz[a]anthracene-7,12-epoxide (DMBA-O2) did not lead to detectable amounts of adducts. Quantitative determination of DNA binding showed that an initiating dose (i = 100 nmol) of DMBA yielded approximately 12 adducts/10(7) normal nucleotides. Adduct formation with the same dose of DMBA-3,4-dihydrodiol was 7-8 times higher. At a 4-fold higher dose level, DMBA-8,9-dihydrodiol exhibited a 3- to 6-times weaker binding and 7-OHM-12-MBA a slightly stronger binding than DMBA. Chromatography of the DMBA and DMBA-3,4-dihydrodiol adducts with a solvent containing borate showed a decreased mobility of two out of four adducts in each case. These adducts were also sensitive to oxidation by periodate. The results suggest that two DMBA adducts carried vicinal cis-hydroxyl groups and thus were probably derived from the anti-3,4-dihydrodiol-1,2-oxide(s) of DMBA. The other two adducts were probably derived from the syn-stereoisomer(s). When the DNA-modifying capabilities and initiating activities of the more prominent mouse-skin metabolites are considered in relation to DMBA, DMBA-3,4-dihydrodiol is postulated to be a proximate and DMBA-3,4-dihydrodiol-1,2-oxide(s) to be ultimate initiators.

Predictive Chemical and Statistical Modeling of Particulate Matter Formation in Turbulent Combustion with Application to Aircraft Engines

DTIC Science & Technology

2012-03-01

the reactant. faster than phenanthrene II, whereas the latter decomposes about as fast as phenanthrene III. The correlation of these rates with the...the spreading rate of the jet at the first station near the nozzle is slightly too fast . Second, at the two downstream stations, the centerline...In previous RANS studies [93–96], the same two discrepancies are observed, that is, an initial jet spreading rate that is too fast and an